CN113120951A - Bimetal co-doped zinc sulfide film, preparation method thereof and quantum dot light-emitting diode - Google Patents
Bimetal co-doped zinc sulfide film, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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- CN113120951A CN113120951A CN201911398455.2A CN201911398455A CN113120951A CN 113120951 A CN113120951 A CN 113120951A CN 201911398455 A CN201911398455 A CN 201911398455A CN 113120951 A CN113120951 A CN 113120951A
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- Prior art keywords
- zinc sulfide
- doped zinc
- indium
- bimetal
- silver
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- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 118
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 115
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002096 quantum dot Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 48
- 239000004332 silver Substances 0.000 claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 claims abstract description 44
- 229910052738 indium Inorganic materials 0.000 claims abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 150000002471 indium Chemical class 0.000 claims abstract description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 23
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 15
- -1 silver ions Chemical class 0.000 claims description 15
- 229910001449 indium ion Inorganic materials 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 5
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 5
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940071536 silver acetate Drugs 0.000 claims description 5
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 claims description 5
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 abstract description 15
- 230000005540 biological transmission Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
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- 239000010410 layer Substances 0.000 description 73
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000000137 annealing Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 2
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Polymers C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- 229910052956 cinnabar Inorganic materials 0.000 description 1
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- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The invention discloses a bimetal co-doped zinc sulfide film, a preparation method thereof and a quantum dot light-emitting diode, wherein the preparation method comprises the following steps: dispersing zinc salt, indium salt and silver salt in an organic solvent to obtain a metal salt solution; mixing the metal salt solution with a sulfur source, and reacting to obtain an indium and silver doped zinc sulfide nanoparticle solution; and preparing the indium and silver doped zinc sulfide nano particle solution into a film to prepare the bimetal co-doped zinc sulfide film. According to the invention, a small amount of In and Ag elements are introduced to ZnS nano particles to replace partial Zn atoms to form a new chemical bond, the intrinsic electronic structure of the ZnS nano particles is adjusted by forming the new chemical bond, the resistivity and the narrowed forbidden bandwidth of the ZnS nano particles are reduced, electrons are more easily transited to a conduction band, the electrons are promoted to enter a quantum dot light-emitting region from an electron transmission layer, and the recombination efficiency of electron-holes In the quantum dot light-emitting layer is improved.
Description
Technical Field
The invention relates to the field of quantum dot light-emitting diodes, in particular to a bimetallic co-doped zinc sulfide film, a preparation method thereof and a quantum dot light-emitting diode.
Background
Quantum dots have been rapidly developed in application to quantum dot light-emitting diodes (QLEDs) because of their excellent light-emitting characteristics. Quantum dots have a variety of properties including: (1) the emission spectrum can be adjusted by changing the particle size; (2) the excitation spectrum is wide, the emission spectrum is narrow, and the absorptivity is strong; (3) the light stability is good; (4) longer fluorescence lifetime, etc. In the conventional inorganic electroluminescent device, electrons and holes are injected from a cathode and an anode, respectively, and then recombined in a light emitting layer to form excitons for light emission. Conduction band electrons in the wide bandgap semiconductor can be accelerated under a high electric field to obtain high enough energy to impact QDs to enable the QDs to emit light; the semiconductor quantum dot material has important commercial application value as a novel inorganic semiconductor fluorescent material.
In recent years, inorganic semiconductors have been studied as an electron transport layer in a relatively hot manner. Zinc oxide is an important inorganic semiconductor with a direct broadband (3.37eV), has the advantages of good stability, high transparency, safety, no toxicity and the like, and can be used as a commonly used electron transport layer material. Meanwhile, zinc sulfide (ZnS) can also be used as an important wide bandgap II-VI intrinsic semiconductor material, but the application of the pure ZnS material in some fields is limited due to the fixed bandgap, so that the reasonable doping of ZnS to regulate the electronic structure and properties of the ZnS material can adapt to the actual requirements of different application fields.
Disclosure of Invention
The invention aims to provide a bimetal co-doped zinc sulfide film, a preparation method thereof and a quantum dot light-emitting diode, and aims to solve the problem of low luminous efficiency.
The technical scheme of the invention is as follows:
a preparation method of a bimetal co-doped zinc sulfide film comprises the following steps:
dispersing zinc salt, indium salt and silver salt in an organic solvent to obtain a metal salt solution;
mixing the metal salt solution with a sulfur source, and reacting to obtain an indium and silver doped zinc sulfide nanoparticle solution;
and preparing the indium and silver doped zinc sulfide nano particle solution into a film to prepare the bimetal co-doped zinc sulfide film.
The preparation method of the bimetal co-doped zinc sulfide film comprises the steps that zinc ions, indium ions and silver ions are contained in a metal salt solution, wherein the ratio of the total molar weight sum of the indium ions and the silver ions to the molar weight of the zinc ions is 0.01-0.1: 1.
The preparation method of the bimetal co-doped zinc sulfide film comprises the step of preparing a metal salt solution, wherein the molar ratio of sulfur element in the sulfur source to zinc ions in the metal salt solution is 1.2-3: 1.
The preparation method of the bimetal co-doped zinc sulfide film comprises the following steps of adding a sulfur source into a metal salt solution, and reacting to obtain an indium and silver doped zinc sulfide nanoparticle solution:
and adding a sulfur source into the metal salt solution, and reacting for 1-4h at the temperature of 60-80 ℃ to prepare the indium and silver doped zinc sulfide nanoparticle solution.
The preparation method of the bimetal co-doped zinc sulfide film comprises the following step of carrying out co-doping on a zinc salt, wherein the zinc salt is one or more of zinc acetate, zinc nitrate, zinc chloride and zinc acetate dihydrate.
The preparation method of the bimetal co-doped zinc sulfide film comprises the following step of preparing a bimetal co-doped zinc sulfide film, wherein the indium salt is one or more of indium nitrate, indium chloride and indium acetate.
The preparation method of the bimetal co-doped zinc sulfide film comprises the step of preparing a zinc sulfide film, wherein the silver salt is one or more of silver acetate, silver acetylacetonate and silver methanesulfonate.
The preparation method of the bimetal co-doped zinc sulfide film comprises the step of preparing a bimetal co-doped zinc sulfide film, wherein the sulfur source is one or more of thiourea, sodium sulfide, thioacetamide and L-cysteine.
The invention discloses a bimetal co-doped zinc sulfide film, which is prepared by the preparation method.
A quantum dot light-emitting diode comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein an electron transmission layer is arranged between the cathode and the quantum dot light-emitting layer, and the electron transmission layer is a bimetal co-doped zinc sulfide film.
Has the advantages that: the invention prepares indium and silver doped zinc sulfide nano particle solution by a simple sol-gel method, prepares the solution into a bimetal zinc sulfide film as an electron transmission layer, forms a new chemical bond by introducing a small amount of In and Ag elements on ZnS nano particles to replace partial Zn atoms, adjusts the intrinsic electronic structure of the ZnS nano particles by forming the new chemical bond, reduces the resistivity and the narrow forbidden bandwidth of the ZnS nano particles, enables electrons to be more easily transited to a conduction band, promotes the electrons to enter a quantum dot light region from the electron transmission layer, improves the recombination efficiency of electron-hole In the quantum dot light emitting layer, and further improves the light emitting efficiency of the quantum dot light emitting diode. In addition, the method for preparing the bimetal co-doped zinc sulfide film is very simple and is suitable for large-area and large-scale preparation.
Drawings
Fig. 1 is a flowchart of a method for preparing a bimetal co-doped zinc sulfide thin film in an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a quantum dot light emitting diode with a front-mounted structure according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a quantum dot light emitting diode with a flip-chip structure according to an embodiment of the present invention.
Detailed Description
The invention provides a bimetal doped zinc sulfide film, a preparation method thereof and a quantum dot light-emitting diode, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a bimetal-doped zinc sulfide thin film according to the present invention, as shown in the figure, the method includes the steps of:
s10, dispersing zinc salt, indium salt and silver salt in an organic solvent to obtain a metal salt solution;
s20, mixing the metal salt solution with a sulfur source, and reacting to obtain an indium and silver doped zinc sulfide nanoparticle solution;
s30, preparing the indium and silver doped zinc sulfide nano particle solution into a film, and preparing the bimetal co-doped zinc sulfide film.
In the embodiment, an indium and silver doped zinc sulfide nanoparticle solution is prepared by a simple sol-gel method, the indium and silver doped zinc sulfide nanoparticle solution is added to a substrate, and a bimetallic co-doped zinc sulfide film is formed after spin-coating annealing treatment, and can be used as an electron transport layer. In the embodiment, a small amount of In and Ag elements are introduced to ZnS nanoparticles to replace partial Zn atoms to form a new chemical bond, and the intrinsic electronic structure of the ZnS nanoparticles is adjusted by forming the new chemical bond, so that the resistivity and the narrowed forbidden band width of the ZnS nanoparticles are reduced; in the embodiment, the bimetal co-doped zinc sulfide film is used as the electron transport layer of the quantum dot light-emitting diode, so that electrons are easier to jump to a conduction band, the electrons are promoted to enter the quantum dot light-emitting region from the electron transport layer, the recombination efficiency of electrons and holes in the quantum dot light-emitting diode is improved, and the light-emitting efficiency of the quantum dot light-emitting diode is improved. In addition, the method for preparing the bimetal co-doped zinc sulfide film is very simple and is suitable for large-area and large-scale preparation.
In this embodiment, In3+Specific ratio of Zn to Zn2+One more electron, In3+The doping is donor-type doping; ag+Specific ratio of Zn to Zn2+One electron less, Ag+The doping is of the acceptor type, In this example by selection of In3+And Ag+The codoping of two metal ions has higher binding energy, so that the doping degree can be improved, and the doping is more favorably carried out; in3+And Ag+In ZnS nanoparticlesThe impurity energy level is introduced, the donor doping enables the conduction band bottom to be reduced, the acceptor doping enables the valence band top to be improved, so that the ZnS forbidden band width is narrowed, electrons can more easily jump from the impurity energy level to enter the conduction band, the electron accumulation is reduced, the recombination efficiency of electron-hole pairs in the quantum dot light-emitting layer is increased, and the light-emitting efficiency of the quantum dot light-emitting diode is improved; in3+And Ag+The ionization energy of the energy level of the commonly doped impurities is very small, and electrons are easily excited to enter a conduction band, so that the conductivity of the bimetal co-doped zinc sulfide film is enhanced, and the resistance is reduced; said In3+And Ag+The co-doping enables the electron Fermi level of the ZnS nano particles to enter a conduction band to show stronger metallicity, and improves the electron transmission performance of the bimetal co-doped ZnS film.
In some embodiments, the zinc salt, the indium salt, and the silver salt are dispersed in the organic solvent and stirred at 60 to 80 ℃ to obtain the metal salt solution. In this embodiment, the zinc salt is a soluble organic zinc salt or a soluble inorganic zinc salt, and the zinc salt may be one or more of zinc acetate, zinc nitrate, zinc chloride, and zinc acetate dihydrate, but is not limited thereto; the indium salt is one or more of indium nitrate, indium chloride and indium acetate, but is not limited thereto; the silver salt is one or more of silver acetate, silver acetylacetonate and silver methane sulfonate, but is not limited thereto; the organic solvent is one or more of DMF, DMSO, and isopropanol, but is not limited thereto.
In some embodiments, the metal salt solution has a total metal ion concentration of 0.1 to 1M.
In some embodiments, the metal salt solution comprises zinc ions, indium ions, and silver ions, wherein the ratio of the sum of the molar amounts of the indium ions and the silver ions to the molar amount of the zinc ions is 0.01-0.1: 1. In this embodiment, the concentration of the doping ions (the indium ions and the silver ions) has a great influence on the performance of the prepared indium and silver doped zinc sulfide nanoparticles, and if the ratio of the sum of the molar amounts of the indium ions and the silver ions to the molar amount of the zinc ions is greater than 0.1:1, the doping ions are excessive and cover the surface of the zinc sulfide crystal grains to form a new phase, which influences the electron transport performance of the zinc sulfide crystal grains; if the ratio of the sum of the molar weights of the indium ions and the silver ions to the molar weight of the zinc ions is less than 0.01:1, the dosage of doping ions is too low, the indium ions and the silver ions are easy to be lost in the reaction process, and cannot be effectively doped with zinc sulfide crystal grains, so that the electron transport performance of the zinc sulfide crystal grains is also influenced.
In some specific embodiments, the ratio of the sum of the molar amounts of the indium ions and the silver ions to the molar amount of the zinc ions is 0.05: 1. Within the proportion range, the finally prepared bimetallic zinc sulfide film has the best electron transmission performance, so that the luminous efficiency of the quantum dot light-emitting diode taking the bimetallic zinc sulfide film as an electron transmission layer is effectively improved.
In some embodiments, the molar ratio of the indium ions to the silver ions is 1: 1-2. When the indium ions and the silver ions are doped with the same amount, the performance of the prepared bimetallic co-doped zinc sulfide film is best, however, due to Zn2+Radius 74, In3+Radius of 81, Ag+The radius is 126, Zn ions are closer to the radius of In ions, and the Zn ions are easier to be doped into zinc sulfide nano particles compared with Ag ions, so when In is In3+：Ag+Is 1: (1-2), when the dosage of Ag is slightly more, indium ions and silver ions are doped into the zinc sulfide nano particles in the same amount, and the bimetal co-doped zinc sulfide film with better performance is obtained.
In some embodiments, the metal salt solution is mixed with a sulfur source and reacted for 1-4 hours at 60-80 ℃ to prepare the indium and silver doped zinc sulfide nanoparticle solution. In this embodiment, a sulfur source, which is one or more of thiourea, sodium sulfide, thioacetamide and L-cysteine, may be added to the metal salt solution or to the sulfur source, but is not limited thereto.
In some embodiments, the molar ratio of elemental sulfur in the sulfur source to zinc ions in the metal salt solution is from 1.2 to 3: 1. In this example, the sulfur source is in excess to ensure that all of the zinc source is fully reacted and converted to ZnS.
The preparation method of the bimetal co-doped zinc sulfide film is explained in detail by the following examples.
Example 1
The details are described below by taking zinc chloride, indium chloride, silver acetylacetonate, sodium sulfide, and N, N-Dimethylformamide (DMF) as an example:
1. adding appropriate amounts of zinc chloride, indium chloride and silver acetylacetonate into 50ml of DMF, and stirring at 60 ℃ to dissolve to form a metal salt solution with a total concentration of 0.5M, wherein the ratio of zinc: the molar ratio of indium to silver is 1: 0.02; (ii) a
2. Dissolving sodium sulfide in a solution of 30ml of ethanol to obtain a sodium sulfide solution, adding the sodium sulfide solution (the molar ratio of zinc to sulfur is 1: 1.2) into the metal salt solution, continuously stirring for 2 hours at 60 ℃ to obtain a uniform solution, centrifuging, cleaning, dispersing with a proper amount of ethanol to obtain an indium and silver doped zinc sulfide nanoparticle solution, spin-coating the indium and silver doped zinc sulfide nanoparticle solution on the treated ITO by using a spin coater, and annealing to obtain the bimetal co-doped zinc sulfide film.
Example 2
The details are given below by way of example of zinc nitrate hexahydrate, indium nitrate, silver methane sulfonate, thioacetamide, dimethyl sulfoxide (DMSO):
1. adding appropriate amounts of zinc nitrate and indium nitrate into 50ml of DMSO, and stirring and dissolving at 70 ℃ to form a metal salt solution with a total concentration of 0.5M, wherein the ratio of zinc: the molar ratio of indium to silver is 1: 0.05;
2. dissolving thioacetamide in a solution of 30ml of ethanol to obtain a thioacetamide solution, adding the thioacetamide solution (the molar ratio of zinc to sulfur is 1: 1.2) into the metal salt solution, continuously stirring for 2 hours at 70 ℃ to obtain a uniform solution, centrifuging, cleaning, dispersing with a proper amount of ethanol to obtain an indium and silver doped zinc sulfide nanoparticle solution, spin-coating the indium and silver doped zinc sulfide nanoparticle solution on the treated ITO by using a spin coater, and annealing to obtain the bimetal co-doped zinc sulfide film.
Example 3
The details are given below by taking zinc acetate dihydrate, indium acetate, silver acetate, L-cysteine, dimethyl sulfoxide (DMSO) as an example:
1. adding a proper amount of zinc acetate dihydrate, indium acetate and silver acetate into 50ml of ethanol, and stirring and dissolving at 80 ℃ to form a metal salt solution with the total concentration of 0.5M, wherein the ratio of zinc: the molar ratio of indium to silver is 1: 0.08;
2. dissolving L-cysteine in a solution of 10ml of ethanol to obtain an L-cysteine solution, adding the L-cysteine solution (the molar ratio of zinc to sulfur is 1: 1.2) into the metal salt solution, continuously stirring for 2 hours at 80 ℃ to obtain a uniform solution, centrifuging, cleaning, dispersing with a proper amount of ethanol to obtain an indium and silver doped zinc sulfide nanoparticle solution, and spin-coating the indium and silver doped zinc sulfide nanoparticle solution on the treated ITO by using a spin coater and carrying out annealing treatment to obtain the bimetal co-doped zinc sulfide film.
In some embodiments, the invention further provides a bimetallic co-doped zinc sulfide thin film, wherein the bimetallic co-doped zinc sulfide thin film is prepared by the preparation method.
In some embodiments, a quantum dot light emitting diode is further provided, which includes an electron transport layer, wherein the electron transport layer is the bimetal co-doped zinc sulfide thin film.
In some embodiments, the quantum dot light emitting diode includes an anode, a quantum dot light emitting layer, an electron transport layer, and a cathode, which are stacked, wherein the electron transport layer is the bimetal co-doped zinc sulfide thin film of the present invention.
In some specific embodiments, the quantum dot light emitting diode includes an anode, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, which are stacked, where the electron transport layer is the bimetal co-doped zinc sulfide thin film of the present invention.
It should be noted that the invention is not limited to the quantum dot light emitting diode with the above structure, and may further include an interface functional layer or an interface modification layer, including but not limited to one or more of an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer. The quantum dot light emitting diode can be partially packaged, fully packaged or not packaged.
The following describes the quantum dot light emitting diode including the electron transport layer and the method for manufacturing the same in detail:
the quantum dot light emitting diode can be divided into a quantum dot light emitting diode with a forward mounting structure and a quantum dot light emitting diode with an inverted mounting structure according to different light emitting types of the quantum dot light emitting diode.
As one embodiment, when the quantum dot light emitting diode is a forward-mounted structure, as shown in fig. 2, the QLED device includes an anode 2 (the anode 2 is stacked on a substrate 1), a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, and a cathode 6, where the electron transport layer 5 is a bimetal co-doped zinc sulfide thin film according to the present invention.
In another embodiment, when the quantum dot light emitting diode is in a flip-chip structure, as shown in fig. 3, the QLED device includes a cathode 6 (the cathode 6 is stacked on a substrate 1), an electron transport layer 5, a quantum dot light emitting layer 4, a hole transport layer 3, and an anode 2, where the electron transport layer 5 is the bimetal co-doped zinc sulfide thin film of the present invention.
In some embodiments, the material of the anode is selected from doped metal oxides; wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO).
In some embodiments, the material of the hole transport layer is selected from organic materials having good hole transport ability, such as but not limited to Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), Poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), Poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1, one or more of 1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, C60, F8, copper oxide, nickel oxide, tungsten trioxide, and molybdenum trioxide.
In some embodiments, the material of the quantum dot light emitting layer is selected from one or more of red quantum dots, green quantum dots, blue quantum dots, and may also be selected from yellow quantum dots. Specifically, the material of the quantum dot light emitting layer is selected from one or more of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe and various core-shell structure quantum dots or alloy structure quantum dots. The quantum dots of the present invention can be selected from cadmium-containing or cadmium-free quantum dots. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like.
In some embodiments, the material of the cathode is selected from one or more of a conductive carbon material, a conductive metal oxide material, and a metallic material; wherein the conductive carbon material includes, but is not limited to, one or more of doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, and porous carbon; the conductive metal oxide material includes, but is not limited to, one or more of ITO, FTO, ATO, and AZO; metallic materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein, the metal material has a form including but not limited to one or more of a compact film, a nanowire, a nanosphere, a nanorod, a nanocone and a hollow nanosphere.
The invention also provides a preparation method of the quantum dot light-emitting diode with the forward mounting structure, which comprises the following steps:
providing a substrate containing an anode, and preparing a hole transport layer on the anode;
preparing a quantum dot light emitting layer on the hole transport layer;
preparing an electron transmission layer on the quantum dot light-emitting layer, wherein the electron transmission layer is the bimetallic co-doped zinc sulfide film;
and preparing a cathode on the electron transport layer to obtain the quantum dot light-emitting diode.
As one embodiment, taking ITO conductive glass as an example of a substrate, in order to obtain a high-quality thin film, the ITO conductive glass needs to undergo a pretreatment process, and the basic specific processing steps include: etching the ITO conductive glass into narrow bands, then respectively ultrasonically cleaning the narrow bands in deionized water, acetone, absolute ethyl alcohol and deionized water in sequence to remove impurities existing on the surfaces, drying the narrow bands, and cleaning the narrow bands by using an ultraviolet cleaning machine to obtain the ITO anode.
As one embodiment, the prepared solution of the hole transport material is coated on the ITO by spinning to form a film; controlling the film thickness by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then carrying out thermal annealing treatment at a proper temperature to obtain a hole transport layer; spin-coating the prepared solution of the hole transport material on ITO to form a film; and (2) carrying out spin coating on the prepared quantum dot solution with a certain concentration on the hole transport layer to form a film, controlling the thickness of the quantum dot light-emitting layer to be about 20-60nm by adjusting the concentration, the spin coating speed and the spin coating time of the solution, and drying at a proper temperature.
As one embodiment, the step of preparing the electron transport layer on the quantum dot light emitting layer specifically includes: and spin-coating the prepared indium and silver doped zinc sulfide nanoparticle solution with a certain concentration on the quantum dot light-emitting layer to form a film, controlling the thickness of the electron transport layer to be about 20-60nm by adjusting the concentration, the spin-coating speed and the spin-coating time of the indium and silver doped zinc sulfide nanoparticle solution, and then annealing to form the film.
In some embodiments, the spin speed is 3000 and 5000 rpm.
As one embodiment, the step of preparing the cathode on the electron transport layer specifically includes: the substrate deposited with the functional layers is placed in an evaporation bin, a layer of 15-30nm metal silver or aluminum and the like is thermally evaporated through a mask plate to be used as a cathode, or a nano Ag wire or a Cu wire and the like are used, and the materials have low resistance so that carriers can be smoothly injected.
The invention also provides a preparation method of the quantum dot light-emitting diode with the flip structure, which comprises the following steps:
providing a substrate containing a cathode, and preparing an electron transport layer on the cathode, wherein the electron transport layer is the bimetallic co-doped zinc sulfide film;
preparing a quantum dot light-emitting layer on the electron transport layer;
preparing a hole transport layer on the quantum dot light emitting layer;
and preparing an anode on the hole transport layer to obtain the quantum dot light-emitting diode.
As one embodiment, the step of preparing the electron transport layer on the cathode specifically includes: and spin-coating the prepared indium and silver doped zinc sulfide nanoparticle solution with a certain concentration on the quantum dot light-emitting layer to form a film, controlling the thickness of the electron transport layer to be about 20-60nm by adjusting the concentration, the spin-coating speed and the spin-coating time of the indium and silver doped zinc sulfide nanoparticle solution, and then annealing to form the film.
The invention also comprises the following steps: and carrying out packaging treatment on the obtained quantum dot light-emitting diode, wherein the packaging treatment can adopt common machine packaging or manual packaging. Preferably, in the environment of the packaging treatment, the oxygen content and the water content are both lower than 0.1ppm so as to ensure the stability of the quantum dot light-emitting diode.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of but not limited to a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein solution methods include, but are not limited to, spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slot coating, bar coating; physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
In summary, the invention prepares indium-silver doped zinc sulfide nanoparticle solution by a simple sol-gel method, prepares the indium-silver doped zinc sulfide nanoparticle solution into a bimetallic zinc sulfide film as an electron transport layer, forms a new chemical bond by introducing a small amount of In and Ag elements on the ZnS nanoparticles to replace partial Zn atoms, adjusts the intrinsic electronic structure of the ZnS nanoparticles by forming the new chemical bond, and reduces the resistivity and the narrowing forbidden bandwidth of the ZnS nanoparticles; the electron is more easily transited to a conduction band, the electron is promoted to enter a quantum dot light emitting region from an electron transmission layer, and the recombination efficiency of the electron-hole in the quantum dot light emitting layer is improved, so that the light emitting efficiency of the quantum dot light emitting diode is improved. In addition, the method for preparing the bimetal co-doped zinc sulfide film is very simple and is suitable for large-area and large-scale preparation.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a bimetal co-doped zinc sulfide film is characterized by comprising the following steps:
dispersing zinc salt, indium salt and silver salt in an organic solvent to obtain a metal salt solution;
mixing the metal salt solution with a sulfur source, and reacting to obtain an indium and silver doped zinc sulfide nanoparticle solution;
and preparing the indium and silver doped zinc sulfide nano particle solution into a film to prepare the bimetal co-doped zinc sulfide film.
2. The method for preparing the bimetal co-doped zinc sulfide film according to claim 1, wherein the metal salt solution comprises zinc ions, indium ions and silver ions, and the ratio of the sum of the molar amounts of the indium ions and the silver ions to the molar amount of the zinc ions is 0.01-0.1: 1.
3. The method for preparing the bimetal co-doped zinc sulfide film according to claim 2, wherein the molar ratio of the sulfur element in the sulfur source to the zinc ions in the metal salt solution is 1.2-3: 1.
4. The method for preparing the bimetal co-doped zinc sulfide film according to claim 1, wherein the step of adding a sulfur source into the metal salt solution to react to obtain the indium and silver doped zinc sulfide nanoparticle solution comprises the following steps:
and adding a sulfur source into the metal salt solution, and reacting for 1-4h at the temperature of 60-80 ℃ to prepare the indium and silver doped zinc sulfide nanoparticle solution.
5. The method for preparing the bimetal co-doped zinc sulfide film according to any one of claims 1 to 4, wherein the zinc salt is one or more of zinc acetate, zinc nitrate, zinc chloride and zinc acetate dihydrate.
6. The method for preparing the bimetal co-doped zinc sulfide film according to any one of claims 1 to 4, wherein the indium salt is one or more of indium nitrate, indium chloride and indium acetate.
7. The method for preparing the bimetal co-doped zinc sulfide thin film according to any one of claims 1 to 4, wherein the silver salt is one or more of silver acetate, silver acetylacetonate and silver methanesulfonate.
8. The method for preparing the bimetal co-doped zinc sulfide thin film according to any one of claims 1 to 4, wherein the sulfur source is one or more of thiourea, sodium sulfide, thioacetamide and L-cysteine.
9. A bimetal co-doped zinc sulfide film, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. A quantum dot light-emitting diode, comprising an anode, a cathode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein an electron transport layer is arranged between the cathode and the quantum dot light-emitting layer, and the electron transport layer is the bimetal co-doped zinc sulfide thin film of claim 9.
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