CN116553598A - Preparation method of zinc oxide nanocrystals, photoelectric device and display device - Google Patents
Preparation method of zinc oxide nanocrystals, photoelectric device and display device Download PDFInfo
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- CN116553598A CN116553598A CN202210097331.6A CN202210097331A CN116553598A CN 116553598 A CN116553598 A CN 116553598A CN 202210097331 A CN202210097331 A CN 202210097331A CN 116553598 A CN116553598 A CN 116553598A
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- Prior art keywords
- zinc oxide
- solution
- precursor solution
- zinc
- salt
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 400
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 199
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 68
- 150000003751 zinc Chemical class 0.000 claims abstract description 23
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 186
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 60
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 230000005693 optoelectronics Effects 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004914 cyclooctane Substances 0.000 claims description 8
- KUOVKYWDAVALSV-UHFFFAOYSA-L dichlorozinc pentahydrate Chemical compound O.O.O.O.O.[Cl-].[Zn+2].[Cl-] KUOVKYWDAVALSV-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 zinc bromide pentahydrate Chemical compound 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- OXAGUGIXGVHDGD-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate;dihydrate Chemical compound O.O.[Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OXAGUGIXGVHDGD-UHFFFAOYSA-H 0.000 claims description 3
- 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 3
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 30
- 238000000151 deposition Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 74
- 239000002096 quantum dot Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 230000008569 process Effects 0.000 description 21
- 238000005119 centrifugation Methods 0.000 description 17
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 238000004321 preservation Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000002346 layers by function Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- 241001411320 Eriogonum inflatum Species 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000366 colloid method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002707 nanocrystalline material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 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
- 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 1
- YWKKLBATUCJUHI-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C)=CC=1)C1=CC=CC=C1 YWKKLBATUCJUHI-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GKDODGRQNSAYGJ-UHFFFAOYSA-N [C].C1CCCCCCC1 Chemical compound [C].C1CCCCCCC1 GKDODGRQNSAYGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical group C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000001748 luminescence spectrum Methods 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
- 239000005022 packaging material Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
Abstract
The application discloses a preparation method of zinc oxide nanocrystals, a photoelectric device and a display device. The preparation method of the zinc oxide comprises the following steps: mixing a cyclic hydrocarbon compound with the carbon number less than or equal to eight and an even number in a first precursor solution containing zinc salt; injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution; and drying the zinc oxide solution to obtain zinc oxide nanocrystals. Therefore, the zinc oxide can keep the original particle size, has high stability, avoids aggregation and particle size increase caused by the storage of the zinc oxide in the solution, and finally can control the consistency of the zinc oxide when being matched with the state of depositing on a photoelectric device, thereby improving the film forming quality of the zinc oxide and improving the performance of the device.
Description
Technical Field
The application relates to the technical field of display, in particular to a preparation method of zinc oxide nanocrystals, a photoelectric device and a display device.
Background
The photoelectric device refers to a device manufactured according to a photoelectric effect, and has wide application in the fields of new energy sources, sensing, communication, display, illumination and the like, such as a solar cell, a photoelectric detector and an organic electroluminescent device (OLED or quantum dot electroluminescent device (or called quantum dot light emitting diode, QLED).
The Quantum Dots (QDs) are semiconductor clusters with a size of 1-10 nm, have photoelectron properties with adjustable band gaps due to quantum size effect, and can be applied to the fields of light emitting diodes, solar cells, bioluminescence marks and the like. The quantum dot is used as an inorganic semiconductor material, and has wide application prospect in the field of photoelectric luminescence due to unique photoluminescence and electroluminescence characteristics, including narrow luminescence spectrum, high color purity and good optical stability.
The quantum dot light emitting diode is a device taking colloid quantum dots as a light emitting layer, and the light emitting layer is introduced between different conductive materials so as to obtain light with required wavelength, and has the advantages of high color gamut, self-luminescence, low starting voltage, high response speed and the like, is used in various display devices such as mobile phones, computers, televisions and the like, and has wide development prospect.
The film prepared by the zinc oxide (ZnO) nanoparticle solution has wider band gap and relatively higher electron mobility and stability, so that the ZnO film is one of the best choices for preparing the QLED electron transport layer material. However, the stability of zinc oxide has been a problem to be solved. At present, most zinc oxide nanocrystalline materials used in QLEDs are generally prepared by adopting a solution-colloid method, and a solvent after stirring synthesis is directly dissolved in a dispersion solvent for preservation after centrifugation, but because the surface of the final zinc oxide material has a large amount of adsorbed oxygen and hydroxyl ligands reduced by a cleaning step, zinc oxide particles are extremely easy to agglomerate in the solution preservation process, so that zinc oxide cannot be preserved for a long time, and finally, the consistency of zinc oxide cannot be controlled when deposition film formation is carried out on a photoelectric device, so that the film formation quality of zinc oxide is poor, and the performance of the device is affected; if the zinc oxide crystals are stored in powder form by suction, the zinc oxide crystals cannot be redispersed in solution if they are completely dried.
Therefore, how to make zinc oxide possible to be stored for a long time while maintaining stability has become an urgent problem for industry to solve.
Disclosure of Invention
In view of the above, the present application provides a method for preparing zinc oxide nanocrystals, a photovoltaic device, and a display device, which aim to solve the problem that the existing zinc oxide is difficult to stably preserve.
The embodiment of the application is realized in such a way that a preparation method of zinc oxide nanocrystals comprises the following steps:
mixing a cyclic hydrocarbon compound with the carbon number less than or equal to eight and an even number in a first precursor solution containing zinc salt;
injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution;
and drying the zinc oxide solution to obtain zinc oxide nanocrystals.
Optionally, the mixing of the cyclic hydrocarbon compound with the carbon number less than or equal to eight and even number in the first precursor solution containing the zinc salt includes:
dissolving zinc salt in a mixed solution of an alcohol solvent and a cyclic hydrocarbon compound;
and heating the mixed solution in which the zinc salt is dissolved to a first preset temperature in an inert atmosphere, and stirring to obtain the first precursor solution.
Optionally, the zinc salt is selected from at least one of zinc chloride pentahydrate, zinc bromide pentahydrate, zinc acetate dihydrate, zinc citrate dihydrate; and/or the number of the groups of groups,
the alcohol solvent is at least one selected from methanol, ethanol and butanol; and/or the number of the groups of groups,
the cyclic hydrocarbon compound is at least one selected from cyclobutane, cyclohexane, cyclooctane, cyclobutane and cyclooctatetraene.
Optionally, the volume ratio of the alcohol solvent to the cyclic hydrocarbon compound is 3:1-4:1.
Optionally, the injecting the second precursor solution containing the alkali salt into the first precursor solution to obtain a zinc oxide solution includes:
dissolving alkali salt into alcohol or amine solvent to obtain second precursor solution;
and injecting the second precursor solution into the first precursor solution to react, so as to obtain the zinc oxide solution.
Optionally, the step of injecting the second precursor solution into the first precursor solution to react, and obtaining the zinc oxide solution further includes: and cooling the mixed solution of the first precursor solution and the second precursor solution to a third preset temperature, adding a precipitator, centrifuging, removing supernatant to obtain precipitate, and dispersing the precipitate with a dispersing agent to obtain zinc oxide solution.
Optionally, the alkali salt is at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide; the alcohol or amine solvent is at least one selected from methanol, ethanol, butanol, triacetonamine and ethanolamine.
Optionally, in the second precursor solution, the molar ratio of the zinc salt to the alkali salt is 1:1.5-1:2.
Optionally, the dispersing agent comprises at least one of ethanol, butanol, amyl alcohol, toluene, chlorobenzene and chloroform.
Optionally, the step of drying the zinc oxide solution to obtain zinc oxide nanocrystals includes:
vacuum drying the zinc oxide solution at a fourth preset temperature to obtain dried zinc oxide nanocrystals;
and sealing the zinc oxide nanocrystals and then preserving the zinc oxide nanocrystals.
Correspondingly, the embodiment of the application also provides a preparation method of the electron transport layer, which comprises the following steps:
providing zinc oxide nanocrystals prepared by the preparation method, and preparing a zinc oxide solution;
providing a substrate, and arranging the zinc oxide solution on the substrate to obtain an electron transport layer.
Correspondingly, the embodiment of the application also provides a photoelectric device which comprises an anode, a light-emitting layer, an electron transport layer and a cathode which are arranged in a stacked mode, wherein the electron transport layer is prepared by the preparation method of the electron transport layer.
Correspondingly, the embodiment of the application also provides a display device, which is characterized by comprising the photoelectric device.
According to the preparation method of the zinc oxide nanocrystals, the photoelectric device and the display device, in the synthesis process of zinc oxide, a first precursor solution containing zinc salt is mixed with a cyclic hydrocarbon compound with the carbon number of eight or less and an even number; and injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution. Therefore, in the synthesis process of zinc oxide, a liquid phase-solid phase-solution synthesis mode is adopted to cause the phase change of zinc oxide crystals, so that the zinc oxide can keep the original particle size, has high stability, and avoids the aggregation and particle size increase of particles caused by the preservation of the zinc oxide in the solution; and the zinc oxide solution is dried to obtain zinc oxide nanocrystals, the original particle size can be kept after the zinc oxide nanocrystals are stored for a long time, and the stability is higher, so that the zinc oxide crystals can be dispersed and dissolved back into the solution again after being completely dried, and finally, the consistency of zinc oxide can be controlled when the zinc oxide is deposited and formed on an optoelectronic device, the quality of zinc oxide film formation is improved, the batch consistency of zinc oxide products required for industrial production is improved, and the performance of the device is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing zinc oxide nanocrystals according to an embodiment of the present application;
fig. 2 is a schematic flow chart of a step of mixing a cyclic hydrocarbon compound with a carbon number less than or equal to eight and an even number in a first precursor solution containing zinc salt in the preparation method of zinc oxide nanocrystals provided in the embodiment of the present application;
FIG. 3 is a schematic flow chart of a step of obtaining a zinc oxide solution in a method for preparing zinc oxide nanocrystals according to an embodiment of the present application;
FIG. 4 is a schematic flow chart showing steps for obtaining zinc oxide nanocrystals in a method for preparing zinc oxide nanocrystals according to an embodiment of the present application;
fig. 5 is a schematic flow chart of a method for preparing an electron transport layer according to an embodiment of the present application;
Fig. 6 is a schematic structural diagram of an optoelectronic device according to an embodiment of the present disclosure;
fig. 7 is a schematic structural diagram of a display device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are within the scope of the protection of the present application, will be within the skill of the art without inventive effort. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The film prepared by the zinc oxide (ZnO) nanoparticle solution has wider band gap and relatively higher electron mobility and stability, so that the ZnO film is one of the best choices for preparing the QLED electron transport layer material. However, the stability of zinc oxide has been a problem to be solved. At present, most zinc oxide nanocrystalline materials used in QLEDs are generally prepared by adopting a solution-colloid method, and a solvent after stirring synthesis is directly dissolved in a dispersion solvent for preservation after centrifugation, but because the surface of the final zinc oxide material has a large amount of adsorbed oxygen and hydroxyl ligands reduced by a cleaning step, zinc oxide particles are extremely easy to agglomerate in the solution preservation process, so that zinc oxide cannot be preserved for a long time, and finally, the consistency of zinc oxide cannot be controlled when deposition film formation is carried out on a photoelectric device, so that the film formation quality of zinc oxide is poor, and the performance of the device is affected; if the zinc oxide crystals are stored in the form of a powder by suction, the zinc oxide crystals cannot be redispersed in solution if they are completely dried.
Therefore, how to make zinc oxide possible to be stored for a long time while maintaining stability has become an urgent problem for industry to solve.
Based on this, the present application provides a method for preparing zinc oxide nanocrystals as follows.
In one embodiment, as shown in fig. 1, the present invention provides a method for preparing zinc oxide nanocrystals, the method comprising the steps of:
s1, mixing a cyclic hydrocarbon compound with the carbon number less than or equal to eight and an even number in a first precursor solution containing zinc salt;
s2, injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution;
and S3, drying the zinc oxide solution to obtain zinc oxide nanocrystals.
In the embodiment, during the synthesis of zinc oxide, a cyclic hydrocarbon compound with the carbon number less than or equal to eight and even number is mixed in a first precursor solution containing zinc salt; injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution; and drying the zinc oxide solution to obtain zinc oxide nanocrystals. Therefore, in the synthesis process of zinc oxide, a liquid phase-solid phase-solution synthesis mode is adopted to cause the phase change of zinc oxide crystals, so that the zinc oxide keeps the original particle size, has high stability, avoids the aggregation and particle size increase of particles caused by the preservation of zinc oxide in the solution, and finally can control the consistency of zinc oxide when depositing and forming films on photoelectric devices, improves the quality of zinc oxide film formation, improves the batch consistency of zinc oxide products required for industrial production, and improves the performance of devices.
In one embodiment, as shown in fig. 2, in the step S1, a cyclic hydrocarbon compound having eight or less carbon atoms and an even number is mixed in a first precursor solution containing a zinc salt; comprising the following steps:
s11, dissolving zinc salt in a mixed solution of an alcohol solvent and a cyclic hydrocarbon compound.
In this step, the zinc salt is preferably, but not limited to, at least one of zinc chloride pentahydrate, zinc bromide pentahydrate, zinc acetate dihydrate, zinc citrate dihydrate. The alcohol solvent is preferably but not limited to at least one of methanol, ethanol, butanol, and the mixed solvent is strongly polar. The cyclic hydrocarbon compound is required to have an even number of carbon atoms of eight or less, and preferably at least one of cyclobutane, cyclohexane, cyclooctane, cyclobutene, and cyclooctatetraene.
The volume ratio of the alcohol solvent to the cyclic hydrocarbon compound is 3:1-4:1.
And S12, heating the mixed solution with the zinc salt dissolved to a first preset temperature in an inert atmosphere, and stirring to obtain the first precursor solution.
In this step, the first preset temperature is 80 ℃, and the stirring time of the magnetons is preferably 10 to 15 minutes. And filling the mixed solution into a three-neck flask, heating to 80 ℃ under an inert atmosphere, and stirring the mixture for 10 to 15 minutes until the mixture is completely dispersed to obtain a first precursor solution. The obtained first precursor solution is a salt precursor solution, the concentration is preferably 0.16-0.2 mmol/mL, and the volume is preferably 40-50 mL.
In one embodiment, as shown in fig. 3, in the step S2, the second precursor solution containing the alkali salt is injected into the first precursor solution to obtain a zinc oxide solution; comprising the following steps:
s21, dissolving alkali salt into alcohol or amine solvent to obtain second precursor solution.
In this step, the alkali salt is preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, and the solvent is preferably at least one of methanol, ethanol, butanol, triacetonamine, ethanolamine (of strong polarity), but not limited thereto. The second precursor solution obtained is a base precursor solution. In the obtained second precursor solution, the ratio of the zinc salt to the alkali salt is 1:1.5-1:2.
S22, injecting the second precursor solution into the first precursor solution for reaction to obtain the zinc oxide solution.
Specifically, the second precursor solution is injected into the first precursor solution, the reaction temperature is raised to a second preset temperature, and stirring is performed. Wherein the second preset temperature is 120 ℃, and the stirring time of the magnetons is preferably 20-30 minutes.
In step S22, the second precursor solution is injected into the flask by means of uniform injection for 10 minutes, the reaction temperature is raised to 120 ℃, and the stirring of the magneton in the flask is maintained for 20 to 30 minutes.
S23, cooling the mixed solution of the first precursor solution and the second precursor solution to a third preset temperature, and adding a precipitant for centrifugation.
Specifically, the flask with the mixed solution is quickly placed into ice water for ice bath, and the precipitant is added for centrifugation after the temperature of the flask is reduced below a third preset temperature.
In this step, the third preset temperature is 15 ℃, that is, the temperature of the ice bath needs to be reduced to below 15 ℃, the amount of the solution in each separation tube is not more than 12.5mL, the precipitant is preferably but not limited to at least one of acetone, n-heptane, n-octane and n-hexane, and the amount of the precipitant is preferably 20-25 mL/tube.
In the step S23, the flask with the mixed solution is quickly placed into ice water for ice bath, and after the temperature of the flask is reduced to below 15 ℃, the flask is separated into eight separation tubes, and 20-25 mL of precipitant is added for centrifugation.
S24, removing the supernatant after centrifugation to obtain a precipitate, and dispersing the precipitate by using a dispersing agent to obtain a zinc oxide solution.
In this step, the dispersant includes, but is not limited to, an alcoholic solvent, or at least one of toluene, chlorobenzene, chloroform, wherein the alcoholic solvent includes at least one of ethanol, butanol, pentanol.
In step S24, the supernatant was removed after centrifugation and dispersed with 1.5 mL/tube of dispersant, and finally eight tubes of the dispersed solution were combined into one tube, to finally obtain 12mL of zinc oxide solution.
In one embodiment, in the step S3, the zinc oxide solution is dried to obtain zinc oxide nanocrystals.
In particular, the drying includes, but is not limited to, at least one of vacuum drying, spray drying, boiling drying. Preferably, the drying is vacuum drying.
As shown in fig. 4, in the step S3, the drying the zinc oxide solution to obtain zinc oxide nanocrystals includes:
and S31, carrying out vacuum drying on the zinc oxide solution at a fourth preset temperature to obtain the dried zinc oxide nanocrystals.
In this embodiment, the fourth preset temperature is 150 ℃, and the duration of vacuum drying is not less than 24 hours.
In this step, the zinc oxide solution is transferred to a suitable glass vessel for preservation, and vacuum drying is performed at 150 ℃ for not less than 24 hours to obtain dried zinc oxide nanocrystals.
And S32, sealing the zinc oxide nanocrystals and then preserving the zinc oxide nanocrystals.
In this step, the zinc oxide nanocrystals are sealed and then stored in a moisture-proof cabinet having a humidity of not more than 40% RH.
In the present application, zinc salt is directly dissolved in a mixed solution of alcohol and cyclic hydrocarbon compound, and then alkali salt-containing solution is added dropwise to rapidly produce a complex product of metal salt, which can cause hydroxyl ions in alkali solution and metal complex product to be dispersed and co-precipitated in nano-scale bubbles generated by dispersing alcohol substances in cyclic hydrocarbon compound due to the hydrophilic property of cyclic hydrocarbon material itself and the difficulty in affinity of the complex product. The injected alkali solution can occupy the center of the core of the nanocrystalline preferentially, zinc oxide clusters generated by coprecipitation wrap the core, and by increasing the reaction temperature, the zinc oxide clusters grow rapidly and gradually occupy the position of the core, and a large number of hydroxyl groups are enriched on the surface to form a 'shell' of hydroxyl ligand. Finally, crystallization is stopped by cooling to control the proper particle size. By adopting the liquid-solid phase-solution synthesis mode, the zinc oxide can keep the original particle size due to the synthesis mode of the product and the difference of the ligand amount on the surface of the final product, so that the stability is high, and the defects that the zinc oxide is kept in the solution and the agglomeration of particles and the particle size increase are necessarily caused are overcome; and the zinc oxide solution is dried to obtain zinc oxide nanocrystals, the original particle size can be still reserved after the zinc oxide nanocrystals are stored in a long-time solid mode, and the stability is higher, so that the zinc oxide nanocrystals can still be redispersed and dissolved back into the solution after being completely dried, and finally, the consistency of zinc oxide can be controlled when the zinc oxide nanocrystals are deposited on a photoelectric device to form a film, the film forming quality of the zinc oxide is improved, the batch consistency of zinc oxide products required by industrial production is improved, and the performance of the device is improved.
Based on the same concept, as shown in fig. 5, in an embodiment, the present application further provides a method for preparing an electron transport layer, the method comprising the steps of:
s51, providing zinc oxide nanocrystals to prepare zinc oxide solution.
In this step, the zinc oxide nanocrystals are obtained by using the method for producing zinc oxide nanocrystals described in any one of the above examples.
And dissolving the zinc oxide nanocrystals in a dispersion solvent to obtain a zinc oxide solution. Specifically, the zinc oxide nanocrystals need to be vacuum-dried and redissolved in a dispersion solvent to obtain a zinc oxide solution. Wherein the vacuum degree is preferably lower than-0.08 mbar, and the vacuum pumping time is not lower than 10 minutes; the dispersing agent comprises, but is not limited to, an alcohol solvent, or at least one of toluene, chlorobenzene and chloroform, wherein the alcohol solvent comprises at least one of ethanol, butanol and amyl alcohol.
And S52, providing a substrate, and arranging the zinc oxide solution on the substrate to obtain the electron transport layer.
In this example, in the preparation of the electron transport layer, zinc oxide nanocrystals were dissolved in a dispersion solvent to obtain a zinc oxide solution to obtain the electron transport layer. In the synthesis process of zinc oxide, a liquid phase-solid phase-solution synthesis mode is adopted to cause the phase change of zinc oxide crystals, so that the zinc oxide can keep the original particle size, has high stability, and avoids the aggregation and particle size increase of particles caused by the preservation of the zinc oxide in the solution; and the zinc oxide solution is dried to obtain zinc oxide nanocrystals, the original particle size can be still reserved after the zinc oxide nanocrystals are stored in a long-time solid mode, and the stability is higher, so that the zinc oxide nanocrystals can still be redispersed and dissolved back into the solution after being completely dried, and finally, the consistency of zinc oxide can be controlled when the zinc oxide nanocrystals are deposited on a photoelectric device to form a film, the film forming quality of the zinc oxide is improved, the batch consistency of zinc oxide products required by industrial production is improved, and the performance of the device is improved.
In this step, the substrate is an anode substrate, and an electron transport layer prepared from the zinc oxide material is disposed on the anode. The substrate may be a conventionally used substrate, for example, may be a rigid substrate, and the material is glass; and the flexible substrate can also be made of polyimide. The material of the anode may be, for example, one or more of a metal, a carbon material, and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be a doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode of doped or undoped transparent metal oxide sandwiching a metal therebetween, including but not limited to one or more of AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO2/Ag/TiO2, tiO2/Al/TiO2, znS/Ag/ZnS, znS/Al/ZnS, tiO2/Ag/TiO2, and TiO2/Al/TiO 2. If the optoelectronic device further comprises other functional layers, the substrate may correspondingly comprise other functional layers.
Specifically, a zinc oxide material solution can be arranged on a substrate by a solution method, and an electron transport layer is obtained by an annealing process. Solution processes include, but are not limited to, spin coating, drop coating, ink jet printing, knife coating, dip-pull, dipping, spray coating, roll coating, evaporation, or casting.
An annealing process in the present application, wherein "annealing process" includes all treatment processes that enable the wet film to obtain higher energy, thereby converting from a wet film state to a dry state, for example, "annealing process" may refer only to a heat treatment process, i.e., heating the wet film to a specific temperature and then for a specific time to sufficiently volatilize the solvent in the wet film; as another example, the "annealing process" may further include a heat treatment process and a cooling process performed sequentially, i.e., heating the wet film to a specific temperature, then maintaining the wet film for a specific time to volatilize the solvent in the first wet film sufficiently, and then cooling at a suitable rate to eliminate residual stress and reduce the risk of layer deformation and cracking of the dried hole transport film.
In this step, the control and adjustment of the thickness of the finally formed electron transport layer can be achieved by controlling and adjusting conditions such as the concentration of the solution used in the solution method. The thickness of the electron transport layer may be in the range of 10 to 70nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, etc. Taking spin coating as an example, the electron transport layer thickness can be controlled by adjusting the concentration of the solution, the spin coating speed, and the spin coating time.
Based on the same concept, in one embodiment, as shown in fig. 6, the present application also provides an optoelectronic device 100, where the optoelectronic device 100 includes an anode 20, a light emitting layer 50, an electron transport layer 60, and a cathode 70, which are sequentially stacked.
The material of the cathode 70 is a material known in the art for a cathode and the material of the anode 20 is a material known in the art for an anode. The materials of the cathode 70 and the anode 20 may be, for example, one or more of a metal, a carbon material, and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be a doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode of doped or undoped transparent metal oxide sandwiching a metal therebetween, including but not limited to one or more of AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO2/Ag/TiO2, tiO2/Al/TiO2, znS/Ag/ZnS, znS/Al/ZnS, tiO2/Ag/TiO2, and TiO2/Al/TiO 2. The thickness of the cathode 70 is a cathode thickness known in the art and may be, for example, 10nm to 200nm, such as 10nm, 35nm, 50nm, 80nm, 120nm, 150nm, 200nm, etc.; the thickness of the anode 20 is an anode thickness known in the art and may be, for example, 10nm to 200nm, such as 10nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, etc.
The electron transport layer 60 is located above the quantum dot light emitting layer 50, and the electron transport layer 60 is prepared by the above-mentioned preparation method of the electron transport layer, and the specific preparation method can be referred to the above related description, which is not repeated here.
The light emitting layer 50 may be a quantum dot light emitting layer, in which case the optoelectronic device 100 may be a quantum dot optoelectronic device. The thickness of the light emitting layer 50 may be in the range of the thickness of the light emitting layer in a quantum dot optoelectronic device known in the art, for example, may be 5nm to 100nm, such as 5nm, 10nm, 20nm, 50nm, 80nm, 100nm, etc.; or may be 60-100nm.
The material of the quantum dot light emitting layer is one of the quantum dots known in the art for the quantum dot light emitting layer, for example, red quantum dot, green quantum dot and blue quantum dot. The quantum dot may be selected from, but not limited to, at least one of a single structure quantum dot and a core-shell structure quantum dot. For example, the quantum dot may be selected from, but is not limited to, at least one of group II-VI compounds, group III-V compounds, and group I-III-VI compounds; the II-VI compound is at least one selected from CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSte; the III-V compound is selected from InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP; the I-III-VI compound is selected from CuInS 2 、CuInSe 2 And AgInS 2 At least one of them.
With further reference to fig. 6, in one embodiment, the optoelectronic device 100 can further include a hole transport layer 40, the hole transport layer 40 being located between the light emitting layer 50 and the anode 20. The material of the hole transport layer 40 may be selected from organic materials having hole transport capability, including, 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 (carbazole-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazole) Biphenyl (CBP), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N ' -diphenyl-N, N ' - (1-naphtyl) -1,1' -biphenyl-4, 4' -diamine (NPB), poly (3, 4-ethylenedioxythiophene) -Poly (PEDOT); PSS), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), doped graphene, undoped graphene, and C60. The material of the hole transport layer 40 may also be selected from inorganic materials having hole transport capabilities, including, but not limited to, one or more of doped or undoped NiO, moOx, WOx and CuO. The thickness of the hole transport layer 40 may be, for example, 10nm to 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
With further reference to fig. 6, in one embodiment, the optoelectronic device 100 can further include a hole injection layer 30. The hole injection layer 30 is located between the hole transport layer 40 and the anode 20. The material of the hole injection layer 30 may be selected from materials having hole injection capability, including but not limited to one or more of PEDOT PSS, MCC, cuPc, F-TCNQ, HATCN, transition metal oxide, transition metal chalcogenide. PEDOT PSS is a high molecular polymer, and the Chinese name is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid). The thickness of the hole injection layer 30 may be, for example, 10nm to 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
With further reference to fig. 6, in one embodiment, the optoelectronic device 100 further comprises a substrate 10. In this embodiment, the substrate is an anode substrate, and an electron transport layer including a zinc oxide material is disposed on the anode. The substrate may be a conventionally used substrate, for example, may be a rigid substrate, and the material is glass; and the flexible substrate can also be made of polyimide. The material of the anode may be, for example, one or more of a metal, a carbon material, and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be a doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode of doped or undoped transparent metal oxide sandwiching a metal therebetween, including but not limited to one or more of AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO2/Ag/TiO2, tiO2/Al/TiO2, znS/Ag/ZnS, znS/Al/ZnS, tiO2/Ag/TiO2, and TiO2/Al/TiO 2.
It will be appreciated that in addition to the above-described functional layers, some functional layers that are conventionally used in optoelectronic devices and help to improve the performance of the optoelectronic device, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, and the like, may be added to the optoelectronic device 100. It will be appreciated that the materials and thicknesses of the various layers of the optoelectronic device 100 may be tailored to the lighting requirements of the optoelectronic device 100.
In some embodiments of the present application, the optoelectronic device 100 is a quantum dot light emitting diode with a front-side structure, and a substrate of the quantum dot light emitting diode with the front-side structure is connected with an anode, and the structure may be a glass substrate-anode- (hole injection layer) -hole transport layer-quantum dot light emitting layer-electron transport layer-cathode. The device emits light from the anode. The hole injection layer is an optional choice, and the quantum dot light emitting diode structure may or may not include the hole injection layer.
Based on the same concept, in one embodiment, as shown in fig. 7, the present application further provides a display apparatus including the optoelectronic device 100 provided herein. The display device may be any electronic product with a display function, including but not limited to a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television set or an electronic book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, etc.
The embodiment also provides a preparation method of the photoelectric device 100, which comprises the step of preparing an electron transport layer.
In one embodiment, the optoelectronic device 100 is a positive quantum dot light emitting diode, and the preparation method of the optoelectronic device 100 specifically includes the following steps:
s61, providing an anode, and forming a light emitting layer on the anode.
S62, preparing an electron transport layer on the light-emitting layer through a preparation method of the electron transport layer.
And S63, forming a cathode on the electron transport layer.
It will be appreciated that when the optoelectronic device further includes a hole transport layer, step S61 is: an anode is provided, and a hole transport layer and a light emitting layer are sequentially formed on the anode. Further, when the optoelectronic device further includes a hole injection layer, step S61 is: an anode is provided, and a hole injection layer, a hole transport layer, and a light-emitting layer are sequentially formed on the anode.
It will be appreciated that where the optoelectronic device further comprises other functional layers such as an electron blocking layer, a hole blocking layer, an electron injection layer and/or an interface modification layer, the method of making the optoelectronic device further comprises the step of forming the functional layers.
It should be noted that, the anode 20, the light-emitting layer 50, the cathode 70, and other functional layers may be prepared by conventional techniques in the art, including but not limited to solution methods and deposition methods, wherein the solution methods include, but are not limited to, spin coating, inkjet printing, knife coating, dip-coating, dipping, spray coating, roll coating, or casting; the deposition method includes a chemical method including, 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, or a coprecipitation method, and a physical method including, but not limited to, a thermal evaporation plating method, an electron beam evaporation plating method, a magnetron sputtering method, a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, or a pulsed laser deposition method. When the anode 20, the light-emitting layer 30, the cathode 40 and other functional layers are prepared by a solution method, an annealing process is added.
It can be appreciated that the method for manufacturing the optoelectronic device may further include a packaging step, the packaging material may be acrylic resin or epoxy resin, the packaging may be machine packaging or manual packaging, and ultraviolet curing glue packaging may be used, where the concentration of oxygen and water in the environment where the packaging step is performed is less than 0.1ppm, so as to ensure stability of the optoelectronic device.
The technical solutions and technical effects of the present application are described in detail below by means of specific examples, comparative examples and experimental examples, and the following examples are only some examples of the present application and are not intended to limit the present application in any way.
Example 1:
in an argon glove box, 8mmol of zinc chloride pentahydrate crystal was first dissolved in a mixed solution of 30mL of butanol and 10mL of cyclooctane, and the mixture was put into a three-necked flask, and stirred at 80 ℃ for 15 minutes by using a magnet to obtain a precursor solution of salt.
The weighed 14mmol lithium hydroxide crystal is dissolved in 40mL of triacetonamine solution, the solution is fully oscillated and is filled into a needle tube, and the solution is injected into a three-neck flask in a constant speed mode of 4mL/min, after the injection is finished, the reaction temperature is increased to 120 ℃ and stirring of magnetons is maintained in the whole process. After stirring for 30 minutes, the reaction was completed, the three-necked flask was rapidly placed in ice water for ice bath, and after the temperature was lowered to 15 ℃, the solution was separated into eight separate tubes (about 10 mL/tube), and 20mL of acetone was added to each tube. After shaking up the mixed solution, centrifugation was performed at 8000rpm for 4 minutes, after centrifugation, the supernatant was removed and dispersed with 1.5 mL/tube of ethanol: pentanol=1:1 mixed solvent, and eight tubes of the dispersed solution were combined into one tube, to obtain 12mL of zinc oxide solution.
Transferring the zinc oxide solution into a glass bottle, and vacuum drying at 150 ℃ for 24 hours to obtain dried zinc oxide nanocrystals, and placing the dried zinc oxide nanocrystals into a constant humidity 30% dampproof cabinet for preservation after drying.
And carrying out vacuum pumping operation for 20mins at the vacuum degree of-0.1 mbar on the first day and the twentieth day after the synthesis is finished, and after pumping, re-decomposing the mixture into 12mL of ethanol and amyl alcohol=1:1 mixed solvent to obtain zinc oxide solution.
Comparative example 1:
comparative example 1 differs from example 1 in that cyclooctane in example 1 was replaced with cycloheptane, and otherwise the same.
Comparative example 2:
comparative example 2 differs from example 1 in that cyclooctane in example 1 was replaced with cyclodecane, and the other is the same.
Comparative example 3:
in an argon glove box, 8mmol of zinc chloride pentahydrate crystal was first dissolved in a mixed solution of 30mL of butanol and 10mL of cyclooctane, and the mixture was put into a three-necked flask, and stirred at 80 ℃ for 15 minutes by using a magnet to obtain a precursor solution of salt.
The weighed 14mmol lithium hydroxide crystal was dissolved in 40mL of triacetonamine solution, and the solution was sufficiently oscillated and then put into a needle tube, and the magnetic particles were injected into a three-necked flask at a constant speed of 4mL/min while maintaining stirring. After stirring for 30 minutes, the reaction was completed, the three-necked flask was rapidly placed in ice water for ice bath, and after the temperature was lowered to 15 ℃, the solution was separated into eight separate tubes (about 10 mL/tube), and 20mL of acetone was added to each tube. After shaking up the mixed solution, centrifugation was performed at 8000rpm for 4 minutes, and after centrifugation, the supernatant was removed and 1.5 mL/tube of ethanol was used: amyl alcohol = 1:1, and mixing eight tubes of the dispersed solution into one tube to obtain 12mL of zinc oxide solution.
Transferring the zinc oxide solution into a glass bottle, and vacuum drying at 150 ℃ for 24hrs to obtain dried zinc oxide nanocrystals, and placing the dried zinc oxide nanocrystals into a constant humidity 30% dampproof cabinet for preservation after drying.
And carrying out vacuum pumping operation for 20mins at the vacuum degree of-0.1 mbar on the first day and the twentieth day after the synthesis is finished, and after pumping, re-decomposing the mixture into 12mL of ethanol and amyl alcohol=1:1 mixed solvent to obtain zinc oxide solution.
Comparative example 4:
in an argon glove box, 8mmol of zinc chloride pentahydrate crystal was first dissolved in a mixed solution of 30mL of butanol and 10mL of cyclooctane, and the mixture was put into a three-necked flask, and stirred at 80 ℃ for 15 minutes by using a magnet to obtain a precursor solution of salt.
The weighed 14mmol lithium hydroxide crystal is dissolved in 40mL of triacetonamine solution, the solution is fully oscillated and is filled into a needle tube, and the solution is injected into a three-neck flask in a constant speed mode of 4mL/min, after the injection is finished, the reaction temperature is increased to 120 ℃ and stirring of magnetons is maintained in the whole process. After stirring was continued for 30 minutes, the reaction was completed, and the solution was separated into eight separate tubes (about 10 mL/tube) in a glove box at room temperature, and 20mL of acetone was added to each tube. After shaking up the mixed solution, centrifugation was performed at 8000rpm for 4 minutes, after centrifugation, the supernatant was removed and dispersed with 1.5 mL/tube of ethanol: pentanol=1:1 mixed solvent, and eight tubes of the dispersed solution were combined into one tube, to obtain 12mL of zinc oxide solution.
Transferring the zinc oxide solution into a glass bottle, and vacuum drying at 150 ℃ for 24hrs to obtain dried zinc oxide nanocrystals, and placing the dried zinc oxide nanocrystals into a constant humidity 30% dampproof cabinet for preservation after drying.
And carrying out vacuum pumping operation for 20mins at the vacuum degree of-0.1 mbar on the first day and the twentieth day after the synthesis is finished, and after pumping, re-decomposing the mixture into 12mL of ethanol and amyl alcohol=1:1 mixed solvent to obtain zinc oxide solution.
Comparative example 5:
in an argon glove box, firstly, 14mmol of lithium hydroxide solid is dissolved in 40mL of ethanol solution, the solution is put into a three-neck flask for 3 hours of ultrasonic treatment, the solution is heated to 80 ℃ after the completion of ultrasonic treatment, a bottle stopper is covered, and the solution is stirred by a magnet to obtain lithium hydroxide precursor solution.
The weighed 8mmol zinc chloride pentahydrate solid is dissolved in 40mL of DMSO and subjected to ultrasonic treatment for 3 hours, after the ultrasonic treatment is completed, the solution is transferred into a needle tube and injected into an alkali liquor precursor at the speed of 4mL/min, the whole process is kept at 80 ℃ and the stirring of a magnet is carried out, and after the complete injection, the stirring is continued for 30 minutes. After the reaction was completed, the sample was allowed to stand, and after the temperature was lowered to room temperature, it was separated into eight separate tubes (10 mL/tube) and 20mL of acetone was added. After shaking up the mixed solution, centrifugation was performed at 8000rpm for 4 minutes, after centrifugation, the supernatant was removed and dispersed with 1.5 mL/tube of ethanol, pentanol=1:1 mixed solvent, and eight tubes of the dispersed solution were combined into one tube, to obtain 12mL of zinc oxide solution.
The solution is put into a refrigerator with the temperature of minus 15 ℃ for preservation, and a certain amount of zinc oxide solution is taken for device preparation and testing on the first day and the twentieth day after the synthesis is finished.
Comparative example 6:
in an argon glove box, firstly, 14mmol of lithium hydroxide solid is dissolved in 40mL of ethanol solution, the solution is put into a three-neck flask for 3 hours of ultrasonic treatment, the solution is heated to 80 ℃ after the completion of ultrasonic treatment, a bottle stopper is covered, and the solution is stirred by a magnet to obtain lithium hydroxide precursor solution.
The weighed 8mmol zinc chloride pentahydrate solid is dissolved in 40mL of DMSO and subjected to ultrasonic treatment for 3 hours, after the ultrasonic treatment is completed, the solution is transferred into a needle tube and injected into an alkali liquor precursor at the speed of 4mL/min, the whole process is kept at 80 ℃ and the stirring of a magnet is carried out, and after the complete injection, the stirring is continued for 30 minutes. After the reaction was completed, the sample was allowed to stand, and after the temperature was lowered to room temperature, it was separated into eight separate tubes (10 mL/tube) and 20mL of acetone was added. After shaking up the mixed solution, centrifugation was performed at 8000rpm for 4 minutes, after centrifugation, the supernatant was removed and dispersed with 1.5 mL/tube ethanol: pentanol=1:1 mixed solvent, and finally eight tubes of the dispersed solution were combined into one tube, to finally obtain 12mL of zinc oxide solution.
Transferring the zinc oxide solution into a glass bottle, and vacuum drying at 150 ℃ for 24hrs to obtain dried zinc oxide nanocrystals, and placing the dried zinc oxide nanocrystals into a constant humidity 30% dampproof cabinet for preservation after drying.
And carrying out vacuum pumping operation for 20mins at the vacuum degree of-0.1 mbar on the first day and the twentieth day after the synthesis is finished, and after pumping, re-decomposing the mixture into 12mL of ethanol and amyl alcohol=1:1 mixed solvent to obtain zinc oxide solution.
Among them, in the zinc oxide solutions synthesized in example 1 and comparative examples 1 to 6, the other samples produced clear zinc oxide solutions except for comparative examples 1 and 6, which were not soluble in the dispersant. Taking 1mL of sample from all the solution samples, performing DLS (dynamic light scattering) molecular hydration particle size test, uniformly preparing QLED devices with a positive structure after the test, and calculating the brightness and external quantum efficiency performance values of each device by using JVL test equipment (current-voltage brightness) after the preparation is finished. The particle size of the zinc oxide solution and the device performance test data are shown in table 1.
TABLE 1 particle size of Zinc oxide solution and QLED device Performance test data
From example 1, it can be seen that the cyclooctane carbon number is less than or equal to eight carbons and is even, so that zinc oxide nanocrystals can be preserved for a long time, the original particle size is still maintained, the stability is higher, and the zinc oxide crystals can still be dissolved back into the solution after being completely dried, and finally the consistency of zinc oxide can be controlled when the zinc oxide crystals are matched with the state of depositing on an optoelectronic device, the film forming quality of zinc oxide is improved, and the performance of the device is improved.
As can be seen from example 1 and comparative example 1, if the alkane carbon chain is uneven, the surface hydrophilicity is changed, and ZnO surface coordination cannot be successfully achieved, so that the dispersion is impossible.
As can be seen from comparative example 2, an excessive number of carbon atoms causes the particle size of the sample itself to become large, and although the stability and consistency can be maintained, the requirement of the present case for small zinc oxide particle nanocrystals cannot be satisfied.
As can be seen from comparative example 3, if the reaction temperature is not increased, the generated zinc oxide clusters do not grow in an accelerated manner, and a large amount of unreacted and occupied alkali still exists in a 'nucleus', so that unreacted alkali impurities in the product are too high, and the device performance is affected.
As can be seen from comparative example 4, if ice bath cooling is not performed, the core-shell structure is formed to stabilize the storage, but the particle size is not controlled from the initial stage, and the particle size is too large, resulting in degradation of the device performance.
However, as can be seen from comparative examples 5 and 6, the conventional solution-colloid synthesis method can result in too few hydroxyl groups on the surface, and the operation of re-preservation after drying cannot be performed, but if the particles are directly preserved in a solution dispersing agent, the particles are continuously agglomerated, and finally the film forming quality of zinc oxide is affected, so that the electric performance is attenuated.
The preparation methods, photoelectric devices and display devices of zinc oxide nanocrystals and electron transport layers provided in the embodiments of the present application are described in detail, and specific examples are applied to illustrate the principles and embodiments of the present application, and the description of the above examples is only used to help understand the methods and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (13)
1. A method for preparing zinc oxide nanocrystals, comprising the steps of:
mixing a cyclic hydrocarbon compound with the carbon number less than or equal to eight and an even number in a first precursor solution containing zinc salt;
injecting a second precursor solution containing alkali salt into the first precursor solution to obtain a zinc oxide solution;
and drying the zinc oxide solution to obtain zinc oxide nanocrystals.
2. The production method according to claim 1, wherein the mixing of the cyclic hydrocarbon compound having eight or less and an even number of carbon atoms in the first precursor solution containing the zinc salt comprises:
Dissolving zinc salt in a mixed solution of an alcohol solvent and a cyclic hydrocarbon compound;
and heating the mixed solution in which the zinc salt is dissolved to a first preset temperature in an inert atmosphere, and stirring to obtain the first precursor solution.
3. The preparation method according to claim 2, wherein the zinc salt is at least one selected from zinc chloride pentahydrate, zinc bromide pentahydrate, zinc acetate dihydrate, zinc citrate dihydrate; and/or the number of the groups of groups,
the alcohol solvent is at least one selected from methanol, ethanol and butanol; and/or the number of the groups of groups,
the cyclic hydrocarbon compound is at least one selected from cyclobutane, cyclohexane, cyclooctane, cyclobutane and cyclooctatetraene.
4. The method according to claim 3, wherein the volume ratio of the alcohol solvent to the cyclic hydrocarbon compound is 3:1 to 4:1.
5. The method of preparing according to claim 2, wherein the injecting the second precursor solution containing the alkali salt into the first precursor solution to obtain the zinc oxide solution comprises:
dissolving alkali salt into alcohol or amine solvent to obtain second precursor solution;
and injecting the second precursor solution into the first precursor solution to react, so as to obtain the zinc oxide solution.
6. The method of claim 5, wherein the step of injecting the second precursor solution into the first precursor solution to react and obtain the zinc oxide solution further comprises: and cooling the mixed solution of the first precursor solution and the second precursor solution to a third preset temperature, adding a precipitator, centrifuging, removing supernatant to obtain precipitate, and dispersing the precipitate with a dispersing agent to obtain zinc oxide solution.
7. The method according to claim 5, wherein the alkali salt is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide; the alcohol or amine solvent is at least one selected from methanol, ethanol, butanol, triacetonamine and ethanolamine.
8. The method according to claim 5, wherein the molar ratio of zinc salt to alkali salt in the second precursor solution is 1:1.5-1:2.
9. The method according to claim 6, wherein the dispersant comprises at least one of ethanol, butanol, amyl alcohol, toluene, chlorobenzene, and chloroform.
10. The method of claim 1, wherein the step of drying the zinc oxide solution to obtain zinc oxide nanocrystals comprises:
Vacuum drying the zinc oxide solution at a fourth preset temperature to obtain dried zinc oxide nanocrystals;
and sealing the zinc oxide nanocrystals and then preserving the zinc oxide nanocrystals.
11. A method of preparing an electron transport layer, the method comprising the steps of:
providing zinc oxide nanocrystals prepared using the preparation method of any one of claims 1 to 10, to produce a zinc oxide solution;
providing a substrate, and arranging the zinc oxide solution on the substrate to obtain an electron transport layer.
12. An optoelectronic device comprising an anode, a light-emitting layer, an electron transport layer and a cathode, wherein the electron transport layer is prepared by the method of preparing an electron transport layer according to claim 11.
13. A display device comprising the optoelectronic device of claim 12.
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