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WO2018139446A1 - Appareil de production de nanoparticules semi-conductrices et procédé de production de nanoparticules semi-conductrices - Google Patents

Appareil de production de nanoparticules semi-conductrices et procédé de production de nanoparticules semi-conductrices Download PDF

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Publication number
WO2018139446A1
WO2018139446A1 PCT/JP2018/001977 JP2018001977W WO2018139446A1 WO 2018139446 A1 WO2018139446 A1 WO 2018139446A1 JP 2018001977 W JP2018001977 W JP 2018001977W WO 2018139446 A1 WO2018139446 A1 WO 2018139446A1
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Prior art keywords
liquid
group
semiconductor nanoparticle
reactor
manufacturing apparatus
Prior art date
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PCT/JP2018/001977
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English (en)
Japanese (ja)
Inventor
佐野　泰三
昭弘 脇坂
勝利 小須田
正彦 平谷
勇介 馬渕
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National Institute of Advanced Industrial Science and Technology AIST
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
National Institute of Advanced Industrial Science and Technology AIST
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Priority to JP2018564579A priority Critical patent/JPWO2018139446A1/ja
Publication of WO2018139446A1 publication Critical patent/WO2018139446A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/04—Binary compounds including binary selenium-tellurium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • 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
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • 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
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • 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
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions

Definitions

  • the present invention relates to a semiconductor nanoparticle manufacturing apparatus and a semiconductor nanoparticle manufacturing method.
  • Semiconductor nanoparticles such as semiconductor quantum dots have excellent fluorescence characteristics and are being applied to displays, lighting, biosensing, and the like. Research on semiconductor quantum dots is also underway as a material that improves the efficiency of solar cells.
  • a semiconductor quantum dot containing a group 12 element or group 13 element and a group 15 element or group 16 element may be an excellent fluorescent material.
  • Examples of such a semiconductor quantum dot include cadmium selenide. (CdSe) and indium phosphide (InP). Since the fluorescence wavelength of the semiconductor quantum dots changes depending on the particle diameter, the fluorescence wavelength can be controlled by controlling the particle diameter. Therefore, a semiconductor quantum dot manufacturing apparatus and manufacturing method that can be controlled to an arbitrary particle size are required.
  • a solvothermal method has been proposed as a method for manufacturing semiconductor quantum dots.
  • a semiconductor quantum dot is synthesized by mixing a metal ion precursor and an anion precursor in a coordinating organic solvent and heating.
  • indium chloride, trisdimethylaminophosphine, dodecylamine, and toluene are put in a sealed container, sealed with argon, and heated at 180 ° C. for 24 hours while being protected with a stainless steel jacket.
  • Is a method for producing indium phosphide see, for example, Patent Document 1). In this method, indium phosphide having a wide particle size distribution is obtained, and the fluorescence spectrum also shows a wide shape.
  • the fluorescence peak wavelength of indium phosphide obtained by the solvothermal method is, for example, about 620 nm to 640 nm, and the production efficiency of indium phosphide having a short fluorescence wavelength (eg, 570 nm or less, preferably 550 nm or less) is very high.
  • the production efficiency of indium phosphide having a short fluorescence wavelength is very high.
  • semiconductor nanoparticles are produced by the solvothermal method, it is difficult to control the particle diameter of the semiconductor nanoparticles so that the fluorescence wavelength becomes a short wavelength. Therefore, as an example, in order to efficiently manufacture semiconductor nanoparticles having a short fluorescent wavelength, semiconductor nanoparticle manufacturing apparatuses and semiconductor nanoparticles that can efficiently manufacture semiconductor nanoparticles with a controlled particle diameter are provided. A manufacturing method is desired.
  • An object of one embodiment of the present invention is to provide a semiconductor nanoparticle manufacturing apparatus and a semiconductor nanoparticle manufacturing method capable of efficiently manufacturing semiconductor nanoparticles with a controlled particle size.
  • the means for solving the above problems include the following embodiments.
  • Nanoparticle production equipment for spraying one of a liquid (1) containing at least one of a group 12 element and a group 13 element or a liquid (2) containing at least one of a group 15 element and a group 16 element; and the liquid (1) And the other liquid (not sprayed) of the liquid (2) is supplied, and the droplet sprayed by the spraying unit comes into contact with the other liquid, and the liquid (1) and the liquid (2) And a reactor that reacts at least one
  • a spray unit that sprays a liquid (3) containing at least one of group 12 element and group 13 element and at least one of group 15 element and group 16 element, and liquid (4) are supplied, and sprayed by the spray unit
  • the liquid droplet contacts the liquid (4), and the liquid (3) and the liquid (4) are mixed to at least one of the group 12 element and the group 13 element contained in the liquid (3) and the group 15
  • a reactor for reacting at least one of an element and a group 16 element.
  • ⁇ 4> At least a part of the spray unit, or at a position where the first electrode attached to at least a part of the spray unit is in contact with the liquid when the liquid is supplied to the reactor.
  • the semiconductor nanoparticle manufacturing apparatus according to ⁇ 3> further comprising: a second electrode that is arranged; and a potential difference forming unit that forms a potential difference between the first electrode and the second electrode.
  • the second electrode is a ring-shaped, cylindrical, mesh-shaped, rod-shaped, spherical, hemispherical, or plate-shaped conductor.
  • ⁇ 6> The semiconductor nanoparticle manufacturing apparatus according to ⁇ 4> or ⁇ 5>, wherein the potential difference forming unit forms a potential difference of 0.3 kV to 30 kV in absolute value.
  • ⁇ 7> The semiconductor nanoparticle manufacturing apparatus according to any one of ⁇ 1> to ⁇ 6>, wherein a diameter of a droplet sprayed from the spraying unit is 0.1 ⁇ m to 100 ⁇ m.
  • ⁇ 8> The semiconductor nanoparticle manufacturing apparatus according to any one of ⁇ 1> to ⁇ 7>, wherein an inner diameter of the spraying part is 0.01 mm to 1 mm.
  • ⁇ 9> The semiconductor according to any one of ⁇ 1> to ⁇ 8>, wherein a liquid feeding speed of the sprayed liquid from the spraying unit is 0.001 mL / min to 1 mL / min per one spraying unit.
  • Nanoparticle production equipment ⁇ 10> The semiconductor nanoparticle production apparatus according to any one of ⁇ 1> to ⁇ 9>, further comprising a heating unit that heats the reactor.
  • the heating unit is a thermal fluid, a solid heat medium, or a heating wire.
  • the semiconductor nanoparticle production apparatus according to any one of ⁇ 1> to ⁇ 11>, further comprising an inert gas supply unit that supplies an inert gas into the reactor.
  • a material supply unit that supplies the reactor with a material that forms a layer that covers at least a part of the core particles and the surface of the core particles produced in the reactor, and the reactor supplies the material.
  • the semiconductor nanoparticle manufacturing apparatus according to any one of ⁇ 1> to ⁇ 12>, wherein a layer covering at least a part of the surface of the core particle is formed.
  • ⁇ 14> A forming device for supplying a core particle produced in the reactor and a material for forming a layer covering at least a part of the surface of the core particle to form a layer covering at least a part of the surface of the core particle.
  • numerical ranges indicated using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the configuration of the embodiment is not limited to the configuration shown in the drawings.
  • size of the member in each figure is notional, The relative relationship of the magnitude
  • the semiconductor nanoparticle manufacturing apparatus 100 includes a liquid (1) including at least one of a group 12 element and a group 13 element (hereinafter also referred to as “liquid (1)”) or at least one of a group 15 element and a group 16 element.
  • a nozzle 1 spraying part for spraying one of the liquids (2) (hereinafter also referred to as “liquid (2)”) and the other liquid not sprayed of the liquids (1) and (2).
  • the liquid droplets supplied and sprayed by the nozzle 1 come into contact with the other liquid, and the liquid (1) and the liquid (2) are mixed to at least one of the group 12 element and the group 13 element contained in the liquid (1).
  • a reactor 6 for reacting at least one of the group 15 element and the group 16 element contained in the liquid (2).
  • the semiconductor nanoparticle manufacturing apparatus 100 includes an inert gas supply pipe 21 (inert gas supply unit) that supplies an inert gas into the reactor 6. Moreover, the semiconductor nanoparticle manufacturing apparatus 100 is provided with a counter electrode 4 that functions as a second electrode and a counter electrode 4 that functions as a second electrode in a reactor 6 together with a nozzle 1 that is metal-plated on the outer peripheral portion. And a power source 5 (potential difference forming unit) for forming a potential difference between the two.
  • the nozzle 1 may be a metal-plated glass thin tube, a stainless steel hollow needle, a stainless steel tube, or the like.
  • the nozzle 1 may be a nozzle provided with an internal electrode functioning as a first electrode in a flow path made of a non-conductive material.
  • the semiconductor nanoparticle manufacturing apparatus 100 includes a thermal fluid 8 (heating unit) that heats the reactor 6.
  • the semiconductor nanoparticle manufacturing apparatus 100 includes a cooling pipe 7 that cools the volatilized components in the reactor 6 and returns them to the reaction field.
  • one of the liquid (1) containing at least one of the group 12 element and the group 13 element or the liquid (2) containing at least one of the group 15 element and the group 16 element is used as the reactor 6. And the sprayed droplets are brought into contact with the other liquid (1) and the liquid (2) which are not sprayed. When both liquids are brought into contact and mixed, at least one of the Group 12 element and Group 13 element contained in the liquid (1) reacts with at least one of the Group 15 element and Group 16 element contained in the liquid (2). Thus, semiconductor nanoparticles are manufactured.
  • the semiconductor nanoparticles are produced by bringing the sprayed droplets, which are one of the liquid (1) and the liquid (2), into contact with the other liquid, the produced semiconductor nanoparticles are compared with the solvothermal method. Control of the particle diameter of the particles is easy, and semiconductor nanoparticles with controlled particle diameter can be efficiently produced.
  • the control of the particle diameter of the manufactured semiconductor nanoparticles is easy, the control of the fluorescence wavelength of the manufactured semiconductor nanoparticles (particularly, the control of the fluorescence wavelength on the short wavelength side) tends to be easy. Therefore, for example, semiconductor nanoparticles having a long fluorescence peak wavelength to a short wavelength can be efficiently produced, and semiconductor nanoparticles having a desired fluorescence peak wavelength tend to be efficiently produced. In addition, for example, semiconductor nanoparticles having a short fluorescent wavelength (for example, 570 nm or less, preferably 550 nm or less) tend to be efficiently produced.
  • semiconductor nanoparticles mean particles having an average particle diameter of 1 nm to 100 nm.
  • the average particle diameter of the semiconductor nanoparticles is the particle diameter (D50) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution measured by the laser diffraction method.
  • the shape of the “semiconductor nanoparticle” is not particularly limited, and may be spherical, oval, flake, rectangular parallelepiped, columnar, irregular, etc., spherical, oval, flake, rectangular A part of the shape, columnar shape or the like may be an irregular shape.
  • the “semiconductor nanoparticles” may include at least one of a group 12 element and a group 13 element and at least one of a group 15 element and a group 16 element.
  • a dispersant other organic solvent
  • a compound containing at least one of group 12 element and group 13 element, a compound containing at least one of group 15 element and group 16 element, etc. May be mixed with atoms and molecules.
  • the liquid (1) containing at least one of the group 12 element and the group 13 element used in the semiconductor nanoparticle manufacturing apparatus 100 may be a liquid containing a component containing at least one of the group 12 element and the group 13 element.
  • the component containing at least one of the group 12 element and the group 13 element include a group 12 metal, a group 13 metal, a group 12 metal compound, a group 13 metal compound, a compound containing a group 12 metal and a group 13 metal, and the like.
  • group 12 element examples include group 12 metals such as zinc (Zn), cadmium (Cd), mercury (Hg), etc. Among them, zinc (Zn) and cadmium (Cd) are preferable.
  • group 13 element examples include group 13 metals such as aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), among which indium (In) is preferable.
  • the group 12 metal compound is not particularly limited as long as it contains a group 12 metal.
  • Halides such as chloride, bromide, iodide, etc., oxides, nitrides, sulfides, hydroxides, including group 12 metals. Products, organic salts such as acetates, and organic complexes.
  • a halide containing a group 12 metal is preferable, and indium chloride is more preferable because it is highly reactive with a phosphorus compound (for example, trisdimethylaminophosphine).
  • examples of the cadmium compound that is a Group 12 metal compound include cadmium halides such as cadmium chloride, cadmium bromide, and cadmium iodide, cadmium oxide, cadmium hydroxide, cadmium acetate, and cadmium acetylacetonate.
  • cadmium oxide is preferable because it is relatively stable, has a low hygroscopicity as compared with cadmium halide, and is easy to handle.
  • the group 13 metal compound is not particularly limited as long as it contains a group 13 metal, and includes halides such as chloride, bromide, iodide, etc., oxides, nitrides, sulfides, hydroxides, including group 13 metals. Products, alkoxides and the like.
  • examples of indium compounds that are Group 13 metal compounds include indium halides such as indium chloride, indium bromide, and indium iodide, indium oxide, indium nitride, indium sulfide, indium hydroxide, indium acetate, and indium.
  • examples thereof include isopropoxide, and among them, indium chloride is preferable because it is highly reactive with a phosphorus compound (for example, trisdimethylaminophosphine) and has a relatively low market price.
  • the liquid (1) preferably contains a dispersant from the viewpoint of suppressing aggregation of a component containing at least one of the group 12 element and the group 13 element in the liquid.
  • a dispersant a coordinating organic solvent is preferable.
  • organic amines such as dodecylamine, tetradecylamine, hexadecylamine, oleylamine, trioctylamine, eicosylamine, lauric acid, capron Acids, myristic acid, palmitic acid, fatty acids such as oleic acid, and organic phosphine oxides such as trioctyl phosphine oxide, among others, have excellent reactivity with phosphorus compounds and promote the generation of indium phosphide.
  • oleylamine is preferred because it has a high boiling point and is difficult to volatilize during high-temperature synthesis.
  • oleic acid is preferable from the viewpoint of high solubility of cadmium oxide.
  • the total content of components containing at least one of group 12 elements and group 13 elements with respect to 1 mL of the dispersant is preferably 0.01 g to 0.2 g.
  • the amount is more preferably 03 g to 0.15 g, and further preferably 0.04 g to 0.10 g.
  • Liquid (1) may contain other organic solvents.
  • Other organic solvents include aliphatic saturated hydrocarbons such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-hexadecane, n-octadecane, 1-undecene, Examples thereof include aliphatic unsaturated hydrocarbons such as 1-dodecene, 1-hexadecene and 1-octadecene, and trioctylphosphine.
  • the liquid (2) containing at least one of the group 15 element and the group 16 element used in the semiconductor nanoparticle manufacturing apparatus 100 may be a liquid containing a component containing at least one of the group 15 element and the group 16 element.
  • the component containing at least one of group 15 element and group 16 element include group 15 element simple substance, group 15 element compound, group 16 element simple substance, group 16 element compound, compound containing group 15 element and group 16 element, and the like. .
  • Examples of the group 15 element include nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), etc. Among them, phosphorus (P) is preferable.
  • Examples of the group 16 element include oxygen (O), sulfur (S), selenium (Se), tellurium (Te), polonium (Po), etc. Among them, sulfur (S) and selenium (Se) are preferable.
  • Examples of the group 15 element compound include compounds containing phosphorus, specifically, trisdimethylaminophosphine, trisdiethylaminophosphine, tristrimethylsilylphosphine, phosphine (PH 3 ) and the like.
  • Trisdimethylaminophosphine is preferred because it is highly reactive, has a high boiling point and is suitable for high-temperature synthesis, and has low toxicity compared to silyl-based phosphorus compounds.
  • group 16 element compounds include compounds containing sulfur or selenium, and specific examples include dodecanethiol, selenurea, diethyl selenide, diphenyl selenide, dimethyl selenide, selenium chloride, and benzene selenol.
  • the liquid (2) used in the semiconductor nanoparticle manufacturing apparatus 100 is obtained by dissolving a solid component in a dispersant, other organic solvent or the like when the component containing at least one of the group 15 element and the group 16 element is a solid. It may be.
  • the liquid (2) may be a liquid component alone or a mixture of a liquid component with a dispersant, other organic solvent, etc., when the component containing at least one of the group 15 element and the group 16 element is a liquid. Good.
  • the dispersant examples include those used in the liquid (1) described above.
  • the liquid (2) may contain the above-mentioned other organic solvent like the above-mentioned liquid (1).
  • the semiconductor nanoparticle manufacturing apparatus 100 At least one of the group 12 element and the group 13 element contained in the liquid (1) reacts with at least one of the group 15 element and the group 16 element contained in the liquid (2), and the semiconductor nanoparticle is reacted. Particles are produced. Therefore, the semiconductor nanoparticles manufactured using the semiconductor nanoparticle manufacturing apparatus 100 are particles that include at least one of a group 12 element and a group 13 element and at least one of a group 15 element and a group 16 element. It is not limited.
  • CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, InN, InP, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb and the like can be mentioned, among which CdSe and InP are preferable.
  • the nozzle 1 is a spraying part that is disposed inside the reactor 6 and sprays one of the liquid (1) and the liquid (2).
  • the nozzle 1 is connected to a sprayed liquid supply source 2 via a supply pipe 3. Therefore, the liquid to be sprayed is supplied from the supply source 2 to the nozzle 1 through the supply pipe 3, and the liquid is sprayed from the spray port 1 a of the nozzle 1.
  • the nozzle 1 is metal-plated at the outer peripheral portion and functions as a first electrode.
  • the 1st electrode may comprise at least one part of the nozzle 1 which is a spraying part, or may be attached to at least one part of the nozzle 1.
  • the nozzle 1 may be a metal-plated glass thin tube, a stainless steel hollow needle, a stainless steel tube, or the like. Further, the nozzle 1 may be a nozzle provided with an internal electrode functioning as a first electrode in a flow path made of a non-conductive material.
  • a counter electrode 4 as a second electrode is disposed at a distance from the nozzle 1.
  • the spray port 1a of the nozzle 1 is preferably disposed so as to face a part of the counter electrode 4, and the spray port 1a of the nozzle 1 sprays liquid in a direction intersecting the plane of the counter electrode 4. It is more preferable that they are arranged as described above.
  • the counter electrode 4 may be disposed in contact with the bottom portion in the reactor 6 or may be disposed away from the bottom portion in the reactor 6.
  • Examples of the shape of the counter electrode 4 include a ring shape, a cylindrical shape, a mesh shape, a rod shape, a spherical shape, a hemispherical shape, and a plate shape.
  • the shape of the counter electrode 4 is a ring shape or a cylindrical shape, the counter electrode 4 may be disposed along the circumferential direction of the reactor 6.
  • the semiconductor nanoparticle manufacturing apparatus 100 includes a power source 5 that forms a potential difference between the nozzle 1 and the counter electrode 4.
  • the power source 5 is preferably a high voltage power source.
  • the power source 5 may be configured such that the nozzle 1 has a positive potential and the counter electrode 4 has a lower potential than the nozzle 1, the nozzle 1 has a negative potential, and the counter electrode 4 has a higher potential than the nozzle 1. You may be comprised so that it may become an electric potential.
  • the semiconductor nanoparticle production apparatus 100 can perform spraying of at least one of the liquid (1) and the liquid (2) by electrospray, and can suitably control the particle diameter of the semiconductor nanoparticles, There is a tendency that semiconductor nanoparticles having a desired fluorescence peak wavelength can be produced more efficiently.
  • electrospray refers to a device that forms an electric field by applying a voltage between electrodes and sprays the liquid by Coulomb force, or a state in which the liquid is sprayed by the device.
  • the counter electrode 4 is disposed at a position away from the spray port 1 a of the nozzle 1 by W1 + W2.
  • W1 is the distance between the liquid level of the stored liquid and the spray port 1a of the nozzle 1 when the other liquid of the liquid (1) and the liquid (2) that is not sprayed is stored in the reactor 6.
  • W2 represents the distance between the counter electrode 4 and the liquid level of the liquid stored when the other liquid (1) and liquid (2) that are not sprayed are stored in the reactor 6. .
  • the distance W1 + W2 between the spray port 1a of the nozzle 1 and the counter electrode 4 affects the electric field strength, the diameter and shape of the droplet generated by electrospray, and is preferably adjusted as appropriate.
  • the distance W1 + W2 between the spray port 1a of the nozzle 1 and the counter electrode 4 is preferably, for example, 3 mm to 300 mm, more preferably 10 mm to 250 mm, and further preferably 15 mm to 200 mm.
  • the distance W1 is preferably 2 mm to 100 mm, more preferably 5 mm to 70 mm, and still more preferably 10 mm to 50 mm, from the viewpoint of suppressing fluctuation of the shape of the sprayed droplets.
  • the inner diameter of the nozzle 1 is preferably 0.01 mm to 1 mm, more preferably 0.1 mm to 0.8 mm from the viewpoint of more efficiently producing semiconductor nanoparticles having a short fluorescent wavelength. More preferably, it is 0.3 to 0.7 mm.
  • the diameter of the droplet sprayed from the nozzle 1 is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, from the viewpoint of more efficiently producing semiconductor nanoparticles having a short fluorescent wavelength. More preferably, it is 1 ⁇ m to 10 ⁇ m.
  • the temperature change of the reaction field is small, and the particle diameter of the semiconductor nanoparticles can be controlled more appropriately.
  • semiconductor nanoparticles having a short fluorescence wavelength tend to be produced more efficiently. It is in.
  • the diameter of the droplet to be sprayed within the above-mentioned numerical range, the droplet to be sprayed is rapidly mixed when it comes into contact with the other liquid not sprayed. Therefore, the reaction time between at least one of the group 12 element and group 13 element contained in the liquid (1) and at least one of the group 15 element and group 16 element contained in the liquid (2) is shortened, and the particle size can be reduced in a short time. Controlled semiconductor nanoparticles can be produced.
  • the diameter of the droplet to be sprayed is adjusted by, for example, adjusting the nozzle diameter, adjusting the liquid feeding speed, surface tension, viscosity, ionic strength and relative dielectric constant of the liquid to be sprayed, or spraying by electrospray.
  • the liquid feeding speed of the liquid sprayed from the nozzle 1 is preferably 0.001 mL / min to 1 mL / min, more preferably 0.01 mL / min to 0.1 mL / min, and 0.02 mL / min. More preferably, it is from min to 0.05 mL / min.
  • the liquid feeding speed in the nozzle satisfies the above numerical range.
  • the liquid feeding speeds of the plurality of nozzles all satisfy the above-described numerical range.
  • the group 12 elements and 13 in the liquid containing at least one of the group 12 elements and the group 13 elements and at least one of the group 15 elements and the group 16 elements in the reactor 6 From the source 2 to the nozzle 1 so that the molar ratio (A: B) of A which is at least one of group elements and B which is at least one of group 15 elements and group 16 elements becomes a predetermined numerical value. It is preferable to adjust the supply of liquid and the spraying of droplets from the nozzle 1.
  • the above-mentioned A: B is preferably 1: 1 to 1:16 from the viewpoint of more efficiently producing semiconductor nanoparticles having a short fluorescent wavelength, and semiconductor nanoparticles having a narrow particle size distribution are preferably used. From the viewpoint of efficient production, it is more preferably more than 1: 2 and less than 1: 8, more preferably 1: 3 to 1: 7, and particularly preferably 1: 4 to 1: 6. .
  • the inert gas supply pipe 21 is an inert gas supply unit that supplies an inert gas into the reactor 6.
  • the semiconductor nanoparticle manufacturing apparatus 100 at least one of the liquid (1) and the liquid (2) is sprayed in an inert gas, and the sprayed liquid droplets are sprayed from the liquid (1) and the liquid (2). Contact the other liquid that is not. Thereby, mixing of oxygen, water vapor or the like into the manufactured semiconductor nanoparticles is suppressed, defects of the semiconductor nanoparticles tend to be suppressed, and a decrease in fluorescence efficiency of the semiconductor nanoparticles tends to be suppressed.
  • the inert gas include nitrogen, argon, carbon dioxide, sulfur hexafluoride (SF 6 ), and a mixed gas thereof.
  • the tip of the inert gas supply pipe 21 may be disposed in the other liquid.
  • the droplet sprayed on the other liquid it is preferable to stop the supply of the inert gas into the reactor 6 from the viewpoint of suppressing a decrease in the production efficiency of the semiconductor nanoparticles.
  • tube 21 and the nozzle 1 separately may be sufficient, for example.
  • the power source 5 preferably forms a potential difference of 0.3 kV to 30 kV in absolute value between the nozzle 1 and the counter electrode 4, and more preferably forms a potential difference of 1.0 kV to 10 kV.
  • the power source 5 has an absolute value of 2.0 kV from the viewpoint of more efficiently producing semiconductor nanoparticles having a short fluorescence wavelength, particularly more efficiently producing semiconductor nanoparticles having a fluorescence wavelength of 500 nm to 550 nm. It is preferable to form a potential difference of ⁇ 8.0 kV.
  • the power source 5 preferably forms a potential difference of more than 4.0 kV and less than 8.0 kV in absolute value, and 5.0 kV to 7.k in absolute value. It is more preferable to form a potential difference of 0 kV.
  • the potential on the nozzle 1 side is preferably -30 kV to 30 kV, and the potential on the counter electrode 4 side is preferably -30 kV to 30 kV.
  • a voltage is applied to the nozzle 1 and the counter electrode 4 by the power source 5, and the micro droplet L 1 is sprayed from the spray port 1 a of the nozzle 1 in a state where an electrostatic field is formed between the nozzle 1 and the counter electrode 4.
  • the micro droplet L1 moves toward the liquid L2 along the electric field gradient in a charged state, and comes into contact with the liquid surface of the liquid L2.
  • the manufactured semiconductor nanoparticles are dispersed in the liquid L2 to obtain a semiconductor nanoparticle dispersion. For example, after adding toluene to the dispersion liquid taken out from the reactor 6, methanol was gradually added, and the semiconductor nanoparticles produced were separated by centrifuging the precipitated suspended solids. Semiconductor nanoparticles may be collected.
  • the thermal fluid 8 is a heating unit that heats the reactor 6. By heating the reactor 6 when manufacturing semiconductor nanoparticles, semiconductor nanoparticles tend to be manufactured more efficiently.
  • the heating temperature of the reactor 6 is not particularly limited, and is preferably 80 ° C. to 350 ° C. From the viewpoint of more efficiently producing semiconductor nanoparticles having a short fluorescence wavelength, the heating temperature is 100 ° C. to 220 ° C. More preferably, it is 120 ° C. to 190 ° C.
  • the heating unit includes a thermal fluid, a solid heat medium, a heating wire, and the like, and more specifically, an oil bath, an aluminum bath, a mantle heater, an electric furnace, an infrared furnace, and the like.
  • the semiconductor nanoparticle production apparatus of the present disclosure may further include a stirring unit that stirs the liquid stored in the reactor 6.
  • the inert gas supply part in the semiconductor nanoparticle manufacturing apparatus of this indication may further be equipped with the decompression means which decompresses the inside of a reactor.
  • FIG. 2 shows a semiconductor nanoparticle manufacturing apparatus 200 that is Modification 1 of the semiconductor nanoparticle manufacturing apparatus 100 of the first embodiment.
  • the semiconductor nanoparticle manufacturing apparatus 200 includes a stirrer 11 and a magnetic stirrer 12 as a stirring unit for stirring the liquid stored in the reactor 6.
  • the semiconductor nanoparticle manufacturing apparatus 200 includes a vacuum pump 13 as a decompression unit, and the valve 10 can switch between decompression in the reactor 6 and supply of inert gas into the reactor 6.
  • the spraying when spraying is performed by electrospraying, the spraying is not limited to a configuration in which a potential difference is applied between the nozzle 1 and the counter electrode 4, and the intermediate electrode 9 having a ring shape or the like is connected to the nozzle 1. It may be configured so as to be installed between the counter electrode 4 and give a potential difference to the intermediate electrode 9 and the counter electrode 4 at the bottom of the container.
  • the semiconductor nanoparticle manufacturing apparatus of the present disclosure includes a liquid (3) including at least one of a group 12 element and a group 13 element and at least one of a group 15 element and a group 16 element (hereinafter, also referred to as “liquid (3)”).
  • the liquid (4) is supplied, the droplet sprayed by the spraying unit comes into contact with the liquid (4), the liquid (3) and the liquid (4) are mixed, and the liquid (3) And a reactor that reacts at least one of the group 12 element and the group 13 element and at least one of the group 15 element and the group 16 element contained in the reactor.
  • the liquid sprayed from the spray section includes at least one of Group 12 element and Group 13 element and at least one of Group 15 element and Group 16 element. This is different from the semiconductor nanoparticle manufacturing apparatus 100 of the first embodiment. Also in this modification, semiconductor nanoparticles with a controlled particle diameter can be efficiently produced. Below, it demonstrates centering on the matter which is different from the above-mentioned 1st Embodiment, and abbreviate
  • the liquid (3) preferably contains the above-mentioned dispersant from the viewpoint of suppressing aggregation of a component containing at least one of the group 12 element and the group 13 element in the liquid.
  • the total content of the component containing at least one of the group 12 element and the group 13 element and the component containing at least one of the group 15 element and the group 16 element with respect to 1 mL of the dispersant is 0. It is preferably 0.01 to 0.2 g, more preferably 0.03 to 0.15 g, and still more preferably 0.04 to 0.10 g.
  • Liquid (4) is not particularly limited, and may include the above-described dispersant, other organic solvents, and the like.
  • the semiconductor nanoparticle manufacturing apparatus of the present disclosure includes a core particle including at least one of a group 12 element and a group 13 element and at least one of a group 15 element and a group 16 element, and a layer (shell) covering at least a part of the surface of the core particle.
  • the apparatus which manufactures the semiconductor nanoparticle which has a layer) may be sufficient.
  • Semiconductor nanoparticles having a core-shell structure tend to have higher quantum efficiency and a narrower particle size distribution.
  • the core particles correspond to the semiconductor nanoparticles produced in the first embodiment described above.
  • the shell layer formed on at least a part of the surface of the core particle may have a single layer structure or a multilayer structure (core multishell structure).
  • the semiconductor nanoparticle production apparatus of the present disclosure further includes a material supply unit that supplies a material for forming a layer covering at least a part of the surface of the core particle to the reactor in terms of producing semiconductor nanoparticles having a core-shell structure, You may form the layer which covers at least one part of the core particle surface with a reactor.
  • a material (1) containing at least one of a group 12 element and a group 13 element (hereinafter also referred to as “material (1)”), and a group 15 are used.
  • the combination with the material (2) (henceforth "material (2)") containing at least one of an element and a group 16 element is mentioned.
  • Specific examples of at least one of the group 12 element and the group 13 element contained in the material (1) and at least one of the group 15 element and the group 16 element contained in the material (2) are the same as those described above.
  • the material supply unit may be configured to supply the material (1) and the material (2) to the reactor, for example.
  • the material (1) and the material (2) it is possible to select the material (1) and the material (2) so that the band gap of the compound constituting the shell layer is wider than the band gap of the compound constituting the core particle.
  • core particles and shell layers core particles / shell layers
  • the method for forming the shell layer on at least a part of the core particle surface is not particularly limited.
  • the materials (1) and (2) are respectively supplied to the liquid containing the particles in the reactor, and the solvent is further added as necessary. Then, the liquid may be heated while stirring. Thereby, the semiconductor nanoparticle which has a shell layer in at least one part of the core particle surface can be manufactured.
  • examples of the zinc source include zinc compounds, and more specifically zinc halides such as zinc stearate and zinc chloride.
  • examples of the sulfur source include sulfur compounds, more specifically thiols such as dodecanethiol and tetradecanethiol, and dihexyl sulfide. And sulfides.
  • the solvent used as necessary include the above-mentioned other organic solvents. Among them, 1-octadecene is preferable.
  • the reaction temperature is preferably 150 ° C. to 350 ° C., more preferably 150 ° C. to 300 ° C.
  • the reaction time is 1 hour to 200 hours. It is preferably 2 hours to 100 hours, more preferably 3 hours to 25 hours.
  • the semiconductor nanoparticle manufacturing apparatus 300 is an apparatus for continuously manufacturing semiconductor nanoparticles having a core-shell structure.
  • the semiconductor nanoparticle manufacturing apparatus 300 includes a plurality of nozzles 1 that spray one liquid into the reactor 36, a supply pipe 31 and a supply source 32 that supply the other liquid into the reactor 36, and a reactor 36.
  • a shell formation reactor 34 (former) is provided which forms a shell layer on at least a part of the surface of the core particle to be produced.
  • the semiconductor nanoparticle production apparatus 300 includes a plurality of nozzles 1 for spraying a liquid into the reactor 36. Therefore, the production efficiency of the core particles produced in the reactor 36 tends to be excellent.
  • the semiconductor nanoparticle production apparatus 300 includes a supply pipe 31 and a supply source 32 that supply the other liquid not sprayed in the reactor 36.
  • the other liquid supplied from the supply pipe 31 flows through the reactor 36 and then is supplied to the shell-forming reactor 34 through the distribution pipe 33.
  • the reactor 36 is connected to the supply pipe 31 and the distribution pipe 33.
  • the other liquid supplied from the supply pipe 31 flows through the reactor 36 and is then discharged from the distribution pipe 33.
  • the reactor 36 it is preferable to spray droplets from the plurality of nozzles 1 while circulating the other liquid from the supply source 32, and bring the sprayed liquid into contact with the other liquid.
  • both liquids are brought into contact with each other and mixed, at least one of the group 12 element and the group 13 element reacts with at least one of the group 15 element and the group 16 element to form core particles.
  • the core particles produced in the reactor 36 circulate in the reactor 36 together with the other liquid, and then are supplied to the shell-forming reactor 34 through the circulation pipe 33. Can be manufactured continuously.
  • the semiconductor nanoparticle production apparatus 300 includes a shell formation reactor 34 that forms a shell layer on at least a part of the surface of the core particles produced in the reactor 36.
  • the shell formation reactor 34 is an apparatus that is supplied with a material for forming a layer covering the core particles and at least a part of the surface of the core particles, and forms a shell layer on at least a part of the surface of the core particles.
  • the semiconductor nanoparticle manufacturing apparatus 300 may include two shell formation reactors 34 in parallel.
  • one shell formation reactor 34 forms a core-shell structure.
  • the core particles supplied from the reactor 36 through the flow pipe 33 are collected in the other shell-forming reactor 34, and the two shell-forming reactors 34 produce semiconductor nanoparticles having a core-shell structure alternately. It may be.
  • the reaction temperature is preferably 150 ° C. to 350 ° C., more preferably 150 ° C. to 300 ° C., and the reaction time. Is preferably 1 hour to 200 hours, more preferably 2 hours to 100 hours, and even more preferably 3 hours to 25 hours.
  • a configuration in which a core-shell structure is manufactured in the reactor 36 instead of providing the shell-forming reactor 34 may be used.
  • the semiconductor nanoparticle production apparatus of the present disclosure can be applied to the production of fluorescent materials for various liquid crystal displays, and further can be applied to the production of various electronic devices equipped with a liquid crystal display. Moreover, the semiconductor nanoparticle manufactured using the semiconductor nanoparticle manufacturing apparatus of this indication can anticipate application to bioimaging, a solar cell, etc.
  • Examples 1 to 5 After synthesizing indium phosphide by electrospray with the voltage shown in Table 1 using the manufacturing apparatus of the first embodiment described above, and forming an outer shell (shell layer) of zinc sulfide on the surface of the synthesized indium phosphide The fluorescence spectrum was measured. Indium chloride and trisdimethylaminophosphine were used as raw materials, and oleylamine was used as a dispersant.
  • This example was performed as follows. First, 0.3 g of indium chloride was weighed into a glass reaction vessel, and 5 mL of oleylamine was added and mixed. This operation was performed under a dry nitrogen atmosphere in order to prevent moisture absorption of indium chloride. Subsequently, while flowing nitrogen through the reaction vessel, the mixture was heated to 120 ° C. in an oil bath to dissolve indium chloride in oleylamine. Subsequently, the reaction vessel was heated to 180 ° C. with an oil bath, and 1.05 mL (0.050 mL / min) of trisdimethylaminophosphine was obtained from a stainless steel tube having an inner diameter of 0.5 mm with the tip at a distance of 3.5 cm from the liquid level. For 21 minutes) by electrospraying. The spray voltage was a value shown in Table 1. Thereafter, it was allowed to cool to room temperature to obtain a solution sample containing indium phosphide.
  • the semiconductor nanoparticles produced in Examples 1 to 5 had a shorter fluorescence peak wavelength than the semiconductor nanoparticles produced in Comparative Example 1. Further, as shown in Table 1, the fluorescence peak wavelength and the half-value width of the fluorescence obtained from the semiconductor nanoparticles produced in Examples 1 to 5 vary depending on the spray voltage. For example, when the fluorescence spectrum was measured for semiconductor nanoparticles produced with a spray voltage of 2.0 kV to 6.0 kV, fluorescence of 525 ⁇ 20 nm was obtained. On the other hand, the half-value width was expanded by making the spray voltage smaller.
  • the spray voltage is preferably set to 2.0 kV to less than 8.0 kV from the viewpoint of obtaining 525 ⁇ 20 nm fluorescence, while the spray voltage is set to exceed 4.0 kV from the viewpoint of reducing the half width. Presumed to be preferable.
  • Example 6 Using the manufacturing apparatus of the first embodiment described above, cadmium selenide was synthesized and the fluorescence spectrum was measured.
  • This example was performed as follows. First, 120 mg of cadmium oxide was weighed into a glass eggplant-shaped flask, 2.5 mL of oleic acid was added, and the mixture was heated at 180 ° C. while circulating argon gas to dissolve cadmium oxide in oleic acid. After cooling the solution in which cadmium oxide was dissolved, 1 mL of trioctylphosphine was added to the solution and stirred for 1 hour, and then 1 mL of hexane was further added and stirred.
  • the obtained cadmium solution was filled into a polypropylene syringe, and the syringe was connected to a spray tube of a glass capillary (inner diameter 0.1 mm) whose outer periphery was gold-plated.
  • 120 mg of selenium powder and 15 mL of trioctylphosphine are placed in a glass three-necked flask and heated to 180 ° C. in an oil bath while nitrogen gas is circulated at 20 mL / min in the three-necked flask to dissolve selenium in trioctylphosphine. It was.
  • the spray tube was adjusted to +8 kV, and the counter electrode previously made of a stainless steel mesh having a diameter of 3 cm previously installed at the bottom of the three-neck flask was adjusted to 0 kV, thereby generating a potential difference of 8 kV.
  • the cadmium solution in the syringe was extruded from the spray tube at a rate of 0.02 mL / min using a syringe pump, and sprayed toward the selenium solution as an electrospray.
  • nitrogen gas was passed through the three-necked flask at 20 mL / min, and the selenium solution was stirred with a magnetic stirrer. After spraying 0.6 mL of cadmium solution as fine droplets in 30 minutes, the three-necked flask was allowed to cool to room temperature to obtain a colloidal solution containing cadmium selenide.
  • a fluorescence spectrophotometer (RF-5300 manufactured by Shimadzu Corporation) was used to irradiate 350 nm light, and the fluorescence spectrum of the obtained dispersion of cadmium selenide semiconductor nanoparticles was measured. As a result, as shown in FIG. 4, light emission with a fluorescence peak wavelength of 425 nm and a half-value width of 80 nm was confirmed.
  • Example 6 it was confirmed that fine droplets were sprayed with the cadmium solution when the potential difference between the spray tube and the counter electrode was adjusted between 4 kV and 10 kV.
  • the potential difference between the spray tube and the counter electrode is 8 kV
  • the speed at which the liquid is pushed out from the spray tube is changed in the range of 0.005 mL / min to 0.1 mL / mL
  • the diameter of the microdroplet varies depending on the potential difference and distance between the spray port and the counter electrode, the inner and outer diameters of the spray port, the dielectric constant of the liquid to be sprayed, the viscosity and the ionic strength, etc. It is estimated that the temperature can be adjusted by an inert gas or the like.
  • This example was performed as follows. First, 100 mg of selenium powder and 4 mL of trioctylphosphine were placed in a two-necked flask, and the selenium was dissolved in trioctylphosphine by heating to 120 ° C. in an oil bath while flowing nitrogen gas at 20 mL / min in the two-necked flask. . The obtained selenium solution was filled into a polypropylene syringe, and the syringe was connected to a spray tube of a stainless steel nozzle (inner diameter 0.6 mm).
  • cadmium oxide is weighed into a glass three-necked flask, 11 mL of liquid paraffin and 4 g of stearic acid are added, heated at 180 ° C. while circulating nitrogen gas, and cadmium oxide is dissolved in liquid paraffin to prepare a cadmium solution. Obtained. The cadmium solution was cooled to 160 ° C.
  • the spray tube was adjusted to +7 kV, and the counter electrode prepared in advance with a stainless steel mesh having a diameter of 3 cm previously installed at the bottom of the three-neck flask was adjusted to 0 kV to generate a potential difference of 7 kV.
  • the selenium solution in the syringe was extruded from the spray tube at a rate of 0.05 mL / min using a syringe pump, and sprayed toward the cadmium solution as an electrospray.
  • nitrogen gas was passed through the three-necked flask at 20 mL / min, and the cadmium solution was stirred with a magnetic stirrer.
  • Cadmium selenide was synthesized by a hot injection method using the same combination of solutions as in Examples 7 to 9, and the fluorescence spectrum was measured.
  • 100 mg of selenium powder and 4 mL of trioctylphosphine were placed in a two-necked flask, and the selenium was dissolved in trioctylphosphine by heating to 120 ° C. in an oil bath while flowing nitrogen gas at 20 mL / min in the two-necked flask. .
  • the obtained selenium solution was filled into a polypropylene syringe, and the syringe was connected to a stainless steel nozzle (inner diameter 0.6 mm).
  • cadmium oxide is weighed into a glass three-necked flask, 11 mL of liquid paraffin and 4 g of stearic acid are added, heated at 180 ° C. while circulating nitrogen gas, and cadmium oxide is dissolved in liquid paraffin to prepare a cadmium solution. Obtained. The cadmium solution was cooled to 160 ° C.
  • Example 9 The obtained cadmium selenide of Comparative Examples 2 to 5 was measured for fluorescence peak wavelength and half width in the same manner as in Examples 7 to 9 described above. The results are shown in FIGS. 6 and 7 and Table 2.
  • (1) represents Comparative Example 2
  • (2) represents Comparative Example 3.
  • (1) represents Comparative Example 4, and (2) represents Comparative Example 5.
  • the cadmium and selenium mixed solution was held at 160 ° C. for 60 minutes, then heated to 180 ° C. and further held for 60 minutes.
  • the half width of the fluorescence peak of cadmium selenide obtained in Examples 7 to 9 showed a small value compared to the half width of Comparative Examples 2 to 5 obtained at similar holding temperatures and holding times. .
  • Comparative Examples 2 and 3 cadmium selenide obtained by the hot injection method at a holding temperature of 160 ° C. did not show a fluorescent peak with good symmetry, but in Examples 7 and 8, it was obtained at a holding temperature of 160 ° C.
  • the obtained cadmium selenide showed a fluorescent peak with good symmetry. This result shows that cadmium selenide nanoparticles having a uniform particle size can be obtained even at 160 ° C., which is a low temperature in the synthesis of semiconductor nanoparticles.

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Abstract

L'invention concerne un appareil de production de nanoparticules semi-conductrices, comprenant : une partie de pulvérisation qui pulvérise un liquide (1), qui contient un élément du groupe 12 et/ou un élément du groupe 13, et/ou un liquide (2), qui contient un élément du groupe 15 et/ou un élément du groupe 16 ; et un réacteur alimenté en l'autre liquide parmi le liquide (1) et le liquide (2) qui n'a pas été pulvérisé, de telle sorte que des gouttelettes du liquide pulvérisé par la partie de pulvérisation entrent en contact avec les gouttelettes de l'autre liquide, mélangeant ainsi le liquide (1) et le liquide (2), de telle sorte que l'élément du groupe 12 et/ou l'élément du groupe 13 contenus dans le liquide (1) et l'élément du groupe 15 et/ou l'élément du groupe 16 contenus dans le liquide (2) sont mis à réagir l'un avec l'autre.
PCT/JP2018/001977 2017-01-25 2018-01-23 Appareil de production de nanoparticules semi-conductrices et procédé de production de nanoparticules semi-conductrices Ceased WO2018139446A1 (fr)

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JP2021195281A (ja) * 2020-06-15 2021-12-27 信越化学工業株式会社 量子ドットの製造方法
JP7427541B2 (ja) 2020-06-15 2024-02-05 信越化学工業株式会社 量子ドットの製造方法
CN115943122B (zh) * 2020-06-15 2024-09-17 信越化学工业株式会社 量子点的制造方法
CN115943122A (zh) * 2020-06-15 2023-04-07 信越化学工业株式会社 量子点的制造方法
KR102858364B1 (ko) 2020-06-15 2025-09-10 신에쓰 가가꾸 고교 가부시끼가이샤 양자 도트의 제조 방법
WO2021256109A1 (fr) * 2020-06-15 2021-12-23 信越化学工業株式会社 Procédé de production de points quantiques

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