CN112397620A - Nano composite particle and preparation method and application thereof - Google Patents
Nano composite particle and preparation method and application thereof Download PDFInfo
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- CN112397620A CN112397620A CN201910762595.7A CN201910762595A CN112397620A CN 112397620 A CN112397620 A CN 112397620A CN 201910762595 A CN201910762595 A CN 201910762595A CN 112397620 A CN112397620 A CN 112397620A
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- indium
- zinc
- quantum dot
- salt
- electron transport
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- 239000002245 particle Substances 0.000 title claims abstract description 64
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000002096 quantum dot Substances 0.000 claims abstract description 114
- 239000000758 substrate Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 69
- 229910052717 sulfur Inorganic materials 0.000 claims description 48
- 239000011593 sulfur Substances 0.000 claims description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 47
- 150000002471 indium Chemical class 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 40
- 150000003751 zinc Chemical class 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 31
- 239000003960 organic solvent Substances 0.000 claims description 30
- 239000013049 sediment Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 19
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine sulfide Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 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 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-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
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 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 2
- 239000000463 material Substances 0.000 abstract description 35
- 239000011258 core-shell material Substances 0.000 abstract description 22
- 239000010410 layer Substances 0.000 description 168
- 239000010408 film Substances 0.000 description 25
- 230000005525 hole transport Effects 0.000 description 25
- 238000000151 deposition Methods 0.000 description 14
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 239000002346 layers by function Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001449 indium ion Inorganic materials 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 238000001894 space-charge-limited current method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 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
- 229910004613 CdTe Inorganic materials 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
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 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
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 having potential barriers 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 having potential barriers 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Mathematical Physics (AREA)
- Theoretical Computer Science (AREA)
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides a nanocomposite particle comprising In2S3Nano core of said In2S3The nano-core is coated by a ZnS shell layer. With the In2S3the/ZnS core-shell nano composite particles can be used as an electron transport material to improve the electron transport capability and enhance the luminous efficiency of a quantum dot luminous layer device.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a nano composite particle and a preparation method thereof, and a quantum dot light-emitting diode and a preparation method thereof.
Background
Semiconductor Quantum Dots (QDs) have a quantum size effect, and thus can achieve light emission of a specific wavelength as required by controlling the size of the quantum dots, wherein the tuning range of the light emission wavelength of CdSe QDs can be from blue light to red light. In a 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 wide bandgap semiconductors can be accelerated under high electric fields to obtain high enough energy to strike QDs to cause it to emit light.
The metal sulfide is a compound formed by combining metal ions and sulfur ions, particularly the sulfide of transition metal is more important modern inorganic material, and as an extremely important inorganic semiconductor material, the excellent various performances of the metal sulfide are not neglected. Chalcogenide semiconductor materials have been widely used in the fields of solar cells, catalysts, conductive coatings, electrodes, sensors, thermoelectric refrigeration materials, and the like. In2S3Is a semiconductor material with n-type conduction and the forbidden band width of 2.0-2.3eV, and has higher electron mobility, and the characteristics determine In2S3Can be used as a suitable electron transport layer material. At the same time, In2S3Is a III-VI semiconductor material, has three crystal structures which are respectively cubic crystal system In2S3In of tetragonal system2S3And trigonal system In2S3. In addition, In2S3Stable chemical property, abundant resource and low price. However, since, In2S3The forbidden band width is narrower, the conduction band is high, and the single use of the material as an electron transport layer can cause the difficulty of electron injection and the insufficient electron transport capability.
Disclosure of Invention
The invention aims to provide a nano composite particle and a preparation method thereof, aiming at solving the problem of In2S3When the material is singly used as an electron transport layer material, electrons are difficult to inject, and the electron transport capability is insufficient.
Another object of the present invention is to provide a quantum dot light emitting diode using the above nanocomposite particles as an electron transport layer material and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nanocomposite particle comprising In2S3Nano core of said In2S3The nano-core is coated by a ZnS shell layer.
In a second aspect, the present invention provides a method for preparing a nanocomposite particle, comprising the steps of:
dissolving indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment;
dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, and mixing and reacting to prepare a precursor solution;
and after the precursor solution is cooled, carrying out sedimentation treatment to obtain the nano composite particles.
The invention provides a quantum dot light-emitting diode In a third aspect, which comprises a laminated structure of a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, wherein the electron transport layer is made of In2S3The core-shell nano composite particles are formed by coating ZnS shells on nano cores.
The fourth aspect of the present invention provides a method for manufacturing a quantum dot light emitting diode, comprising the steps of:
providing a substrate;
providing indium salt, zinc salt and a sulfur source, and dissolving the indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment; dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, and mixing and reacting to prepare a precursor solution;
and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
The nano composite particles provided by the invention are In2S3the/ZnS core-shell nano composite particles adopt ZnS shell to coat In2S3The nanometer core can effectively prevent the problem that the electron and hole recombination efficiency of the light-emitting layer is reduced due to the fact that holes are transmitted from the light-emitting layer to the cathode. Specifically, the invention takes wide band gap semiconductor (ZnS) as a shell layer to coat a band gap phaseFor narrower semiconductor (In)2S3) The nano particles, ZnS as shell layer, can fill In2S3The surface sulfur vacancy reduces the formation of surface sulfur defects, so that the radiation combination of electron hole pairs in an electron transport layer is reduced, the electron transport performance is improved, and the luminous efficiency of a quantum dot luminous layer device is enhanced; with ZnS as In2S3The shell layer of the nano-core can improve the stability of the core-shell structure nanocrystal, is beneficial to the transmission of electrons, further improves the electron transmission performance, and enhances the luminous efficiency of a quantum dot luminous layer device.
The preparation method of the nano composite particles provided by the invention comprises the steps of preparing a first sediment, dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source for reaction, and settling to obtain the nano composite particles. The method is simple to operate and easy to realize large-scale preparation. More importantly, the nano composite particles prepared by the method provided by the invention can improve the electron transmission capability and enhance the luminous efficiency of a quantum dot luminous layer device.
The quantum dot light-emitting diode provided by the invention takes the nano composite particles as an electron transport layer material. The nano composite particles can be used as an electron transport material to improve the electron transport capability and enhance the luminous efficiency of a quantum dot luminous layer device.
The preparation method of the quantum dot light-emitting diode provided by the invention comprises the steps of firstly preparing a first sediment, then dissolving the first sediment and zinc salt in an organic solvent, then adding a sulfur source for reaction, depositing a formed precursor solution on the surface of a substrate, and then carrying out annealing treatment to prepare the electron transport layer. The nano composite particles can be used as an electron transport material to improve the electron transport capability and enhance the luminous efficiency of a quantum dot luminous layer device. In addition, the method only needs to change the material of the electron transport layer on the basis of the conventional preparation method of the quantum dot light-emitting diode, and is simple to operate and mature and reliable in process.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing an electron transport material according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Embodiments of the present invention provide, In a first aspect, a nanocomposite particle including In2S3Nano core of said In2S3The nano-core is coated by a ZnS shell layer.
The nano composite particles provided by the embodiment of the invention are In2S3the/ZnS core-shell nano composite particles are prepared by coating In with ZnS shell2S3The nanometer core can effectively prevent the problem that the electron and hole recombination efficiency of the light-emitting layer is reduced due to the fact that holes are transmitted from the light-emitting layer to the cathode. Specifically, the invention takes a wide band gap semiconductor (ZnS) as a shell layer to coat a semiconductor (In) with a relatively narrow band gap2S3) The nano particles, ZnS as shell layer, can fill In2S3The surface sulfur vacancy reduces the formation of surface sulfur defects, so that the radiation combination of electron hole pairs in an electron transport layer is reduced, the electron transport performance is improved, and the luminous efficiency of a quantum dot luminous layer device is enhanced; with ZnS as In2S3The shell layer of the nano-core can improve the stability of the core-shell structure nanocrystal, is beneficial to the transmission of electrons, further improves the electron transmission performance, and enhances the luminescence of a quantum dot luminescent layer deviceLight efficiency.
In a preferred embodiment, the molar ratio of indium to zinc in the nanocomposite particle is 1: 0.05-0.1, so that the ZnS shell layer can completely cover In2S3The nano-core is adopted, and the thickness of the ZnS shell layer is controlled within a proper range, so that the electron transmission performance is improved, and the luminous efficiency of a quantum dot luminous layer device is enhanced. When the In is2S3The mol ratio of indium to zinc in the/ZnS core-shell nano composite particles is more than 1: 0.05 (zinc content too small), ZnS cannot be uniformly In2S3The surface of the nano-core forms a shell layer, or the coverage of the shell layer is insufficient. When the In is2S3The mol ratio of indium to zinc in the/ZnS core-shell nano composite particles is 1: at 0.1, ZnS shell In2S3The thickness of the shell layer on the surface of the nano crystal grain is larger and larger, and the nano In2S3The ratio of (b) decreases, and the electron transport property is rather lowered.
The nano composite particles provided by the embodiment of the invention can be prepared by the following method.
Accordingly, with reference to fig. 1, a second aspect of the present invention provides a method for preparing a nanocomposite particle, comprising the steps of:
s01, dissolving indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment;
s02, dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, mixing and reacting to prepare a precursor solution;
and S03, after the precursor solution is cooled, settling to obtain the nano composite particles.
The preparation method of the nano composite particles provided by the embodiment of the invention comprises the steps of firstly preparing the first sediment, then dissolving the first sediment and zinc salt in an organic solvent, then adding a sulfur source for reaction, and obtaining the nano composite particles through sedimentation. The method is simple to operate and easy to realize large-scale preparation. More importantly, the nano composite particles prepared by the method provided by the embodiment of the invention can improve the electron transmission capability and enhance the luminous efficiency of a quantum dot luminous layer device.
Specifically, In the above step S01, the method for preparing In is provided2S3Indium salt, zinc salt and sulfur source of/ZnS core-shell nano composite particles. The indium salt and the zinc salt are selected from metal salts which can be dissolved in an organic solvent, in the organic solvent environment, indium ions in the indium salt and zinc ions in the zinc salt can react with sulfur in the sulfur source to grow into nano-crystalline grains, and the zinc salt is soluble inorganic tin salt or organic tin salt. Wherein, the indium salt is preferably at least one of indium acetate, indium nitrate, indium chloride and indium sulfate, but is not limited thereto; the zinc salt is preferably at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate dihydrate, but is not limited thereto; the sulfur source is preferably at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide, but is not limited thereto.
Dissolving the indium salt in an organic solvent, preferably an organic alcohol solvent, to prepare an indium salt solution. The organic alcohol solvent not only has better solubility for the indium salt listed above, but also is milder as a reaction medium, and provides a good reaction environment for indium salt ions and sulfur to react and grow into nano-crystalline grains. Preferably, the organic solvent is selected from at least one of methanol, isopropanol, ethanol, propanol, butanol, pentanol, hexanol, but is not limited thereto.
Specifically, the indium salt is dissolved in an organic solvent, and the dissolution of the metal salt can be promoted by stirring at a constant temperature to prepare an indium salt solution. Preferably, the constant-temperature stirring is carried out at a temperature of 60 ℃ to 80 ℃. This temperature generally prevents volatilization of the organic solvent in which the metal salt is dissolved, and also promotes rapid dissolution of the indium salt.
Further, a sulfur source is added into the indium salt solution, In the step, the sulfur source is preferably added into the mixed solution according to the mol ratio of S to indium ions of 2.8-3.2: 2, and In with a good crystal form can be obtained2S3The nano material is convenient for obtaining compact and compact In2S3The nano material layer, and the particles on the surface of the film are uniformly distributed. When the molar amount of S and the indium ionMolar weight ratio of less than 2.8: 2, the indium salt is excessive and cannot be completely reacted, and the indium salt remaining in the film affects the performance of the film as an electron transport layer. When the ratio of the molar weight of S to the molar weight of indium ions is more than 3.2:2, the sulfur salt is in excess and excess sulfur salt is not easily removed in subsequent steps. In the embodiment of the invention, the mixed solution after the sulfur source is added is mixed and reacted under the condition that the temperature is not higher than the boiling point temperature of the organic solvent. The mixing reaction is preferably carried out by stirring at constant temperature. Particularly preferably, the mixing reaction is carried out at a temperature of 60-80 ℃ and the reaction time is 2-4 h.
And after the mixed reaction is finished, cooling the solution, and then carrying out sedimentation treatment, wherein the sedimentation treatment can be realized by adding a weak polar or non-polar solvent as a precipitator into the reaction system, specifically, the precipitator is at least one selected from ethyl acetate, heptane and octane, and collecting a first sediment.
In the step S02, the first sediment and the zinc salt are dissolved in an organic solvent, and the zinc salt is a soluble inorganic zinc salt or an organic zinc salt and is at least one selected from zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate. The organic solvent is selected from at least one of isopropanol, ethanol, propanol, butanol, and methanol, but is not limited thereto. Preferably, in the step of preparing the precursor solution, the ratio of the molar ratio of indium to zinc is 1: 0.05 to 0.1, adding the In2S3The nanoparticles and zinc salt are dissolved in an organic solvent. When the molar ratio of indium to zinc is more than 1: 0.05 (zinc content too small), ZnS cannot be uniformly In2S3The surface of the nano-core forms a shell layer, or the coverage of the shell layer is insufficient. When the molar ratio of the indium to the zinc is larger than 1: at 0.1, ZnS shell In2S3The thickness of the shell layer on the surface of the nano crystal grain is larger and larger, and the nano In2S3The ratio of (b) decreases, and the electron transport property is rather lowered. Most preferably, in the step of preparing the precursor solution, the ratio of the molar ratio of indium to zinc is 1: 1, dissolving the first sediment and the zinc salt in an organic solvent.
Further, adding a sulfur source selected from sulfur for mixing reactionAt least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide, and preferably the same sulfur source as used for preparing the first sediment. The zinc salt and the sulfur source are In2S3And reacting the surface of the nano-particles to generate a ZnS shell layer. In a preferred embodiment, in the step of preparing the precursor solution, the molar ratio of the sulfur atoms in the sulfur source to the zinc atoms in the zinc salt is 0.8-1.2: 1, the sulfur source is added into the mixed solution of the first sediment and the zinc salt, so as to be convenient for obtaining compact and compact In subsequently2S3the/ZnS film has uniform particle distribution on the surface. When the molar ratio of the sulfur atoms in the sulfur source to the zinc atoms in the zinc salt is less than 0.8: 1, excessive metal salt and low sulfur content, and insufficient indium sulfide is generated; when the molar ratio of the sulfur atoms in the sulfur source to the zinc atoms in the zinc salt is more than 1.2: in case 1, the sulfur salt is excessive, and thus, an impurity compound is easily formed and is not easily removed.
In the step S03, after the precursor solution is cooled to room temperature, which is the room temperature in the embodiment of the present invention, the room temperature is 10 ℃ to 35 ℃, and the precursor solution is cooled and then subjected to a settling treatment. The sedimentation treatment can be realized by adding a precipitator into the precursor solution to separate out In the precursor solution2S3And collecting sediments of the/ZnS core-shell nano composite particles, cleaning and drying to obtain the electron transport material.
In another embodiment, the precursor solution may be further prepared into a film to obtain an electron transport thin film. Specifically, after the precursor solution is deposited on a substrate, an electron transport film is prepared through annealing treatment. The specific process can refer to the preparation of the electron transport layer in the preparation method of the quantum dot light-emitting diode.
The quantum dot light-emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, wherein the electron transport layer is made of In2S3The nano-core is coated with ZnS shell layer of nano-composite particles.
The quantum dot light-emitting diode provided by the embodiment of the invention takes the nano composite particles as an electron transport layer material. The nano composite particles can be used as an electron transport material to improve the electron transport capability and enhance the luminous efficiency of a quantum dot luminous layer device.
In the embodiment of the present invention, the material of the electron transport layer is the above-mentioned nanocomposite particles, and the specific principle of improving the electron transport performance of the device by using the nanocomposite particles and the preferred ratio of indium to zinc are as described above, and are not described herein again for brevity. Such as, the In2S3In the/ZnS core-shell nano composite particles, the molar ratio of indium to zinc is 1: 0.05 to 0.1.
In some preferred embodiments, the thickness of the electron transport layer is 20nm to 60nm, and when the thickness of the electron transport layer is in this range, the electron transport performance of the device can be effectively improved.
Specifically, the quantum dot light emitting diode according to the embodiment of the present invention has a positive structure and an inversion structure.
In one embodiment, a positive-type structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and the anode is disposed on a substrate. Furthermore, an electron injection layer can be arranged between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer can be arranged between the cathode and the quantum dot light-emitting layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of the positive-type structure device, the quantum dot light emitting diode includes a substrate, an anode disposed on a surface of the substrate, the hole injection layer disposed on a surface of the anode, a hole transport layer disposed on a surface of the hole injection layer, a quantum dot light emitting layer disposed on a surface of the hole transport layer, an electron transport layer disposed on a surface of the quantum dot light emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, a positive-type structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and the cathode is disposed on a substrate. Furthermore, an electron injection layer can be arranged between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer can be arranged between the cathode and the quantum dot light-emitting layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of the device with the inverted structure, the quantum dot light emitting diode includes a substrate, a cathode disposed on a surface of the substrate, an electron transport layer disposed on a surface of the cathode, a quantum dot light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the quantum dot light emitting layer, an electron injection layer disposed on a surface of the hole transport layer, and an anode disposed on a surface of the electron injection layer.
Specifically, the selection of the anode is not limited strictly, and ITO may be selected, but is not limited thereto.
The material of the quantum dot light-emitting layer can be conventional quantum dot material according to conventional quantum dot type. The quantum dots of the quantum dot light-emitting layer can be one of red quantum dots, green quantum dots, blue quantum dots and yellow quantum dots. The quantum dot material may or may not contain cadmium. Specifically, the quantum dot material may be at least one of semiconductor nanocrystals of CdS, CdSe, CdTe, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, and CuInSe, and core-shell structure quantum dots or alloy structure quantum dots formed by the above materials. The quantum dot light-emitting layer formed by the quantum dot material has the characteristics of wide excitation spectrum, continuous distribution, high emission spectrum stability and the like. The thickness of the quantum dot light-emitting layer is 20-60 nm.
The cathode can be made of conventional cathode materials, such as metal silver or metal aluminum, or a nano Ag wire or a nano Cu wire, and the materials have low resistance so that carriers can be injected smoothly.
The material of the hole transport layer can be made of a hole transport material which is conventional in the field, and can be TFB, PVK, Poly-TPD, TCTA, PEDOT: PSS, CBP, but not limited thereto.
In some embodiments, the qd-led may further comprise an encapsulation layer. The packaging layer can be arranged on the surface of a top electrode (an electrode far away from the substrate) and can also be arranged on the surface of the whole quantum dot light-emitting diode.
The quantum dot light-emitting diode provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, as shown in fig. 2, an embodiment of the present invention provides a method for manufacturing a quantum dot light emitting diode, including the following steps:
E01. providing a substrate;
E02. providing indium salt, zinc salt and a sulfur source, and dissolving the indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment; dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, and mixing and reacting to prepare a precursor solution;
E03. and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
The preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention comprises the steps of firstly preparing the first sediment, then dissolving the first sediment and zinc salt in an organic solvent, then adding a sulfur source for reaction, depositing the formed precursor solution on the surface of a substrate, and then carrying out annealing treatment to prepare the electron transport layer. In the above-mentioned2S3the/ZnS core-shell nano composite particles can be used as an electron transport material to improve the electron transport capability and enhance the luminous efficiency of a quantum dot luminous layer device. In addition, the method only needs to change the material of the electron transport layer on the basis of the conventional preparation method of the quantum dot light-emitting diode, and is simple to operate and mature and reliable in process.
In step S01, in the case of the inverted structure quantum dot light emitting diode, the bottom electrode provided on the substrate is a cathode, that is, the substrate at least includes a cathode substrate. In some embodiments of the invention, the substrate is a cathode substrate with a cathode disposed on a substrate. In still other embodiments of the present invention, the substrate may be a laminated substrate in which a cathode is provided on a substrate and an electron injection layer is provided on a surface of the cathode. It should be understood that the present invention is not limited to the structures of the above-described embodiments.
In the case of a positive type structure quantum dot light emitting diode, the bottom electrode provided on the substrate is an anode, that is, the substrate at least includes an anode substrate. In some embodiments of the present invention, the substrate is a laminated substrate in which an anode is disposed on a substrate and a quantum dot light emitting layer is disposed on a surface of the anode. In still other embodiments of the present invention, the substrate is a laminated substrate in which an anode is provided on a substrate, a hole transport layer is provided on a surface of the anode, and a quantum dot light emitting layer is provided on a surface of the hole injection layer. Of course, other hole-functional layers, such as a hole-injection layer, may also be disposed between the anode and the hole-transport layer. It should be understood that the present invention is not limited to the structures of the above-described embodiments.
In the preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention, before the functional layer is prepared on the surface of the anode substrate or the cathode substrate, the anode substrate or the cathode substrate is preferably subjected to pretreatment. In a preferred embodiment, the step of pre-treating comprises: cleaning the anode substrate or the cathode substrate with a cleaning agent to primarily remove stains on the surface, and then sequentially performing ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 10-30 min, preferably 20min, to remove impurities on the surface; and finally, drying the anode substrate or the cathode substrate by using high-purity nitrogen to obtain the surface of the anode substrate or the cathode substrate.
In the above step S02, the precursor solution is the same as the precursor solution in the method for preparing nano composite particles, and the method for preparing the precursor solution is also the same as the method for preparing the precursor solution in the method for preparing nano composite particles, which is specifically as described above. Preferably, in the step of preparing the precursor solution, the ratio of the molar ratio of indium to zinc is 1: and (3) dissolving the first sediment and the zinc salt in an organic solvent at a ratio of 0.05-0.1. Preferably, in the step of preparing the precursor solution, the molar ratio of sulfur atoms in the sulfur source to zinc atoms in the zinc salt is 0.8-1.2: 1, and adding the sulfur source into the mixed solution of the first sediment and the zinc salt. Preferably, the step of adding a sulfur source into the indium salt solution for mixing reaction is carried out at the temperature of 60-80 ℃ and the reaction time is 2-4 h.
In step S03, the deposition of the precursor solution on the substrate surface can be achieved by using a conventional solution processing method, including but not limited to spin coating, inkjet printing, and the like. The embodiment of the invention can control the film thickness by adjusting the concentration of the solution, the printing or spin coating speed and the deposition time.
After the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to remove the solvent In the precursor solution and improve In at the same time2S3The crystallization property of the/ZnS core-shell nano composite particles. Preferably, the annealing step is performed at a temperature of 300 to 350 ℃.
The functional layers (including but not limited to hole injection layer, electron transport layer, hole blocking layer, electron blocking layer) except the anode and cathode of the embodiments of the present invention can be prepared by conventional solution processing methods including but not limited to inkjet printing, spin coating. Similarly, the film thickness of each layer can be controlled by adjusting the concentration of the solution, the printing or spin coating speed and the deposition time; and thermal annealing treatment is carried out after the solution is deposited.
In some embodiments, the packaging process of the obtained QLED device is further included. The packaging process can adopt common machine packaging or manual packaging. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1ppm so as to ensure the stability of the device.
The following description will be given with reference to specific examples.
Example 1
A preparation method of an electron transport film comprises the following steps:
adding a proper amount of indium chloride into 50ml of ethanol to form a solution with the total concentration of 0.5M, and stirring and dissolving at the temperature of 70 ℃ to obtain an indium salt solution; adding sodium sulfide, dissolving in 10ml ethanol, and adding sodium sulfide2-And In3+The molar ratio of the sodium sulfide solution to the indium salt solution is 3:2, and the mixture is stirred for 4 hours at 70 ℃ to obtain a uniform solution. Cooling, precipitating with ethyl acetate, centrifuging, dissolving with small amount of ethanol (repeating operation, washing for 3 times) to obtain In2S3And (3) nanoparticles.
In is mixed with2S3The nanoparticles and a suitable amount of zinc acetate were added to 30ml of ethanol to form a solution with a total concentration of 1M, wherein indium: the molar ratio of zinc is 1: 0.05, stirring and dissolving at 70 ℃; dissolving sodium sulfide in 5ml ethanol solution, as per S2And Zn2+In a molar ratio of 1: 1, adding the sodium sulfide solution into the solution, and continuously stirring the solution for 2 hours at the temperature of 70 ℃ to obtain a uniform and transparent solution. .
Cooling the precursor solution, depositing on a substrate such as ITO, and annealing at 300 deg.C to obtain In2S3An electron transport film formed by the/ZnS core-shell nano composite particles.
Example 2
A preparation method of an electron transport film comprises the following steps:
adding a proper amount of indium nitrate into 50ml of methanol to form a solution with the total concentration of 0.5M, and stirring and dissolving at the temperature of 60 ℃ to obtain an indium salt solution; adding potassium sulfide, dissolving in 10ml methanol, and adding2-And In3+The molar ratio of the potassium sulfide solution to the indium salt solution is 3:2, and the mixture is stirred for 4 hours at the temperature of 60 ℃ to obtain a uniform solution. After the solution was cooled, it was separated out with heptane, centrifuged and dissolved In a small amount of methanol (repeated operation, washing 3 times) to obtain In2S3And (3) nanoparticles.
In is mixed with2S3The nanoparticles and a suitable amount of zinc nitrate were added to 30ml of ethanol to give a total concentrationA solution of 1M, wherein indium: the molar ratio of zinc is 1: 0.1, stirring and dissolving at 60 ℃; dissolving potassium sulfide in 5ml methanol as S2And Zn2+In a molar ratio of 1: 1, adding the potassium sulfide solution into the solution, and continuously stirring the solution for 2 hours at the temperature of 60 ℃ to obtain a uniform and transparent solution. .
Cooling the precursor solution, depositing on a substrate such as ITO, and annealing at 300 deg.C to obtain In2S3An electron transport film formed by the/ZnS core-shell nano composite particles.
Example 3
A preparation method of an electron transport film comprises the following steps:
adding a proper amount of indium sulfate into 50ml of propanol to form a solution with the total concentration of 0.5M, and stirring and dissolving at the temperature of 80 ℃ to obtain an indium salt solution; adding thiourea, dissolving in 10ml propanol, and adding2-And In3+The molar ratio of thiourea solution to the indium salt solution was 3:2, and stirred at 80 ℃ for 4h to obtain a homogeneous solution. Cooling, separating out with octane, centrifuging, dissolving with small amount of propanol (repeating operation, washing for 3 times) to obtain In2S3And (3) nanoparticles.
In is mixed with2S3Nanoparticles and appropriate amount of zinc sulfate were added to 30ml of propanol to form a solution with a total concentration of 1M, where indium: the molar ratio of zinc is 1: 0.1, stirring and dissolving at 80 ℃; dissolving thiourea in 5ml propanol as S2And Zn2+In a molar ratio of 1: 1, adding the thiourea solution into the solution, and continuously stirring at 80 ℃ for 2 hours to obtain a uniform and transparent solution. .
Cooling the precursor solution, depositing on a substrate such as ITO, and annealing at 350 deg.C to obtain In2S3An electron transport film formed by the/ZnS core-shell nano composite particles.
Example 4
A quantum dot light emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light emitting layer arranged between the anode and the cathode, and electron transmission arranged between the cathode and the quantum dot light emitting layerAnd the layer is a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and the anode is arranged on the substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of In2S3The cathode of the/ZnS core-shell nano composite particle is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
an ITO substrate is provided, and an ITO substrate,
depositing the precursor solution obtained in the method of embodiment 1 on the ITO substrate, and annealing at 300 ℃ to prepare an electron transport layer;
depositing 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.
Example 5
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of In2S3The cathode of the/ZnS core-shell nano composite particle is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
an ITO substrate is provided, and an ITO substrate,
depositing the precursor solution obtained in the method of embodiment 2 on the ITO substrate, and annealing at 300 ℃ to prepare an electron transport layer;
depositing 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.
Example 6
Quantum dot light-emitting diodeThe LED comprises a laminated structure which comprises an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer which is arranged between the anode and the cathode, an electron transmission layer which is arranged between the cathode and the quantum dot light-emitting layer, and a hole transmission layer which is arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of In2S3The cathode of the/ZnS core-shell nano composite particle is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
an ITO substrate is provided, and an ITO substrate,
depositing the precursor solution obtained in the method of embodiment 3 on the ITO substrate, and annealing at 300 ℃ to prepare an electron transport layer;
depositing 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.
Comparative example 1
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of undoped In2S3Nanomaterial or commercial In2S3The cathode is made of Al.
The performance of the electron transport films prepared in examples 1 to 3, the electron transport layer prepared in comparative example 1, the quantum dot light emitting diodes prepared in examples 4 to 6 and comparative example 1 was tested, and the test indexes and the test method were as follows:
(1) electron mobility: testing the current density (J) -voltage (V) of the quantum dot light-emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) region in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes the electron mobility in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and resistivity were tested as single layer thin film structure devices, namely: cathode/electron transport film/anode. The external quantum efficiency test is the external quantum efficiency of the QLED device, namely: anode/hole transport film/quantum dot/electron transport film/cathode, or cathode/electron transport film/quantum dot/hole transport film/anode.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1 above, examples 1 to 3 of the present invention provide In as the material2S3The electron transport film of/ZnS core-shell nano composite particles has the resistivity obviously lower than that of In comparative example 12S3The resistivity of the electron transport film made of the nanomaterial was significantly higher than that of In comparative example 12S3Electron transport film made of nano materialAnd (3) a membrane.
The quantum dot light-emitting diodes (electron transport layer material In) provided In embodiments 4 to 6 of the present invention2S3/ZnS core-shell nanocomposite particle) has an external quantum efficiency significantly higher than that of the electron transport layer material In comparative example 12S3The external quantum efficiency of the quantum dot light-emitting diode made of the nano material shows that the quantum dot light-emitting diode obtained by the embodiment has better luminous efficiency.
It is noted that the embodiments provided by the present invention all use blue light quantum dots CdXZn1-XS/InS is used as a material of a light emitting layer, and is based on a blue light emitting system, which is a system that is used more (in addition, a light emitting diode based on blue light quantum dots is relatively difficult to manufacture, and therefore has a higher reference value), and does not mean that the present invention is only used for a blue light emitting system.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (12)
1. A method of preparing a nanocomposite particle, comprising the steps of:
dissolving indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment;
dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, and mixing and reacting to prepare a precursor solution;
and after the precursor solution is cooled, carrying out sedimentation treatment to obtain the nano composite particles.
2. The method of preparing nanocomposite particles according to claim 1, wherein in the step of preparing the precursor solution, the ratio of the molar ratio of indium to zinc is 1: and (3) dissolving the first sediment and the zinc salt in an organic solvent at a ratio of 0.05-0.1.
3. The method for preparing nanocomposite particles according to claim 2, wherein in the step of preparing the precursor solution, the molar ratio of sulfur atoms in the sulfur source to zinc atoms in the zinc salt is from 0.8 to 1.2: 1, adding the sulfur source into the mixed solution of the first sediment and the zinc salt.
4. The method for preparing nanocomposite particles according to any one of claims 1 to 3, wherein the step of adding a sulfur source to the indium salt solution for mixing reaction is performed at a temperature of 60 ℃ to 80 ℃ for 2 hours to 4 hours.
5. The method for producing nanocomposite particles according to any one of claims 1 to 3, wherein the indium salt is at least one selected from the group consisting of indium acetate, indium nitrate, indium chloride, and indium sulfate; and/or
The sulfur source is at least one selected from sodium sulfide, potassium sulfide, thiourea and amine sulfide; and/or
The organic solvent is at least one of isopropanol, ethanol, propanol, butanol and methanol; and/or
The zinc salt is soluble inorganic zinc salt or organic zinc salt, and is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate dihydrate.
6. A nanocomposite particle comprising In2S3Nano core of said In2S3The nano-core is coated by a ZnS shell layer.
7. The nanocomposite particle of claim 6, wherein the molar ratio of indium and zinc in the nanocomposite particle is 1: 0.05 to 0.1.
8. A quantum dot light emitting diode comprising a laminated structure of a cathode and an anode which are oppositely disposed, a quantum dot light emitting layer disposed between the cathode and the anode,and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, wherein the electron transport layer is made of In2S3The nano-core is coated with ZnS shell layer of nano-composite particles.
9. The quantum dot light-emitting diode of claim 8, wherein the molar ratio of indium to zinc in the nanocomposite particles is 1: 0.05 to 0.1.
10. The qd-led of claim 8 or claim 9, wherein the electron transport layer has a thickness of 20nm to 60 nm.
11. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing a substrate;
providing indium salt, zinc salt and a sulfur source, and dissolving the indium salt in an organic solvent to prepare an indium salt solution; adding a sulfur source into the indium salt solution, mixing and reacting, and then performing sedimentation treatment to obtain a first sediment; dissolving the first sediment and zinc salt in an organic solvent, adding a sulfur source, and mixing and reacting to prepare a precursor solution;
and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
12. The method of claim 11, wherein the annealing step is performed at a temperature of 300 ℃ to 350 ℃.
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