CN116004226B - Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof - Google Patents

Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof Download PDF

Info

Publication number
CN116004226B
CN116004226B CN202111227197.9A CN202111227197A CN116004226B CN 116004226 B CN116004226 B CN 116004226B CN 202111227197 A CN202111227197 A CN 202111227197A CN 116004226 B CN116004226 B CN 116004226B
Authority
CN
China
Prior art keywords
quantum dot
perovskite quantum
inorganic
parts
polymer
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.)
Active
Application number
CN202111227197.9A
Other languages
Chinese (zh)
Other versions
CN116004226A (en
Inventor
李飞
周家栋
韩登宝
钟海政
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.)
Zhijing Technology Beijing Co ltd
Hefei Innovation Research Institute of Beihang University
Original Assignee
Zhijing Technology Beijing Co ltd
Hefei Innovation Research Institute of Beihang University
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 Zhijing Technology Beijing Co ltd, Hefei Innovation Research Institute of Beihang University filed Critical Zhijing Technology Beijing Co ltd
Priority to CN202111227197.9A priority Critical patent/CN116004226B/en
Publication of CN116004226A publication Critical patent/CN116004226A/en
Application granted granted Critical
Publication of CN116004226B publication Critical patent/CN116004226B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Luminescent Compositions (AREA)

Abstract

The invention discloses a composite perovskite quantum dot material, a perovskite quantum dot composition, a preparation method and application thereof, wherein the composite perovskite quantum dot material comprises perovskite quantum dots/polymers and an inorganic-organic layer; the inorganic-organic layer coats perovskite quantum dots/polymers; the inorganic-organic layer includes an inorganic layer and an organic layer; the inorganic layer and the organic layer undergo hydrolysis condensation reaction to obtain the inorganic-organic layer; the organic layer coats the inorganic layer; the composition of the inorganic layer comprises a metal oxide selected from oxides of aluminum, silicon, titanium or zirconium; the composition of the organic layer includes a cycloaliphatic epoxy-containing silane. The perovskite quantum dot containing alicyclic epoxy on the surface of the material has good dispersibility and compatibility in a cationic curing glue system. Meanwhile, the perovskite quantum dots with the organic-inorganic coating structure can effectively improve the aging resistance and the luminous uniformity of the perovskite quantum dots.

Description

Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof
Technical Field
The invention relates to a composite perovskite quantum dot material, a perovskite quantum dot composition, a preparation method and application thereof, and belongs to the field of quantum dot materials.
Background
The perovskite quantum dot is used as a novel semiconductor luminescent material, has optical performance equivalent to that of the traditional quantum dot, has very simple preparation process, and can be prepared at room temperature or low temperature. The perovskite quantum dot has the greatest characteristic of improving the display color gamut to more than 100% NTSC. However, the long-term stability of perovskite quantum dots in practical applications has a problem, and water oxygen in the use environment invades, resulting in fluorescence quenching of the quantum dots. Therefore, there is an urgent need to improve perovskite quantum dot material stability.
In the prior art, UV curing glue is mostly used as a packaging barrier material of quantum dots, for example, in chinese patent zl201711434422.X, it is proposed to mix a perovskite quantum dot precursor with an acrylic monomer, and then add an acrylic oligomer to obtain a sol, and the sol can be directly used for coating and UV curing after adding a UV curing agent to form a material with a required shape by directly forming a film. The Chinese patent application publication CN109251717A adopts one or more of polybutadiene chain segment modified polyurethane acrylate, polyisoprene chain segment modified polyurethane acrylate and polyisobutylene chain segment modified polyurethane acrylate as an oligomer, and is matched with a monofunctional acrylate monomer and a polyfunctional acrylate monomer to form the glue composition. The glue composition has good compatibility with the quantum dots, the quantum dot composition has good water blocking performance after being cured, and the formed quantum dot composite material has excellent aging stability. Chinese patent ZL201710865772.5 synthesizes an organosilicon modified hyperbranched acrylic resin, and functional groups such as radiation curable groups, high heat resistance and the like are connected to the molecular terminal to be used as a main material of the quantum dot sealant composition. The water-oxygen permeability is effectively reduced, the bonding strength is higher, the compatibility to the quantum dot material is good, the influence on the luminous efficiency of the quantum dot is small, the weather resistance is excellent, the water-oxygen barrier property is excellent, and the quantum dot material can be effectively protected.
The prior art uses free radical photo-curing system glue, but under the aerobic condition, the free radical photo-curing can cause the problem of low crosslinking density due to oxygen polymerization inhibition, so that the sealing performance is poor, and the luminous stability of the quantum dots is further affected. In addition, the free radical photo-curing has the problem of large volume shrinkage, the intermolecular acting force is changed from Van der Waals force before polymerization into a covalent bond form, the degree of tightness of the arrangement between atoms before and after polymerization is changed, and the internal stress caused by the volume shrinkage can cause defects such as poor adhesive force, microcrack generation and the like.
Disclosure of Invention
The invention provides a composite perovskite quantum dot material, which aims to solve the problems of poor compatibility and poor curing of perovskite quantum dots in a cation curing system. Firstly, coating an inorganic layer on the surface of a perovskite quantum dot by an atomic layer deposition technology, then, reacting vinyl-terminated silane, vinyl-containing alicyclic epoxy and hydrogen-containing double-end socket to obtain alicyclic epoxy-containing silane, and finally, carrying out condensation reaction on alicyclic epoxy-modified silane and free hydroxyl on the surface of the quantum dot inorganic coating layer to obtain the perovskite quantum dot material with the alicyclic epoxy on the surface. (1) The organic-inorganic coating structure can effectively improve the ageing resistance and the luminous uniformity of the perovskite quantum dots. (2) The alicyclic epoxy modified silane structure is prepared, and the alicyclic epoxy modified silane structure and the isolated hydroxyl on the surface of the inorganic coating layer are subjected to condensation reaction, so that the quantum dot can have good dispersibility and compatibility in a cationic curing glue system. (3) The cationic curing glue is used for packaging perovskite quantum dots, so that the problem of poor adhesive force caused by shrinkage when the free radical photo-curing glue is cured is avoided.
In one aspect, a composite perovskite quantum dot material is provided, the composite perovskite quantum dot material comprising perovskite quantum dots/polymers, inorganic-organic layers; the inorganic-organic layer coats perovskite quantum dots/polymers; the inorganic-organic layer includes an inorganic layer and an organic layer; the inorganic layer and the organic layer undergo hydrolysis condensation reaction to obtain the inorganic-organic layer; the organic layer coats the inorganic layer; the composition of the inorganic layer comprises a metal oxide selected from oxides of aluminum, silicon, titanium or zirconium; the composition of the organic layer comprises silane containing alicyclic epoxy; the chemical structure of the alicyclic epoxy-containing silane is shown as a formula I:
i is a kind of
Wherein:
R 1 ：-CH 2 -
R 2 selected from the group consisting of
R 3 Selected from-CH 3 Or (b)
R 4 Selected from-CH 2 -or
R 5 Selected from the group consisting of-O-CH 3 or-O-CH 2 -CH 3
R 6 Selected from the group consisting of-O-CH 3 or-O-CH 2 -CH 3 or-CH 3
p is more than or equal to 0; q is more than or equal to O; n=0 or 1
The inorganic layer is an inorganic coating layer of one or more of an aluminum source, a silicon source, a titanium source and a zirconium source, which is prepared on the surface of the perovskite quantum dot by an atomic layer deposition method; the organic layer is prepared by reacting the inorganic layer with silane containing alicyclic epoxy, and the surface of the organic layer contains the alicyclic epoxy.
The perovskite quantum dots/polymers include perovskite quantum dots and polymers in which the perovskite quantum dots are embedded. Preferably the perovskite quantum dot/polymer powder is prepared by a spray drying process.
The mass ratio of the alicyclic epoxy-containing silane to the inorganic coated perovskite quantum dot/polymer powder is (5-20): (3-8).
The mass ratio of the metal oxide of the inorganic layer is not particularly limited, and the inorganic layers with different thicknesses on the surface of the coated perovskite quantum dot/polymer can be obtained through cyclic coating times according to specific requirements in the preparation process.
Preferably, the metal oxide is selected from at least one of aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, and the like.
Preferably, the thickness of the inorganic layer is 5nm to 100nm; the thickness of the inorganic-organic layer is 10 nm-300 nm.
Preferably, the metal oxide is selected from at least one of aluminum oxide, silicon dioxide, titanium dioxide or zirconium dioxide.
A perovskite quantum dot/polymer composite powder material, wherein the particle size of the powder material is 0.1-200 mu m.
Alternatively, the particle size of the powder material is independently selected from any value or range of values between any two of 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 170 μm, 190 μm, 200 μm.
Optionally, in the perovskite quantum dot/polymer composite powder material, the perovskite quantum dot has a size of 2 to 50nm in at least one dimension.
Alternatively, the perovskite quantum dots have a size in at least one dimension independently selected from any of 2nm, 5nm, 10nm, 12nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm or a range of values between any two.
Preferably, in the perovskite quantum dot/polymer, the perovskite quantum dot has a size of 2-50 nm in at least one dimension; the perovskite quantum dot has a structural AMX 3 、A 3 M 2 X 9 、A 2 MX 6 、Q 2 A m-1 M m X 3m+1 At least one of (a) and (b); wherein A is NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + At least one of (a) and (b); m is Pb 2+ 、Cd 2+ 、Mn 2+ 、Zn 2+ 、Sn 2+ 、Ge 2+ 、Bi 3+ At least one of (a) and (b); x is at least one of halogen anions; q is an aromatic group or an alkyl organic amine cation having not less than 3 carbon atoms; m is any number between 1 and 100.
In the present application, the halogen anion is F - 、Cl - 、Br - Or I - 。
Alternatively, the aromatic group is benzene, naphthalene, anthracene, phenanthrene, and homologs thereof.
Alternatively, the alkyl organoamine cation has a carbon number of from 4 to 25.
Preferably, the polymer is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate.
Preferably, in the perovskite quantum dot/polymer, the mass ratio of the perovskite quantum dot to the polymer is 1:1 to 500.
Optionally, in the perovskite quantum dot/polymer composite powder material, the mass ratio of perovskite quantum dot to polymer matrix is independently selected from any value or range between any two values of 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:20, 1:30, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:400, 1:500.
The application also provides a method for preparing the perovskite quantum dot/polymer composite powder material in situ. The preparation method solves the preparation problem of the perovskite quantum dot/polymer composite material ultrafine powder with high luminous performance and high stability, and the whole process can be carried out in an anhydrous and anaerobic environment, and the stability of the perovskite quantum dot/polymer composite material is enhanced by the anhydrous and anaerobic preparation process.
A method for preparing perovskite quantum dot/polymer composite powder material in situ, atomize perovskite quantum dot precursor solution into small liquid drops, then dry the atomized small liquid drops, produce perovskite quantum dot/polymer composite powder material.
Optionally, the perovskite quantum dot precursor solution includes a solvent, a perovskite quantum dot raw material, and a polymer matrix.
Optionally, the solvent is at least one selected from N, N-dimethylformamide, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone and dimethylacetamide.
In the present application, the solvent may dissolve the perovskite quantum dot raw material and the polymer matrix.
Optionally, the perovskite quantum dot feedstock comprises AX, QX and MX t The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is selected from NH2CHNH 2 + (FA)、CH 3 NH 3 + (MA)、C s + At least one of (a) and (b);
m is selected from Pb 2+ 、Cd 2+ 、Mn 2+ 、Zn 2+ 、Sn 2+ 、Ge 2+ 、Bi 3+ At least one of (a) and (b);
q is selected from aryl or alkyl organic amine cation with carbon number not less than 3;
x is selected from at least one of halogen anions; t=2 or 3.
In the present application, the mass of perovskite quantum dot raw material includes the mass of all raw materials.
In the actual application process, the corresponding perovskite quantum dot raw materials can be selected according to actual needs. It is pointed out that the preparation method of the application can be amplified and has good industrial practical application value.
Optionally, the polymer matrix is selected from at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate.
Optionally, the mass ratio of polymer matrix to solvent is 1:2 to 200.
Optionally, the mass ratio of polymer matrix to solvent is 1:5 to 50.
Alternatively, the mass ratio of polymer matrix to solvent is independently selected from any value or range between any two of 1:2, 1:5, 1:10, 1:15, 1:20, 1:50, 1:80, 1:100, 1:120, 1:150, 1:180, 1:200.
Optionally, the mass ratio of perovskite quantum dot raw material to polymer matrix is 1:1 to 500.
Optionally, the mass ratio of perovskite quantum dot raw material to polymer matrix is 1:5 to 100.
Optionally, the mass ratio of perovskite quantum dot starting material to polymer matrix is independently selected from any value or range of values between any two of 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:20, 1:30, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:400, 1:500.
Optionally, the perovskite quantum dot precursor solution further comprises additives and/or surface ligands.
Optionally, the additive is at least one selected from zinc bromide, zinc iodide, stannous bromide, stannous iodide, cadmium bromide, cadmium iodide, hypophosphorous acid.
Optionally, the mass ratio of the additive to the perovskite quantum dot raw material is 1:1 to 500.
Optionally, the mass ratio of the additive to the perovskite quantum dot raw material is 1:4 to 100.
Optionally, the mass ratio of additive to perovskite quantum dot feedstock is independently selected from any value or range of values between any two of 1:1, 1:2, 1:4, 1:5, 1:10, 1:15, 1:20, 1:30, 1:50, 1:70, 1:80, 1:90, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, 1:500.
Optionally, the surface ligand comprises at least one of an organic acid, an organic acid halide, a long chain organic amine, a halide of a long chain organic amine.
Alternatively, the organic acid includes a saturated or unsaturated alkyl acid having at least 3 carbon atoms.
Optionally, the organic acid includes a saturated alkyl acid or an unsaturated alkyl acid having 4 to 24 carbon atoms.
Alternatively, the long chain organic amine is an alkylamine amine or an aromatic amine of 4 to 24 carbon atoms.
Optionally, the halide of the organic acid or long-chain organic amine is the halide corresponding to the organic acid or long-chain organic amine.
Optionally, the mass ratio of the surface ligand to the perovskite quantum dot raw material is 1:1 to 50.
Optionally, the mass ratio of the surface ligand to the perovskite quantum dot raw material is 1:2 to 20.
Optionally, the mass ratio of perovskite quantum dot starting material to surface ligand is independently selected from any value or range of values between any two of 1:1, 1:2, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50.
Optionally, the feed flow of the perovskite quantum dot precursor solution is 1 mL/min-5000 mL/min;
the temperature of the inlet air is 40-200 ℃.
Alternatively, the atomized droplets become perovskite quantum dot/polymer composite powder material and solvent vapor after drying, and the solvent is recovered by separation.
Optionally, an inert gas is used as the recycle gas.
Optionally, the inactive gas is at least one selected from nitrogen and helium. The inactive gas is used as the circulating gas, so that the whole preparation process further maintains an oxygen-free and water-free state, and is used as the protective gas, and is sensitive to water and oxygen in the production process 2 、CHNH 2 Raw materials such as NH HX (X is halogen) and the like can also be produced, and the obtained product has better performance and higher stability.
In the application, the property of the perovskite quantum dot/polymer composite material ultrafine powder prepared in situ by a spray drying method is mainly determined by the composition of a perovskite quantum dot precursor solution and the production process. The production process mainly adjusts the air inlet temperature, the material concentration, the rotating speed of the atomizer and the feeding flow.
Optionally, the air inlet temperature is 40-200 ℃.
Optionally, the rotation speed of the atomizer is 5000-70000 r/min.
Optionally, the feeding flow is 1 mL/min-5000 mL/min.
Alternatively, the material concentration (polymer to solvent mass ratio) is 1:2 to 200.
Alternatively, the polymer to solvent mass ratio is independently selected from any value or range of values between any two of 1:2, 1:5, 1:10, 1:15, 1:20, 1:50, 1:80, 1:100, 1:120, 1:150, 1:180, 1:200.
On the other hand, the invention also provides a preparation method of the composite perovskite quantum dot material, which comprises the following steps:
(1) Obtaining perovskite quantum dot/polymer powder;
(2) Depositing a metal source on the surface of the perovskite quantum dot/polymer powder by an atomic deposition (ALD) method, and hydrolyzing to obtain a perovskite quantum dot/polymer coated with metal oxide;
(3) Obtaining silane containing alicyclic epoxy;
(4) And (3) carrying out hydrolysis condensation reaction on the alicyclic epoxy-containing silane and the perovskite quantum dot/polymer coated by the metal oxide to obtain the composite perovskite quantum dot material.
As a preferred technical scheme, in the step (2), the metal source is at least one selected from an aluminum source, a silicon source, a titanium source and a zirconium source; the aluminum source is at least one selected from trimethylaluminum, triethylaluminum and aluminum trichloride; the silicon source is at least one selected from methyl orthosilicate or ethyl orthosilicate; the titanium source is at least one of tetrabutyl titanate, isopropyl titanate and tetraethyl titanate; the zirconium source is at least one selected from zirconium dimethylamino, tetrabutyl zirconate, zirconium n-butoxide, zirconium tert-butoxide and zirconium isopropoxide.
The metal oxide is formed on the surface of the perovskite quantum dot/polymer by an atomic deposition (ALD), and the deposition temperature of the step (2) is preferably 80-100 ℃ by setting the technological parameters of the ALD; the time is 5 s-90 s; the vacuum degree is 100-1000 Pa, the time of introducing steam is 3-20 s, the cycle number is 10-500, the required deposition thickness is obtained, and the inorganic layer coating is completed. According to specific needs, the inorganic layers with different thicknesses are obtained through cyclic coating times in the preparation process.
Preferably, in the step (3), the alicyclic epoxy-containing silane is prepared by adding vinyl-terminated silane, vinyl-terminated alicyclic epoxy and double-terminated hydrosilane through hydrosilylation under the action of a platinum-series catalyst; the mol ratio of the vinyl-terminated silane to the vinyl-terminated alicyclic epoxy compound to the double-terminated hydrosilane is 1-1.02: 1 to 1.1:1, a step of; the platinum catalyst accounts for 0.001 to 0.5 percent of the sum of the masses of vinyl-terminated silane, vinyl-terminated alicyclic epoxy and bi-terminal hydrosilane, and is preferably 0.02 to 0.5 percent; the reaction temperature is 110-130 ℃.
Optionally, the molar ratio of the vinyl-terminated silane, the vinyl-terminated cycloaliphatic epoxy compound, the bis-terminal hydrosilane is any value or range between any two values independently selected from 1:1.05:1, 1:1.1:1, 1:1.07:1, 1:1.02:1, 1.02:1.02:1.
Alternatively, the platinum-based catalyst is used in an amount that is a ratio of the sum of the mass of the terminal vinylsilane, the alicyclic epoxy of the terminal vinyl group, and the bis-terminal hydrosilane, and is independently selected from any value or range of values between any two of 0.001%, 0.005%, 0.009%, 0.011%, 0.019%, 0.02%, 0.1%, 0.2%, 0.5%.
Alternatively, the reaction temperature of the hydrosilylation reaction is independently selected from any value or range of values between any two of 110 ℃, 120 ℃, 130 ℃.
Preferably, the vinyl-terminated silane is at least one selected from the group consisting of vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, and methacryloxypropylmethyldimethoxysilane.
Preferably, the vinyl-terminated alicyclic epoxy is preferably at least one of 1, 2-epoxy-4-vinylcyclohexane, 3, 4-epoxycyclohexyl methacrylate or 3, 4-epoxycyclohexyl methacrylate.
Preferably, the double-terminal hydrosilane is at least one selected from tetramethyl dihydro disiloxane, tetramethyl diphenyl dihydro trisiloxane, double-terminal hydrogen polydimethyl siloxane and tetraisopropyl dihydro disiloxane; preferably the double-ended hydrogen polydimethylsiloxane is dodecamethyldihydrohexasiloxane.
Preferably, the platinum-group catalyst is at least one selected from chloroplatinic acid, complexes of platinum and vinyl siloxane, and platinum-olefin complexes.
Preferably, in the step (4), the mass ratio of the alicyclic epoxy modified silane to the perovskite quantum dot/polymer coated by the metal oxide is 5-20: 3 to 8; the conditions of the hydrolytic condensation reaction are that the temperature is 25-60 ℃ and the time is 0.5-30 h.
Optionally, in step (4), the mass ratio of the cycloaliphatic epoxy modified silane and the metal oxide coated perovskite quantum dot/polymer is independently selected from any value or range of values between any two of 0.6, 1, 2, 2.62, 3, 3.26, 4, 4.11, 5, 6, 6.7.
As a preferred technical scheme, in the step (1), the method for obtaining the perovskite quantum dot/polymer powder comprises the steps of atomizing a perovskite quantum dot precursor solution into small droplets, and then drying the atomized small droplets to generate the perovskite quantum dot/polymer powder; the perovskite quantum dot precursor solution comprises a solvent, a perovskite quantum dot raw material and a polymer matrix;
the particle size of the perovskite quantum dot/polymer powder is 0.1-200 mu m;
preferably, the solvent is at least one selected from N, N-dimethylformamide, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone and dimethylacetamide;
On the other hand, the invention also provides a perovskite quantum dot composition, which comprises the following components in parts by weight: 2 to 21 parts of complex perovskite quantum dot material, 40 to 260 parts of epoxy resin, 20 to 180 parts of reactive diluent, 0.1 to 18 parts of cationic initiator, 5 to 35 parts of light scattering particles and 0.5 to 10 parts of auxiliary agent;
the perovskite quantum dot material is at least one of any one of the composite perovskite quantum dot materials or the composite perovskite quantum dot material prepared by any one of the preparation methods.
Optionally, the perovskite quantum dot composition comprises the following components in parts by weight: 11 to 20.5 parts of perovskite quantum dot material, 170 to 200 parts of epoxy resin, 40 to 130 parts of reactive diluent, 0.5 to 14 parts of cationic initiator, 20 to 30 parts of light scattering particles and 1 to 6 parts of auxiliary agent;
alternatively, the parts by weight of the perovskite quantum dot material are independently selected from any value or range of values between any two of 2 parts, 5 parts, 10 parts, 11 parts, 11.9 parts, 12 parts, 12.6 parts, 15.1 parts, 16.9 parts, 17 parts, 20.5 parts, 21 parts.
Optionally, the parts by weight of the epoxy resin are independently selected from: 40 parts, 60 parts, 80 parts, 100 parts, 150 parts, 179.5 parts, 196.7 parts, 232.1 parts, 246 parts, 250 parts, 257 parts, 260 parts, or a range of values therebetween.
Optionally, the reactive diluents are independently selected from the group consisting of: any value or range of values between any two of 20 parts, 40 parts, 41.7 parts, 50 parts, 72.5 parts, 82.9 parts, 100 parts, 120 parts, 129.5 parts, 130 parts, 150 parts, 170.3 parts, 180 parts.
Optionally, the parts by weight of the cationic initiator are independently selected from: any value or range of values between any two of 0.1 part, 0.5 part, 1 part, 5 parts, 10 parts, 10.44 parts, 14.9 parts, 15 parts.
Optionally, the parts by weight of the light scattering particles are independently selected from: any value or range of values between any of 5 parts, 10 parts, 20 parts, 20.5 parts, 25.3 parts, 29.1 parts, 30 parts, 31.3 parts, 35 parts.
Optionally, the weight parts of the auxiliary agent are independently selected from: any value or range of values between any two of 0.5 parts, 1 part, 1.8 parts, 2.5 parts, 4.4 parts, 5 parts, 5.9 parts, 6.8 parts, 6.9 parts, 10 parts, 15 parts, 17.8 parts, 18 parts.
The epoxy, reactive diluent, cationic initiator, light scattering particles and auxiliary agent combination is referred to as a cationically cured glue or epoxy glue or glue.
The perovskite quantum dot material is any one of the composite perovskite quantum dot materials or the composite perovskite quantum dot material prepared according to any one of the preparation methods.
The epoxy resin is at least one selected from alicyclic epoxy resins and glycidyl type epoxy resins.
Preferably, the alicyclic epoxy resin comprises at least one of bis (di (3, 4-epoxycyclohexyl) methyl) adipic acid, poly [ (2-epoxyethyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1), 1, 4-bis (3, 4-epoxycyclohexyl-1-methoxy) methylbenzene, 1, 4-bis (3, 4-epoxycyclohexyl-1-methoxy) butane, epoxypolybutadiene (japanese celluloid epolate PB series), dicyclopentadiene dioxide, methyl 3, 4-epoxycyclohexane carboxylate.
Preferably, the glycidyl type epoxy resin is at least one selected from hydrogenated bisphenol A type diglycidyl ether, hydrogenated bisphenol F type diglycidyl ether, hydrogenated bisphenol E type diglycidyl ether, hydrogenated bisphenol S type diglycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, polytetramethylene glycol glycidyl ether;
the reactive diluent is at least one selected from ethyl (propyl) alkenyl ethers, oxygen heterocycle reactive diluents and glycidyl ether ethers.
The cationic initiator is selected from a photo cationic initiator and/or a thermal cationic initiator.
The photo cation initiator is selected from sulfonium salts such as 4-phenylsulfanylphenyl diphenylsulfonium salt, tris [4- [ (4-acetylphenyl) thio ] -hexafluorophosphate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-phenylsulfanylphenyl sulfonium hexafluoroantimonate, diphenyl-4-phenylsulfanylphenyl sulfonium hexafluorophosphate, 4-dodecylphenyldiphenylsulfonium hexafluorophosphate, 4' -bis (diphenylsulfonium) phenylsulfide-bis-hexafluoroantimonate, 4' -bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] phenylsulfide-bis-hexafluoroantimonate, 4- [4' - (benzoyl) phenylthio ] phenyl-bis- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate; iodonium salts such as at least one of diphenyliodohexafluoroantimonate, bis (4-methylphenyl) iodohexafluorophosphate, bis (4-tert-butylphenyl) iodohexafluorophosphate, tolyltetra (pentafluorophenyl) borate diaryliodonium salts, and arylferrocenium salts such as [ cyclopentadiene-iron-isopropylbenzene ] hexafluorophosphate;
The thermal cation initiator is selected from anhydride compounds such as methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and tetrahydrophthalic anhydride; imidazole derivatives such as N- (2- (2-methyl-1-imidazolyl) ethyl) urea, N' - (2-methyl-1-imidazolylethyl) adipamide, 2-phenyl-4, 5-dimethylol imidazole, hycat TM At least one of AO-4 (DTCS, U.S.), CXC-1612 (King's chemical, U.S.);
the light scattering particles are selected from inorganic light dispersing agents or organic light dispersing agents; the light scattering particles are dispersed into the glue to form micron-sized concave-convex surfaces, and the concave-convex surfaces can enable incident light to be scattered, so that the effect of improving light diffusion uniformity and brightness is achieved. Selected from inorganic light diffusion agents and organic light diffusion.
Preferably, the inorganic light dispersing agent is at least one of nano barium sulfate, nano zinc oxide and nano silicon dioxide;
preferably, the organic light diffusion is at least one selected from PMMA microspheres, organosilicon microspheres, polytetrafluoroethylene wax, polypropylene wax, polyethylene wax microspheres, polyamide wax microspheres and amide modified polyethylene wax;
the auxiliary agent is at least one selected from flatting agent, defoamer and antioxidant.
In still another aspect, the invention further provides a preparation method of the perovskite quantum dot composition, the perovskite quantum dot composition is obtained by mixing the perovskite quantum dot material with epoxy resin, reactive diluent, cationic initiator, light scattering particles and auxiliary agent according to the proportion, and dispersing under vacuum condition.
On the other hand, the invention also provides the composite perovskite quantum dot material prepared by any one of the preparation methods, the perovskite quantum dot composition prepared by any one of the preparation methods and the application of the perovskite quantum dot composition prepared by any one of the preparation methods in the semiconductor luminescent material.
As a preferred technical solution, for light emitting diodes, light conversion devices, display devices, photovoltaic devices, lighting devices, uv detection, sensors, hybrid composites, biomarkers, inkjet printing inks, etc.; the display device is preferably a liquid crystal display or an imaging sensor; the photovoltaic device is preferably a solar cell; the sensor is preferably a biosensor; the light emitting diode is preferably an electroluminescent diode or an organic light emitting diode.
The invention has the beneficial effects that:
1. in the prior art, the inorganic coated perovskite quantum dots and the organic phase are not combined by chemical bonds, so that the quantum dots are easy to agglomerate and difficult to disperse in polymer matrix resin. According to the invention, the inorganic coated quantum dots are further modified by adopting an epoxy-containing organic structure, so that the inorganic coated quantum dots have a structure similar to that of an epoxy glue system, thus the inorganic coated quantum dots have good compatibility and dispersibility in the glue system, are not easy to generate sedimentation, and the coated or printed quantum dot film emits light more uniformly.
2. The silane containing alicyclic epoxy is grafted on the surface of the perovskite quantum dot, after the quantum dot with the epoxy introduced on the surface is subjected to photo/thermal curing, the quantum dot can be polymerized in a molecular chain main body, and the phenomenon of migration and precipitation in the aging process is avoided, so that the water and oxygen are difficult to damage, and the perovskite quantum dot has excellent aging resistance.
3. In the prior art, free radical UV curing is mostly adopted, and the problem of low crosslinking density caused by oxygen polymerization inhibition can be caused when curing under the aerobic condition, and even the product performance is affected seriously. The surface of the coating layer is alicyclic epoxy, and cation curing occurs under the condition of photo/thermal initiation, so that the problem of low curing degree caused by oxygen polymerization inhibition is avoided. In addition, the problem of poor adhesive force caused by the shrinkage of the free radical curing volume is avoided.
Drawings
FIG. 1 example 1 schematic diagram of the preparation of inorganic-organic perovskite quantum dot compositions
And 2, a morphology electron microscope SEM image of perovskite quantum dot/polymer green powder microsphere MAPbBr 3/PVDF.
FIG. 3 is an SEM image of an inorganic-organic coated perovskite quantum dot/polymer prepared according to example 1.
FIG. 4 is a SEM image of an inorganic-organic coated perovskite quantum dot/polymer prepared according to example 1.
FIG. 5 is a schematic diagram of the structure of the inorganic-organic coated perovskite quantum dots prepared in example 1;
FIG. 6 is MAPbBr 3 and/PVDF composite material superfine powder fluorescence emission spectrum.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Instrument name and model
(1) Spray drying: closed-circuit nitrogen circulation spray dryer, safety grinding instrument and AYAN-BL-5L
(2) ALD coating: internal and external cavity atomic deposition system, xiamen Mao technology, G10
(3) Morphology of the sample: scanning Electron Microscope (SEM) test analysis, sigma 500 field emission scanning electron microscope.
Preparation of perovskite Quantum dots/Polymer
Firstly, coating an inorganic layer on the surface of a perovskite quantum dot by an atomic layer deposition technology, then, reacting vinyl-terminated silane, vinyl-containing alicyclic epoxy and bi-terminal hydrosilane to obtain alicyclic epoxy-containing silane, and finally, performing condensation reaction on the alicyclic epoxy-containing silane and free hydroxyl on the surface of the quantum dot inorganic coating layer to obtain the perovskite quantum dot/polymer with the organic-inorganic coating structure. The perovskite quantum dot with the alicyclic epoxy on the surface has good dispersibility and compatibility in a cationic curing glue system. Meanwhile, the perovskite quantum dots with the organic-inorganic coating structure can effectively improve the aging resistance and the luminous uniformity of the perovskite quantum dots. The method comprises the following specific steps:
a. And (3) blending the quantum dot material precursor, the polymer matrix, the organic solvent and the ligand, and dissolving and drying to prepare the perovskite quantum dot/polymer green powder microsphere. b. And (3) depositing an oxide film on the surface of the perovskite quantum dot/polymer powder by an atomic layer deposition technology to obtain the inorganic matter coated perovskite quantum dot with hydroxyl on the surface.
c. The alicyclic epoxy silane is obtained through hydrosilylation of vinyl-terminated silane and vinyl-terminated alicyclic epoxy and hydrogen-containing double seal heads under the action of a platinum catalyst.
d. Adding the inorganic coated perovskite quantum dot into silane containing alicyclic epoxy, and obtaining the perovskite quantum dot material with the surface containing alicyclic epoxy groups through hydrolytic condensation reaction.
e. Uniformly mixing the perovskite quantum dot material with the surface containing the alicyclic epoxy group with epoxy resin, an active diluent, a cationic initiator and an auxiliary agent according to a certain proportion to obtain the perovskite quantum dot composition.
The perovskite quantum dot/polymer green powder microspheres used in the embodiment of the application are MAPbBr prepared by adopting a spray drying method 3 The PVDF composite material ultrafine powder is prepared by the following steps:
MA refers to an amine ion and PVDF refers to polyvinylidene fluoride. MABr mass 1g.
MABr：PbBr 2 Mass ratio = 1:1.2.
(MABr+PbBr 2 ): dodecylamine mass ratio = 3:1.
(MABr+PbBr 2 ): PVDF mass ratio = 1:10.
PVDF: n, N-dimethylformamide mass ratio = 1:10.
all the raw materials are mixed and mechanically stirred for 3 hours to fully dissolve the raw materials to obtain a precursor solution. The precursor solution is poured into a precursor tank, the feeding flow is 50mL/min, the rotating speed of an atomizer is 20000r/min, and the air inlet temperature is 80 ℃. The obtained perovskite quantum dot/polymer green powder emitting green fluorescence.
MAPbBr 3 The fluorescence emission spectrum of the ultra-fine powder of the PVDF composite material is shown in FIG. 6, and the emission peak is 537nm; SEM is shown in FIG. 2, and it can be seen that the uncoated perovskite quantum dots/polymers are ellipsoidal with particle sizes of 1-10 μm, and have smooth and uniform surfaces.
Example 1
MAPbBr 3 PVDF perovskite quantum dot/polymer green powder is put into ALD equipment, and trimethylaluminum precursor is fully contacted with the quantum dot/polymer green powder by pulse argon under 500Pa and 80 ℃. And then introducing water vapor for 5s to hydrolyze trimethyl aluminum adsorbed on the surface of the quantum dot into aluminum oxide, repeating the process for 100 times, and obtaining the perovskite quantum dot/polymer green powder coated by aluminum oxide with the thickness of 20 nm.
13.4g of tetramethyl dihydro disiloxane, 26.2g of methacryloxymethyl triethoxysilane and 0.006g of chloroplatinic acid (5% by weight in isopropanol) were reacted at 120℃for 1 hour, then 13.04g of 1, 2-epoxy-4-vinylcyclohexane was added and the reaction was continued for 1 hour, and after no Si-H bond was contained in the test system, the reaction was stopped to give a cycloaliphatic epoxy-containing silane:
10g of aluminum oxide coated perovskite quantum dot green powder, 26.2g of alicyclic epoxy-containing silane and 120mL of ethanol solution are stirred for 10 hours at 40 ℃ and then ethanol is removed by a rotary evaporation method, so that inorganic-organic coated perovskite quantum dot green powder is obtained.
Fig. 3 is an SEM image of the inorganic-organic coated perovskite quantum dot green powder/polymer prepared in example 1, and it can be seen from the image that the particle size of the inorganic-organic coated perovskite quantum dot/polymer is not significantly changed, there is no cross-linked hardening between the particles, and the surface of the perovskite quantum dot/polymer presents a rough shape, which indicates that the inorganic-organic coating layer is formed on the surface of the perovskite quantum dot/polymer.
FIG. 4 is a cross-sectional SEM image of the inorganic-organic coated perovskite quantum dot/polymer prepared in example 1, wherein the coated perovskite quantum dot/polymer is coated by a dense shell layer on the surface, and the thickness of the inorganic-organic shell layer is 130-190 nm.
12.6g of inorganic-organic coated perovskite quantum dot green powder, 179.5g of 3, 4-epoxycyclohexylformic acid-3 ',4' -epoxycyclohexylmethyl ester, 72.5g of triethylene glycol divinyl ether, 15.7g of 4-phenylsulfanylphenyl diphenylsulfonium salt and 0.5g of Hycat are added in sequence TM AO-4 thermally initiated cationic initiator (DTCS Co., USA), 4.4g antioxidant 1010, 5.5g polyamide wax microsphere and 15.5g nano hydrophobic silica. Under the vacuum condition, inorganic-organic coated perovskite quantum dot/polymer composition is obtained after non-intrusive dispersion for 3min by a homogenizer, and is marked as No. 1.
Example 2
After reacting 38.7 g of dodecamethyldihydrohexasiloxane, 17.1g of vinyltriethoxysilane and 0.014g of chloroplatinic acid (5 wt% in isopropanol) at 120℃for 1 hour, 20.0g of 3, 4-epoxycyclohexylmethacrylate was added and the reaction was continued for 1 hour, and the reaction was stopped after no Si-H bond was contained in the test system to give a cycloaliphatic epoxy-containing silane:
10g of the alumina-coated perovskite quantum dot green powder prepared in the embodiment 1 is added into 41.1g of silane containing alicyclic epoxy and 170ml of ethanol solution, and the mixture is stirred for 10 hours at 40 ℃ and then removed by a rotary evaporation method to obtain the inorganic-organic-coated perovskite quantum dot green powder.
11.9g of inorganic-organic coated perovskite quantum dot green powder, 196.7g of 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 41.7g of 3-ethyl-3-hydroxymethyl oxetane, 14.9g of 4,4' -bis [ bis (. Beta. -hydroxyethoxy) phenyl sulfonium ] phenyl sulfide-bis-hexafluoroantimonate, 1.8g of antioxidant 1076, 5g of polyamide wax microsphere and 24.1g of organosilicon microsphere are added in sequence. Under the vacuum condition, inorganic-organic coated perovskite quantum dot/polymer composition is obtained after non-intrusive dispersion for 3min by a homogenizer, and is marked as No. 2.
Example 3
After 23.2g of tetramethyl diphenyl dihydrotrisiloxane, 13.3g of vinyltriethoxysilane and 0.009g of chloroplatinic acid (5 wt% in isopropanol) were reacted at 120℃for 1 hour, 9.3g of 1, 2-epoxy-4-vinylcyclohexane was added and the reaction was continued for 1 hour, and after the test system had no Si-H bond, the reaction was stopped to give a cycloaliphatic epoxy-containing silane:
10g of the perovskite quantum dot green powder coated with aluminum oxide prepared in the embodiment 1 is added into 32.6g of silane containing alicyclic epoxy and 142mL of ethanol solution, and the mixture is stirred for 10 hours at 40 ℃ and then removed by a rotary evaporation method to obtain the inorganic-organic coated perovskite quantum dot green powder.
16.9g of inorganic-organic coated perovskite quantum dot green powder, 232.1g of 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 129.5g of n-butyl glycidyl ether, 5.44g of bis (4-tert-butylphenyl) iodohexafluorophosphate, 5g of methyltetrahydrofuran, 5.9g of antioxidant 168 and 25.3g of amide modified polyethylene wax are added in sequence. And (3) carrying out non-invasive dispersion for 3min by a homogenizer under a vacuum condition to obtain the inorganic-organic coated perovskite quantum dot/polymer composition, which is marked as No. 3.
Example 4
The inorganic-organic coated perovskite quantum dot green powder was consistent with example 1. 15.1g of inorganic-organic coated perovskite quantum dot green powder, 245.8g of 1, 4-bis (3, 4-epoxycyclohexyl-1-methoxy) methylbenzene, 82.9g of glycerol carbonate propenyl ether, 3.5g of diphenyl-4-thiophenylphenyl sulfonium hexafluoroantimonate, 0.5g of CXC-1612 heat-initiated cationic initiator (U.S. gold's chemical), 5.1g of defoamer TEGO Rad 2010, 1.8g of antioxidant 264 and 18.8g of organosilicon microspheres, and 12.5g of polytetrafluoroethylene wax are added in sequence. Under the vacuum condition, inorganic-organic coated perovskite quantum dot composition is obtained after non-intrusive dispersion for 5min by a homogenizer, and is marked as No. 4.
Example 5
The inorganic-organic coated perovskite quantum dot green powder was consistent with example 1. 20.5g of the inorganic-organic coated perovskite quantum dot green powder 1# prepared in example 1, 257.0g of epoxidized polybutadiene, 170.3gl, 4-cyclohexanedimethanol divinyl ether, 10.2g of diphenyliodohexafluoroantimonate, 7.6g of methyl hexahydrophthalic anhydride, 4.3g of defoamer TEGO Rad 2010,2.5g of antioxidant 626 and 41.4g of polypropylene wax were added sequentially. Under the vacuum condition, inorganic-organic coated perovskite quantum dot composition is obtained after non-intrusive dispersion for 5min by a homogenizer, and is marked as No. 5.
Example 6
And (3) replacing the precursor trimethylaluminum of the inorganic layer for ALD coating with zirconium tetrachloride to obtain the perovskite quantum dot green powder coated with zirconium dioxide.
Otherwise, in accordance with example 1, an inorganic-organic coated perovskite quantum dot composition was obtained, designated 6#.
Example 7
And (3) changing precursor trimethylaluminum of the ALD coating inorganic layer into silicon tetrachloride to obtain the perovskite quantum dot green powder coated with silicon dioxide. Otherwise in accordance with example 1, the inorganic-organic coated perovskite quantum dot composition was designated 7#.
Comparative example 1
Sequentially adding 10g of uncoated perovskite quantum dot/polymer green powder microsphere and MAPbBr 3 The same proportion of cationic curing glue as in example 1 was compounded to give an uncoated perovskite quantum dot/polymer composition, designated 8#. The cationically curable glue of example 1 comprises 179.5g of 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 72.5g of triethylene glycol divinyl ether, 15.7g of 4-phenylsulfanylphenyl diphenylsulfonium salt, 0.5g of Hycat TM AO-4 thermally initiated cationic initiator (DTCS Co., USA), 4.4g antioxidant 1010, 5.5g polyamide wax microsphere and 15.5gNano hydrophobic silica.
Comparative example 2
Titanium ore quantum dot/polymer green powder microsphere, MAPbBr 3 And (3) placing the PVDF composite material ultrafine powder into ALD equipment, and fully contacting the zirconium tetrachloride precursor with the quantum dot/polymer green powder by pulse argon at 500Pa and 85 ℃. And then introducing water vapor for 5s to hydrolyze zirconium tetrachloride adsorbed on the surface of the quantum dot into zirconium dioxide, repeating the process for 200 times, and obtaining the perovskite quantum dot/polymer coated with zirconium dioxide with the thickness of 10 nm.
The zirconium dioxide coated perovskite quantum dot/polymer green powder was compounded with the same proportion of cationic curing glue as in example 1 to obtain an inorganic coated perovskite quantum dot/polymer, designated 9#.
Comparative example 3
Titanium ore quantum dot/polymer green powder microsphere, MAPbBr 3 And (3) placing the ultrafine powder of the PVDF composite material into an ALD device, and fully contacting the silicon tetrachloride precursor with the quantum dot/polymer green powder by pulse argon at 50KPa and 70 ℃. And introducing water vapor for 5s to hydrolyze silicon tetrachloride adsorbed on the surface of the quantum dot into silicon dioxide, repeating the process for 100 times, and obtaining the perovskite quantum dot/polymer green powder coated with the silicon dioxide with the thickness of 10 nm.
The same proportion of cationic curing glue is compounded with the perovskite quantum dot/polymer coated by silicon dioxide as in the embodiment 1 to obtain the perovskite quantum dot/polymer coated by inorganic, which is marked as 10#.
Examples 1-7 and comparative examples 1-3 above are applicable to perovskite quantum dot yellow powders, red powders, pink powders, and other colored powders.
The quantum dot compositions of examples 1 to 7 and comparative examples 1 to 3 were coated on the PET surface of the barrier film with a diffusion layer by means of slit coating, and were converted into solid films after irradiation with a UV light source having a main wavelength of 365 nm. And then the film is bonded and packaged with another barrier film coated with OCR optical adhesive.
Wherein the water vapor transmission rate of the barrier film is 10 -1 g/m 2 Permeability of oxygen of 10g/m per 24h 2 And/24 h, wherein the coating thickness is 40 mu m, and the curing energy of the UV light source is 900-3000 mJ/cm 2 . After cutting the packaged quantum dot film into 50mm 60mm samples, the following tests were performed:
the quantum dot light-emitting efficiency, pce= (red quantum dot absorption peak area+green quantum dot absorption peak area)/(blue backlight peak area-blue peak area not absorbed through the quantum dot film) ×100%.
Reliability detection: exposing the sample to a. High temperature blue light (40 ℃ +90% RH+38W/m) 2 Blue light irradiation), b. aging for 1000 hours under high temperature and high humidity (60 ℃ +90%RH), detecting brightness decay before and after aging, x color point drift and y color point drift, repeating the three groups of tests and taking average values.
Failure edge test: the sample wafer is subjected to 40 ℃ +90%RH+38W/m 2 And (3) aging for 1000 hours under the blue light irradiation condition, testing the non-luminous width of the edge of the membrane by using a film ruler, taking the maximum width of four sides as the numerical value of the failure side, and repeating three groups of tests to obtain the average value.
Compatibility test: the inorganic-organic coated perovskite quantum dot composition is placed under the condition of 23 ℃ plus 50% RH for 500 hours, and the luminescent state of the quantum dot and the sedimentation condition in glue are observed.
Tensile properties: preparing a dumbbell-shaped spline from the inorganic-organic coated perovskite quantum dot composition, wherein the specification of the test part is 5cm x 2cm, and placing the spline at 70 ℃ plus 38W/m 2 After 240 hours of blue light storage, the elongation at break of the film was measured by a universal tester at a stretching rate of 30mm/min under a test environment of 23 ℃ and 50% RH, and the average value was obtained by repeating three sets of tests.
Adhesion test: the evaluation was carried out using ASTM grades based on GB/T9286-98 hundred methods.
The PCE of No. 1-No. 7 reaches 80-90%, and the difference between the PCE and No. 9 and No. 10 is not great, which shows that the luminous efficiency is not reduced although the thickness of the double-layer coated quantum dot is increased. The PCE of 8# was only 55%, indicating that the uncoated quantum dots were not resistant to uv irradiation.
The inorganic coated quantum dots are further modified by adopting an epoxy-containing organic structure, so that the inorganic coated quantum dots have a structure similar to an epoxy glue system, and therefore have good compatibility and dispersibility in the glue system. Sedimentation and quenching phenomena occur in 8# due to poor compatibility with cationic glues.
after aging for 1000 hours under ab conditions, the luminance decay of 1# to 7# is <10%, and the color point drift is < 10%o. The luminance decay of 8# is >30% and the color point drift is > 20%. The brightness attenuation of 9# and 10# is more than 10%, and the y color point drift is more than 10%o, which indicates that the organic-inorganic coated perovskite quantum dot/polymer has more stable aging resistance. The failure sides of # 1 to # 7 are within 1.7mm, while the failure sides of # 8 to # 10 are all >2mm. The film edges of 1# to 7# are provided with good performances of resisting water vapor, oxygen and blue light, so that the whole light is more uniform.
The sample wafer is subjected to 70 ℃ plus 38W/m 2 After the blue light is stored for 240 hours, the elongation at break of 1# -7# is greater than 8# -10#, which indicates that the composition 1-7 has good tensile property, and is mainly derived from the fact that after photo/thermal curing, the quantum dots with the alicyclic epoxy on the surface can be uniformly dispersed in a system and polymerized onto a molecular chain main body, and the quantum dots cannot migrate and separate out in the aging process, and no phase separation exists. The 8# -11# has poor compatibility in the system, phase separation exists between inorganic and organic, and the quantum dots precipitated in the aging process easily generate stress in the cured film, so that the elongation at break is low. The adhesion test result shows that the adhesion of the quantum dot composition using the cationic curing system to the barrier film can reach 4B, the falling area is less than 5%, and the quantum dot composition has good adhesion effect.
Table 1 comparison of test data
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, are intended to be included within the scope of the present invention, such as, for example, free radical-cationic dual cure compositions, moisture-cationic dual cure compositions, and the like.

Claims (43)

1. The composite perovskite quantum dot material is characterized by comprising perovskite quantum dots/polymers and an inorganic-organic layer; the inorganic-organic layer coats perovskite quantum dots/polymers;
the inorganic-organic layer includes an inorganic layer and an organic layer; the inorganic layer and the organic layer undergo hydrolysis condensation reaction to obtain the inorganic-organic layer; the organic layer coats the inorganic layer;
the composition of the inorganic layer comprises a metal oxide selected from oxides of aluminum, silicon, titanium or zirconium;
the composition of the organic layer comprises silane containing alicyclic epoxy; the chemical structure of the alicyclic epoxy-containing silane is shown as a formula I:
Wherein:
R 1 ：-CH 2 -
R 2 selected from the group consisting ofor-CH 2 -CH 2 -
R 3 Selected from-CH 3 Or (b)
R 4 Selected from-CH 2 -or
R 5 Selected from the group consisting of-O-CH 3 or-O-CH 2 -CH 3
R 6 Selected from the group consisting of-O-CH 3 or-O-CH 2 -CH 3 or-CH 3
p is more than or equal to 0; q is more than or equal to 0; n=0 or 1.
2. The composite perovskite quantum dot material according to claim 1, wherein the mass ratio of the alicyclic epoxy-containing silane to the inorganic coated perovskite quantum dot/polymer powder is 5-20:3-8.
3. The composite perovskite quantum dot material according to claim 1, wherein the thickness of the inorganic layer is 5nm to 100nm; the thickness of the inorganic-organic layer is 10 nm-300 nm.
4. The composite perovskite quantum dot material of claim 1, wherein the metal oxide is selected from at least one of aluminum oxide, silicon dioxide, titanium dioxide, or zirconium dioxide.
5. The composite perovskite quantum dot material according to claim 1, wherein in the perovskite quantum dot/polymer, the perovskite quantum dot has a size of 2 to 50nm in at least one dimension; the perovskite quantum dot has a structural AMX 3 、A 3 M 2 X 9 、A 2 MX 6 、Q 2 A m-1 M m X 3m+1 At least one of (a) and (b); wherein A is NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + At least one of (a) and (b); m is Pb 2+ 、Cd 2+ 、Mn 2+ 、Zn 2+ 、Sn 2+ 、Ge 2+ 、Bi 3+ At least one of (a) and (b); x is at least one of halogen anions; q is an aromatic group or an alkyl organic amine cation having not less than 3 carbon atoms; m is any number between 1 and 100.
6. The composite perovskite quantum dot material according to claim 1, wherein the polymer is selected from at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate.
7. The composite perovskite quantum dot material according to claim 1, wherein the mass ratio of perovskite quantum dot to polymer in the perovskite quantum dot/polymer is 1:1 to 500.
8. The preparation method of the composite perovskite quantum dot material is characterized by comprising the following steps of:
(1) Obtaining perovskite quantum dot/polymer powder;
(2) Depositing a metal source on the surface of perovskite quantum dots/polymer powder by an atomic deposition method, and hydrolyzing to obtain inorganic coated perovskite quantum dots/polymer;
(3) Obtaining silane containing alicyclic epoxy;
(4) Carrying out hydrolytic condensation reaction on silane containing alicyclic epoxy and perovskite quantum dot/polymer coated by metal oxide to obtain the composite perovskite quantum dot material;
in the step (2), the metal source is selected from at least one of an aluminum source, a silicon source, a titanium source and a zirconium source; the aluminum source is at least one selected from trimethylaluminum, triethylaluminum and aluminum trichloride; the silicon source is at least one selected from methyl orthosilicate or ethyl orthosilicate; the titanium source is at least one of tetrabutyl titanate, isopropyl titanate and tetraethyl titanate; the zirconium source is at least one selected from dimethylaminozirconium, tetrabutyl zirconate, zirconium n-butoxide, zirconium tert-butoxide and zirconium isopropoxide;
In the step (3), the alicyclic epoxy-containing silane is prepared by adding vinyl-terminated silane and vinyl-terminated alicyclic epoxy and double-terminated hydrosilane through hydrosilylation under the action of a platinum catalyst; the mol ratio of the vinyl-terminated silane to the vinyl-terminated alicyclic epoxy to the double-terminal hydrosilane is 1-1.02: 1 to 1.1:1 to 1.02; the dosage of the platinum-based catalyst accounts for 0.001 to 0.5 percent of the sum of the masses of vinyl-terminated silane, vinyl-terminated alicyclic epoxy and double-terminated hydrosilane; the reaction temperature is 110-130 ℃.
9. The method according to claim 8, wherein in the step (2), the deposition temperature is 80 to 100 ℃; the time is 5 s-90 s; the vacuum degree is 100-1000 Pa, the time of introducing steam is 3-20 s, and the cycle number is 10-500.
10. The method according to claim 8, wherein the vinyl-terminated silane is at least one selected from the group consisting of vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, and methacryloxypropylmethyldimethoxysilane.
11. The method according to claim 8, wherein the vinyl-terminated alicyclic epoxy is at least one selected from the group consisting of 1, 2-epoxy-4-vinylcyclohexane, 3, 4-epoxycyclohexylmethacrylate and 3, 4-epoxycyclohexylmethacrylate.
12. The method according to claim 8, wherein the double-terminal hydrosilane is at least one selected from the group consisting of tetramethyl disiloxane, tetramethyl diphenyl dihydrotrisiloxane, double-terminal hydrosilyl polydimethylsiloxane and tetraisopropyl dihydrodisiloxane.
13. The method according to claim 8, wherein the platinum-group catalyst is at least one selected from the group consisting of chloroplatinic acid, a complex of platinum and vinyl siloxane, and a platinum-olefin complex.
14. The method of claim 8, wherein in step (4), the mass ratio of the alicyclic epoxy-modified silane to the metal oxide coated perovskite quantum dot/polymer is 5 to 20:3 to 8; the conditions of the hydrolytic condensation reaction are that the temperature is 25-60 ℃; the time is 0.5 h-30 h.
15. The method according to claim 8, wherein,
In the step (1), the method for obtaining the perovskite quantum dot/polymer powder comprises the steps of atomizing a perovskite quantum dot precursor solution into small liquid drops, and then drying the atomized small liquid drops to generate the perovskite quantum dot/polymer powder; the perovskite quantum dot precursor solution comprises a solvent, a perovskite quantum dot raw material and a polymer matrix;
the particle size of the perovskite quantum dot/polymer powder is 0.1-200 mu m.
16. The method according to claim 15, wherein the solvent is at least one selected from the group consisting of N, N-dimethylformamide, dimethylsulfoxide, trimethylphosphate, triethylphosphate, N-methylpyrrolidone, dimethylacetamide.
17. The method of claim 15, wherein the perovskite quantum dot material comprises AX, QX, and MX t The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + At least one of (a) and (b); m is Pb 2+ 、Cd 2+ 、Mn 2+ 、Zn 2+ 、Sn 2+ 、Ge 2+ 、Bi 3 + At least one of (a) and (b);
q is an aromatic group or an alkyl organic amine cation having not less than 3 carbon atoms;
x is at least one of halogen anions; t=2 or 3.
18. The method of claim 15, wherein the polymer matrix is at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymers, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, and polymethyl methacrylate.
19. The method of claim 15, wherein the mass ratio of polymer matrix to solvent is 1:2 to 200.
20. The method of claim 19, wherein the mass ratio of polymer matrix to solvent is 1:5 to 50.
21. The method of claim 15, wherein the mass ratio of perovskite quantum dot material to polymer matrix is 1:1 to 500.
22. The method of claim 21, wherein the mass ratio of perovskite quantum dot material to polymer matrix is 1:5 to 100.
23. The method of preparing according to claim 15, wherein the perovskite quantum dot precursor solution further comprises additives and/or surface ligands.
24. The method of claim 23, wherein the additive is at least one selected from the group consisting of zinc bromide, zinc iodide, stannous bromide, stannous iodide, cadmium bromide, cadmium iodide, and hypophosphorous acid.
25. The preparation method according to claim 15, wherein the mass ratio of the additive to the perovskite quantum dot raw material is 1:1 to 500.
26. The method of claim 25, wherein the mass ratio of the additive to the perovskite quantum dot material is 1:4 to 100.
27. The method of claim 23, wherein the surface ligand comprises at least one of an organic acid, an organic acid halide, a long-chain organic amine halide; the organic acid comprises a saturated or unsaturated alkyl acid having at least 3 carbon atoms; the long-chain organic amine is alkyl amine or aromatic amine with 4-24 carbon atoms; the halide of the organic acid or the long-chain organic amine is the halide corresponding to the organic acid or the long-chain organic amine.
28. The method of claim 27, wherein the mass ratio of surface ligand to perovskite quantum dot material is 1:1 to 50.
29. The method of claim 28, wherein the mass ratio of surface ligand to perovskite quantum dot material is 1:2 to 20.
30. The method of claim 15, wherein the perovskite quantum dot precursor solution is fed at a flow rate of 1mL/min to 5000mL/min; the temperature of the inlet air is 40-200 ℃.
31. The method of claim 15, wherein the atomized droplets are dried to form perovskite quantum dot/polymer powder and solvent vapor, and the solvent is recovered by separation.
32. The method according to claim 15, wherein the inert gas is used as the circulating gas.
33. The method according to claim 32, wherein the inert gas is at least one selected from nitrogen and helium.
34. The perovskite quantum dot composition is characterized by comprising the following components in parts by weight:
2 to 21 parts of perovskite quantum dot material, 40 to 260 parts of epoxy resin, 20 to 180 parts of reactive diluent, 0.1 to 18 parts of cationic initiator, 5 to 45 parts of light scattering particles and 0.5 to 10 parts of auxiliary agent;
the perovskite quantum dot material is at least one of the composite perovskite quantum dot material according to any one of claims 1 to 7 and the composite perovskite quantum dot material prepared by the preparation method according to any one of claims 8 to 33.
35. The perovskite quantum dot composition as claimed in claim 34, wherein,
the composition comprises the following components in parts by weight: 11 to 20.5 parts of perovskite quantum dot material, 170 to 200 parts of epoxy resin, 40 to 130 parts of reactive diluent, 0.5 to 14 parts of cationic initiator, 20 to 30 parts of light scattering particles and 1 to 6 parts of auxiliary agent;
the epoxy resin is at least one selected from alicyclic epoxy resins and glycidyl type epoxy resins.
36. The perovskite quantum dot composition of claim 35, wherein the perovskite quantum dot composition is,
the alicyclic epoxy resin is at least one selected from bis (di (3, 4-epoxycyclohexyl) methyl) adipic acid, poly [ (2-epoxyethane group) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1), 1, 4-bis (3, 4-epoxycyclohexyl-1-methoxy) methylbenzene, 1, 4-bis (3, 4-epoxycyclohexyl-1-methoxy) butane, epoxypolybutadiene, dicyclopentadiene dioxide and 3, 4-epoxycyclohexane carboxylic acid methyl ester.
37. The perovskite quantum dot composition of claim 35, wherein the perovskite quantum dot composition is,
the glycidyl type epoxy resin comprises at least one of hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether and polybutylene glycol glycidyl ether;
the reactive diluent is at least one selected from vinyl ethers, propenyl ethers, oxygen heterocyclic reactive diluents and glycidyl ethers.
38. The perovskite quantum dot composition as claimed in claim 37, wherein,
The vinyl ether is at least one selected from 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, l, 4-cyclohexyl dimethanol divinyl ether, dodecyl vinyl ether and 1, 4-cyclohexane dimethanol vinyl ether; the propenyl ether is selected from glycerol carbonate propenyl ether.
39. The perovskite quantum dot composition as claimed in claim 37, wherein,
the oxygen heterocyclic reactive diluent is at least one selected from 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 3' - (oxybis methylene) -bis- (3-ethyl) oxetane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 4-bis [3- (ethyl-3-oxymethylene oxetane) methyl ] benzene and bis (3-ethyl-3-oxethyl) ether.
40. The perovskite quantum dot composition as claimed in claim 37, wherein,
the glycidyl ether is at least one selected from n-butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether and tert-butyl phenol glycidyl ether;
the cationic initiator is selected from a photo cationic initiator and/or a thermal cationic initiator;
The photo cation initiator is selected from sulfonium salts such as 4-phenylsulfanylphenyl diphenylsulfonium salt, tris [4- [ (4-acetylphenyl) thio ] -hexafluorophosphate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-phenylsulfanylphenyl sulfonium hexafluoroantimonate, diphenyl-4-phenylsulfanylphenyl sulfonium hexafluorophosphate, 4-dodecylphenyldiphenylsulfonium hexafluorophosphate, 4' -bis (diphenylsulfonium) phenylsulfide-bis-hexafluoroantimonate, 4' -bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] phenylsulfide-bis-hexafluoroantimonate, 4- [4' - (benzoyl) phenylthio ] phenyl-bis- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate; iodonium salts such as at least one of diphenyliodohexafluoroantimonate, bis (4-methylphenyl) iodohexafluorophosphate, bis (4-tert-butylphenyl) iodohexafluorophosphate, tolyltetra (pentafluorophenyl) borate diaryliodonium salts, and arylferrocenium salts such as [ cyclopentadiene-iron-isopropylbenzene ] hexafluorophosphate;
the thermal cation initiator is selected from anhydride compounds such as methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and tetrahydrophthalic anhydride; imidazole derivatives such as N- (2- (2-methyl-1-imidazolyl) ethyl) urea, N' - (2-methyl-1-imidazolylethyl) adipamide, 2-phenyl-4, 5-dimethylol imidazole, hycat TM At least one of AO-4 and CXC-1612;
the light scattering particles are selected from inorganic light dispersing agents or organic light dispersing agents; the inorganic light dispersing agent is at least one selected from nano barium sulfate, nano zinc oxide and nano silicon dioxide; the organic light diffusion is at least one selected from PMMA microsphere, organosilicon microsphere, polytetrafluoroethylene wax, polypropylene wax, polyethylene wax microsphere, polyamide wax microsphere and amide modified polyethylene wax;
the auxiliary agent is at least one selected from flatting agent, defoamer and antioxidant.
41. The method for preparing a perovskite quantum dot composition according to any one of claims 34 to 40, wherein the perovskite quantum dot composition is obtained by mixing the perovskite quantum dot material with epoxy resin, reactive diluent, cationic initiator, light scattering particles and auxiliary agent in proportion and dispersing under vacuum condition.
42. Use of a composite perovskite quantum dot material according to any one of claims 1 to 7, a composite perovskite quantum dot material prepared by a preparation method according to any one of claims 8 to 33, a perovskite quantum dot composition according to any one of claims 34 to 40 in a semiconductor luminescent material.
43. The use according to claim 42 for a display device.
CN202111227197.9A 2021-10-21 2021-10-21 Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof Active CN116004226B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111227197.9A CN116004226B (en) 2021-10-21 2021-10-21 Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111227197.9A CN116004226B (en) 2021-10-21 2021-10-21 Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof

Publications (2)

Publication Number Publication Date
CN116004226A CN116004226A (en) 2023-04-25
CN116004226B true CN116004226B (en) 2023-12-15

Family

ID=86025353

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111227197.9A Active CN116004226B (en) 2021-10-21 2021-10-21 Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof

Country Status (1)

Country Link
CN (1) CN116004226B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116676027B (en) * 2023-07-10 2024-01-16 阿梓萨科技(深圳)有限公司 Preparation method of carbon-point-modified epoxy resin photoinduction cationic curing coating
CN117777788B (en) * 2024-01-05 2024-09-10 青岛卓英社科技股份有限公司 Printing ink containing luminous quantum dots and preparation method thereof
CN117956812B (en) * 2024-03-27 2024-09-10 合肥市旭熠科技有限公司 Preparation method of composite perovskite thick film X-ray detector

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4694029A (en) * 1985-04-09 1987-09-15 Cook Paint And Varnish Company Hybrid photocure system
WO2016070713A1 (en) * 2014-11-04 2016-05-12 北京理工大学 Perovskite quantum dot material and preparation method therefor
WO2016180364A1 (en) * 2015-05-14 2016-11-17 北京理工大学 Perovskite/polymer composite luminescent material, preparation method and application
CN107955199A (en) * 2017-11-09 2018-04-24 合肥乐凯科技产业有限公司 Perovskite quantum dot film, quantum dot diffusion composite membrane and preparation method thereof
CN110707219A (en) * 2019-10-14 2020-01-17 合肥乐凯科技产业有限公司 Organic-inorganic perovskite quantum dot film and preparation method thereof
CN112029494A (en) * 2019-06-04 2020-12-04 致晶科技（北京）有限公司 Perovskite nano material, composite luminescent material containing perovskite nano material, and preparation method and application of perovskite nano material
WO2020244046A1 (en) * 2019-06-04 2020-12-10 致晶科技（北京）有限公司 Composite luminescent material, preparation method therefor and use thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4694029A (en) * 1985-04-09 1987-09-15 Cook Paint And Varnish Company Hybrid photocure system
WO2016070713A1 (en) * 2014-11-04 2016-05-12 北京理工大学 Perovskite quantum dot material and preparation method therefor
WO2016180364A1 (en) * 2015-05-14 2016-11-17 北京理工大学 Perovskite/polymer composite luminescent material, preparation method and application
CN107955199A (en) * 2017-11-09 2018-04-24 合肥乐凯科技产业有限公司 Perovskite quantum dot film, quantum dot diffusion composite membrane and preparation method thereof
CN112029494A (en) * 2019-06-04 2020-12-04 致晶科技（北京）有限公司 Perovskite nano material, composite luminescent material containing perovskite nano material, and preparation method and application of perovskite nano material
WO2020244047A1 (en) * 2019-06-04 2020-12-10 致晶科技（北京）有限公司 Perovskite nanomaterial, composite light-emitting material containing same and preparation method therefor and application thereof
WO2020244046A1 (en) * 2019-06-04 2020-12-10 致晶科技（北京）有限公司 Composite luminescent material, preparation method therefor and use thereof
CN110707219A (en) * 2019-10-14 2020-01-17 合肥乐凯科技产业有限公司 Organic-inorganic perovskite quantum dot film and preparation method thereof

Also Published As

Publication number Publication date
CN116004226A (en) 2023-04-25

Similar Documents

Publication Publication Date Title
CN116004226B (en) Composite perovskite quantum dot material, perovskite quantum dot composition, and preparation methods and applications thereof
US11365347B2 (en) Method for preparation of perovskite quantum dot (PQD)/polymer/ceramic ternary complex
KR101430892B1 (en) Gas-barrier film and electronic device
JP6193245B2 (en) Encapsulated barrier stack
TWI687322B (en) Electronic device and its manufacturing method
KR20160012146A (en) Encapsulation barrier stack comprising dendrimer encapsulated nanoparticles
CN107001583A (en) Light and hot curing resin composition, solidfied material and laminate
JP2017515935A5 (en)
CN1909978A (en) Polyhedral oligomeric silsesquioxanes and metallized polyhedral oligomeric silsesquioxanes as coatings, composites and additives
JPWO2012090665A1 (en) Method for producing gas barrier film, gas barrier film and electronic device
JP5906550B2 (en) Encapsulant with high barrier properties
Park et al. Characteristics of transparent encapsulation materials for OLEDs prepared from mesoporous silica nanoparticle-polyurethane acrylate resin composites
EP4032961A1 (en) Ligand-supported perovskite luminescent crystal composition and method for producing the same
CN112048296A (en) Method for preparing perovskite quantum dot/polymer/ceramic ternary complex
TW202219232A (en) Composition for electronic device sealing, method for forming electronic device sealing film, and electronic device sealing film
JP4035148B2 (en) Complex of organic polymer and metal oxide, production method and use thereof
JP6878925B2 (en) Gas barrier laminate and method for manufacturing gas barrier laminate
JP2011110455A (en) Coated film and composition
JP5231884B2 (en) Porous membrane, coating solution for forming porous membrane, laminated substrate and wiring material
CN109021963A (en) Containing fluorophor particle and using the light emitting device containing fluorophor particle, contain fluorescent sheets
CN112898781B (en) Silica gel film with water and gas blocking characteristic
TW202229383A (en) Low refractive thermosetting composition, optical material and display device formed therefrom
US11242482B2 (en) Quantum dot, method for producing the same, resin composition, wavelength conversion material, and light emitting device
JP6816568B2 (en) Gas barrier laminate and method for manufacturing gas barrier laminate
WO2011099505A1 (en) Outdoor device, and antireflective layer for outdoor device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant