WO2023022093A1 - ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法 - Google Patents

ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法 Download PDF

Info

Publication number
WO2023022093A1
WO2023022093A1 PCT/JP2022/030583 JP2022030583W WO2023022093A1 WO 2023022093 A1 WO2023022093 A1 WO 2023022093A1 JP 2022030583 W JP2022030583 W JP 2022030583W WO 2023022093 A1 WO2023022093 A1 WO 2023022093A1
Authority
WO
WIPO (PCT)
Prior art keywords
quantum dot
perovskite quantum
composite material
dot composite
shell layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/030583
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
聡 浅倉
貴弘 佐藤
陽人 増原
亮太 佐藤
直晃 大下
圭祐 菊池
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yamagata University NUC
Ise Chemicals Corp
Original Assignee
Yamagata University NUC
Ise Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yamagata University NUC, Ise Chemicals Corp filed Critical Yamagata University NUC
Priority to JP2023542375A priority Critical patent/JP7784673B2/ja
Priority to KR1020247007986A priority patent/KR102845308B1/ko
Priority to CN202280053735.3A priority patent/CN117795036A/zh
Publication of WO2023022093A1 publication Critical patent/WO2023022093A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/66—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/66—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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

Definitions

  • the present invention relates to a method for producing perovskite quantum dots with high photoluminescence quantum yield, and the perovskite quantum dots and inks.
  • a perovskite quantum dot is a particle (dot) with a perovskite crystal structure that expresses specific optical properties according to quantum mechanics, with a diameter of 1 nm to several tens of nm per particle. It has been attracting attention in recent years because the emission wavelength emitted when excited can be continuously controlled by chemical composition and particle size, and it exhibits emission characteristics with very little variation in the emission wavelength distribution. As a wavelength conversion material by photoexcitation or a self-luminous material by electrical excitation, practical application in a wide range of fields such as electronics, medicine, and agriculture is being studied (Patent Document 1).
  • Perovskite quantum dots are susceptible to surface defects due to their large specific surface area. Therefore, surface protection is generally performed by capping organic ligands such as organic amines and organic acids, but it is difficult to completely protect the defects formed on the particle surface. This is the main cause of lowering the photoluminescence quantum yield (also referred to as PLQY). In particular, perovskite quantum dots are prone to halogen defects on the particle surface.
  • an all-inorganic perovskite with a chemical formula of CsPb(Cl a Br 1-ab I b ) 3 (where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1)
  • Quantum dot composites comprising quantum dots and a mutated protective film on the surface of the all-inorganic perovskite quantum dots have been described (US Pat.
  • the mutation protective film includes mesoporous particles, inorganic shell layer encapsulants, ligand exchangers, microcapsules, polymer encapsulants, silicon-containing material encapsulants, oxide or nitride dielectrics. An encapsulant, or a combination thereof, is used.
  • Non-Patent Document 1 reports a technique of silica-coating the surface of pre-synthesized perovskite quantum dots CsPbBr 3 in multiple synthesis steps.
  • the perovskite quantum dot surface is coated with SiO 2 , it does not compensate for the surface defect sites of the already formed perovskite quantum dots, so although the durability increases, the PLQY does not increase. In addition, it is inefficient because it is necessary to carry out the reaction in two steps, the preparation of the perovskite quantum dots and the formation of the coat layer. Furthermore, SiO 2 whose coat layer is an insulator layer does not allow electricity to flow through the perovskite quantum dots, which are cores, and cannot be used for applications that require electron transfer, such as electrically excited light-emitting devices and solar cells.
  • the present invention provides a method for producing a perovskite quantum dot composite material that easily forms core-shell particles in a single synthesis step, and a perovskite quantum dot composite material by forming an ion crystal layer made of an organic halide in the shell layer. It is an object of the present invention to provide a perovskite quantum dot composite material with suppressed surface defects and a very high PLQY and an ink containing the same.
  • the present invention consists of the following matters.
  • Consists of a core particle and a shell layer surrounding the core particle wherein the core particle is made of a metal halide perovskite, and the shell layer has an ionic crystal structure with the same halogen composition as the core.
  • a perovskite quantum dot composite material comprising an organic halogen compound, having a PLQY of 75% or more, and having an emission wavelength change of 5 nm or less for 10,000 minutes at room temperature.
  • It consists of a core particle and a shell layer that surrounds the core particle, and the core particle material of the core particle is selected from the elements of Groups 1, 14 and 17 of the periodic table.
  • a perovskite quantum characterized by being composed inorganic perovskite nanocrystals, wherein the shell layer material of the shell layer is an ionic crystal composed of an organic cation and a Group 17 element, and having a PLQY of 75% or more. dot composites.
  • the perovskite quantum dot composite material according to any one of [1] to [3], wherein the perovskite quantum dot composite material has an average particle size of 1 to 30 nm.
  • the step 1 is a step of mixing a core particle material composed of an alkali metal halide and a metal halide and a shell layer material composed of an organic halogen compound to prepare a precursor solution, and The perovskite quantum dots according to [6], wherein the ratio of the added molar amount of the shell layer material (added amount/required amount) to the required minimum molar amount of the shell layer material covering the perovskite quantum dots is 1.00 to 2.40 A method of manufacturing a composite material.
  • the present invention it is possible to provide a method for producing a perovskite quantum dot composite material that can easily form core-shell particles in a single synthesis step.
  • an ion crystal layer is formed on the surface of the core particles during the formation of the shell layer. Therefore, the surface defects of the perovskite quantum dots are suppressed and the resulting perovskite quantum dot composites have a very high PLQY.
  • FIG. 1 shows the formation of a perovskite quantum dot composite material by injecting a precursor solution containing a core particle material and a shell layer material into a solution containing a nonpolar solvent, an organic acid and an organic amine compound with a liquid dielectric constant of 10 or less.
  • FIG. 10 is a diagram showing the steps to be performed;
  • the average particle diameter (nm) of the core particles, which are the light emitters is plotted on the x-axis (horizontal axis), and the shell layer material actually added to coat the surface of the core particles.
  • FIG. 1 shows the formation of a perovskite quantum dot composite material by injecting a precursor solution containing a core particle material and a shell layer material into a solution containing a nonpolar solvent, an organic acid and an organic amine compound with a liquid dielectric constant of 10 or less.
  • FIG. 10
  • 3 shows the shell layer material actually added with respect to the molar amount of the shell layer material required to coat the surface of the core particles for the perovskite quantum dot composites of Examples 1 to 6 and Comparative Examples 1 to 7.
  • 2 is a graph plotting the molar amount ratio of , on the horizontal axis, and the PLQY of the perovskite quantum dot composite material on the vertical axis.
  • the perovskite quantum dot composite material of the present invention comprises a core particle and a shell layer that surrounds the core particle, the core particle comprises a metal halide perovskite, and the shell layer is the same as the core particle. It is composed of an organic halogen compound having an ionic crystal structure with a halogen composition, and has an emission wavelength change of 5 nm or less and a PLQY change rate of 5% or less for 10,000 minutes at room temperature.
  • the core particle material is an inorganic material with a perovskite-type crystal structure represented by the general formula AMX 3 , specifically, an inorganic perovskite nanostructure composed of elements from Groups 1, 14 and 17 of the periodic table of elements.
  • A represents an alkali metal such as cesium, rubidium, potassium, sodium and lithium. Of these, cesium is preferred.
  • M represents lead, germanium, tin, silicon and the like. Among these, lead and tin are preferred.
  • antimony, bismuth, copper, nickel, cobalt, iron, manganese, chromium, cadmium, europium, ytterbium, and silver may be included within the range of the element ratio of M to 5% or less.
  • X represents halogen such as chlorine, bromine and iodine.
  • AMX 3 examples include CsPb(Cl a Br 1-ab I b ) 3 (0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, a+b ⁇ 1), CsSn(Cl a Br 1-ab I b ) 3 (0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, a+b ⁇ 1), CsGe(Cl a Br 1-ab I b ) 3 (0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, a+b ⁇ 1), CsSn y Pb (1-y) (Cl a Br 1-ab I b ) 3 (0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, a + b ⁇ 1, 0 ⁇ y ⁇ 1), CsGe z Pb (1-z) (Cl a Br 1-a-b I b ) 3 (0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, a+b ⁇ 1, 0 ⁇ z ⁇ 1), CsGe z Sn (1- z) (Cl a Br 1-ab I
  • the shell layer material forming the shell layer is represented by the general formula BX, and is specifically an organic halogen compound composed of an organic cation and a Group 17 element.
  • X represents a halogen
  • B represents an organic acid that forms a halide with X.
  • BX includes, for example, formamidine hydrohalide (FAX), methylamine hydrohalide (MAX), guanidine hydrohalide (GAX) and ethylamine hydrohalide (EAX). These are usually present as salts.
  • formamidine hydrohalide exists as formamidine hydrobromide, formamidine hydrochloride and formamidine hydroiodide
  • methylamine hydrohalide exists as methylamine
  • GX exists as hydrobromide, methylamine hydrochloride and methylamine hydroiodide
  • guanidine hydrobromide guanidine hydrochloride and guanidine hydroiodide
  • Ethylamine hydrohalide is present as ethylamine hydrobromide, ethylamine hydrochloride and ethylamine hydroiodide.
  • the shell layer material BX should have the same halogen composition as the core grain AMX3 .
  • BX is an ammonium halide instead of an amine hydrohalide, since BX is in a solid state at room temperature.
  • the shell layer material is soluble in polar solvents and sparingly soluble in non-polar solvents.
  • the solubility of the shell layer material in a polar solvent is preferably at least twice the solubility of the core particle material in a polar solvent.
  • a polar solvent is an aprotic solvent that has a liquid dielectric constant of 20 or more and is miscible with the nonpolar solvent described below.
  • the polar solvent include N-methylpyrrolidone (NMP; liquid dielectric constant 32.2), N,N-dimethylformamide (DMF; liquid dielectric constant 36.7) and acetonitrile (liquid dielectric constant 35.9). and is not limited to this.
  • NMP N-methylpyrrolidone
  • DMF N,N-dimethylformamide
  • acetonitrile liquid dielectric constant 35.9
  • a non-polar solvent is a solvent having a liquid dielectric constant of 10 or less.
  • the non-polar solvents include toluene (liquid dielectric constant 2.4), hexane (liquid dielectric constant 1.9), octadecene, ethyl acetate (liquid dielectric constant 6.4), chlorobenzene (liquid dielectric constant 5.6) and Examples include, but are not limited to, chloroform (liquid dielectric constant: 4.8).
  • the core particles are inorganic perovskite nanocrystals made of a metal halide
  • the shell layer is made of an organic halogen compound that forms an ionic crystal structure with the same halogen composition as the core particles.
  • the perovskite quantum dot composite material can exist stably for a long time, and the change in emission wavelength is 5 nm or less for 10,000 minutes at room temperature.
  • the average particle size of the perovskite quantum dot composite material is usually 1-30 nm, preferably 2-20 nm, more preferably 4-16 nm. By setting the average particle diameter of the perovskite quantum dot composite material within the above range, an ink containing the perovskite quantum dot composite material having high solvent dispersibility can be prepared.
  • the perovskite quantum dot composite material is composed of core particles and a shell layer surrounding the core particles.
  • the shell layer In order for the shell layer to function, the shell layer must be formed with a certain thickness on the surface of the core particles.
  • y the molar amount of the shell layer material required to coat the surface of the core particles
  • x the average particle diameter of the core particles
  • the amount of shell layer material required depends on the total surface area of the core particles. For the same molar amount of core particles, if the core particle size is larger, its total surface area will be smaller and less shell layer material will be required. On the other hand, if the particle size of the core particles is small, the surface area per particle will be small, but the total surface area will also be large due to the increase in the number of core particles, and the necessary amount of the shell layer material will be large. That is, the required molar amount of the shell layer material can be determined from the molar amount and particle size of the core particles.
  • the ratio of the added molar amount of the shell layer material (addition amount/required amount) to the necessary minimum molar amount of the shell layer material covering the surface of the core particles is usually 1.00 to 2.40, preferably 1.05 to 1.05. 2.00, more preferably 1.05 to 1.60.
  • the surface of the core particles is coated with the shell layer material, which significantly improves PLQY.
  • FIG. 3 shows the shell layer material actually added with respect to the molar amount of the shell layer material required to coat the surface of the core particles for the perovskite quantum dot composite materials of Examples 1 to 6 and Comparative Examples 1 to 5.
  • 2 is a graph plotting the molar amount ratio of , on the horizontal axis, and the PLQY of the perovskite quantum dot composite material on the vertical axis.
  • the average particle size of the core particles of the perovskite quantum dot composite material which is the luminescent material, is usually 1 to 25 nm, preferably 1 to 18 nm, more preferably 3 to 15 nm. If the core particles are extremely small, the change in emission wavelength becomes large due to the quantum confinement effect, and the crystal structure cannot be maintained satisfactorily, resulting in large variations in emission wavelength. When the core particle becomes extremely large, PLQY decreases due to decreased exciton stability during excitation. From the viewpoint of light emission properties, the average particle size of the core particles is preferably within a predetermined range. On the other hand, the thickness of the shell layer is generally 0.5 to 5 nm, depending on the size of the core particles. If the shell layer is too thin, halogen deficiency, Ostwald ripening, aggregation and fusion will occur from the insufficiently coated portion, resulting in a decrease in PLQY.
  • the average particle size of the perovskite quantum dot composite material of the present invention can be determined using a dynamic light scattering photometer (DLS), a transmission electron microscope (TEM), or the like. For example, it can be obtained from the average value in the longitudinal direction measured by observing 50 to 100 perovskite quantum dot composites with a TEM.
  • the average particle size of the core particles can be obtained from the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) measured by a fluorescence spectrophotometer or the like.
  • the energy bandgap of the core particle which is a light emitter, changes depending on the particle size, and the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) changes.
  • the core particles have an average particle size of 2.6 nm and a maximum wavelength ( ⁇ PL ) of 450 nm, an average particle size of 6.2 nm and a maximum wavelength ( ⁇ PL ) of 500 nm, and an average particle size of At 15 nm, the maximum wavelength ( ⁇ PL ) is 523 nm.
  • the thickness of the shell layer can be determined by dividing the difference between the average particle size of the perovskite quantum dot composite material and the average particle size of the core particles by two.
  • the perovskite quantum dot composites of the present invention can emit light in the visible to near-infrared wavelength region. It preferably has a property of emitting light upon excitation, and preferably has a property of emitting light upon excitation by excitation light and excitation by electricity.
  • the wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 750 nm, or 300 nm to 600 nm.
  • the ink of the present invention contains the perovskite quantum dot composite material, a polar solvent having a liquid dielectric constant of 20 or more, and a non-polar solvent having a liquid dielectric constant of 10 or less and miscible with the polar solvent.
  • the ink has a stable structure in which the surface of the perovskite quantum dots is covered with a shell layer represented by the general formula BX.
  • Observation of the core-shell state of the perovskite quantum dot composite material in the ink by transmission electron microscope (TEM) and electron diffraction (ED) reveals that the surface of the core particles is coated with the shell layer material.
  • excitation light for example, ultraviolet light with a wavelength of 370 nm, it emits blue to red fluorescence (with a wavelength of 450 to 800 nm).
  • the volume ratio of the non-polar solvent to the polar solvent is usually 7 times or more, preferably 10 times or more, more preferably 15 times or more. From the viewpoint of suppressing re-dissolution of the precipitated perovskite quantum dot composite material and increasing the reaction yield, it is desirable that the amount of the polar solvent is less than that of the non-polar solvent.
  • the polar solvent may be partially removed after synthesis of the perovskite quantum dot composite. Also, a non-polar solvent may be added after the synthesis.
  • the method for producing a perovskite quantum dot composite material of the present invention includes a step of mixing a polar solvent having a liquid dielectric constant of 20 or more, an alkali metal halide, a metal halide, and an organic halogen compound to prepare a precursor solution. 1 and step 2 of injecting the precursor solution into a non-polar solvent having a liquid dielectric constant of 10 or less.
  • a precursor solution is prepared by mixing a polar solvent having a liquid dielectric constant of 20 or higher, an alkali metal halide, a metal halide, and an organic halogen compound.
  • Alkali metal halides include, for example, cesium bromide (CsBr), cesium iodide (CsI), cesium chloride (CsCl), rubidium bromide (RbBr), rubidium iodide (RbI), rubidium chloride (RbCl), bromine Potassium (KBr), potassium iodide (KI), potassium chloride (KCl), sodium bromide (NaBr), sodium iodide (NaI), sodium chloride (NaCl) and the like are used.
  • Metal halides include, for example, lead (II) bromide (PbBr 2 ), lead (II) iodide (PbI 2 ), lead (II) chloride (PbCl 2 ), tin (II) bromide (SnBr 2 ). , tin(II) iodide (SnI 2 ), tin(II) chloride (SnCl 2 ), germanium(II) bromide (GeBr 2 ), germanium(II) iodide (GeI 2 ) and germanium(II) chloride ( GeCl 2 ) or the like is used. These compounds can be used singly or as a mixture of two or more at any ratio.
  • Organic halogen compounds include methylamine hydrobromide (CH 5 N.HBr), methylamine hydroiodide (CH 5 N.HI), methylamine hydrochloride (CH 5 N.HCl), formamidine hydrobromide ( CH4N2.HBr ), formamidine hydroiodide (CH4N2.HI), formamidine hydrochloride (CH4N2.HCl ) , guanidinium hydrobromide ( CH5N3 - HBr), Guazinium hydroiodide ( CH5N3 - HI), Guazinium hydrochloride ( CH5N3 - HCl), Ethylamine hydrobromide ( C2H7N -HBr), Ethylamine hydrochloride (C 2 H 7 N.HCl) and ethylamine hydroiodide (C 2 H 7 N.HI) are used.
  • the mixing ratio of alkali metal halide and metal halide is generally 1:10 to 10:1, preferably 1:3 to 3:1, more preferably 1:1.5 to 1.5:1 molar ratio. is. As the difference in the mixing ratio increases, the metal element at the M site of the core particles assumes a perovskite crystal structure with a different valence, and PLQY tends to decrease.
  • the mixing ratio of the alkali metal halide or the metal halide, which is the material of the core particles and which has a smaller molar amount, to the organic halogen compound is generally 1:0.6 to 1:10, preferably 1:0.8.
  • the concentration of the alkali metal halide and metal halide in the precursor solution is 0.01-0.30 mol/l, preferably 0.02-0.10 mol/l, and the concentration of the organic halogen compound is 0.01-1. 0 mol/l, preferably 0.02 to 0.60 mol/l.
  • step 2 the precursor solution prepared in step 1 is injected into a nonpolar solvent having a liquid dielectric constant of 10 or less.
  • a feature of the present invention is that a precursor solution containing both the core particle material and the shell layer material is injected into a nonpolar solvent having a liquid dielectric constant of 10 or less, that is, the core particle material and the shell layer material are At the same time, it is injected into a non-polar solvent.
  • the core particles are mixed with the nonpolar solvent before the shell layer material is injected. Precipitate and disperse inside. Since the core particles are completely dispersed in the non-polar solvent at a relatively low density, when the shell layer material is injected therein, the number of core particles existing at the reaction interface is small, and the surface of the core particles is Since the shell layer material is difficult to coat, most of the shell layer material precipitates alone. As a result, the coating of the surface of the core particles is insufficient and non-uniform, the core particles contain surface defects, and the PLQY of the resulting perovskite quantum dot composites is not sufficiently improved.
  • the nonpolar solvent having a liquid dielectric constant of 10 or less preferably further contains at least one selected from the group consisting of organic acids and organic amine compounds.
  • the shell layer or core particles are partially modified with alkyl chains. With such a modification site, the crystal growth of the core particles can be adjusted during the synthesis of the perovskite quantum dot composite, and the particle size of the core particles can be controlled. As a result, it is possible to change the maximum wavelength to a predetermined emission wavelength and reduce variations in emission wavelength distribution.
  • Organic acids include, for example, carboxylic acids such as oleic acid, stearic acid, palmitic acid, glutaric acid, sebacic acid and benzoic acid; Acid compounds, as well as sulfinic acids such as benzenesulfinic acid.
  • the organic amine compound may be any of aliphatic amine compounds, aromatic amine compounds, and quaternary ammonium salts.
  • aliphatic amine compounds having 3 to 16 carbon atoms such as oleylamine, propylamine, butylamine, pentylamine, octylamine, hexadecylamine and octadecylamine, aniline, benzylamine, phenethylamine, 3-phenyl-2-propene-1 -amine, phenylmethylamine, 2,2'-iminodibenzoic acid, 3-phenylpropylamine, 4-phenylbutylamine, naphthylamine, 4-aminobiphenyl and 3,4,5-tris(prop-2-en-1-yloxy ) aromatic amine compounds having 6 to 34 carbon atoms such as benzylamine, didecyldimethylammonium salts, benzyltrimethylammonium bromide, 3-(N,N-dimethyloctadecylammonio)propanesulfonate salts and stearyl
  • a single compound may be a compound having an acid or amino group, and examples thereof include ⁇ -aminobutyric acid and 3-[(3-methacrylamidopropyl)dimethylammonio]propane-1-sulfonic acid.
  • the concentrations of the organic acid and the organic amine compound to be added may be the concentrations at which they are dissolved in the precursor solution and the non-polar solvent in step 2 or less. Usually, it is preferably 1% by mass or more based on the total added weight of the alkali metal halide and the metal halide.
  • the organic acid and organic amine compounds may be removed after synthesis of the perovskite quantum dot composite. In addition, another organic acid or organic amine compound may be added after removal in order to impart higher dispersion stability to the perovskite quantum dot composite material. Further, another organic acid and organic amine compound may be added without removing the organic acid and organic amine compound.
  • step 2 it is preferable to set the temperature of the precursor solution and the non-polar solvent to 40°C or less from the viewpoint of process simplicity and stability of the shell layer material.
  • an organic halogen compound partially dissociates due to chemical equilibrium in a polar solvent and vaporizes. Higher temperatures reduce the amount of shell layer material in the precursor solution, resulting in undercoat.
  • the perovskite quantum dot composites of the present invention have a very high PLQY, specifically 75% or higher, preferably 80% or higher, more preferably 90% or higher.
  • the shell layer has an ion crystal layer that is an organic halogen compound, and has a stable structure in which surface defects are suppressed. Therefore, even after 10,000 minutes at room temperature, the amount of change in emission wavelength is 5 nm or less, and PLQY can be stably maintained. It is believed that the reason for this is that the shell layer material forms ionic crystals of BMX 3 with the crystal ends of the core particle surface, and the crystal layer strongly holds halogen, thereby improving PLQY.
  • the perovskite quantum dot composite material of the present invention can be used as a wavelength conversion material as a composition containing the perovskite quantum dot composite material and a curable material.
  • the hardening material may be thermoplastic resin, thermosetting resin, glass, or ceramics.
  • an ink in which the perovskite quantum dot composite material of the present invention is dispersed to a substrate it can be used as a light-emitting material upon electrical excitation.
  • a glass plate, a resin plate, a semiconductor plate, etc. are mentioned as a base material.
  • Example 1 As a precursor solution, the molar amount (mol/mol) of the shell layer material actually added (hereinafter referred to as "addition The solution was prepared so that the ratio (referred to as “amount/required amount") was 1.05. Namely, 1.41 mg of cesium bromide (CsBr), 2.42 mg of lead (II) bromide (PbBr 2 ) and 3.34 mg of methylamine hydrobromide (CH 5 N.HBr) were mixed with N,N-dimethylformamide ( DMF) was dissolved in 0.2 ml.
  • CsBr cesium bromide
  • PbBr 2 2.42 mg of lead (II) bromide
  • DMF N,N-dimethylformamide
  • a nonpolar solvent was prepared by adding 4.5 ml of ethyl acetate, 16.7 ⁇ l of oleic acid and 13.3 ⁇ l of oleylamine to a 9 ml screw tube.
  • the precursor solution was injected into the chamber under stirring at room temperature in the atmosphere.
  • the resulting mixture was centrifuged at 16500 rpm in a desktop centrifuge AS165W (manufactured by AS ONE Corporation), and after centrifugation for 2 minutes, a portion of the supernatant was removed, and the precipitate was redispersed with toluene.
  • the speed was set to 16,500 rpm, and the supernatant was collected after centrifugation for 3 minutes to obtain an ink in which the perovskite quantum dot composite material was dispersed.
  • PLQY was measured by setting an integrating sphere in a fluorescence spectrophotometer FP-8600 (manufactured by JASCO Corporation; excitation wavelength 350 nm).
  • the PLQY was 95%, and the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 461 nm. From the ⁇ PL , the particle size of the core of the perovskite quantum dot composite material, which is the emitter, was obtained.
  • the particle size of the core was 3.5 nm.
  • Table 1 shows the addition method of the shell layer material, the molar amount of the shell layer material required to coat the surface of the core particle (hereinafter referred to as "required amount"), and the molar amount of the shell layer material actually added (hereinafter referred to as " ), the amount added/required, the maximum wavelength ( ⁇ PL ) and particle size of photoluminescence (PL) of the perovskite quantum dot composite material, and PLQY.
  • the ink in which the perovskite quantum dot composite material was dispersed was placed in a screw tube, closed with a lid, and left at room temperature for 10,000 minutes.
  • a comparison of the maximum wavelength ( ⁇ PL ) and PLQY of photoluminescence (PL) before and after the exposure revealed that the change in the maximum wavelength ( ⁇ PL ) was 2 nm, and the rate of change in PLQY was ⁇ 3%.
  • Example 2 As a precursor solution, a solution was prepared so that the added amount/required amount was 1.26. That is, a perovskite quantum dot composite material of ink was produced.
  • Example 1 the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the PLQY was 97%
  • the photoluminescence (PL) maximum wavelength ( ⁇ PL ) was 461 nm
  • the core particle size was 3.5 nm.
  • Example 3 As a precursor solution, a solution was prepared so that the added amount/required amount was 1.60. That is, 4.26 mg of cesium bromide (CsBr), 7.34 mg of lead (II) bromide (PbBr 2 ) and 4.48 mg of methylamine hydrobromide (CH 5 N.HBr) were mixed with N,N-dimethylformamide ( DMF) was dissolved in 0.6 ml. A nonpolar solvent was prepared by putting 4.5 ml of ethyl acetate, 120 ⁇ l of oleic acid and 6.0 ⁇ l of oleylamine into a 9 ml screw tube. The precursor solution was injected into the chamber under stirring at room temperature in the atmosphere.
  • CsBr cesium bromide
  • PbBr 2 7.34 mg of lead (II) bromide
  • DMF N,N-dimethylformamide
  • a nonpolar solvent was prepared by putting 4.5 ml of ethyl acetate,
  • the resulting mixture was centrifuged at 16500 rpm in a desktop centrifuge AS165W (manufactured by AS ONE Corporation), and after centrifugation for 3 minutes, a portion of the supernatant was removed, and the precipitate was redispersed with toluene. Furthermore, the speed was set to 16,500 rpm, and the supernatant was collected after centrifugation for 3 minutes to obtain an ink in which the perovskite quantum dot composite material was dispersed.
  • PLQY was measured by setting an integrating sphere in a fluorescence spectrophotometer FP-8600 (manufactured by JASCO Corporation; excitation wavelength 400 nm).
  • PLQY, photoluminescence (PL) maximum wavelength ( ⁇ PL ), and core size of perovskite quantum dot composites were determined.
  • the PLQY was 96%
  • the photoluminescence (PL) maximum wavelength ( ⁇ PL ) was 515 nm
  • the core particle size was 12 nm. The results are shown in Table 1 and FIG.
  • Example 4 As a precursor solution, a solution was prepared so that the added amount/required amount was 2.40. That is, a perovskite quantum dot composite material was produced in the same manner as in Example 3, except that the amount of methylamine hydrobromide (CH 5 N.HBr) was changed from 4.48 mg to 6.72 mg. Ink was made.
  • CH 5 N.HBr methylamine hydrobromide
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the PLQY was 95%
  • the photoluminescence (PL) maximum wavelength ( ⁇ PL ) was 516 nm
  • the core particle size was 12 nm.
  • Example 5 As a precursor solution, a solution was prepared so that the added amount/required amount was 1.26. Specifically, 169.2 mg of cesium bromide (CsBr), 290.4 mg of lead (II) bromide (PbBr 2 ), and 480 mg of methylamine hydrobromide (CH 5 N.HBr) were mixed with N,N-dimethylformamide (DMF). Dissolved in 24.0 ml. A nonpolar solvent was prepared by mixing 600 ml of ethyl acetate, 2220 ⁇ l of oleic acid and 1780 ⁇ l of oleylamine.
  • the precursor solution was introduced into the device at 4 ml per minute, non-polar, while stirring at a disk rotation speed of 4000 rpm in the atmosphere at room temperature.
  • the solvent was injected at a rate of 90 ml per minute, and after 3 minutes from the start of injection, the mixed solution discharged from the apparatus was sampled for 1 minute.
  • the obtained mixed liquid was recovered as an ink of a perovskite quantum dot composite material.
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the PLQY was 99%, the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 460 nm, and the particle size of the core was 3.5 nm.
  • the results are shown in Table 1 and FIG.
  • Example 6 As a precursor solution, a solution was prepared so that the added amount/required amount was 1.00. That is, 4.26 mg of cesium bromide (CsBr), 7.34 mg of lead (II) bromide (PbBr 2 ) and 3.76 mg of formamidine hydrobromide (CH 4 N 2 HBr) were mixed with N,N-dimethylformamide. (DMF) was dissolved in 0.6 ml. A non-polar solvent was prepared by adding 4.5 ml of ethyl acetate, 60.0 ⁇ l of oleic acid and 3.0 ⁇ l of oleylamine to a 9 ml screw tube. The precursor solution was injected into the chamber under stirring at room temperature in the atmosphere. Ink of the perovskite quantum dot composite material was recovered from the obtained mixed liquid in the same manner as in Example 3.
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the PLQY was 91%
  • the photoluminescence (PL) maximum wavelength ( ⁇ PL ) was 512 nm
  • the core particle size was 10 nm.
  • a precursor solution was prepared by dissolving 1.41 mg of cesium bromide (CsBr) and 2.42 mg of lead (II) bromide (PbBr 2 ) in 0.2 ml of N,N-dimethylformamide (DMF).
  • CsBr cesium bromide
  • PbBr 2 lead (II) bromide
  • DMF N,N-dimethylformamide
  • 4.5 ml of ethyl acetate, 16.7 ⁇ l of oleic acid and 13.3 ⁇ l of oleylamine were placed in a 9 ml screw tube, and the precursor solution was injected while stirring at room temperature in the atmosphere.
  • the obtained mixed liquid was recovered as an ink of a perovskite quantum dot composite material.
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 507 nm, and the particle size of the core was 7.0 nm.
  • the PLQY was as low as 15% for the perovskite quantum dot composite of Comparative Example 1, which does not have a shell layer. The results are shown in Table 1 and FIG.
  • the ink in which the perovskite quantum dot composite material was dispersed was placed in a screw tube and left in the air at room temperature for 30 minutes with the lid closed.
  • a comparison of the maximum wavelength ( ⁇ PL ) and PLQY of photoluminescence (PL) before and after the exposure revealed that the maximum wavelength ( ⁇ PL ) changed by 16 nm and the PLQY changed by ⁇ 52%. After being left for 10000 minutes, it was deactivated and stopped emitting light.
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 461 nm, and the particle size of the core was 3.5 nm.
  • the small amount added/required resulted in insufficient surface protection of the perovskite quantum dots with a PLQY of 13%.
  • the results are shown in Table 1 and FIG.
  • Comparative Example 3 As a precursor solution, a solution was prepared so that the added amount/required amount was 0.84. That is, in Comparative Example 2, a perovskite quantum dot composite material was produced in the same manner as in Comparative Example 2, except that the amount of methylamine hydrobromide (CH 5 N.HBr) was changed from 2.00 mg to 2.67 mg. made.
  • CH 5 N.HBr methylamine hydrobromide
  • Example 1 the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 461 nm, and the particle size of the core was 3.5 nm.
  • PLQY was 28%. Although the added amount/necessary amount was larger than Comparative Example 2, it was as small as 0.84, so the PLQY was insufficient.
  • a precursor solution was prepared by dissolving 4.26 mg of cesium bromide (CsBr) and 7.34 mg of lead (II) bromide (PbBr 2 ) in 0.6 ml of N,N-dimethylformamide (DMF).
  • 4.5 ml of ethyl acetate, 120 ⁇ l of oleic acid and 6.0 ⁇ l of oleylamine were placed in a 9 ml screw tube, and the precursor solution was injected while stirring at room temperature in the atmosphere.
  • Ink of the perovskite quantum dot composite material was recovered from the obtained mixed liquid in the same manner as in Example 3.
  • Example 3 the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 518 nm, and the particle size of the core was 12 nm.
  • PLQY was 50%.
  • Comparative Example 1 although PLQY is insufficient in Comparative Example 4 because it does not have a shell layer, PLQY is higher than in Comparative Example 1 because the core particles that are light emitters have a large particle size. .
  • the results are shown in Table 1 and FIG.
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 516 nm, and the particle size of the core was 12 nm.
  • PLQY was 22%. The results are shown in Table 1 and FIG.
  • a precursor solution was prepared by dissolving 1.41 mg of cesium bromide (CsBr) and 2.42 mg of lead (II) bromide (PbBr 2 ) in 0.2 ml of N,N-dimethylformamide (DMF). 4.5 ml of ethyl acetate, 16.7 ⁇ l of oleic acid and 13.3 ⁇ l of oleylamine were placed in a 9 ml screw tube. When the precursor solution was injected into the solution under stirring at room temperature in the atmosphere, the perovskite quantum dots were precipitated and completely dispersed.
  • CsBr cesium bromide
  • PbBr 2 lead (II) bromide
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 461 nm, and the particle size of the core was 3.5 nm.
  • PLQY was 68%.
  • the added amount/required amount was 1.17 and greater than 1, the perovskite quantum dots contained surface defects and the PLQY was insufficient due to the post-addition of the shell layer material.
  • a precursor solution was prepared by dissolving 4.26 mg of cesium bromide (CsBr) and 7.34 mg of lead (II) bromide (PbBr 2 ) in 0.6 ml of N,N-dimethylformamide (DMF). 4.5 ml of ethyl acetate, 120 ⁇ l of oleic acid and 6.0 ⁇ l of oleylamine were placed in a 9 ml screw tube. When the precursor solution was injected into the solution under stirring at room temperature in the atmosphere, the perovskite quantum dots were precipitated and completely dispersed.
  • CsBr cesium bromide
  • PbBr 2 lead (II) bromide
  • the PLQY, the maximum wavelength of photoluminescence (PL) ( ⁇ PL ), and the particle size of the core of the perovskite quantum dot composite material were determined.
  • the maximum wavelength ( ⁇ PL ) of photoluminescence (PL) was 518 nm, and the particle size of the core was 12 nm.
  • PLQY was 70%.
  • Comparative Example 7 in which the shell layer material was added later and the added/required amount was 1.60, the PLQY was higher than in Comparative Example 4, in which no shell layer material was added, but was insufficient. Met. The results are shown in Table 1 and FIG.
  • Examples 1 to 6 in which a predetermined amount or more of the coating layer material was added at the same time, have extremely high PLQY. Although the PLQY was slightly improved by post-addition, simultaneous addition was superior because the coat layer was non-uniform. As described above, the perovskite quantum dot composite material of the present invention has excellent emission wavelength stability and high PLQY.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Luminescent Compositions (AREA)
PCT/JP2022/030583 2021-08-16 2022-08-10 ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法 Ceased WO2023022093A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2023542375A JP7784673B2 (ja) 2021-08-16 2022-08-10 ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法
KR1020247007986A KR102845308B1 (ko) 2021-08-16 2022-08-10 페로브스카이트 양자점 복합 재료, 잉크 및 페로브스카이트 양자점 복합 재료의 제조 방법
CN202280053735.3A CN117795036A (zh) 2021-08-16 2022-08-10 钙钛矿量子点复合材料、油墨及钙钛矿量子点复合材料的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021132131 2021-08-16
JP2021-132131 2021-08-16

Publications (1)

Publication Number Publication Date
WO2023022093A1 true WO2023022093A1 (ja) 2023-02-23

Family

ID=85240679

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/030583 Ceased WO2023022093A1 (ja) 2021-08-16 2022-08-10 ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法

Country Status (4)

Country Link
JP (1) JP7784673B2 (https=)
KR (1) KR102845308B1 (https=)
CN (1) CN117795036A (https=)
WO (1) WO2023022093A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025220422A1 (ja) * 2024-04-18 2025-10-23 日本ゼオン株式会社 発光性樹脂インク、前記発光性樹脂インクを用いた光学部材、前記光学部材を用いた発光装置、発電装置及び表示体、並びに発光性樹脂インクの製造方法及び光学部材の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116359188B (zh) * 2023-03-16 2026-04-21 常州大学 一种CsPbBr3@SiO2钙钛矿量子点的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221833A1 (ja) * 2016-06-24 2017-12-28 住友化学株式会社 組成物、及び化合物
US20180002354A1 (en) * 2016-06-29 2018-01-04 Nanyang Technological University Perovskite core-shell nanocrystals
CN111349429A (zh) * 2018-12-24 2020-06-30 苏州星烁纳米科技有限公司 钙钛矿量子点及其制备方法
CN111500287A (zh) * 2019-01-30 2020-08-07 苏州星烁纳米科技有限公司 钙钛矿量子点的制备方法
CN113025312A (zh) * 2019-12-25 2021-06-25 致晶科技（北京）有限公司 一种异质钙钛矿晶体材料的制备方法、其制备方法及应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201513272D0 (en) 2015-07-28 2015-09-09 Isis Innovation Luminescent material
CN107017325B (zh) 2015-11-30 2020-06-23 隆达电子股份有限公司 量子点复合材料及其制造方法与应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221833A1 (ja) * 2016-06-24 2017-12-28 住友化学株式会社 組成物、及び化合物
US20180002354A1 (en) * 2016-06-29 2018-01-04 Nanyang Technological University Perovskite core-shell nanocrystals
CN111349429A (zh) * 2018-12-24 2020-06-30 苏州星烁纳米科技有限公司 钙钛矿量子点及其制备方法
CN111500287A (zh) * 2019-01-30 2020-08-07 苏州星烁纳米科技有限公司 钙钛矿量子点的制备方法
CN113025312A (zh) * 2019-12-25 2021-06-25 致晶科技（北京）有限公司 一种异质钙钛矿晶体材料的制备方法、其制备方法及应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIN HECHUN, ZHANG XU, CAI LELE, LAO JIE, QI RUIJUAN, LUO CHUNHUA, CHEN SHIYOU, PENG HUI, HUANG RONG, DUAN CHUNGANG: "High-stability fluorescent perovskites embedded in PbBrOH triggered by imidazole derivatives in water", JOURNAL OF MATERIALS CHEMISTRY C, vol. 8, no. 16, 1 January 2020 (2020-01-01), GB , pages 5594 - 5599, XP093036098, ISSN: 2050-7526, DOI: 10.1039/D0TC00939C *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025220422A1 (ja) * 2024-04-18 2025-10-23 日本ゼオン株式会社 発光性樹脂インク、前記発光性樹脂インクを用いた光学部材、前記光学部材を用いた発光装置、発電装置及び表示体、並びに発光性樹脂インクの製造方法及び光学部材の製造方法

Also Published As

Publication number Publication date
KR20240044481A (ko) 2024-04-04
JPWO2023022093A1 (https=) 2023-02-23
JP7784673B2 (ja) 2025-12-12
CN117795036A (zh) 2024-03-29
KR102845308B1 (ko) 2025-08-11

Similar Documents

Publication Publication Date Title
Lou et al. Nanocomposites of CsPbBr 3 perovskite nanocrystals in an ammonium bromide framework with enhanced stability
US7394091B2 (en) Composite nano-particle and method for preparing the same
JP6431171B2 (ja) ルミネッセント複合材料
KR100841186B1 (ko) 다층 쉘 구조의 나노결정 및 그의 제조방법
Ren et al. Water triggered interfacial synthesis of highly luminescent CsPbX3: Mn2+ quantum dots from nonluminescent quantum dots
WO2023022093A1 (ja) ペロブスカイト量子ドット複合材料、インク、及び、ペロブスカイト量子ドット複合材料の製造方法
EP3898885B1 (en) Small molecule passivation of quantum dots for increased quantum yield
Li et al. Consecutive interfacial transformation of cesium lead halide nanocubes to ultrathin nanowires with improved stability
JP2010132906A (ja) 発光ナノ粒子およびそれらの調製方法
TW201723151A (zh) 發光晶體及其製造
JP2020180278A (ja) エレクトロルミネッセンスデバイスのための無機配位子を有するナノ構造
CN1610062A (zh) 合金型半导体纳米晶体及其制备方法
US10202545B2 (en) Interfused nanocrystals and method of preparing the same
EP4189032B1 (en) Method for preparing metal halide nanocomposites
KR20180073165A (ko) 페로브스카이트 발광 구조체 및 이의 제조 방법
JP2024031023A (ja) ペロブスカイト量子ドット複合体、ペロブスカイト量子ドット複合体の製造方法、インク、及び、ペロブスカイト量子ドット膜の製造方法
Zhou et al. Shape-controlled synthesis of one-dimensional cesium lead halide perovskite nanocrystals: methods and advances
Wang et al. Strain modulation for high brightness blue luminescence of Pr3+-doped perovskite nanocrystals via siloxane passivation
Ramolahloane et al. Controlled synthesis and photoluminescence study of blue-emitting Cs3Bi2Br9 nanocrystals prepared by the ligand-assisted reprecipitation (LARP) method
Shi et al. One-pot synthesis of CsPbBr 3 nanocrystals in methyl methacrylate: a kinetic study, in situ polymerization, and backlighting applications
Ha et al. Revealing the role of organic ligands in deep-blue-emitting colloidal Europium bromide perovskite nanocrystals
CN116042217B (zh) 荧光发光波长可调的卤化物钙钛矿超晶格的制备方法
CN110041918A (zh) 一种全无机铟锡合金钙钛矿纳米晶及其合成方法
CN115477945A (zh) 一种核壳结构量子点及其制备方法
EP3447108B1 (en) Luminescent crystals and manufacturing thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22858414

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023542375

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280053735.3

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22858414

Country of ref document: EP

Kind code of ref document: A1