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WO2020085364A1 - Composition, film, structure stratifiée, dispositif électroluminescent et dispositif d'affichage - Google Patents

Composition, film, structure stratifiée, dispositif électroluminescent et dispositif d'affichage Download PDF

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Publication number
WO2020085364A1
WO2020085364A1 PCT/JP2019/041474 JP2019041474W WO2020085364A1 WO 2020085364 A1 WO2020085364 A1 WO 2020085364A1 JP 2019041474 W JP2019041474 W JP 2019041474W WO 2020085364 A1 WO2020085364 A1 WO 2020085364A1
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group
carbon atoms
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formula
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翔太 内藤
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • 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

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.
  • one embodiment of the present invention is a composition including a component (1) and a component (2).
  • Component (1) Light-emitting semiconductor material (2)
  • Component (2) Component: Compound or ion having fluoroalkyl group (excluding silicon compound having one fluoroalkyl group, alcohol having fluoroalkyl group and fluorine-containing hydrocarbon)
  • the component (2) comprises a fluoroalkyl group-containing ammonium ion, a fluoroalkyl group-containing amine, a fluoroalkyl group-containing primary to quaternary ammonium cation, and a fluoroalkyl group-containing ammonium salt.
  • R 18 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R 19 to R 21 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. It represents an alkyl group having 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, and M ⁇ represents a counter anion.
  • a 1 represents a single bond or an oxygen atom.
  • R 22 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • a 2 and A 3 each independently represent a single bond or an oxygen atom.
  • R 23 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • R 24 represents a fluoroalkyl group having 1 to 20 carbon atoms, 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; May have a substituent.
  • a 4 represents a single bond or an oxygen atom.
  • R 25 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • a 5 to A 7 each independently represent a single bond or an oxygen atom.
  • R 26 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • R 27 and R 28 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl having 6 to 30 carbon atoms.
  • a 8 to A 10 each independently represent a single bond or an oxygen atom.
  • R 29 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • R 30 and R 31 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl having 6 to 30 carbon atoms.
  • the component (1) may be a perovskite compound having 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.
  • 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 configuration may further include the component (5).
  • Component (5) silazane, silazane modified product, compound represented by the following formula (C1), modified product of compound represented by the following formula (C1), compound represented by the following formula (C2), below A modified product of the compound represented by formula (C2), a compound represented by the following formula (A5-51), a modified product of the compound represented by the following formula (A5-51), and a compound represented by the following formula (A5-52) ), One or more compounds selected from the group consisting of a compound represented by the following formula (A5-52), a modified product of sodium silicate, and a modified product of sodium silicate.
  • Y 5 represents a single bond, an oxygen atom or a sulfur atom.
  • R 30 and R 31 each independently represent a hydrogen atom or a carbon atom number of 1 to 20. It represents an alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.
  • R 30 has 1 carbon atom.
  • R 31 represents a hydrogen atom
  • an alkyl group having 1 to 20 carbon atoms Represents a cycloalkyl group having 3 to 30 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms
  • R 30 , R 31 and R 32 each independently represent hydrogen.
  • the hydrogen atoms contained in the group, cycloalkyl group and unsaturated hydrocarbon group may each independently be substituted with a halogen atom or an amino group, a is an integer of 1 to 3, and a is 2 or 3.
  • a plurality of Y 5 s may be the same or different, and when a is 2 or 3, a plurality of R 30 s may be the same or different.
  • a plurality of R 32 s may be the same or different, and when a is 1 or 2, a plurality of R 31 s may be the same. , May be different.
  • a C represents a divalent hydrocarbon group
  • Y 15 represents an oxygen atom or a sulfur atom
  • R 122 and R 123 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms
  • R 124 is an alkyl group having 1 to 20 carbon atoms.
  • R 125 and R 126 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Alternatively, it represents a cycloalkyl group having 3 to 30 carbon atoms.
  • the hydrogen atoms contained in the alkyl group and cycloalkyl group represented by R 122 to R 126 may be each independently substituted with a halogen atom or an amino group.
  • the composition may further include at least one selected from the group consisting of the component (3), the component (4), and the component (4-1).
  • component solvent (4) component: polymerizable compound (4-1) component: polymer
  • One aspect of the present invention provides a film using the above composition as a forming material.
  • One aspect of the present invention provides a laminated structure including the above film.
  • One embodiment of the present invention provides a light-emitting device including the above laminated structure.
  • One embodiment of the present invention provides a display including the above laminated structure.
  • 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 (1) light emitting semiconductor material 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
  • Component Fluoroalkyl group-containing compound or ion (however, excluding silicon compound having one fluoroalkyl group, fluoroalkyl group-containing alcohol, and fluorine-containing hydrocarbon)
  • the composition of the present embodiment may be a composition containing (1) a semiconductor material and (2) a compound or ion having a fluoroalkyl group, and (1) a semiconductor material and (2) a compound having a fluoroalkyl group or It may further contain components other than ions.
  • composition of the present embodiment contains (1) a semiconductor material and (2) a compound or ion having a fluoroalkyl group, and further comprises (3) component, (4) component and (4-1) group. It may include at least one selected from the above.
  • (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) silazane, silazane modified product, compound represented by the formula (C1), modified product of the compound represented by the formula (C1), compound represented by the formula (C2), the formula A modified product of the compound represented by (C2), a compound represented by the formula (A5-51), a modified product of the compound represented by the formula (A5-51), and the formula (A5-52)
  • 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 (2) the compound or ion having a fluoroalkyl group to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, the content ratio of the compound or ion having the fluoroalkyl group (2) to the total mass of the composition is preferably 70% by mass or less, more preferably 30% by mass or less, It is more preferably 10% by mass or less.
  • Examples of the combination of the upper limit value and the lower limit value include 0.001 to 70% by mass, 0.01 to 30% by mass, and 0.1 to 10% by mass.
  • a composition in which the content ratio of the compound or ion having a fluoroalkyl group to the total mass of the composition is within the above range is preferable because (1) the surface of the semiconductor material has high water repellency and excellent water resistance.
  • the content ratio of the modified body group (5) to the total mass of the composition is not particularly limited.
  • the content ratio of the (5) modified body group to the total mass of the composition is preferably 30% by mass or less, It is more preferably 10% by mass or less, and further preferably 7.5% by mass or less.
  • the content ratio of (1) semiconductor material to the total mass of the composition is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. Is more preferably 0.1% by mass or more.
  • 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 in which the content ratio of the (5) modifier group to the total mass of the composition is within the above range is preferable from the viewpoint of water resistance.
  • 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) Semiconductor material containing group II-VI compound semiconductor ii) Semiconductor material containing group II-V compound semiconductor (iii) Semiconductor material containing group III-V compound semiconductor (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 .
  • the compound semiconductor of the system (ii-3) 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
  • the compound semiconductor (iii-3) of the group may be a quaternary compound semiconductor containing two kinds of group 13 elements and two kinds of group 15 elements.
  • 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 .
  • (Iv-1) A ternary compound semiconductor containing one group 13 element and two group 14 elements
  • (iv-2) A ternary compound semiconductor containing two group 13 elements and one group 14 element
  • the compound semiconductor (iv-3) of the group 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
  • the compound semiconductor (vi-3) of the system may be a quaternary compound semiconductor containing two kinds of Group 14 elements and two kinds of Group 16 elements.
  • 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.
  • 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.
  • 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.
  • B is a metal cation capable of adopting the octahedral coordination of X.
  • 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.
  • the perovskite compound having 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 (quasi-2D) structure.
  • 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 group represented by R 6 to R 9 may 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 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 + .
  • amidinium ion examples include an amidinium ion represented by the following formula (A4).
  • R 10 R 11 N CH—NR 12 R 13 ) + ...
  • 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 can 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.).
  • Cesium ion is preferable as A in the perovskite compound.
  • 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 not particularly limited.
  • 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 size 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 the semiconductor particles is not particularly limited, but is preferably 3 nm or more because the crystal structure can be maintained well.
  • 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-mentioned semiconductor materials may be used alone or in combination of two or more.
  • the compound (2) having a fluoroalkyl group included in the present embodiment is a compound having a fluoroalkyl group except for a silicon compound having one fluoroalkyl group, an alcohol having a fluoroalkyl group and a fluorine-containing hydrocarbon.
  • the fluorinated hydrocarbon is a hydrocarbon compound having a fluoroalkyl group.
  • the compound or ion having a fluoroalkyl group is an ammonium ion having a fluoroalkyl group, an amine having a fluoroalkyl group, a primary to quaternary ammonium cation having a fluoroalkyl group, an ammonium salt having a fluoroalkyl group.
  • composition of the present embodiment only one type of compound or ion having a fluoroalkyl group may be used, or two or more types may be used in combination.
  • ammonium ion having a fluoroalkyl group from the viewpoint of durability, ammonium ion having a fluoroalkyl group, amine having a fluoroalkyl group, and primary to quaternary ammonium having a fluoroalkyl group A cation, an ammonium salt having a fluoroalkyl group, a carboxylate ion, and a carboxylate salt having a fluoroalkyl group are preferable, and an amine having a fluoroalkyl group is more preferable.
  • the compound or ion having a fluoroalkyl group is a compound having the action of adsorbing on the surface of (1) component (semiconductor particles) and (1) stably dispersing the semiconductor material in the composition.
  • (2) a compound or ion having a fluoroalkyl group may be simply referred to as “(2) surface modifier”.
  • ammonium ion having fluoroalkyl group, primary to quaternary ammonium cation having fluoroalkyl group, ammonium salt having fluoroalkyl group is represented by the following formula (A1).
  • the ammonium salt having a fluoroalkyl group, which is a surface modifier, is a salt containing an ion represented by the following formula (A1).
  • R 1 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R 2 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group.
  • the fluoroalkyl group represented by R 1 may be linear or branched.
  • the number of carbon atoms of the fluoroalkyl group represented by R 1 is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more.
  • the fluoroalkyl group represented by R 1 preferably has 18 or less carbon atoms, more preferably 16 or less carbon atoms, and even more preferably 10 or less carbon atoms.
  • the upper limit and the lower limit of the number of carbon atoms can be arbitrarily combined.
  • the number of fluorine atoms contained in the fluoroalkyl group represented by R 1 is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more.
  • the hydrocarbon group represented by R 2 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 2 to R 4 may be linear or branched.
  • the alkyl group represented by R 2 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 2 to R 4 may have an alkyl group as a substituent.
  • the number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11.
  • the number of carbon atoms includes the number of carbon atoms of the substituent.
  • the unsaturated hydrocarbon group of R 2 to R 4 may be linear or branched.
  • the unsaturated hydrocarbon group of R 2 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 2 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 2 to R 4 are preferably alkenyl groups having 8 to 20 carbon atoms.
  • alkyl group of R 2 to R 4 include the alkyl groups exemplified in R 6 to R 9 .
  • cycloalkyl group of R 2 to R 4 include the cycloalkyl groups exemplified in R 6 to R 9 .
  • Preferred alkenyl groups for R 2 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 having a fluoroalkyl group which is a 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.
  • 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.
  • 1H, 1H-undecafluorohexylamine and 1H, 1H-perfluorobutylamine are preferable 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 bonded to the carboxylate anion represented by (A2) above.
  • R 5 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 5 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the fluoroalkyl group represented by R 5 may be linear or branched.
  • the carboxylate anion represented by the formula (A2) is perfluorooctanoic acid, perfluoroundecanoic acid, 2H, 2H, 3H, 3H-perfluoroundecanoic acid, perfluorodecanoic acid, tridecafluoroheptanoic acid, perfluorododecanoic acid, perfluoro. Hexanoic acid is preferred.
  • the counter cation is not particularly limited, but preferable examples include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.
  • R 18 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 18 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • R 19 to R 21 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, 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 structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 19 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the alkyl group represented by R 19 to R 21 may be linear or branched.
  • the alkyl group represented by R 19 to R 21 preferably has an aryl group as a substituent.
  • the alkyl group represented by R 19 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 19 to R 21 preferably has an aryl group as a substituent.
  • the cycloalkyl group represented by R 19 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 19 to R 21 preferably has an alkyl group as a substituent.
  • the aryl group represented by R 19 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 19 to R 21 is preferably an alkyl group.
  • alkyl group represented by R 19 to R 21 include the alkyl groups exemplified as the alkyl groups represented by R 6 to R 9 .
  • cycloalkyl group represented by R 19 to R 21 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
  • aryl group represented by R 19 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 19 to R 21 may each independently be substituted with a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a fluorine atom is preferable as the halogen atom to be substituted because the chemical stability of the compound substituted with a halogen atom is high.
  • 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.
  • a 1 represents a single bond or an oxygen atom.
  • R 22 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 22 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the anionic group is represented by the following formula (X2-1).
  • examples of the counter cation paired with the formula (X2-1) include an ammonium salt.
  • 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.
  • a 2 and A 3 each independently represent a single bond or an oxygen atom.
  • R 23 represents a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, the number of carbon atoms, and the number of fluorine atoms of the fluoroalkyl group represented by R 23 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • R 24 is a fluoroalkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 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 structure of the fluoroalkyl group represented by R 24 , the number of carbon atoms and the number of fluorine atoms are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the alkyl group represented by R 24 may be linear or branched.
  • alkyl group represented by R 24 the same group as the alkyl group represented by R 19 to R 21 can be adopted.
  • cycloalkyl group represented by R 24 the same group as the cycloalkyl group represented by R 19 to R 21 can be adopted.
  • aryl group represented by R 24 the same group as the aryl group represented by R 19 to R 21 can be adopted.
  • R 24 is preferably an alkyl group.
  • alkyl group represented by R 24 include the alkyl groups exemplified as the alkyl groups represented by R 6 to R 9 .
  • cycloalkyl group represented by R 24 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
  • aryl group represented by R 24 include the aryl groups exemplified as the aryl group represented by R 19 to R 21 .
  • the hydrogen atoms contained in the group represented by 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, From the viewpoint of chemical stability, a fluorine atom is preferable.
  • the anionic group is represented by the following formula (X3-1).
  • examples of the counter cation paired with the formula (X3-1) include an ammonium salt.
  • 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.
  • a 4 represents a single bond or an oxygen atom.
  • the group represented by R 25 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 25 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • Examples of the compound represented by the formula (X4) include nonafluoro-1-butanesulfonic acid, perfluoro-1-butanesulfonic acid, and perfluoro-1-octanesulfonic acid.
  • 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 with the formula (X4-1) is not particularly limited, but is, for example, a monovalent one such as Na + , K + , Cs + , and H +. Ion is mentioned.
  • Examples of the salt of the compound represented by the formula (X4) include lithium nonafluoro-1-butanesulfonate, potassium perfluoro-1-butanesulfonate, lithium perfluoro-1-octanesulfonate, and potassium perfluoro-1-octanesulfonate. Can be mentioned.
  • thermo durability of the composition can be expected to increase, perfluorooctanesulfonic acid and lithium perfluoro-1-octanesulfonate are preferable, and perfluorooctanesulfonic acid is more preferable.
  • a 5 to A 7 each independently represent a single bond or an oxygen atom.
  • R 26 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 26 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • R 27 and R 28 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms which may have a substituent.
  • a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, a carbon which may have a substituent It represents an alkenyl group having 2 to 20 atoms or an alkynyl group having 2 to 20 carbon atoms which may have a substituent.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 27 and R 28 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the alkyl groups represented by R 27 and R 28 may each independently be linear or branched.
  • alkyl group represented by R 27 and R 28 the same group as the alkyl group represented by R 19 to R 21 can be adopted.
  • cycloalkyl group represented by R 27 and R 28 the same group as the cycloalkyl group represented by R 19 to R 21 can be adopted.
  • aryl group represented by R 27 and R 28 the same group as the aryl group represented by R 19 to R 21 can be adopted.
  • the alkenyl groups represented by R 27 and R 28 each independently have an alkyl group or an aryl group as a substituent.
  • the number of carbon atoms of the alkenyl group represented by R 27 and R 28 is usually 2 to 20, preferably 6 to 20, and more preferably 12 to 18.
  • the number of carbon atoms includes the number of carbon atoms of the substituent.
  • the alkynyl groups represented by R 27 and R 28 each independently have an alkyl group or an aryl group as a substituent.
  • the alkynyl group represented by R 27 and 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 27 and R 28 are each independently an alkyl group.
  • alkyl group represented by R 27 and R 28 include the alkyl groups exemplified as the alkyl groups represented by R 6 to R 9 .
  • cycloalkyl group represented by R 27 and R 28 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
  • aryl group represented by R 27 and R 28 include the aryl groups exemplified as the aryl groups represented by R 19 to R 21 .
  • alkenyl group represented by R 27 and 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 27 and 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 27 and R 28 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.
  • Examples of the compound represented by the formula (X5) include bis (pentafluorophenyl) phenylphosphine, diphenyl (pentafluorophenyl) phosphine, and tris (perfluorophenyl) phosphine.
  • tris (perfluorophenyl) phosphine and diphenyl (pentafluorophenyl) phosphine are preferable, and tris (perfluorophenyl) phosphine is more preferable.
  • a 8 to A 10 each independently represent a single bond or an oxygen atom.
  • R 29 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the structure, the number of carbon atoms, and the number of fluorine atoms of the fluoroalkyl group represented by R 29 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • R 30 and R 31 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms which may have a substituent.
  • a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, a carbon which may have a substituent It represents an alkenyl group having 2 to 20 atoms or an alkynyl group having 2 to 20 carbon atoms which may have a substituent.
  • the structure, carbon atom number, and fluorine atom number of the fluoroalkyl group represented by R 30 and R 31 are the same as those of the fluoroalkyl group represented by R 1 described above.
  • the alkyl groups represented by R 30 and R 31 may each independently be linear or branched.
  • alkyl group represented by R 30 and R 31 the same group as the alkyl group represented by R 19 to R 21 can be adopted.
  • cycloalkyl group represented by R 30 and R 31 the same group as the cycloalkyl group represented by R 19 to R 21 can be adopted.
  • aryl group represented by R 30 and R 31 the same group as the aryl group represented by R 19 to R 21 can be adopted.
  • alkenyl group represented by R 30 and R 31 the same group as the alkenyl group represented by R 27 and R 28 can be adopted.
  • alkynyl group represented by R 30 and R 31 the same group as the alkynyl group represented by R 27 and R 28 can be adopted.
  • R 30 and R 31 are preferably each independently an alkyl group.
  • alkyl group represented by R 30 and R 31 include the alkyl groups exemplified as the alkyl groups represented by R 6 to R 9 .
  • cycloalkyl group represented by R 30 and R 31 include the cycloalkyl groups exemplified in the cycloalkyl group represented by R 6 to R 9 .
  • aryl group represented by R 30 and R 31 include the aryl groups exemplified as the aryl group represented by R 19 to R 21 .
  • alkenyl group represented by R 30 and R 31 include the alkenyl groups exemplified in the alkenyl groups represented by R 27 and R 28 .
  • alkynyl group represented by R 30 and R 31 include the alkynyl groups exemplified in the alkynyl group represented by R 27 and R 28 .
  • the hydrogen atoms contained in the groups represented by R 30 and R 31 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.
  • ammonium salts having a fluoroalkyl group ammonium ions having a fluoroalkyl group, primary to quaternary ammonium cations having a fluoroalkyl group, carboxylate salts having a fluoroalkyl group, fluoro Carboxylate ions having an alkyl group are preferred.
  • ammonium salts having a fluoroalkyl group and ammonium ions having a fluoroalkyl group 1H, 1H-undecafluorohexylamine ammonium salt or 1H, 1H-undecafluorohexylammonium ion is more preferable.
  • carboxylate salt having a fluoroalkyl group and the carboxylate ion having a fluoroalkyl group a perfluorohexanoate or a perfluorohexanoate ion is more preferable.
  • composition of the present embodiment may include (2) a compound or ion having a fluoroalkyl group, and other compounds that function as a surface modifier.
  • Examples of such other compounds include (2) a compound having a fluoroalkyl group or a compound in which all the fluorine atoms of the fluoroalkyl group of the ion are replaced with hydrogen atoms.
  • Amine and carboxylic acid are preferable as such other compounds.
  • Oleylamine is preferred as the amine.
  • carboxylic acid oleic acid is more preferable.
  • 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 below.
  • solvent examples 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 polymerizable compound contained in the composition of the present embodiment is preferably one that is difficult to dissolve (1) the 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 it 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 it 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, the 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, and 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 polymer may be used alone or in combination of two or more kinds.
  • the modified product group is represented by silazane, silazane modified product, a compound represented by the formula (C1) described later, a modified compound of the compound represented by the formula (C1), and a formula (C2) described below.
  • composition of the present embodiment only one type of the above-mentioned modified body group may be used, or two or more types may be used in combination.
  • the modified body group preferably forms a shell structure with (2) a surface modifier at least a part of the surface of which is covered with (1) a semiconductor material as a core.
  • a surface modifier at least a part of the surface of which is covered with (1) a semiconductor material as a core.
  • the modified substance group overlaps with (1) the surface modifying agent that covers the surface of the semiconductor material, and (2) covers the surface of the surface modifying agent.
  • the surface modifier may not be coated (1)
  • the surface of the semiconductor material may be coated.
  • (1) the semiconductor material or (2) the surface of the surface modifier is coated with (5) the modified body group is confirmed by, for example, observing the composition using SEM or TEM. be able to. Further, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.
  • the term “modified” means that a silicon compound having a Si—N bond, a Si—SR bond (R is a hydrogen atom or an organic group) or a Si—OR bond (R is a hydrogen atom or an organic group) is hydrolyzed. Then, a silicon compound having a Si—O—Si bond is produced.
  • the Si-O-Si bond may be formed by an intermolecular condensation reaction or an intramolecular condensation reaction.
  • the “modified form” refers to a compound obtained by modifying a silicon compound having a Si—N bond, a Si—SR bond or a Si—OR bond.
  • Silazane is a compound having a Si-N-Si bond.
  • the silazane may be linear, branched or cyclic.
  • the silazane may be a low molecular weight silazane or a high molecular weight silazane.
  • the polymer silazane may be referred to as polysilazane.
  • low molecular weight means that the number average molecular weight is less than 600.
  • polymer means that the number average molecular weight is 600 or more and 2000 or less.
  • the “number average molecular weight” means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
  • the silazane is preferably a low-molecular silazane, for example, a disilazane represented by the following formula (B1).
  • R 14 and R 15 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.
  • R 14 and R 15 may have a substituent such as an amino group.
  • a plurality of R 15's may be the same or different.
  • Examples of the low-molecular silazane represented by the formula (B1) include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, and 1,1,1, 3,3,3-hexamethyldisilazane can be mentioned.
  • silazane for example, a low molecular silazane represented by the following formula (B2) is also preferable.
  • a plurality of R 14's may be the same or different.
  • a plurality of R 15's may be the same or different.
  • n 1 represents an integer of 1 or more and 20 or less. n 1 may be an integer of 1 or more and 10 or less, or 1 or 2.
  • Examples of the low-molecular silazane represented by the formula (B2) include octamethylcyclotetrasilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, and 2,4,6-trimethyl-2,4. , 6-trivinylcyclotrisilazane.
  • octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane are preferable, and octamethylcyclotetrasilazane is more preferable.
  • silazane for example, a polymer silazane represented by the following formula (B3) (polysilazane) is preferable.
  • Polysilazane is a polymer compound having a Si—N—Si bond.
  • the constitutional unit of the polysilazane represented by the formula (B3) may be one kind or plural kinds.
  • R 14, and R 15 are the same as R 14, and R 15 in the formula (B1).
  • * represents a bond.
  • R 14 is bonded to the bond of the N atom at the end of the molecular chain.
  • R 15 is bonded to the bond of the Si atom at the end of the molecular chain.
  • a plurality of R 14's may be the same or different.
  • a plurality of R 15's may be the same or different.
  • M represents an integer of 2 or more and 10000 or less.
  • the polysilazane represented by the formula (B3) may be, for example, perhydropolysilazane in which all of R 14 and R 15 are hydrogen atoms.
  • the polysilazane represented by the formula (B3) may be, for example, an organopolysilazane in which at least one R 15 is a group other than a hydrogen atom.
  • perhydropolysilazane and organopolysilazane may be appropriately selected, or they may be mixed and used.
  • silazane for example, polysilazane having a structure represented by the following formula (B4) is also preferable.
  • the polysilazane may have a ring structure in a part of the molecule, for example, may have the structure represented by the formula (B4).
  • * represents a bond.
  • the bond of the formula (B4) may be bonded to the bond of the polysilazane represented by the formula (B3) or the bond of the constitutional unit of the polysilazane represented by the formula (B3).
  • the bond of the structure represented by the formula (B4) is a bond of the structure represented by another formula (B4). It may be directly connected to the hand.
  • R 14 is bonded to the bond of the non-N atom.
  • R 15 is bonded to the bond of the non-Si atom.
  • n 2 represents an integer of 1 or more and 10000 or less. n 2 may be an integer of 1 or more and 10 or less, or 1 or 2.
  • General polysilazane has, for example, a structure in which a linear structure and a ring structure such as a 6-membered ring or an 8-membered ring are present, that is, the structure represented by the above (B3) (B4).
  • a general polysilazane has a number average molecular weight (Mn) of about 600 to 2000 (in terms of polystyrene), and may be a liquid or solid substance depending on the molecular weight.
  • a commercially available product may be used as the polysilazane.
  • (Manufactured by the company) AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane 1500 Rapid Rapid, Durazane 1800, and Durazane 1033 (manufactured by Merck Performance Materials Co., Ltd.).
  • the polysilazane is preferably AZNN-120-20, Durazane 1500 Slow Cure, Durazane 1500 Rapid Cure, and more preferably Durazane 1500 Slow Cure.
  • the proportion of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100%. Further, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, further preferably 30 to 95%.
  • the “ratio of silicon atoms not bonded to nitrogen atoms” is ((Si (mol) ⁇ (N (mol) in SiN bond) / Si (mol) ⁇ 100), using the measured value described later. Considering the reforming reaction, the “ratio of silicon atoms not bonded to nitrogen atoms” means the “ratio of silicon atoms contained in the siloxane bond generated in the modification treatment”.
  • the proportion of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100%. Further, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, further preferably 30 to 95%.
  • the proportion of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 99%. Further, the proportion of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 97%, further preferably 30 to 95%.
  • the number of Si atoms and the number of SiN bonds in the modified product can be measured by X-ray photoelectron spectroscopy (XPS).
  • the “ratio of silicon atoms not bonded to nitrogen atoms” of the modified product which is determined by using the value measured by the above method, is preferably 0.1 to 99%, and 10 to 99%. Is more preferable, and further preferably 30 to 95%.
  • the silazane contained in the modified product group or a modified product thereof is not particularly limited, but organopolysilazane or a modified product thereof is preferable from the viewpoint of improving dispersibility and suppressing aggregation.
  • organopolysilazane examples are represented by the formula (B3), and at least one of R 14 and R 15 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or 3 to It may be a cycloalkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an organopolysilazane which is an alkylsilyl group having 1 to 20 carbon atoms.
  • the organopolysilazane includes, for example, a structure represented by the formula (B4), at least one bond is bound to R 14 or R 15, and at least one of R 14 and R 15 is the number of carbon atoms.
  • the organopolysilazane includes an organopolysilazane represented by the formula (B3) and at least one of R 14 and R 15 is a methyl group, or a structure represented by the formula (B4), and at least one bond is R 14 or It is preferable that the polysilazane is bonded to R 15 and at least one of R 14 and R 15 is a methyl group.
  • the modified compound group may be a compound represented by the following formula (C1) or a compound represented by the following formula (C2).
  • Y 5 represents a single bond, an oxygen atom or a sulfur atom.
  • R 30 and R 31 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or 2 carbon atoms. It represents up to 20 unsaturated hydrocarbon groups.
  • R 30 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.
  • R 31 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.
  • R 30 , R 31 and R 32 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or a carbon atom having 3 to 30 carbon atoms. It represents 2 to 20 unsaturated hydrocarbon groups.
  • the hydrogen atoms contained in the alkyl group, cycloalkyl group and unsaturated hydrocarbon group represented by R 30 , R 31 and R 32 are each independently a halogen atom or amino. It may be substituted with a group.
  • halogen atom which may be substituted for the hydrogen atom contained in the alkyl group, cycloalkyl group or unsaturated hydrocarbon group represented by R 30 , R 31 and R 32 include, for example, a fluorine atom, a chlorine atom and a bromine atom. , And iodine atoms are preferable, and fluorine atoms are preferable from the viewpoint of chemical stability.
  • a is an integer of 1 to 3.
  • a plurality of Y 5 s may be the same or different.
  • a plurality of R 30's may be the same or different.
  • a plurality of R 32's may be the same or different.
  • a plurality of R 31's may be the same or different.
  • the alkyl group represented by R 30 and R 31 may be linear or branched.
  • the number of carbon atoms of the alkyl group represented by R 30 is 1 to 20 because reforming proceeds rapidly. preferable.
  • the number of carbon atoms of the alkyl group represented by R 30 is more preferably 1 to 3, and even more preferably 1.
  • the alkyl group represented by R 30 preferably has 5 to 20 carbon atoms, and 8 to 20 carbon atoms. Is more preferable.
  • Y 5 is preferably an oxygen atom because reforming proceeds rapidly.
  • the number of carbon atoms of the alkyl group represented by R 30 and R 32 is preferably 1 to 20 each independently because reforming proceeds rapidly. Further, the number of carbon atoms of the alkyl group represented by R 30 and R 32 is more preferably independently 1 to 3, and further preferably 1.
  • the alkyl group represented by R 31 preferably has 1 to 5 carbon atoms and 1 to 2 carbon atoms. More preferably, it is more preferably 1.
  • alkyl group represented by R 30 , R 31 and R 32 include the alkyl groups exemplified in the groups represented by R 6 to R 9 .
  • the cycloalkyl group represented by R 30 , R 31 and R 32 preferably has 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 cycloalkyl group represented by R 30 , R 31 and R 32 When the hydrogen atoms in the cycloalkyl group represented by R 30 , R 31 and R 32 are each independently substituted with an alkyl group, the cycloalkyl group has 4 or more carbon atoms.
  • the alkyl group in which the hydrogen atom in the cycloalkyl group may be substituted has 1 to 27 carbon atoms.
  • cycloalkyl group represented by R 30 , R 31 and R 32 include the cycloalkyl groups exemplified in the groups represented by R 6 to R 9 .
  • the unsaturated hydrocarbon group represented by R 30 , R 31 and R 32 may be linear, branched, or cyclic.
  • the unsaturated hydrocarbon group represented by R 30 , R 31 and R 32 preferably has 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
  • the unsaturated hydrocarbon group represented by R 30 , R 31 and R 32 is preferably an alkenyl group, and more preferably an alkenyl group having 8 to 20 carbon atoms.
  • Examples of the alkenyl group represented by R 30 , R 31 and R 32 include linear or branched alkyl groups exemplified in the groups represented by R 6 to R 9 and having one carbon atom
  • An example is one in which a single bond (C—C) is replaced with a double bond (C ⁇ C).
  • the position of the double bond in the alkenyl group is not limited.
  • alkenyl group examples 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, 9 An octadecenyl group.
  • R 30 and R 32 are preferably an alkyl group or an unsaturated hydrocarbon group, and more preferably an alkyl group.
  • R 31 is preferably a hydrogen atom, an alkyl group, or an unsaturated hydrocarbon group, and more preferably an alkyl group.
  • the compound represented by the formula (C1) and the compound represented by the formula (C2) are hydrolyzed. It is liable to be modified and a modified product is easily generated. Therefore, the modified body of the compound represented by the formula (C1) and the modified body of the compound represented by the formula (C2) easily cover the surface of the semiconductor material (1). As a result, it is considered that even in a thermal environment, (1) a semiconductor material is less likely to deteriorate and a composition having high durability can be obtained.
  • Specific examples of the compound represented by the formula (C1) include tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrisilane.
  • trimethoxyphenylsilane methoxydimethyl (phenyl) silane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, cyclohexyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane.
  • the modified compound group may be a compound represented by the following formula (A5-51) or a compound represented by the following formula (A5-52).
  • a C represents a divalent hydrocarbon group
  • Y 15 represents an oxygen atom or a sulfur atom.
  • R 122 and R 123 each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
  • R 124 represents an alkyl group or a cycloalkyl group.
  • R 125 and R 126 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a cycloalkyl group.
  • R 122 to R 126 are alkyl groups, they may be linear or branched.
  • the alkyl group has usually 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.
  • the cycloalkyl group may have an alkyl group as a substituent.
  • the cycloalkyl group has usually 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 hydrogen atoms contained in the alkyl group and cycloalkyl group represented by R 122 to R 126 may be each independently substituted with a halogen atom or an amino group.
  • halogen atom which may be substituted for the hydrogen atom contained in the alkyl group and cycloalkyl group represented by R 122 to R 126 , include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a fluorine atom is preferable from the viewpoint of stability.
  • alkyl group of R 122 to R 126 include the alkyl groups exemplified in R 6 to R 9 .
  • cycloalkyl group of R 122 to R 126 include the cycloalkyl group exemplified in R 6 to R 9 .
  • Examples of the alkoxy group of R 125 and R 126 include monovalent groups in which the linear or branched alkyl group exemplified in R 6 to R 9 is bonded to an oxygen atom.
  • R 125 and R 126 are alkoxy groups, a methoxy group, an ethoxy group, a butoxy group and the like can be mentioned, and a methoxy group is preferable.
  • Divalent hydrocarbon group represented by A C may be any group obtained by removing two hydrogen atoms from the hydrocarbon compound, the hydrocarbon compound may be aliphatic hydrocarbons, aromatic It may be a hydrocarbon or a saturated aliphatic hydrocarbon.
  • A is an alkylene group, it may be linear or branched.
  • the alkylene group has usually 1 to 100 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • Examples of the compound represented by the formula (A5-51) include trimethoxy [3- (methylamino) propyl] silane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropyldiethoxymethylsilane. , 3-aminopropyltrimethoxysilane is preferred.
  • the compound represented by the formula (A5-51) is preferably a compound in which R 122 and 123 are hydrogen atoms, R 124 is an alkyl group, and R 125 and R 126 are alkoxy groups.
  • R 122 and 123 are hydrogen atoms
  • R 124 is an alkyl group
  • R 125 and R 126 are alkoxy groups.
  • 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are more preferable.
  • 3-aminopropyltrimethoxysilane is more preferable.
  • 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are more preferable.
  • the modified body group may be sodium silicate (Na 2 SiO 3 ).
  • the compounding ratio of (1) the semiconductor material and (2) the surface modifier may be such that (1) the semiconductor material exhibits a favorable light emitting action. It can be appropriately determined according to the type of constituent components and the like.
  • the molar ratio [(1) semiconductor material / (2) surface modifier] of (1) semiconductor material to (2) 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 (2) 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.
  • the compounding ratio of (1) the semiconductor material and (5) the modified body group may be such that (5) the modified body group exhibits the action of improving the durability. , (1) semiconductor material and (5) type of modified body group, etc.
  • the semiconductor material when (1) the semiconductor material is a perovskite compound, (1) the molar ratio of the metal ion that is the B component of the semiconductor material to (5) the Si element of the modified body group [Si / B] may be 0.001 to 2000 or 0.01 to 500.
  • the modified compound group is a silazane represented by the formula (B1) or (B2) and a modified compound thereof, and (1) the semiconductor material is a perovskite compound.
  • the molar ratio [Si / B] of the metal ion, which is the B component of the semiconductor material, and (5) the Si of the modified body group may be 1 to 1000, or 10 to 500. It may be 20 to 300.
  • the modified body group is polysilazane having the structure represented by the formula (B3), and (1) the semiconductor material is a perovskite compound, the (1) semiconductor material is The molar ratio [Si / B] between the metal ion that is the B component and the Si element in the modified body group (5) may be 0.001 to 2000, or 0.01 to 2000. , 0.1 to 1000, 1 to 500, or 2 to 300.
  • composition in which the compounding ratio of the (1) semiconductor material and the (5) modified body group is within the above range exhibits the effect of improving the durability of the (5) modified body group particularly well. It is preferable in that
  • the molar ratio [Si / B] between the metal ion, which is the B component of the perovskite compound, and the Si element of the modified product can be determined by the following method.
  • the substance amount (B) (unit: mol) of the metal ion that is the B component of the perovskite compound is measured by inductively coupled plasma mass spectrometry (ICP-MS) to measure the mass of the metal that is the B component, and the measured value is the substance amount. Converted to.
  • ICP-MS inductively coupled plasma mass spectrometry
  • the substance amount (Si) of the Si element of the reformer is calculated from the value obtained by converting the mass of the raw material compound of the reformer used into the substance amount and the Si amount (substance amount) contained in the unit mass of the raw material compound. .
  • the unit mass of the raw material compound is the molecular weight of the raw material compound if the raw material compound is a low molecular compound, and the molecular weight of the repeating unit of the raw material compound if the raw material compound is a high molecular compound.
  • the molar ratio [Si / B] can be calculated from the substance amount (Si) of the Si element and the substance amount (B) of the metal ion that is the B component of the perovskite compound.
  • 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 elements constituting the semiconductor material or a compound of 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.
  • 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, or may be added to the 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 X component may contain the B component.
  • 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 can be produced by mixing (1) a semiconductor material and (2) a surface modifier with one or both of (3) a solvent and (4) a polymerizable compound. it can.
  • the temperature at the time of mixing there is no particular limitation on the temperature at the time of mixing. Since the semiconductor material (1) and the surface modifier (2) are easily mixed uniformly, the temperature range is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 80 ° C.
  • the method for producing a composition containing (1) a semiconductor material, (2) a surface modifier and (3) a solvent may be, for example, the following production method (a1) or the following production method (a2). May be.
  • Manufacturing method (a1) A method for manufacturing a composition, which comprises: (1) mixing a semiconductor material with (3) a solvent; and (2) mixing the obtained mixture with a surface modifier.
  • Manufacturing method (a2) A method for manufacturing a composition including the steps of (1) mixing a semiconductor material with (2) a surface modifier, and mixing the resulting mixture with (3) a solvent.
  • the solvent (3) used in the production methods (a1) and (a2) is preferably one that does not easily dissolve the above-mentioned semiconductor material (1).
  • a solvent (3) is used, the mixture obtained by the production method (a1) and the composition obtained by the production methods (a1) and (a2) become a dispersion liquid.
  • the method for producing the composition may be the production method (a3) using the following (5A) or the production method (a4). May be.
  • the above (5A) is referred to as “(5A) raw material compound”.
  • the (5A) raw material compound becomes a (5) modified body group by performing a modification treatment.
  • the polymer (4-1) may be dissolved or dispersed in the solvent (3).
  • stirring is preferable from the viewpoint of improving dispersibility.
  • the temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0 ° C or higher and 100 ° C or lower, and in the range of 10 ° C or higher and 80 ° C or lower. Is more preferable.
  • the manufacturing method of the composition is preferably (1) the manufacturing method (a1) or the manufacturing method (a3) from the viewpoint of improving the dispersibility of the semiconductor material.
  • modification treatment method examples include known methods such as (5A) a method of irradiating the raw material compound with ultraviolet rays, and (5A) a method of reacting the raw material compound with water vapor.
  • 5A a method of irradiating the raw material compound with ultraviolet rays
  • 5A a method of reacting the raw material compound with water vapor.
  • the treatment of reacting the starting compound (5A) with water vapor may be referred to as “humidification treatment”.
  • the wavelength of ultraviolet rays used in the method of irradiating ultraviolet rays is usually 10 to 400 nm, preferably 10 to 350 nm, more preferably 100 to 180 nm.
  • Examples of the light source for generating ultraviolet rays include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV laser light.
  • the composition When the humidification treatment is performed, the composition may be left standing or stirred for a certain period of time under the temperature and humidity conditions described below.
  • the temperature in the humidification treatment may be a temperature at which reforming progresses sufficiently.
  • the temperature in the humidifying treatment is, for example, preferably 5 to 150 ° C., more preferably 10 to 100 ° C., and further preferably 15 to 80 ° C.
  • the humidity in the humidification treatment may be such that the (5A) raw material compound in the composition is sufficiently supplied with water.
  • the humidity in the humidifying treatment is, for example, preferably 30% to 100%, more preferably 40% to 95%, and further preferably 60% to 90%.
  • the above temperature means the relative humidity at the temperature at which the humidifying process is performed.
  • the time required for the humidification treatment may be any time that allows the reforming to proceed sufficiently.
  • the time required for the humidification treatment is, for example, preferably 10 minutes or more and 1 week or less, more preferably 1 hour or more and 5 days or less, and further preferably 2 hours or more and 3 days or less.
  • stirring is preferable.
  • Supply of water in the humidification treatment may be carried out by circulating a gas containing water vapor in the reaction container, or by stirring in an atmosphere containing water vapor, water may be supplied from the interface.
  • the durability of the resulting composition is improved, so that the flow rate of the gas containing water vapor is preferably 0.01 L / min or more and 100 L / min or less, and 0.1 L / min. 10 L / min or more is more preferable, 0.15 L / min or more and 5 L / min or more is more preferable.
  • the gas containing steam include nitrogen containing a saturated amount of steam.
  • the semiconductor material is a perovskite compound
  • the surface modifier is the same as the above-mentioned (1) semiconductor material. They may be mixed in any step included in the manufacturing method. For example, the following manufacturing method (a5) may be used, or the following manufacturing method (a6) may be used.
  • Production method (a5) First, a compound containing a B component, a compound containing an X component, a compound containing an A component, which constitutes a perovskite compound, (2) a surface modifier, and (5) a modified body group.
  • a manufacturing method including a step of dissolving in a solvent to obtain a solution and a step of mixing the obtained solution and a second solvent can be mentioned.
  • the first solvent and the second solvent are the same as the above-mentioned solvents.
  • the manufacturing method includes a step of dissolving the solution in a third solvent to obtain a solution, and a step of cooling the solution.
  • the third solvent is the same as the above-mentioned solvent.
  • Production method (c1) (4) a step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, the obtained dispersion, (2) a surface modifier, and (5) a group of modified products. And a mixing step.
  • Production method (c2) a step of dispersing (2) a surface modifier and (5) a group of modifiers in (4) a polymerizable compound to obtain a dispersion, the obtained dispersion and (1) a semiconductor material. And a step of mixing.
  • Production method (c3) A production method including a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modifiers in (4) a polymerizable compound.
  • the manufacturing method (c1) is preferable from the viewpoint of (1) enhancing dispersibility of the semiconductor material.
  • the polymerizable compound (4) in the step of obtaining each dispersion, may be added dropwise to each material, or each material may be added dropwise to the polymerizable compound (4).
  • a semiconductor material, (2) a surface modifier, and (5) a modified compound group is preferably added dropwise to (4) a polymerizable compound because it is easily dispersed uniformly.
  • the dispersion in each mixing step, may be dropped onto each material, or each material may be dropped onto the dispersion. At least one of (1) a semiconductor material, (2) a surface modifier, and (5) a modified body group is preferably added dropwise to the dispersion because it is easily dispersed uniformly.
  • At least one of the solvent (3) and the polymer (4-1) may be dissolved or dispersed in the polymerizable compound (4).
  • the solvent that dissolves or disperses the polymer is not particularly limited.
  • the solvent is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
  • Examples of the solvent in which the (4-1) polymer 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 composition of the present embodiment may be the following production method (c4) or production method (c5).
  • Production method (c4) (1) a step of dispersing a semiconductor material in a solvent (3) to obtain a dispersion liquid, and at least the polymerizable compound (4-1) and the polymer (4-1) in the obtained dispersion liquid.
  • a method for producing a composition comprising: a step of mixing one of them to obtain a mixed solution; and a step of mixing the obtained mixed solution, (2) a surface modifier, and (5) a group of modified bodies.
  • Production method (c5) (1) a step of dispersing a semiconductor material in a solvent to obtain a dispersion liquid, the obtained dispersion liquid, (2) a surface modifier and (5A) a raw material compound are mixed and mixed. A step of obtaining a liquid, a step of subjecting the obtained mixed solution to a modification treatment (5) to obtain a mixed solution containing a modified body group, and a step of mixing the obtained mixed solution with (3) a solvent.
  • a method for producing the composition having.
  • composition Manufacturing Method 2 a step of mixing (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a modified body group, 4) a step of polymerizing the polymerizable compound, and a production method including the step.
  • the composition obtained by the method 2 for producing a composition has a total of (1) a semiconductor material, (2) a surface modifier, (4-1) a polymer, and (5) a group of modified substances of 90% by mass of the entire composition. % Or more is preferable.
  • the method for producing the composition of the present embodiment includes (1) a semiconductor material, (2) a surface modifier, (3) a polymer (4-1) dissolved in a solvent, and (5).
  • a manufacturing method including a step of mixing the modified body group and a step of (3) removing the solvent can also be mentioned.
  • the same mixing method as the method shown in the above-mentioned production method 1 of the composition can be used.
  • Examples of the method for producing the composition include the following production methods (d1) to (d6).
  • Production method (d1) (4) a step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, the obtained dispersion, (2) a surface modifier, and (5) a group of modified products.
  • a production method comprising a step of mixing and a step (4) of polymerizing a polymerizable compound.
  • Production method (d3) a step of dispersing (2) a surface modifier and (5) a group of modifiers in a polymerizable compound (4) to obtain a dispersion, the obtained dispersion and (1) a semiconductor material. And a step of polymerizing the polymerizable compound (4).
  • Production method (d4) a step of dispersing (2) a surface modifier and (5) a group of modifiers in (3) a solvent in which (4-1) a polymer is dissolved to obtain a dispersion,
  • a manufacturing method comprising a step of mixing a dispersion and (1) a semiconductor material, and a step of removing a solvent.
  • Production method (d5) a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modified compounds in (4) a polymerizable compound, and (4) a polymerizable compound. And a step of polymerizing the method.
  • Production method (d6) a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modifiers in (3) a solvent in which (4-1) a polymer is dissolved And a step of removing the 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.
  • the drying may be performed under reduced pressure, or the step (3) of evaporating the solvent by heating may be performed.
  • the solvent (3) can be removed by, for example, drying at 0 ° C. or higher and 300 ° C. or lower for 1 minute or more and 7 days or less.
  • the step (4) of polymerizing the polymerizable compound included in the production methods (d1), (d3) and (d5) can be carried out by appropriately using a known polymerization reaction such as radical polymerization.
  • radical polymerization a radical polymerization initiator is added to a mixture of (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a modified group,
  • the polymerization reaction can be promoted by generating radicals.
  • 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 surface modifier, and (4-1) a polymer.
  • Production method (d9) a step of producing a liquid composition containing (1) a semiconductor material and (2) a surface modifier, a step of extracting solid matter from the obtained liquid composition, and the obtained solid matter And a step of melt-kneading (4-1) the polymer.
  • Production method (d10) (1) a step of producing a liquid composition containing a semiconductor material, (2) a surface modifier, and (5) a group of modified substances, and taking out a solid content from the obtained liquid composition.
  • a production method comprising the steps of: and a step of melt-kneading the obtained solid content and (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 surface modifier, (5A) a raw material compound, and (5) Refers to a group of modified substances.
  • the (5) modified product group added in the melt-kneading step of the production method (d11) can be obtained by modifying the starting compound (5A).
  • 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 method described above can be adopted for the step of performing the modification treatment of the manufacturing method (d8).
  • the above-mentioned production method (a1) or (a2) can be adopted in the step of producing the liquid composition of the production methods (d9) and (d11).
  • the above-mentioned production method (a3) or (a4) can be adopted in the step of producing the liquid composition of the production method (d10).
  • 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.
  • ⁇ Measurement method >> ⁇ Measurement of emission intensity >> The emission intensity of the composition of the present embodiment is measured using a fluorometer (trade name: FT-6500, manufactured by JASCO Corporation, excitation light 430 nm, sensitivity High).
  • the composition of the present embodiment is allowed to stand in a constant temperature and constant humidity chamber kept at a temperature of 65 ° C. and a humidity of 95%. Then, the composition is cut into a size of 1 cm ⁇ 1 cm ⁇ 100 ⁇ m to obtain a film of the composition.
  • the durability test is carried out by storing the obtained film at a temperature of 65 ° C and a humidity of 95% for 5 days.
  • the emission intensity of the film as the test piece is measured before and after the durability test.
  • the composition of the present embodiment may have a retention rate of 10% or more, 40% or more, or 45% or more in each of the above-described measurement methods. The higher the retention rate, the better the water resistance of the composition.
  • the Feret diameter as the distance between parallel lines when the image of the semiconductor material shown in the obtained electron micrograph is sandwiched by two parallel lines.
  • the arithmetic average value of the Feret diameters of 20 semiconductor materials is obtained, and the average Feret diameter is obtained.
  • composition having the above-mentioned constitution it is possible to provide a composition containing a light emitting semiconductor material having high durability against water vapor.
  • 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) a surface modifier, and (4-1) a polymer, and (1) a semiconductor material, (2) a surface modifier, and (4). -1)
  • the total amount of polymers 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 among 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 suitable light guide plate may be used, such as a light guide plate on which the like is 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 suitable 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, an n-type transport layer is laminated on one surface, and the other surface is laminated on the other surface. It has a structure in which p-type transport layers are laminated, and when a current is passed, holes of a p-type semiconductor and electrons of an n-type semiconductor are included in the composition of the junction surface. There is a method of emitting light by canceling.
  • 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 invention, 2, 2
  • FTO fluorine-doped tin oxide
  • TiO titanium oxide dense layer
  • porous aluminum oxide layer an active layer containing the composition of the present invention
  • a hole transport layer such as', 7,7'-tetrakis (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-MeOTAD) and a silver (Ag) electrode are provided in this order.
  • a solar cell is mentioned.
  • 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 for the step 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 (3) solvent in the production method (f1) may be the same step as the step of removing the (3) solvent included in the above-mentioned production methods (d2), (d4), and (d6). it can.
  • the step of polymerizing the (4) polymerizable compound in the production method (f3) is the same step as the step of polymerizing the (4) polymerizable compound included in the above-mentioned production methods (d1), (d3) and (d5).
  • 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.
  • the semiconductor material containing the above-mentioned (viii) perovskite compound was used as the (1) semiconductor material.
  • 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 obtained film was stored at a temperature of 65 ° C and a humidity of 95% for 5 days, and a durability test was conducted. With respect to the film as the test piece, the emission intensity before and after the durability test was measured.
  • 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 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.
  • 1H, 1H-undecafluorohexylamine (specific gravity: 1.64 g / mL) was mixed with the above dispersion liquid.
  • 1H, 1H-undecafluorohexylamine corresponds to “(2) compound or ion having fluoroalkyl group” in the present invention.
  • the molar ratio of 1H, 1H-undecafluorohexylamine and Pb was determined by the amount of 1H, 1H-undecafluorohexylamine charged (amount of substance, unit: mol) and ICP-MS as described above. The amount of Pb (amount of substance, unit: mol) was calculated.
  • 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, it was baked at 65 ° C and 95% humidity for 2 days.
  • a film of a composition having a perovskite compound concentration of 500 ⁇ g / mL was obtained.
  • the film of the composition was cut into a size of 1 cm ⁇ 1 cm.
  • the light emission intensity of the film of the obtained composition was evaluated to be 31.3. Further, the maintenance factor of the emission intensity measured under the above conditions was 44%.
  • Example 2 A composition was synthesized in the same manner as in Example 1 except that the amount of 1H, 1H-undecafluorohexylamine added was 30 ⁇ L, and a film of the composition was obtained.
  • the luminescence intensity of the film of the obtained composition was evaluated to be 31.5. Further, the maintenance factor of the emission intensity measured under the above conditions was 39.4%.
  • Example 3 A composition was synthesized in the same manner as in Example 1 except that the addition amount of 1H, 1H-undecafluorohexylamine was 50 ⁇ L, and a film of the composition was obtained.
  • the light emission intensity of the film of the obtained composition was evaluated to be 25.9. Further, the maintenance factor of the emission intensity measured under the above conditions was 47.3%.
  • Example 1 A composition was synthesized in the same manner as in Example 1 except that 1H, 1H-undecafluorohexylamine was not used to obtain a film of the composition.
  • the light emission intensity of the film of the obtained composition was evaluated, it was 1.6. Further, the maintenance factor of the emission intensity measured under the above conditions was 0%.
  • 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.
  • hole transport such as 2,2 ′, 7,7′-tetrakis- (N, N′-di-p-methoxyphenylamine) -9,9′-spirobifluorene (Spiro-OMeTAD) is carried out from above.
  • a layer is laminated
  • composition of the present invention can be obtained by removing the solvent of the composition described in Examples 1 to 3 and molding, and by placing this composition in the subsequent stage of the blue light emitting diode, the composition from 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.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Electroluminescent Light Sources (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention concerne une composition comprenant le composant (1) et le composant (2). Composant (1) : Un matériau semi-conducteur électroluminescent. Composant (2) : Un composé ou un ion ayant un groupe fluoroalkyle (cependant, à l'exclusion de composés de silicium ayant un groupe fluoroalkyle, d'alcools ayant un groupe fluoroalkyle, et d'hydrocarbures contenant du fluor).
PCT/JP2019/041474 2018-10-26 2019-10-23 Composition, film, structure stratifiée, dispositif électroluminescent et dispositif d'affichage Ceased WO2020085364A1 (fr)

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CN115594413B (zh) * 2022-10-21 2023-12-29 榆林学院 一种钠掺杂二维钙钛矿薄膜的制备方法

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