WO2020085363A1 - Composition, film, laminate structure, light-emitting device, and display - Google Patents
Composition, film, laminate structure, light-emitting device, and display Download PDFInfo
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- WO2020085363A1 WO2020085363A1 PCT/JP2019/041473 JP2019041473W WO2020085363A1 WO 2020085363 A1 WO2020085363 A1 WO 2020085363A1 JP 2019041473 W JP2019041473 W JP 2019041473W WO 2020085363 A1 WO2020085363 A1 WO 2020085363A1
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/822—Materials of the light-emitting regions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a composition, a film, a laminated structure, a light emitting device and a display.
- Non-Patent Document 1 a composition containing a light emitting semiconductor material coated with 3-aminopropyltriethoxysilane is reported.
- composition containing the light emitting semiconductor material as described in Non-Patent Document 1 does not always have sufficient durability against water vapor.
- the present invention has been made in view of the above circumstances, high durability against water vapor, a composition containing a light-emitting semiconductor material, a film using the composition, a laminated structure using the film, An object of the present invention is to provide a light emitting device and a display including the laminated structure.
- Component (1) Light-emitting semiconductor material (2)
- A is a component located at each vertex of a hexahedron centered on B in the perovskite type crystal structure, and is a monovalent cation.
- X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
- B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion.
- Component (5) ammonium ion, amine, primary to quaternary ammonium cation, ammonium salt, carboxylic acid, carboxylate ion, carboxylate salt, compounds represented by the following formulas (X1) to (X6), And at least one compound or ion selected from the group consisting of salts of compounds represented by the following formulas (X2) to (X4)
- R 18 to R 21 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. , They may have a substituent, and M ⁇ represents a counter anion.
- a 1 represents a single bond or an oxygen atom.
- R 22 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
- a 2 and A 3 each independently represent a single bond or an oxygen atom.
- R 23 and R 24 each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, each of which has a substituent. You may have.
- a 4 represents a single bond or an oxygen atom.
- R 25 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
- a 5 to A 7 each independently represent a single bond or an oxygen atom.
- R 26 to R 28 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. Or represents an alkynyl group having 2 to 20 carbon atoms, which may have a substituent.
- a 8 to A 10 each independently represent a single bond or an oxygen atom.
- R 29 to R 31 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms.
- a composition containing a light-emitting semiconductor material having high durability against water vapor, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure can be provided.
- the component (1) may be described as “(1) semiconductor material”.
- the semiconductor material (1) contained in the composition of the present embodiment has a light emitting property.
- Luminescent refers to the property of emitting light.
- the light emitting property is preferably a property of emitting light when excited by an electron, and more preferably a property of emitting light when excited by an electron by excitation light.
- the wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 750 nm, or 300 nm to 700 nm.
- composition of the present embodiment contains the component (1) and the component (2).
- Component Luminescent semiconductor material (2)
- Component -R 31 SH group-containing silicone
- R 31 is a hydrocarbylene group which may have a substituent.
- composition of the present embodiment may be any composition containing (1) a semiconductor material and (2) -R 31 SH group-containing silicone, and has (1) a semiconductor material and (2) -R 31 SH group. It may further contain components other than silicone.
- composition of the present embodiment contains (1) a semiconductor material and (2) -R 31 SH group-containing silicone, and further comprises (3) component, (4) component, and (4-1) component. It may include at least one selected from the group.
- (3) solvent, (4) polymerizable compound, and (4-1) polymer may be collectively referred to as “dispersion medium”.
- the composition of the present embodiment may be dispersed in these dispersion media.
- dispersed means (1) a state in which a semiconductor material is suspended in a dispersion medium, or (1) a state in which a semiconductor material is suspended in a dispersion medium. (1) When the semiconductor material is dispersed in the dispersion medium, (1) part of the semiconductor material may be precipitated.
- the content ratio of the dispersion medium with respect to the total mass of the composition is not particularly limited.
- the content ratio of the dispersion medium with respect to the total mass of the composition is preferably 99.99% by mass or less, and 99.9% by mass. It is more preferably at most% by mass, further preferably at most 99% by mass.
- the content ratio of the dispersion medium to the total mass of the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and 10% by mass or more. Is more preferred, 50% by mass or more is more preferred, 80% by mass or more is more preferred, and 90% by mass or more is most preferred.
- Examples of combinations of the upper limit value and the lower limit value are 0.1 to 99.99% by mass, 1 to 99.9% by mass, 1 to 99% by mass, 10 to 99% by mass, 20 to 99% by mass, and 50. ⁇ 99% by mass and 90 to 99% by mass.
- composition of the present embodiment may further contain the component (5).
- component (5) ammonium ion, ammonium salt, amine, primary to quaternary ammonium cation, carboxylic acid, carboxylate ion, carboxylate salt, compounds represented by the formulas (X1) to (X6), And at least one compound or ion selected from the group consisting of salts of the compounds represented by the above formulas (X2) to (X4)
- component (5) is referred to as "(5) surface modifier”.
- the content ratio of (1) semiconductor material to the total mass of the composition is not particularly limited. From the viewpoint of making the light-emitting semiconductor material less likely to aggregate and preventing the concentration quenching, the content ratio of (1) the semiconductor material to the total mass of the composition is preferably 50 mass% or less, and 1 mass% or less. Is more preferable, and 0.3% by mass or less is further preferable. From the viewpoint of obtaining good emission intensity, the content ratio of (1) semiconductor material to the total mass of the composition is preferably 0.0001 mass% or more, and more preferably 0.0005 mass% or more. It is more preferably 0.001% by mass or more.
- Examples of combinations of the upper limit value and the lower limit value include 0.0001 to 50% by mass, 0.0005 to 1% by mass, and 0.001 to 0.3% by mass.
- a composition in which the content ratio of (1) semiconductor material to the total mass of the composition is within the above range is preferable because (1) aggregation of the semiconductor material is less likely to occur and luminescence is excellently exhibited.
- the content ratio of the (2) -R 31 SH group-containing silicone to the total mass of the composition is not particularly limited.
- the content ratio of (2) -R 31 SH group-containing silicone to the total mass of the composition is 30% by mass or less. It is preferably 10% by mass or less, more preferably 7.5% by mass or less.
- the content ratio of (2) -R 31 SH group-containing silicone to the total mass of the composition is preferably 0.001% by mass or more, and 0.01% by mass or more. Is more preferable, and 0.1% by mass or more is further preferable.
- Examples of combinations of the upper limit value and the lower limit value include 0.001 to 30% by mass, 0.001 to 10% by mass, and 0.1 to 7.5% by mass.
- a composition having a content ratio of (2) -R 31 SH group-containing silicone within the above range relative to the total mass of the composition is preferable from the viewpoint of durability.
- the content ratio of the (5) surface modifier to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, the content ratio of the (5) surface modifier to the total mass of the composition is preferably 30% by mass or less, more preferably 1% by mass or less, and 0.1% by mass. The following is more preferable. Further, from the viewpoint of improving thermal durability, it is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and further preferably 0.01 mass% or more.
- Examples of combinations of the upper limit value and the lower limit value include 0.0001 to 30% by mass, 0.001 to 1% by mass, and 0.01 to 0.1% by mass.
- a composition in which the content ratio of the (5) surface modifier to the total mass of the composition is within the above range is preferable in terms of excellent heat durability.
- composition of the present embodiment may have other components other than the above (1) to (5).
- the composition of the present embodiment may further contain a small amount of impurities, (1) a compound having an amorphous structure composed of the elements constituting the semiconductor material, and a polymerization initiator.
- the total content of some impurities, (1) the compound having an amorphous structure composed of the elements constituting the semiconductor material, and the polymerization initiator is 10% by mass or less based on the total mass of the composition. Is preferable, 5 mass% or less is more preferable, and 1 mass% or less is further preferable.
- (1) semiconductor material contained in the composition of the present embodiment include the following (i) to (viii).
- (I) Group II-VI compound semiconductor-containing semiconductor material ii) Group II-V compound semiconductor-containing semiconductor material (iii) Group III-V compound semiconductor-containing semiconductor material (iv) Group III-IV Semiconductor Material Containing Compound Semiconductor (v) Semiconductor Material Containing Group III-VI Compound Semiconductor (vi) Semiconductor Material Containing Group IV-VI Compound Semiconductor (vii) Semiconductor Material Containing Transition Metal-p-Block Compound Semiconductor ( viii) a semiconductor material containing a compound semiconductor having a perovskite structure
- the group II-VI compound semiconductor include a compound semiconductor containing a group 2 element and a group 16 element of the periodic table, and a compound semiconductor containing a group 12 element and a group 16 element of the periodic table.
- a "periodic table” means a long period type periodic table.
- a compound semiconductor containing a Group 2 element and a Group 16 element is referred to as a “compound semiconductor (i-1)” and a compound semiconductor containing a Group 12 element and a Group 16 element is referred to as a “compound semiconductor (i-1)”. -2) ".
- examples of binary compound semiconductors include MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, or BaTe.
- (i-1), (I-1-1) A ternary compound semiconductor containing one group 2 element and two group 16 elements (i-1-2) Two group 2 elements and one group 16 element A ternary compound semiconductor (i-1-3) containing two kinds of elements and a quaternary compound semiconductor containing two kinds of group 16 elements may be used.
- binary compound semiconductors include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe.
- a ternary compound semiconductor containing one group 12 element and two group 16 elements (i-2-2) two group 12 elements and one group 16 element
- a ternary compound semiconductor (i-2-3) including two kinds may include a quaternary compound semiconductor including two kinds of Group 12 elements and two kinds of Group 16 elements.
- the group II-VI compound semiconductor may contain an element other than the group 2 element, the group 12 element, and the group 16 element as a doping element.
- the group II-V compound semiconductor contains a group 12 element and a group 15 element.
- binary compound semiconductors include, for example, Zn 3 P 2 , Zn 3 As 2 , Cd 3 P 2 , Cd 3 As 2 , Cd 3 N 2 , or Zn 3 N. 2 .
- (Ii-1) A ternary compound semiconductor containing one group 12 element and two group 15 elements
- (ii-2) A ternary compound semiconductor containing two group 12 elements and one group 15 element
- the compound semiconductor (ii-3) of the group may be a quaternary compound semiconductor containing two kinds of Group 12 elements and two kinds of Group 15 elements.
- the group II-V compound semiconductor may contain an element other than the group 12 element and the group 15 element as a doping element.
- the Group III-V compound semiconductor contains a Group 13 element and a Group 15 element.
- binary compound semiconductors include, for example, BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN. Can be mentioned.
- (Iii-1) A ternary compound semiconductor containing one group 13 element and two group 15 elements
- (iii-2) A ternary compound semiconductor containing two group 13 elements and one group 15 element System compound semiconductor (iii-3)
- a quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 15 elements may be used.
- the group III-V compound semiconductor may contain an element other than the group 13 element and the group 15 element as a doping element.
- the group III-IV compound semiconductor contains a group 13 element and a group 14 element.
- examples of binary compound semiconductors include B 4 C 3 , Al 4 C 3 , and Ga 4 C 3 .
- the compound semiconductor (iv-3) of the system may be a quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 14 elements.
- the group III-IV compound semiconductor may contain an element other than the group 13 element and the group 14 element as a doping element.
- the group III-VI compound semiconductor contains a group 13 element and a group 16 element.
- binary compound semiconductors include, for example, Al 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , GaTe, In 2 S 3 , In 2 Se 3 , In 2 Te 3 , or InTe.
- (V-1) A ternary compound semiconductor containing one group 13 element and two group 16 elements
- (v-2) A ternary compound semiconductor containing two group 13 elements and one group 16 element
- the compound semiconductor (v-3) of the system may be a quaternary compound semiconductor containing two kinds of group 13 elements and two kinds of group 16 elements.
- the group III-VI compound semiconductor may contain an element other than the group 13 element and the group 16 element as a doping element.
- the group IV-VI compound semiconductor contains a group 14 element and a group 16 element.
- binary compound semiconductors include PbS, PbSe, PbTe, SnS, SnSe, or SnTe.
- (Vi-1) A ternary compound semiconductor containing one group 14 element and two group 16 elements
- (vi-2) A ternary compound semiconductor containing two group 14 elements and one group 16 element System compound semiconductor
- (vi-3) A quaternary compound semiconductor containing two kinds of Group 14 elements and two kinds of Group 16 elements may be used.
- the group III-VI compound semiconductor may contain an element other than the group 14 element and the group 16 element as a doping element.
- the transition metal-p-block compound semiconductor contains a transition metal element and a p-block element.
- the "p-block element” is an element belonging to Groups 13 to 18 of the periodic table.
- transition metal-p-block compound semiconductors examples include NiS and CrS.
- transition metal-p-block compound semiconductor (Vii-1) ternary compound semiconductor containing one transition metal element and two p-block elements (vii-2) ternary compound semiconductor containing two transition metal elements and one p-block element Compound semiconductor (vii-3) A quaternary compound semiconductor containing two kinds of transition metal elements and two kinds of p-block elements may be used.
- the transition metal-p-block compound semiconductor may contain a transition metal element and an element other than the p-block element as a doping element.
- a compound semiconductor containing Cd which is a Group 12 element and a compound semiconductor containing In which is a Group 13 element are preferable.
- the compound semiconductor containing Cd and Se and the compound semiconductor containing In and P are preferable.
- the compound semiconductor containing Cd and Se is preferably a binary compound semiconductor, a ternary compound semiconductor, or a quaternary compound semiconductor.
- CdSe which is a binary compound semiconductor, is particularly preferable.
- the compound semiconductor containing In and P is preferably a binary compound semiconductor, a ternary compound semiconductor, or a quaternary compound semiconductor.
- InP which is a binary compound semiconductor, is particularly preferable.
- the compound semiconductor having a perovskite structure has a perovskite type crystal structure having A, B and X as constituent components.
- a compound semiconductor having a perovskite structure may be simply referred to as “perovskite compound”.
- A is a component located at each vertex of a hexahedron centered on B and is a monovalent cation.
- X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
- B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion.
- the perovskite compound containing A, B, and X as constituent components is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a pseudo two-dimensional structure (quasi-2D). .
- the composition formula of the perovskite compound is represented by ABX (3 + ⁇ ) .
- the composition formula of the perovskite compound is represented by A 2 BX (4 + ⁇ ) .
- ⁇ is a number that can be appropriately changed according to the charge balance of B, and is ⁇ 0.7 or more and 0.7 or less.
- A is a monovalent cation
- B is a divalent cation
- X is a monovalent anion
- ⁇ can be selected so that the perovskite compound becomes electrically neutral.
- the electrically neutral perovskite compound means that the charge of the perovskite compound is zero.
- the perovskite compound includes an octahedron whose center is B and whose apex is X.
- the octahedron is represented by BX 6 . If perovskite compound has a 3-dimensional structure, BX 6 contained in the perovskite compound, share one X is located at the apex in octahedral (BX 6), 2 octahedral adjacent in the crystal (BX 6) By doing so, a three-dimensional network is constructed.
- perovskite compound has a two-dimensional structure, BX 6 contained in the perovskite compound, shared by the two X located at the vertices in octahedral (BX 6), 2 octahedral adjacent in the crystal (BX 6) By doing so, the ridgeline of the octahedron is shared and a two-dimensionally continuous layer is formed.
- the perovskite compound has a structure in which two-dimensionally continuous layers of BX 6 and layers of A are alternately laminated.
- the crystal structure of the perovskite compound can be confirmed by an X-ray diffraction pattern.
- the perovskite compound preferably has a three-dimensional structure.
- a constituting the perovskite compound is a monovalent cation.
- Examples of A include cesium ion, organic ammonium ion, and amidinium ion.
- organic ammonium ion Specific examples of the organic ammonium ion of A include a cation represented by the following formula (A3).
- R 6 to R 9 each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group. However, at least one of R 6 to R 9 is an alkyl group or a cycloalkyl group, and all of R 6 to R 9 are not hydrogen atoms at the same time.
- the alkyl groups represented by R 6 to R 9 may each independently be linear or branched.
- the alkyl groups represented by R 6 to R 9 may each independently have an amino group as a substituent.
- R 6 to R 9 are each an alkyl group
- the number of carbon atoms is independently 1 to 20, usually 1 to 4, preferably 1 to 3, and more preferably 1. Is more preferable.
- the cycloalkyl groups represented by R 6 to R 9 may each independently have an amino group as a substituent.
- the number of carbon atoms of the cycloalkyl group represented by R 6 to R 9 is, independently of each other, usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8.
- the number of carbon atoms also includes the number of carbon atoms of the substituent.
- the groups represented by R 6 to R 9 are preferably each independently a hydrogen atom or an alkyl group.
- the perovskite compound contains, as A, an organic ammonium ion represented by the above formula (A3)
- A an organic ammonium ion represented by the above formula (A3)
- the number of alkyl groups and cycloalkyl groups contained in the formula (A3) be small.
- the number of carbon atoms of the alkyl group and the cycloalkyl group which can be included in the formula (A3) is preferably small. Thereby, a perovskite compound having a three-dimensional structure with high emission intensity can be obtained.
- the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R 6 to R 9 is preferably 1 to 4.
- one of R 6 ⁇ R 9 is an alkyl group having 1 to 3 carbon atoms
- three of R 6 ⁇ R 9 is a hydrogen atom More preferably.
- the alkyl group of R 6 to R 9 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group.
- the cycloalkyl group of R 6 ⁇ R 9, include those independently R 6 ⁇ exemplified alkyl group having 3 or more carbon atoms in the alkyl group R 9 is to form a ring.
- Examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group.
- Etc. can be illustrated.
- Examples of the organic ammonium ion represented by A include CH 3 NH 3 + (also called methylammonium ion), C 2 H 5 NH 3 + (also called ethylammonium ion) or C 3 H 7 NH 3 + (propyl). It is also preferably an ammonium ion), more preferably CH 3 NH 3 + or C 2 H 5 NH 3 + , and further preferably CH 3 NH 3 + .
- Examples of the amidinium ion represented by A include an amidinium ion represented by the following formula (A4).
- R 10 R 11 N CH—NR 12 R 13 ) + ... (A4)
- R 10 to R 13 are each independently a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl which may have an amino group as a substituent. Represents a group.
- the alkyl groups represented by R 10 to R 13 may each independently be linear or branched.
- the alkyl groups represented by R 10 to R 13 may each independently have an amino group as a substituent.
- the number of carbon atoms of the alkyl group represented by R 10 to R 13 is independently 1 to 20, usually 1 to 4, and more preferably 1 to 3.
- the cycloalkyl groups represented by R 10 to R 13 may each independently have an amino group as a substituent.
- the number of carbon atoms of the cycloalkyl group represented by R 10 to R 13 is, independently of each other, usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- alkyl group of R 10 to R 13 include the same groups as the alkyl groups exemplified in R 6 to R 9 each independently.
- cycloalkyl group of R 10 to R 13 include the same groups as the cycloalkyl group exemplified in R 6 to R 9 each independently.
- the groups represented by R 10 to R 13 are preferably each independently a hydrogen atom or an alkyl group.
- the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R 10 to R 13 is preferably 1 to 4, and R 10 is an alkyl group having 1 to 3 carbon atoms. More preferably, it is a group and R 11 to R 13 are hydrogen atoms.
- the perovskite compound when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the perovskite compound generally has a three-dimensional structure.
- the perovskite compound when A is an organic ammonium ion having 4 or more carbon atoms or an amidinium ion having 4 or more carbon atoms, the perovskite compound has either a two-dimensional structure or a pseudo two-dimensional (quasi-2D) structure. Have one or both. In this case, the perovskite compound may have a two-dimensional structure or a pseudo-two-dimensional structure in a part or the whole of the crystal. When a plurality of two-dimensional perovskite type crystal structures are laminated, it becomes equivalent to a three-dimensional perovskite type crystal structure (references: P. PBoix et al., J. Phys. Chem. Lett. 2015, 6, 898-907, etc.).
- a of the perovskite compound is preferably a cesium ion or an amidinium ion.
- Component B constituting the perovskite compound may be one or more kinds of metal ions selected from the group consisting of monovalent metal ions, divalent metal ions, and trivalent metal ions.
- B preferably contains a divalent metal ion, more preferably contains at least one metal ion selected from the group consisting of lead and tin, and even more preferably lead.
- Component X constituting the perovskite compound may be at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
- halide ion chloride ion, bromide ion, fluoride ion, iodide ion can be mentioned.
- X preferably contains bromide ion or iodide ion, more preferably contains bromide ion, and further preferably contains bromide ion and iodide ion.
- the content ratio of halide ions can be appropriately selected depending on the emission wavelength.
- a combination of bromide ion and chloride ion or a combination of bromide ion and iodide ion can be used.
- X is preferably a combination of bromide ion and iodide ion.
- X can be appropriately selected according to the desired emission wavelength.
- a perovskite compound in which X is a bromide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more.
- the perovskite compound in which X is a bromide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 700 nm or less, preferably 600 nm or less, more preferably 580 nm or less.
- the upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
- the peak of fluorescence emitted is usually 480 to 700 nm, preferably 500 to 600 nm, and more preferably 520 to 580 nm.
- the perovskite compound in which X is an iodide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 520 nm or more, preferably 530 nm or more, more preferably 540 nm or more.
- a perovskite compound in which X is an iodide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 800 nm or less, preferably 750 nm or less, more preferably 730 nm or less.
- the upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
- the fluorescence peak emitted is usually 520 to 800 nm, preferably 530 to 750 nm, and more preferably 540 to 730 nm.
- a perovskite compound in which X is a chloride ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 300 nm or more, preferably 310 nm or more, more preferably 330 nm or more.
- the perovskite compound in which X is a chloride ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 600 nm or less, preferably 580 nm or less, and more preferably 550 nm or less.
- the upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
- the peak of fluorescence emitted is usually 300 to 600 nm, preferably 310 to 580 nm, and more preferably 330 to 550 nm.
- the perovskite compound having a three-dimensional structure examples include CH 3 NH 3 Pb (1-a) Ca a Br 3 (0 ⁇ a ⁇ 0.7), CH 3 NH 3 Pb (1-a) Sr a Br 3 (0 ⁇ a ⁇ 0.7), CH 3 NH 3 Pb (1-a) La a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ 0.7), CH 3 NH 3 Pb ( 1-a) Ba a Br 3 (0 ⁇ a ⁇ 0.7), CH 3 NH 3 Pb (1-a) Dy a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ 0.7 ) Can also be mentioned.
- Preferred examples of the three-dimensional perovskite compound include CH 3 NH 3 Pb (1-a) Na a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0), CH 3 NH 3 Pb (1-a) Li a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0) can also be mentioned.
- Preferred examples of the three-dimensional perovskite compound include CsPb (1-a) Na a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0) and CsPb (1-a) Li. There can also be mentioned a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0).
- the three-dimensional perovskite compound include CH 3 NH 3 Pb (1-a) Na a Br (3 + ⁇ y) I y (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0, 0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Li a Br (3 + ⁇ y) I y (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0, 0 ⁇ y ⁇ 3 ), CH 3 NH 3 Pb (1-a) Na a Br (3 + ⁇ y) Cl y (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0, 0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Li a Br (3 + ⁇ -y) Cl y (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ ⁇ 0, 0 ⁇ y ⁇ 3) can also be mentioned.
- Preferred examples of the three-dimensional perovskite compound include CsPbBr 3 , CsPbCl 3 , CsPbI 3 , CsPbBr (3-y) I y (0 ⁇ y ⁇ 3), CsPbBr (3-y) Cl y (0 ⁇ y ⁇ 3) can also be mentioned.
- Preferred examples of the perovskite compound having a three-dimensional structure include CH 3 NH 3 Pb (1-a) Zn a Br 3 (0 ⁇ a ⁇ 0.7), CH 3 NH 3 Pb (1-a) Al a Br ( 3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.7), CH 3 NH 3 Pb (1-a) Co a Br 3 (0 ⁇ a ⁇ 0.7), CH 3 NH 3 Pb ( 1-a) Mn a Br 3 (0 ⁇ a ⁇ 0.7) and CH 3 NH 3 Pb (1-a) Mg a Br 3 (0 ⁇ a ⁇ 0.7) can also be mentioned.
- Preferred examples of perovskite compound having a three-dimensional structure is, CsPb (1-a) Zn a Br 3 (0 ⁇ a ⁇ 0.7), CsPb (1-a) Al a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0 .7, 0 ⁇ ⁇ 0.7), CsPb (1-a) Co a Br 3 (0 ⁇ a ⁇ 0.7), CsPb (1-a) Mna a Br 3 (0 ⁇ a ⁇ 0.7) ) And CsPb (1-a) Mg a Br 3 (0 ⁇ a ⁇ 0.7) can also be mentioned.
- Preferred examples of the three-dimensional perovskite compound are CH 3 NH 3 Pb (1-a) Zn a Br (3-y) I y (0 ⁇ a ⁇ 0.7, 0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Al a Br (3 + ⁇ -y) I y (0 ⁇ a ⁇ 0.7,0 ⁇ ⁇ 0.7,0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1- a) Co a Br (3- y) I y (0 ⁇ a ⁇ 0.7,0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Mn a Br (3-y) I y (0 ⁇ A ⁇ 0.7, 0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Mg a Br (3-y) I y (0 ⁇ a ⁇ 0.7, 0 ⁇ y ⁇ 3), CH 3 NH 3 Pb (1-a) Zn a Br (3-y) Cl y (0
- CsPbBr 3 , CsPbBr (3-y) I y (0 ⁇ y ⁇ 3), and (H 2 N CH—NH 2 ) PbBr 3 are more preferable, and (H 2 N Further preferred is ⁇ CH—NH 2 ) PbBr 3 .
- Preferred examples of the perovskite compound having a two-dimensional structure include (C 4 H 9 NH 3 ) 2 PbBr 4 , (C 4 H 9 NH 3 ) 2 PbCl 4 , (C 4 H 9 NH 3 ) 2 PbI 4 , and (C 7 H 15 NH 3 ) 2 PbBr 4 , (C 7 H 15 NH 3 ) 2 PbCl 4 , (C 7 H 15 NH 3 ) 2 PbI 4 , (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ 0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4 + ⁇ ) (0 ⁇ a ⁇ 0.7, ⁇ 0.7 ⁇ ⁇ 0), (C 4 H 9 NH 3 ) 2 Pb (1-a)
- Preferable examples of the two-dimensional perovskite compound also include (C 4 H 9 NH 3 ) 2 PbBr 4 and (C 7 H 15 NH 3 ) 2 PbBr 4 .
- Preferred examples of the two-dimensional perovskite compound include (C 4 H 9 NH 3 ) 2 PbBr (4-y) Cl y (0 ⁇ y ⁇ 4), (C 4 H 9 NH 3 ) 2 PbBr (4- y) I y (0 ⁇ y ⁇ 4) can also be mentioned.
- the perovskite compound having a two-dimensional structure examples include (C 4 H 9 NH 3 ) 2 Pb (1-a) Zn a Br 4 (0 ⁇ a ⁇ 0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 ⁇ a ⁇ 0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br 4 (0 ⁇ a ⁇ 0.7), ( C 4 H 9 NH 3) 2 Pb (1-a) Mn a Br 4 (0 ⁇ a ⁇ 0.7) may also be mentioned.
- the perovskite compound having a two-dimensional structure examples include (C 7 H 15 NH 3 ) 2 Pb (1-a) Zn a Br 4 (0 ⁇ a ⁇ 0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 ⁇ a ⁇ 0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Co a Br 4 (0 ⁇ a ⁇ 0.7), ( C 7 H 15 NH 3) 2 Pb (1-a) Mn a Br 4 (0 ⁇ a ⁇ 0.7) may also be mentioned.
- the average particle size of the particulate (1) semiconductor material is particularly limited as long as it has the effect of the present invention. Not done.
- the average particle size of the semiconductor particles is preferably 1 nm or more because the crystal structure can be maintained well.
- the average particle diameter of the semiconductor particles is more preferably 2 nm or more, further preferably 3 nm or more.
- the average particle size of the semiconductor particles is preferably 10 ⁇ m or less because the semiconductor material is unlikely to settle and the desired light emitting characteristics are easily maintained.
- the average particle diameter of the semiconductor particles is more preferably 1 ⁇ m or less, further preferably 500 nm or less.
- the “emission characteristic” refers to optical properties such as quantum yield of converted light, emission intensity, and color purity obtained by irradiating light-emitting semiconductor particles with excitation light. The color purity can be evaluated by the full width at half maximum of the spectrum of converted light.
- the upper limit value and the lower limit value of the average particle diameter of the semiconductor particles can be arbitrarily combined.
- the average particle size of the semiconductor particles is preferably 1 nm or more and 10 ⁇ m or less, more preferably 2 nm or more and 1 ⁇ m or less, and further preferably 3 nm or more and 500 nm or less.
- the average particle size of semiconductor particles can be measured by, for example, a transmission electron microscope (hereinafter, also referred to as TEM) or a scanning electron microscope (hereinafter, also referred to as SEM).
- TEM transmission electron microscope
- SEM scanning electron microscope
- the average particle diameter can be obtained by measuring the maximum Feret diameter of 20 semiconductor particles by TEM or SEM and calculating the average maximum Feret diameter which is the arithmetic mean value of the measured values.
- the “maximum Feret diameter” means the maximum distance between two parallel straight lines sandwiching a semiconductor particle on a TEM or SEM image.
- the median diameter (D50) of semiconductor particles is not particularly limited as long as it has the effect of the present invention.
- the thickness is preferably 3 nm or more because the crystal structure can be favorably maintained.
- the median diameter of the semiconductor particles is more preferably 4 nm or more, further preferably 5 nm or more.
- the median diameter (D50) of the semiconductor particles is preferably 5 ⁇ m or less because the semiconductor material is less likely to settle and the desired light emission characteristics are easily maintained.
- the median diameter of the semiconductor particles is more preferably 500 nm or less, further preferably 100 nm or less.
- the upper limit value and the lower limit value of the median diameter (D50) of the semiconductor particles can be arbitrarily combined.
- the median diameter (D50) of the semiconductor particles is preferably 3 nm or more and 5 ⁇ m or less, more preferably 4 nm or more and 500 nm or less, and further preferably 5 nm or more and 100 nm or less.
- the particle size distribution of semiconductor particles can be measured by, for example, TEM or SEM. Specifically, the maximum Feret diameter of 20 semiconductor particles is observed by TEM or SEM, and the median diameter (D50) can be obtained from the distribution of the maximum Feret diameter.
- the above (1) semiconductor material may be used alone or in combination of two or more.
- the silicone having a —R 31 SH group is a silicone in which a —R 31 SH group is bonded to a silicon atom contained in the main chain of the silicone.
- R 31 is a hydrocarbylene group which may have a substituent.
- sicone means a compound having a structure having a siloxane bond as a main chain and an organic group connected to a side chain.
- the silicone having the (2) -R 31 SH group has a shell structure having (5) the surface modifier-coated semiconductor material as a core. Is preferably formed. Specifically, the silicone having the (2) -R 31 SH group covers (1) at least a part of the surface of the semiconductor material and (5) covers at least a part of the surface of the surface modifier. It is preferable that (5) the surface modifier is not coated, and (1) at least a part of the surface of the semiconductor material may be coated.
- a semiconductor material or (5) a silicone having a (2) -R 31 SH group that covers at least a part of the surface of the surface modifier is, for example, a composition obtained by SEM or TEM. It is possible to confirm the coated state by observing with use. Furthermore, detailed element distribution can be analyzed by energy dispersive X-ray analysis (EDX) measurement using SEM or TEM.
- EDX energy dispersive X-ray analysis
- the silicone having (2) —R 31 SH group is preferably, for example, a silicone represented by the following formula (B).
- R 31 is a hydrocarbylene group which may have a substituent.
- R 32 is a hydrocarbyl group which may have a substituent, and a plurality of R 32 may be the same, may be different from each other, or may be the same only in part.
- m is not particularly limited, but is preferably an integer of 10 to 100,000.
- n is not particularly limited, but is preferably an integer of 1 to 100,000.
- m + n is not particularly limited, but is preferably an integer of 11 to 200,000.
- the hydrocarbylene group represented by R 31 may be linear or branched.
- Examples of the hydrocarbylene group represented by R 31 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and an aralkylene group.
- the number of carbon atoms of the hydrocarbylene group represented by R 31 is usually 20 to 200,000, preferably 100 to 100,000, and more preferably 1,000 to 90,000.
- the number of carbon atoms is the number including the number of carbon atoms of the substituent.
- Examples of the substituent which the hydrocarbylene group represented by R 31 has include a hydrocarbon group, an amino group, a cyano group, a mercapto group, a nitro group and a halogeno group.
- Examples of the hydrocarbyl group represented by R 32 include an alkyl group, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group. Among the above, R 32 is preferably an alkyl group.
- the number of carbon atoms of the hydrocarbyl group represented by R 32 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. The number of carbon atoms is the number including the number of carbon atoms of the substituent.
- Examples of the substituent of the hydrocarbyl group represented by R 32 include a hydrocarbon group, an amino group, a cyano group, a mercapto group, a nitro group and a halogeno group.
- alkyl group of R 32 include the alkyl groups exemplified in R 6 to R 9 , and include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group.
- M is preferably 10 to 20000, and more preferably 10 to 10000.
- n is preferably 1 to 70,000, and more preferably 1 to 30,000.
- m + n is preferably 100 to 100,000, and more preferably 1000 to 10000.
- the above-mentioned silicone having a (2) -R 31 SH group may be used alone or in combination of two or more.
- the surface modifier is represented by ammonium ion, amine, primary to quaternary ammonium cation, ammonium salt, carboxylic acid, carboxylate ion, carboxylate salt, and formulas (X1) to (X6), respectively. At least one compound or ion selected from the group consisting of compounds and salts of the compounds represented by formulas (X2) to (X4).
- the surface modifier is preferably at least one selected from the group consisting of amines, primary to quaternary ammonium cations, ammonium salts, carboxylic acids, carboxylate ions and carboxylate salts as a forming material. And at least one compound or ion selected from the group consisting of carboxylic acids.
- the surface modifier is located on the surface of (1) semiconductor material in the composition of the present embodiment, and acts as (1) surface modifier of semiconductor material (also referred to as capping ligand). More specifically, (5) the surface modifier preferably covers at least a part of the surface of (1) the semiconductor material. (5) The surface modifier covers at least a part of the surface of (1) the semiconductor material, so that the durability of the (1) semiconductor material is improved.
- the surface modifier that covers at least a part of the surface of the semiconductor material can be confirmed by observing the composition using SEM, TEM, or the like. Further, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.
- ammonium ion, primary to quaternary ammonium cation, ammonium salt The ammonium ion and the primary to quaternary ammonium cations that are the surface modifier are represented by the following formula (A1).
- the ammonium salt that is the surface modifier is a salt containing an ion represented by the following formula (A1).
- R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group.
- the hydrocarbon group represented by R 1 to R 4 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- saturated hydrocarbon group include an alkyl group and a cycloalkyl group.
- the alkyl group represented by R 1 to R 4 may be linear or branched.
- the alkyl group represented by R 1 to R 4 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
- the cycloalkyl group represented by R 1 to R 4 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- the unsaturated hydrocarbon group of R 1 to R 4 may be linear or branched.
- the unsaturated hydrocarbon group of R 1 to R 4 usually has 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
- R 1 to R 4 are preferably a hydrogen atom, an alkyl group, or an unsaturated hydrocarbon group.
- the unsaturated hydrocarbon group is preferably an alkenyl group.
- R 1 to R 4 are preferably alkenyl groups having 8 to 20 carbon atoms.
- alkyl group of R 1 to R 4 include the alkyl groups exemplified in R 6 to R 9 .
- cycloalkyl group of R 1 to R 4 include the cycloalkyl groups exemplified in R 6 to R 9 .
- the alkenyl group for R 1 to R 4 is the linear or branched alkyl group exemplified for R 6 to R 9 and is a single bond (C—C) between carbon atoms.
- Preferred alkenyl groups for R 1 to R 4 include, for example, ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group. Group, a 9-octadecenyl group.
- the counter anion is not particularly limited.
- the counter anion halide ion, carboxylate ion and the like are preferable.
- the halide ion include bromide ion, chloride ion, iodide ion, and fluoride ion.
- ammonium salt having the ammonium cation represented by the formula (A1) and the counter anion include n-octyl ammonium salt and oleyl ammonium salt.
- the amine as the surface modifier can be represented by the following formula (A11).
- R 1 ⁇ R 3 represent the same groups as R 1 ⁇ R 3 to the formula (A1) has. However, at least one of R 1 to R 3 is a monovalent hydrocarbon group.
- the amine as the surface modifier may be any of primary to tertiary amines, but primary amines and secondary amines are preferable, and primary amines are more preferable.
- Oleylamine is preferred as the amine as the surface modifier.
- the carboxylate ion, which is a surface modifier is represented by the following formula (A2).
- the carboxylate salt, which is a surface modifier is a salt containing an ion represented by the following formula (A2). R 5 -CO 2 - ⁇ (A2 )
- Examples of the carboxylic acid that is the surface modifier include a carboxylic acid having a proton (H + ) bonded to the carboxylate anion represented by (A2) above.
- R 5 represents a monovalent hydrocarbon group.
- the hydrocarbon group represented by R 5 may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- Examples of the saturated hydrocarbon group include an alkyl group and a cycloalkyl group.
- the alkyl group represented by R 5 may be linear or branched.
- the alkyl group represented by R 5 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
- the cycloalkyl group represented by R 5 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms.
- the number of carbon atoms also includes the number of carbon atoms of the substituent.
- the unsaturated hydrocarbon group represented by R 5 may be linear or branched.
- the unsaturated hydrocarbon group represented by R 5 usually has 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
- R 5 is preferably an alkyl group or an unsaturated hydrocarbon group.
- the unsaturated hydrocarbon group is preferably an alkenyl group.
- alkyl group of R 5 include the alkyl groups exemplified in R 6 to R 9 .
- cycloalkyl group for R 5 include the cycloalkyl groups exemplified for R 6 to R 9 .
- alkenyl group for R 5 include the alkenyl groups exemplified for R 1 to R 4 .
- the oleate anion is preferable as the carboxylate anion represented by the formula (A2).
- the counter cation is not particularly limited, but preferable examples include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.
- Oleic acid is preferred as the carboxylic acid that is the surface modifier.
- R 18 to R 21 each independently have an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent.
- the alkyl group represented by R 18 to R 21 may be linear or branched.
- the alkyl group represented by R 18 to R 21 preferably has an aryl group as a substituent.
- the alkyl group represented by R 18 to R 21 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- the cycloalkyl group represented by R 18 to R 21 preferably has an aryl group as a substituent.
- the cycloalkyl group represented by R 18 to R 21 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- the aryl group represented by R 18 to R 21 preferably has an alkyl group as a substituent.
- the aryl group represented by R 18 to R 21 usually has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- the group represented by R 18 to R 21 is preferably an alkyl group.
- alkyl group represented by R 18 to R 21 include the alkyl groups exemplified in the alkyl group represented by R 6 to R 9 .
- cycloalkyl group represented by R 18 to R 21 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
- aryl group represented by R 18 to R 21 examples include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group and the like.
- the hydrogen atoms contained in the groups represented by R 18 to R 21 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Can be mentioned. Since the chemical stability of the compound substituted with a halogen atom is high, the halogen atom to be substituted is preferably a fluorine atom.
- M ⁇ represents a counter anion.
- halide ion As the counter anion, halide ion, carboxylate ion and the like are preferable.
- the halide ion include bromide ion, chloride ion, iodide ion, and fluoride ion, and bromide ion is preferable.
- Specific examples of the compound represented by the formula (X1) include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide; tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide: tetraphenylphosphonium chloride, tetra Phenylphosphonium bromide, tetraphenylphosphonium iodide; tetra-n-octylphosphonium chloride, tetra-n-octylphosphonium bromide, tetra-n-octylphosphonium iodide; tributyl-n-octylphosphonium bromide; tributyldodecylphosphonium bromide; tributylhexa Decylphospho
- tributylhexadecylphosphonium bromide and tributyl-n-octylphosphonium bromide are preferable as the compound represented by the formula (X1), and tributyl-n-octylphosphonium bromide is more preferable. .
- a 1 represents a single bond or an oxygen atom.
- R 22 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 3 to 30 carbon atoms which may have a substituent. It represents a cycloalkyl group or an aryl group having 6 to 30 carbon atoms which may have a substituent.
- the alkyl group represented by R 22 may be linear or branched.
- alkyl group represented by R 22 the same group as the alkyl group represented by R 18 to R 21 can be adopted.
- cycloalkyl group represented by R 22 the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
- aryl group represented by R 22 the same group as the aryl group represented by R 18 to R 21 can be adopted.
- the group represented by R 22 is preferably an alkyl group.
- the hydrogen atoms contained in the group represented by R 22 may be each independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, From the viewpoint of chemical stability, a fluorine atom is preferable.
- the anionic group is represented by the following formula (X2-1).
- an example of the counter cation forming a pair with the formula (X2-1) is an ammonium ion.
- the counter cation forming a pair in the formula (X2-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
- the compound represented by the formula (X2) and the salt of the compound represented by the formula (X2) include phenyl phosphate, phenyl disodium phosphate hydrate, 1-naphthyl disodium phosphate hydrate, and 1 -Naphthyl phosphate monosodium monohydrate, lauryl phosphate, sodium lauryl phosphate, oleyl phosphate, benzhydrylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, ethylphosphonic acid, hexadecylphosphonic acid, heptylphosphonic acid, Hexylphosphonic acid, methylphosphonic acid, nonylphosphonic acid, octadecylphosphonic acid, n-octylphosphonic acid, benzenephosphonic acid, phenylphosphonic acid disodium hydrate, phenethylphosphonic acid, propylphosphonic acid, undecylphosphonic acid,
- examples of the compound represented by the formula (X2) include oleylphosphoric acid, dodecylphosphonic acid, ethylphosphonic acid, hexadecylphosphonic acid, heptylphosphonic acid, hexylphosphonic acid, and methylphosphone. Acid, nonylphosphonic acid, octadecylphosphonic acid and n-octylphosphonic acid are more preferable, and octadecylphosphonic acid is still more preferable.
- a 2 and A 3 each independently represent a single bond or an oxygen atom.
- R 23 and R 24 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. It represents a cycloalkyl group having 3 to 30 atoms or an aryl group having 6 to 30 carbon atoms which may have a substituent.
- the alkyl groups represented by R 23 and R 24 may each independently be linear or branched.
- alkyl group represented by R 23 and R 24 the same group as the alkyl group represented by R 18 to R 21 can be adopted.
- cycloalkyl group represented by R 23 and R 24 the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
- aryl group represented by R 23 and R 24 the same group as the aryl group represented by R 18 to R 21 can be adopted.
- R 23 and R 24 are preferably each independently an alkyl group.
- the hydrogen atoms contained in the groups represented by R 23 and R 24 may each independently be substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
- the anionic group is represented by the following formula (X3-1).
- an example of the counter cation paired with the formula (X3-1) is an ammonium ion.
- the counter cation forming a pair in the formula (X3-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
- Examples of the salt of the compound represented by the formula (X3) include diphenylphosphinic acid, dibutyl phosphate, didecyl phosphate and diphenyl phosphate. Examples of the salt of the compound represented by the formula (X3) include salts of the above compounds.
- diphenylphosphinic acid dibutyl phosphate and didecyl phosphate are preferable, and diphenylphosphinic acid is more preferable.
- a 4 represents a single bond or an oxygen atom.
- the group represented by R 25 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, a carbon atom which may have a substituent. It represents a cycloalkyl group of 3 to 30 or an aryl group of 6 to 30 carbon atoms which may have a substituent.
- the alkyl group represented by R 25 may be linear or branched.
- alkyl group represented by R 25 the same group as the alkyl group represented by R 18 to R 21 can be adopted.
- cycloalkyl group represented by R 25 the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
- aryl group represented by R 25 the same group as the aryl group represented by R 18 to R 21 can be adopted.
- the group represented by R 25 is preferably an alkyl group.
- the hydrogen atoms contained in the group represented by R 25 may each independently be substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, From the viewpoint of chemical stability, a fluorine atom is preferable.
- Examples of the compound represented by the formula (X4) include 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, hexadecylsulfate, laurylsulfate, myristylsulfate, laurethsulfate and dodecylsulfate.
- the anionic group is represented by the following formula (X4-1).
- examples of the counter cation paired with the formula (X4-1) include an ammonium salt.
- the counter cation forming a pair in the formula (X4-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
- Examples of the salt of the compound represented by the formula (X4) include sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium hexadecyl sulfate, sodium lauryl sulfate, sodium myristyl sulfate and sodium laureth sulfate. , Sodium dodecyl sulfate.
- sodium hexadecyl sulfate and sodium dodecyl sulfate are preferable, and sodium dodecyl sulfate is more preferable.
- a 5 to A 7 each independently represent a single bond or an oxygen atom.
- R 26 to R 28 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent.
- a cycloalkyl group having 3 to 30 atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent Represents an alkynyl group having 2 to 20 carbon atoms which may have a group.
- the alkyl groups represented by R 26 to R 28 may each independently be linear or branched.
- alkyl group represented by R 26 to R 28 the same group as the alkyl group represented by R 18 to R 21 can be adopted.
- cycloalkyl group represented by R 26 to R 28 the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
- aryl group represented by R 26 to R 28 the same group as the aryl group represented by R 18 to R 21 can be adopted.
- the alkenyl groups represented by R 26 to R 28 each independently have an alkyl group or an aryl group as a substituent.
- the alkenyl group represented by R 26 to R 28 usually has 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- the alkynyl groups represented by R 26 to R 28 each independently preferably have an alkyl group or an aryl group as a substituent.
- the alkynyl group represented by R 26 to R 28 usually has 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
- the number of carbon atoms includes the number of carbon atoms of the substituent.
- R 26 to R 28 are each independently an alkyl group.
- alkenyl group represented by R 26 to R 28 examples include a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and an icosenyl group.
- alkynyl group represented by R 26 to R 28 examples include a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a tetradecynyl group, a hexadecynyl group, an octadecynyl group, and an icosinyl group.
- the hydrogen atoms contained in the groups represented by R 26 to R 28 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
- Examples of the compound represented by the formula (X5) include trioleyl phosphite, tributyl phosphite, triethyl phosphite, trihexyl phosphite, triisodecyl phosphite, trimethyl phosphite, cyclohexyldiphenylphosphine and di-tert.
- trioleyl phosphite tributylphosphine, trihexylphosphine and trihexyl phosphite are preferable, and trioleyl phosphite is more preferable.
- a 8 to A 10 each independently represent a single bond or an oxygen atom.
- R 29 to R 31 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent.
- a cycloalkyl group having 3 to 30 atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent Represents an alkynyl group having 2 to 20 carbon atoms which may have a group.
- the alkyl groups represented by R 29 to R 31 may each independently be linear or branched.
- alkyl group represented by R 29 to R 31 the same group as the alkyl group represented by R 18 to R 21 can be adopted.
- cycloalkyl group represented by R 29 to R 31 the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
- aryl group represented by R 29 to R 31 the same group as the aryl group represented by R 18 to R 21 can be adopted.
- alkenyl group represented by R 29 to R 31 the same group as the alkenyl group represented by R 26 to R 28 can be adopted.
- alkynyl group represented by R 29 to R 31 the same group as the alkynyl group represented by R 26 to R 28 can be adopted.
- R 29 to R 31 are preferably each independently an alkyl group.
- the hydrogen atoms contained in the groups represented by R 29 to R 31 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
- Examples of the compound represented by the formula (X6) include tri-n-octylphosphine oxide, tributylphosphine oxide, methyl (diphenyl) phosphine oxide, triphenylphosphine oxide, tri-p-tolylphosphine oxide, cyclohexyldiphenylphosphine oxide and phosphorus.
- Trimethyl phosphate, tributyl phosphate, triamyl phosphate, tris (2-butoxyethyl) phosphate, triphenyl phosphate, tri-p-cresyl phosphate, tri-m-cresyl phosphate, tri-o-cresyl phosphate Can be mentioned.
- tri-n-octylphosphine oxide and tributylphosphine oxide are preferable, and tri-n-octylphosphine oxide is more preferable.
- ammonium salts ammonium ions, primary to quaternary ammonium cations, carboxylate salts and carboxylate ions are preferable.
- ammonium salts and ammonium ions oleylamine salt and oleylammonium ion are more preferable.
- carboxylate salts and carboxylate ions oleate and oleate cation are more preferable.
- the above-mentioned (5) surface modifier may be used alone or in combination of two or more kinds.
- the solvent (3) contained in the composition of the present embodiment is not particularly limited as long as it is a medium in which (1) the semiconductor material can be dispersed.
- the solvent contained in the composition of this embodiment is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
- solvent refers to a substance that is in a liquid state at 1 atm and 25 ° C. However, the solvent does not include a polymerizable compound and a polymer described later.
- Examples of the solvent include the following (a) to (k).
- Examples of (a) ester include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and the like.
- ketones examples include ⁇ -butyrolactone, N-methyl-2-pyrrolidone, acetone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone.
- ether (c) examples include diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole and phenetole. Etc. can be mentioned.
- glycol ethers examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether.
- Examples of the organic solvent having an amide group include N, N-dimethylformamide, acetamide, N, N-dimethylacetamide and the like.
- Examples of the organic solvent having a nitrile group include acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile.
- Examples of the organic solvent having a carbonate group include ethylene carbonate and propylene carbonate.
- halogenated hydrocarbons examples include methylene chloride and chloroform.
- Examples of the (j) hydrocarbon include n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene and xylene.
- the above solvent may be used alone or in combination of two or more.
- the (4) polymerizable compound contained in the composition of the present embodiment is preferably one that is difficult to dissolve the (1) semiconductor material of the present embodiment at the temperature for producing the composition of the present embodiment.
- the “polymerizable compound” means a monomer compound (monomer) having a polymerizable group.
- the polymerizable compound may include a monomer that is in a liquid state at 1 atmosphere and 25 ° C.
- the polymerizable compound when the composition is produced at room temperature under normal pressure, is not particularly limited.
- the polymerizable compound include known polymerizable compounds such as styrene, acrylic acid ester, methacrylic acid ester, and acrylonitrile. Among them, as the polymerizable compound, one or both of acrylic acid ester and methacrylic acid ester, which are monomers of the acrylic resin, are preferable.
- the polymerizable compound may be used alone or in combination of two or more.
- the ratio of the total amount of acrylic acid ester and methacrylic acid ester to all (4) polymerizable compounds may be 10 mol% or more. The same ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, and 100 mol%.
- the polymer contained in the composition of the present embodiment is preferably a polymer having a low solubility of (1) the semiconductor material of the present embodiment at the temperature for producing the composition of the present embodiment.
- the polymer when the composition is produced at room temperature under normal pressure, is not particularly limited, and examples thereof include known polymers such as polystyrene, acrylic resin, and epoxy resin. Among them, acrylic resin is preferable as the polymer.
- the acrylic resin contains either one or both of a structural unit derived from an acrylate ester and a structural unit derived from a methacrylic acid ester.
- the ratio of the total amount of the structural unit derived from the acrylate ester and the structural unit derived from the methacrylic acid ester to all the structural units contained in the (4-1) polymer is 10 mol%. It may be more than. The same ratio may be 30% mol or more, 50 mol% or more, 80 mol% or more, or 100 mol%.
- the weight average molecular weight of the (4-1) polymer is preferably 100 to 1200000, more preferably 1000 to 800000, and further preferably 5000 to 150,000.
- the “weight average molecular weight” means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
- the above-mentioned (4-1) polymer may be used alone or in combination of two or more kinds.
- the compounding ratio of (1) the semiconductor material and the silicone having the (2) -R 31 SH group is (1) the kind of the semiconductor material and the silicone having the (2) -R 31 SH group, etc. Can be appropriately determined according to
- the compounding ratio of (1) the semiconductor material and (5) the surface modifier may be such that (1) the semiconductor material exhibits a favorable light-emission action. It can be appropriately determined according to the type of constituent components and the like.
- the molar ratio [(1) semiconductor material / (5) surface modifier] of (1) semiconductor material to (5) surface modifier is 0.0001 to 1,000. It may be 0.01 to 100.
- the resin composition in which the range of the compounding ratio of (1) the semiconductor material and (5) the surface modifier is within the above range is (1) the aggregation of the semiconductor material is less likely to occur and the light emitting property is also excellently exhibited. It is preferable in terms.
- composition of the present embodiment is not limited to that produced by the method for producing the composition of the following embodiments.
- the semiconductor materials (i) to (vii) can be manufactured by a method of heating a mixed liquid obtained by mixing a simple substance of the elements constituting the semiconductor material or a compound of the elements constituting the semiconductor material and a fat-soluble solvent. .
- Examples of the compound containing an element constituting the semiconductor material are not particularly limited, but include oxides, acetates, organometallic compounds, halides, nitrates and the like.
- the fat-soluble solvent examples include nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms and oxygen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms.
- hydrocarbon group having 4 to 20 carbon atoms examples include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- saturated aliphatic hydrocarbon group having 4 to 20 carbon atoms examples include n-butyl group, isobutyl group, n-pentyl group, octyl group, decyl group, dodecyl group, hexadecyl group and octadecyl group.
- an oleyl group As an unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms, an oleyl group can be mentioned.
- Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclopentyl group and cyclohexyl group.
- aromatic hydrocarbon group having 4 to 20 carbon atoms examples include phenyl group, benzyl group, naphthyl group and naphthylmethyl group.
- hydrocarbon group having 4 to 20 carbon atoms a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferable.
- Examples of the nitrogen-containing compound include amines and amides.
- Examples of the oxygen-containing compound include fatty acids.
- nitrogen-containing compounds having a hydrocarbon group with 4 to 20 carbon atoms are preferable.
- nitrogen-containing compounds include alkylamines such as n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine and octadecylamine, and oleylamine.
- Alkenylamines are preferred.
- a fat-soluble solvent can bind to the surface of a semiconductor material produced by synthesis.
- Examples of the bond when the lipophilic solvent bonds to the surface of the semiconductor material include chemical bonds such as covalent bond, ionic bond, coordination bond, hydrogen bond, and van der Waals bond.
- the heating temperature of the above mixed solution may be appropriately set depending on the type of raw material (single substance or compound) used.
- the heating temperature of the mixed solution is, for example, preferably 130 to 300 ° C, more preferably 240 to 300 ° C. It is preferable for the heating temperature to be at least the above lower limit value because the crystal structure is easily unified. When the heating temperature is not higher than the above upper limit, the crystal structure of the semiconductor material that is produced is less likely to collapse, and the target product is easily obtained, which is preferable.
- the heating time of the mixed solution may be appropriately set depending on the types of raw materials (single or compound) used and the heating temperature.
- the heating time of the mixed liquid is, for example, preferably several seconds to several hours, more preferably 1 to 60 minutes.
- a precipitate containing the target semiconductor material can be obtained.
- the target semiconductor material can be obtained.
- a solvent in which the synthesized semiconductor material is insoluble or sparingly soluble is added to reduce the solubility of the semiconductor material in the supernatant liquid to form a precipitate, and the semiconductor material contained in the supernatant liquid is added. You may collect it.
- the “solvent in which the semiconductor material is insoluble or sparingly soluble” include methanol, ethanol, acetone, acetonitrile and the like.
- the separated precipitate may be put in an organic solvent (eg, chloroform, toluene, hexane, n-butanol, etc.) to form a solution containing the semiconductor material.
- an organic solvent eg, chloroform, toluene, hexane, n-butanol, etc.
- the manufacturing method of the semiconductor material of (viii) can be manufactured by the method described below with reference to known literatures (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542).
- First manufacturing method As a method for producing a perovskite compound, a step of dissolving a compound containing an A component, a compound containing a B component, and a compound containing an X component, which form the perovskite compound, in a first solvent; A manufacturing method including a step of mixing two solvents.
- the second solvent has a lower solubility for the perovskite compound than the first solvent.
- the solubility means the solubility at the temperature at which the step of mixing the obtained solution and the second solvent is performed.
- the first solvent and the second solvent at least two kinds selected from the group of organic solvents mentioned above as (a) to (k) can be mentioned.
- the above-mentioned (d) alcohol, (e) glycol ether, and (f) amide group are used as the first solvent.
- the organic solvent which it has and (k) dimethyl sulfoxide can be mentioned.
- the second solvent may be the above-mentioned (a) ester, (b) ketone, (c) ether, or (g). ) Organic solvents having a nitrile group, (h) organic solvents having a carbonate group, (i) halogenated hydrocarbons, and (j) hydrocarbons.
- the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in the first solvent to obtain a solution.
- the “compound including the component A” may include the component X.
- the “compound including the component B” may include the component X.
- the solution obtained and the second solvent are mixed.
- the (I) solution may be added to the second solvent, or the (II) second solvent may be added to the solution. Since the particles of the perovskite compound generated in the first production method are easily dispersed in the solution, it is advisable to add the solution (I) to the second solvent.
- the temperature of the solution and the second solvent there is no particular limitation on the temperature of the solution and the second solvent. Since the obtained perovskite compound is easily precipitated, the temperature is preferably in the range of -20 ° C to 40 ° C, more preferably in the range of -5 ° C to 30 ° C. The temperature of the solution and the temperature of the second solvent may be the same or different.
- the difference in solubility between the first solvent and the second solvent in the perovskite compound is preferably 100 ⁇ g / solvent 100 g to 90 g / solvent 100 g, and more preferably 1 mg / solvent 100 g to 90 g / solvent 100 g.
- the first solvent is an organic solvent having an amide group such as N, N-dimethylacetamide or dimethyl sulfoxide
- the second solvent is a halogenated hydrocarbon or a hydrocarbon.
- the solubility of the first solvent and the second solvent in the perovskite compound when performing the step of mixing at room temperature (10 ° C to 30 ° C) Is preferable because it is easy to control the difference of 100 ⁇ g / solvent 100 g to 90 g / solvent 100 g.
- the solubility of the perovskite compound decreases in the resulting mixed solution, and the perovskite compound precipitates. As a result, a dispersion liquid containing the perovskite compound is obtained.
- the perovskite compound By performing solid-liquid separation on the obtained dispersion liquid containing the perovskite compound, the perovskite compound can be recovered.
- the solid-liquid separation method include filtration and concentration by evaporation of the solvent. By performing solid-liquid separation, only the perovskite compound can be recovered.
- the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
- the step of adding the surface modifier is preferably performed before the step of mixing the solution and the second solvent.
- the surface modifier may be added to the first solvent, the solution, or the second solvent. Further, the surface modifier may be added to both the first solvent and the second solvent.
- the above-mentioned manufacturing method includes a step of removing coarse particles by a method such as centrifugation or filtration after the step of mixing the solution and the second solvent.
- the size of the coarse particles removed in the removing step is preferably 10 ⁇ m or more, more preferably 1 ⁇ m or more, and further preferably 500 nm or more.
- (Second manufacturing method) As a method for producing a perovskite compound, a step of dissolving a compound including an A component, a compound including a B component, and a compound including an X component, which form the perovskite compound, in a high temperature third solvent, and cooling the solution. And a manufacturing method including a step.
- the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in a high-temperature third solvent to obtain a solution.
- the “compound including the component A” may include the component X.
- the “compound including the component B” may include the component X.
- each compound may be added to and dissolved in a high temperature third solvent to obtain a solution. Further, in this step, after adding each compound to the third solvent, the temperature may be raised to obtain a solution.
- the third solvent includes a solvent capable of dissolving a compound containing the component A, which is a raw material, a compound containing the component B, and a compound containing the component X.
- examples of the third solvent include the above-mentioned first solvent and second solvent.
- High temperature means a solvent at a temperature at which each raw material dissolves.
- the temperature of the high temperature third solvent is preferably 60 to 600 ° C., and more preferably 80 to 400 ° C.
- the resulting solution is then cooled.
- the cooling temperature is preferably ⁇ 20 to 50 ° C., more preferably ⁇ 10 to 30 ° C.
- the cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.
- the perovskite compound By cooling the hot solution, the perovskite compound can be precipitated due to the difference in solubility due to the temperature difference between the solutions. As a result, a dispersion liquid containing the perovskite compound is obtained.
- the perovskite compound can be recovered by solid-liquid separation of the obtained dispersion liquid containing the perovskite compound.
- the solid-liquid separation method include the method described in the first manufacturing method.
- the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
- the step of adding the surface modifier is preferably performed before the step of cooling.
- the surface modifier may be added to the third solvent, and is added to a solution containing at least one of the compound containing the component A, the compound containing the component B, and the compound containing the component X. Good.
- a step of removing coarse particles by a method such as centrifugation and filtration shown in the first manufacturing method is included.
- the manufacturing method includes a step of obtaining the second solution, a step of mixing the first solution and the second solution to obtain a mixed solution, and a step of cooling the obtained mixed solution.
- the compound containing the component A and the compound containing the component B are dissolved in a high temperature fourth solvent to obtain a first solution.
- the fourth solvent includes a solvent capable of dissolving the compound containing the component A and the compound containing the component B.
- examples of the fourth solvent include the above-mentioned third solvent.
- the “high temperature” may be a temperature at which the compound containing the component A and the compound containing the component B are dissolved.
- the temperature of the high-temperature fourth solvent is preferably 60 to 600 ° C, more preferably 80 to 400 ° C.
- the compound containing the X component is dissolved in the fifth solvent to obtain the second solution.
- the compound containing the component X may contain a compound containing the component B.
- Examples of the fifth solvent include a solvent capable of dissolving the compound containing the component X.
- examples of the fifth solvent include the above-mentioned third solvent.
- the first solution and the second solution obtained are mixed to obtain a mixed solution.
- mixing the first solution and the second solution one may be dropped on the other. Further, it is advisable to mix the first solution and the second solution while stirring.
- the cooling temperature is preferably ⁇ 20 to 50 ° C., more preferably ⁇ 10 to 30 ° C.
- the cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.
- the perovskite compound By cooling the mixed solution, the perovskite compound can be precipitated due to the difference in solubility due to the difference in temperature of the mixed solution. As a result, a dispersion liquid containing the perovskite compound is obtained.
- the perovskite compound can be recovered by solid-liquid separation of the obtained dispersion liquid containing the perovskite compound.
- the solid-liquid separation method include the method described in the first manufacturing method.
- the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
- the step of adding the surface modifier is preferably performed before the step of cooling.
- the surface modifier may be added to any of the fourth solvent, the fifth solvent, the first solution, the second solution and the mixed solution.
- a step of removing coarse particles by a method such as centrifugation and filtration shown in the first manufacturing method is included.
- composition obtained by the method 1 for producing a composition is referred to as a “liquid composition”.
- the liquid composition of the present embodiment should be mixed with (1) a semiconductor material, (2) a silicone having a —R 31 SH group, and (3) a solvent and / or (4) a polymerizable compound. Can be manufactured in.
- the mixing temperature is not particularly limited. ) Since it is easy to uniformly mix one or both of the semiconductor material and the silicone having the (2) -R 31 SH group, the range of 0 ° C to 100 ° C is preferable, and the range of 10 ° C to 80 ° C is preferable. More preferably.
- the polymerizable compound is (1) a semiconductor material and (2) a silicone having a R 31 SH group.
- the polymerizable compound is (1) a semiconductor material and (2) a silicone having a R 31 SH group.
- One or both of the above may be dropped, and one or both of (1) the semiconductor material and (2) -R 31 SH group-containing silicone may be dropped into the (4) polymerizable compound. .
- (1) a semiconductor material or (2) a silicone having a —R 31 SH group may be added dropwise to the dispersion, or the dispersion may be added. It may be dropped onto (1) a semiconductor material or (2) -R 31 SH group-containing silicone. Since it is easy to uniformly disperse, it is preferable to drop (1) the semiconductor material or (2) -R 31 SH group-containing silicone into the dispersion.
- the (4-1) polymer may be dissolved in the (4) polymerizable compound. Further, in the production methods (c1) to (c3), the (4-1) polymer dissolved in a solvent may be used instead of the (4) polymerizable compound.
- the solvent for dissolving the (4-1) polymer is not particularly limited as long as it is a solvent capable of dissolving the (4-1) polymer.
- the solvent is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
- Examples of the solvent in which the polymer (4-1) is dissolved include the same solvents as the above-mentioned third solvent.
- the second solvent is preferable because it has low polarity and (1) it is considered that the semiconductor material is difficult to dissolve.
- halogenated hydrocarbons and hydrocarbons are more preferable.
- the method for producing the liquid composition of the present embodiment may be the following production method (c4).
- the method for producing the composition of the present embodiment includes (1) a step of mixing a semiconductor material, (2) a silicone having an R 31 SH group, and (4) a polymerizable compound, and (4) a polymerizable compound. And a step of polymerizing the compound.
- the method for producing the composition of the present embodiment includes (1) a semiconductor material, (2) a silicone having a R 31 SH group, (3) a polymer dissolved in a solvent (4-1) a polymer. There can also be mentioned a production method including a step of mixing and, and a step of removing the solvent (3).
- the same mixing method as the above-described manufacturing method of the composition can be used.
- Examples of the method for producing the composition include the following production methods (d1) to (d6).
- Production method (d3) a step of dispersing a silicone having a (2) -R 31 SH group and (5) a surface modifier in (4) a polymerizable compound to obtain a dispersion, and the obtained dispersion.
- a manufacturing method comprising: (1) mixing a semiconductor material; and (4) polymerizing a polymerizable compound.
- a manufacturing method comprising: a step, a step of mixing the obtained dispersion, (1) a semiconductor material, and (3) a step of removing a solvent.
- the step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) may be a step of allowing to stand at room temperature and naturally drying, or using a vacuum dryer. It may be a step (3) of evaporating the solvent by drying under reduced pressure or heating.
- the solvent (3) can be removed by drying at 0 to 300 ° C. for 1 minute to 7 days, for example.
- the step (4) of polymerizing the polymerizable compound contained in the production methods (d1), (d3) and (d5) can be carried out by appropriately using a known polymerization reaction such as radical polymerization.
- a radical polymerization initiator is added to a mixture of (1) a semiconductor material, (2) a silicone having a R 31 SH group, and (4) a polymerizable compound to generate radicals. This allows the polymerization reaction to proceed.
- the radical polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator.
- photo-radical polymerization initiator examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
- composition Manufacturing Method 3 ⁇ Composition Manufacturing Method 3 >> Further, as the method for producing the composition of the present embodiment, the following production method (d7) can also be adopted.
- Manufacturing method (d7) A manufacturing method including a step of melt-kneading (1) a semiconductor material, (2) a silicone having a R 31 SH group, and (4-1) a polymer.
- Production method (d9) (1) a step of producing a liquid composition containing a semiconductor material and (2) a silicone having a R 31 SH group, and a step of extracting solid content from the obtained liquid composition, A production method comprising a step of melt-kneading the obtained solid content and (4-1) polymer.
- Production method (d10) (1) a step of producing a liquid composition containing a semiconductor material, (2) a silicone having a —R 31 SH group, and (5) a surface modifier, and from the obtained liquid composition
- a production method comprising a step of taking out a solid content and a step of melt-kneading the obtained solid content and the (4-1) polymer.
- a mixture of the (4-1) polymer and another material may be melt-kneaded, and the melted (4-1) polymer may be mixed with other materials.
- Materials may be added.
- the "other material” refers to a material used in each production method in addition to (4-1) a polymer, and specifically, (1) a semiconductor material, (2) a silicone having a R 31 SH group, ( 5) Refers to a surface modifier.
- melt-kneading the polymer (4-1) in the production methods (d7) to (d11) a known method of kneading the polymer can be adopted.
- extrusion processing using a single screw extruder or a twin screw extruder can be adopted.
- the above-mentioned manufacturing methods (c1) to (c4) can be adopted for the step of manufacturing the liquid composition of the manufacturing methods (d9) and (d11).
- the amount of the perovskite compound contained in the composition of the present embodiment is determined by an inductively coupled plasma mass spectrometer ICP-MS (for example, PerkinElmer, ELAN DRCII), and an ion chromatograph (for example, Thermo Fisher Scientific Co., Ltd.). , Integration) can be used for the measurement.
- ICP-MS for example, PerkinElmer, ELAN DRCII
- ion chromatograph for example, Thermo Fisher Scientific Co., Ltd.
- Integration can be used for the measurement.
- the perovskite compound is dissolved in a good solvent such as N, N-dimethylformamide and then measured.
- the emission intensity of the composition of the present embodiment is measured with a fluorescence altimeter (for example, FT-6500 manufactured by JASCO Corporation) with excitation light of 430 nm and sensitivity of High.
- a fluorescence altimeter for example, FT-6500 manufactured by JASCO Corporation
- composition of the embodiment may have a luminescence intensity measured by the above measuring method of 10 or higher, 100 or higher, 200 or higher, and 300 or higher. .
- the composition of the present embodiment has a thickness of 100 ⁇ m, 1 cm ⁇ 1 cm, and is placed in a constant temperature and constant humidity chamber kept at a temperature of 65 ° C. and a humidity of 95% to perform a durability test against water vapor.
- the emission intensity is measured before and after the test, and the maintenance rate is evaluated using the following formula.
- Maintenance rate (%) (emission intensity after the durability test against water vapor for X ′ days) / (emission intensity before the durability test against water vapor) ⁇ 100
- the composition of the embodiment has a maintenance rate after a durability test against water vapor for 2 days of 30% or more, 40% or more, and 80% or more. , 82% or more, or 83% or more. Since the effect of the thermal durability of the composition is high, the maintenance rate is preferably high.
- the film according to this embodiment uses the above-mentioned composition as a forming material.
- the film according to the present embodiment contains (1) a semiconductor material, (2) -R 31 SH group-containing silicone, and (4-1) a polymer, and (1) a semiconductor material, (2) -R.
- the total amount of the 31 SH group-containing silicone and the (4-1) polymer is 90% by mass or more based on the total mass of the film.
- the shape of the film is not particularly limited and may be any shape such as a sheet shape or a bar shape.
- the “bar-like shape” means, for example, a band-like shape in plan view extending in one direction. Examples of the band-like shape in plan view include a plate-like shape in which each side has a different length.
- the thickness of the film may be 0.01 ⁇ m to 1000 mm, 0.1 ⁇ m to 10 mm, or 1 ⁇ m to 1 mm.
- the thickness of the film refers to the front surface and the back surface in the thickness direction of the film when the side having the smallest value in the length, width and height of the film is defined as the “thickness direction”. Refers to the distance between. Specifically, the thickness of the film is measured at any three points on the film using a micrometer, and the average value of the measured values at the three points is taken as the film thickness.
- the film may be a single layer or multiple layers. In the case of multiple layers, the same type of composition may be used for each layer, or different types of compositions may be used for each layer.
- the laminated structure according to the present embodiment has a plurality of layers, and at least one layer is the above-mentioned film.
- examples of layers other than the above-mentioned films include arbitrary layers such as a substrate, a barrier layer, and a light scattering layer.
- the shape of the laminated film is not particularly limited, and may be any shape such as a sheet shape and a bar shape.
- the substrate is not particularly limited, but may be a film.
- the substrate is preferably light transmissive.
- a laminated structure including a substrate having a light-transmitting property is preferable because (1) it is easy to extract light emitted from the semiconductor material.
- a material for forming the substrate for example, a polymer such as polyethylene terephthalate or a known material such as glass can be used.
- a polymer such as polyethylene terephthalate or a known material such as glass can be used.
- the above-mentioned film may be provided on the substrate.
- FIG. 1 is a sectional view schematically showing the configuration of the laminated structure of this embodiment.
- the film 10 of the present embodiment is provided between the first substrate 20 and the second substrate 21.
- the film 10 is sealed by the sealing layer 22.
- One aspect of the present invention is a first substrate 20, a second substrate 21, a film 10 according to the present embodiment located between the first substrate 20 and the second substrate 21, and a sealing.
- a laminated structure having a layer 22 and the encapsulating layer 22 is disposed on a surface of the film 10 which is not in contact with the first substrate 20 and the second substrate 21. It is the structure 1a.
- the layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a barrier layer.
- a barrier layer may be included from the viewpoint of protecting the above-mentioned composition from water vapor in the outside air and air in the atmosphere.
- the barrier layer is not particularly limited, but is preferably transparent from the viewpoint of extracting emitted light.
- a polymer such as polyethylene terephthalate or a known barrier layer such as a glass film can be used.
- the layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a light scattering layer. From the viewpoint of effectively utilizing the incident light, a light scattering layer may be included.
- the light scattering layer is not particularly limited, but is preferably transparent from the viewpoint of extracting emitted light.
- As the light scattering layer light scattering particles such as silica particles, or a known light scattering layer such as an amplification diffusion film can be used.
- the light emitting device according to this embodiment can be obtained by combining the film or laminated structure of this embodiment with a light source.
- the light-emitting device is a device that emits light by irradiating a film or a laminated structure provided in a light emission direction of the light source with light emitted from the light source so that the film or the laminated structure emits light.
- the layers other than the above-mentioned film, substrate, barrier layer, and light scattering layer include a light reflection member, a brightness enhancement portion, a prism sheet, a light guide plate, and a medium between elements Any layer such as a material layer may be used.
- One aspect of the present invention is a light emitting device 2 in which a prism sheet 50, a light guide plate 60, a first laminated structure 1a, and a light source 30 are laminated in this order.
- a light source that constitutes the light emitting device of this embodiment (1) a light source that emits light included in the absorption wavelength band of the semiconductor material is used.
- a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of emitting the semiconductor material in the film or the laminated structure described above.
- a known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, or an EL can be used.
- the layer that may be included in the laminated structure forming the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light reflecting member.
- a light emitting device having a light reflecting member can efficiently irradiate light from a light source toward a film or a laminated structure.
- the light reflection member is not particularly limited, but may be a reflection film.
- a known reflecting film such as a reflecting mirror, a film of reflecting particles, a reflecting metal film or a reflector can be used.
- the layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a brightness enhancement portion.
- the brightness enhancement section may be included from the viewpoint of reflecting a part of the light back toward the direction in which the light is transmitted.
- the layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, but a prism sheet can be used.
- the prism sheet typically has a base material portion and a prism portion. The base material portion may be omitted depending on the adjacent member.
- the prism sheet can be attached to an adjacent member via any appropriate adhesive layer (eg, adhesive layer, pressure-sensitive adhesive layer).
- adhesive layer e.g, adhesive layer, pressure-sensitive adhesive layer.
- the prism sheet is configured by arranging a plurality of unit prisms that are convex on the side opposite to the viewing side (back side).
- the convex portion of the prism sheet By arranging the convex portion of the prism sheet so as to face the back surface side, it becomes easy to collect light that passes through the prism sheet.
- the convex portion of the prism sheet is arranged facing the back side, compared to the case where the convex portion is arranged facing the viewing side, less light is reflected without entering the prism sheet, and a display with high brightness is displayed. Can be obtained.
- the layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light guide plate.
- a light guide plate for example, a light guide plate having a lens pattern formed on the back side so that light from the lateral direction can be deflected in the thickness direction, a prism shape on either or both of the back side and the viewing side. Any appropriate light guide plate can be used, such as a light guide plate on which the above are formed.
- the layer that may be included in the laminated structure that constitutes the light emitting device of the present embodiment is not particularly limited, but a layer composed of one or more medium materials (on the optical path between adjacent elements (layers) ( Media material layers between elements).
- the one or more media contained in the media material layer between the elements include, but are not limited to, vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, cured. Materials, optical coupling materials, index matching or index mismatching materials, gradient index materials, cladding or anti-cladding materials, spacers, silica gel, brightness enhancing materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selection Materials, wavelength selective anti-reflective materials, color filters, or suitable media known in the art.
- the light emitting device of the present embodiment include those provided with a wavelength conversion material for EL displays and liquid crystal displays. Specifically, the following respective structures (E1) to (E4) can be mentioned.
- composition of the present embodiment is put in a glass tube or the like and sealed, and the composition is arranged between the blue light emitting diode as a light source and the light guide plate so as to be along the end surface (side surface) of the light guide plate. Then, a backlight that converts blue light into green light or red light (on-edge backlight).
- the composition of the present embodiment is formed into a sheet, and a film obtained by sandwiching the composition with two barrier films and sealing is placed on the light guide plate and placed on the end surface (side surface) of the light guide plate.
- a backlight surface-mounted backlight that converts blue light emitted from the blue light emitting diode to the sheet through a light guide plate into green light or red light.
- E3 A backlight (on-chip) that disperses the composition of the present embodiment in a resin or the like and installs it in the vicinity of a light emitting portion of a blue light emitting diode to convert the emitted blue light into green light or red light. Method backlight).
- the composition of the present embodiment is molded and placed in the subsequent stage of the blue light emitting diode as a light source to convert blue light into green light or red light. Illumination that emits white light is included.
- the display 3 of this embodiment includes a liquid crystal panel 40 and the above-described light emitting device 2 in this order from the viewing side.
- the light emitting device 2 includes a second stacked structure body 1b and a light source 30.
- the above-mentioned first laminated structure 1a further includes a prism sheet 50 and a light guide plate 60.
- the display may further comprise any suitable other member.
- One aspect of the present invention is a liquid crystal display 3 in which a liquid crystal panel 40, a prism sheet 50, a light guide plate 60, a first laminated structure 1a, and a light source 30 are laminated in this order.
- the liquid crystal panel typically includes a liquid crystal cell, a viewing side polarizing plate arranged on the viewing side of the liquid crystal cell, and a back side polarizing plate arranged on the back side of the liquid crystal cell.
- the viewing-side polarizing plate and the back-side polarizing plate may be arranged such that their absorption axes are substantially orthogonal or parallel.
- the liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the pair of substrates.
- one substrate is provided with a color filter and a black matrix
- the other substrate is provided with a switching element for controlling electro-optical characteristics of liquid crystal and a scanning line for giving a gate signal to this switching element.
- a signal line for supplying a source signal, a pixel electrode, and a counter electrode.
- the distance (cell gap) between the substrates can be controlled by a spacer or the like.
- An alignment film made of polyimide, for example, can be provided on the side of the substrate that is in contact with the liquid crystal layer.
- the polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer.
- the polarizer is typically an absorption-type polarizer. Any appropriate polarizer is used as the polarizer.
- a dichroic substance such as iodine or a dichroic dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer partially saponified film.
- Uniaxially stretched film, polyene oriented film such as polyvinyl alcohol dehydrated product, polyvinyl chloride dehydrochlorinated product and the like.
- a polarizer obtained by uniaxially stretching a polyvinyl alcohol film by adsorbing a dichroic substance such as iodine has a high polarization dichroic ratio, and is particularly preferable.
- composition of the present embodiment include the following uses.
- composition of this embodiment can be used, for example, as a material for a light emitting layer of a light emitting diode (LED).
- the composition of the present embodiment and conductive particles such as ZnS are mixed and laminated in a film shape, the n-type transport layer is laminated on one surface, and the other surface is laminated on the other surface.
- Particles of (1) and (2) which have a structure in which a p-type transport layer is laminated and in which a hole of a p-type semiconductor and an electron of an n-type semiconductor are included in the composition of the junction surface by passing an electric current. Among them, there is a method of emitting light by canceling charges.
- composition of the present embodiment can be used as an electron transporting material contained in the active layer of a solar cell.
- the structure of the solar cell is not particularly limited, but examples thereof include a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, an active layer containing the composition of the present embodiment, and 2. It has a hole transport layer such as 2 ', 7,7'-tetrakis (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-MeOTAD), and a silver (Ag) electrode in this order.
- FTO fluorine-doped tin oxide
- the titanium oxide dense layer has a function of electron transport, an effect of suppressing the roughness of FTO, and a function of suppressing reverse electron transfer.
- the porous aluminum oxide layer has a function of improving light absorption efficiency.
- composition of the present embodiment contained in the active layer has the functions of charge separation and electron transport.
- the composition of the present embodiment is applied to a living body such as an image detection unit (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection unit, a face detection unit, a vein detection unit and an iris detection unit. It can be used as a photoelectric conversion element (photodetection element) material included in a detection section for detecting a predetermined characteristic of a part or a detection section of an optical biosensor such as a pulse oximeter.
- a photoelectric conversion element photodetection element
- Examples of the film production method include the following production methods (e1) to (e3).
- Manufacturing method (e1) A method for manufacturing a film, which includes a step of applying a liquid composition to obtain a coating film, and a step of (3) removing a solvent from the coating film.
- a method of manufacturing a film including.
- Production method (e3) A method for producing a film by molding the composition obtained by the above-mentioned production methods (d1) to (d6).
- the film produced by the above production methods (e1) and (e2) may be peeled off from the production position and used.
- Examples of the method for manufacturing the laminated structure include the following manufacturing methods (f1) to (f3).
- Production method (f1) Lamination including a step of producing a liquid composition, a step of applying the obtained liquid composition onto a substrate, and a step of removing (3) a solvent from the obtained coating film Structure manufacturing method.
- Manufacturing method (f2) A manufacturing method of a laminated structure including a step of attaching a film to a substrate.
- Production method (f3) (4) A step of producing a liquid composition containing a polymerizable compound, a step of applying the obtained liquid composition on a substrate, and a step of applying the obtained coating film (4) And a step of polymerizing the polymerizable compound.
- the above-mentioned manufacturing methods (c1) to (c5) can be adopted in the steps of manufacturing the liquid composition in the manufacturing methods (f1) and (f3).
- the step of applying the liquid composition on the substrate in the production methods (f1) and (f3) is not particularly limited, but is a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, Known coating and coating methods such as a die coating method can be used.
- the step of removing the solvent (3) in the production method (f1) may be the same step as the step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) described above. it can.
- the step of polymerizing the (4) polymerizable compound in the production method (f3) is the same as the step of polymerizing the (4) polymerizable compound contained in the above-mentioned production methods (d1), (d3), and (d5). be able to.
- any adhesive can be used.
- the adhesive is (1) not particularly limited as long as it does not dissolve the semiconductor material, and a known adhesive can be used.
- the method for producing a laminated structure may further include a step of laminating an arbitrary film on the obtained laminated structure.
- a reflection film or a diffusion film can be mentioned.
- Arbitrary adhesives can be used in the process of laminating the films.
- the above-mentioned adhesive is not particularly limited as long as it does not dissolve (1) the semiconductor material, and a known adhesive can be used.
- ⁇ Manufacturing Method of Light-Emitting Device For example, a manufacturing method including the above-mentioned light source and a step of installing the above-mentioned film or laminated structure on the optical path of light emitted from the light source can be mentioned.
- a dispersion liquid was obtained by redispersing (1) the semiconductor material obtained by the method described below in toluene that was precisely weighed. Then, the perovskite compound was dissolved in the obtained dispersion by adding N, N-dimethylformamide.
- Cs and Pb contained in the dispersion were quantified using ICP-MS (ELAN DRCII manufactured by PerkinElmer). Moreover, Br and I contained in the dispersion liquid were quantified using an ion chromatograph (Integration, manufactured by Thermo Fisher Scientific Co., Ltd.). The mass of the perovskite compound contained in the dispersion was calculated from the sum of the measured values, and the dispersion concentration was calculated from the mass of the perovskite compound and the amount of toluene.
- the distance between the parallel lines when the image of the semiconductor material shown in the obtained electron micrograph was sandwiched by two parallel lines was calculated as the Feret diameter.
- the arithmetic average value of the Feret diameters of 20 semiconductor materials was obtained, and the average Feret diameter was obtained.
- Example 1 0.814 g of cesium carbonate, 40 mL of a solvent of 1-octadecene, and 2.5 mL of oleic acid were mixed. The mixture was stirred with a magnetic stirrer and heated at 150 ° C. for 1 hour while flowing nitrogen to prepare a cesium carbonate solution.
- lead bromide (PbBr 2 ) and 0.208 g of lead iodide (PbI 2 ) were mixed with 20 mL of 1-octadecene solvent. After stirring with a magnetic stirrer and heating at a temperature of 120 ° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added to prepare a lead bromide-lead iodide dispersion.
- the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, whereby a perovskite compound of the precipitate was obtained.
- a perovskite compound of the precipitate was obtained.
- 500 ⁇ L of the dispersion was collected and re-dispersed in 4.5 mL of toluene to obtain a dispersion containing the perovskite compound and the solvent.
- the concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1500 ppm ( ⁇ g / g).
- the average ferret diameter of the perovskite compound observed by TEM was 19 nm.
- the methacrylic resin and toluene were mixed so that the methacrylic resin (PMMA, Sumipex methacrylic resin manufactured by Sumitomo Chemical Co., Ltd., MH, molecular weight of about 120,000, specific gravity of 1.2 g / ml) was 16.5% by mass. Then, it heated at 60 degreeC for 3 hours, and obtained the solution in which the polymer melt
- PMMA Sumipex methacrylic resin manufactured by Sumitomo Chemical Co., Ltd., MH, molecular weight of about 120,000, specific gravity of 1.2 g / ml
- toluene was naturally dried and evaporated to obtain a composition having a perovskite compound concentration of 500 ⁇ g / mL.
- the composition was cut into a size of 1 cm x 1 cm.
- the luminescence intensity of the composition was evaluated to be 376.
- the retention rate of luminescence intensity after the durability test against water vapor was 83.3%. The results are shown in Table 1.
- Example 2 A composition was synthesized in the same manner as in Example 1 except that the addition amount of mercapto-modified silicone (KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C .: 0.98 g / cm 3 ) was 300 ⁇ L.
- the emission intensity of the composition was evaluated to be 304.
- the maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 80.1%.
- Example 3 Instead of mercapto-modified silicone (KF-2001, Shin-Etsu Chemical Co., Ltd .: 0.98 g / cm 3 ), mercapto-modified silicone (KF-2004, Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C. 0.97 g / cm 3 ).
- KF-2001 Shin-Etsu Chemical Co., Ltd .: 0.98 g / cm 3
- KF-2004 Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C. 0.97 g / cm 3 .
- a composition was synthesized in the same manner as in Example 1 except that was used. The light emission intensity of the composition was evaluated to be 192. The maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 33.5%.
- Example 1 A composition was synthesized in the same manner as in Example 1 except that the mercapto-modified silicone was not added.
- the light emission intensity of the composition was 6.57.
- the maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 22.9%.
- compositions according to Examples 1 to 3 to which the present invention is applied have higher initial emission intensity and excellent durability against water vapor as compared with the composition of Comparative Example 1 to which the present invention is not applied. It was confirmed that the product has the property.
- a film can be obtained by forming the composition described in Examples 1 to 3 into a sheet, and the film sandwiched by two barrier films is placed on the light guide plate to obtain a light guide plate.
- a backlight capable of converting blue light emitted from the blue light emitting diode placed on the end face (side surface) of the sheet through the light guide plate into green light or red light is manufactured.
- the wavelength conversion material can be obtained by mixing the composition described in Examples 1 to 3 and the resist and then removing the solvent. By arranging the obtained wavelength conversion material between the blue light emitting diode which is the light source and the light guide plate or in the subsequent stage of the OLED which is the light source, a backlight capable of converting the blue light of the light source into green light or red light is provided. To manufacture.
- a titanium oxide dense layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the composition described in Examples 1 to 3 is laminated thereon. Then, after removing the solvent, 2,2 '-, 7,7'-tetrakis- (N, N'-di-p-methoxyphenylamine) 9,9'-spirobifluorene (Spiro-OMeTAD) and other holes are transported from above. A layer is laminated
- composition of the present embodiment can be obtained by removing the solvent of the compositions described in Examples 1 to 3 and molding. By placing this composition in the subsequent stage of the blue light emitting diode, the composition of the blue light emitting diode can be obtained.
- the composition of this embodiment can be obtained by removing the solvent of the composition described in Examples 1 to 3 and molding.
- a photoelectric conversion element (photodetection element) material used for a detection unit that detects light is manufactured.
- the photoelectric conversion element material is used for a part of a living body such as an image detection part (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection part, a face detection part, a vein detection part and an iris detection part. It is used in optical biosensors such as pulse oximeters that detect specific characteristics.
- a composition containing a light-emitting semiconductor material having high durability against water vapor, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure can be provided. Therefore, the composition of the present invention, the film using the composition, the laminated structure using the film, and the light emitting device and the display including the laminated structure can be suitably used for light emitting applications.
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Abstract
Description
本発明は、組成物、フィルム、積層構造体、発光装置及びディスプレイに関する。 The present invention relates to a composition, a film, a laminated structure, a light emitting device and a display.
近年、発光材料として、高い量子収率を有する発光性の半導体材料に対する関心が高まっている。一方、発光材料には安定性が求められており、発光性の半導体材料を含む組成物として、例えば、3-アミノプロピルトリエトキシシランで被覆されている発光性の半導体材料を含む組成物が報告されている(非特許文献1)。 In recent years, interest in light-emitting semiconductor materials with high quantum yield has increased as light-emitting materials. On the other hand, stability is required for light emitting materials, and as a composition containing a light emitting semiconductor material, for example, a composition containing a light emitting semiconductor material coated with 3-aminopropyltriethoxysilane is reported. (Non-Patent Document 1).
しかしながら、上記非特許文献1に記載のような発光性の半導体材料を含む組成物は、必ずしも水蒸気に対する耐久性が十分ではない。 However, the composition containing the light emitting semiconductor material as described in Non-Patent Document 1 does not always have sufficient durability against water vapor.
本発明は、上記事情に鑑みてなされたものであって、水蒸気に対する耐久性が高い、発光性の半導体材料を含む組成物、前記組成物を用いたフィルム、前記フィルムを用いた積層構造体、前記積層構造体を備える発光装置及びディスプレイを提供することを課題とする。 The present invention has been made in view of the above circumstances, high durability against water vapor, a composition containing a light-emitting semiconductor material, a film using the composition, a laminated structure using the film, An object of the present invention is to provide a light emitting device and a display including the laminated structure.
上記課題を解決するため、本発明は、以下の態様を有する。
[1] (1)成分と、(2)成分と、を含む組成物。
(1)成分:発光性の半導体材料
(2)成分:-R31SH基を有するシリコーン
(上記-R31SH基中、R31は置換基を有していてもよいヒドロカルビレン基である[2] (1)成分がA、B、及びXを構成成分とするペロブスカイト化合物である、[1]に記載の組成物。
(Aは、ペロブスカイト型結晶構造において、Bを中心とする六面体の各頂点に位置する成分であって、1価の陽イオンである。
Xは、ペロブスカイト型結晶構造において、Bを中心とする八面体の各頂点に位置する成分を表し、ハロゲン化物イオン、及びチオシアン酸イオンからなる群より選ばれる少なくとも一種の陰イオンである。
Bは、ペロブスカイト型結晶構造において、Aを頂点に配置する六面体、及びXを頂点に配置する八面体の中心に位置する成分であって、金属イオンである。)
[3] さらに(5)成分を含む[1]又は[2]に記載の組成物。
(5)成分:アンモニウムイオン、アミン、第1級~第4級アンモニウムカチオン、アンモニウム塩、カルボン酸、カルボキシレートイオン、カルボキシレート塩、下記式(X1)~(X6)でそれぞれ表される化合物、及び下記式(X2)~(X4)でそれぞれ表される化合物の塩からなる群より選ばれる少なくとも1種の化合物又はイオン
In order to solve the above-mentioned subject, the present invention has the following modes.
[1] A composition containing the component (1) and the component (2).
Component (1): Light-emitting semiconductor material (2) Component: -R 31 SH group-containing silicone (in the above-R 31 SH group, R 31 is a hydrocarbylene group which may have a substituent) [2] The composition according to [1], wherein the component (1) is a perovskite compound containing A, B, and X as constituent components.
(A is a component located at each vertex of a hexahedron centered on B in the perovskite type crystal structure, and is a monovalent cation.
X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
In the perovskite type crystal structure, B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion. )
[3] The composition according to [1] or [2], which further contains the component (5).
Component (5): ammonium ion, amine, primary to quaternary ammonium cation, ammonium salt, carboxylic acid, carboxylate ion, carboxylate salt, compounds represented by the following formulas (X1) to (X6), And at least one compound or ion selected from the group consisting of salts of compounds represented by the following formulas (X2) to (X4)
式(X2)中、A1は単結合又は酸素原子を表す。R22は、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X3)中、A2及びA3はそれぞれ独立に、単結合又は酸素原子を表す。R23及びR24はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X4)中、A4は単結合又は酸素原子を表す。R25は、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X5)中、A5~A7はそれぞれ独立に、単結合又は酸素原子を表す。R26~R28はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、炭素原子数6~30のアリール基、炭素原子数2~20のアルケニル基、又は炭素原子数2~20のアルキニル基を表し、それらは置換基を有していてもよい。
式(X6)中、A8~A10はそれぞれ独立に、単結合又は酸素原子を表す。R29~R31はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、炭素原子数6~30のアリール基、炭素原子数2~20のアルケニル基、又は炭素原子数2~20のアルキニル基を表し、それらは置換基を有していてもよい。
R18~R31でそれぞれ表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよい。)
[4] さらに(3)成分、(4)成分、及び(4-1)成分からなる群より選ばれる少なくとも一種を含む、[1]~[3]のいずれか1に記載の組成物。
(3)成分:溶媒
(4)成分:重合性化合物
(4-1)成分:重合体
[5] [1]~[4]のいずれか1に記載の組成物を形成材料とするフィルム。
[6] [5]に記載のフィルムを含む積層構造体。
[7] [6]に記載の積層構造体を備える発光装置。
[8] [6]に記載の積層構造体を備えるディスプレイ。
In formula (X2), A 1 represents a single bond or an oxygen atom. R 22 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
In formula (X3), A 2 and A 3 each independently represent a single bond or an oxygen atom. R 23 and R 24 each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, each of which has a substituent. You may have.
In formula (X4), A 4 represents a single bond or an oxygen atom. R 25 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
In formula (X5), A 5 to A 7 each independently represent a single bond or an oxygen atom. R 26 to R 28 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. Or represents an alkynyl group having 2 to 20 carbon atoms, which may have a substituent.
In formula (X6), A 8 to A 10 each independently represent a single bond or an oxygen atom. R 29 to R 31 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. Or represents an alkynyl group having 2 to 20 carbon atoms, which may have a substituent.
The hydrogen atoms contained in the groups represented by R 18 to R 31 may each independently be substituted with a halogen atom. )
[4] The composition according to any one of [1] to [3], which further contains at least one selected from the group consisting of the component (3), the component (4), and the component (4-1).
Component (3): Solvent (4) Component: Polymerizable compound (4-1) Component: Polymer [5] A film using the composition according to any one of [1] to [4] as a forming material.
[6] A laminated structure including the film according to [5].
[7] A light emitting device including the laminated structure according to [6].
[8] A display including the laminated structure according to [6].
本発明によれば、水蒸気に対する耐久性が高い、発光性の半導体材料を含む組成物、前記組成物を用いたフィルム、前記フィルムを用いた積層構造体、前記積層構造体を備える発光装置及びディスプレイを提供することができる。 According to the present invention, a composition containing a light-emitting semiconductor material having high durability against water vapor, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure. Can be provided.
<組成物>
以下、本実施形態の組成物を構成する各成分について説明する。
以下において、(1)成分を、「(1)半導体材料」と記載する場合がある。
本実施形態の組成物に含まれる(1)の半導体材料は、発光性を有する。「発光性」とは、光を発する性質を指す。発光性は、電子の励起により発光する性質であることが好ましく、励起光による電子の励起により発光する性質であることがより好ましい。励起光の波長は、例えば、200nm~800nmであってもよく、250nm~750nmであってもよく、300nm~700nmであってもよい。
<Composition>
Hereinafter, each component constituting the composition of this embodiment will be described.
In the following, the component (1) may be described as “(1) semiconductor material”.
The semiconductor material (1) contained in the composition of the present embodiment has a light emitting property. “Luminescent” refers to the property of emitting light. The light emitting property is preferably a property of emitting light when excited by an electron, and more preferably a property of emitting light when excited by an electron by excitation light. The wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 750 nm, or 300 nm to 700 nm.
本実施形態の組成物は、(1)成分、及び(2)成分と、を含む。
(1)成分:発光性の半導体材料
(2)成分:-R31SH基を有するシリコーン
The composition of the present embodiment contains the component (1) and the component (2).
(1) Component: Luminescent semiconductor material (2) Component: -R 31 SH group-containing silicone
上記-R31SH基中、R31は置換基を有していてもよいヒドロカルビレン基である。 In the above-R 31 SH group, R 31 is a hydrocarbylene group which may have a substituent.
本実施形態の組成物は(1)半導体材料と(2)-R31SH基を有するシリコーンとを含む組成物であればよく、(1)半導体材料及び(2)-R31SH基を有するシリコーン以外の成分をさらに含んでいてもよい。 The composition of the present embodiment may be any composition containing (1) a semiconductor material and (2) -R 31 SH group-containing silicone, and has (1) a semiconductor material and (2) -R 31 SH group. It may further contain components other than silicone.
本実施形態の組成物は、(1)半導体材料と、(2)-R31SH基を有するシリコーンとを含み、さらに(3)成分、(4)成分、及び(4-1)成分からなる群より選ばれる少なくとも一種を含んでいてもよい。
(3)成分:溶媒
(4)成分:重合性化合物
(4-1)成分:重合体
The composition of the present embodiment contains (1) a semiconductor material and (2) -R 31 SH group-containing silicone, and further comprises (3) component, (4) component, and (4-1) component. It may include at least one selected from the group.
(3) component: solvent (4) component: polymerizable compound (4-1) component: polymer
以下の説明においては、(3)溶媒、(4)重合性化合物、(4-1)重合体を総称して「分散媒」と称することがある。本実施形態の組成物は、これらの分散媒に分散していてもよい。 In the following description, (3) solvent, (4) polymerizable compound, and (4-1) polymer may be collectively referred to as “dispersion medium”. The composition of the present embodiment may be dispersed in these dispersion media.
本明細書において「分散している」とは、(1)半導体材料が、分散媒に浮遊している状態、又は(1)半導体材料が、分散媒に懸濁している状態のことを指す。(1)半導体材料が分散媒に分散している場合、(1)半導体材料の一部は沈降していてもよい。 In this specification, “dispersed” means (1) a state in which a semiconductor material is suspended in a dispersion medium, or (1) a state in which a semiconductor material is suspended in a dispersion medium. (1) When the semiconductor material is dispersed in the dispersion medium, (1) part of the semiconductor material may be precipitated.
組成物において、組成物の総質量に対する分散媒の含有割合は、特に限定されるものではない。(1)半導体材料の分散性を向上させる観点、及び耐久性を向上させる観点から、組成物の総質量に対する分散媒の含有割合は、99.99質量%以下であることが好ましく、99.9質量%以下であることがより好ましく、99質量%以下であることがさらに好ましい。 In the composition, the content ratio of the dispersion medium with respect to the total mass of the composition is not particularly limited. (1) From the viewpoint of improving the dispersibility of the semiconductor material and improving the durability, the content ratio of the dispersion medium with respect to the total mass of the composition is preferably 99.99% by mass or less, and 99.9% by mass. It is more preferably at most% by mass, further preferably at most 99% by mass.
また、耐久性を向上させる観点から、組成物の総質量に対する分散媒の含有割合は、0.1質量%以上であることが好ましく、1質量%以上であることがより好ましく、10質量%以上であることがさらに好ましく、50質量%以上であることがさらに好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることがもっとも好ましい。 From the viewpoint of improving durability, the content ratio of the dispersion medium to the total mass of the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and 10% by mass or more. Is more preferred, 50% by mass or more is more preferred, 80% by mass or more is more preferred, and 90% by mass or more is most preferred.
上記上限値及び下限値は任意に組み合わせることができる。 The above upper and lower limits can be combined arbitrarily.
上記上限値及び下限値の組み合わせの一例としては、0.1~99.99質量%、1~99.9質量%、1~99質量%、10~99質量%、20~99質量%、50~99質量%、90~99質量%が挙げられる。 Examples of combinations of the upper limit value and the lower limit value are 0.1 to 99.99% by mass, 1 to 99.9% by mass, 1 to 99% by mass, 10 to 99% by mass, 20 to 99% by mass, and 50. ˜99% by mass and 90 to 99% by mass.
本実施形態の組成物は、さらに(5)成分を含んでいてもよい。なお、(5)成分の詳細については後述する。
(5)成分:アンモニウムイオン、アンモニウム塩、アミン、第1級~第4級アンモニウムカチオン、カルボン酸、カルボキシレートイオン、カルボキシレート塩、前記式(X1)~(X6)でそれぞれ表される化合物、及び前記式(X2)~(X4)でそれぞれ表される化合物の塩からなる群より選択される少なくとも1種の化合物又はイオン
The composition of the present embodiment may further contain the component (5). The details of component (5) will be described later.
Component (5): ammonium ion, ammonium salt, amine, primary to quaternary ammonium cation, carboxylic acid, carboxylate ion, carboxylate salt, compounds represented by the formulas (X1) to (X6), And at least one compound or ion selected from the group consisting of salts of the compounds represented by the above formulas (X2) to (X4)
以下の説明では、(5)成分のことを「(5)表面修飾剤」と称する。 In the following explanation, the component (5) is referred to as "(5) surface modifier".
組成物において、組成物の総質量に対する(1)半導体材料の含有割合は、特に限定されるものではない。発光性の半導体材料を凝集させにくくする観点、及び濃度消光を防ぐ観点から、組成物の総質量に対する(1)半導体材料の含有割合は、50質量%以下であることが好ましく、1質量%以下であることがより好ましく、0.3質量%以下であることがさらに好ましい。また、良好な発光強度を得る観点から、組成物の総質量に対する(1)半導体材料の含有割合は、0.0001質量%以上であることが好ましく、0.0005質量%以上であることがより好ましく、0.001質量%以上であることがさらに好ましい。 In the composition, the content ratio of (1) semiconductor material to the total mass of the composition is not particularly limited. From the viewpoint of making the light-emitting semiconductor material less likely to aggregate and preventing the concentration quenching, the content ratio of (1) the semiconductor material to the total mass of the composition is preferably 50 mass% or less, and 1 mass% or less. Is more preferable, and 0.3% by mass or less is further preferable. From the viewpoint of obtaining good emission intensity, the content ratio of (1) semiconductor material to the total mass of the composition is preferably 0.0001 mass% or more, and more preferably 0.0005 mass% or more. It is more preferably 0.001% by mass or more.
上記上限値及び下限値は任意に組み合わせることができる。 The above upper and lower limits can be combined arbitrarily.
上記上限値及び下限値の組み合わせの一例としては、0.0001~50質量%、0.0005~1質量%、0.001~0.3質量%が挙げられる。 Examples of combinations of the upper limit value and the lower limit value include 0.0001 to 50% by mass, 0.0005 to 1% by mass, and 0.001 to 0.3% by mass.
組成物の総質量に対する(1)半導体材料の含有割合が上記範囲内である組成物は、(1)半導体材料の凝集が生じ難く、発光性も良好に発揮される点で好ましい。 A composition in which the content ratio of (1) semiconductor material to the total mass of the composition is within the above range is preferable because (1) aggregation of the semiconductor material is less likely to occur and luminescence is excellently exhibited.
組成物において、組成物の総質量に対する(2)-R31SH基を有するシリコーンの含有割合は、特に限定されるものではない。(1)半導体材料の分散性を向上させる観点、及び耐久性を向上させる観点から、組成物の総質量に対する(2)-R31SH基を有するシリコーンの含有割合は、30質量%以下であることが好ましく、10質量%以下であることがより好ましく、7.5質量%以下であることがさらに好ましい。また、耐久性を向上させる観点から、組成物の総質量に対する(2)-R31SH基を有するシリコーンの含有割合は、0.001質量%以上であることが好ましく、0.01質量%以上であることがより好ましく、0.1質量%以上であることがさらに好ましい。 In the composition, the content ratio of the (2) -R 31 SH group-containing silicone to the total mass of the composition is not particularly limited. (1) From the viewpoint of improving the dispersibility of the semiconductor material and the viewpoint of improving durability, the content ratio of (2) -R 31 SH group-containing silicone to the total mass of the composition is 30% by mass or less. It is preferably 10% by mass or less, more preferably 7.5% by mass or less. From the viewpoint of improving durability, the content ratio of (2) -R 31 SH group-containing silicone to the total mass of the composition is preferably 0.001% by mass or more, and 0.01% by mass or more. Is more preferable, and 0.1% by mass or more is further preferable.
上記上限値及び下限値は任意に組み合わせることができる。 The above upper and lower limits can be combined arbitrarily.
上記上限値及び下限値の組み合わせの一例としては、0.001~30質量%、0.001~10質量%、0.1~7.5質量%が挙げられる。 Examples of combinations of the upper limit value and the lower limit value include 0.001 to 30% by mass, 0.001 to 10% by mass, and 0.1 to 7.5% by mass.
組成物の総質量に対する(2)-R31SH基を有するシリコーンの含有割合が上記範囲内である組成物は、耐久性の観点で好ましい。 A composition having a content ratio of (2) -R 31 SH group-containing silicone within the above range relative to the total mass of the composition is preferable from the viewpoint of durability.
組成物において、組成物の総質量に対する(5)表面修飾剤の含有割合は、特に限定されるものではない。耐久性向上の観点から、組成物の総質量に対する(5)表面修飾剤の含有割合は、30質量%以下であることが好ましく、1質量%以下であることがより好ましく、0.1質量%以下であることがさらに好ましい。また、熱耐久性を向上させる観点から、0.0001質量%以上であることが好ましく、0.001質量%以上であることがより好ましく、0.01質量%以上であることがさらに好ましい。 In the composition, the content ratio of the (5) surface modifier to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, the content ratio of the (5) surface modifier to the total mass of the composition is preferably 30% by mass or less, more preferably 1% by mass or less, and 0.1% by mass. The following is more preferable. Further, from the viewpoint of improving thermal durability, it is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and further preferably 0.01 mass% or more.
上記上限値及び下限値は任意に組み合わせることができる。 The above upper and lower limits can be combined arbitrarily.
上記上限値及び下限値の組み合わせの一例としては、0.0001~30質量%、0.001~1質量%、0.01~0.1質量%が挙げられる。 Examples of combinations of the upper limit value and the lower limit value include 0.0001 to 30% by mass, 0.001 to 1% by mass, and 0.01 to 0.1% by mass.
組成物の総質量に対する(5)表面修飾剤の含有割合が上記範囲内である組成物は、熱耐久性に優れる点で好ましい。 A composition in which the content ratio of the (5) surface modifier to the total mass of the composition is within the above range is preferable in terms of excellent heat durability.
本実施形態の組成物は、上述の(1)~(5)以外のその他の成分を有していてもよい。例えば、本実施形態の組成物は、若干の不純物、(1)半導体材料を構成する元素からなるアモルファス構造を有する化合物、重合開始剤をさらに含んでいてもよい。 The composition of the present embodiment may have other components other than the above (1) to (5). For example, the composition of the present embodiment may further contain a small amount of impurities, (1) a compound having an amorphous structure composed of the elements constituting the semiconductor material, and a polymerization initiator.
本実施形態の組成物における、若干の不純物、(1)半導体材料を構成する元素からなるアモルファス構造を有する化合物、重合開始剤の合計含有割合は、組成物の総質量に対して10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることがさらに好ましい。 In the composition of the present embodiment, the total content of some impurities, (1) the compound having an amorphous structure composed of the elements constituting the semiconductor material, and the polymerization initiator is 10% by mass or less based on the total mass of the composition. Is preferable, 5 mass% or less is more preferable, and 1 mass% or less is further preferable.
以下、本実施形態の組成物に含まれる(1)半導体材料、(2)-R31SH基を有するシリコーン、(3)溶媒、(4)重合性化合物、(4-1)重合体、(5)表面修飾剤について説明を行う。 Hereinafter, (1) a semiconductor material, (2) a silicone having a R 31 SH group, (3) a solvent, (4) a polymerizable compound, (4-1) a polymer, () included in the composition of the present embodiment 5) The surface modifier will be described.
<<(1)半導体材料>>
本実施形態の組成物に含まれる(1)半導体材料としては、下記(i)~(viii)を挙げることができる。
(i)II族-VI族化合物半導体を含む半導体材料
(ii)II族-V族化合物半導体を含む半導体材料
(iii)III族-V族化合物半導体を含む半導体材料
(iv)III族-IV族化合物半導体を含む半導体材料
(v)III族-VI族化合物半導体を含む半導体材料
(vi)IV族-VI族化合物半導体を含む半導体材料
(vii)遷移金属-p-ブロック化合物半導体を含む半導体材料
(viii)ペロブスカイト構造を有する化合物半導体を含む半導体材料
<< (1) Semiconductor material >>
Examples of the (1) semiconductor material contained in the composition of the present embodiment include the following (i) to (viii).
(I) Group II-VI compound semiconductor-containing semiconductor material (ii) Group II-V compound semiconductor-containing semiconductor material (iii) Group III-V compound semiconductor-containing semiconductor material (iv) Group III-IV Semiconductor Material Containing Compound Semiconductor (v) Semiconductor Material Containing Group III-VI Compound Semiconductor (vi) Semiconductor Material Containing Group IV-VI Compound Semiconductor (vii) Semiconductor Material Containing Transition Metal-p-Block Compound Semiconductor ( viii) a semiconductor material containing a compound semiconductor having a perovskite structure
<(i)II族-VI族化合物半導体を含む半導体材料>
II族-VI族化合物半導体としては、周期表の第2族元素と第16族元素とを含む化合物半導体と、周期表の第12族元素と第16族元素とを含む化合物半導体とを挙げることができる。
なお、本明細書において、「周期表」とは、長周期型周期表を意味する。
<(I) Semiconductor Material Containing Group II-VI Compound Semiconductor>
Examples of the group II-VI compound semiconductor include a compound semiconductor containing a
In addition, in this specification, a "periodic table" means a long period type periodic table.
以下の説明では、第2族元素と第16族元素とを含む化合物半導体を「化合物半導体(i-1)」、第12族元素と第16族元素とを含む化合物半導体を「化合物半導体(i-2)」と称することがある。
In the following description, a compound semiconductor containing a
化合物半導体(i-1)のうち、二元系の化合物半導体としては、例えば、MgS、MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、BaS、BaSe、又はBaTeが挙げられる。 Among the compound semiconductors (i-1), examples of binary compound semiconductors include MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, or BaTe.
また、化合物半導体(i-1)としては、
(i-1-1)第2族元素を1種類、第16族元素を2種類含む三元系の化合物半導体
(i-1-2)第2族元素を2種類、第16族元素を1種類含む三元系の化合物半導体
(i-1-3)第2族元素を2種類、第16族元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the compound semiconductor (i-1),
(I-1-1) A ternary compound semiconductor containing one
化合物半導体(i-2)のうち、二元系の化合物半導体としては、例えば、ZnS、ZnSe、ZnTe、CdS、CdSe、CdTe、HgS、HgSe、又はHgTeが挙げられる。 Among the compound semiconductors (i-2), examples of binary compound semiconductors include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe.
また、化合物半導体(i-2)としては、
(i-2-1)第12族元素を1種類、第16族元素を2種類含む三元系の化合物半導体(i-2-2)第12族元素を2種類、第16族元素を1種類含む三元系の化合物半導体(i-2-3)第12族元素を2種類、第16族元素を2種類含む四元系の化合物半導体であってもよい。
Further, as the compound semiconductor (i-2),
(I-2-1) A ternary compound semiconductor containing one group 12 element and two group 16 elements (i-2-2) two group 12 elements and one group 16 element A ternary compound semiconductor (i-2-3) including two kinds may include a quaternary compound semiconductor including two kinds of Group 12 elements and two kinds of Group 16 elements.
II族-VI族化合物半導体は、第2族元素、第12族元素、及び第16族元素以外の元素をドープ元素として含んでいてもよい。
The group II-VI compound semiconductor may contain an element other than the
<(ii)II族-V族化合物半導体を含む半導体材料>
II族-V族化合物半導体は、第12族元素と、第15族元素とを含む。
<(Ii) Semiconductor Material Containing Group II-V Compound Semiconductor>
The group II-V compound semiconductor contains a group 12 element and a group 15 element.
II族-V族化合物半導体のうち、二元系の化合物半導体としては、例えば、Zn3P2、Zn3As2、Cd3P2、Cd3As2、Cd3N2、又はZn3N2が挙げられる。 Among the group II-V group compound semiconductors, examples of binary compound semiconductors include, for example, Zn 3 P 2 , Zn 3 As 2 , Cd 3 P 2 , Cd 3 As 2 , Cd 3 N 2 , or Zn 3 N. 2 .
また、II族-V族化合物半導体としては、
(ii-1)第12族元素を1種類、第15族元素を2種類含む三元系の化合物半導体
(ii-2)第12族元素を2種類、第15族元素を1種類含む三元系の化合物半導体
(ii-3)第12族元素を2種類、第15族元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the II-V compound semiconductor,
(Ii-1) A ternary compound semiconductor containing one group 12 element and two group 15 elements (ii-2) A ternary compound semiconductor containing two group 12 elements and one group 15 element The compound semiconductor (ii-3) of the group may be a quaternary compound semiconductor containing two kinds of Group 12 elements and two kinds of Group 15 elements.
II族-V族化合物半導体は、第12族元素、及び第15族元素以外の元素をドープ元素として含んでいてもよい。 The group II-V compound semiconductor may contain an element other than the group 12 element and the group 15 element as a doping element.
<(iii)III族-V族化合物半導体を含む半導体材料>
III族-V族化合物半導体は、第13族元素と、第15族元素とを含む。
<(Iii) Semiconductor Material Containing Group III-V Compound Semiconductor>
The Group III-V compound semiconductor contains a Group 13 element and a Group 15 element.
III族-V族化合物半導体のうち、二元系の化合物半導体としては、例えば、BP、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、AlN、又はBNが挙げられる。 Among the group III-V group compound semiconductors, binary compound semiconductors include, for example, BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN. Can be mentioned.
また、III族-V族化合物半導体としては、
(iii-1)第13族元素を1種類、第15族元素を2種類含む三元系の化合物半導体(iii-2)第13族元素を2種類、第15族元素を1種類含む三元系の化合物半導体(iii-3)第13族元素を2種類、第15族元素を2種類含む四元系の化合物半導体であってもよい。
Further, as the group III-V compound semiconductor,
(Iii-1) A ternary compound semiconductor containing one group 13 element and two group 15 elements (iii-2) A ternary compound semiconductor containing two group 13 elements and one group 15 element System compound semiconductor (iii-3) A quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 15 elements may be used.
III族-V族化合物半導体は、第13族元素、及び第15族元素以外の元素をドープ元素として含んでいてもよい。 The group III-V compound semiconductor may contain an element other than the group 13 element and the group 15 element as a doping element.
<(iv)III族-IV族化合物半導体を含む半導体材料>
III族-IV族化合物半導体は、第13族元素と、第14族元素とを含む。
<(Iv) Semiconductor Material Containing Group III-IV Compound Semiconductor>
The group III-IV compound semiconductor contains a group 13 element and a group 14 element.
III族-IV族化合物半導体のうち、二元系の化合物半導体としては、例えば、B4C3、Al4C3、Ga4C3が挙げられる。 Among the group III-IV group compound semiconductors, examples of binary compound semiconductors include B 4 C 3 , Al 4 C 3 , and Ga 4 C 3 .
また、III族-IV族化合物半導体としては、
(iv-1)第13族元素を1種類、第14族元素を2種類含む三元系の化合物半導体
(iv-2)第13族元素を2種類、第14族元素を1種類含む三元系の化合物半導体
(iv-3)第13族元素を2種類、第14族元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the group III-IV compound semiconductor,
(Iv-1) ternary compound semiconductor containing one group 13 element and two group 14 elements (iv-2) ternary compound semiconductor containing two group 13 elements and one group 14 element The compound semiconductor (iv-3) of the system may be a quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 14 elements.
III族-IV族化合物半導体は、第13族元素、及び第14族元素以外の元素をドープ元素として含んでいてもよい。 The group III-IV compound semiconductor may contain an element other than the group 13 element and the group 14 element as a doping element.
<(v)III族-VI族化合物半導体を含む半導体材料>
III族-VI族化合物半導体は、第13族元素と、第16族元素とを含む。
<(V) Semiconductor Material Containing Group III-VI Compound Semiconductor>
The group III-VI compound semiconductor contains a group 13 element and a group 16 element.
III族-VI族化合物半導体のうち、二元系の化合物半導体としては、例えば、Al2S3、Al2Se3、Al2Te3、Ga2S3、Ga2Se3、Ga2Te3、GaTe、In2S3、In2Se3、In2Te3、又はInTeが挙げられる。 Of the group III-VI compound semiconductors, binary compound semiconductors include, for example, Al 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , GaTe, In 2 S 3 , In 2 Se 3 , In 2 Te 3 , or InTe.
また、III族-VI族化合物半導体としては、
(v-1)第13族元素を1種類、第16族元素を2種類含む三元系の化合物半導体
(v-2)第13族元素を2種類、第16族元素を1種類含む三元系の化合物半導体
(v-3)第13族元素を2種類、第16族元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the group III-VI compound semiconductor,
(V-1) A ternary compound semiconductor containing one group 13 element and two group 16 elements (v-2) A ternary compound semiconductor containing two group 13 elements and one group 16 element The compound semiconductor (v-3) of the system may be a quaternary compound semiconductor containing two kinds of group 13 elements and two kinds of group 16 elements.
III族-VI族化合物半導体は、第13族元素、及び第16族元素以外の元素をドープ元素として含んでいてもよい。 The group III-VI compound semiconductor may contain an element other than the group 13 element and the group 16 element as a doping element.
<(vi)IV族-VI族化合物半導体を含む半導体材料>
IV族-VI族化合物半導体は、第14族元素と、第16族元素とを含む。
<(Vi) Semiconductor Material Containing Group IV-VI Compound Semiconductor>
The group IV-VI compound semiconductor contains a group 14 element and a group 16 element.
IV族-VI族化合物半導体のうち、二元系の化合物半導体としては、例えば、PbS、PbSe、PbTe、SnS、SnSe、又はSnTeが挙げられる。 Among the group IV-VI compound semiconductors, examples of binary compound semiconductors include PbS, PbSe, PbTe, SnS, SnSe, or SnTe.
また、IV族-VI族化合物半導体としては、
(vi-1)第14族元素を1種類、第16族元素を2種類含む三元系の化合物半導体
(vi-2)第14族元素を2種類、第16族元素を1種類含む三元系の化合物半導体
(vi-3)第14族元素を2種類、第16族元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the group IV-VI compound semiconductor,
(Vi-1) A ternary compound semiconductor containing one group 14 element and two group 16 elements (vi-2) A ternary compound semiconductor containing two group 14 elements and one group 16 element System compound semiconductor (vi-3) A quaternary compound semiconductor containing two kinds of Group 14 elements and two kinds of Group 16 elements may be used.
III族-VI族化合物半導体は、第14族元素、及び第16族元素以外の元素をドープ元素として含んでいてもよい。 The group III-VI compound semiconductor may contain an element other than the group 14 element and the group 16 element as a doping element.
<(vii)遷移金属-p-ブロック化合物半導体を含む半導体材料>
遷移金属-p-ブロック化合物半導体は、遷移金属元素と、p-ブロック元素とを含む。「p-ブロック元素」とは、周期表の第13族から第18族に属する元素である。
<(Vii) Semiconductor Material Including Transition Metal-p-Block Compound Semiconductor>
The transition metal-p-block compound semiconductor contains a transition metal element and a p-block element. The "p-block element" is an element belonging to Groups 13 to 18 of the periodic table.
遷移金属-p-ブロック化合物半導体のうち、二元系の化合物半導体としては、例えば、NiS、CrSが挙げられる。 Among the transition metal-p-block compound semiconductors, examples of binary compound semiconductors include NiS and CrS.
また、遷移金属-p-ブロック化合物半導体としては、
(vii-1)遷移金属元素を1種類、p-ブロック元素を2種類含む三元系の化合物半導体
(vii-2)遷移金属元素を2種類、p-ブロック元素を1種類含む三元系の化合物半導体
(vii-3)遷移金属元素を2種類、p-ブロック元素を2種類含む四元系の化合物半導体
であってもよい。
Further, as the transition metal-p-block compound semiconductor,
(Vii-1) ternary compound semiconductor containing one transition metal element and two p-block elements (vii-2) ternary compound semiconductor containing two transition metal elements and one p-block element Compound semiconductor (vii-3) A quaternary compound semiconductor containing two kinds of transition metal elements and two kinds of p-block elements may be used.
遷移金属-p-ブロック化合物半導体は、遷移金属元素、及びp-ブロック元素以外の元素をドープ元素として含んでいてもよい。 The transition metal-p-block compound semiconductor may contain a transition metal element and an element other than the p-block element as a doping element.
上述の三元系の化合物半導体や四元系の化合物半導体の具体例としては、ZnCdS、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、ZnCdSSe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTe、GaNP、GaNAs、GaPAs、AlNP、AlNAs、AlPAs、InNP、InNAs、InPAs、GaAlNP、GaAlNAs、GaAlPAs、GaInNP、GaInNAs、GaInPAs、InAlNP、InAlNAs、CuInS2、又はInAlPAs等が挙げられる。 Specific examples of the compound semiconductor of a compound semiconductor or quaternary ternary above, ZnCdS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe , CdHgTe, HgZnS, HgZnSe, HgZnTe, ZnCdSSe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs , GaAlPAs, GaInNP, GaInNAs, GaInP s, InAlNP, InAlNAs, CuInS 2 , or InAlPAs the like.
本実施形態の組成物においては、上述の化合物半導体の中でも、第12族元素であるCdを含む化合物半導体、及び第13族元素であるInを含む化合物半導体が好ましい。また、本実施形態の組成物においては、上述の化合物半導体の中でも、CdとSeとを含む化合物半導体、及びInとPとを含む化合物半導体が好ましい。 In the composition of the present embodiment, among the above compound semiconductors, a compound semiconductor containing Cd which is a Group 12 element and a compound semiconductor containing In which is a Group 13 element are preferable. In the composition of the present embodiment, among the above compound semiconductors, the compound semiconductor containing Cd and Se and the compound semiconductor containing In and P are preferable.
CdとSeとを含む化合物半導体は、二元系の化合物半導体、三元系の化合物半導体、四元系の化合物半導体のいずれも好ましい。中でも、二元系の化合物半導体であるCdSeが特に好ましい。 The compound semiconductor containing Cd and Se is preferably a binary compound semiconductor, a ternary compound semiconductor, or a quaternary compound semiconductor. Among them, CdSe, which is a binary compound semiconductor, is particularly preferable.
InとPとを含む化合物半導体は、二元系の化合物半導体、三元系の化合物半導体、四元系の化合物半導体のいずれも好ましい。中でも、二元系の化合物半導体であるInPが特に好ましい。 The compound semiconductor containing In and P is preferably a binary compound semiconductor, a ternary compound semiconductor, or a quaternary compound semiconductor. Of these, InP, which is a binary compound semiconductor, is particularly preferable.
<(viii)ペロブスカイト構造を有する化合物半導体を含む半導体材料>
ペロブスカイト構造を有する化合物半導体は、A、B、及びXを構成成分とするペロブスカイト型結晶構造を有する。以下の説明においては、ペロブスカイト構造を有する化合物半導体を、単に「ペロブスカイト化合物」と称することがある。
<(Viii) Semiconductor Material Including Compound Semiconductor Having Perovskite Structure>
The compound semiconductor having a perovskite structure has a perovskite type crystal structure having A, B and X as constituent components. In the following description, a compound semiconductor having a perovskite structure may be simply referred to as “perovskite compound”.
Aは、ペロブスカイト型結晶構造において、Bを中心とする六面体の各頂点に位置する成分であって、1価の陽イオンである。
Xは、ペロブスカイト型結晶構造において、Bを中心とする八面体の各頂点に位置する成分を表し、ハロゲン化物イオン、及びチオシアン酸イオンからなる群より選ばれる少なくとも一種の陰イオンである。
Bは、ペロブスカイト型結晶構造において、Aを頂点に配置する六面体、及びXを頂点に配置する八面体の中心に位置する成分であって、金属イオンである。
In the perovskite type crystal structure, A is a component located at each vertex of a hexahedron centered on B and is a monovalent cation.
X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
In the perovskite type crystal structure, B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion.
A、B、及びXを構成成分とするペロブスカイト化合物としては、特に限定されず、3次元構造、2次元構造、疑似2次元構造(quasi-2D)のいずれの構造を有する化合物であってもよい。
3次元構造の場合、ペロブスカイト化合物の組成式は、ABX(3+δ)で表される。
2次元構造の場合、ペロブスカイト化合物の組成式は、A2BX(4+δ)で表される。
The perovskite compound containing A, B, and X as constituent components is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a pseudo two-dimensional structure (quasi-2D). .
In the case of a three-dimensional structure, the composition formula of the perovskite compound is represented by ABX (3 + δ) .
In the case of a two-dimensional structure, the composition formula of the perovskite compound is represented by A 2 BX (4 + δ) .
ここで、δは、Bの電荷バランスに応じて適宜変更が可能な数であり、-0.7以上0.7以下である。例えば、Aが1価の陽イオン、Bが2価の陽イオン、Xが1価の陰イオンである場合、ペロブスカイト化合物が電気的に中性となるようにδを選択することができる。ペロブスカイト化合物が電気的に中性とは、ペロブスカイト化合物の電荷が0であることを意味する。 Here, δ is a number that can be appropriately changed according to the charge balance of B, and is −0.7 or more and 0.7 or less. For example, when A is a monovalent cation, B is a divalent cation, and X is a monovalent anion, δ can be selected so that the perovskite compound becomes electrically neutral. The electrically neutral perovskite compound means that the charge of the perovskite compound is zero.
ペロブスカイト化合物は、Bを中心とし、頂点をXとする八面体を含む。八面体は、BX6で表される。
ペロブスカイト化合物が3次元構造を有する場合、ペロブスカイト化合物に含まれるBX6は、八面体(BX6)において頂点に位置する1つのXを、結晶中で隣り合う2つの八面体(BX6)で共有することで、3次元ネットワークを構成する。
The perovskite compound includes an octahedron whose center is B and whose apex is X. The octahedron is represented by BX 6 .
If perovskite compound has a 3-dimensional structure, BX 6 contained in the perovskite compound, share one X is located at the apex in octahedral (
ペロブスカイト化合物が2次元構造を有する場合、ペロブスカイト化合物に含まれるBX6は、八面体(BX6)において頂点に位置する2つのXを、結晶中で隣り合う2つの八面体(BX6)で共有することで八面体の稜線を共有し、2次元的に連なった層を構成する。ペロブスカイト化合物では、2次元的に連なったBX6からなる層と、Aからなる層と、が交互に積層された構造を有する。
If perovskite compound has a two-dimensional structure, BX 6 contained in the perovskite compound, shared by the two X located at the vertices in octahedral (
本明細書において、ペロブスカイト化合物の結晶構造は、X線回折パターンにより確認することができる。 In the present specification, the crystal structure of the perovskite compound can be confirmed by an X-ray diffraction pattern.
ペロブスカイト化合物が3次元構造のペロブスカイト型結晶構造を有する場合、通常、X線回折パターンにおいて、2θ=12~18°の位置に(hkl)=(001)に由来するピークが確認される。又は2θ=18~25°の位置に(hkl)=(110)に由来するピークが確認される。 When the perovskite compound has a three-dimensional perovskite type crystal structure, a peak derived from (hkl) = (001) is usually confirmed at a position of 2θ = 12 to 18 ° in the X-ray diffraction pattern. Alternatively, a peak derived from (hkl) = (110) is confirmed at a position of 2θ = 18 to 25 °.
ペロブスカイト化合物が3次元構造のペロブスカイト型結晶構造を有する場合、2θ=13~16°の位置に、(hkl)=(001)に由来するピークが確認される、又は2θ=20~23°の位置に、(hkl)=(110)に由来するピークが確認されることが好ましい。 When the perovskite compound has a three-dimensional perovskite type crystal structure, a peak derived from (hkl) = (001) is confirmed at a position of 2θ = 13 to 16 °, or a position of 2θ = 20 to 23 ° In addition, it is preferable that a peak derived from (hkl) = (110) is confirmed.
ペロブスカイト化合物が2次元構造のペロブスカイト型結晶構造を有する場合、通常、X線回折パターンにおいて、2θ=1~10°の位置に、(hkl)=(002)由来のピークが確認される。また、2θ=2~8°の位置に、(hkl)=(002)由来のピークが確認されることが好ましい。 When the perovskite compound has a two-dimensional perovskite type crystal structure, a peak derived from (hkl) = (002) is usually confirmed at the position of 2θ = 1 to 10 ° in the X-ray diffraction pattern. Further, it is preferable to confirm a peak derived from (hkl) = (002) at a position of 2θ = 2 to 8 °.
ペロブスカイト化合物は、3次元構造を有することが好ましい。 The perovskite compound preferably has a three-dimensional structure.
(構成成分A)
ペロブスカイト化合物を構成するAは、1価の陽イオンである。Aとしては、セシウムイオン、有機アンモニウムイオン、又はアミジニウムイオンが挙げられる。
(Component A)
A constituting the perovskite compound is a monovalent cation. Examples of A include cesium ion, organic ammonium ion, and amidinium ion.
(有機アンモニウムイオン)
Aの有機アンモニウムイオンとして具体的には、下記式(A3)で表される陽イオンが挙げられる。
(Organic ammonium ion)
Specific examples of the organic ammonium ion of A include a cation represented by the following formula (A3).
式(A3)中、R6~R9は、それぞれ独立に、水素原子、アルキル基、又はシクロアルキル基を表す。但し、R6~R9は、少なくとも1つがアルキル基又はシクロアルキル基であり、R6~R9の全てが同時に水素原子となることはない。 In formula (A3), R 6 to R 9 each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group. However, at least one of R 6 to R 9 is an alkyl group or a cycloalkyl group, and all of R 6 to R 9 are not hydrogen atoms at the same time.
R6~R9で表されるアルキル基は、それぞれ独立に直鎖状であっても、分岐鎖状であってもよい。また、R6~R9で表されるアルキル基は、それぞれ独立に置換基としてアミノ基を有していてもよい。 The alkyl groups represented by R 6 to R 9 may each independently be linear or branched. The alkyl groups represented by R 6 to R 9 may each independently have an amino group as a substituent.
R6~R9がアルキル基である場合、炭素原子数は、それぞれ独立に通常1~20であり、1~4であることが好ましく、1~3であることがより好ましく、1であることがさらに好ましい。 When R 6 to R 9 are each an alkyl group, the number of carbon atoms is independently 1 to 20, usually 1 to 4, preferably 1 to 3, and more preferably 1. Is more preferable.
R6~R9で表されるシクロアルキル基は、それぞれ独立に置換基として、アミノ基を有していてもよい。 The cycloalkyl groups represented by R 6 to R 9 may each independently have an amino group as a substituent.
R6~R9で表されるシクロアルキル基の炭素原子数は、それぞれ独立に通常3~30であり、3~11であることが好ましく、3~8であることがより好ましい。炭素原子数は、置換基の炭素原子数も含む。 The number of carbon atoms of the cycloalkyl group represented by R 6 to R 9 is, independently of each other, usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms also includes the number of carbon atoms of the substituent.
R6~R9で表される基としては、それぞれ独立に、水素原子又はアルキル基であることが好ましい。 The groups represented by R 6 to R 9 are preferably each independently a hydrogen atom or an alkyl group.
ペロブスカイト化合物が、Aとして上記式(A3)で表される有機アンモニウムイオンを含む場合、式(A3)に含まれ得るアルキル基及びシクロアルキル基の数は少ないとよい。また、式(A3)に含まれ得るアルキル基及びシクロアルキル基の炭素原子数は小さいとよい。これにより、発光強度が高い3次元構造のペロブスカイト化合物を得ることができる。 When the perovskite compound contains, as A, an organic ammonium ion represented by the above formula (A3), it is preferable that the number of alkyl groups and cycloalkyl groups contained in the formula (A3) be small. In addition, the number of carbon atoms of the alkyl group and the cycloalkyl group which can be included in the formula (A3) is preferably small. Thereby, a perovskite compound having a three-dimensional structure with high emission intensity can be obtained.
式(A3)で表される有機アンモニウムイオンにおいて、R6~R9で表されるアルキル基及びシクロアルキル基に含まれる炭素原子数の合計数は1~4であることが好ましい。また、式(A3)で表される有機アンモニウムイオンにおいて、R6~R9のうちの1つが炭素原子数1~3のアルキル基であり、R6~R9のうちの3つが水素原子であることがより好ましい。 In the organic ammonium ion represented by the formula (A3), the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R 6 to R 9 is preferably 1 to 4. In the organic ammonium ion of the formula (A3), one of R 6 ~ R 9 is an alkyl group having 1 to 3 carbon atoms, three of R 6 ~ R 9 is a hydrogen atom More preferably.
R6~R9のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、tert-ペンチル基、1-メチルブチル基、n-ヘキシル基、2-メチルペンチル基、3-メチルペンチル基、2,2-ジメチルブチル基、2,3-ジメチルブチル基、n-ヘプチル基、2-メチルヘキシル基、3-メチルヘキシル基、2,2-ジメチルペンチル基、2,3-ジメチルペンチル基、2,4-ジメチルペンチル基、3,3-ジメチルペンチル基、3-エチルペンチル基、2,2,3-トリメチルブチル基、n-オクチル基、イソオクチル基、2-エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基が例示できる。 The alkyl group of R 6 to R 9 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group. , Neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group Group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group Group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group can be exemplified.
R6~R9のシクロアルキル基としては、それぞれ独立にR6~R9のアルキル基で例示した炭素原子数3以上のアルキル基が環を形成したものが挙げられる。一例として、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ノルボルニル基、イソボルニル基、1-アダマンチル基、2-アダマンチル基、トリシクロデシル基等を例示できる。 The cycloalkyl group of R 6 ~ R 9, include those independently R 6 ~ exemplified alkyl group having 3 or more carbon atoms in the alkyl group R 9 is to form a ring. Examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group. Etc. can be illustrated.
Aで表される有機アンモニウムイオンとしては、CH3NH3 +(メチルアンモニウムイオンともいう。)、C2H5NH3 +(エチルアンモニウムイオンともいう。)又はC3H7NH3 +(プロピルアンモニウムイオンともいう。)であることが好ましく、CH3NH3 +又はC2H5NH3 +であることより好ましく、CH3NH3 +であることがさらに好ましい。 Examples of the organic ammonium ion represented by A include CH 3 NH 3 + (also called methylammonium ion), C 2 H 5 NH 3 + (also called ethylammonium ion) or C 3 H 7 NH 3 + (propyl). It is also preferably an ammonium ion), more preferably CH 3 NH 3 + or C 2 H 5 NH 3 + , and further preferably CH 3 NH 3 + .
Aで表されるアミジニウムイオンとしては、例えば、下記式(A4)で表されるアミジニウムイオンが挙げられる。
(R10R11N=CH-NR12R13)+・・・(A4)
Examples of the amidinium ion represented by A include an amidinium ion represented by the following formula (A4).
(R 10 R 11 N = CH—NR 12 R 13 ) + ... (A4)
式(A4)中、R10~R13は、それぞれ独立に、水素原子、置換基としてアミノ基を有していてもよいアルキル基、又は置換基としてアミノ基を有していてもよいシクロアルキル基を表す。 In formula (A4), R 10 to R 13 are each independently a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl which may have an amino group as a substituent. Represents a group.
R10~R13で表されるアルキル基は、それぞれ独立に直鎖状であっても、分岐鎖状であってもよい。また、R10~R13で表されるアルキル基は、それぞれ独立に置換基としてアミノ基を有していてもよい。 The alkyl groups represented by R 10 to R 13 may each independently be linear or branched. The alkyl groups represented by R 10 to R 13 may each independently have an amino group as a substituent.
R10~R13で表されるアルキル基の炭素原子数は、それぞれ独立に通常1~20であり、1~4であることが好ましく、1~3であることがより好ましい。 The number of carbon atoms of the alkyl group represented by R 10 to R 13 is independently 1 to 20, usually 1 to 4, and more preferably 1 to 3.
R10~R13で表されるシクロアルキル基は、それぞれ独立に置換基として、アミノ基を有していてもよい。 The cycloalkyl groups represented by R 10 to R 13 may each independently have an amino group as a substituent.
R10~R13で表されるシクロアルキル基の炭素原子数は、それぞれ独立に通常3~30であり、3~11であることが好ましく、3~8であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The number of carbon atoms of the cycloalkyl group represented by R 10 to R 13 is, independently of each other, usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms of the substituent.
R10~R13のアルキル基の具体例としては、それぞれ独立にR6~R9において例示したアルキル基と同じ基が挙げられる。
R10~R13のシクロアルキル基の具体例としては、それぞれ独立にR6~R9において例示したシクロアルキル基と同じ基が挙げられる。
Specific examples of the alkyl group of R 10 to R 13 include the same groups as the alkyl groups exemplified in R 6 to R 9 each independently.
Specific examples of the cycloalkyl group of R 10 to R 13 include the same groups as the cycloalkyl group exemplified in R 6 to R 9 each independently.
R10~R13で表される基としては、それぞれ独立に水素原子又はアルキル基が好ましい。 The groups represented by R 10 to R 13 are preferably each independently a hydrogen atom or an alkyl group.
式(A4)に含まれる、アルキル基及びシクロアルキル基の数を少なくすること、並びにアルキル基及びシクロアルキル基の炭素原子数を小さくすることにより、発光強度が高い3次元構造のペロブスカイト化合物を得ることができる。 By reducing the number of alkyl groups and cycloalkyl groups contained in the formula (A4) and reducing the number of carbon atoms of the alkyl groups and cycloalkyl groups, a perovskite compound having a three-dimensional structure with high emission intensity is obtained. be able to.
アミジニウムイオンにおいて、R10~R13で表されるアルキル基及びシクロアルキル基に含まれる炭素原子数の合計数は1~4であることが好ましく、R10が炭素原子数1~3のアルキル基であり、R11~R13が水素原子であることがより好ましい。 In the amidinium ion, the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R 10 to R 13 is preferably 1 to 4, and R 10 is an alkyl group having 1 to 3 carbon atoms. More preferably, it is a group and R 11 to R 13 are hydrogen atoms.
ペロブスカイト化合物において、Aがセシウムイオン、炭素原子数が3以下の有機アンモニウムイオン、又は炭素原子数が3以下のアミジニウムイオンである場合、一般的にペロブスカイト化合物は3次元構造を有する。 In the perovskite compound, when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the perovskite compound generally has a three-dimensional structure.
ペロブスカイト化合物において、Aが炭素原子数4以上の有機アンモニウムイオン、又は炭素原子数4以上のアミジニウムイオンである場合、ペロブスカイト化合物は、2次元構造及び擬似2次元(quasi-2D)構造のいずれか一方または両方を有する。この場合、ペロブスカイト化合物は、2次元構造または疑似2次元構造を、結晶の一部または全体に有することができる。
2次元のペロブスカイト型結晶構造が複数積層すると3次元のペロブスカイト型結晶構造と同等になる(参考文献:P.PBoixら、J.Phys.Chem.Lett.2015,6,898-907など)。
In the perovskite compound, when A is an organic ammonium ion having 4 or more carbon atoms or an amidinium ion having 4 or more carbon atoms, the perovskite compound has either a two-dimensional structure or a pseudo two-dimensional (quasi-2D) structure. Have one or both. In this case, the perovskite compound may have a two-dimensional structure or a pseudo-two-dimensional structure in a part or the whole of the crystal.
When a plurality of two-dimensional perovskite type crystal structures are laminated, it becomes equivalent to a three-dimensional perovskite type crystal structure (references: P. PBoix et al., J. Phys. Chem. Lett. 2015, 6, 898-907, etc.).
ペロブスカイト化合物中のAは、セシウムイオン又はアミジニウムイオンが好ましい。 A of the perovskite compound is preferably a cesium ion or an amidinium ion.
(構成成分B)
ペロブスカイト化合物を構成するBは、1価の金属イオン、2価の金属イオン、及び3価の金属イオンからなる群より選ばれる1種類以上の金属イオンであってよい。Bは2価の金属イオンを含むことが好ましく、鉛、及びスズからなる群より選ばれる1種類以上の金属イオンを含むことがより好ましく、鉛がさらに好ましい。
(Component B)
B constituting the perovskite compound may be one or more kinds of metal ions selected from the group consisting of monovalent metal ions, divalent metal ions, and trivalent metal ions. B preferably contains a divalent metal ion, more preferably contains at least one metal ion selected from the group consisting of lead and tin, and even more preferably lead.
(構成成分X)
ペロブスカイト化合物を構成するXは、ハロゲン化物イオン、及びチオシアン酸イオンからなる群より選ばれる少なくとも一種の陰イオンであってよい。
(Component X)
X constituting the perovskite compound may be at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
ハロゲン化物イオンとしては、塩化物イオン、臭化物イオン、フッ化物イオン、ヨウ化物イオンを挙げることができる。Xは、臭化物イオン又はヨウ化物イオンを含むことが好ましく、臭化物イオンを含むことがより好ましく、臭化物イオン及びヨウ化物イオンを含むことがさらに好ましい。 As the halide ion, chloride ion, bromide ion, fluoride ion, iodide ion can be mentioned. X preferably contains bromide ion or iodide ion, more preferably contains bromide ion, and further preferably contains bromide ion and iodide ion.
Xが2種以上のハロゲン化物イオンである場合、ハロゲン化物イオンの含有比率は、発光波長により適宜選ぶことができる。例えば、臭化物イオンと塩化物イオンとの組み合わせ、又は、臭化物イオンとヨウ化物イオンとの組み合わせとすることができる。
Xは、臭化物イオンとヨウ化物イオンとの組み合わせであることが好ましい。
When X is two or more kinds of halide ions, the content ratio of halide ions can be appropriately selected depending on the emission wavelength. For example, a combination of bromide ion and chloride ion or a combination of bromide ion and iodide ion can be used.
X is preferably a combination of bromide ion and iodide ion.
Xは、所望の発光波長に応じて適宜選択することができる。 X can be appropriately selected according to the desired emission wavelength.
Xが臭化物イオンであるペロブスカイト化合物は、通常480nm以上、好ましくは500nm以上、より好ましくは520nm以上の波長範囲に強度の極大ピークがある蛍光を発することができる。 A perovskite compound in which X is a bromide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more.
また、Xが臭化物イオンであるペロブスカイト化合物は、通常700nm以下、好ましくは600nm以下、より好ましくは580nm以下の波長範囲に強度の極大ピークがある蛍光を発することができる。
上記波長範囲の上限値及び下限値は、任意に組み合わせることができる。
The perovskite compound in which X is a bromide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 700 nm or less, preferably 600 nm or less, more preferably 580 nm or less.
The upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
ペロブスカイト化合物中のXが臭化物イオンの場合、発する蛍光のピークは、通常480~700nmであり、500~600nmであることが好ましく、520~580nmであることがより好ましい。 When X in the perovskite compound is a bromide ion, the peak of fluorescence emitted is usually 480 to 700 nm, preferably 500 to 600 nm, and more preferably 520 to 580 nm.
Xがヨウ化物イオンであるペロブスカイト化合物は、通常520nm以上、好ましくは530nm以上、より好ましくは540nm以上の波長範囲に強度の極大ピークがある蛍光を発することができる。 The perovskite compound in which X is an iodide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 520 nm or more, preferably 530 nm or more, more preferably 540 nm or more.
また、Xがヨウ化物イオンであるペロブスカイト化合物は、通常800nm以下、好ましくは750nm以下、より好ましくは730nm以下の波長範囲に強度の極大ピークがある蛍光を発することができる。
上記波長範囲の上限値及び下限値は、任意に組み合わせることができる。
A perovskite compound in which X is an iodide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 800 nm or less, preferably 750 nm or less, more preferably 730 nm or less.
The upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
ペロブスカイト化合物中のXがヨウ化物イオンの場合、発する蛍光のピークは、通常520~800nmであり、530~750nmであることが好ましく、540~730nmであることがより好ましい。 When X in the perovskite compound is an iodide ion, the fluorescence peak emitted is usually 520 to 800 nm, preferably 530 to 750 nm, and more preferably 540 to 730 nm.
Xが塩化物イオンであるペロブスカイト化合物は、通常300nm以上、好ましくは310nm以上、より好ましくは330nm以上の波長範囲に強度の極大ピークがある蛍光を発することができる。 A perovskite compound in which X is a chloride ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 300 nm or more, preferably 310 nm or more, more preferably 330 nm or more.
また、Xが塩化物イオンであるペロブスカイト化合物は、通常600nm以下、好ましくは580nm以下、より好ましくは550nm以下の波長範囲に強度の極大ピークがある蛍光を発することができる。
上記波長範囲の上限値及び下限値は、任意に組み合わせることができる。
Further, the perovskite compound in which X is a chloride ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 600 nm or less, preferably 580 nm or less, and more preferably 550 nm or less.
The upper limit value and the lower limit value of the above wavelength range can be arbitrarily combined.
ペロブスカイト化合物中のXが塩化物イオンの場合、発する蛍光のピークは、通常300~600nmであり、310~580nmであることが好ましく、330~550nmであることがより好ましい。 When X in the perovskite compound is a chloride ion, the peak of fluorescence emitted is usually 300 to 600 nm, preferably 310 to 580 nm, and more preferably 330 to 550 nm.
(3次元構造のペロブスカイト化合物の例示)
ABX(3+δ)で表される3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbI3、CH3NH3PbBr(3-y)Iy(0<y<3)、CH3NH3PbBr(3-y)Cly(0<y<3)、(H2N=CH-NH2)PbBr3、(H2N=CH-NH2)PbCl3、(H2N=CH-NH2)PbI3を挙げることができる。
(Exemplary perovskite compound having a three-dimensional structure)
Preferred examples of the perovskite compound having a three-dimensional structure represented by ABX (3 + δ) include CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr (3-y. ) I y (0 <y <3), CH 3 NH 3 PbBr (3-y) Cl y (0 <y <3), (H 2 N = CH—NH 2 ) PbBr 3 , (H 2 N = CH) --NH 2 ) PbCl 3 and (H 2 N═CH—NH 2 ) PbI 3 may be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3Pb(1-a)CaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)SraBr3(0<a≦0.7)、CH3NH3Pb(1-a)LaaBr(3+δ)(0<a≦0.7,0<δ≦0.7)、CH3NH3Pb(1-a)BaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)DyaBr(3+δ)(0<a≦0.7,0<δ≦0.7)も挙げることができる。 Preferable examples of the perovskite compound having a three-dimensional structure include CH 3 NH 3 Pb (1-a) Ca a Br 3 (0 <a ≦ 0.7), CH 3 NH 3 Pb (1-a) Sr a Br 3 (0 <a ≦ 0.7), CH 3 NH 3 Pb (1-a) La a Br (3 + δ) (0 <a ≦ 0.7, 0 <δ ≦ 0.7), CH 3 NH 3 Pb ( 1-a) Ba a Br 3 (0 <a ≦ 0.7), CH 3 NH 3 Pb (1-a) Dy a Br (3 + δ) (0 <a ≦ 0.7, 0 <δ ≦ 0.7 ) Can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3Pb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、CH3NH3Pb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)も挙げることができる。 Preferred examples of the three-dimensional perovskite compound include CH 3 NH 3 Pb (1-a) Na a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0), CH 3 NH 3 Pb (1-a) Li a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0) can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CsPb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、CsPb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)も挙げることができる。 Preferred examples of the three-dimensional perovskite compound include CsPb (1-a) Na a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0) and CsPb (1-a) Li. There can also be mentioned a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0).
3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3Pb(1-a)NaaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)LiaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)NaaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)LiaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)も挙げることができる。 Preferable examples of the three-dimensional perovskite compound include CH 3 NH 3 Pb (1-a) Na a Br (3 + δ−y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3), CH 3 NH 3 Pb (1-a) Li a Br (3 + δ−y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3 ), CH 3 NH 3 Pb (1-a) Na a Br (3 + δ−y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3), CH 3 NH 3 Pb (1-a) Li a Br (3 + δ-y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3) can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、(H2N=CH-NH2)Pb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)も挙げることができる。 As a preferable example of the perovskite compound having a three-dimensional structure, (H 2 N═CH—NH 2 ) Pb (1-a) Na a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ < 0), (H 2 N = CH—NH 2 ) Pb (1-a) Li a Br (3 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0), (H 2 N = CH -NH 2 ) Pb (1-a) Na a Br (3 + δ-y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3), (H 2 N = CH-NH 2 ) Pb (1-a) Na a Br (3 + δ-y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3) can also be mentioned. .
3次元構造のペロブスカイト化合物の好ましい例としては、CsPbBr3、CsPbCl3、CsPbI3、CsPbBr(3-y)Iy(0<y<3)、CsPbBr(3-y)Cly(0<y<3)も挙げることができる。 Preferred examples of the three-dimensional perovskite compound include CsPbBr 3 , CsPbCl 3 , CsPbI 3 , CsPbBr (3-y) I y (0 <y <3), CsPbBr (3-y) Cl y (0 <y < 3) can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3Pb(1-a)ZnaBr3(0<a≦0.7)、CH3NH3Pb(1-a)AlaBr(3+δ)(0<a≦0.7、0≦δ≦0.7)、CH3NH3Pb(1-a)CoaBr3(0<a≦0.7)、CH3NH3Pb(1-a)MnaBr3(0<a≦0.7)、CH3NH3Pb(1-a)MgaBr3(0<a≦0.7)も挙げることができる。 Preferred examples of the perovskite compound having a three-dimensional structure include CH 3 NH 3 Pb (1-a) Zn a Br 3 (0 <a ≦ 0.7), CH 3 NH 3 Pb (1-a) Al a Br ( 3 + δ) (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH 3 NH 3 Pb (1-a) Co a Br 3 (0 <a ≦ 0.7), CH 3 NH 3 Pb ( 1-a) Mn a Br 3 (0 <a ≦ 0.7) and CH 3 NH 3 Pb (1-a) Mg a Br 3 (0 <a ≦ 0.7) can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CsPb(1-a)ZnaBr3(0<a≦0.7)、CsPb(1-a)AlaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、CsPb(1-a)CoaBr3(0<a≦0.7)、CsPb(1-a)MnaBr3(0<a≦0.7)、CsPb(1-a)MgaBr3(0<a≦0.7)も挙げることができる。 Preferred examples of perovskite compound having a three-dimensional structure is, CsPb (1-a) Zn a Br 3 (0 <a ≦ 0.7), CsPb (1-a) Al a Br (3 + δ) (0 <a ≦ 0 .7, 0 <δ ≦ 0.7), CsPb (1-a) Co a Br 3 (0 <a ≦ 0.7), CsPb (1-a) Mna a Br 3 (0 <a ≦ 0.7) ) And CsPb (1-a) Mg a Br 3 (0 <a ≦ 0.7) can also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、CH3NH3Pb(1-a)ZnaBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)AlaBr(3+δ-y)Iy(0<a≦0.7,0<δ≦0.7,0<y<3)、CH3NH3Pb(1-a)CoaBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)MnaBr(3-y)Iy(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)MgaBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)ZnaBr(3-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)AlaBr(3+δ-y)Cly(0<a≦0.7、0<δ≦0.7、0<y<3)、CH3NH3Pb(1-a)CoaBr(3+δ-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)MnaBr(3-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)MgaBr(3-y)Cly(0<a≦0.7、0<y<3)も挙げることができる。 Preferred examples of the three-dimensional perovskite compound are CH 3 NH 3 Pb (1-a) Zn a Br (3-y) I y (0 <a ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Al a Br (3 + δ-y) I y (0 <a ≦ 0.7,0 <δ ≦ 0.7,0 <y <3), CH 3 NH 3 Pb (1- a) Co a Br (3- y) I y (0 <a ≦ 0.7,0 <y <3), CH 3 NH 3 Pb (1-a) Mn a Br (3-y) I y (0 <A ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Mg a Br (3-y) I y (0 <a ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Zn a Br (3-y) Cl y (0 <a ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Al a Br ( 3 + δ- ) Cl y (0 <a ≦ 0.7,0 <δ ≦ 0.7,0 <y <3), CH 3 NH 3 Pb (1-a) Co a Br (3 + δ-y) Cl y (0 < a ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Mn a Br (3-y) Cl y (0 <a ≦ 0.7, 0 <y <3), CH 3 NH 3 Pb (1-a) Mg a Br (3-y) Cl y (0 <a ≦ 0.7, 0 <y <3) may also be mentioned.
3次元構造のペロブスカイト化合物の好ましい例としては、(H2N=CH-NH2)ZnaBr3(0<a≦0.7)、(H2N=CH-NH2)MgaBr3(0<a≦0.7)、(H2N=CH-NH2)Pb(1-a)ZnaBr(3-y)Iy(0<a≦0.7、0<y<3)、(H2N=CH-NH2)Pb(1-a)ZnaBr(3-y)Cly(0<a≦0.7、0<y<3)も挙げることができる。 Preferable examples of the three-dimensional perovskite compound include (H 2 N═CH—NH 2 ) Zn a Br 3 (0 <a ≦ 0.7), (H 2 N═CH—NH 2 ) Mga a Br 3 (0 <a ≦ 0.7), (H 2 N═CH—NH 2 ) Pb (1-a) Zn a Br (3-y) I y (0 <a ≦ 0.7, 0 <y <3 ), (H 2 N = CH—NH 2 ) Pb (1-a) Zn a Br (3-y) Cl y (0 <a ≦ 0.7, 0 <y <3).
上述した3次元構造のペロブスカイト化合物の中でも、CsPbBr3、CsPbBr(3-y)Iy(0<y<3)、(H2N=CH-NH2)PbBr3がより好ましく、(H2N=CH-NH2)PbBr3がさらに好ましい。 Among the three-dimensional perovskite compounds described above, CsPbBr 3 , CsPbBr (3-y) I y (0 <y <3), and (H 2 N = CH—NH 2 ) PbBr 3 are more preferable, and (H 2 N Further preferred is ═CH—NH 2 ) PbBr 3 .
(2次元構造のペロブスカイト化合物の例示)
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2PbBr4、(C4H9NH3)2PbCl4、(C4H9NH3)2PbI4、(C7H15NH3)2PbBr4、(C7H15NH3)2PbCl4、(C7H15NH3)2PbI4、(C4H9NH3)2Pb(1-a)LiaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)、(C4H9NH3)2Pb(1-a)NaaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)を挙げることができる。
(Examples of perovskite compounds having a two-dimensional structure)
Preferred examples of the perovskite compound having a two-dimensional structure include (C 4 H 9 NH 3 ) 2 PbBr 4 , (C 4 H 9 NH 3 ) 2 PbCl 4 , (C 4 H 9 NH 3 ) 2 PbI 4 , and (C 7 H 15 NH 3 ) 2 PbBr 4 , (C 7 H 15 NH 3 ) 2 PbCl 4 , (C 7 H 15 NH 3 ) 2 PbI 4 , (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0) can be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C7H15NH3)2Pb(1-a)NaaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)、(C7H15NH3)2Pb(1-a)LiaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)、(C7H15NH3)2Pb(1-a)RbaBr(4+δ)(0<a≦0.7、-0.7≦δ<0)も挙げることができる。 As a preferable example of the perovskite compound having a two-dimensional structure, (C 7 H 15 NH 3 ) 2 Pb (1-a) Na a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0 ), (C 7 H 15 NH 3 ) 2 Pb (1-a) Li a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0), (C 7 H 15 NH 3 ). 2 Pb (1-a) Rb a Br (4 + δ) (0 <a ≦ 0.7, −0.7 ≦ δ <0) can also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Iy(0<a≦0.7、-0.7≦δ<0、0<y<4)、(C4H9NH3)2Pb(1-a)LiaBr(4+δ-y)Iy(0<a≦0.7、-0.7≦δ<0、0<y<4)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Iy(0<a≦0.7、-0.7≦δ<0、0<y<4)も挙げることができる。 As a preferable example of the perovskite compound having a two-dimensional structure, (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4 + δ-y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4 + δ−y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4 + δ−y) I y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4) can also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Cly(0<a≦0.7、-0.7≦δ<0、0<y<4)、(C4H9NH3)2Pb(1-a)LiaBr(4+δ-y)Cly(0<a≦0.7、-0.7≦δ<0、0<y<4)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Cly(0<a≦0.7、-0.7≦δ<0、0<y<4)も挙げることができる。 As a preferable example of the perovskite compound having a two-dimensional structure, (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4 + δ-y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4 + δ−y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4 + δ−y) Cl y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <4) can also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2PbBr4、(C7H15NH3)2PbBr4も挙げることができる。 Preferable examples of the two-dimensional perovskite compound also include (C 4 H 9 NH 3 ) 2 PbBr 4 and (C 7 H 15 NH 3 ) 2 PbBr 4 .
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2PbBr(4-y)Cly(0<y<4)、(C4H9NH3)2PbBr(4-y)Iy(0<y<4)も挙げることができる。 Preferred examples of the two-dimensional perovskite compound include (C 4 H 9 NH 3 ) 2 PbBr (4-y) Cl y (0 <y <4), (C 4 H 9 NH 3 ) 2 PbBr (4- y) I y (0 <y <4) can also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2Pb(1-a)ZnaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)MgaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)CoaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)MnaBr4(0<a≦0.7)も挙げることができる。 Preferable examples of the perovskite compound having a two-dimensional structure include (C 4 H 9 NH 3 ) 2 Pb (1-a) Zn a Br 4 (0 <a ≦ 0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 <a ≦ 0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br 4 (0 <a ≦ 0.7), ( C 4 H 9 NH 3) 2 Pb (1-a) Mn a Br 4 (0 <a ≦ 0.7) may also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C7H15NH3)2Pb(1-a)ZnaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)MgaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)CoaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)MnaBr4(0<a≦0.7)も挙げることができる。 Preferable examples of the perovskite compound having a two-dimensional structure include (C 7 H 15 NH 3 ) 2 Pb (1-a) Zn a Br 4 (0 <a ≦ 0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 <a ≦ 0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Co a Br 4 (0 <a ≦ 0.7), ( C 7 H 15 NH 3) 2 Pb (1-a) Mn a Br 4 (0 <a ≦ 0.7) may also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2Pb(1-a)ZnaBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)MgaBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)CoaBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)MnaBr(4-y)Iy(0<a≦0.7、0<y<4)も挙げることができる。 As a preferable example of the perovskite compound having a two-dimensional structure, (C 4 H 9 NH 3 ) 2 Pb (1-a) Zn a Br (4-y) I y (0 <a ≦ 0.7, 0 <y < 4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br (4-y) I y (0 <a ≦ 0.7, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br (4-y) I y (0 <a ≦ 0.7, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mn a Br (4-y) I y (0 <a ≦ 0.7,0 <y <4) can also be mentioned.
2次元構造のペロブスカイト化合物の好ましい例としては、(C4H9NH3)2Pb(1-a)ZnaBr(4-y)Cly(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)MgaBr(4-y)Cly(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)CoaBr(4-y)Cly(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)MnaBr(4-y)Cly(0<a≦0.7、0<y<4)も挙げることができる。 As a preferable example of the perovskite compound having a two-dimensional structure, (C 4 H 9 NH 3 ) 2 Pb (1-a) Zn a Br (4-y) Cl y (0 <a ≦ 0.7, 0 <y < 4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br (4-y) Cl y (0 <a ≦ 0.7, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br (4-y) Cl y (0 <a ≦ 0.7, 0 <y <4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mn a Br (4-y) Cl y (0 <a ≦ 0.7,0 <y <4) can also be mentioned.
(半導体材料の粒径)
組成物に含まれる、(1)半導体材料が粒子状である場合、粒子状の(1)半導体材料(以下、半導体粒子と称する)の平均粒径は、本発明の効果を有する限り、特に限定されない。半導体粒子の平均粒径は、良好に結晶構造を維持させることができるため、1nm以上であることが好ましい。半導体粒子の平均粒径は、2nm以上であることがより好ましく、3nm以上であることがさらに好ましい。
(Particle size of semiconductor material)
When the (1) semiconductor material contained in the composition is in a particulate form, the average particle size of the particulate (1) semiconductor material (hereinafter referred to as semiconductor particles) is particularly limited as long as it has the effect of the present invention. Not done. The average particle size of the semiconductor particles is preferably 1 nm or more because the crystal structure can be maintained well. The average particle diameter of the semiconductor particles is more preferably 2 nm or more, further preferably 3 nm or more.
また、半導体粒子の平均粒径は、半導体材料が沈降しにくくなるため、また所望の発光特性を維持しやすくなるため、10μm以下であることが好ましい。半導体粒子の平均粒径は、1μm以下であることがより好ましく、500nm以下であることがさらに好ましい。なお、「発光特性」とは、発光性の半導体粒子に励起光を照射して得られる変換光の量子収率、発光強度、色純度などの光学物性を指す。色純度は、変換光のスペクトルの半値幅で評価することができる。 Further, the average particle size of the semiconductor particles is preferably 10 μm or less because the semiconductor material is unlikely to settle and the desired light emitting characteristics are easily maintained. The average particle diameter of the semiconductor particles is more preferably 1 μm or less, further preferably 500 nm or less. The “emission characteristic” refers to optical properties such as quantum yield of converted light, emission intensity, and color purity obtained by irradiating light-emitting semiconductor particles with excitation light. The color purity can be evaluated by the full width at half maximum of the spectrum of converted light.
半導体粒子の平均粒径の上限値及び下限値は任意に組み合わせることができる。
例えば、半導体粒子の平均粒径は、1nm以上10μm以下であることが好ましく、2nm以上1μm以下であることがより好ましく、3nm以上500nm以下であることがさらに好ましい。
The upper limit value and the lower limit value of the average particle diameter of the semiconductor particles can be arbitrarily combined.
For example, the average particle size of the semiconductor particles is preferably 1 nm or more and 10 μm or less, more preferably 2 nm or more and 1 μm or less, and further preferably 3 nm or more and 500 nm or less.
本明細書において、半導体粒子の平均粒径は、例えば、透過型電子顕微鏡(以下、TEMともいう。)、又は走査型電子顕微鏡(以下、SEMともいう。)により測定することができる。具体的には、TEM、又はSEMにより、20個の半導体粒子の最大フェレー径を測定し、測定値の算術平均値である平均最大フェレー径を計算することにより、平均粒径を求めることができる。
本明細書において「最大フェレー径」とは、TEM又はSEM画像上において、半導体粒子を挟む2本の平行な直線の最大距離を意味する。
In the present specification, the average particle size of semiconductor particles can be measured by, for example, a transmission electron microscope (hereinafter, also referred to as TEM) or a scanning electron microscope (hereinafter, also referred to as SEM). Specifically, the average particle diameter can be obtained by measuring the maximum Feret diameter of 20 semiconductor particles by TEM or SEM and calculating the average maximum Feret diameter which is the arithmetic mean value of the measured values. .
In the present specification, the “maximum Feret diameter” means the maximum distance between two parallel straight lines sandwiching a semiconductor particle on a TEM or SEM image.
半導体の粒子のメディアン径(D50)は、本発明の効果を有する限り、特に限定されない。良好に結晶構造を維持させることができるため、3nm以上であることが好ましい。半導体粒子のメディアン径は、4nm以上であることがより好ましく、5nm以上であることがさらに好ましい。 The median diameter (D50) of semiconductor particles is not particularly limited as long as it has the effect of the present invention. The thickness is preferably 3 nm or more because the crystal structure can be favorably maintained. The median diameter of the semiconductor particles is more preferably 4 nm or more, further preferably 5 nm or more.
また、半導体粒子のメディアン径(D50)は、半導体材料が沈降しにくくなるため、また所望の発光特性を維持しやすくなるため、5μm以下であることが好ましい。半導体粒子のメディアン径は、500nm以下であることがより好ましく、100nm以下であることがさらに好ましい。 Further, the median diameter (D50) of the semiconductor particles is preferably 5 μm or less because the semiconductor material is less likely to settle and the desired light emission characteristics are easily maintained. The median diameter of the semiconductor particles is more preferably 500 nm or less, further preferably 100 nm or less.
半導体粒子のメディアン径(D50)の上限値及び下限値は、任意に組み合わせることができる。
例えば、半導体粒子のメディアン径(D50)は、3nm以上5μm以下であることが好ましく、4nm以上500nm以下であることがより好ましく、5nm以上100nm以下であることがさらに好ましい。
The upper limit value and the lower limit value of the median diameter (D50) of the semiconductor particles can be arbitrarily combined.
For example, the median diameter (D50) of the semiconductor particles is preferably 3 nm or more and 5 μm or less, more preferably 4 nm or more and 500 nm or less, and further preferably 5 nm or more and 100 nm or less.
本明細書において、半導体粒子の粒度分布は、例えばTEM、SEMにより測定することができる。具体的には、TEM、又はSEMにより、20個の半導体粒子の最大フェレー径を観察し、最大フェレー径の分布から、メディアン径(D50)を求めることができる。 In the present specification, the particle size distribution of semiconductor particles can be measured by, for example, TEM or SEM. Specifically, the maximum Feret diameter of 20 semiconductor particles is observed by TEM or SEM, and the median diameter (D50) can be obtained from the distribution of the maximum Feret diameter.
本実施形態においては、上述の(1)半導体材料を1種のみ用いてもよく、2種以上を併用してもよい。
<(2)-R31SH基を有するシリコーン>
(2)-R31SH基を有するシリコーンは、シリコーンの主鎖に含まれるケイ素原子に-R31SH基が結合したシリコーンである。
上記-R31SH基中、R31は置換基を有していてもよいヒドロカルビレン基である。
本明細書において、「シリコーン」とは、シロキサン結合を主鎖として有し、側鎖に有機基がつながった構造を有する化合物を意味する。
In the present embodiment, the above (1) semiconductor material may be used alone or in combination of two or more.
<Silicone having (2) -R 31 SH group>
(2) The silicone having a —R 31 SH group is a silicone in which a —R 31 SH group is bonded to a silicon atom contained in the main chain of the silicone.
In the above-R 31 SH group, R 31 is a hydrocarbylene group which may have a substituent.
In the present specification, “silicone” means a compound having a structure having a siloxane bond as a main chain and an organic group connected to a side chain.
また、組成物が後述の(5)表面修飾剤を含む場合、(2)-R31SH基を有するシリコーンは、(5)表面修飾剤に被覆された(1)半導体材料をコアとしてシェル構造を形成することが好ましい。具体的には、(2)-R31SH基を有するシリコーンは、(1)半導体材料の表面の少なくとも一部を被覆している(5)表面修飾剤の表面の少なくとも一部を被覆していることが好ましく、(5)表面修飾剤が被覆していない(1)半導体材料の表面の少なくとも一部を被覆していてもよい。 In addition, when the composition includes the below-mentioned (5) surface modifier, the silicone having the (2) -R 31 SH group has a shell structure having (5) the surface modifier-coated semiconductor material as a core. Is preferably formed. Specifically, the silicone having the (2) -R 31 SH group covers (1) at least a part of the surface of the semiconductor material and (5) covers at least a part of the surface of the surface modifier. It is preferable that (5) the surface modifier is not coated, and (1) at least a part of the surface of the semiconductor material may be coated.
本実施形態において、(1)半導体材料又は(5)表面修飾剤の表面の少なくとも一部を被覆する(2)-R31SH基を有するシリコーンは、例えば、組成物をSEM、又はTEMなどを用いて観察することによって被覆状態を確認することができる。さらに、SEM、又はTEMを用いたエネルギー分散型X線分析(EDX)測定によって、詳細な元素分布を解析することができる。 In the present embodiment, (1) a semiconductor material or (5) a silicone having a (2) -R 31 SH group that covers at least a part of the surface of the surface modifier is, for example, a composition obtained by SEM or TEM. It is possible to confirm the coated state by observing with use. Furthermore, detailed element distribution can be analyzed by energy dispersive X-ray analysis (EDX) measurement using SEM or TEM.
(2)-R31SH基を有するシリコーンとしては、例えば、下記の式(B)で表されるシリコーンであることが好ましい。 The silicone having (2) —R 31 SH group is preferably, for example, a silicone represented by the following formula (B).
R31は、置換基を有していてもよいヒドロカルビレン基である。R32は、置換基を有していてもよいヒドロカルビル基であり、複数あるR32はそれぞれ同一であってもよいし、全て異なっていてもよいし、一部のみ同一であってもよい。mは特に制限はないが、好ましくは10~100000の整数である。nは特に制限はないが、好ましくは1~100000の整数である。m+nは特に制限はないが、好ましくは11~200000 の整数である。 R 31 is a hydrocarbylene group which may have a substituent. R 32 is a hydrocarbyl group which may have a substituent, and a plurality of R 32 may be the same, may be different from each other, or may be the same only in part. m is not particularly limited, but is preferably an integer of 10 to 100,000. n is not particularly limited, but is preferably an integer of 1 to 100,000. m + n is not particularly limited, but is preferably an integer of 11 to 200,000.
R31で表されるヒドロカルビレン基は、直鎖状、分岐鎖状であってもよい。
R31で表されるヒドロカルビレン基は、例えば、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、アラルキレン基等が例として挙げられる。
R31で表されるヒドロカルビレン基の炭素原子数は、通常20~200000であり、100~100000であることが好ましく、1000~90000であることがより好ましい。なお、炭素原子数は置換基の炭素原子数を含めた数である。
R31で表されるヒドロカルビレン基が有する置換基としては、炭化水素基、アミノ基、シアノ基、メルカプト基、ニトロ基、ハロゲノ基等が例として挙げられる。
The hydrocarbylene group represented by R 31 may be linear or branched.
Examples of the hydrocarbylene group represented by R 31 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and an aralkylene group.
The number of carbon atoms of the hydrocarbylene group represented by R 31 is usually 20 to 200,000, preferably 100 to 100,000, and more preferably 1,000 to 90,000. The number of carbon atoms is the number including the number of carbon atoms of the substituent.
Examples of the substituent which the hydrocarbylene group represented by R 31 has include a hydrocarbon group, an amino group, a cyano group, a mercapto group, a nitro group and a halogeno group.
R32で表されるヒドロカルビル基は、アルキル基、アルキル基、シクロアルキル基、アリール基、アルケニル基、又はアルキニル基が例として挙げられる。上記の中でもR32はアルキル基であることが好ましい。
R32で表されるヒドロカルビル基の炭素原子数は、特に制限はないが20以下であることが好ましく、10以下であることがより好ましい。なお、炭素原子数は置換基の炭素原子数を含めた数である。
R32で表されるヒドロカルビル基が有する置換基としては、炭化水素基、アミノ基、シアノ基、メルカプト基、ニトロ基、ハロゲノ基等が例として挙げられる。
Examples of the hydrocarbyl group represented by R 32 include an alkyl group, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group. Among the above, R 32 is preferably an alkyl group.
The number of carbon atoms of the hydrocarbyl group represented by R 32 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. The number of carbon atoms is the number including the number of carbon atoms of the substituent.
Examples of the substituent of the hydrocarbyl group represented by R 32 include a hydrocarbon group, an amino group, a cyano group, a mercapto group, a nitro group and a halogeno group.
R32のアルキル基の具体例としては、R6~R9において例示したアルキル基が挙げられ、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、tert-ペンチル基、エチル基、プロピル基であることが好ましく、メチル基、エチル基であることがより好ましく、メチル基であることが特に好ましい。 Specific examples of the alkyl group of R 32 include the alkyl groups exemplified in R 6 to R 9 , and include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. Group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, ethyl group, propyl group, preferably methyl group, ethyl group, and more preferably methyl group. Is particularly preferred.
mは10~20000であることが好ましく、10~10000であることがより好ましい。nは1~70000であることが好ましく、1~30000であることがより好ましい。また、m+nは100~100000であることが好ましく、1000~10000であることがより好ましい。 M is preferably 10 to 20000, and more preferably 10 to 10000. n is preferably 1 to 70,000, and more preferably 1 to 30,000. Further, m + n is preferably 100 to 100,000, and more preferably 1000 to 10000.
本実施形態においては、上述の(2)-R31SH基を有するシリコーンを1種のみ用いてもよく、2種以上を併用してもよい。 In the present embodiment, the above-mentioned silicone having a (2) -R 31 SH group may be used alone or in combination of two or more.
<<(5)表面修飾剤>>
(5)表面修飾剤は、アンモニウムイオン、アミン、第1級~第4級アンモニウムカチオン、アンモニウム塩、カルボン酸、カルボキシレートイオン、カルボキシレート塩、式(X1)~(X6)でそれぞれ表される化合物、及び式(X2)~(X4)でそれぞれ表される化合物の塩からなる群より選択される少なくとも1種化合物又はイオンである。
中でも、表面修飾剤は、アミン、第1級~第4級アンモニウムカチオン、アンモニウム塩、カルボン酸、カルボキシレートイオン及びカルボキシレート塩からなる群より選ばれる少なくとも一種を形成材料とすることが好ましく、アミン、及びカルボン酸からなる群より選ばれる少なくとも一種の化合物又はイオンであることがより好ましい。
<< (5) Surface modifier >>
(5) The surface modifier is represented by ammonium ion, amine, primary to quaternary ammonium cation, ammonium salt, carboxylic acid, carboxylate ion, carboxylate salt, and formulas (X1) to (X6), respectively. At least one compound or ion selected from the group consisting of compounds and salts of the compounds represented by formulas (X2) to (X4).
Among them, the surface modifier is preferably at least one selected from the group consisting of amines, primary to quaternary ammonium cations, ammonium salts, carboxylic acids, carboxylate ions and carboxylate salts as a forming material. And at least one compound or ion selected from the group consisting of carboxylic acids.
(5)表面修飾剤は、本実施形態の組成物中において、(1)半導体材料の表面に位置し、(1)半導体材料の表面修飾剤(キャッピング配位子ともいう)として作用する。より具体的には、(5)表面修飾剤は、(1)半導体材料の表面の少なくとも一部を被覆していることが好ましい。(5)表面修飾剤が、(1)半導体材料の表面の少なくとも一部を被覆することにより、(1)半導体材料の耐久性が向上する。 (5) The surface modifier is located on the surface of (1) semiconductor material in the composition of the present embodiment, and acts as (1) surface modifier of semiconductor material (also referred to as capping ligand). More specifically, (5) the surface modifier preferably covers at least a part of the surface of (1) the semiconductor material. (5) The surface modifier covers at least a part of the surface of (1) the semiconductor material, so that the durability of the (1) semiconductor material is improved.
本実施形態において、(1)半導体材料の表面の少なくとも一部を被覆する(5)表面修飾剤は、例えば、組成物をSEM、又はTEMなどを用いて観察することによって確認することができる。さらに、SEM、又はTEMを用いたEDX測定によって、詳細な元素分布を解析することができる。 In this embodiment, (1) the surface modifier that covers at least a part of the surface of the semiconductor material can be confirmed by observing the composition using SEM, TEM, or the like. Further, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.
<アンモニウムイオン、第1級~第4級アンモニウムカチオン、アンモニウム塩>
表面修飾剤であるアンモニウムイオン及び第1級~第4級アンモニウムカチオンは、下記式(A1)で表される。表面修飾剤であるアンモニウム塩は、下記式(A1)で表されるイオンを含む塩である。
<Ammonium ion, primary to quaternary ammonium cation, ammonium salt>
The ammonium ion and the primary to quaternary ammonium cations that are the surface modifier are represented by the following formula (A1). The ammonium salt that is the surface modifier is a salt containing an ion represented by the following formula (A1).
式(A1)で表されるイオンにおいて、R1~R4は、それぞれ独立に、水素原子、又は1価の炭化水素基を表す。 In the ion represented by the formula (A1), R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group.
R1~R4で表される炭化水素基は、飽和炭化水素基であってもよく、不飽和炭化水素基であってもよい。飽和炭化水素基としては、アルキル基、又はシクロアルキル基を挙げることができる。 The hydrocarbon group represented by R 1 to R 4 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the saturated hydrocarbon group include an alkyl group and a cycloalkyl group.
R1~R4で表されるアルキル基は、直鎖状であっても、分岐鎖状であってもよい。
R1~R4で表されるアルキル基の炭素原子数は、通常1~20であり、5~20であることが好ましく、8~20であることがより好ましい。
The alkyl group represented by R 1 to R 4 may be linear or branched.
The alkyl group represented by R 1 to R 4 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
R1~R4で表されるシクロアルキル基の炭素原子数は、通常3~30であり、3~20であることが好ましく、3~11であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The cycloalkyl group represented by R 1 to R 4 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R1~R4の不飽和炭化水素基は、直鎖状であっても、分岐鎖状であってもよい。 The unsaturated hydrocarbon group of R 1 to R 4 may be linear or branched.
R1~R4の不飽和炭化水素基の炭素原子数は、通常2~20であり、5~20であることが好ましく、8~20であることがより好ましい。 The unsaturated hydrocarbon group of R 1 to R 4 usually has 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
R1~R4は、水素原子、アルキル基、又は不飽和炭化水素基であることが好ましい。
不飽和炭化水素基としては、アルケニル基が好ましい。R1~R4は、炭素原子数8~20のアルケニル基であることが好ましい。
R 1 to R 4 are preferably a hydrogen atom, an alkyl group, or an unsaturated hydrocarbon group.
The unsaturated hydrocarbon group is preferably an alkenyl group. R 1 to R 4 are preferably alkenyl groups having 8 to 20 carbon atoms.
R1~R4のアルキル基の具体例としては、R6~R9において例示したアルキル基が挙げられる。 Specific examples of the alkyl group of R 1 to R 4 include the alkyl groups exemplified in R 6 to R 9 .
R1~R4のシクロアルキル基の具体例としては、R6~R9において例示したシクロアルキル基が挙げられる。 Specific examples of the cycloalkyl group of R 1 to R 4 include the cycloalkyl groups exemplified in R 6 to R 9 .
R1~R4のアルケニル基としては、R6~R9において例示した前記直鎖状又は分岐鎖状のアルキル基において、いずれか一つの炭素原子間の単結合(C-C)が、二重結合(C=C)に置換されたものが例示でき、二重結合の位置は限定されない。 The alkenyl group for R 1 to R 4 is the linear or branched alkyl group exemplified for R 6 to R 9 and is a single bond (C—C) between carbon atoms The thing substituted by the heavy bond (C = C) can be illustrated, and the position of a double bond is not limited.
R1~R4のアルケニル基の好ましいものとしては、例えば、エテニル基、プロペニル基、3-ブテニル基、2-ブテニル基、2-ペンテニル基、2-ヘキセニル基、2-ノネニル基、2-ドデセニル基、9-オクタデセニル基が挙げられる。 Preferred alkenyl groups for R 1 to R 4 include, for example, ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group. Group, a 9-octadecenyl group.
式(A1)で表されるアンモニウムカチオンが塩を形成する場合、カウンターアニオンとしては、特に制限は無い。カウンターアニオンとしては、ハロゲン化物イオンや、カルボキシレートイオンなどが好ましい。ハロゲン化物イオンとしては、臭化物イオン、塩化物イオン、ヨウ化物イオン、フッ化物イオンが挙げられる。 When the ammonium cation represented by the formula (A1) forms a salt, the counter anion is not particularly limited. As the counter anion, halide ion, carboxylate ion and the like are preferable. Examples of the halide ion include bromide ion, chloride ion, iodide ion, and fluoride ion.
式(A1)で表されるアンモニウムカチオンと、カウンターアニオンとを有するアンモニウム塩としては、n-オクチルアンモニウム塩、オレイルアンモニウム塩が好ましい例として挙げられる。 Preferred examples of the ammonium salt having the ammonium cation represented by the formula (A1) and the counter anion include n-octyl ammonium salt and oleyl ammonium salt.
<アミン>
表面修飾剤であるアミンとしては、下記式(A11)で表すことができる。
<Amine>
The amine as the surface modifier can be represented by the following formula (A11).
上記式(A11)において、R1~R3は、上記式(A1)が有するR1~R3と同じ基を表す。ただし、R1~R3のうち少なくとも1つは1価の炭化水素基である。 In the above formula (A11), R 1 ~ R 3 represent the same groups as R 1 ~ R 3 to the formula (A1) has. However, at least one of R 1 to R 3 is a monovalent hydrocarbon group.
表面修飾剤であるアミンとしては、第1級~第3級アミンのいずれであってもよいが、第1級アミン及び第2級アミンが好ましく、第1級アミンがより好ましい。 The amine as the surface modifier may be any of primary to tertiary amines, but primary amines and secondary amines are preferable, and primary amines are more preferable.
表面修飾剤であるアミンとしては、オレイルアミンが好ましい。 Oleylamine is preferred as the amine as the surface modifier.
<カルボン酸、カルボキシレートイオン、カルボキシレート塩>
表面修飾剤であるカルボキシレートイオンは、下記式(A2)で表される。表面修飾剤であるカルボキシレート塩は、下記式(A2)で表されるイオンを含む塩である。
R5―CO2
-・・・(A2)
<Carboxylic acid, carboxylate ion, carboxylate salt>
The carboxylate ion, which is a surface modifier, is represented by the following formula (A2). The carboxylate salt, which is a surface modifier, is a salt containing an ion represented by the following formula (A2).
R 5 -CO 2 - ··· (A2 )
表面修飾剤であるカルボン酸は、上記(A2)で表されるカルボキシレートアニオンにプロトン(H+)が結合したカルボン酸が挙げられる。 Examples of the carboxylic acid that is the surface modifier include a carboxylic acid having a proton (H + ) bonded to the carboxylate anion represented by (A2) above.
式(A2)で表されるイオンにおいて、R5は、一価の炭化水素基を表す。R5で表される炭化水素基は、飽和炭化水素基であってもよく、不飽和炭化水素基であってもよい。
飽和炭化水素基としては、アルキル基、又はシクロアルキル基を挙げることができる。
In the ion represented by the formula (A2), R 5 represents a monovalent hydrocarbon group. The hydrocarbon group represented by R 5 may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Examples of the saturated hydrocarbon group include an alkyl group and a cycloalkyl group.
R5で表されるアルキル基は、直鎖状であっても分岐鎖状であってもよい。 The alkyl group represented by R 5 may be linear or branched.
R5で表されるアルキル基の炭素原子数は、通常1~20であり、5~20であることが好ましく、8~20であることがより好ましい。 The alkyl group represented by R 5 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
R5で表されるシクロアルキル基の炭素原子数は、通常3~30であり、3~20であることが好ましく、3~11であることがより好ましい。炭素原子数は、置換基の炭素原子数も含む。 The cycloalkyl group represented by R 5 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms. The number of carbon atoms also includes the number of carbon atoms of the substituent.
R5で表される不飽和炭化水素基は、直鎖状であっても、分岐鎖状であってもよい。 The unsaturated hydrocarbon group represented by R 5 may be linear or branched.
R5で表される不飽和炭化水素基の炭素原子数は、通常2~20であり、5~20であることが好ましく、8~20であることがより好ましい。 The unsaturated hydrocarbon group represented by R 5 usually has 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
R5はアルキル基又は不飽和炭化水素基であることが好ましい。不飽和炭化水素基としては、アルケニル基が好ましい。 R 5 is preferably an alkyl group or an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an alkenyl group.
R5のアルキル基の具体例としては、R6~R9において例示したアルキル基が挙げられる。
R5のシクロアルキル基の具体例としては、R6~R9において例示したシクロアルキル基が挙げられる。
Specific examples of the alkyl group of R 5 include the alkyl groups exemplified in R 6 to R 9 .
Specific examples of the cycloalkyl group for R 5 include the cycloalkyl groups exemplified for R 6 to R 9 .
R5のアルケニル基の具体例としては、R1~R4において例示したアルケニル基が挙げられる。 Specific examples of the alkenyl group for R 5 include the alkenyl groups exemplified for R 1 to R 4 .
式(A2)で表されるカルボキシレートアニオンは、オレイン酸アニオンが好ましい。 The oleate anion is preferable as the carboxylate anion represented by the formula (A2).
カルボキシレートアニオンが塩を形成する場合、カウンターカチオンとしては、特に制限は無いが、アルカリ金属カチオン、アルカリ土類金属カチオン、アンモニウムカチオンなどが好ましい例として挙げられる。 When the carboxylate anion forms a salt, the counter cation is not particularly limited, but preferable examples include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.
表面修飾剤であるカルボン酸としては、オレイン酸が好ましい。 Oleic acid is preferred as the carboxylic acid that is the surface modifier.
<式(X1)で表される化合物> <Compound represented by Formula (X1)>
式(X1)で表される化合物(塩)において、R18~R21はそれぞれ独立に、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、又は置換基を有していてもよい炭素原子数6~30のアリール基を表す。 In the compound (salt) represented by the formula (X1), R 18 to R 21 each independently have an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent. Represents a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms which may have a substituent.
R18~R21で表されるアルキル基は、直鎖状であっても分岐鎖状であってもよい。 The alkyl group represented by R 18 to R 21 may be linear or branched.
R18~R21で表されるアルキル基は、置換基としてアリール基を有することが好ましい。R18~R21で表されるアルキル基の炭素原子数は、通常1~20であり、5~20であることが好ましく、8~20であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The alkyl group represented by R 18 to R 21 preferably has an aryl group as a substituent. The alkyl group represented by R 18 to R 21 usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R18~R21で表されるシクロアルキル基は、置換基としてアリール基を有することが好ましい。R18~R21で表されるシクロアルキル基の炭素原子数は、通常3~30であり、3~20であることが好ましく、3~11であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The cycloalkyl group represented by R 18 to R 21 preferably has an aryl group as a substituent. The cycloalkyl group represented by R 18 to R 21 usually has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R18~R21で表されるアリール基は、置換基としてアルキル基を有することが好ましい。R18~R21で表されるアリール基の炭素原子数は、通常6~30であり、6~20であることが好ましく、6~10であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The aryl group represented by R 18 to R 21 preferably has an alkyl group as a substituent. The aryl group represented by R 18 to R 21 usually has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R18~R21で表される基は、アルキル基であることが好ましい。 The group represented by R 18 to R 21 is preferably an alkyl group.
R18~R21で表されるアルキル基の具体例としては、R6~R9で表されるアルキル基において例示したアルキル基が挙げられる。 Specific examples of the alkyl group represented by R 18 to R 21 include the alkyl groups exemplified in the alkyl group represented by R 6 to R 9 .
R18~R21で表されるシクロアルキル基の具体例としては、R6~R9で表されるシクロアルキル基において例示したシクロアルキル基が挙げられる。 Specific examples of the cycloalkyl group represented by R 18 to R 21 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
R18~R21で表されるアリール基の具体例としては、フェニル基、ベンジル基、トリル基、o-キシリル基等が挙げられる。 Specific examples of the aryl group represented by R 18 to R 21 include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group and the like.
R18~R21で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。ハロゲン原子で置換した化合物の化学的安定性が高いため、置換するハロゲン原子としては、フッ素原子が好ましい。 The hydrogen atoms contained in the groups represented by R 18 to R 21 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Can be mentioned. Since the chemical stability of the compound substituted with a halogen atom is high, the halogen atom to be substituted is preferably a fluorine atom.
式(X1)で表される化合物において、M-はカウンターアニオンを表す。カウンターアニオンとしては、ハロゲン化物イオンや、カルボキシレートイオンなどが好ましい。ハロゲン化物イオンとしては、臭化物イオン、塩化物イオン、ヨウ化物イオン、フッ化物イオンが挙げられ、臭化物イオンが好ましい。 In the compound represented by the formula (X1), M − represents a counter anion. As the counter anion, halide ion, carboxylate ion and the like are preferable. Examples of the halide ion include bromide ion, chloride ion, iodide ion, and fluoride ion, and bromide ion is preferable.
式(X1)で表される化合物の具体例としては、テトラエチルホスホニウムクロリド、テトラエチルホスホニウムブロミド、テトラエチルホスホニウムヨージド;テトラブチルホスホニウムクロリド、テトラブチルホスホニウムブロミド、テトラブチルホスホニウムヨージド:テトラフェニルホスホニウムクロリド、テトラフェニルホスホニウムブロミド、テトラフェニルホスホニウムヨージド;テトラ-n-オクチルホスホニウムクロリド、テトラ-n-オクチルホスホニウムブロミド、テトラ-n-オクチルホスホニウムヨージド;トリブチル-n-オクチルホスホニウムブロミド;トリブチルドデシルホスホニウムブロミド;トリブチルヘキサデシルホスホニウムクロリド、トリブチルヘキサデシルホスホニウムブロミド、トリブチルヘキサデシルホスホニウムヨージドが挙げられる。 Specific examples of the compound represented by the formula (X1) include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide; tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide: tetraphenylphosphonium chloride, tetra Phenylphosphonium bromide, tetraphenylphosphonium iodide; tetra-n-octylphosphonium chloride, tetra-n-octylphosphonium bromide, tetra-n-octylphosphonium iodide; tributyl-n-octylphosphonium bromide; tributyldodecylphosphonium bromide; tributylhexa Decylphosphonium chloride, tributylhexadecylphosphonium bromide, tributy It is mentioned hexadecyl phosphonium iodide.
組成物の耐久性が高まることが期待できるため、式(X1)で表される化合物としてはトリブチルヘキサデシルホスホニウムブロミド、トリブチル-n-オクチルホスホニウムブロミドが好ましく、トリブチル-n-オクチルホスホニウムブロミドがより好ましい。 Since the durability of the composition can be expected to increase, tributylhexadecylphosphonium bromide and tributyl-n-octylphosphonium bromide are preferable as the compound represented by the formula (X1), and tributyl-n-octylphosphonium bromide is more preferable. .
<式(X2)で表される化合物、式(X2)で表される化合物の塩> <Compound represented by formula (X2), salt of the compound represented by formula (X2)>
式(X2)で表される化合物において、A1は単結合又は酸素原子を表す。 In the compound represented by the formula (X2), A 1 represents a single bond or an oxygen atom.
式(X2)で表される化合物において、R22は、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、又は置換基を有していてもよい炭素原子数6~30のアリール基を表す。 In the compound represented by the formula (X2), R 22 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 3 to 30 carbon atoms which may have a substituent. It represents a cycloalkyl group or an aryl group having 6 to 30 carbon atoms which may have a substituent.
R22で表されるアルキル基は、直鎖状であっても分岐鎖状であってもよい。 The alkyl group represented by R 22 may be linear or branched.
R22で表されるアルキル基としては、R18~R21で表されるアルキル基と同じ基を採用することができる。 As the alkyl group represented by R 22 , the same group as the alkyl group represented by R 18 to R 21 can be adopted.
R22で表されるシクロアルキル基としては、R18~R21で表されるシクロアルキル基と同じ基を採用することができる。 As the cycloalkyl group represented by R 22 , the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
R22で表されるアリール基としては、R18~R21で表されるアリール基と同じ基を採用することができる。 As the aryl group represented by R 22 , the same group as the aryl group represented by R 18 to R 21 can be adopted.
R22で表される基は、アルキル基であることが好ましい。 The group represented by R 22 is preferably an alkyl group.
R22で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、化学的安定性の観点から、フッ素原子が好ましい。 The hydrogen atoms contained in the group represented by R 22 may be each independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, From the viewpoint of chemical stability, a fluorine atom is preferable.
式(X2)で表される化合物の塩において、陰イオン性基は下記式(X2-1)で表される。 In the salt of the compound represented by the formula (X2), the anionic group is represented by the following formula (X2-1).
式(X2)で表される化合物の塩において、式(X2-1)の対となるカウンターカチオンとしては、例えば、アンモニウムイオンが挙げられる。 In the salt of the compound represented by the formula (X2), an example of the counter cation forming a pair with the formula (X2-1) is an ammonium ion.
式(X2)で表される化合物の塩において、式(X2-1)の対となるカウンターカチオンとしては、特に制限は無いが、例えばNa+、K+、Cs+等の一価のイオンが挙げられる。 In the salt of the compound represented by the formula (X2), the counter cation forming a pair in the formula (X2-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
式(X2)で表される化合物、及び式(X2)で表される化合物の塩としては、りん酸フェニル、りん酸フェニル二ナトリウム水和物、1-ナフチルりん酸二ナトリウム水和物、1-ナフチルりん酸一ナトリウム一水和物、ラウリルリン酸、ラウリルリン酸ナトリウム、オレイルリン酸、ベンズヒドリルホスホン酸、デシルホスホン酸、ドデシルホスホン酸、エチルホスホン酸、ヘキサデシルホスホン酸、ヘプチルホスホン酸、ヘキシルホスホン酸、メチルホスホン酸、ノニルホスホン酸、オクタデシルホスホン酸、n-オクチルホスホン酸、ベンゼンホスホン酸、フェニルホスホン酸二ナトリウム水和物、フェネチルホスホン酸、プロピルホスホン酸、ウンデシルホスホン酸、テトラデシルホスホン酸、シンナミルホスホン酸が挙げられる。 The compound represented by the formula (X2) and the salt of the compound represented by the formula (X2) include phenyl phosphate, phenyl disodium phosphate hydrate, 1-naphthyl disodium phosphate hydrate, and 1 -Naphthyl phosphate monosodium monohydrate, lauryl phosphate, sodium lauryl phosphate, oleyl phosphate, benzhydrylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, ethylphosphonic acid, hexadecylphosphonic acid, heptylphosphonic acid, Hexylphosphonic acid, methylphosphonic acid, nonylphosphonic acid, octadecylphosphonic acid, n-octylphosphonic acid, benzenephosphonic acid, phenylphosphonic acid disodium hydrate, phenethylphosphonic acid, propylphosphonic acid, undecylphosphonic acid, tetradecylphosphonic acid Acid, cinnamylphosphonic acid .
組成物の耐久性が高まることが期待できるため、式(X2)で表される化合物としては、オレイルリン酸、ドデシルホスホン酸、エチルホスホン酸、ヘキサデシルホスホン酸、ヘプチルホスホン酸、ヘキシルホスホン酸、メチルホスホン酸、ノニルホスホン酸、オクタデシルホスホン酸、n-オクチルホスホン酸、がより好ましく、オクタデシルホスホン酸がさらに好ましい。 Since the durability of the composition can be expected to increase, examples of the compound represented by the formula (X2) include oleylphosphoric acid, dodecylphosphonic acid, ethylphosphonic acid, hexadecylphosphonic acid, heptylphosphonic acid, hexylphosphonic acid, and methylphosphone. Acid, nonylphosphonic acid, octadecylphosphonic acid and n-octylphosphonic acid are more preferable, and octadecylphosphonic acid is still more preferable.
<式(X3)で表される化合物、式(3)で表される化合物の塩> <Compound represented by formula (X3), salt of compound represented by formula (3)>
式(X3)で表される化合物において、R23及びR24はそれぞれ独立に、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、又は置換基を有していてもよい炭素原子数6~30のアリール基を表す。 In the compound represented by the formula (X3), R 23 and R 24 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. It represents a cycloalkyl group having 3 to 30 atoms or an aryl group having 6 to 30 carbon atoms which may have a substituent.
R23及びR24で表されるアルキル基はそれぞれ独立に、直鎖状であっても分岐鎖状であってもよい。 The alkyl groups represented by R 23 and R 24 may each independently be linear or branched.
R23及びR24で表されるアルキル基としては、R18~R21で表されるアルキル基と同じ基を採用することができる。 As the alkyl group represented by R 23 and R 24 , the same group as the alkyl group represented by R 18 to R 21 can be adopted.
R23及びR24で表されるシクロアルキル基としては、R18~R21で表されるシクロアルキル基と同じ基を採用することができる。 As the cycloalkyl group represented by R 23 and R 24 , the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
R23及びR24で表されるアリール基としては、R18~R21で表されるアリール基と同じ基を採用することができる。 As the aryl group represented by R 23 and R 24 , the same group as the aryl group represented by R 18 to R 21 can be adopted.
R23及びR24はそれぞれ独立に、アルキル基であることが好ましい。 R 23 and R 24 are preferably each independently an alkyl group.
R23及びR24で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、化学的安定性の観点から、フッ素原子が好ましい。 The hydrogen atoms contained in the groups represented by R 23 and R 24 may each independently be substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
式(X3)で表される化合物の塩において、陰イオン性基は下記式(X3-1)で表される。 In the salt of the compound represented by the formula (X3), the anionic group is represented by the following formula (X3-1).
式(X3)で表される化合物の塩において、式(X3-1)の対となるカウンターカチオンとしては、例えば、アンモニウムイオンが挙げられる。 In the salt of the compound represented by the formula (X3), an example of the counter cation paired with the formula (X3-1) is an ammonium ion.
式(X3)で表される化合物の塩において、式(X3-1)の対となるカウンターカチオンとしては、特に制限は無いが、例えばNa+、K+、Cs+等の一価のイオンが挙げられる。 In the salt of the compound represented by the formula (X3), the counter cation forming a pair in the formula (X3-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
式(X3)で表される化合物の塩としては、ジフェニルホスフィン酸、りん酸ジブチル、りん酸ジデシル、りん酸ジフェニルが挙げられる。式(X3)で表される化合物の塩としては上記化合物の塩が挙げられる。 Examples of the salt of the compound represented by the formula (X3) include diphenylphosphinic acid, dibutyl phosphate, didecyl phosphate and diphenyl phosphate. Examples of the salt of the compound represented by the formula (X3) include salts of the above compounds.
組成物の耐久性が高まることが期待できるため、ジフェニルホスフィン酸、りん酸ジブチル、りん酸ジデシルが好ましく、ジフェニルホスフィン酸がより好ましい。 Since it is expected that the durability of the composition will be enhanced, diphenylphosphinic acid, dibutyl phosphate and didecyl phosphate are preferable, and diphenylphosphinic acid is more preferable.
<式(X4)で表される化合物、式(X4)で表される化合物の塩> <Compound Represented by Formula (X4), Salt of Compound Represented by Formula (X4)>
式(X4)で表される化合物において、A4は単結合又は酸素原子を表す。 In the compound represented by the formula (X4), A 4 represents a single bond or an oxygen atom.
式(X4)で表される化合物において、R25で表される基は、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、又は置換基を有していてもよい炭素原子数6~30のアリール基を表す。 In the compound represented by the formula (X4), the group represented by R 25 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, a carbon atom which may have a substituent. It represents a cycloalkyl group of 3 to 30 or an aryl group of 6 to 30 carbon atoms which may have a substituent.
R25で表されるアルキル基は、直鎖状であっても分岐鎖状であってもよい。 The alkyl group represented by R 25 may be linear or branched.
R25で表されるアルキル基としては、R18~R21で表されるアルキル基と同じ基を採用することができる。 As the alkyl group represented by R 25 , the same group as the alkyl group represented by R 18 to R 21 can be adopted.
R25で表されるシクロアルキル基としては、R18~R21で表されるシクロアルキル基と同じ基を採用することができる。 As the cycloalkyl group represented by R 25 , the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
R25で表されるアリール基としては、R18~R21で表されるアリール基と同じ基を採用することができる。 As the aryl group represented by R 25 , the same group as the aryl group represented by R 18 to R 21 can be adopted.
R25で表される基は、アルキル基であることが好ましい。 The group represented by R 25 is preferably an alkyl group.
R25で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、化学的安定性の観点から、フッ素原子が好ましい。 The hydrogen atoms contained in the group represented by R 25 may each independently be substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, From the viewpoint of chemical stability, a fluorine atom is preferable.
式(X4)で表される化合物としては、1-オクタンスルホン酸、1-デカンスルホン酸、1-ドデカンスルホン酸、ヘキサデシル硫酸、ラウリル硫酸、ミリスチル硫酸、ラウレス硫酸、ドデシル硫酸が挙げられる。 Examples of the compound represented by the formula (X4) include 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, hexadecylsulfate, laurylsulfate, myristylsulfate, laurethsulfate and dodecylsulfate.
式(X4)で表される化合物の塩において、陰イオン性基は下記式(X4-1)で表される。 In the salt of the compound represented by the formula (X4), the anionic group is represented by the following formula (X4-1).
式(X4)で表される化合物の塩において、式(X4-1)の対となるカウンターカチオンとしては、例えば、アンモニウム塩が挙げられる。 In the salt of the compound represented by the formula (X4), examples of the counter cation paired with the formula (X4-1) include an ammonium salt.
式(X4)で表される化合物の塩において、式(X4-1)の対となるカウンターカチオンとしては、特に制限は無いが、例えばNa+、K+、Cs+等の一価のイオンが挙げられる。 In the salt of the compound represented by the formula (X4), the counter cation forming a pair in the formula (X4-1) is not particularly limited, but for example, a monovalent ion such as Na + , K + and Cs + can be used. Can be mentioned.
式(X4)で表される化合物の塩としては、1-オクタンスルホン酸ナトリウム、1-デカンスルホン酸ナトリウム、1-ドデカンスルホン酸ナトリウム、ヘキサデシル硫酸ナトリウム、ラウリル硫酸ナトリウム、ミリスチル硫酸ナトリウム、ラウレス硫酸ナトリウム、ドデシル硫酸ナトリウムが挙げられる。 Examples of the salt of the compound represented by the formula (X4) include sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium hexadecyl sulfate, sodium lauryl sulfate, sodium myristyl sulfate and sodium laureth sulfate. , Sodium dodecyl sulfate.
組成物の耐久性が高まることが期待できるため、ヘキサデシル硫酸ナトリウム、ドデシル硫酸ナトリウムが好ましく、ドデシル硫酸ナトリウムがより好ましい。 Since the durability of the composition can be expected to increase, sodium hexadecyl sulfate and sodium dodecyl sulfate are preferable, and sodium dodecyl sulfate is more preferable.
<式(X5)で表される化合物> <Compound represented by formula (X5)>
式(X5)で表される化合物において、A5~A7はそれぞれ独立に、単結合又は酸素原子を表す。 In the compound represented by the formula (X5), A 5 to A 7 each independently represent a single bond or an oxygen atom.
式(X5)で表される化合物において、R26~R28はそれぞれ独立に、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、置換基を有していてもよい炭素原子数6~30のアリール基、置換基を有していてもよい炭素原子数2~20のアルケニル基、又は置換基を有していてもよい炭素原子数2~20のアルキニル基を表す。 In the compound represented by the formula (X5), R 26 to R 28 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. A cycloalkyl group having 3 to 30 atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent Represents an alkynyl group having 2 to 20 carbon atoms which may have a group.
R26~R28で表されるアルキル基はそれぞれ独立に、直鎖状であっても分岐鎖状であってもよい。 The alkyl groups represented by R 26 to R 28 may each independently be linear or branched.
R26~R28で表されるアルキル基としては、R18~R21で表されるアルキル基と同じ基を採用することができる。 As the alkyl group represented by R 26 to R 28 , the same group as the alkyl group represented by R 18 to R 21 can be adopted.
R26~R28で表されるシクロアルキル基としては、R18~R21で表されるシクロアルキル基と同じ基を採用することができる。 As the cycloalkyl group represented by R 26 to R 28 , the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
R26~R28で表されるアリール基としては、R18~R21で表されるアリール基と同じ基を採用することができる。 As the aryl group represented by R 26 to R 28 , the same group as the aryl group represented by R 18 to R 21 can be adopted.
R26~R28で表されるアルケニル基はそれぞれ独立に、置換基としてアルキル基、又はアリール基を有することが好ましい。R26~R28で表されるアルケニル基の炭素原子数は、通常2~20であり、6~20であることが好ましく、12~18であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 It is preferable that the alkenyl groups represented by R 26 to R 28 each independently have an alkyl group or an aryl group as a substituent. The alkenyl group represented by R 26 to R 28 usually has 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R26~R28で表されるアルキニル基はそれぞれ独立に、置換基としてアルキル基、又はアリール基を有することが好ましい。R26~R28で表されるアルキニル基の炭素原子数は、通常2~20であり、6~20であることが好ましく、12~18であることがより好ましい。炭素原子数は、置換基の炭素原子数を含む。 The alkynyl groups represented by R 26 to R 28 each independently preferably have an alkyl group or an aryl group as a substituent. The alkynyl group represented by R 26 to R 28 usually has 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.
R26~R28で表される基はそれぞれ独立に、アルキル基であることが好ましい。 It is preferable that the groups represented by R 26 to R 28 are each independently an alkyl group.
R26~R28で表されるアルケニル基の具体例としては、ヘキセニル基、オクテニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基、イコセニル基が挙げられる。 Specific examples of the alkenyl group represented by R 26 to R 28 include a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and an icosenyl group.
R26~R28で表されるアルキニル基の具体例としては、ヘキシニル基、オクチニル基、デシニル基、ドデシニル基、テトラデシニル基、ヘキサデシニル基、オクタデシニル基、イコシニル基が挙げられる。 Specific examples of the alkynyl group represented by R 26 to R 28 include a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a tetradecynyl group, a hexadecynyl group, an octadecynyl group, and an icosinyl group.
R26~R28で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、化学的安定性の観点から、フッ素原子が好ましい。 The hydrogen atoms contained in the groups represented by R 26 to R 28 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
式(X5)で表される化合物としては、亜りん酸トリオレイル、亜りん酸トリブチル、亜りん酸トリエチル、亜りん酸トリヘキシル、亜りん酸トリイソデシル、亜りん酸トリメチル、シクロヘキシルジフェニルホスフィン、ジ-tert-ブチルフェニルホスフィン、ジシクロヘキシルフェニルホスフィン、ジエチルフェニルホスフィン、トリブチルホスフィン、トリ-tert-ブチルホスフィン、トリヘキシルホスフィン、トリメチルホスフィン、トリ-n-オクチルホスフィン、トリフェニルホスフィンが挙げられる。 Examples of the compound represented by the formula (X5) include trioleyl phosphite, tributyl phosphite, triethyl phosphite, trihexyl phosphite, triisodecyl phosphite, trimethyl phosphite, cyclohexyldiphenylphosphine and di-tert. -Butylphenylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, tributylphosphine, tri-tert-butylphosphine, trihexylphosphine, trimethylphosphine, tri-n-octylphosphine, triphenylphosphine.
組成物の耐久性が高まることが期待できるため、亜りん酸トリオレイル、トリブチルホスフィン、トリヘキシルホスフィン、亜りん酸トリヘキシルが好ましく、亜りん酸トリオレイルがより好ましい。 Since the durability of the composition can be expected to increase, trioleyl phosphite, tributylphosphine, trihexylphosphine and trihexyl phosphite are preferable, and trioleyl phosphite is more preferable.
<式(X6)で表される化合物> <Compound represented by formula (X6)>
式(X6)で表される化合物において、A8~A10はそれぞれ独立に、単結合又は酸素原子を表す。 In the compound represented by the formula (X6), A 8 to A 10 each independently represent a single bond or an oxygen atom.
式(X6)で表される化合物において、R29~R31はそれぞれ独立に、置換基を有していてもよい炭素原子数1~20のアルキル基、置換基を有していてもよい炭素原子数3~30のシクロアルキル基、置換基を有していてもよい炭素原子数6~30のアリール基、置換基を有していてもよい炭素原子数2~20のアルケニル基、又は置換基を有していてもよい炭素原子数2~20のアルキニル基を表す。 In the compound represented by the formula (X6), R 29 to R 31 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. A cycloalkyl group having 3 to 30 atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent Represents an alkynyl group having 2 to 20 carbon atoms which may have a group.
R29~R31で表されるアルキル基はそれぞれ独立に、直鎖状であっても分岐鎖状であってもよい。 The alkyl groups represented by R 29 to R 31 may each independently be linear or branched.
R29~R31で表されるアルキル基としては、R18~R21で表されるアルキル基と同じ基を採用することができる。 As the alkyl group represented by R 29 to R 31 , the same group as the alkyl group represented by R 18 to R 21 can be adopted.
R29~R31で表されるシクロアルキル基としては、R18~R21で表されるシクロアルキル基と同じ基を採用することができる。 As the cycloalkyl group represented by R 29 to R 31 , the same group as the cycloalkyl group represented by R 18 to R 21 can be adopted.
R29~R31で表されるアリール基としては、R18~R21で表されるアリール基と同じ基を採用することができる。 As the aryl group represented by R 29 to R 31 , the same group as the aryl group represented by R 18 to R 21 can be adopted.
R29~R31で表されるアルケニル基としては、R26~R28で表されるアルケニル基と同じ基を採用することができる。 As the alkenyl group represented by R 29 to R 31 , the same group as the alkenyl group represented by R 26 to R 28 can be adopted.
R29~R31で表されるアルキニル基としては、R26~R28で表されるアルキニル基と同じ基を採用することができる。 As the alkynyl group represented by R 29 to R 31 , the same group as the alkynyl group represented by R 26 to R 28 can be adopted.
R29~R31で表される基はそれぞれ独立に、アルキル基であることが好ましい。
The groups represented by R 29 to R 31 are preferably each independently an alkyl group.
R29~R31で表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、化学的安定性の観点から、フッ素原子が好ましい。 The hydrogen atoms contained in the groups represented by R 29 to R 31 may be independently substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of chemical stability.
式(X6)で表される化合物としては、トリ-n-オクチルホスフィンオキシド、トリブチルホスフィンオキシド、メチル(ジフェニル)ホスフィンオキシド、トリフェニルホスフィンオキシド、トリ-p-トリルホスフィンオキシド、シクロヘキシルジフェニルホスフィンオキシド、りん酸トリメチル、りん酸トリブチル、りん酸トリアミル、りん酸トリス(2-ブトキシエチル)、りん酸トリフェニル、りん酸トリ-p-クレジル、りん酸トリ-m-クレジル、りん酸トリ-o-クレジルが挙げられる。 Examples of the compound represented by the formula (X6) include tri-n-octylphosphine oxide, tributylphosphine oxide, methyl (diphenyl) phosphine oxide, triphenylphosphine oxide, tri-p-tolylphosphine oxide, cyclohexyldiphenylphosphine oxide and phosphorus. Trimethyl phosphate, tributyl phosphate, triamyl phosphate, tris (2-butoxyethyl) phosphate, triphenyl phosphate, tri-p-cresyl phosphate, tri-m-cresyl phosphate, tri-o-cresyl phosphate Can be mentioned.
組成物の耐久性が高まることが期待できるため、トリ-n-オクチルホスフィンオキシド、トリブチルホスフィンオキシドが好ましく、トリ-n-オクチルホスフィンオキシドがより好ましい。 Since the durability of the composition can be expected to increase, tri-n-octylphosphine oxide and tributylphosphine oxide are preferable, and tri-n-octylphosphine oxide is more preferable.
上述した表面修飾剤の中では、アンモニウム塩、アンモニウムイオン、第1級~第4級アンモニウムカチオン、カルボキシレート塩、カルボキシレートイオンが好ましい。 Among the above surface modifiers, ammonium salts, ammonium ions, primary to quaternary ammonium cations, carboxylate salts and carboxylate ions are preferable.
アンモニウム塩、アンモニウムイオンの中では、オレイルアミン塩、オレイルアンモニウムイオンがより好ましい。 Among the ammonium salts and ammonium ions, oleylamine salt and oleylammonium ion are more preferable.
カルボキシレート塩、カルボキシレートイオンの中では、オレイン酸塩、オレイン酸カチオンがより好ましい。 Among the carboxylate salts and carboxylate ions, oleate and oleate cation are more preferable.
本実施形態においては、上述の(5)表面修飾剤を1種のみ用いてもよく、2種以上を併用してもよい。 In the present embodiment, the above-mentioned (5) surface modifier may be used alone or in combination of two or more kinds.
<<(3)溶媒>>
本実施形態の組成物が有する(3)溶媒は、(1)半導体材料を分散させることができる媒体であれば特に限定されない。本実施形態の組成物が有する溶媒は、(1)半導体材料を溶解し難いものが好ましい。
<< (3) Solvent >>
The solvent (3) contained in the composition of the present embodiment is not particularly limited as long as it is a medium in which (1) the semiconductor material can be dispersed. The solvent contained in the composition of this embodiment is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
本明細書において「溶媒」とは、1気圧、25℃において液体状態である物質のことをいう。但し、溶媒には、後述する重合性化合物及び重合体は含まない。 The term “solvent” as used herein refers to a substance that is in a liquid state at 1 atm and 25 ° C. However, the solvent does not include a polymerizable compound and a polymer described later.
溶媒としては、下記(a)~(k)を挙げることができる。
(a):エステル
(b):ケトン
(c):エーテル
(d):アルコール
(e):グリコールエーテル
(f):アミド基を有する有機溶媒
(g):ニトリル基を有する有機溶媒
(h):カーボネート基を有する有機溶媒
(i):ハロゲン化炭化水素
(j):炭化水素
(k):ジメチルスルホキシド
Examples of the solvent include the following (a) to (k).
(A): Ester (b): Ketone (c): Ether (d): Alcohol (e): Glycol ether (f): Organic solvent having an amide group (g): Organic solvent having a nitrile group (h): Organic solvent having a carbonate group (i): halogenated hydrocarbon (j): hydrocarbon (k): dimethyl sulfoxide
(a)エステルとしては、例えば、メチルホルメート、エチルホルメート、プロピルホルメート、ペンチルホルメート、メチルアセテート、エチルアセテート、ペンチルアセテート等を挙げることができる。 Examples of (a) ester include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and the like.
(b)ケトンとしては、γ-ブチロラクトン、N-メチル-2-ピロリドン、アセトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン等を挙げることができる。 Examples of (b) ketones include γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone.
(c)エーテルとしては、ジエチルエーテル、メチル-tert-ブチルエーテル、ジイソプロピルエーテル、ジメトキシメタン、ジメトキシエタン、1,4-ジオキサン、1,3-ジオキソラン、4-メチルジオキソラン、テトラヒドロフラン、メチルテトラヒドロフラン、アニソール、フェネトール等を挙げることができる。 Examples of the ether (c) include diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole and phenetole. Etc. can be mentioned.
(d)アルコールとしては、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、tert-ブタノール、1-ペンタノール、2-メチル-2-ブタノール、メトキシプロパノール、ジアセトンアルコール、シクロヘキサノール、2-フルオロエタノール、2,2,2-トリフルオロエタノール、2,2,3,3-テトラフルオロ-1-プロパノール等を挙げることができる。 (D) As alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol , Cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.
(e)グリコールエーテルとしては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、トリエチレングリコールジメチルエーテル等を挙げることができる。 Examples of (e) glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether.
(f)アミド基を有する有機溶媒としては、N,N-ジメチルホルムアミド、アセトアミド、N,N-ジメチルアセトアミド等を挙げることができる。 (F) Examples of the organic solvent having an amide group include N, N-dimethylformamide, acetamide, N, N-dimethylacetamide and the like.
(g)ニトリル基を有する有機溶媒としては、アセトニトリル、イソブチロニトリル、プロピオニトリル、メトキシアセトニトリル等を挙げることができる。 (G) Examples of the organic solvent having a nitrile group include acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile.
(h)カーボネート基を有する有機溶媒としては、エチレンカーボネート、プロピレンカーボネート等を挙げることができる。 (H) Examples of the organic solvent having a carbonate group include ethylene carbonate and propylene carbonate.
(i)ハロゲン化炭化水素としては、塩化メチレン、クロロホルム等を挙げることができる。 (I) Examples of halogenated hydrocarbons include methylene chloride and chloroform.
(j)炭化水素としては、n-ペンタン、シクロヘキサン、n-ヘキサン、1-オクタデセン、ベンゼン、トルエン、キシレン等を挙げることができる。 Examples of the (j) hydrocarbon include n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene and xylene.
これらの溶媒の中でも、(a)エステル、(b)ケトン、(c)エーテル、(g)ニトリル基を有する有機溶媒、(h)カーボネート基を有する有機溶媒、(i)ハロゲン化炭化水素及び(j)炭化水素は、極性が低く、(1)半導体材料を溶解し難いと考えられるため好ましい。 Among these solvents, (a) ester, (b) ketone, (c) ether, (g) nitrile group-containing organic solvent, (h) carbonate group-containing organic solvent, (i) halogenated hydrocarbon and ( j) Hydrocarbons are preferable because they have low polarity and are considered to be difficult to dissolve (1) semiconductor materials.
さらに、本実施形態の組成物に用いる溶媒としては、(i)ハロゲン化炭化水素、(j)炭化水素がより好ましい。 Further, as the solvent used in the composition of the present embodiment, (i) halogenated hydrocarbon and (j) hydrocarbon are more preferable.
本実施形態の組成物においては、上述の溶媒を1種のみ用いてもよく、2種以上を併用してもよい。 In the composition of the present embodiment, the above solvent may be used alone or in combination of two or more.
<<(4)重合性化合物>>
本実施形態の組成物が有する(4)重合性化合物は、本実施形態の組成物を製造する温度において、本実施形態の(1)半導体材料を溶解し難いものが好ましい。
<< (4) Polymerizable compound >>
The (4) polymerizable compound contained in the composition of the present embodiment is preferably one that is difficult to dissolve the (1) semiconductor material of the present embodiment at the temperature for producing the composition of the present embodiment.
本明細書において「重合性化合物」とは、重合性基を有する単量体化合物(モノマー)を意味する。例えば、重合性化合物は、1気圧、25℃において液体状態であるモノマーを挙げることができる。 In the present specification, the “polymerizable compound” means a monomer compound (monomer) having a polymerizable group. For example, the polymerizable compound may include a monomer that is in a liquid state at 1 atmosphere and 25 ° C.
例えば、室温、常圧下において組成物を製造する場合、重合性化合物としては、特に制限は無い。重合性化合物としては、例えば、スチレン、アクリル酸エステル、メタクリル酸エステル、アクリロニトリル等の公知の重合性化合物が挙げられる。中でも、重合性化合物としては、アクリル系樹脂の単量体であるアクリル酸エステル及びメタクリル酸エステルのいずれか一方又は両方が好ましい。 For example, when the composition is produced at room temperature under normal pressure, the polymerizable compound is not particularly limited. Examples of the polymerizable compound include known polymerizable compounds such as styrene, acrylic acid ester, methacrylic acid ester, and acrylonitrile. Among them, as the polymerizable compound, one or both of acrylic acid ester and methacrylic acid ester, which are monomers of the acrylic resin, are preferable.
本実施形態の組成物においては、重合性化合物を1種のみ用いてもよく、2種以上を併用してもよい。 In the composition of the present embodiment, the polymerizable compound may be used alone or in combination of two or more.
本実施形態の組成物において、全ての(4)重合性化合物に対する、アクリル酸エステル及びメタクリル酸エステルの合計量の割合は、10mol%以上であってもよい。同割合は、30mol%以上であってもよく、50mol%以上であってもよく、80mol%以上であってもよく、100mol%であってもよい。 In the composition of the present embodiment, the ratio of the total amount of acrylic acid ester and methacrylic acid ester to all (4) polymerizable compounds may be 10 mol% or more. The same ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, and 100 mol%.
<<(4-1)重合体>>
本実施形態の組成物に含まれる重合体は、本実施形態の組成物を製造する温度において、本実施形態の(1)半導体材料の溶解度が低い重合体が好ましい。
<< (4-1) Polymer >>
The polymer contained in the composition of the present embodiment is preferably a polymer having a low solubility of (1) the semiconductor material of the present embodiment at the temperature for producing the composition of the present embodiment.
例えば、室温、常圧下において組成物を製造する場合、重合体としては、特に制限は無いが、例えば、ポリスチレン、アクリル系樹脂、エポキシ樹脂等の公知の重合体が挙げられる。中でも、重合体としては、アクリル系樹脂が好ましい。アクリル系樹脂は、アクリル酸エステルに由来する構成単位及びメタクリル酸エステルに由来する構成単位のいずれか一方又は両方を含む。 For example, when the composition is produced at room temperature under normal pressure, the polymer is not particularly limited, and examples thereof include known polymers such as polystyrene, acrylic resin, and epoxy resin. Among them, acrylic resin is preferable as the polymer. The acrylic resin contains either one or both of a structural unit derived from an acrylate ester and a structural unit derived from a methacrylic acid ester.
本実施形態の組成物において、(4-1)重合体に含まれる全ての構成単位に対する、アクリル酸エステルに由来する構成単位及びメタクリル酸エステルに由来する構成単位の合計量の割合は、10mol%以上であってもよい。同割合は、30%mol以上であってもよく、50mol%以上であってもよく、80mol%以上であってもよく100mol%であってもよい。 In the composition of the present embodiment, the ratio of the total amount of the structural unit derived from the acrylate ester and the structural unit derived from the methacrylic acid ester to all the structural units contained in the (4-1) polymer is 10 mol%. It may be more than. The same ratio may be 30% mol or more, 50 mol% or more, 80 mol% or more, or 100 mol%.
(4-1)重合体の重量平均分子量は、100~1200000であることが好ましく、1000~800000であることがより好ましく、5000~150000であることがさらに好ましい。 The weight average molecular weight of the (4-1) polymer is preferably 100 to 1200000, more preferably 1000 to 800000, and further preferably 5000 to 150,000.
本明細書において「重量平均分子量」とは、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値を意味する。 In the present specification, the “weight average molecular weight” means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
本実施形態においては、上述の(4-1)重合体を1種のみ用いてもよく、2種以上を併用してもよい。 In the present embodiment, the above-mentioned (4-1) polymer may be used alone or in combination of two or more kinds.
<各成分の配合比について>
実施形態の組成物において、(1)半導体材料と(2)-R31SH基を有するシリコーンとの配合比は、(1)半導体材料及び(2)-R31SH基を有するシリコーンの種類等に応じて、適宜定めることができる。
<Regarding the compounding ratio of each component>
In the composition of the embodiment, the compounding ratio of (1) the semiconductor material and the silicone having the (2) -R 31 SH group is (1) the kind of the semiconductor material and the silicone having the (2) -R 31 SH group, etc. Can be appropriately determined according to
本実施形態の組成物において、(1)半導体材料と、(5)表面修飾剤との配合比は、(1)半導体材料による発光作用が良好に発揮される程度であればよく、組成物を構成する成分の種類等に応じて、適宜定めることができる。
本実施形態の組成物において、(1)半導体材料と、(5)表面修飾剤とのモル比[(1)半導体材料/(5)表面修飾剤]は、0.0001~1000であってもよく、0.01~100であってもよい。
(1)半導体材料と、(5)表面修飾剤との配合比に係る範囲が上記範囲内である樹脂組成物は、(1)半導体材料の凝集が生じ難く、発光性も良好に発揮される点で好ましい。
In the composition of this embodiment, the compounding ratio of (1) the semiconductor material and (5) the surface modifier may be such that (1) the semiconductor material exhibits a favorable light-emission action. It can be appropriately determined according to the type of constituent components and the like.
In the composition of the present embodiment, the molar ratio [(1) semiconductor material / (5) surface modifier] of (1) semiconductor material to (5) surface modifier is 0.0001 to 1,000. It may be 0.01 to 100.
The resin composition in which the range of the compounding ratio of (1) the semiconductor material and (5) the surface modifier is within the above range is (1) the aggregation of the semiconductor material is less likely to occur and the light emitting property is also excellently exhibited. It is preferable in terms.
<組成物の製造方法>
以下、本発明における組成物の製造方法に関し、実施形態を示して説明する。なお、本実施形態の組成物は、以下の実施形態の組成物の製造方法によって製造されるものに限定されるものではない。
<Method for producing composition>
Hereinafter, the method for producing the composition of the present invention will be described with reference to embodiments. The composition of the present embodiment is not limited to that produced by the method for producing the composition of the following embodiments.
<(1)半導体材料の製造方法>
((i)~(vii)の半導体材料の製造方法)
(i)~(vii)の半導体材料は、半導体材料を構成する元素の単体又は半導体材料を構成する元素の化合物と、脂溶性溶媒とを混合した混合液を加熱する方法で製造することができる。
<(1) Method for manufacturing semiconductor material>
(Methods for manufacturing semiconductor materials (i) to (vii))
The semiconductor materials (i) to (vii) can be manufactured by a method of heating a mixed liquid obtained by mixing a simple substance of the elements constituting the semiconductor material or a compound of the elements constituting the semiconductor material and a fat-soluble solvent. .
半導体材料を構成する元素を含む化合物の例としては、特に制限はないが、酸化物、酢酸塩、有機金属化合物、ハロゲン化物、硝酸塩等が挙げられる。 Examples of the compound containing an element constituting the semiconductor material are not particularly limited, but include oxides, acetates, organometallic compounds, halides, nitrates and the like.
脂溶性溶媒としては、例えば炭素原子数4~20の炭化水素基を有する含窒素化合物、炭素原子数4~20の炭化水素基を有する含酸素化合物などが挙げられる。 Examples of the fat-soluble solvent include nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms and oxygen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms.
炭素原子数4~20の炭化水素基としては、飽和脂肪族炭化水素基、不飽和脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基を挙げることができる。 Examples of the hydrocarbon group having 4 to 20 carbon atoms include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
炭素原子数4~20の飽和脂肪族炭化水素基としては、n-ブチル基、イソブチル基、n-ペンチル基、オクチル基、デシル基、ドデシル基、ヘキサデシル基、オクタデシル基などを挙げることができる。 Examples of the saturated aliphatic hydrocarbon group having 4 to 20 carbon atoms include n-butyl group, isobutyl group, n-pentyl group, octyl group, decyl group, dodecyl group, hexadecyl group and octadecyl group.
炭素原子数4~20の不飽和脂肪族炭化水素基としては、オレイル基を挙げることができる。 As an unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms, an oleyl group can be mentioned.
炭素原子数4~20の脂環式炭化水素基としては、シクロペンチル基、シクロヘキシル基などを挙げることができる。 Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclopentyl group and cyclohexyl group.
炭素原子数4~20の芳香族炭化水素基としては、フェニル基、ベンジル基、ナフチル基、ナフチルメチル基などを挙げることができる。 Examples of the aromatic hydrocarbon group having 4 to 20 carbon atoms include phenyl group, benzyl group, naphthyl group and naphthylmethyl group.
炭素原子数4~20の炭化水素基としては、飽和脂肪族炭化水素基、及び不飽和脂肪族炭化水素基が好ましい。 As the hydrocarbon group having 4 to 20 carbon atoms, a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferable.
含窒素化合物としては、アミン類やアミド類を挙げることができる。
含酸素化合物としては、脂肪酸類を挙げることができる。
Examples of the nitrogen-containing compound include amines and amides.
Examples of the oxygen-containing compound include fatty acids.
このような脂溶性溶媒のうち、炭素原子数4~20の炭化水素基を有する含窒素化合物が好ましい。このような含窒素化合物としては、例えばn-ブチルアミン、イソブチルアミン、n-ペンチルアミン、n-ヘキシルアミン、オクチルアミン、デシルアミン、ドデシルアミン、ヘキサデシルアミン、オクタデシルアミンなどのアルキルアミンや、オレイルアミンなどのアルケニルアミンが好ましい。 Among such fat-soluble solvents, nitrogen-containing compounds having a hydrocarbon group with 4 to 20 carbon atoms are preferable. Examples of such nitrogen-containing compounds include alkylamines such as n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine and octadecylamine, and oleylamine. Alkenylamines are preferred.
こうした脂溶性溶媒は、合成により生じる半導体材料の表面に結合可能である。脂溶性溶媒が半導体材料の表面に結合する際の結合としては、例えば共有結合、イオン結合、配位結合、水素結合、ファンデルワールス結合等の化学結合が挙げられる。 -Such a fat-soluble solvent can bind to the surface of a semiconductor material produced by synthesis. Examples of the bond when the lipophilic solvent bonds to the surface of the semiconductor material include chemical bonds such as covalent bond, ionic bond, coordination bond, hydrogen bond, and van der Waals bond.
上記混合液の加熱温度は、使用する原料(単体や化合物)の種類によって適宜設定すればよい。混合液の加熱温度は、例えば、130~300℃が好ましく、240~300℃がより好ましい。加熱温度が上記下限値以上であると結晶構造が単一化しやすいため好ましい。加熱温度が上記上限値以下であると、生じる半導体材料の結晶構造が崩壊しにくく、目的物が得られやすいため好ましい。 The heating temperature of the above mixed solution may be appropriately set depending on the type of raw material (single substance or compound) used. The heating temperature of the mixed solution is, for example, preferably 130 to 300 ° C, more preferably 240 to 300 ° C. It is preferable for the heating temperature to be at least the above lower limit value because the crystal structure is easily unified. When the heating temperature is not higher than the above upper limit, the crystal structure of the semiconductor material that is produced is less likely to collapse, and the target product is easily obtained, which is preferable.
混合液の加熱時間は、使用する原料(単体や化合物)の種類、加熱温度によって適宜設定すればよい。混合液の加熱時間は、例えば、数秒間~数時間が好ましく、1~60分間がより好ましい。 The heating time of the mixed solution may be appropriately set depending on the types of raw materials (single or compound) used and the heating temperature. The heating time of the mixed liquid is, for example, preferably several seconds to several hours, more preferably 1 to 60 minutes.
上述の半導体材料の製造方法においては、加熱後の混合液を冷却することにより、目的物である半導体材料を含む沈殿物が得られる。沈殿物を分離して適宜洗浄することで、目的物である半導体材料が得られる。 In the above-mentioned semiconductor material manufacturing method, by cooling the mixed solution after heating, a precipitate containing the target semiconductor material can be obtained. By separating the precipitate and washing it appropriately, the target semiconductor material can be obtained.
沈殿物を分離した上澄み液については、合成した半導体材料が不溶又は難溶な溶媒を添加し、上澄み液における半導体材料の溶解度を低下させて沈殿物を生じさせ、上澄み液に含まれる半導体材料を回収してもよい。「半導体材料が不溶又は難溶な溶媒」としては、例えばメタノール、エタノール、アセトン、アセトニトリルなどを挙げることができる。 For the supernatant liquid from which the precipitate is separated, a solvent in which the synthesized semiconductor material is insoluble or sparingly soluble is added to reduce the solubility of the semiconductor material in the supernatant liquid to form a precipitate, and the semiconductor material contained in the supernatant liquid is added. You may collect it. Examples of the “solvent in which the semiconductor material is insoluble or sparingly soluble” include methanol, ethanol, acetone, acetonitrile and the like.
上述の半導体材料の製造方法においては、分離した沈殿物を有機溶媒(例えばクロロホルム、トルエン、ヘキサン、n-ブタノールなど)に入れて半導体材料を含む溶液としてもよい。 In the above-mentioned semiconductor material manufacturing method, the separated precipitate may be put in an organic solvent (eg, chloroform, toluene, hexane, n-butanol, etc.) to form a solution containing the semiconductor material.
((viii)の半導体材料の製造方法)
(viii)の半導体材料の製造方法は、既知文献(Nano Lett. 2015, 15, 3692-3696、ACSNano,2015,9,4533-4542)を参考に、以下に述べる方法によって製造することができる。
(Method for manufacturing semiconductor material of (viii))
The manufacturing method of the semiconductor material of (viii) can be manufactured by the method described below with reference to known literatures (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542).
(第1の製造方法)
ペロブスカイト化合物の製造方法としては、ペロブスカイト化合物を構成するA成分を含む化合物、B成分を含む化合物、及びX成分を含む化合物を第1溶媒に溶解させ溶液を得る工程と、得られた溶液と第2溶媒とを混合する工程とを含む製造方法が挙げられる。
(First manufacturing method)
As a method for producing a perovskite compound, a step of dissolving a compound containing an A component, a compound containing a B component, and a compound containing an X component, which form the perovskite compound, in a first solvent; A manufacturing method including a step of mixing two solvents.
第2溶媒は、ペロブスカイト化合物に対する溶解度が第1溶媒よりも低い溶媒である。
なお、溶解度とは、得られた溶液と第2溶媒とを混合する工程を行う温度における溶解度を意味する。
The second solvent has a lower solubility for the perovskite compound than the first solvent.
The solubility means the solubility at the temperature at which the step of mixing the obtained solution and the second solvent is performed.
第1溶媒及び第2溶媒としては、上述の(a)~(k)として挙げる有機溶媒の群から選ばれる少なくとも2種を挙げることができる。 As the first solvent and the second solvent, at least two kinds selected from the group of organic solvents mentioned above as (a) to (k) can be mentioned.
例えば、室温(10℃~30℃)で溶液と第2溶媒とを混合する工程を行う場合、第1溶媒としては、上述の(d)アルコール、(e)グリコールエーテル、(f)アミド基を有する有機溶媒、(k)ジメチルスルホキシドを挙げることができる。 For example, when performing the step of mixing the solution and the second solvent at room temperature (10 ° C. to 30 ° C.), the above-mentioned (d) alcohol, (e) glycol ether, and (f) amide group are used as the first solvent. The organic solvent which it has and (k) dimethyl sulfoxide can be mentioned.
また、室温(10℃~30℃)で溶液と第2溶媒とを混合する工程を行う場合、第2溶媒としては、上述の(a)エステル、(b)ケトン、(c)エーテル、(g)ニトリル基を有する有機溶媒、(h)カーボネート基を有する有機溶媒、(i)ハロゲン化炭化水素、(j)炭化水素を挙げることができる。 When the step of mixing the solution and the second solvent at room temperature (10 ° C. to 30 ° C.) is performed, the second solvent may be the above-mentioned (a) ester, (b) ketone, (c) ether, or (g). ) Organic solvents having a nitrile group, (h) organic solvents having a carbonate group, (i) halogenated hydrocarbons, and (j) hydrocarbons.
以下、第1の製造方法を具体的に説明する。
まず、A成分を含む化合物、B成分を含む化合物、及びX成分を含む化合物を第1溶媒に溶解させ、溶液を得る。「A成分を含む化合物」は、X成分を含んでいてもよい。「B成分を含む化合物」は、X成分を含んでいてもよい。
Hereinafter, the first manufacturing method will be specifically described.
First, the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in the first solvent to obtain a solution. The “compound including the component A” may include the component X. The “compound including the component B” may include the component X.
次いで、得られた溶液と第2溶媒とを混合する。溶液と、第2溶媒とを混合する工程は、(I)溶液を第2溶媒に加えることとしてもよく、(II)第2溶媒を溶液に加えることとしてもよい。第1の製造方法で生じるペロブスカイト化合物の粒子が溶液中に分散しやすいため、(I)溶液を第2溶媒に加えるとよい。 Next, the solution obtained and the second solvent are mixed. In the step of mixing the solution and the second solvent, the (I) solution may be added to the second solvent, or the (II) second solvent may be added to the solution. Since the particles of the perovskite compound generated in the first production method are easily dispersed in the solution, it is advisable to add the solution (I) to the second solvent.
溶液と第2溶媒とを混合する際には、一方を他方に滴下するとよい。また、撹拌しながら溶液と第2溶媒とを混合するとよい。 When mixing the solution and the second solvent, one may be dropped on the other. Moreover, it is good to mix a solution and a 2nd solvent, stirring.
溶液と第2溶媒とを混合する工程において、溶液と第2溶媒との温度には特に制限は無い。得られるペロブスカイト化合物が析出し易いため、-20℃~40℃の範囲であることが好ましく、-5℃~30℃の範囲であることがより好ましい。溶液の温度及び第2溶媒の温度は、同じであってもよく、異なっていてもよい。 In the step of mixing the solution and the second solvent, there is no particular limitation on the temperature of the solution and the second solvent. Since the obtained perovskite compound is easily precipitated, the temperature is preferably in the range of -20 ° C to 40 ° C, more preferably in the range of -5 ° C to 30 ° C. The temperature of the solution and the temperature of the second solvent may be the same or different.
第1溶媒と第2溶媒とのペロブスカイト化合物に対する溶解度の差は100μg/溶媒100g~90g/溶媒100gであることが好ましく、1mg/溶媒100g~90g/溶媒100gであることがより好ましい。 The difference in solubility between the first solvent and the second solvent in the perovskite compound is preferably 100 μg / solvent 100 g to 90 g / solvent 100 g, and more preferably 1 mg / solvent 100 g to 90 g / solvent 100 g.
第1溶媒と第2溶媒との組み合わせとして、第1溶媒がN,N-ジメチルアセトアミド等のアミド基を有する有機溶媒やジメチルスルホキシドであり、第2溶媒がハロゲン化炭化水素や炭化水素であると好ましい。第1溶媒と第2溶媒とがこれらの溶媒の組み合わせであると、例えば、室温(10℃~30℃)で混合する工程を行う場合に、第1溶媒と第2溶媒とのペロブスカイト化合物に対する溶解度の差を100μg/溶媒100g~90g/溶媒100gに制御しやすいため好ましい。 As a combination of the first solvent and the second solvent, the first solvent is an organic solvent having an amide group such as N, N-dimethylacetamide or dimethyl sulfoxide, and the second solvent is a halogenated hydrocarbon or a hydrocarbon. preferable. When the first solvent and the second solvent are a combination of these solvents, for example, the solubility of the first solvent and the second solvent in the perovskite compound when performing the step of mixing at room temperature (10 ° C to 30 ° C) Is preferable because it is easy to control the difference of 100 μg / solvent 100 g to 90 g / solvent 100 g.
溶液と第2溶媒とを混合することにより、得られる混合液においてはペロブスカイト化合物の溶解度が低下し、ペロブスカイト化合物が析出する。これにより、ペロブスカイト化合物を含む分散液が得られる。 By mixing the solution and the second solvent, the solubility of the perovskite compound decreases in the resulting mixed solution, and the perovskite compound precipitates. As a result, a dispersion liquid containing the perovskite compound is obtained.
得られたペロブスカイト化合物を含む分散液について固液分離を行うことで、ペロブスカイト化合物を回収することができる。固液分離の方法としては、ろ過、溶媒の蒸発による濃縮などが挙げられる。固液分離を行うことで、ペロブスカイト化合物のみを回収することができる。 By performing solid-liquid separation on the obtained dispersion liquid containing the perovskite compound, the perovskite compound can be recovered. Examples of the solid-liquid separation method include filtration and concentration by evaporation of the solvent. By performing solid-liquid separation, only the perovskite compound can be recovered.
なお、上述した製造方法においては、得られるペロブスカイト化合物の粒子が分散液中で安定して分散しやすいため、上述の表面修飾剤を加える工程を含んでいることが好ましい。 Note that the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
表面修飾剤を加える工程は、溶液と第2溶媒とを混合する工程の前に行うことが好ましい。具体的には、表面修飾剤は、第1溶媒に添加してもよく、溶液に添加してもよく、第2溶媒に添加してもよい。また、表面修飾剤は、第1溶媒、及び第2溶媒の両方に添加してもよい。 The step of adding the surface modifier is preferably performed before the step of mixing the solution and the second solvent. Specifically, the surface modifier may be added to the first solvent, the solution, or the second solvent. Further, the surface modifier may be added to both the first solvent and the second solvent.
また、上述した製造方法においては、溶液と第2溶媒とを混合する工程のあと、遠心分離、ろ過などの手法により粗大粒子を除去する工程を含んでいていることが好ましい。除去する工程によって除去する粗大粒子のサイズは、好ましくは10μm以上、より好ましくは1μm以上、さらに好ましくは500nm以上である。 In addition, it is preferable that the above-mentioned manufacturing method includes a step of removing coarse particles by a method such as centrifugation or filtration after the step of mixing the solution and the second solvent. The size of the coarse particles removed in the removing step is preferably 10 μm or more, more preferably 1 μm or more, and further preferably 500 nm or more.
(第2の製造方法)
ペロブスカイト化合物の製造方法としては、ペロブスカイト化合物を構成するA成分を含む化合物、B成分を含む化合物、及びX成分を含む化合物を高温の第3溶媒に溶解させ溶液を得る工程と、溶液を冷却する工程とを含む製造方法が挙げられる。
(Second manufacturing method)
As a method for producing a perovskite compound, a step of dissolving a compound including an A component, a compound including a B component, and a compound including an X component, which form the perovskite compound, in a high temperature third solvent, and cooling the solution. And a manufacturing method including a step.
以下、第2の製造方法を具体的に説明する。 The following will specifically describe the second manufacturing method.
まず、A成分を含む化合物、B成分を含む化合物、及びX成分を含む化合物を高温の第3溶媒に溶解させ溶液を得る。「A成分を含む化合物」は、X成分を含んでいてもよい。
「B成分を含む化合物」は、X成分を含んでいてもよい。
本工程は、高温の第3溶媒に各化合物を加えて溶解させ溶液を得ることとしてもよい。
また、本工程は、第3溶媒に各化合物を加えた後、昇温することで溶液を得ることとしてもよい。
First, the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in a high-temperature third solvent to obtain a solution. The “compound including the component A” may include the component X.
The “compound including the component B” may include the component X.
In this step, each compound may be added to and dissolved in a high temperature third solvent to obtain a solution.
Further, in this step, after adding each compound to the third solvent, the temperature may be raised to obtain a solution.
第3溶媒としては、原料であるA成分を含む化合物と、B成分を含む化合物と、及びX成分を含む化合物とを溶解することができる溶媒が挙げられる。具体的には、第3溶媒としては、例えば、上述の第1溶媒、第2溶媒が挙げられる。 The third solvent includes a solvent capable of dissolving a compound containing the component A, which is a raw material, a compound containing the component B, and a compound containing the component X. Specifically, examples of the third solvent include the above-mentioned first solvent and second solvent.
「高温」とは、各原料が溶解する温度の溶媒であればよい。例えば、高温の第3溶媒の温度として、60~600℃であることが好ましく、80~400℃であることがより好ましい。 “High temperature” means a solvent at a temperature at which each raw material dissolves. For example, the temperature of the high temperature third solvent is preferably 60 to 600 ° C., and more preferably 80 to 400 ° C.
次いで、得られた溶液を冷却する。
冷却する温度としては、-20~50℃が好ましく、-10~30℃がより好ましい。
冷却速度としては、0.1~1500℃/分が好ましく、10~150℃/分がより好ましい。
The resulting solution is then cooled.
The cooling temperature is preferably −20 to 50 ° C., more preferably −10 to 30 ° C.
The cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.
高温の溶液を冷却することで、溶液の温度差に起因した溶解度の差により、ペロブスカイト化合物を析出させることができる。これにより、ペロブスカイト化合物を含む分散液が得られる。 By cooling the hot solution, the perovskite compound can be precipitated due to the difference in solubility due to the temperature difference between the solutions. As a result, a dispersion liquid containing the perovskite compound is obtained.
得られたペロブスカイト化合物を含む分散液については、固液分離を行うことで、ペロブスカイト化合物を回収することができる。固液分離の方法としては、第1の製造方法で示した方法が挙げられる。 The perovskite compound can be recovered by solid-liquid separation of the obtained dispersion liquid containing the perovskite compound. Examples of the solid-liquid separation method include the method described in the first manufacturing method.
なお、上述した製造方法においては、得られるペロブスカイト化合物の粒子が分散液中で安定して分散しやすいため、上述の表面修飾剤を加える工程を含んでいることが好ましい。 Note that the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
表面修飾剤を加える工程は、冷却する工程の前に行うことが好ましい。具体的には、表面修飾剤は、第3溶媒に添加してもよく、A成分を含む化合物、B成分を含む化合物、及びX成分を含む化合物のうち少なくとも1種を含む溶液に添加してもよい。 The step of adding the surface modifier is preferably performed before the step of cooling. Specifically, the surface modifier may be added to the third solvent, and is added to a solution containing at least one of the compound containing the component A, the compound containing the component B, and the compound containing the component X. Good.
また、上述した製造方法においては、冷却する工程のあと、第1の製造方法で示した遠心分離、ろ過などの手法により粗大粒子を除去する工程を含んでいていることが好ましい。 Further, in the above-mentioned manufacturing method, it is preferable that after the cooling step, a step of removing coarse particles by a method such as centrifugation and filtration shown in the first manufacturing method is included.
(第3の製造方法)
ペロブスカイト化合物の製造方法としては、ペロブスカイト化合物を構成するA成分を含む化合物と、B成分を含む化合物とを溶解させた第1溶液を得る工程と、ペロブスカイト化合物を構成するX成分を含む化合物を溶解させた第2溶液を得る工程と、第1溶液と第2溶液を混合して混合液を得る工程と、得られた混合液を冷却する工程とを含む製造方法が挙げられる。
(Third manufacturing method)
As a method for producing a perovskite compound, a step of obtaining a first solution in which a compound containing an A component constituting a perovskite compound and a compound containing a B component are dissolved, and a compound containing an X component constituting a perovskite compound are dissolved. The manufacturing method includes a step of obtaining the second solution, a step of mixing the first solution and the second solution to obtain a mixed solution, and a step of cooling the obtained mixed solution.
以下、第3の製造方法を具体的に説明する。 The following will specifically describe the third manufacturing method.
まず、A成分を含む化合物と、B成分を含む化合物とを高温の第4溶媒に溶解させ第1溶液を得る。 First, the compound containing the component A and the compound containing the component B are dissolved in a high temperature fourth solvent to obtain a first solution.
第4溶媒としては、A成分を含む化合物と、B成分を含む化合物とを溶解することができる溶媒が挙げられる。具体的には、第4溶媒としては、上述の第3溶媒が挙げられる。 The fourth solvent includes a solvent capable of dissolving the compound containing the component A and the compound containing the component B. Specifically, examples of the fourth solvent include the above-mentioned third solvent.
「高温」とは、A成分を含む化合物と、B成分を含む化合物とが溶解する温度であればよい。例えば、高温の第4溶媒の温度として、60~600℃であることが好ましく、80~400℃であることがより好ましい。 The “high temperature” may be a temperature at which the compound containing the component A and the compound containing the component B are dissolved. For example, the temperature of the high-temperature fourth solvent is preferably 60 to 600 ° C, more preferably 80 to 400 ° C.
また、X成分を含む化合物を第5溶媒に溶解させ第2溶液を得る。X成分を含む化合物は、B成分を含む化合物を含んでいてもよい。 Also, the compound containing the X component is dissolved in the fifth solvent to obtain the second solution. The compound containing the component X may contain a compound containing the component B.
第5溶媒としては、X成分を含む化合物とを溶解することができる溶媒が挙げられる。
具体的には、第5溶媒としては、上述の第3溶媒が挙げられる。
Examples of the fifth solvent include a solvent capable of dissolving the compound containing the component X.
Specifically, examples of the fifth solvent include the above-mentioned third solvent.
次いで、得られた第1溶液と第2溶液を混合して混合液を得る。第1溶液と第2溶液とを混合する際には、一方を他方に滴下するとよい。また、撹拌しながら第1溶液と第2溶液とを混合するとよい。 Next, the first solution and the second solution obtained are mixed to obtain a mixed solution. When mixing the first solution and the second solution, one may be dropped on the other. Further, it is advisable to mix the first solution and the second solution while stirring.
次いで、得られた混合液を冷却する。
冷却する温度としては、-20~50℃が好ましく、-10~30℃がより好ましい。
冷却速度としては、0.1~1500℃/分が好ましく、10~150℃/分がより好ましい。
Then, the obtained mixed liquid is cooled.
The cooling temperature is preferably −20 to 50 ° C., more preferably −10 to 30 ° C.
The cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.
混合液を冷却することで、混合液の温度差に起因した溶解度の差により、ペロブスカイト化合物を析出させることができる。これにより、ペロブスカイト化合物を含む分散液が得られる。 By cooling the mixed solution, the perovskite compound can be precipitated due to the difference in solubility due to the difference in temperature of the mixed solution. As a result, a dispersion liquid containing the perovskite compound is obtained.
得られたペロブスカイト化合物を含む分散液については、固液分離を行うことで、ペロブスカイト化合物を回収することができる。固液分離の方法としては、第1の製造方法で示した方法が挙げられる。 The perovskite compound can be recovered by solid-liquid separation of the obtained dispersion liquid containing the perovskite compound. Examples of the solid-liquid separation method include the method described in the first manufacturing method.
なお、上述した製造方法においては、得られるペロブスカイト化合物の粒子が分散液中で安定して分散しやすいため、上述の表面修飾剤を加える工程を含んでいることが好ましい。 Note that the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.
表面修飾剤を加える工程は、冷却する工程の前に行うことが好ましい。具体的には、表面修飾剤は、第4溶媒、第5溶媒、第1溶液、第2溶液、混合液のいずれに添加してもよい。 The step of adding the surface modifier is preferably performed before the step of cooling. Specifically, the surface modifier may be added to any of the fourth solvent, the fifth solvent, the first solution, the second solution and the mixed solution.
また、上述した製造方法においては、冷却する工程のあと、第1の製造方法で示した遠心分離、ろ過などの手法により粗大粒子を除去する工程を含んでいていることが好ましい。 Further, in the above-mentioned manufacturing method, it is preferable that after the cooling step, a step of removing coarse particles by a method such as centrifugation and filtration shown in the first manufacturing method is included.
<<組成物の製造方法1>>
以下、得られる組成物の性状を理解しやすくするため、組成物の製造方法1で得られる組成物を「液状組成物」と称する。
<< Production Method 1 of Composition >>
Hereinafter, in order to facilitate understanding of the properties of the obtained composition, the composition obtained by the method 1 for producing a composition is referred to as a “liquid composition”.
本実施形態の液状組成物は、(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(3)溶媒及び(4)重合性化合物のいずれか一方又は両方と混合することで製造することができる。 The liquid composition of the present embodiment should be mixed with (1) a semiconductor material, (2) a silicone having a —R 31 SH group, and (3) a solvent and / or (4) a polymerizable compound. Can be manufactured in.
(1)半導体材料及び(2)-R31SH基を有するシリコーンのいずれか一方又は両方と(4)重合性化合物とを混合する際には、撹拌しながら行うことが好ましい。 When one or both of (1) the semiconductor material and (2) —R 31 SH group-containing silicone and (4) the polymerizable compound are mixed, it is preferable to perform the stirring.
(1)半導体材料及び(2)-R31SH基を有するシリコーンのいずれか一方又は両方と(4)重合性化合物とを混合する際、混合時の温度には特に制限は無いが、(1)半導体材料及び(2)-R31SH基を有するシリコーンのいずれか一方又は両方が均一に混合しやすいため、0℃~100℃の範囲であることが好ましく、10℃~80℃の範囲であることがより好ましい。 When one or both of (1) the semiconductor material and (2) —R 31 SH group-containing silicone and (4) the polymerizable compound are mixed, the mixing temperature is not particularly limited. ) Since it is easy to uniformly mix one or both of the semiconductor material and the silicone having the (2) -R 31 SH group, the range of 0 ° C to 100 ° C is preferable, and the range of 10 ° C to 80 ° C is preferable. More preferably.
その他、液状組成物の製造方法は、下記(c1)~(c3)の製造方法が挙げられる。 In addition, as the method for producing the liquid composition, the following production methods (c1) to (c3) can be mentioned.
製造方法(c1):(4)重合性化合物に(1)半導体材料を分散させ分散体を得る工程と、得られた分散体と(2)-R31SH基を有するシリコーンとを混合する工程と、を含む製造方法。 Production method (c1): (4) a step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, and a step of mixing the obtained dispersion with (2) a silicone having a —R 31 SH group. And a manufacturing method including.
製造方法(c2):(4)重合性化合物に(2)-R31SH基を有するシリコーンを分散させ分散体を得る工程と、得られた分散体と(1)半導体材料を混合する工程と、を含む製造方法。 Production method (c2): (4) a step of dispersing a silicone having a (2) -R 31 SH group in a polymerizable compound to obtain a dispersion, and a step of mixing the obtained dispersion and (1) a semiconductor material. And a manufacturing method including.
製造方法(c3):(4)重合性化合物に(1)半導体材料及び(2)-R31SH基を有するシリコーンを分散させ分散体を得る工程と、を含む製造方法。 Production method (c3): (4) a step of dispersing (1) a semiconductor material and (2) a silicone having a R 31 SH group in a polymerizable compound to obtain a dispersion.
上記(c1)~(c3)の製造方法のステップ1において、各分散体を得る工程では、(4)重合性化合物を、(1)半導体材料と(2)-R31SH基を有するシリコーンとのいずれか一方又は両方に滴下してもよく、(1)半導体材料と(2)-R31SH基を有するシリコーンとのいずれか一方又は両方を(4)重合性化合物に滴下してもよい。 In the step 1 of the production method of the above (c1) to (c3), in the step of obtaining each dispersion, (4) the polymerizable compound is (1) a semiconductor material and (2) a silicone having a R 31 SH group. One or both of the above may be dropped, and one or both of (1) the semiconductor material and (2) -R 31 SH group-containing silicone may be dropped into the (4) polymerizable compound. .
均一に分散しやすいため、(1)半導体材料と(2)-R31SH基を有するシリコーンとのいずれか一方又は両方を(4)重合性化合物に滴下することが好ましい。 Since it is easy to uniformly disperse, it is preferable to drop one or both of (1) a semiconductor material and (2) a silicone having a R 31 SH group in (4) a polymerizable compound.
上記(c1)~(c3)の製造方法において、各混合する工程では、(1)半導体材料又は(2)-R31SH基を有するシリコーンを分散体に滴下してもよいし、分散体を(1)半導体材料又は(2)-R31SH基を有するシリコーンに滴下してもよい。
均一に分散しやすいため、(1)半導体材料又は(2)-R31SH基を有するシリコーンを分散体に滴下することが好ましい。
In the manufacturing methods (c1) to (c3), in each mixing step, (1) a semiconductor material or (2) a silicone having a —R 31 SH group may be added dropwise to the dispersion, or the dispersion may be added. It may be dropped onto (1) a semiconductor material or (2) -R 31 SH group-containing silicone.
Since it is easy to uniformly disperse, it is preferable to drop (1) the semiconductor material or (2) -R 31 SH group-containing silicone into the dispersion.
(4)重合性化合物には、(4-1)重合体が溶解していてもよい。
また、製造方法(c1)~(c3)において、(4)重合性化合物の代わりに、溶媒に溶解させた(4-1)重合体を用いてもよい。
The (4-1) polymer may be dissolved in the (4) polymerizable compound.
Further, in the production methods (c1) to (c3), the (4-1) polymer dissolved in a solvent may be used instead of the (4) polymerizable compound.
(4-1)重合体を溶解させる溶媒は、(4-1)重合体を溶解しうる溶媒であれば特に限定されない。溶媒としては、(1)半導体材料を溶解し難いものが好ましい。
(4-1)重合体が溶解している溶媒としては、例えば、上述の第3溶媒とおなじ溶媒が挙げられる。
The solvent for dissolving the (4-1) polymer is not particularly limited as long as it is a solvent capable of dissolving the (4-1) polymer. The solvent is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
Examples of the solvent in which the polymer (4-1) is dissolved include the same solvents as the above-mentioned third solvent.
中でも第2溶媒は極性が低く、(1)半導体材料を溶解し難いと考えられるため好ましい。 Among them, the second solvent is preferable because it has low polarity and (1) it is considered that the semiconductor material is difficult to dissolve.
第2溶媒の中でも、ハロゲン化炭化水素、及び炭化水素がより好ましい。 Among the second solvents, halogenated hydrocarbons and hydrocarbons are more preferable.
本実施形態の液状組成物の製造方法は、下記(c4)の製造方法であってもよい。
製造方法(c4):(1)半導体材料を(3)溶媒に分散させ分散液を得る工程と、分散液と(4)重合性化合物とを混合し混合液を得る工程と、混合液と(2)-R31SH基を有するシリコーンとを混合する工程と、を含む製造方法。
The method for producing the liquid composition of the present embodiment may be the following production method (c4).
Manufacturing method (c4): (1) a step of dispersing a semiconductor material in a solvent to obtain a dispersion, a step of mixing the dispersion and (4) a polymerizable compound to obtain a mixed solution, and a mixed solution ( 2) mixing with a silicone having —R 31 SH groups.
<<組成物の製造方法2>>
本実施形態の組成物の製造方法としては、(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(4)重合性化合物とを混合する工程と、(4)重合性化合物を重合させる工程と、を含む製造方法を挙げることができる。
<<
The method for producing the composition of the present embodiment includes (1) a step of mixing a semiconductor material, (2) a silicone having an R 31 SH group, and (4) a polymerizable compound, and (4) a polymerizable compound. And a step of polymerizing the compound.
また、本実施形態の組成物の製造方法としては、(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(3)溶媒に溶解している(4-1)重合体とを混合する工程と、(3)溶媒を除去する工程と、を含む製造方法も挙げることができる。 The method for producing the composition of the present embodiment includes (1) a semiconductor material, (2) a silicone having a R 31 SH group, (3) a polymer dissolved in a solvent (4-1) a polymer. There can also be mentioned a production method including a step of mixing and, and a step of removing the solvent (3).
上述の製造方法に含まれる混合する工程には、上述の組成物の製造方法と同様の混合方法を用いることができる。 For the mixing step included in the above-mentioned manufacturing method, the same mixing method as the above-described manufacturing method of the composition can be used.
組成物の製造方法は、例えば、下記(d1)~(d6)の製造方法が挙げられる。 Examples of the method for producing the composition include the following production methods (d1) to (d6).
製造方法(d1):(4)重合性化合物に、(1)半導体材料を分散させ、分散体を得る工程と、得られた分散体と、(2)-R31SH基を有するシリコーンと(5)表面修飾剤とを混合する工程と、(4)重合性化合物を重合させる工程とを含む製造方法。 Production Method (d1): (4) A step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, the obtained dispersion, and (2) a silicone having a R 31 SH group ( 5) A production method including a step of mixing a surface modifier and (4) a step of polymerizing a polymerizable compound.
製造方法(d2):(4-1)重合体を溶解させた(3)溶媒に、(1)半導体材料を分散させ、分散体を得る工程と、得られた分散体と、(2)-R31SH基を有するシリコーンと(5)表面修飾剤とを混合する工程と、(3)溶媒を除去する工程と、を含む製造方法。 Production method (d2): (4-1) a step of dispersing a semiconductor material in a solvent in which a polymer is dissolved (3) to obtain a dispersion, the obtained dispersion, and (2)- A production method comprising a step of mixing (5) a surface modifier with a silicone having an R 31 SH group, and (3) a step of removing a solvent.
製造方法(d3):(4)重合性化合物に、(2)-R31SH基を有するシリコーンと(5)表面修飾剤とを分散させ、分散体を得る工程と、得られた分散体と(1)半導体材料とを混合する工程と、(4)重合性化合物を重合させる工程と、を含む製造方法。 Production method (d3): a step of dispersing a silicone having a (2) -R 31 SH group and (5) a surface modifier in (4) a polymerizable compound to obtain a dispersion, and the obtained dispersion. A manufacturing method comprising: (1) mixing a semiconductor material; and (4) polymerizing a polymerizable compound.
製造方法(d4):(4-1)重合体を溶解させた(3)溶媒に、(2)-R31SH基を有するシリコーンと(5)表面修飾剤とを分散させ、分散体を得る工程と、得られた分散体と、(1)半導体材料とを混合する工程と、(3)溶媒を除去する工程と、を含む製造方法。 Production method (d4): (4) The polymer having the (3) solvent dissolved therein is dispersed with (2) -R 31 SH group-containing silicone and (5) surface modifier to obtain a dispersion. A manufacturing method comprising: a step, a step of mixing the obtained dispersion, (1) a semiconductor material, and (3) a step of removing a solvent.
製造方法(d5):(4)重合性化合物に、(1)半導体材料と(2)-R31SH基を有するシリコーンと(5)表面修飾剤との混合物を分散させる工程と、(4)重合性化合物を重合させる工程と、を含む製造方法。 Production Method (d5): (4) Dispersing a mixture of (1) a semiconductor material, (2) a silicone having an R 31 SH group, and (5) a surface modifier in a polymerizable compound, (4) And a step of polymerizing the polymerizable compound.
製造方法(d6):(4-1)重合体を溶解させた(3)溶媒に、(1)半導体材料と(2)-R31SH基を有するシリコーンと(5)表面修飾剤との混合物を分散させる工程と、(3)溶媒を除去する工程と、を含む製造方法。 Production method (d6): (4-1) Mixture of (1) semiconductor material, (2) silicone having R 31 SH group, and (5) surface modifier in (3) solvent in which polymer is dissolved And a step of removing the solvent (3).
製造方法(d2)、(d4)、(d6)に含まれる、(3)溶媒を除去する工程は、室温で静置し、自然乾燥させる工程であってもよいし、真空乾燥機を用いた減圧乾燥や加熱によって(3)溶媒を蒸発させる工程であってもよい。 The step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) may be a step of allowing to stand at room temperature and naturally drying, or using a vacuum dryer. It may be a step (3) of evaporating the solvent by drying under reduced pressure or heating.
(3)溶媒を除去する工程では、例えば、0~300℃で、1分間~7日間乾燥させることで、(3)溶媒を除去することができる。 In the step (3) of removing the solvent, the solvent (3) can be removed by drying at 0 to 300 ° C. for 1 minute to 7 days, for example.
製造方法(d1)、(d3)、(d5)に含まれる、(4)重合性化合物を重合させる工程は、ラジカル重合などの公知の重合反応を適宜用いることで行うことができる。 The step (4) of polymerizing the polymerizable compound contained in the production methods (d1), (d3) and (d5) can be carried out by appropriately using a known polymerization reaction such as radical polymerization.
例えばラジカル重合の場合は、(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(4)重合性化合物との混合物に、ラジカル重合開始剤を添加し、ラジカルを発生させることで重合反応を進行させることができる。 For example, in the case of radical polymerization, a radical polymerization initiator is added to a mixture of (1) a semiconductor material, (2) a silicone having a R 31 SH group, and (4) a polymerizable compound to generate radicals. This allows the polymerization reaction to proceed.
ラジカル重合開始剤は特に限定されるものではないが、例えば、光ラジカル重合開始剤等が挙げられる。 The radical polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator.
光ラジカル重合開始剤としては、例えば、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド等が挙げられる。 Examples of the photo-radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
<<組成物の製造方法3>>
また、本実施形態の組成物の製造方法は、下記(d7)の製造方法も採用することができる。
<< Composition Manufacturing Method 3 >>
Further, as the method for producing the composition of the present embodiment, the following production method (d7) can also be adopted.
製造方法(d7):(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(4-1)重合体とを溶融混練する工程を含む製造方法。 Manufacturing method (d7): A manufacturing method including a step of melt-kneading (1) a semiconductor material, (2) a silicone having a R 31 SH group, and (4-1) a polymer.
製造方法(d8):(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(4-1)重合体と、(5)表面修飾剤とを溶融混練する工程と、を含む製造方法。 Production method (d8): (1) melt-kneading a semiconductor material, (2) a silicone having a R 31 SH group, (4-1) a polymer, and (5) a surface modifier. Manufacturing method including.
製造方法(d9):(1)半導体材料と、(2)-R31SH基を有するシリコーンとを含む液状組成物を製造する工程と、得られた液状組成物から固形分を取り出す工程と、得られた固形分と(4-1)重合体とを溶融混練する工程と、を含む製造方法。 Production method (d9): (1) a step of producing a liquid composition containing a semiconductor material and (2) a silicone having a R 31 SH group, and a step of extracting solid content from the obtained liquid composition, A production method comprising a step of melt-kneading the obtained solid content and (4-1) polymer.
製造方法(d10):(1)半導体材料と、(2)-R31SH基を有するシリコーンと、(5)表面修飾剤を含む液状組成物を製造する工程と、得られた液状組成物から固形分を取り出す工程と、得られた固形分と(4-1)重合体とを溶融混練する工程と、を含む製造方法。 Production method (d10): (1) a step of producing a liquid composition containing a semiconductor material, (2) a silicone having a —R 31 SH group, and (5) a surface modifier, and from the obtained liquid composition A production method comprising a step of taking out a solid content and a step of melt-kneading the obtained solid content and the (4-1) polymer.
製造方法(d11):(1)半導体材料と、(2)-R31SH基を有するシリコーンとを含む液状組成物を製造する工程と、得られた液状組成物から固形分を取り出す工程と、得られた固形分と、(5)表面修飾剤と、(4-1)重合体とを溶融混練する工程と、を含む製造方法。 Production method (d11): (1) a step of producing a liquid composition containing a semiconductor material and (2) —R 31 SH group-containing silicone, and a step of extracting solids from the obtained liquid composition, A production method comprising the step of melt-kneading the obtained solid content, (5) a surface modifier and (4-1) a polymer.
製造方法(d7)~(d11)の溶融混練する工程では、(4-1)重合体と他の材料との混合物を溶融混練してもよく、溶融した(4-1)重合体に他の材料を添加してもよい。「他の材料」とは、(4-1)重合体の他に各製造方法で用いる材料を指し、具体的には(1)半導体材料、(2)-R31SH基を有するシリコーン、(5)表面修飾剤を指す。 In the melt-kneading step of the production methods (d7) to (d11), a mixture of the (4-1) polymer and another material may be melt-kneaded, and the melted (4-1) polymer may be mixed with other materials. Materials may be added. The "other material" refers to a material used in each production method in addition to (4-1) a polymer, and specifically, (1) a semiconductor material, (2) a silicone having a R 31 SH group, ( 5) Refers to a surface modifier.
製造方法(d7)~(d11)において(4-1)重合体を溶融混練する方法としては、重合体の混練方法として公知の方法を採用することができる。例えば、単軸押出機、又は二軸押出機を用いた押出加工を採用することができる。 As the method of melt-kneading the polymer (4-1) in the production methods (d7) to (d11), a known method of kneading the polymer can be adopted. For example, extrusion processing using a single screw extruder or a twin screw extruder can be adopted.
製造方法(d9)及び(d11)の液状組成物を製造する工程は、上述の製造方法(c1)~(c4)を採用することができる。 The above-mentioned manufacturing methods (c1) to (c4) can be adopted for the step of manufacturing the liquid composition of the manufacturing methods (d9) and (d11).
製造方法(d9)~(d11)の固形分を取り出す工程は、例えば加熱、減圧、送風及びこれらの組み合わせにより、液状組成物から液状組成物を構成する(3)溶媒及び(4)重合性化合物を除去することで行う。 In the steps of taking out the solid content in the production methods (d9) to (d11), (3) the solvent and (4) the polymerizable compound constituting the liquid composition from the liquid composition by, for example, heating, decompression, air blowing and a combination thereof. By removing.
≪ペロブスカイト化合物の測定≫
本実施形態の組成物に含まれるペロブスカイト化合物の量は、誘導結合プラズマ質量分析計ICP-MS(例えば、PerkinElmer社製、ELAN DRCII)、及びイオンクロマトグラフ(例えば、サーモフィッシャーサイエンティフィック株式会社製、Integrion)を用いて測定することができる。
ペロブスカイト化合物をN,N-ジメチルホルムアミド等の良溶媒を用いて溶解した後に測定を行う。
<< Measurement of perovskite compounds >>
The amount of the perovskite compound contained in the composition of the present embodiment is determined by an inductively coupled plasma mass spectrometer ICP-MS (for example, PerkinElmer, ELAN DRCII), and an ion chromatograph (for example, Thermo Fisher Scientific Co., Ltd.). , Integration) can be used for the measurement.
The perovskite compound is dissolved in a good solvent such as N, N-dimethylformamide and then measured.
≪発光強度の測定≫
本実施形態の組成物の発光強度は、蛍光高度計(例えば、日本分光製、FT-6500)を用いて、励起光430nm、感度Highで測定する。
<< Measurement of emission intensity >>
The emission intensity of the composition of the present embodiment is measured with a fluorescence altimeter (for example, FT-6500 manufactured by JASCO Corporation) with excitation light of 430 nm and sensitivity of High.
実施形態の組成物は、上記の測定方法により測定された発光強度が、10以上であってもよく、100以上であってもよく、200以上であってもよく、300以上であってもよい。 The composition of the embodiment may have a luminescence intensity measured by the above measuring method of 10 or higher, 100 or higher, 200 or higher, and 300 or higher. .
≪水蒸気に対する耐久性の評価≫
本実施形態の組成物を、厚み100μm、1cm×1cmとして、65℃の温度、95%湿度で一定にした恒温恒湿槽中に置き、水蒸気に対する耐久性試験を行う。試験前後に発光強度を測定し、以下の式を用いて維持率を評価する。
維持率(%)=(X’日間の水蒸気に対する耐久性試験後の発光強度)/(水蒸気に対する耐久性試験前の発光強度)×100
<< Evaluation of durability against water vapor >>
The composition of the present embodiment has a thickness of 100 μm, 1 cm × 1 cm, and is placed in a constant temperature and constant humidity chamber kept at a temperature of 65 ° C. and a humidity of 95% to perform a durability test against water vapor. The emission intensity is measured before and after the test, and the maintenance rate is evaluated using the following formula.
Maintenance rate (%) = (emission intensity after the durability test against water vapor for X ′ days) / (emission intensity before the durability test against water vapor) × 100
実施形態の組成物は、上記の測定方法において、2日間の水蒸気に対する耐久性試験後の維持率が、30%以上であってもよく、40%以上であってもよく、80%以上であってもよく、82%以上であってもよく、83%以上であってもよい。組成物の熱耐久性の作用が高いことから、維持率は高いほうがよい。 In the above measurement method, the composition of the embodiment has a maintenance rate after a durability test against water vapor for 2 days of 30% or more, 40% or more, and 80% or more. , 82% or more, or 83% or more. Since the effect of the thermal durability of the composition is high, the maintenance rate is preferably high.
<<フィルム>>
本実施形態に係るフィルムは、上述の組成物を形成材料とする。例えば、本実施形態に係るフィルムは、(1)半導体材料、(2)-R31SH基を有するシリコーン、及び(4-1)重合体を含み、(1)半導体材料、(2)-R31SH基を有するシリコーン、及び(4-1)重合体の合計がフィルムの総質量に対し90質量%以上である。
<< film >>
The film according to this embodiment uses the above-mentioned composition as a forming material. For example, the film according to the present embodiment contains (1) a semiconductor material, (2) -R 31 SH group-containing silicone, and (4-1) a polymer, and (1) a semiconductor material, (2) -R. The total amount of the 31 SH group-containing silicone and the (4-1) polymer is 90% by mass or more based on the total mass of the film.
フィルム形状は特に限定されるものではなく、シート状、バー状等の任意の形状であることができる。本明細書において「バー状の形状」とは、例えば、一方向に延在する平面視帯状の形状を意味する。平面視帯状の形状としては、各辺の長さが異なる板状の形状が例示される。 The shape of the film is not particularly limited and may be any shape such as a sheet shape or a bar shape. In the present specification, the “bar-like shape” means, for example, a band-like shape in plan view extending in one direction. Examples of the band-like shape in plan view include a plate-like shape in which each side has a different length.
フィルムの厚みは、0.01μm~1000mmであってもよく、0.1μm~10mmであってもよく、1μm~1mmであってもよい。 The thickness of the film may be 0.01 μm to 1000 mm, 0.1 μm to 10 mm, or 1 μm to 1 mm.
本明細書において前記フィルムの厚みは、フィルムの縦、横、高さの中で最も値の小さい辺を「厚さ方向」としたときの、フィルムの厚さ方向のおもて面と裏面との間の距離を指す。具体的には、マイクロメータを用い、フィルムの任意の3点においてフィルムの厚みを測定し、3点の測定値の平均値を、フィルムの厚みとする。 In the present specification, the thickness of the film refers to the front surface and the back surface in the thickness direction of the film when the side having the smallest value in the length, width and height of the film is defined as the “thickness direction”. Refers to the distance between. Specifically, the thickness of the film is measured at any three points on the film using a micrometer, and the average value of the measured values at the three points is taken as the film thickness.
フィルムは、単層であってもよく、複層であってもよい。複層の場合、各層は同一の種類の組成物が用いられていてもよく、互いに異なる種類の組成物が用いられていてもよい。 The film may be a single layer or multiple layers. In the case of multiple layers, the same type of composition may be used for each layer, or different types of compositions may be used for each layer.
<<積層構造体>>
本実施形態に係る積層構造体は、複数の層を有し、少なくとも一層が、上述のフィルムである。
<< laminated structure >>
The laminated structure according to the present embodiment has a plurality of layers, and at least one layer is the above-mentioned film.
積層構造体が有する複数の層のうち、上述のフィルム以外の層としては、基板、バリア層、光散乱層等の任意の層が挙げられる。
積層されるフィルムの形状は特に限定されるものではなく、シート状、バー状等の任意の形状であることができる。
Among the plurality of layers included in the laminated structure, examples of layers other than the above-mentioned films include arbitrary layers such as a substrate, a barrier layer, and a light scattering layer.
The shape of the laminated film is not particularly limited, and may be any shape such as a sheet shape and a bar shape.
(基板)
基板は、特に制限はないが、フィルムであってもよい。基板は、光透過性を有するものが好ましい。光透過性を有する基板を有する積層構造体では、(1)半導体材料が発した光を取り出しやすいため好ましい。
(substrate)
The substrate is not particularly limited, but may be a film. The substrate is preferably light transmissive. A laminated structure including a substrate having a light-transmitting property is preferable because (1) it is easy to extract light emitted from the semiconductor material.
基板の形成材料としては、例えば、ポリエチレンテレフタレートなどのポリマーや、ガラスなどの公知の材料を用いることができる。
例えば、積層構造体において、上述のフィルムを、基板上に設けていてもよい。
As a material for forming the substrate, for example, a polymer such as polyethylene terephthalate or a known material such as glass can be used.
For example, in the laminated structure, the above-mentioned film may be provided on the substrate.
図1は、本実施形態の積層構造体の構成を模式的に示す断面図である。第1の積層構造体1aは、第1の基板20及び第2の基板21の間に、本実施形態のフィルム10が設けられている。フィルム10は、封止層22によって封止されている。
FIG. 1 is a sectional view schematically showing the configuration of the laminated structure of this embodiment. In the first laminated structure 1 a, the
本発明の一つの側面は、第1の基板20と、第2の基板21と、第1の基板20と第2の基板21との間に位置する本実施形態に係るフィルム10と、封止層22と、を有する積層構造体であって、封止層22が、フィルム10の第1の基板20、及び第2の基板21と接していない面上に配置されることを特徴とする積層構造体1aである。
One aspect of the present invention is a
(バリア層)
本実施形態に係る積層構造体が有していてもよい層としては、特に制限は無いが、バリア層が挙げられる。外気の水蒸気、及び大気中の空気から前述の組成物を保護する観点から、バリア層を含んでいてもよい。
(Barrier layer)
The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a barrier layer. A barrier layer may be included from the viewpoint of protecting the above-mentioned composition from water vapor in the outside air and air in the atmosphere.
バリア層は、特に制限は無いが、発光した光を取り出す観点から、透明なものが好ましい。バリア層としては、例えば、ポリエチレンテレフタレートなどのポリマーや、ガラス膜などの公知のバリア層を用いることができる。 The barrier layer is not particularly limited, but is preferably transparent from the viewpoint of extracting emitted light. As the barrier layer, for example, a polymer such as polyethylene terephthalate or a known barrier layer such as a glass film can be used.
(光散乱層)
本実施形態に係る積層構造体が有していてもよい層としては、特に制限は無いが、光散乱層が挙げられる。入射した光を有効に利用する観点から、光散乱層を含んでいてもよい。
光散乱層は、特に制限は無いが、発光した光を取り出す観点から、透明なものが好ましい。光散乱層としては、シリカ粒子などの光散乱粒子や、増幅拡散フィルムなどの公知の光散乱層を用いることができる。
(Light scattering layer)
The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a light scattering layer. From the viewpoint of effectively utilizing the incident light, a light scattering layer may be included.
The light scattering layer is not particularly limited, but is preferably transparent from the viewpoint of extracting emitted light. As the light scattering layer, light scattering particles such as silica particles, or a known light scattering layer such as an amplification diffusion film can be used.
<<発光装置>>
本実施形態に係る発光装置は、本実施形態のフィルム又は積層構造体と、光源とを合せることで得ることができる。発光装置は、光源から発光した光を、光源の光射出方向に設置したフィルム又は積層構造体に照射することで、フィルム又は積層構造体を発光させ、光を取り出す装置である。
<< Light emitting device >>
The light emitting device according to this embodiment can be obtained by combining the film or laminated structure of this embodiment with a light source. The light-emitting device is a device that emits light by irradiating a film or a laminated structure provided in a light emission direction of the light source with light emitted from the light source so that the film or the laminated structure emits light.
発光装置における積層構造体が有する複数の層のうち、上述のフィルム、基板、バリア層、光散乱層以外の層としては、光反射部材、輝度強化部、プリズムシート、導光板、要素間の媒体材料層等の任意の層が挙げられる。 Among the plurality of layers included in the laminated structure in the light emitting device, the layers other than the above-mentioned film, substrate, barrier layer, and light scattering layer include a light reflection member, a brightness enhancement portion, a prism sheet, a light guide plate, and a medium between elements Any layer such as a material layer may be used.
本発明の一つの側面は、プリズムシート50と、導光板60と、第1の積層構造体1aと、光源30と、がこの順に積層された発光装置2である。
One aspect of the present invention is a light emitting
(光源)
本実施形態の発光装置を構成する光源としては、(1)半導体材料の吸収波長帯に含まれる光を射出する光源を用いる。例えば、上述のフィルム、又は積層構造体中の半導体材料を発光させるという観点から、600nm以下の発光波長を有する光源が好ましい。光源としては、例えば、青色発光ダイオードなどの発光ダイオード(LED)、レーザー、ELなどの公知の光源を用いることができる。
(light source)
As a light source that constitutes the light emitting device of this embodiment, (1) a light source that emits light included in the absorption wavelength band of the semiconductor material is used. For example, a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of emitting the semiconductor material in the film or the laminated structure described above. As the light source, for example, a known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, or an EL can be used.
(光反射部材)
本実施形態の発光装置を構成する積層構造体が有していてもよい層としては、特に制限は無いが、光反射部材が挙げられる。光反射部材を有する発光装置は、光源の光を効率的にフィルム、又は積層構造体に向かって照射することができる。
(Light reflection member)
The layer that may be included in the laminated structure forming the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light reflecting member. A light emitting device having a light reflecting member can efficiently irradiate light from a light source toward a film or a laminated structure.
光反射部材は、特に制限は無いが、反射フィルムであってもよい。反射フィルムとしては、例えば、反射鏡、反射粒子のフィルム、反射金属フィルムや反射体などの公知の反射フィルムを用いることができる。 The light reflection member is not particularly limited, but may be a reflection film. As the reflecting film, for example, a known reflecting film such as a reflecting mirror, a film of reflecting particles, a reflecting metal film or a reflector can be used.
(輝度強化部)
本実施形態の発光装置を構成する積層構造体が有していてもよい層としては、特に制限は無いが、輝度強化部が挙げられる。光の一部分を、光が伝送された方向に向かって反射して戻す観点から、輝度強化部を含んでいてもよい。
(Brightness enhancement section)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a brightness enhancement portion. The brightness enhancement section may be included from the viewpoint of reflecting a part of the light back toward the direction in which the light is transmitted.
(プリズムシート)
本実施形態の発光装置を構成する積層構造体が有していてもよい層としては、特に制限は無いが、プリズムシートが挙げられる。プリズムシートは、代表的には、基材部とプリズム部とを有する。なお、基材部は、隣接する部材に応じて省略してもよい。
(Prism sheet)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, but a prism sheet can be used. The prism sheet typically has a base material portion and a prism portion. The base material portion may be omitted depending on the adjacent member.
プリズムシートは、任意の適切な接着層(例えば、接着剤層、粘着剤層)を介して隣接する部材に貼り合わせることができる。 The prism sheet can be attached to an adjacent member via any appropriate adhesive layer (eg, adhesive layer, pressure-sensitive adhesive layer).
発光装置を後述のディスプレイに用いる場合、プリズムシートは、視認側とは反対側(背面側)に凸となる複数の単位プリズムが並列されて構成されている。プリズムシートの凸部を背面側に向けて配置することにより、プリズムシートを透過する光が集光されやすくなる。また、プリズムシートの凸部を背面側に向けて配置すれば、凸部を視認側に向けて配置する場合と比較して、プリズムシートに入射せずに反射する光が少なく、輝度の高いディスプレイを得ることができる。 When the light emitting device is used in a display described later, the prism sheet is configured by arranging a plurality of unit prisms that are convex on the side opposite to the viewing side (back side). By arranging the convex portion of the prism sheet so as to face the back surface side, it becomes easy to collect light that passes through the prism sheet. Also, when the convex portion of the prism sheet is arranged facing the back side, compared to the case where the convex portion is arranged facing the viewing side, less light is reflected without entering the prism sheet, and a display with high brightness is displayed. Can be obtained.
(導光板)
本実施形態の発光装置を構成する積層構造体が有していてもよい層としては、特に制限は無いが、導光板が挙げられる。導光板としては、例えば、横方向からの光を厚さ方向に偏向可能となるよう、背面側にレンズパターンが形成された導光板、背面側と視認側とのいずれか一方又は両方にプリズム形状等が形成された導光板など、任意の適切な導光板を用いることができる。
(Light guide plate)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light guide plate. As the light guide plate, for example, a light guide plate having a lens pattern formed on the back side so that light from the lateral direction can be deflected in the thickness direction, a prism shape on either or both of the back side and the viewing side. Any appropriate light guide plate can be used, such as a light guide plate on which the above are formed.
(要素間の媒体材料層)
本実施形態の発光装置を構成する積層構造体が有していてもよい層としては、特に制限は無いが、隣接する要素(層)間の光路上に1つ以上の媒体材料からなる層(要素間の媒体材料層)が挙げられる。
(Medium material layer between elements)
The layer that may be included in the laminated structure that constitutes the light emitting device of the present embodiment is not particularly limited, but a layer composed of one or more medium materials (on the optical path between adjacent elements (layers) ( Media material layers between elements).
要素間の媒体材料層に含まれる1つ以上の媒体には、特に制限は無いが、真空、空気、ガス、光学材料、接着剤、光学接着剤、ガラス、ポリマー、固体、液体、ゲル、硬化材料、光学結合材料、屈折率整合又は屈折率不整合材料、屈折率勾配材料、クラッディング又は抗クラッディング材料、スペーサー、シリカゲル、輝度強化材料、散乱又は拡散材料、反射又は抗反射材料、波長選択性材料、波長選択性抗反射材料、色フィルター、又は上記技術分野で既知の好適な媒体、が含まれる。 The one or more media contained in the media material layer between the elements include, but are not limited to, vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, cured. Materials, optical coupling materials, index matching or index mismatching materials, gradient index materials, cladding or anti-cladding materials, spacers, silica gel, brightness enhancing materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selection Materials, wavelength selective anti-reflective materials, color filters, or suitable media known in the art.
本実施形態の発光装置の具体例としては、例えば、ELディスプレイや液晶ディスプレイ用の波長変換材料を備えたものが挙げられる。
具体的には、以下の(E1)~(E4)の各構成を挙げることができる。
Specific examples of the light emitting device of the present embodiment include those provided with a wavelength conversion material for EL displays and liquid crystal displays.
Specifically, the following respective structures (E1) to (E4) can be mentioned.
構成(E1):本実施形態の組成物をガラスチューブ等の中に入れて封止し、これを導光板の端面(側面)に沿うように、光源である青色発光ダイオードと導光板の間に配置して、青色光を緑色光や赤色光に変換するバックライト(オンエッジ方式のバックライト)。 Configuration (E1): The composition of the present embodiment is put in a glass tube or the like and sealed, and the composition is arranged between the blue light emitting diode as a light source and the light guide plate so as to be along the end surface (side surface) of the light guide plate. Then, a backlight that converts blue light into green light or red light (on-edge backlight).
構成(E2):本実施形態の組成物をシート化し、これを2枚のバリアーフィルムで挟んで封止したフィルムを、導光板の上に設置して、導光板の端面(側面)に置かれた青色発光ダイオードから導光板を通して前記シートに照射される青色の光を緑色光や赤色光に変換するバックライト(表面実装方式のバックライト)。 Configuration (E2): The composition of the present embodiment is formed into a sheet, and a film obtained by sandwiching the composition with two barrier films and sealing is placed on the light guide plate and placed on the end surface (side surface) of the light guide plate. A backlight (surface-mounted backlight) that converts blue light emitted from the blue light emitting diode to the sheet through a light guide plate into green light or red light.
構成(E3):本実施形態の組成物を、樹脂等に分散させて青色発光ダイオードの発光部近傍に設置し、照射される青色の光を緑色光や赤色光に変換するバックライト(オンチップ方式のバックライト)。 Configuration (E3): A backlight (on-chip) that disperses the composition of the present embodiment in a resin or the like and installs it in the vicinity of a light emitting portion of a blue light emitting diode to convert the emitted blue light into green light or red light. Method backlight).
構成(E4):本実施形態の組成物を、レジスト中に分散させて、カラーフィルター上に設置し、光源から照射される青色の光を緑色光や赤色光に変換するバックライト。 [Structure (E4): A backlight that disperses the composition of the present embodiment in a resist and installs it on a color filter to convert blue light emitted from a light source into green light or red light.
また、本実施形態に係る発光装置の具体例としては、本実施形態の組成物を成形し、光源である青色発光ダイオードの後段に配置して、青色光を緑色光や赤色光に変換して白色光を発する照明が挙げられる。 Further, as a specific example of the light emitting device according to the present embodiment, the composition of the present embodiment is molded and placed in the subsequent stage of the blue light emitting diode as a light source to convert blue light into green light or red light. Illumination that emits white light is included.
<<ディスプレイ>>
図2に示すように、本実施形態のディスプレイ3は、液晶パネル40と、前述の発光装置2とを視認側からこの順に備える。発光装置2は、第2の積層構造体1bと光源30とを備える。第2の積層構造体1bは、前述の第1の積層構造体1aが、プリズムシート50と、導光板60と、をさらに備えたものである。ディスプレイは、任意の適切なその他の部材をさらに備えていてもよい。
<< Display >>
As shown in FIG. 2, the display 3 of this embodiment includes a
本発明の一つの側面は、液晶パネル40と、プリズムシート50と、導光板60と、第1の積層構造体1aと、光源30と、がこの順に積層された液晶ディスプレイ3である。
One aspect of the present invention is a liquid crystal display 3 in which a
(液晶パネル)
上記液晶パネルは、代表的には、液晶セルと、液晶セルの視認側に配置された視認側偏光板と、液晶セルの背面側に配置された背面側偏光板とを備える。視認側偏光板及び背面側偏光板は、それぞれの吸収軸が実質的に直交又は平行となるようにして配置され得る。
(LCD panel)
The liquid crystal panel typically includes a liquid crystal cell, a viewing side polarizing plate arranged on the viewing side of the liquid crystal cell, and a back side polarizing plate arranged on the back side of the liquid crystal cell. The viewing-side polarizing plate and the back-side polarizing plate may be arranged such that their absorption axes are substantially orthogonal or parallel.
(液晶セル)
液晶セルは、一対の基板と、一対の基板間に挟持された表示媒体としての液晶層とを有する。一般的な構成においては、一方の基板に、カラーフィルター及びブラックマトリクスが設けられており、他方の基板に、液晶の電気光学特性を制御するスイッチング素子と、このスイッチング素子にゲート信号を与える走査線及びソース信号を与える信号線と、画素電極及び対向電極とが設けられている。上記基板の間隔(セルギャップ)は、スペーサー等によって制御できる。上記基板の液晶層と接する側には、例えば、ポリイミドからなる配向膜等を設けることができる。
(Liquid crystal cell)
The liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the pair of substrates. In a general configuration, one substrate is provided with a color filter and a black matrix, and the other substrate is provided with a switching element for controlling electro-optical characteristics of liquid crystal and a scanning line for giving a gate signal to this switching element. And a signal line for supplying a source signal, a pixel electrode, and a counter electrode. The distance (cell gap) between the substrates can be controlled by a spacer or the like. An alignment film made of polyimide, for example, can be provided on the side of the substrate that is in contact with the liquid crystal layer.
(偏光板)
偏光板は、代表的には、偏光子と、偏光子の両側に配置された保護層とを有する。偏光子は、代表的には、吸収型偏光子である。
偏光子としては、任意の適切な偏光子が用いられる。例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムにヨウ素などの二色性物質を吸着させて一軸延伸した偏光子が、偏光二色比が高く、特に好ましい。
(Polarizer)
The polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorption-type polarizer.
Any appropriate polarizer is used as the polarizer. For example, a dichroic substance such as iodine or a dichroic dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer partially saponified film. Uniaxially stretched film, polyene oriented film such as polyvinyl alcohol dehydrated product, polyvinyl chloride dehydrochlorinated product and the like. Among these, a polarizer obtained by uniaxially stretching a polyvinyl alcohol film by adsorbing a dichroic substance such as iodine, has a high polarization dichroic ratio, and is particularly preferable.
<<組成物の用途>>
本実施形態の組成物の用途としては、以下のような用途を挙げることができる。
<< Application of composition >>
The uses of the composition of the present embodiment include the following uses.
<LED>
本実施形態の組成物は、例えば、発光ダイオード(LED)の発光層の材料として用いることができる。
<LED>
The composition of this embodiment can be used, for example, as a material for a light emitting layer of a light emitting diode (LED).
本実施形態の組成物を含むLEDとしては、例えば、本実施形態の組成物とZnSなどの導電性粒子を混合して膜状に積層し、片面にn型輸送層を積層し、もう片面にp型輸送層を積層した構造をしており、電流を流すことで、p型半導体の正孔と、n型半導体の電子が接合面の組成物に含まれる(1)及び(2)の粒子中で電荷を打ち消すことで発光する方式が挙げられる。 As the LED including the composition of the present embodiment, for example, the composition of the present embodiment and conductive particles such as ZnS are mixed and laminated in a film shape, the n-type transport layer is laminated on one surface, and the other surface is laminated on the other surface. Particles of (1) and (2), which have a structure in which a p-type transport layer is laminated and in which a hole of a p-type semiconductor and an electron of an n-type semiconductor are included in the composition of the junction surface by passing an electric current. Among them, there is a method of emitting light by canceling charges.
<太陽電池>
本実施形態の組成物は、太陽電池の活性層に含まれる電子輸送性材料として利用することができる。
<Solar cell>
The composition of the present embodiment can be used as an electron transporting material contained in the active layer of a solar cell.
前記太陽電池としては、構成は特に限定されないが、例えば、フッ素ドープされた酸化スズ(FTO)基板、酸化チタン緻密層、多孔質酸化アルミニウム層、本実施形態の組成物を含む活性層、2,2’,7,7’-tetrakis(N,N’-di-p-methoxyphenylamine)-9,9’-spirobifluorene (Spiro-MeOTAD)などのホール輸送層、及び銀(Ag)電極をこの順で有する太陽電池が挙げられる。 The structure of the solar cell is not particularly limited, but examples thereof include a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, an active layer containing the composition of the present embodiment, and 2. It has a hole transport layer such as 2 ', 7,7'-tetrakis (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-MeOTAD), and a silver (Ag) electrode in this order. A solar cell is mentioned.
酸化チタン緻密層は、電子輸送の機能、FTOのラフネスを抑える効果、及び逆電子移動を抑制する機能を有する。 The titanium oxide dense layer has a function of electron transport, an effect of suppressing the roughness of FTO, and a function of suppressing reverse electron transfer.
多孔質酸化アルミニウム層は、光吸収効率を向上させる機能を有する。 The porous aluminum oxide layer has a function of improving light absorption efficiency.
活性層に含まれる、本実施形態の組成物は、電荷分離及び電子輸送の機能を有する。 The composition of the present embodiment contained in the active layer has the functions of charge separation and electron transport.
<センサー>
本実施形態の組成物は、X線撮像装置及びCMOSイメージセンサーなどの固体撮像装置用のイメージ検出部(イメージセンサー)、指紋検出部、顔検出部、静脈検出部及び虹彩検出部などの生体の一部分の所定の特徴を検出する検出部、パルスオキシメーターなどの光学バイオセンサーの検出部に使用する含まれる光電変換素子(光検出素子)材料として利用することができる。
<Sensor>
The composition of the present embodiment is applied to a living body such as an image detection unit (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection unit, a face detection unit, a vein detection unit and an iris detection unit. It can be used as a photoelectric conversion element (photodetection element) material included in a detection section for detecting a predetermined characteristic of a part or a detection section of an optical biosensor such as a pulse oximeter.
<<フィルムの製造方法>>
フィルムの製造方法は、例えば、下記(e1)~(e3)の製造方法が挙げられる。
<< Film manufacturing method >>
Examples of the film production method include the following production methods (e1) to (e3).
製造方法(e1):液状組成物を塗工して塗膜を得る工程と、塗膜から(3)溶媒を除去する工程と、を含むフィルムの製造方法。 Manufacturing method (e1): A method for manufacturing a film, which includes a step of applying a liquid composition to obtain a coating film, and a step of (3) removing a solvent from the coating film.
製造方法(e2):(4)重合性化合物を含む液状組成物を塗工して塗膜を得る工程と、得られた塗膜に含まれる(4)重合性化合物を重合させる工程と、を含むフィルムの製造方法。 Production method (e2): (4) a step of applying a liquid composition containing a polymerizable compound to obtain a coating film, and a step of polymerizing the (4) polymerizable compound contained in the obtained coating film. A method of manufacturing a film including.
製造方法(e3):上述の製造方法(d1)~(d6)で得られた組成物を成形加工するフィルムの製造方法。 Production method (e3): A method for producing a film by molding the composition obtained by the above-mentioned production methods (d1) to (d6).
上記製造方法(e1)(e2)で製造したフィルムは、製造位置から剥離して用いてもよい。 The film produced by the above production methods (e1) and (e2) may be peeled off from the production position and used.
<<積層構造体の製造方法>>
積層構造体の製造方法は、例えば、下記(f1)~(f3)の製造方法が挙げられる。
<< Manufacturing Method of Laminated Structure >>
Examples of the method for manufacturing the laminated structure include the following manufacturing methods (f1) to (f3).
製造方法(f1):液状組成物を製造する工程と、得られた液状組成物を基板上に塗工する工程と、得られた塗膜から(3)溶媒を除去する工程と、を含む積層構造体の製造方法。 Production method (f1): Lamination including a step of producing a liquid composition, a step of applying the obtained liquid composition onto a substrate, and a step of removing (3) a solvent from the obtained coating film Structure manufacturing method.
製造方法(f2):フィルムを基板に張り合わせる工程を含む積層構造体の製造方法。 Manufacturing method (f2): A manufacturing method of a laminated structure including a step of attaching a film to a substrate.
製造方法(f3):(4)重合性化合物を含む液状組成物を製造する工程と、得られた液状組成物を基板上に塗工する工程と、得られた塗膜に含まれる(4)重合性化合物を重合させる工程と、を含む製造方法。 Production method (f3): (4) A step of producing a liquid composition containing a polymerizable compound, a step of applying the obtained liquid composition on a substrate, and a step of applying the obtained coating film (4) And a step of polymerizing the polymerizable compound.
製造方法(f1)、(f3)における液状組成物を製造する工程は、上述の製造方法(c1)~(c5)を採用することができる。 The above-mentioned manufacturing methods (c1) to (c5) can be adopted in the steps of manufacturing the liquid composition in the manufacturing methods (f1) and (f3).
製造方法(f1)、(f3)における液状組成物を基板上に塗工する工程は、特に制限は無いが、グラビア塗布法、バー塗布法、印刷法、スプレー法、スピンコーティング法、ディップ法、ダイコート法などの、公知の塗布、塗工方法を用いることができる。 The step of applying the liquid composition on the substrate in the production methods (f1) and (f3) is not particularly limited, but is a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, Known coating and coating methods such as a die coating method can be used.
製造方法(f1)における(3)溶媒を除去する工程は、上述した製造方法(d2)、(d4)、(d6)に含まれる(3)溶媒を除去する工程と同様の工程とすることができる。 The step of removing the solvent (3) in the production method (f1) may be the same step as the step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) described above. it can.
製造方法(f3)における(4)重合性化合物を重合させる工程は、上述した製造方法(d1)(d3)(d5)に含まれる(4)重合性化合物を重合させる工程と同様の工程とすることができる。 The step of polymerizing the (4) polymerizable compound in the production method (f3) is the same as the step of polymerizing the (4) polymerizable compound contained in the above-mentioned production methods (d1), (d3), and (d5). be able to.
製造方法(f2)におけるフィルムを基板に張り合わせる工程では、任意の接着剤を用いることができる。 In the step of bonding the film to the substrate in the manufacturing method (f2), any adhesive can be used.
接着剤は、(1)半導体材料を溶解しない物であれば特に制限は無く、公知の接着剤を用いることができる。 The adhesive is (1) not particularly limited as long as it does not dissolve the semiconductor material, and a known adhesive can be used.
積層構造体の製造方法は、得られた積層構造体に、さらに任意のフィルムを張り合わせる工程を含んでいてもよい。 The method for producing a laminated structure may further include a step of laminating an arbitrary film on the obtained laminated structure.
張り合わせる任意のフィルムとしては、例えば、反射フィルム、拡散フィルムが挙げられる。 As an arbitrary film to be laminated, for example, a reflection film or a diffusion film can be mentioned.
フィルムを張り合わせる工程では、任意の接着剤を用いることができる。 Arbitrary adhesives can be used in the process of laminating the films.
上述の接着剤は、(1)半導体材料を溶解しない物であれば特に制限は無く、公知の接着剤を用いることができる。 The above-mentioned adhesive is not particularly limited as long as it does not dissolve (1) the semiconductor material, and a known adhesive can be used.
<<発光装置の製造方法>>
例えば、上述の光源と、光源から射出される光の光路上に上述のフィルム、又は積層構造体を設置する工程とを含む製造方法が挙げられる。
<< Manufacturing Method of Light-Emitting Device >>
For example, a manufacturing method including the above-mentioned light source and a step of installing the above-mentioned film or laminated structure on the optical path of light emitted from the light source can be mentioned.
なお、本発明の技術範囲は上述した実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 The technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
(ペロブスカイト化合物の濃度測定)
実施例1~3、及び比較例1で得られた組成物におけるペロブスカイト化合物の濃度は下記の方法により測定した。
(Measurement of concentration of perovskite compound)
The concentration of the perovskite compound in the compositions obtained in Examples 1 to 3 and Comparative Example 1 was measured by the following method.
まず、後述の方法で得られた(1)半導体材料を、精秤したトルエンに再分散させることで分散液を得た。次いで、得られた分散液に、N,N-ジメチルホルムアミドを添加することでペロブスカイト化合物を溶解させた。 First, a dispersion liquid was obtained by redispersing (1) the semiconductor material obtained by the method described below in toluene that was precisely weighed. Then, the perovskite compound was dissolved in the obtained dispersion by adding N, N-dimethylformamide.
その後、ICP-MS(PerkinElmer社製、ELAN DRCII)を用いて分散液に含まれるCs及びPbを定量した。また、イオンクロマトグラフ(サーモフィッシャーサイエンティフィック株式会社製、Integrion)を用いて分散液に含まれるBr及びIを定量した。各測定値の合計から分散液に含まれるペロブスカイト化合物の質量を求め、ペロブスカイト化合物の質量とトルエン量とから分散液濃度を求めた。 After that, Cs and Pb contained in the dispersion were quantified using ICP-MS (ELAN DRCII manufactured by PerkinElmer). Moreover, Br and I contained in the dispersion liquid were quantified using an ion chromatograph (Integration, manufactured by Thermo Fisher Scientific Co., Ltd.). The mass of the perovskite compound contained in the dispersion was calculated from the sum of the measured values, and the dispersion concentration was calculated from the mass of the perovskite compound and the amount of toluene.
(発光強度測定)
実施例1~3及び比較例1で得られた組成物の発光強度を、蛍光光度計(日本分光製、商品名FT-6500、励起光430nm、感度High)を用いて測定した。
(Measurement of emission intensity)
The emission intensity of the compositions obtained in Examples 1 to 3 and Comparative Example 1 was measured using a fluorometer (manufactured by JASCO Corporation, trade name FT-6500, excitation light 430 nm, sensitivity High).
(耐熱耐湿性評価)
実施例1~3、及び比較例1で得られた組成物を65℃の温度、95%湿度で一定にした恒温恒湿槽中に置き、2日間保管し、試験後の発光強度を測定して、下記の式を用いて維持率を求めた。こうして求めた維持率が高いほど水蒸気に対する耐久性が高いと評価できる。
維持率(%)=(2日間の水蒸気に対する耐久性試験後の発光強度)/(水蒸気に対する耐久性試験前の発光強度)×100
(Heat and humidity resistance evaluation)
The compositions obtained in Examples 1 to 3 and Comparative Example 1 were placed in a constant temperature and humidity bath kept at a temperature of 65 ° C. and 95% humidity for 2 days, and the emission intensity after the test was measured. Then, the maintenance rate was calculated using the following formula. It can be evaluated that the higher the maintenance rate thus obtained is, the higher the durability against water vapor is.
Maintenance rate (%) = (emission intensity after a durability test against water vapor for 2 days) / (emission intensity before a durability test against water vapor) × 100
(透過型電子顕微鏡による(1)半導体材料の観察)
(1)半導体材料は透過型電子顕微鏡(日本電子株式会社製、JEM-2200FS)を用いて観察した。観察用の試料は、組成物から支持膜付きグリッドに(1)半導体材料を採取することで得た。観察条件は、加速電圧を200kVとした。
((1) Observation of semiconductor material by transmission electron microscope)
(1) The semiconductor material was observed using a transmission electron microscope (JEM-2200FS manufactured by JEOL Ltd.). The sample for observation was obtained by collecting (1) a semiconductor material from the composition on a grid with a supporting film. The observation conditions were an acceleration voltage of 200 kV.
得られた電子顕微鏡写真に写る半導体材料の像を、2本の平行線で挟んだときの平行線の間隔をフェレー径として求めた。20個の半導体材料のフェレー径の算術平均値を求め、平均のフェレー径を求めた。 The distance between the parallel lines when the image of the semiconductor material shown in the obtained electron micrograph was sandwiched by two parallel lines was calculated as the Feret diameter. The arithmetic average value of the Feret diameters of 20 semiconductor materials was obtained, and the average Feret diameter was obtained.
[実施例1]
炭酸セシウム0.814gと、1-オクタデセンの溶媒40mLと、オレイン酸2.5mLとを混合した。マグネチックスターラーで攪拌して、窒素を流しながら150℃で1時間加熱して炭酸セシウム溶液を調製した。
[Example 1]
0.814 g of cesium carbonate, 40 mL of a solvent of 1-octadecene, and 2.5 mL of oleic acid were mixed. The mixture was stirred with a magnetic stirrer and heated at 150 ° C. for 1 hour while flowing nitrogen to prepare a cesium carbonate solution.
臭化鉛(PbBr2)0.110g、及びヨウ化鉛(PbI2)0.208gを1-オクタデセンの溶媒20mLと混合した。マグネチックスターラーで攪拌して窒素を流しながら120℃の温度で1時間加熱した後、オレイン酸2mL、及びオレイルアミン2mLを添加して臭化鉛‐ヨウ化鉛分散液を調製した。 0.110 g of lead bromide (PbBr 2 ) and 0.208 g of lead iodide (PbI 2 ) were mixed with 20 mL of 1-octadecene solvent. After stirring with a magnetic stirrer and heating at a temperature of 120 ° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added to prepare a lead bromide-lead iodide dispersion.
臭化鉛‐ヨウ化鉛分散液を160℃の温度に昇温した後、上述の炭酸セシウム溶液を1.6mL添加した。添加後、反応容器を氷水に漬けることで、室温まで降温し、分散液を得た。 After heating the lead bromide-lead iodide dispersion to a temperature of 160 ° C, 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was soaked in ice water to lower the temperature to room temperature to obtain a dispersion liquid.
次いで、分散液を10000rpm、5分間遠心分離し、沈殿物を分離することで、沈殿物のペロブスカイト化合物を得た。ペロブスカイト化合物をトルエン5mLに分散させた後、分散液500μLを分取して、トルエン4.5mLに再分散させることで、ペロブスカイト化合物及び溶媒を含む分散液を得た。 Next, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, whereby a perovskite compound of the precipitate was obtained. After the perovskite compound was dispersed in 5 mL of toluene, 500 μL of the dispersion was collected and re-dispersed in 4.5 mL of toluene to obtain a dispersion containing the perovskite compound and the solvent.
ICP-MS、及びイオンクロマトグラフによって測定したペロブスカイト化合物の濃度は、1500ppm(μg/g)であった。 The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1500 ppm (μg / g).
溶媒を自然乾燥させて回収した化合物のX線回折パターンをX線回折測定装置(XRD、Cu Kα線、X’pert PRO MPD、スペクトリス社製)で測定した所、2θ=14°の位置に(hkl)=(001)由来のピークを有しており、3次元のペロブスカイト型結晶構造を有していることを確認した。 When the X-ray diffraction pattern of the compound recovered by naturally drying the solvent was measured by an X-ray diffraction measurement device (XRD, Cu Kα ray, X'pert PRO MPD, Spectris Co., Ltd.), it was found at the position of 2θ = 14 ° ( It has a peak derived from hkl) = (001) and was confirmed to have a three-dimensional perovskite type crystal structure.
TEMで観察したペロブスカイト化合物の平均のフェレー径は19nmであった。 The average ferret diameter of the perovskite compound observed by TEM was 19 nm.
次いで上述の分散液にメルカプト変性シリコーン(KF-2001、信越化学株式会社製:25℃における比重 0.98g/cm3)を100μL混合した。 Next, 100 μL of mercapto-modified silicone (KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C .: 0.98 g / cm 3 ) was mixed with the above-mentioned dispersion liquid.
次いで、メタクリル樹脂(PMMA、住友化学社製、スミペックス・メタクリル樹脂、MH、分子量約12万、比重1.2g/ml)が16.5質量%となるように、メタクリル樹脂とトルエンとを混合した後、60℃、3時間加熱して、重合体が溶解した溶液を得た。 Then, the methacrylic resin and toluene were mixed so that the methacrylic resin (PMMA, Sumipex methacrylic resin manufactured by Sumitomo Chemical Co., Ltd., MH, molecular weight of about 120,000, specific gravity of 1.2 g / ml) was 16.5% by mass. Then, it heated at 60 degreeC for 3 hours, and obtained the solution in which the polymer melt | dissolved.
上記のペロブスカイト化合物及び溶媒を含む分散液0.3gと、上記の重合体が溶解した溶液1.826gと混合した後、1.128gをガラスシャーレ(φ3.2cm)にキャストした。 After mixing 0.3 g of the dispersion containing the perovskite compound and the solvent with 1.826 g of the solution in which the polymer was dissolved, 1.128 g was cast on a glass petri dish (φ 3.2 cm).
さらに、トルエンを自然乾燥で蒸発させ、ペロブスカイト化合物の濃度が500μg/mLの組成物を得た。組成物は1cm×1cmのサイズに切断した。 Further, toluene was naturally dried and evaporated to obtain a composition having a perovskite compound concentration of 500 μg / mL. The composition was cut into a size of 1 cm x 1 cm.
組成物の発光強度を評価すると、376であった。水蒸気に対する耐久性試験後の発光強度の維持率は、83.3%であった。結果を表1に示す。 The luminescence intensity of the composition was evaluated to be 376. The retention rate of luminescence intensity after the durability test against water vapor was 83.3%. The results are shown in Table 1.
[実施例2]
メルカプト変性シリコーン(KF-2001、信越化学株式会社製:25℃における比重 0.98g/cm3)の添加量を300μLとした以外は、実施例1と同様の方法で組成物を合成した。
組成物の発光強度を評価すると、304であった。水蒸気に対する耐久性試験後の発光強度の発光強度の維持率は、80.1%であった。
[Example 2]
A composition was synthesized in the same manner as in Example 1 except that the addition amount of mercapto-modified silicone (KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C .: 0.98 g / cm 3 ) was 300 μL.
The emission intensity of the composition was evaluated to be 304. The maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 80.1%.
[実施例3]
メルカプト変性シリコーン(KF-2001、信越化学株式会社製:0.98g/cm3)に代えて、メルカプト変性シリコーン(KF-2004、信越化学株式会社製:25℃における比重 0.97g/cm3)を使用した以外は、実施例1と同様の方法で組成物を合成した。
組成物の発光強度を評価すると、192であった。水蒸気に対する耐久性試験後の発光強度の発光強度の維持率は、33.5%であった。
[Example 3]
Instead of mercapto-modified silicone (KF-2001, Shin-Etsu Chemical Co., Ltd .: 0.98 g / cm 3 ), mercapto-modified silicone (KF-2004, Shin-Etsu Chemical Co., Ltd .: specific gravity at 25 ° C. 0.97 g / cm 3 ). A composition was synthesized in the same manner as in Example 1 except that was used.
The light emission intensity of the composition was evaluated to be 192. The maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 33.5%.
[比較例1]
メルカプト変性シリコーンを添加しなかった以外は、実施例1と同様の方法で組成物を合成した。
組成物の発光強度を評価すると、6.57であった。水蒸気に対する耐久性試験後の発光強度の発光強度の維持率は、22.9%であった。
[Comparative Example 1]
A composition was synthesized in the same manner as in Example 1 except that the mercapto-modified silicone was not added.
The light emission intensity of the composition was 6.57. The maintenance rate of the emission intensity of the emission intensity after the durability test against water vapor was 22.9%.
上記の結果から、本発明を適用した実施例1~3に係る組成物は、本発明を適用しない比較例1の組成物と比べて、初期の発光強度が高く、かつ、優れた水蒸気に対する耐久性を有していることが確認できた。 From the above results, the compositions according to Examples 1 to 3 to which the present invention is applied have higher initial emission intensity and excellent durability against water vapor as compared with the composition of Comparative Example 1 to which the present invention is not applied. It was confirmed that the product has the property.
[参考例1]
実施例1~3に記載の組成物を、ガラスチューブ等の中に入れて封止した後に、これを光源である青色発光ダイオードと導光板の間に配置することで、青色発光ダイオードの青色光を緑色光や赤色光に変換することができるバックライトを製造する。
[Reference Example 1]
The composition described in Examples 1 to 3 is put in a glass tube or the like and sealed, and then the composition is placed between a blue light emitting diode which is a light source and a light guide plate, whereby blue light of the blue light emitting diode is emitted. Manufacture backlights that can be converted into green and red light.
[参考例2]
実施例1~3に記載の組成物をシート化する事でフィルムを得ることができ、これを2枚のバリアーフィルムで挟んで封止したフィルムを導光板の上に設置することで、導光板の端面(側面)に置かれた青色発光ダイオードから導光板を通して前記シートに照射される青色の光を緑色光や赤色光に変換することができるバックライトを製造する。
[Reference example 2]
A film can be obtained by forming the composition described in Examples 1 to 3 into a sheet, and the film sandwiched by two barrier films is placed on the light guide plate to obtain a light guide plate. A backlight capable of converting blue light emitted from the blue light emitting diode placed on the end face (side surface) of the sheet through the light guide plate into green light or red light is manufactured.
[参考例3]
実施例1~3に記載の組成物を、青色発光ダイオードの発光部近傍に設置することで照射される青色の光を緑色光や赤色光に変換することができるバックライトを製造する。
[Reference Example 3]
By installing the compositions described in Examples 1 to 3 in the vicinity of the light emitting portion of a blue light emitting diode, a backlight capable of converting the emitted blue light into green light or red light is manufactured.
[参考例4]
実施例1~3に記載の組成物とレジストを混合した後に、溶媒を除去する事で波長変換材料を得ることができる。得られた波長変換材料を光源である青色発光ダイオードと導光板の間や、光源であるOLEDの後段に配置することで、光源の青色光を緑色光や赤色光に変換することができるバックライトを製造する。
[Reference Example 4]
The wavelength conversion material can be obtained by mixing the composition described in Examples 1 to 3 and the resist and then removing the solvent. By arranging the obtained wavelength conversion material between the blue light emitting diode which is the light source and the light guide plate or in the subsequent stage of the OLED which is the light source, a backlight capable of converting the blue light of the light source into green light or red light is provided. To manufacture.
[参考例5]
実施例1~3に記載の組成物をZnSなどの導電性粒子を混合して成膜し、片面にn型輸送層を積層し、もう片面をp型輸送層で積層することでLEDを得る。電流を流すことによりp型半導体の正孔と、n型半導体の電子が接合面のペロブスカイト化合物中で電荷を打ち消されることで発光させることができる。
[Reference Example 5]
The composition described in Examples 1 to 3 is mixed with conductive particles such as ZnS to form a film, an n-type transport layer is laminated on one side, and a p-type transport layer is laminated on the other side to obtain an LED. . When a current is passed, holes in the p-type semiconductor and electrons in the n-type semiconductor cancel out the charges in the perovskite compound on the junction surface, so that light can be emitted.
[参考例6]
フッ素ドープされた酸化スズ(FTO)基板の表面上に、酸化チタン緻密層を積層させ、その上から多孔質酸化アルミニウム層を積層し、その上に実施例1~3に記載の組成物を積層し、溶媒を除去した後にその上から2,2’-,7,7’-tetrakis-(N,N’-di-p-methoxyphenylamine)9,9’-spirobifluorene (Spiro-OMeTAD)などのホール輸送層を積層し、その上に銀(Ag)層を積層し、太陽電池を作製する。
[Reference Example 6]
A titanium oxide dense layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the composition described in Examples 1 to 3 is laminated thereon. Then, after removing the solvent, 2,2 '-, 7,7'-tetrakis- (N, N'-di-p-methoxyphenylamine) 9,9'-spirobifluorene (Spiro-OMeTAD) and other holes are transported from above. A layer is laminated | stacked and a silver (Ag) layer is laminated | stacked on it, and a solar cell is produced.
[参考例7]
実施例1~3に記載の組成物の溶媒を除去して成形する事で本実施形態の組成物を得ることができ、これを青色発光ダイオードの後段に設置することで、青色発光ダイオードから組成物に照射される青色の光を緑色光や赤色光に変換して白色光を発するレーザーダイオード照明を製造する。
[Reference Example 7]
The composition of the present embodiment can be obtained by removing the solvent of the compositions described in Examples 1 to 3 and molding. By placing this composition in the subsequent stage of the blue light emitting diode, the composition of the blue light emitting diode can be obtained. We manufacture laser diode lighting that emits white light by converting the blue light that illuminates an object into green light and red light.
[参考例8]
実施例1~3に記載の組成物の溶媒を除去して成形する事で本実施形態の組成物を得ることができる。得られた組成物を光電変換層の一部とすることで、光を検知する検出部に使用する含まれる光電変換素子(光検出素子)材料を製造する。光電変換素子材料は、X線撮像装置及びCMOSイメージセンサーなどの固体撮像装置用のイメージ検出部(イメージセンサー)、指紋検出部、顔検出部、静脈検出部及び虹彩検出部などの生体の一部分の所定の特徴を検出する検出部、パルスオキシメーターなどの光学バイオセンサーに用いられる。
[Reference Example 8]
The composition of this embodiment can be obtained by removing the solvent of the composition described in Examples 1 to 3 and molding. By using the obtained composition as a part of a photoelectric conversion layer, a photoelectric conversion element (photodetection element) material used for a detection unit that detects light is manufactured. The photoelectric conversion element material is used for a part of a living body such as an image detection part (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection part, a face detection part, a vein detection part and an iris detection part. It is used in optical biosensors such as pulse oximeters that detect specific characteristics.
本発明によれば、水蒸気に対する耐久性が高い、発光性の半導体材料を含む組成物、前記組成物を用いたフィルム、前記フィルムを用いた積層構造体、前記積層構造体を備える発光装置及びディスプレイを提供することが可能となる。
したがって、本発明の組成物、前記組成物を用いたフィルム、前記フィルムを用いた積層構造体、前記積層構造体を備える発光装置及びディスプレイは、発光用途において好適に使用することができる。
According to the present invention, a composition containing a light-emitting semiconductor material having high durability against water vapor, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure. Can be provided.
Therefore, the composition of the present invention, the film using the composition, the laminated structure using the film, and the light emitting device and the display including the laminated structure can be suitably used for light emitting applications.
1a…第1の積層構造体、1b…第2の積層構造体、10…フィルム、20…第1の基板、21…第2の基板、22…封止層、2…発光装置、3…ディスプレイ、30…光源、40…液晶パネル、50…プリズムシート、60…導光板 1a ... 1st laminated structure, 1b ... 2nd laminated structure, 10 ... film, 20 ... 1st substrate, 21 ... 2nd substrate, 22 ... sealing layer, 2 ... light-emitting device, 3 ... display , 30 ... Light source, 40 ... Liquid crystal panel, 50 ... Prism sheet, 60 ... Light guide plate
Claims (8)
(1)成分:発光性の半導体材料
(2)成分:-R31SH基を有するシリコーン
(上記-R31SH基中、R31は置換基を有していてもよいヒドロカルビレン基である。) A composition comprising the component (1) and the component (2).
Component (1): Light-emitting semiconductor material (2) Component: -R 31 SH group-containing silicone (in the above-R 31 SH group, R 31 is a hydrocarbylene group which may have a substituent) .)
(Aは、ペロブスカイト型結晶構造において、Bを中心とする六面体の各頂点に位置する成分であって、1価の陽イオンである。
Xは、ペロブスカイト型結晶構造において、Bを中心とする八面体の各頂点に位置する成分を表し、ハロゲン化物イオン、及びチオシアン酸イオンからなる群より選ばれる少なくとも一種の陰イオンである。
Bは、ペロブスカイト型結晶構造において、Aを頂点に配置する六面体、及びXを頂点に配置する八面体の中心に位置する成分であって、金属イオンである。) The composition according to claim 1, wherein the component (1) is a perovskite compound containing A, B, and X as constituent components.
(A is a component located at each vertex of a hexahedron centered on B in the perovskite type crystal structure, and is a monovalent cation.
X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
In the perovskite type crystal structure, B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion. )
(5)成分:アンモニウムイオン、アミン、第1級~第4級アンモニウムカチオン、アンモニウム塩、カルボン酸、カルボキシレートイオン、カルボキシレート塩、下記式(X1)~(X6)でそれぞれ表される化合物、及び下記式(X2)~(X4)でそれぞれ表される化合物の塩からなる群より選ばれる少なくとも1種の化合物又はイオン
式(X2)中、A1は単結合又は酸素原子を表す。R22は、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X3)中、A2及びA3はそれぞれ独立に、単結合又は酸素原子を表す。R23及びR24はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X4)中、A4は単結合又は酸素原子を表す。R25は、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、又は炭素原子数6~30のアリール基を表し、それらは置換基を有していてもよい。
式(X5)中、A5~A7はそれぞれ独立に、単結合又は酸素原子を表す。R26~R28はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、炭素原子数6~30のアリール基、炭素原子数2~20のアルケニル基、又は炭素原子数2~20のアルキニル基を表し、それらは置換基を有していてもよい。
式(X6)中、A8~A10はそれぞれ独立に、単結合又は酸素原子を表す。R29~R31はそれぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数3~30のシクロアルキル基、炭素原子数6~30のアリール基、炭素原子数2~20のアルケニル基、又は炭素原子数2~20のアルキニル基を表し、それらは置換基を有していてもよい。
R18~R31でそれぞれ表される基に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよい。) The composition according to claim 1 or 2, further comprising (5) component.
Component (5): ammonium ion, amine, primary to quaternary ammonium cation, ammonium salt, carboxylic acid, carboxylate ion, carboxylate salt, compounds represented by the following formulas (X1) to (X6), And at least one compound or ion selected from the group consisting of salts of compounds represented by the following formulas (X2) to (X4)
In formula (X2), A 1 represents a single bond or an oxygen atom. R 22 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
In formula (X3), A 2 and A 3 each independently represent a single bond or an oxygen atom. R 23 and R 24 each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, each of which has a substituent. You may have.
In formula (X4), A 4 represents a single bond or an oxygen atom. R 25 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have a substituent.
In formula (X5), A 5 to A 7 each independently represent a single bond or an oxygen atom. R 26 to R 28 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. Or represents an alkynyl group having 2 to 20 carbon atoms, which may have a substituent.
In formula (X6), A 8 to A 10 each independently represent a single bond or an oxygen atom. R 29 to R 31 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. Or represents an alkynyl group having 2 to 20 carbon atoms, which may have a substituent.
The hydrogen atoms contained in the groups represented by R 18 to R 31 may each independently be substituted with a halogen atom. )
(3)成分:溶媒
(4)成分:重合性化合物
(4-1)成分:重合体 The composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of component (3), component (4), and component (4-1).
(3) component: solvent (4) component: polymerizable compound (4-1) component: polymer
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| CN201980070405.3A CN112912444A (en) | 2018-10-26 | 2019-10-23 | Composition, film, laminated structure, light-emitting device, and display |
| KR1020217015331A KR20210084519A (en) | 2018-10-26 | 2019-10-23 | Compositions, Films, Laminate Structures, Light-Emitting Devices and Displays |
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| JP2018202352A JP7179581B2 (en) | 2018-10-26 | 2018-10-26 | Compositions, films, laminated structures, light-emitting devices and displays |
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| KR (1) | KR20210084519A (en) |
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| JP2022038930A (en) * | 2020-08-27 | 2022-03-10 | 住友化学株式会社 | Luminescent compound particle, and luminescent compound particle composition |
| EP4032961A1 (en) * | 2021-01-21 | 2022-07-27 | Universität für Bodenkultur Wien | Ligand-supported perovskite luminescent crystal composition and method for producing the same |
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| JP7179581B2 (en) | 2022-11-29 |
| JP2020068365A (en) | 2020-04-30 |
| KR20210084519A (en) | 2021-07-07 |
| TW202028424A (en) | 2020-08-01 |
| CN112912444A (en) | 2021-06-04 |
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