CN109962127B - Film, preparation method and application thereof - Google Patents
Film, preparation method and application thereof Download PDFInfo
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- CN109962127B CN109962127B CN201711426983.5A CN201711426983A CN109962127B CN 109962127 B CN109962127 B CN 109962127B CN 201711426983 A CN201711426983 A CN 201711426983A CN 109962127 B CN109962127 B CN 109962127B
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- 238000002360 preparation method Methods 0.000 title claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 121
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 121
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 125000000524 functional group Chemical group 0.000 claims abstract description 38
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 126
- 239000002096 quantum dot Substances 0.000 claims description 51
- 239000002159 nanocrystal Substances 0.000 claims description 46
- 239000012702 metal oxide precursor Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- -1 octanediamine Chemical compound 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- PHVRKFUGOYTAKT-UHFFFAOYSA-N 1,12-diaminododecane-4,9-dione Chemical compound NCCCC(=O)CCCCC(=O)CCCN PHVRKFUGOYTAKT-UHFFFAOYSA-N 0.000 claims description 2
- YVLHRYOHNHUVOA-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diamine Chemical compound CC(C)(C)C(N)N YVLHRYOHNHUVOA-UHFFFAOYSA-N 0.000 claims description 2
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- IZKZIDXHCDIZKY-UHFFFAOYSA-N heptane-1,1-diamine Chemical compound CCCCCCC(N)N IZKZIDXHCDIZKY-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 230000001568 sexual effect Effects 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 45
- 230000005525 hole transport Effects 0.000 description 40
- 239000011787 zinc oxide Substances 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 20
- 238000004528 spin coating Methods 0.000 description 15
- 229910000480 nickel oxide Inorganic materials 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004054 semiconductor nanocrystal Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 229910017676 MgTiO3 Inorganic materials 0.000 description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000707 layer-by-layer assembly Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BQOMQMMVTRAAEH-UPHRSURJSA-N (z)-18-aminooctadec-9-ene-1-thiol Chemical compound NCCCCCCCC\C=C/CCCCCCCCS BQOMQMMVTRAAEH-UPHRSURJSA-N 0.000 description 1
- JYPFIWQRWKQDKH-KTKRTIGZSA-N (z)-2-sulfanyloctadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCC(S)C(O)=O JYPFIWQRWKQDKH-KTKRTIGZSA-N 0.000 description 1
- PBFKVYVGYHNCGT-UHFFFAOYSA-N 1-sulfanylpropane-1,2,3-triol Chemical compound OCC(O)C(O)S PBFKVYVGYHNCGT-UHFFFAOYSA-N 0.000 description 1
- WNLWBCIUNCAMPH-UHFFFAOYSA-N 2-n,2-n-dimethylpropane-1,2-diamine Chemical compound NCC(C)N(C)C WNLWBCIUNCAMPH-UHFFFAOYSA-N 0.000 description 1
- CFPHMAVQAJGVPV-UHFFFAOYSA-N 2-sulfanylbutanoic acid Chemical compound CCC(S)C(O)=O CFPHMAVQAJGVPV-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FAQSSRBQWPBYQC-VGKOASNMSA-N dioxomolybdenum;(z)-4-hydroxypent-3-en-2-one Chemical compound O=[Mo]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FAQSSRBQWPBYQC-VGKOASNMSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 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
- H01L33/005—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
- H01L33/04—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
-
- 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
- H01L33/48—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 body packages
- H01L33/52—Encapsulations
-
- 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
- H01L33/48—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 body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a film, which is a metal oxide film and contains a grafting compound, wherein the grafting compound is grafted on the metal oxide in the film to form a grafted metal oxide, and the structural formula of the grafted metal oxide is Y-X2‑R‑X1Wherein Y is a metal oxide, R is a hydrocarbyl group or a hydrocarbyl derivative, X is1Is a first reactive functional group.
Description
Technical Field
The invention belongs to the technical field of light emitting diodes, and particularly relates to a thin film and a preparation method and application thereof.
Background
Quantum dot electroluminescence is a novel solid-state lighting technology, has the advantages of low cost, light weight, high response speed, high color saturation and the like, has wide development prospect, and has become one of important research directions of new generation Light Emitting Diode (LED) lighting.
In quantum dot light emitting diode (QLED) devices currently under study, metal oxide materials are mostly used as carrier transport layers. The carrier transport layer prepared by adopting the metal oxide material can effectively make up the defects of sensitivity of the device to oxygen and water vapor, poor stability, short service life and the like. Based on the consideration of light extraction efficiency, the prior art tends to make an inorganic metal oxide film layer into an uneven surface which is advantageous for improving the light extraction efficiency. Due to the fact that the surface of the inorganic metal oxide film layer is not flat, the flatness of the quantum dot light emitting layer combined with the inorganic metal oxide film layer is poor, and a large number of defects are introduced, so that the light emitting performance of a device is affected. .
Disclosure of Invention
The invention aims to provide a film and a preparation method thereof, and aims to solve the problem that when the surface of a film made of inorganic metal oxide is uneven in a light-emitting device, the flatness of a quantum dot light-emitting layer is influenced, and the light-emitting performance of the device is further influenced.
Another object of the present invention is to provide a light emitting device application comprising the above thin film.
In order to achieve the above object, according to one aspect of the present invention, there is provided a thin film which is a metal oxide thin film and contains a grafted structureA compound, wherein the grafting compound is grafted on the metal oxide in the film to form a grafted metal oxide, and the structural formula of the grafting compound is X1-R-X2H, wherein Y is a metal oxide, R is a hydrocarbyl or a hydrocarbyl derivative, X1Is a first reactive functional group, X2Is a group that can be bonded to a metal.
The invention also provides a preparation method of the film, which comprises the following steps:
providing a metal oxide nanocrystal, a metal oxide precursor and a grafting compound, dissolving the metal oxide nanocrystal, the metal oxide precursor and the grafting compound in a solvent to obtain a mixed solution, wherein one end of the grafting compound contains a first active functional group X1And the other end contains a group X which can be bonded to the metal2The organic matter of (a);
depositing the mixed solution on a substrate, heating to the thermal decomposition temperature of the metal oxide precursor, annealing, and preparing the graft X1-R-X2-a metal oxide film of (a).
In still another aspect, the present invention provides a light emitting device comprising the above film or the film prepared by the above method.
According to the film provided by the invention, organic compounds are used for carrying out graft modification, such as amination, on metal oxides, a large number of active functional groups, such as amino groups, are arranged on the surface of an uneven metal oxide film layer, so that luminescent materials, particularly quantum dots, can be stably anchored on the surface of the metal oxide film layer, the flatness of the formed film is improved, the influence of the uneven structure on the flatness of each subsequent film layer on the surface of the metal oxide film layer is effectively reduced, surface defects are reduced, and the luminescent performance of a device is improved.
The preparation method of the film provided by the invention is characterized in that the metal oxide nanocrystal, the metal oxide precursor and the grafting compound are mixed and deposited on the substrate, and the substrate is heated to the thermal decomposition temperature of the metal oxide precursor. In the heating process, the grafting compound is grafted on the metal oxide through the active functional group through the heating process to form grafted metal oxide, so that the influence of the corrugated structure on the surface of the metal oxide film layer on the flatness of each subsequent film layer is reduced.
The luminescent device provided by the invention contains the film, and the surface flatness of the metal oxide can be repaired, so that the luminescent performance of the device is improved.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode device in a face-up structure according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a quantum dot light emitting diode device with an inverted structure 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.
According to an aspect of the embodiments of the present invention, there is provided a film, the film is a metal oxide film, and the film contains a graft compound, the graft compound is grafted on the metal oxide in the film to form a grafted metal oxide, and the structural formula of the graft compound is X1-R-X2H, wherein Y is a metal oxide, R is a hydrocarbyl or a hydrocarbyl derivative, X1Is a first reactive functional group, X2Is a group bonded to a metal.
According to the film provided by the embodiment of the invention, organic compounds are used for carrying out graft modification, such as amination, on metal oxides, so that a large number of active functional groups, such as amino groups, are arranged on the surface of an uneven metal oxide film layer, luminescent materials, particularly quantum dots, can be stably anchored on the surface of the metal oxide film layer, the flatness of the formed film is improved, the influence of the uneven structure of the surface of the metal oxide film layer on the flatness of each subsequent film layer is effectively reduced, surface defects are reduced, and the luminescent performance of a device is improved.
As an embodiment, the constituent material of the film is a grafted metal oxide, i.e. the grafted metal oxide is dispersed in the film, including the surface of the film. In the embodiment, the surface of the film contains the grafted active functional group, so that the influence of the uneven structure of the surface of the metal oxide film layer on the flatness of each subsequent film layer can be realized, and the performance of a device can be improved.
In another embodiment, the film is a metal oxide layer, and the metal oxide on at least one surface of the film is grafted with the graft compound to form a grafted metal oxide. With this embodiment, it is understood that the grafting compound may be grafted onto the metal oxide on one surface of the film, particularly the surface in contact with the luminescent material, or may be grafted onto the metal oxide on both surfaces of the film. The portion of the film other than the surface to which the graft compound is grafted may be an ungrafted metal oxide. In this embodiment, since the surface of the thin film contains the active functional group grafted thereto, the influence of the corrugated structure on the surface of the metal oxide film layer on the flatness of each subsequent film layer can be reduced, and the device performance can be improved. However, from the viewpoint of product performance and preparation method, the first method is easier to ensure stable and uniform performance and is easier to prepare.
Preferably, the film has a concave-convex surface. The metal oxide film layer with the concave-convex surface is adopted, so that the problem of high reflectivity of the conventional planar inorganic metal oxide film layer in a light-emitting device such as a QLED device and an OLED device can be effectively solved, and the light extraction efficiency of the device is improved. Further preferably, the concave-convex surface is a corrugated surface, thereby improving the light extraction efficiency of the device to a greater extent.
Hair brushIn the illustrated embodiment, the graft compound for grafting onto the metal oxide is organic, i.e., the resulting film is an organic/inorganic composite film. The structure of the graft compound is X1-R-X2H (i.e. the second reactive functional group is X)2H) The grafting compound being obtained by removing X2The above-attached protic hydrogen is bound to a metal atom in the metal oxide, in particular the metal oxide. Wherein, preferably, the first active functional group is selected from-SH, -COOH, -NH2、-OH、-SO3H. At least one of phosphine group and phosphate group. Preferably, the second reactive functional group is selected from-SH, -COOH, -NH2、-OH、-SO3H. At least one of phosphine group and phosphate group. The active functional group can graft a grafting compound on the surface of a metal organic matter, and meanwhile, the active functional group remained after grafting can play an anchoring role in a luminescent layer deposited subsequently, stably anchor luminescent materials, particularly quantum dots, on the surface of an oxide film layer, improve the flatness of formed films, thereby effectively reducing the influence of uneven surface structures of the metal oxide film layer on the flatness of each subsequent film layer and improving the performance of devices.
In the embodiment of the present invention, the grafting compound for grafting onto the metal oxide is a small molecule organic substance, and preferably, R is a hydrocarbyl group or a hydrocarbyl derivative having a carbon number of 1 to 13. When the molecular weight of the grafting compound is too large, which means that R is the number of carbon atoms is too large, the insulating property of the film is increased and the conductive property is reduced due to the increase of the hydrophobic carbon chain, so that the turn-on voltage of the device is increased, and the service life of the device is influenced.
In the embodiment of the present invention, the first reactive functional group and the second reactive functional group may be the same or different. Preferably, the first reactive functional group is the same as the second reactive functional group. Further preferably, the first reactive functional group and the second reactive functional group are both amino groups, i.e., the graft compound is a diamine compound. The amino group at one end of the two amino groups of the diamine compound is subjected to a coordination reaction with metal ions in the metal oxide, so that a molecular chain is grafted on the surface of the metal oxide nanocrystal; the amino at the other end is in a suspended state, namely the surface of the finally obtained corrugated metal oxide film layer is modified with a diamine compound molecular chain with amino. After the light emitting layer, particularly the quantum dot light emitting layer, is deposited on the corrugated metal oxide film layer, the positively charged amino group at one end of the molecular chain of the diamine compound can generate electrostatic force action with the negatively charged group such as mercapto group on the surface of the quantum dot layer, so that electrostatic self-assembly is realized, the quantum dot is ensured to be firmly anchored on the oxide film layer, defects and cavities caused by the corrugated structure on the surface of the metal oxide film layer in the film forming process of the subsequent film layer are effectively avoided, and the influence of the corrugated structure on the surface of the metal oxide film layer on the flatness of the subsequent film layers is reduced.
Specifically, the graft compound is preferably at least one selected from the group consisting of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, dimethylpropylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, 4, 9-dioxo-1, 12-dodecanediamine, and 4,7, 10-trioxa-1, 13-tridecanediamine. The preferable active functional group has a good grafting ratio with metal oxide, and has a small molecular weight, so that the starting voltage of the film is not increased.
In the embodiment of the present invention, the metal oxide in the film and the metal oxide in the grafted metal oxide may be conventional inorganic oxides for films, including but not limited to MoO3、WO3、NiO、V2O5、CuO、CrO3、ZnO、TiO2、ZrO2、HfO2. Specifically, when the thin film is a hole transport layer, the metal oxide includes, but is not limited to, MoO3、WO3、NiO、V2O5、CuO、CrO3(ii) a When the thin film is an electron transport layer, the metal oxide includes, but is not limited to, ZnO, TiO2、ZrO2、HfO2、SrTiO3、BaTiO3、MgTiO3。
The film of the embodiment of the invention can be prepared by the following method.
In another aspect, the embodiment of the present invention provides a method for preparing a thin film, including the following steps:
s01, providing a metal oxide nanocrystal, a metal oxide precursor and a grafting compound, and dissolving the metal oxide nanocrystal, the metal oxide precursor and the grafting compound in a solvent to obtain a mixed solution, wherein one end of the grafting compound contains a first active functional group X1And the other end contains a group X bonded to the metal2The organic matter of (a);
s02, depositing the mixed solution on a substrate, heating to the thermal decomposition temperature of the metal oxide precursor, annealing, and preparing the graft X1-R-X2-a metal oxide film of (a).
According to the preparation method of the film provided by the embodiment of the invention, the metal oxide nanocrystal, the metal oxide precursor and the grafting compound are mixed and deposited on the substrate, and the substrate is heated to the thermal decomposition temperature of the metal oxide precursor. In the heating process, the grafting compound is grafted on the metal oxide through the active functional group through the heating process to form grafted metal oxide, so that the influence of the corrugated structure on the surface of the metal oxide film layer on the flatness of each subsequent film layer is reduced.
Specifically, in step S01, the metal oxide nanocrystals are used as seed crystals, and in step S02, it is advantageous to control the nucleation density of the nanocrystals formed by thermal decomposition of the metal oxide precursor, thereby controlling the density of the surface acoustic wave pattern distribution of the film layer. Specifically, the metal oxide nanocrystal may be MoO3、WO3、NiO、V2O5、CuO、CrO3、ZnO、TiO2、ZrO2、HfO2、Ta2O5But is not limited thereto. Specifically, when the prepared film is a hole transport layer, the metal oxide nanocrystals include, but are not limited to, MoO3、WO3、NiO、V2O5、CuO、CrO3(ii) a When the prepared film is an electron transport layer, the metal oxide nanocrystal comprises but is not limited to ZnO and TiO2、ZrO2、HfO2。
Further, in the embodiment of the present invention, the metal oxide nanocrystal is used as a seed crystal, and the influence on the nucleation density of the nano metal oxide formed after the metal oxide precursor is decomposed by heating is large. Preferably, the particle size of the metal oxide nanocrystal is 40-60 nm. The metal oxide nanocrystalline with too small grain size easily causes the formed metal oxide corrugation to be sharper, so that the roughness of the film layer is too high, and the light extraction efficiency of the device is reduced; the metal oxide nanocrystals with too large particle sizes are not easy to disperse and easily agglomerate in the film forming process, so that the uniformity of the formed film is influenced, a large number of defects are introduced into the film layer, and finally the performance of the device is deteriorated.
The metal oxide precursor is a precursor substance that can form a corresponding metal oxide after a heating or annealing treatment, and the form thereof is not strictly limited. For example, when the thin film to be prepared is a hole transport layer, the precursor of molybdenum oxide may be (NH)4)6Mo7O24·4H2O、MoO2(acac)2(ii) a The precursor of tungsten oxide may be W (OC)2H5)5、Na2WO4(ii) a The precursor of nickel oxide can be Ni (OH)2、Ni(Ac)2、Ni(acac)2(ii) a The precursor of vanadium oxide can be VO (acac)2(ii) a The precursor of copper oxide can be Cu (acac)2(ii) a The precursor of chromium oxide can be Cr (acac)3. When the prepared film is an electron transport layer, the precursor of zinc oxide can be Zn (Ac)2(ii) a The precursor of titanium oxide may be C12H28O4Ti、C16H36O4Ti、TiCl4(ii) a The precursor of the zirconium oxide can be ZrOCl2·8H2O、Zr(NO3)4·5H2O、Zr(Ac)4(ii) a The precursor of hafnium oxide may be HfCl2·6H2And O. Of course, not limited thereto.
The grafting compound is an organic modifier for modifying metal oxide, and specifically, the structure of the grafting compound is X1-R-X2H. Wherein, X1、R、X2As mentioned above, for economy of text, it is not described here in detail.
Preferably, the molar ratio of the metal oxide nanocrystal to the metal oxide precursor to the grafting compound is 1 (1-3) to 0.5-1. The content of the metal oxide nanocrystals has a great influence on the nucleation density of the nano metal oxide formed after the metal oxide precursor is subjected to thermal decomposition, and the too low content of the metal oxide nanocrystals can cause the too low nucleation density of the metal oxide, so that the formed ripples are few, the peak surfaces are sharp, the light extraction efficiency cannot be obviously improved, and the deposition of a subsequent film layer is not facilitated; if the content of the metal oxide nanocrystals is too high, the nucleation density of the metal oxide is too high, so that the corrugation peak surface is smooth, even a corrugated structure cannot be formed, and the light extraction efficiency cannot be obviously improved. The content of the grafting compound mainly affects the modification degree and the performance of a device, the insufficient modification degree of the film layer is directly caused by the excessively low content of the grafting compound, and the active functional groups cannot be modified on the partial surface area of the corrugated metal oxide film layer, so that the deposition of the subsequent film layer is affected; the high content of the graft compound deteriorates the device performance, and since the graft compound is an insulating material and occupies a part of the volume after film formation, the mobility of the carrier in the transport layer is low, which finally affects the light emitting efficiency of the device.
In the embodiment of the invention, the solvent can dissolve the metal oxide nanocrystal and the metal oxide precursor, and meanwhile, the boiling point of the solvent is higher than the normal temperature, i.e. the solvent which is extremely easy to volatilize is not suitable to be selected, so that the volatilization rate of the solvent can be conveniently controlled in the reaction process. . In view of the above, the solvent is preferably at least one selected from the group consisting of C1 to C5 linear alcohols, C1 to C5 branched alcohols, chlorobenzene, and dimethyl sulfoxide.
In the step S02, the mixed solution is deposited on the substrate, and the deposition method may be, but is not limited to, one of spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slit coating, and stripe coating.
Further, will sinkHeating the accumulated sample to the thermal decomposition temperature of the metal oxide precursor, and annealing to obtain the graft X1-R-X2-a metal oxide film of (a). In the step of heating to the thermal decomposition temperature of the metal oxide precursor, preferably, the heating rate is 20 to 30 ℃/min. By controlling a proper temperature rise rate (20-30 ℃/min), the metal oxide precursor is influenced by the volatilization rate of the solvent while being thermally decomposed, and a film with a concave-convex structure, particularly a corrugated three-dimensional shape, on the surface is formed. On the other hand, the grafting compound is grafted on the metal oxide through the active functional group through the heating process to form the grafted metal oxide, so that the influence of the corrugated structure on the surface of the metal oxide film layer on the flatness of each subsequent film layer is reduced.
Specifically, in the process of heating to the thermal decomposition temperature of the metal oxide precursor, when the metal oxide precursor reaches the thermal decomposition temperature, the size and morphology of the oxide nanocrystals are highly susceptible to the annealing rate. This is mainly caused by the difference in the thermal decomposition rate of the metal oxide precursor and the volatilization of the solvent. When the annealing speed is higher than 30 ℃/s, the solvent in the reaction system can be completely volatilized in time, the thermal decomposition of the reaction precursor can avoid the interference of solvent volatilization, and the oxide nanocrystal obtained by decomposition forms a uniform and flat film. When the annealing rate is reduced, the volatilization rate of the solvent in the reaction system is slowed down, so that the solvent cannot be volatilized completely in time, and at the moment, because the volatilization of the solvent and the thermal decomposition rate of the reaction precursor are carried out simultaneously, the directional growth of the oxide nanocrystal is interfered by the volatilization of the solvent. In practical situations, the solvent evaporation in different areas on the same plane is not uniform, so that the generated oxide nanocrystals in different areas have different sizes, and finally the film layer has a corrugated three-dimensional appearance. However, when the annealing rate is too low, which is lower than 20 ℃/s, the volatilization rate of the solvent in the reaction system is too slow, which easily causes agglomeration among the metal nanocrystals in the reaction process. In view of this, in the embodiment of the present invention, the heating rate of 20 to 30 ℃/s is used as an annealing condition to prepare the metal oxide thin film with a corrugated surface.
Meanwhile, in the thermal decomposition process of the metal oxide precursor, the metal oxide nanocrystals mixed with the metal oxide precursor in the solution can be used as seed crystals, so that the control of the nucleation density of the nanocrystals is facilitated, and the control of the density of the surface wave pattern distribution of the film layer is realized.
Taking the preparation of the corrugated zinc oxide film with aminated surface as an example, the preparation method is as follows: adding 0.1-0.5 mg zinc oxide nano-crystal with particle size less than 100nm into Zn (CH) with concentration of 0.5-1 mmol/mL3COO)2And (3) carrying out ultrasonic treatment on the mixed solution for 30min in the ethylene glycol monomethyl ether solution to uniformly disperse the zinc oxide nanocrystals. And then adding 0.02-0.1 mg of low-molecular-weight diamine compound into the mixed solution, fully dissolving, uniformly depositing the solution on a substrate, raising the temperature to 300 ℃ at a heating rate of 20-25 ℃/s, and annealing for 30min to obtain the zinc oxide film with a corrugated surface.
In another aspect, the present invention provides a use of a thin film, a light emitting device, including the thin film or the thin film prepared by the method.
The luminescent device provided by the embodiment of the invention contains the film, and the surface flatness of the metal oxide can be repaired, so that the luminescent performance of the device is improved.
Specifically, the film is used as a hole transport layer and/or an electron transport layer of a light emitting device such as a QLED device or an OLED device, and the reflection effect of the film on light emitted from the light emitting layer can be effectively reduced, thereby improving the light extraction rate of the device.
As an embodiment, there is provided a use of the thin film in a QLED device. Specifically, as an example, as shown in fig. 1, the QLED device is a quantum dot light emitting diode device with an upright structure, and includes an anode 10, a metal oxide hole transport layer 11, a quantum dot light emitting layer 12, an electron transport layer 13, and a cathode 14, which are stacked. At this time, the QLED device emits light from the anode 10, and the metal oxide hole transport layer 11 contains a graft compound, which can effectively anchor quantum dots, improve the light extraction efficiency of the device, reduce surface defects, and improve the light emitting performance.
As another embodiment, as shown in fig. 2, the QLED device is a quantum dot light emitting diode device with an inverted structure, and includes a cathode 20, a metal oxide electron transport layer 21, a quantum dot light emitting layer 22, a hole transport layer 23, and an anode 24, which are stacked. At this time, the QLED device emits light from the cathode 24, and the metal oxide electron transport layer 21 contains a graft compound, which can effectively anchor quantum dots, improve the light extraction efficiency of the device, reduce surface defects, and improve the light emitting performance.
In the above embodiments, the material of the anode is preferably indium-doped tin oxide (ITO), but is not limited thereto. Materials of the hole transport layer include, but are not limited to, MoO3、WO3、NiO、V2O5、CuO、CrO3When the hole transport layer is a hole transport layer, the material thereof may be a graft compound X1-R-X2MoO of H medium3、WO3、NiO、V2O5、CuO、CrO3One kind of (1).
In the quantum dot light emitting layer, the quantum dot material can be one or more of but not limited to II-IV group semiconductor nanocrystals, III-V group semiconductor nanocrystals, II-V group semiconductor nanocrystals, III-VI group semiconductor nanocrystals, IV-VI group semiconductor nanocrystals and core-shell structures thereof. The surface ligand of the quantum dot material is preferably one of thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptooleic acid, mercaptoglycerol, mercaptoethylamine, mercaptooleylamine and glutathione. After the ligand is coordinated with atoms on the surface of the quantum dot, sulfydryl can be modified on the surface of the quantum dot. Graft compound X1-R-X2H, like an amino group with positive electricity at one end of a molecular chain of a diamine compound, can generate an electrostatic force effect with a sulfhydryl group with negative electricity on the surface of a quantum dot layer, so that electrostatic self-assembly is realized, the film forming quality of the quantum dots is favorably improved, the surface defect of a film interface is reduced, and the performance and the stability of the QLED device are further improved. The material of the electron transport layer includes but is not limited to ZnO, TiO2、ZrO2、HfO2、SrTiO3、BaTiO3、MgTiO3When the electron transport layer is an electron transport layer, the material thereof may be a graft compound X1-R-X2ZnO, TiO of H medium2、ZrO2、HfO2、SrTiO3、BaTiO3、MgTiO3One kind of (1). The material of the cathode is preferably Al or Ag, but is not limited thereto.
Correspondingly, the invention also provides a preparation method of the QLED device.
As an embodiment, the QLED device is a quantum dot light emitting diode device with a positive structure, and the preparation method thereof includes the following steps:
depositing a metal oxide hole transport layer as described above on a substrate comprising an anode;
depositing a quantum dot light-emitting layer on the metal oxide hole transport layer;
depositing an electron transport layer on the quantum dot light emitting layer;
and manufacturing a cathode, and packaging to obtain the quantum dot light-emitting diode device with the positive structure.
As another embodiment, the QLED device is a quantum dot light emitting diode device with an inverted structure, and the preparation method thereof includes the following steps:
depositing a metal oxide electron transport layer as described above on a substrate comprising a cathode;
depositing quantum dot luminescent layers on the metal oxide electron transport layer;
depositing a hole transport layer on the quantum dot light emitting layer;
and manufacturing an anode, and packaging to obtain the quantum dot light-emitting diode device with the inverted structure.
After depositing a metal oxide hole transport layer or a metal oxide electron transport layer, grafting a compound X1-R-X2The group with positive charge at one end of the molecular chain of the diamine compound, such as amino, can generate electrostatic force action with the group with negative charge on the surface of the quantum dot layer, such as sulfhydryl, so that electrostatic self-assembly is realized, and the process can be carried out at normal temperature.
In the embodiment of the invention, the metal oxide is preferably prepared on the electrode, so that the structure of the quantum dot light-emitting layer is prevented from being damaged by overhigh temperature.
Of course, it should be understood that the above-described thin films or thin films prepared by the above-described methods can also be used as thin films for OLED devices, resulting device structures, and methods for preparing device structures, similar to QLED devices.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a molybdenum oxide hole transport layer with an aminated surface comprises the following steps:
adding 0.35mg of molybdenum oxide nanocrystalline with the particle size of less than 100nm into MoO with the concentration of 0.5mmol/mL2(acac)2And then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the molybdenum oxide nanocrystals. And then 0.035mg of ethylenediamine is added into the mixed solution, the solution is uniformly deposited on a substrate after being fully dissolved, then the temperature is raised to 300 ℃ at the heating rate of 25 ℃/s, and the molybdenum oxide film layer is obtained after annealing for 30 min.
A preparation method of a QLED device with a positive structure comprises the following steps:
preparing a molybdenum oxide hole transport layer with aminated surface on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the hole transport layer;
spin-coating a ZnO hole transport layer on the quantum dot light-emitting layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 2
A preparation method of a nickel oxide hole transport layer with aminated surface comprises the following steps:
adding 0.2mg of nickel oxide nanocrystal with particle size less than 100nm into Ni (NO) with concentration of 0.5mmol/mL3)2Then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the nickel oxide nanocrystals. Then 0.02mg of 1, 2-propane diamine is added into the mixed solution, and after the solution is fully dissolved, the solution is evenly deposited on a liningAnd heating to 300 ℃ at the heating rate of 25 ℃/s, and annealing for 30min to obtain the nickel oxide film.
A preparation method of a QLED device with a positive structure comprises the following steps:
preparing a nickel oxide hole transport layer with aminated surface on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the hole transport layer;
spin-coating a ZnO hole transport layer on the quantum dot light-emitting layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 3
A preparation method of a tungsten oxide hole transport layer with aminated surface comprises the following steps:
adding 0.25mg tungsten oxide nanocrystal with particle size less than 100nm into W (OC) with concentration of 0.5mmol/mL2H5)5And then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the nickel oxide nanocrystals. And then 0.025mg of dimethyl propane diamine is added into the mixed solution, the solution is uniformly deposited on a substrate after being fully dissolved, the temperature is raised to 300 ℃ at the heating rate of 25 ℃/s, and the tungsten oxide film layer is obtained after annealing for 30 min.
A preparation method of a QLED device with a positive structure comprises the following steps:
preparing a tungsten oxide hole transport layer with aminated surface on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the hole transport layer;
spin-coating a ZnO hole transport layer on the quantum dot light-emitting layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 4
A preparation method of a zinc oxide electron transport layer with aminated surface comprises the following steps:
adding 0.2mg of nickel oxide nanocrystal with particle size less than 100nm into Ni (NO) with concentration of 0.5mmol/mL3)2Then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the zinc oxide nanocrystals. And then adding 0.02mg of hexamethylene diamine into the mixed solution, uniformly depositing the solution on a substrate after fully dissolving, raising the temperature to 300 ℃ at the heating rate of 30 ℃/s, and annealing for 30min to obtain the zinc oxide film layer.
A preparation method of an inverted structure QLED device comprises the following steps:
preparing a zinc oxide electron transport layer with aminated surface on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the electron transport layer;
spin coating a layer of MoO on the quantum dot light emitting layer3A hole transport layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 5
A preparation method of a corrugated titanium dioxide electron transport layer with aminated surface comprises the following steps:
adding 0.2mg of titanium dioxide nano-crystal with the particle size of less than 100nm into 0.5mmol/mL ethylene glycol monomethyl ether solution of isopropyl titanate, and then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the titanium dioxide nano-crystal. And then 0.02mg of 4,7, 10-trioxane-1, 13-tridecane diamine is added into the mixed solution, the solution is uniformly deposited on a substrate after being fully dissolved, then the temperature is raised to 200 ℃ at the heating rate of 20 ℃/s, and the titanium dioxide film layer with the corrugated surface is obtained after annealing for 30 min.
A preparation method of an inverted structure QLED device comprises the following steps:
preparing a corrugated titanium dioxide electron transport layer with aminated surface on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the electron transport layer;
spin coating a layer of MoO on the quantum dot light emitting layer3A hole transport layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 6
A preparation method of a corrugated nickel oxide hole transport layer with active functional groups modified on the surface comprises the following steps:
adding 0.2mg of nickel oxide nanocrystal with particle size less than 100nm into Ni (NO) with concentration of 0.5mmol/mL3)2Then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the nickel oxide nanocrystals. And then 0.02mg of mercaptopropionic acid is added into the mixed solution, the solution is uniformly deposited on a substrate after being fully dissolved, then the temperature is raised to 300 ℃ at the heating rate of 25 ℃/s, and the nickel oxide film layer with the corrugated surface is obtained after annealing for 30 min.
A preparation method of a QLED device with a positive structure comprises the following steps:
preparing a corrugated nickel oxide hole transport layer with the surface modified with active functional groups on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the hole transport layer;
spin-coating a ZnO hole transport layer on the quantum dot light-emitting layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
Example 7
A preparation method of a corrugated zinc oxide electron transport layer with active functional groups modified on the surface comprises the following steps:
adding 0.2mg of nickel oxide nanocrystal with particle size less than 100nm into Ni (NO) with concentration of 0.5mmol/mL3)2Then carrying out ultrasonic treatment on the mixed solution for 30min to uniformly disperse the zinc oxide nanocrystals. And then adding 0.02mg of adipic acid into the mixed solution, uniformly depositing the solution on a substrate after fully dissolving, raising the temperature to 300 ℃ at the rate of 30 ℃/s, and annealing for 30min to obtain the zinc oxide film with the corrugated surface.
A preparation method of an inverted structure QLED device comprises the following steps:
preparing a corrugated zinc oxide electron transport layer with the surface modified with active functional groups on an ITO substrate;
spin-coating a CdSe @ ZnS quantum dot light-emitting layer on the electron transport layer;
spin coating a layer of MoO on the quantum dot light emitting layer3A hole transport layer;
and (4) evaporating and plating an Al electrode on the hole transport layer, and packaging to obtain the QLED device with the inverted structure.
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 (15)
1. A film for use in a light emitting device, wherein the film is disposed on at least one surface of a quantum dot light emitting layer; the film is a metal oxide film, a grafting compound is contained in the film, the grafting compound is grafted on the metal oxide in the film to form a grafted metal oxide, and the structural formula of the grafted metal oxide is Y-X2-R-X1Wherein Y is a metal oxide, R is a hydrocarbyl group or a hydrocarbyl derivative, X is1Is a first reactive functional group, X2Is a group that can be bonded to a metal.
2. The film of claim 1, wherein the metal oxide of at least one surface of the film is grafted with the grafting compound.
3. The film of claim 1, wherein the constituent material of the film is the grafted metal oxide.
4. A film according to any of claims 1 to 3, wherein the film has a concave-convex surface.
5. The film of any one of claims 1-3, wherein the grafted compound has the formula X1-R-X2H，X2H is the second activityA sexual functional group, wherein the first active functional group is selected from-SH, -COOH, -NH2、-OH、-SO3H. At least one of phosphine group and phosphate group, and the second active functional group is selected from-SH, -COOH and-NH2、-OH、-SO3H. At least one of phosphine group and phosphate group; and/or
And R is alkyl or alkyl derivative with the carbon number of 1-13.
6. The film of claim 5, wherein the first reactive functional group is the same as the second reactive functional group.
7. The film of claim 6, wherein the first reactive functional group and the second reactive functional group are both amino groups.
8. The film of claim 7, wherein the grafting compound is selected from at least one of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, dimethylpropanediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, 4, 9-dioxo-1, 12-dodecanediamine, 4,7, 10-trioxa-1, 13-tridecanediamine.
9. A preparation method of a film is characterized in that the film is used in a light-emitting device and is arranged on at least one surface of a quantum dot light-emitting layer; the preparation method of the film comprises the following steps:
providing a metal oxide nanocrystal, a metal oxide precursor and a grafting compound, dissolving the metal oxide nanocrystal, the metal oxide precursor and the grafting compound in a solvent to obtain a mixed solution, wherein one end of the grafting compound contains a first active functional group X1And the other end contains a group X which can be bonded to the metal2The organic matter of (a);
depositing the mixed solution on a substrate, heating to the thermal decomposition temperature of the metal oxide precursor, annealing, and preparing the graft X1-R-X2Of (a) to (b)An oxide thin film.
10. The method for preparing a thin film according to claim 9, wherein in the step of depositing the mixed solution on a substrate and heating to the thermal decomposition temperature of the metal oxide precursor, the heating rate is 20 to 30 ℃/min.
11. The method of claim 9, wherein the molar ratio of the metal oxide nanocrystal, the metal oxide precursor, and the graft compound is 1 (1-3) to (0.5-1).
12. The method of preparing a thin film according to any one of claims 9 to 11, wherein the metal oxide nanocrystal has a particle size of 40 to 60 nm.
13. The method for preparing a thin film according to any one of claims 9 to 11, wherein the solvent is at least one selected from the group consisting of C1 to C5 linear alcohols, C1 to C5 branched alcohols, chlorobenzene, and dimethyl sulfoxide.
14. A light-emitting device comprising the film according to any one of claims 1 to 8 or the film produced by the method according to any one of claims 9 to 13.
15. The light-emitting device according to claim 14, wherein the thin film is a hole-transporting layer and/or an electron-transporting layer.
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