CN113707777B - Composite material, preparation method thereof and light-emitting device - Google Patents
Composite material, preparation method thereof and light-emitting device Download PDFInfo
- Publication number
- CN113707777B CN113707777B CN202010434605.7A CN202010434605A CN113707777B CN 113707777 B CN113707777 B CN 113707777B CN 202010434605 A CN202010434605 A CN 202010434605A CN 113707777 B CN113707777 B CN 113707777B
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- graphite alkyne
- metal
- composite material
- metal compound
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 192
- -1 graphite alkyne Chemical class 0.000 claims abstract description 176
- 239000010439 graphite Substances 0.000 claims abstract description 170
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 112
- 239000000243 solution Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002096 quantum dot Substances 0.000 claims description 77
- 229910021645 metal ion Inorganic materials 0.000 claims description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 150000003608 titanium 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
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- GPWILPBSXYXSMN-UHFFFAOYSA-J propane-1-sulfonate;tin(4+) Chemical compound [Sn+4].CCCS([O-])(=O)=O.CCCS([O-])(=O)=O.CCCS([O-])(=O)=O.CCCS([O-])(=O)=O GPWILPBSXYXSMN-UHFFFAOYSA-J 0.000 claims description 2
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 2
- BJDDAXVXMQYXHL-UHFFFAOYSA-J tris(ethylsulfonyloxy)stannyl ethanesulfonate Chemical compound [Sn+4].CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O BJDDAXVXMQYXHL-UHFFFAOYSA-J 0.000 claims description 2
- 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 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910001432 tin ion Inorganic materials 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 33
- 238000009825 accumulation Methods 0.000 abstract description 8
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- 239000002086 nanomaterial Substances 0.000 description 12
- 238000000137 annealing Methods 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 8
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- 150000003463 sulfur Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/14—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0083—Processes for devices with an active region comprising only II-VI compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of group II and group VI of the periodic system
Abstract
The invention belongs to the technical field of display devices, and particularly relates to a preparation method of a composite material, which comprises the following steps: obtaining a mixed solution of graphite alkyne and first metal salt, mixing a reducing agent with the mixed solution, and performing hydrothermal reaction to obtain metallized graphite alkyne; and obtaining a metal compound solution and an organic solution of the metallized graphite alkyne, and mixing the organic solution of the metallized graphite alkyne with the metal compound solution to obtain the composite material of the metallized graphite alkyne doped metal compound. The preparation method of the composite material provided by the invention is simple to operate, is suitable for industrialized mass production and application functions, improves the electron transmission capacity of an electron transmission layer, promotes the effective recombination of electrons and holes in a light-emitting layer, reduces the influence of exciton accumulation on the performance of a device, and further improves the photoelectric performance of a light-emitting device.
Description
Technical Field
The invention belongs to the technical field of display devices, and particularly relates to a composite material and a preparation method thereof, and a light-emitting device.
Background
The semiconductor quantum dots have quantum size effect, and the required luminescence with specific wavelength can be realized by regulating the size of the quantum dots, and the luminescence wavelength tuning range of the CdSe QDs can be from blue light to red light. In the conventional inorganic electroluminescent device, electrons and holes are injected from a cathode and an anode, respectively, and then are recombined in a light emitting layer to form exciton light emission.
In recent years, inorganic semiconductors have been the subject of relatively hot research as electron transport layers. The semiconductor materials such as nano ZnO and ZnS are wide-bandgap semiconductor materials, and attract the eyes of a plurality of researchers due to the advantages of quantum confinement effect, size effect, excellent fluorescence characteristic and the like. ZnO is an n-type semiconductor material with a direct band gap, has a wide band gap of 3.37eV and a low work function of 3.7eV, and the structural characteristics of the energy band determine that ZnO can be a proper electron transport layer material. In addition, znS is a semiconductor material of II-VI families, and has the characteristics of two different structures of sphalerite and wurtzite, stable chemical property of forbidden band width (3.62 eV), abundant resources, low price and the like. Therefore, in recent decades, znO, znS II-VI and other conductor nanomaterials have shown great development potential in the fields of photocatalysis, sensors, transparent electrodes, fluorescent probes, diodes, solar cells, lasers and the like.
At present, semiconductor materials such as ZnO, znS and the like are often poor in crystallinity, a large number of active groups and surface defect states exist on the surface, and loss of photocurrent is easily caused, so that the performance of a device is reduced; meanwhile, the active groups can also cause bonding action among the nano particles, so that agglomeration among the particles is caused to influence the dispersibility of the nano particles, and the injection efficiency of electrons is reduced to influence the recombination efficiency of electrons and holes in the quantum dot luminescent layer. Therefore, the application performance of semiconductor materials such as ZnO, znS and the like in an electron transport layer of an optoelectronic device is still required to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a composite material, which aims to improve the electron transmission performance of the existing ZnO, znS and other semiconductor materials to a certain extent and improve the photoelectric performance of devices.
It is another object of the present invention to provide a composite material.
It is still another object of the present invention to provide a light emitting device.
In order to achieve the above object, the present invention adopts the following technical scheme:
a method of preparing a composite material comprising the steps of:
obtaining a mixed solution of graphite alkyne and first metal salt, mixing a reducing agent with the mixed solution, and performing hydrothermal reaction to obtain metallized graphite alkyne;
And obtaining a metal compound solution and an organic solution of the metallized graphite alkyne, and mixing the organic solution of the metallized graphite alkyne with the metal compound solution to obtain the composite material of the metallized graphite alkyne doped metal compound.
Accordingly, a composite material, the composite material comprising: metallized graphite alkyne and metal compound bonded to the metallized graphite alkyne.
Accordingly, a light emitting device includes an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, and an electron functional layer disposed between the cathode and the quantum dot light emitting layer; the electronic functional layer comprises the composite material prepared by the method or comprises the composite material.
According to the preparation method of the composite material, firstly, the reducing agent and the mixed solution are mixed and then subjected to hydrothermal reaction, so that the metallized graphite alkyne doped with metal atoms is obtained. Reducing the first metal ion into first metal atom by reducing agent, doping the first metal atom into the graphite alkyne material, transferring electrons to sp of graphite alkyne by outer electron rich in metal atom 2 On the benzene ring, n-type doping is formed, and the electron transmission performance of the graphite alkyne is improved. And then, after obtaining a metal compound solution, mixing the organic solution of the metallized graphite alkyne with the metal compound solution, and obtaining the metallized graphite alkyne doped metal compound composite material through stronger adsorption between metal atoms in the metallized graphite alkyne and metal atoms in the metal compound. On one hand, the metallized graphite alkyne provides a two-dimensional network structure with a special electronic structure and a special hole structure for the metal compound, so that agglomeration of the metal compound in the application process is effectively prevented, and the stability of the electron transmission film is improved; on the other hand, by doping metallized graphite alkyne, graphite alkyne pz orbit and metallization are realized The hybridization between 3d orbitals of metal ions in the compound can generate electronic interaction between graphite alkyne and metal compounds, so that the electron transmission capability of the composite material is improved. In still another aspect, in the composite material of the metallized graphite alkyne doped with the metal compound, the work function of the graphite alkyne is about 5.0eV, and the graphite alkyne is arranged between the electrode and the electron transport material such as the metal compound, so that the electron transport barrier is reduced, and the energy level matching of the electron transport layer and the electrode is facilitated. The electron transport capability of the electron transport layer is improved, the electron-hole is promoted to be effectively combined in the light-emitting layer, the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of the light-emitting device is improved.
The composite material provided by the invention comprises: the metallized graphite alkyne is a graphite alkyne material combined with metal atoms, has a two-dimensional network structure with a special electronic structure and a hole structure, effectively prevents agglomeration of the metal compound in the application process, and improves the stability of the electron transport film. In addition, the metal compound is combined on the metallized graphite alkyne, so that the hybridization between the pz orbit of the graphite alkyne and the 3d orbit of the metal ion in the metal compound is realized, the electronic interaction between the graphite alkyne and the metal compound can be generated, and the electronic transmission capability of the composite material is improved. In addition, in the composite material of the metallized graphite alkyne doped with the metal compound, the work function of the graphite alkyne is about 5.0eV, and the graphite alkyne is arranged between an electrode, the electron transport barrier is reduced, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer is improved, the effective recombination of electrons and holes in a light-emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of a light-emitting device is improved.
The light-emitting device provided by the invention comprises the composite material which has good stability and high electron transmission efficiency and can reduce the electron transmission barrier between the electrode and the electron transmission material such as the metal compound. Therefore, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer in the light-emitting device is improved, the effective recombination of electrons and holes in the light-emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of the light-emitting device is improved.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a composite material according to an embodiment of the present invention.
Fig. 2 is a schematic view of a light emitting device of a positive configuration according to an embodiment of the present invention.
Fig. 3 is a schematic view of a light emitting device in an inverted configuration according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and technical effects of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art without undue burden in connection with the embodiments of the present invention, are intended to be within the scope of the present invention.
In the description of the present invention, it should 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 a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the present invention may be mass units known in the chemical industry field such as μ g, mg, g, kg.
As shown in fig. 1, the embodiment of the invention provides a preparation method of a composite material, which comprises the following steps:
s10, obtaining a mixed solution of graphite alkyne and first metal salt, mixing a reducing agent with the mixed solution, and performing hydrothermal reaction to obtain metallized graphite alkyne;
S20, obtaining a metal compound solution and an organic solution of metallized graphite alkyne, and mixing the organic solution of metallized graphite alkyne with the metal compound solution to obtain the composite material of the metallized graphite alkyne doped metal compound.
According to the preparation method of the composite material, firstly, the reducing agent and the mixed solution are mixed and then subjected to hydrothermal reaction, so that the metallized graphite alkyne doped with metal atoms is obtained. Reducing the first metal ion into first metal atom by reducing agent, doping the first metal atom into the graphite alkyne material, transferring electrons to sp of graphite alkyne by outer electron rich in metal atom 2 On the benzene ring, n-type doping is formed, and the electron transmission performance of the graphite alkyne is improved. Then, after obtaining a metal compound solution, mixing the organic solution of the metallized graphite alkyne with the metal compound solution, and obtaining the composite material of the metallized graphite alkyne doped metal compound through stronger adsorption between metal atoms in the metallized graphite alkyne and metal atoms in the metal compound. On one hand, the metallized graphite alkyne provides a two-dimensional network structure with a special electronic structure and a special hole structure for the metal compound, so that agglomeration of the metal compound in the application process is effectively prevented, and the stability of the electron transmission film is improved; on the other hand, through doping of metallized graphite alkyne, hybridization between graphite alkyne pz orbits and 3d orbits of metal ions in metal compounds is realized, electron interaction can be generated between graphite alkyne and metal compounds, and electron transmission capacity of the composite material is improved. In still another aspect, in the composite material of the metallized graphite alkyne doped with the metal compound, the work function of the graphite alkyne is about 5.0eV, and the graphite alkyne is arranged between the electrode and the electron transport material such as the metal compound, so that the electron transport barrier is reduced, and the energy level matching of the electron transport layer and the electrode is facilitated. Improving the electron transmission capability of the electron transmission layer and promoting electron-air Holes are effectively combined in the light-emitting layer, so that the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of the light-emitting device is improved.
Specifically, in the above-mentioned embodiment S10, a mixed solution of a graphite alkyne and a first metal salt is obtained, and a reducing agent is mixed with the mixed solution and then subjected to a hydrothermal reaction to obtain a metallized graphite alkyne. According to the embodiment of the invention, the reducing agent and the mixed solution are mixed and then subjected to hydrothermal reaction, the first metal ions are reduced into first metal atoms by the reducing agent and doped into the graphite alkyne material, and electrons are transferred to sp of the graphite alkyne by outer electrons rich in metal atoms 2 On the benzene ring, n-type doping is formed, and the electron transmission performance of the graphite alkyne is improved. Meanwhile, graphite alkyne doped with the first metal atom has stronger adsorption effect on metal atoms in the metal compound, can generate better electronic interaction with electron transport materials such as the metal compound and the like, and is more beneficial to obtaining the composite material by doping the metal compound with the metallized graphite alkyne.
The invention is composed of sp and sp 2 The new carbon allotrope-graphite alkyne is a base material, which is formed by conjugated connection of benzene rings by 1, 3-diacetylene bond, and has a two-dimensional plane super-conjugated structure with rich carbon chemical bonds and huge conjugated system, which not only becomes a good electron acceptor due to huge highly conjugated structure, but also has good electron donating property due to own mass free electrons, special electronic structure and hole structure, and excellent chemical and thermal stability, semiconductor performance and other performances. The composite material can be applied to a composite material, so that an adhesion carrier is provided for a metal compound, the dispersion stability of the metal compound is improved, the electron transmission performance of the metal compound can be effectively improved, and the electron-hole is effectively compounded in a light-emitting layer, so that the photoelectric performance of a light-emitting device is improved.
In some embodiments, the step of obtaining a mixed solution of the graphite alkyne and the first metal salt may include, but is not limited to, dissolving the first metal salt in deionized water, adding the graphite alkyne, and stirring to sufficiently disperse the graphite alkyne into the solution system to form a mixed solution of the graphite alkyne and the first metal salt.
In some embodiments, the molar ratio of graphite alkyne to first metal ion in the mixed solution is 1: (0.05-0.2), the first metal ion with the molar ratio has better doping and metallization effect on the graphite alkyne, and can better improve the electron transmission performance of the graphite alkyne. When the doping mole ratio of the first metal atoms is larger than 0.2, the first metal ions react with the subsequently added reducing agent to form metal atoms, so that agglomeration is easy to form on the surface of the graphite alkyne, the dispersibility is poor, and the electron transmission performance of the graphite alkyne cannot be improved well; when the doping mole ratio of the first metal atoms is less than 0.05, the first metal ions are lost during the reaction, and effective doping cannot be achieved. In a further embodiment, the molar ratio of graphite alkyne to first metal ion in the mixed solution is 1: (0.05-0.15), the graphite alkyne and the first metal ion in the mixed solution have the optimal metallization doping effect on the graphite alkyne, and after the first metal ion is reduced into the first metal atom by the reducing agent and doped in the graphite alkyne material, the graphite alkyne and the metal compound have better electron interaction, so that the electron transmission capability of the composite material is improved. In some embodiments, the molar ratio of graphite alkyne to first metal ion in the mixed solution can be 1:0.05, 1:0.07, 1:0.08, 1:0.1, 1:0.12, 1:0.14, or 1:0.15.
In some embodiments, the concentration of the first metal salt in the mixed solution is 0.2-1 mol/L, and the concentration of the first metal salt fully ensures the content of the first metal ion in the mixed solution, thereby fully ensuring that the first metal ion is fully adsorbed in the graphite alkyne, and facilitating the subsequent full metallization of the graphite alkyne. In some embodiments, the concentration of the first metal salt in the mixed solution is 0.2 to 1mol/L; the molar ratio of graphite alkyne to first metal ion is 1: (0.05-0.2).
In some embodiments, the first metal salt is selected from: at least one of iron salt, cobalt salt and platinum salt. The first metal salt is at least one transition metal salt selected from ferric salt, cobalt salt and platinum salt, and the transition metal atoms obtained after the transition metal salt is reduced by a reducing agent can be very firmly adsorbed on graphiteIn alkyne ring vacancies, stable structures can be formed between alkyne chains of graphite alkynes by bonding to sp hybridized carbons on adjacent two alkyne chains. And, these transition metal atoms have abundant outer electrons by transferring the electrons to the sp of the graphite alkyne 2 N-type doping is formed on the benzene ring, so that the electron transmission performance of the graphite alkyne can be effectively improved.
In some embodiments, the step of mixing the reducing agent with the mixed solution followed by a hydrothermal reaction comprises: mixing reducer with the mixed solution, mixing at 130-150 deg.c for 18-24 hr, and separating to obtain metallized graphite alkyne. According to the embodiment of the invention, the first metal ions are fully reduced into first metal atoms by the reducing agent and doped into the graphite alkyne material by mixing treatment for 18-24 hours at the temperature of 130-150 ℃, and under the reaction condition, the first metal ions have the optimal reduction rate, so that the reduced metal atoms are uniformly doped into the graphite alkyne to obtain metallized graphite alkyne, and the situation that the metal atoms are agglomerated into larger particles due to too high reduction rate of the first metal ions is avoided, so that the graphite alkyne cannot be effectively doped.
In some embodiments, the molar ratio of the first metal ion to the reducing agent in the system after mixing the reducing agent with the mixed solution is 1: (0.2-0.5). When the mole ratio of the first metal ions to the reducing agent is less than 1:0.2, the reducing effect on the first metal ions is poor, and the doping effect of metal atoms on the graphite alkyne is affected; when the molar ratio of the first metal ions to the reducing agent is less than 1:0.5, the reducing agent is excessive, so that raw materials are wasted and are not easy to remove in subsequent cleaning. Thus, the molar ratio of the first metal ion to the reducing agent is controlled to be 1: (0.2-0.5).
In some embodiments, the reducing agent is selected from: at least one of sodium borohydride and hydrazine hydrate has better reducing property on the first metal salt in the hydrothermal reaction, so that the first metal ion is reduced to metal atoms which are combined on the graphite alkyne, and the metallized graphite alkyne material is obtained.
Specifically, in the step S20, a metal compound solution and an organic solution of metallized graphite alkyne are obtained, and the organic solution of metallized graphite alkyne and the metal compound solution are mixed and treated to obtain the composite material of metallized graphite alkyne doped with metal compound. After the metal compound solution and the organic solution of the metallized graphite alkyne are obtained, the organic solution of the metallized graphite alkyne and the metal compound solution are mixed for treatment, and the composite material of the metallized graphite alkyne doped with the metal compound is obtained through stronger adsorption between metal atoms in the metallized graphite alkyne and metal atoms in the metal compound. The composite material is stable in dispersion, the hybridization between the pz orbit of the graphite alkyne and the 3d orbit of the metal ion in the metal compound is realized through doping of the metallized graphite alkyne, the electronic interaction between the graphite alkyne and the metal compound can be generated, and the electronic transmission capacity of the composite material is improved. And the graphite alkyne can reduce the transmission barrier of electrons, is favorable for the energy level matching of the electron transmission layer and the electrode, improves the electron transmission capacity of the electron transmission layer, promotes the effective recombination of electrons and holes in the light-emitting layer, and reduces the influence of exciton accumulation on the performance of the device, thereby improving the photoelectric performance of the light-emitting device.
In some embodiments, the step of obtaining a metal compound solution comprises: and mixing and dissolving the second metal salt and alkaline substances or sulfur sources in the first organic solvent at the temperature of 60-90 ℃ and then carrying out mixing treatment for 4-6 hours to obtain a metal compound solution. In the embodiment of the invention, under the condition of 60-90 ℃, the second metal salt and the alkaline substance or the sulfur source are mixed and dissolved in the first organic solvent, and then mixed and treated for 4-6 hours, the second metal salt reacts with the alkaline substance to generate hydroxide, then the hydroxide is subjected to polycondensation reaction, and the second metal oxide is generated by dehydration, or the second metal sulfide is generated by the reaction of the second metal salt and the sulfur source. After the reaction or cooling, the metal compound of the second metal oxide or the second metal sulfide is separated out by using weak polar and nonpolar solvents such as ethyl acetate, heptane, octane and the like as precipitants, and the metal compound solution is obtained by washing and extracting for multiple times. The metal compound solution can be directly used for the subsequent reaction with the metallized graphite alkyne without drying, and if the metal compound is dried, some active groups on the surface of the material can be destroyed, so that the subsequent doping and combination reaction with the metallized graphite alkyne is not facilitated.
In some embodiments, the second metal salt is mixed with the alkaline substance and dissolved in the system after the first organic solvent, and the pH value is 12-13. In some embodiments, the second metal salt is mixed with the alkaline substance and dissolved in the system after the first organic solvent, and the molar ratio of the second metal ion to the alkaline substance is 1: (1.8-4.5). In some embodiments, the second metal ion is a divalent metal ion, the molar ratio of the second metal ion to the alkaline material being 1: (1.8-3). In some embodiments, the second metal ion is a tetravalent metal ion, the molar ratio of the second metal ion to the basic species being 1: (3-4.5). In the embodiment of the invention, the second metal salt reacts with the alkaline substance to prepare the metal compound of the second metal oxide, at the moment, the pH value and the addition amount of the alkaline substance in the reaction system are directly related to the metal compound of the second metal oxide, and when the H value in the system is smaller than 12, the alkaline substance is insufficient, the second metal salt is excessive, and the reaction is insufficient; when the H value in the system is larger than 12, the pH value is too high, so that the hydrolysis and polycondensation speeds of the sol in the system are reduced, and the preparation of the second metal oxide semiconductor material is not facilitated. Similarly, when the second metal ion is Zn 2+ When the divalent metal is equal, the molar ratio of the second metal ion to the alkaline substance is 1: (1.8-3) when the second metal ion is Ti 4+ 、Sn 4+ When the tetravalent metal is isovalent, the mole ratio of the second metal ion to the alkaline substance is 1: (3-4.5) if the alkaline substance is excessive, the hydrolysis and polycondensation speeds of the sol in the system are reduced, which is unfavorable for the preparation of the second metal oxide semiconductor material; if the alkaline substance is too small, the second metal salt is excessive and the reaction is insufficient.
In some embodiments, the second metal salt is mixed with the sulfur source and dissolved in the system after the first organic solvent, the molar ratio of the second metal ion to the sulfur source is 1: (1-1.5). In the embodiment of the invention, the second metal salt reacts with the sulfur source to prepare the metal compound of the second metal sulfide, wherein the molar ratio of the second metal ion to the sulfur source is 1: (1-1.5) is advantageous for producing a second metal sulfide semiconductor material having a small and uniform particle size when the molar ratio of the second metal ion to the sulfur source is less than 1:1, zinc salt is excessive, the amount of sulfur source is small, and the generated zinc sulfide is insufficient; when the molar ratio of the second metal ion to the sulfur source is greater than 1: at 1.5, the sulfur salt is excessive, so that an impurity compound is easily formed, and the removal is not easy.
In some embodiments, the step of mixing the organic solution of metallized graphite alkyne with the metal compound solution comprises: adding an organic solution of metallized graphite alkyne into a metal compound solution under the stirring condition of 60-80 ℃ for reaction for 1-2 hours, and separating to obtain the composite material of the metallized graphite alkyne doped metal compound. According to the embodiment of the invention, under the stirring condition of 60-80 ℃, the organic solution of the metallized graphite alkyne is added into the metal compound solution in a dropwise adding mode, so that the added metallized graphite alkyne can be quickly and uniformly combined with the metal compound, and the composite material of the metallized graphite alkyne doped with the metal compound is obtained through stronger adsorption between metal atoms in the metallized graphite alkyne and metal atoms in the metal compound. The metallized graphite alkyne provides a two-dimensional network structure with a special electronic structure and a special hole structure for the metal compound, so that agglomeration of the metal compound in the application process is effectively prevented, and the stability of the electron transport film is improved. Meanwhile, through doping of the metallized graphite alkyne, hybridization between a graphite alkyne pz orbit and a 3d orbit of metal ions in the metal compound is realized, electronic interaction can be generated between the metallized graphite alkyne and the metal compound, and the electronic transmission capacity of the metal compound is improved.
In some embodiments, the organic solution of the metallized graphite alkyne is added into the system after the metal compound solution by a dropwise adding method, and the molar ratio of the metallized graphite alkyne to the metal compound is (0.1-0.3): 1. when the molar ratio of metallized graphite alkyne to metal compound is less than 0.1:1, the metal compound is excessive, the metal compound cannot be well dispersed, and the effect of improving the conductivity is not great; when the molar ratio of metallized graphite alkyne to metal compound is greater than 0.3: in the process 1, excessive metalized graphite alkyne cannot generate hybridization with metal ions in the gold nano material, and the improvement of the electron transmission performance of the composite transmission material is not obvious. In some embodiments, the molar ratio of metallized graphite alkyne to metal compound can be 0.1:1, 0.15:1, 0.2:1, 0.25:1, or 0.3:1, etc.
In some embodiments, the second metal salt is selected from: at least one of zinc salt, titanium salt and tin salt. In some embodiments, the zinc salt is selected from: at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate. In some embodiments, the titanium salt is selected from: at least one of titanium nitrate, titanium chloride, titanium sulfate and titanium bromide. In some embodiments, the tin salt is selected from: at least one of tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate and tin propane sulfonate. The second metal salts used in the examples of the present invention can all react with an alkaline substance or a sulfur source to produce a metal compound having an electron transporting property.
In some embodiments, the alkaline material is selected from: at least one of ammonia water, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, glycol, diethanolamine, triethanolamine and ethylenediamine, and the alkaline substances can react with a second metal salt such as zinc salt, titanium salt and tin salt to generate hydroxide, then perform polycondensation reaction and dehydration to generate the second metal oxide semiconductor material.
In some embodiments, the sulfur source is selected from: at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide, and the sulfur sources can react with second metal salts such as zinc salt, titanium salt and tin salt to generate a second metal sulfide semiconductor material.
In some embodiments, the first organic solvent is selected from: at least one of isopropanol, ethanol, propanol, butanol and methanol, and the organic solvents have better solubility to the second metal salt, alkaline substances and sulfur sources, provide a better solvent system for the reaction among the substances, and are beneficial to the reaction.
In some embodiments, the organic solvent in the organic solution of metallized graphite alkyne is selected from: at least one of isopropanol, ethanol, propanol, butanol and methanol, and the organic solvents have good dispersion characteristics on the metallized graphite alkyne, are favorable for the mutual doping reaction between the metallized graphite alkyne and the metal compound, and obtain the composite material of the metallized graphite alkyne doped with the metal compound.
Correspondingly, the embodiment of the invention also provides a composite material, which comprises the following components: metallized graphite alkynes and metal compounds bonded to metallized graphite alkynes.
The composite material provided by the embodiment of the invention comprises the following components: the metallized graphite alkyne is a graphite alkyne material combined with metal atoms, has a two-dimensional network structure with a special electronic structure and a hole structure, effectively prevents agglomeration of the metal compound in the application process, and improves the stability of the electron transport film. In addition, the metal compound is combined on the metallized graphite alkyne, so that the hybridization between the pz orbit of the graphite alkyne and the 3d orbit of the metal ion in the metal compound is realized, the electronic interaction between the graphite alkyne and the metal compound can be generated, and the electronic transmission capability of the composite material is improved. In addition, in the composite material of the metallized graphite alkyne doped with the metal compound, the work function of the graphite alkyne is about 5.0eV, and the graphite alkyne is arranged between an electrode, the electron transport barrier is reduced, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer is improved, the effective recombination of electrons and holes in a light-emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of a light-emitting device is improved.
In some embodiments, the composite material comprises a metallized graphite alkyne and a metal compound bonded to the metallized graphite alkyne, wherein the metallized graphite alkyne comprises a graphite alkyne and a first metal atom bonded to the graphite alkyne, and the molar ratio of the graphite alkyne to the first metal ion in the metallized graphite alkyne is 1: (0.05-0.2).
In some embodiments, the first metal ion bound to the graphite alkyne is selected from: at least one of iron ion, cobalt ion and platinum ion.
In some embodiments, the metal compound is selected from: at least one of zinc oxide, titanium oxide, tin oxide, zinc sulfide, titanium sulfide, and tin sulfide.
In some embodiments, the molar ratio of metallized graphite alkyne to metal compound is (0.1 to 0.3): 1.
correspondingly, the embodiment of the invention also provides a light-emitting device, which comprises an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer; the electron transport layer comprises the composite material prepared by the method or comprises the composite material.
The light-emitting device provided by the embodiment of the invention has good stability and high electron transmission efficiency due to the inclusion of the composite material which can reduce the electron transmission barrier between the electrode and the electron transmission material such as the metal compound. Therefore, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer in the light-emitting device is improved, the effective recombination of electrons and holes in the light-emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the photoelectric performance of the light-emitting device is improved.
In some embodiments, the light emitting devices of embodiments of the present invention are divided into positive and negative structures.
In one embodiment, a positive-type structure light emitting device includes a stacked structure of an anode and a cathode disposed opposite to each other, a light emitting layer disposed between the anode and the cathode, and the anode is disposed on a substrate. Furthermore, a hole injection layer, a hole transport layer, an electron blocking layer and other hole functional layers can be arranged between the anode and the luminescent layer; an electron transport layer, an electron injection layer, a hole blocking layer, and other electron functional layers may be further disposed between the cathode and the light emitting layer, as shown in fig. 2. In some embodiments of positive-type structure devices, the light-emitting device includes a substrate, an anode disposed on a surface of the substrate, a hole transport layer disposed on a surface of the anode, a light-emitting layer disposed on a surface of the hole transport layer, an electron transport layer disposed on a surface of the light-emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, an inverted structure light emitting device includes a stacked structure of an anode and a cathode disposed opposite to each other, a light emitting layer disposed between the anode and the cathode, and the cathode disposed on a substrate. Furthermore, a hole injection layer, a hole transport layer, an electron blocking layer and other hole functional layers can be arranged between the anode and the luminescent layer; an electron transport layer, an electron injection layer, a hole blocking layer, and other electron functional layers may be further disposed between the cathode and the light emitting layer, as shown in fig. 3. In some embodiments of the inversion structure device, the light emitting device includes a substrate, a cathode disposed on a surface of the substrate, an electron transport layer disposed on a surface of the cathode, a light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the light emitting layer, and an anode disposed on a surface of the hole transport layer.
In further embodiments, the substrate layer comprises a rigid, flexible substrate, or the like;
the anode includes: ITO, FTO, ZTO, etc.;
the hole injection layer includes PEODT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid)), woO 3 、MoO 3 、NiO、V 2 O 5 HATCN (2, 3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene), cuS, and the like;
the hole transport layer may be a small molecule organic material or a high molecule conductive polymer, including: TFB (Poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4, 4' - (N- (4-N-butyl) phenyl) -diphenylamine)]) PVK (polyvinylcarbazole), TCTA (4, 4 '-tris (carbazol-9-yl) triphenylamine), TAPC (4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline)]) Poly-TBP, poly-TPD, NPB (N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine), CBP (4, 4' -bis (9-carbazole) biphenyl), PEODT: PSS, moO 3 、WoO 3 、NiO、CuO、V 2 O 5 CuS, and the like, or a mixture of any combination thereof, may also be other high performance hole transporting materials.
The light-emitting layer is a quantum dot light-emitting layer, wherein the quantum dot is one of red, green and blue quantum dots. Including but not limited to: at least one of the group II-IV, group II-VI, group II-V, group III-VI, group IV-VI, group I-III-VI, group II-IV-V semiconductor compounds, or a core-shell structure semiconductor compound composed of at least two of the above semiconductor compounds. In some embodiments, the quantum dot light emitting layer material is selected from: cdSe, cdS, cdTe, znO, znSe, znS, znTe, hgS, hgSe, hgTe, cdZnSe, or a semiconductor nanocrystalline compound of a structure such as a mixed type, a gradient mixed type, a core-shell structure type or a combination type of at least two components. In other embodiments, the quantum dot light emitting layer material is selected from the group consisting of: inAs, inP, inN, gaN, inSb, inAsP, inGaAs, gaAs, gaP, gaSb, alP, alN, alAs, alSb, cdSeTe, znCdSe, or a semiconductor nanocrystalline compound of a structure such as a mixed type, a gradient mixed type, a core-shell structure type or a combination type of at least two components. In other embodiments, the quantum dot light emitting layer material is selected from: at least one of perovskite nanoparticle materials (in particular luminescent perovskite nanoparticle materials), metal nanoparticle materials, metal oxide nanoparticle materials. The quantum dot materials have the characteristics of quantum dots and have good photoelectric performance;
The electron transport layer comprises the composite material;
the cathode includes: al, ag, au, cu, mo, or an alloy thereof.
In some embodiments, the preparation of the light emitting device of the embodiments of the present invention includes the steps of:
s30, obtaining a substrate deposited with an anode;
s40, growing a hole transport layer on the anode;
s50, depositing a quantum dot luminescent layer on the hole transport layer;
s60, finally depositing an electron transport layer on the quantum dot luminescent layer, and depositing a cathode on the electron transport layer to obtain the luminescent device.
In some embodiments, in step S30, the ITO substrate is subjected to a pretreatment process in order to obtain a high quality zinc oxide nanomaterial film. The specific processing steps of the substrate comprise: and cleaning the ITO conductive glass with a cleaning agent to preliminarily remove stains on the surface, sequentially and respectively ultrasonically cleaning the ITO conductive glass in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally drying the ITO conductive glass with high-purity nitrogen to obtain the ITO positive electrode.
In some embodiments, in step S40, the step of growing the hole transport layer includes: depositing the prepared solution of the hole transport material on an ITO substrate to form a film by spin coating and the like; the film thickness is controlled by adjusting the concentration of the solution, spin-coating speed and spin-coating time, and then thermally annealed at an appropriate temperature.
In some embodiments, in step S50, the step of depositing the quantum dot light emitting layer on the hole transport layer includes: and (3) depositing the prepared luminescent substance solution with a certain concentration on the hole transport layer in a spin coating mode, controlling the thickness of the luminescent layer by adjusting the concentration, spin coating speed and spin coating time, and drying at a proper temperature to form the quantum dot luminescent layer at about 20-60 nm.
In some embodiments, in step S60, the step of depositing an electron transport layer on the quantum dot light emitting layer includes: the electron transport layer is a zinc oxide nano material (a/c-ZnO) film mixed by crystalline phase and amorphous phase, zinc oxide composite material solution with certain concentration is deposited on the quantum dot luminescent layer by spin coating, the thickness of the electron transport layer is controlled by adjusting the concentration of the solution, the spin coating speed (preferably, the rotating speed is between 2000 and 6000 rpm) and the spin coating time, the thickness is about 20 to 60nm, and then annealing is carried out at the temperature of 200 to 250 ℃ to form the electron transport layer film.
In some embodiments, in step S60, the step of cathode preparation includes: the substrate on which all the functional layers are deposited is placed in an evaporation bin, a layer of 15-30nm metal silver or aluminum is thermally evaporated through a mask plate to serve as a cathode, or a nano Ag wire or a nano Cu wire is used, so that the carrier can be smoothly injected due to the fact that the resistance is small.
Further, the obtained photoelectric device is packaged, and the packaging process can be performed by a common machine or manually. Preferably, in the environment of the encapsulation process, both the oxygen content and the water content are less than 0.1ppm to ensure the stability of the device.
In order that the above implementation details and operation of the present invention may be clearly understood by those skilled in the art, and that the composite material of the embodiments of the present invention, the preparation method thereof, and the advanced performance of the optoelectronic device are significantly embodied, the following examples are given to illustrate the above technical solutions.
Example 1
An fe@graphite alkyne doped ZnS electron transport film comprising the steps of:
(1) dissolving appropriate amount of ferric chloride in 30ml deionized water to obtain solution with total concentration of 0.5M, adding graphite alkyne, and stirring (molar ratio, C: fe) 3+ =1:0.2). Adding sodium borohydride solution (molar ratio, fe 3+ Sodium borohydride=1:0.5), pouring the mixture into a hydrothermal kettle of a polytetrafluoroethylene liner for hydrothermal reaction, reacting for 24 hours at 150 ℃, and placing the obtained black precipitate into a vacuum drying oven for drying at 60 ℃ for one night after the obtained black precipitate is clearly treated with deionized water and ethanol for several times to obtain the Fe@graphite alkyne.
(2) An appropriate amount of zinc chloride was added to 50ml of ethanol to form a solution having a total concentration of 0.5M, and dissolved by stirring at 70 ℃. Sodium sulfide in 10ml ethanol solution (molar ratio, S 2- ：Zn 2+ =1.2: 1). Stirring was continued at 70℃for 4h to give a homogeneous ZnS solution.
(3) To the ZnS solution, fe@graphite alkyne was slowly added dropwise and dispersed in 10ml of an ethanol solution (molar ratio, fe@graphite alkyne: zns=0.2:1), and stirring was continued at 70 ℃ for 1.5 hours to obtain an fe@graphite alkyne doped ZnS solution.
(4) And (3) after the solution is cooled, depositing on the treated ITO by a spin coater and annealing at 200 ℃ to obtain the Fe@graphite alkyne doped ZnS electron transport film.
Example 2
An Pt@ graphene-doped ZnO electron transport film comprising the steps of:
(1) an appropriate amount of platinum nitrate was dissolved in 30ml of deionized water to form a solution having a total concentration of 0.5M, and graphite alkyne was added and stirred uniformly (molar ratio, C: pt) 2+ =1:0.05). Adding sodium borohydride solution (molar ratio, pt) 2+ : sodium borohydride=1:0.2) and then poured into polytetrafluoroethyleneCarrying out hydrothermal reaction in a hydrothermal kettle of an ethylene liner, reacting for 20 hours at 130 ℃, and placing the obtained black precipitate into a vacuum drying oven to be dried at 60 ℃ for one night after the obtained black precipitate is clear with deionized water and ethanol for several times, thus obtaining Pt@ graphite alkyne.
(2) An appropriate amount of zinc nitrate was added to 50ml of propanol to form a solution having a total concentration of 0.5M, and dissolved by stirring at 80 ℃. Sodium hydroxide was added to a solution (molar ratio, OH - ：Zn 2+ =2: 1). Stirring was continued at 80℃for 4h to give a homogeneous ZnO solution.
(3) Pt@ graphite alkyne was slowly added dropwise to the ZnO solution dispersed in 10ml of propanol solution (molar ratio Pt@ graphite alkyne: zno=0.3:1), and stirring was continued at 80 ℃ for 2 hours to obtain a Pt@ graphite alkyne-doped ZnO solution.
(4) Spin-coating the treated ITO by a spin coater after the solution is cooled and annealing the ITO at 150 ℃ to obtain the Pt@ graphene-doped ZnO electron transport film.
Example 3
Co@ graphite alkyne doped TiO 2 An electron transport film of (a), comprising the steps of:
(1) dissolving appropriate amount of platinum nitrate in 30ml deionized water to obtain solution with total concentration of 0.5M, adding graphite alkyne, and stirring (molar ratio, C: co) 2+ =1:0.1). Adding hydrazine hydrate solution (molar ratio, co) 2+ : hydrazine hydrate=1:0.3), pouring the mixture into a hydrothermal kettle of a polytetrafluoroethylene liner for hydrothermal reaction, reacting at 130 ℃ for 24 hours, and placing the obtained black precipitate into a vacuum drying oven for drying at 60 ℃ for one night after the obtained black precipitate is clear with deionized water and ethanol for several times, thus obtaining Co@ graphite alkyne.
(2) An appropriate amount of titanium sulfate was added to 50ml of methanol to form a solution having a total concentration of 0.5M, and dissolved by stirring at 60 ℃. Adding potassium hydroxide to a solution (molar ratio, OH - ：Ti 4+ =4: 1). Stirring at 60deg.C for 4 hr to obtain uniform TiO 2 A solution.
(3) To TiO 2 Co@ graphite alkyne is slowly added dropwise into the solution and dispersed in 10ml of methanol solution (molar ratio, co@ graphite alkyne: znO=0.1:1), and stirring is continued for 1h at 60 ℃ to obtain Co@ graphite alkyne doped TiO 2 A solution.
(4) Spraying the solution on the treated ITO by a spin coater after the solution is cooled, and annealing at 200 ℃ to obtain Co@ graphite alkyne doped TiO 2 Electron transport films of (a) are provided.
Example 4
The positive structure quantum dot light emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the anode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode, an electron transport layer is arranged between the cathode and the quantum dot light emitting layer, a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the anode is arranged on the substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the hole transport layer is a material TFB, the Fe@graphite alkyne doped ZnS nano material is obtained in the method of the material embodiment 1 of the electron transport layer, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 5
The positive structure quantum dot light emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the anode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode, an electron transport layer is arranged between the cathode and the quantum dot light emitting layer, a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the anode is arranged on the substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the hole transport layer is a material TFB, the Pt@ graphite alkyne doped ZnO nano material is obtained in the method of the material embodiment 2 of the electron transport layer, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 6
A positive structure quantum dot light emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the anode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode and is arranged between the cathode and the quantumAn electron transport layer between the dot light emitting layers, a hole transport layer disposed between the anode and the quantum dot light emitting layers, and the anode disposed 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 Co@ graphite alkyne doped TiO obtained by the method of embodiment 3 2 Annealing the nano material at 250 ℃ to prepare an electron transport layer, wherein the cathode is made of Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 7
The quantum dot light emitting diode with the inversion structure comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the cathode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode, an electron transport layer is arranged between the cathode and the quantum dot light emitting layer, a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the anode is arranged on the substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the hole transport layer is a material TFB, the Fe@graphite alkyne doped ZnS nano material is obtained in the method of the material embodiment 1 of the electron transport layer, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 8
The quantum dot light emitting diode with the inversion structure comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the anode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode, an electron transport layer is arranged between the cathode and the quantum dot light emitting layer, a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the anode is arranged on the substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the hole transport layer is a material TFB, the Pt@ graphite alkyne doped ZnO nano material is obtained in the method of the material embodiment 2 of the electron transport layer, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS as luminescent layer material, wherein 0 < X < 1。
Example 9
The quantum dot light emitting diode with the inversion structure comprises a laminated structure of an anode and a cathode which are oppositely arranged, wherein the anode is arranged on a substrate, a quantum dot light emitting layer is arranged between the anode and the cathode, an electron transport layer is arranged between the cathode and the quantum dot light emitting layer, a hole transport layer is 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 Co@ graphite alkyne doped TiO obtained by the method of embodiment 3 2 Annealing the nano material at 250 ℃ to prepare an electron transport layer, wherein the cathode is made of Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Comparative example 1
A quantum dot light emitting diode includes a stacked structure of 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, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and the cathode disposed on a substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the material of the hole transport layer is TFB, the material of the electron transport layer is commercial ZnS material, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Comparative example 2
A quantum dot light emitting diode includes a stacked structure of 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, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and the cathode disposed on a substrate. Wherein, the material of the substrate is a glass sheet, the material of the anode is an ITO substrate, the material of the hole transport layer is TFB, the material of the electron transport layer is a commercial ZnO material, and the material of the cathode is Al; with blue light quantum dots Cd X Zn 1-X S/ZnS as light-emitting layerThe material, wherein 0 < X < 1.
Comparative example 3
A quantum dot light emitting diode includes a stacked structure of 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, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and the cathode disposed on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO base plate, the hole transport layer is made of TFB, and the electron transport layer is made of commercial TiO 2 The cathode is made of Al; with blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Furthermore, in order to verify the progress of the electron transport film and the quantum dot light emitting diode prepared by the embodiment of the invention, the embodiment of the invention performs performance test.
The performance test of the electron transport films prepared in examples 1-3, the electron transport films in comparative examples 1-3, the quantum dot light emitting diodes prepared in examples 4-9 and comparative examples 1-3 is carried out according to the following test indexes and test methods:
(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 Limiting Current (SCLC) area in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)ε r ε 0 μ e V 2 /d 3 the method comprises the steps of carrying out a first treatment on the surface of the Wherein J represents current density in mAcm -2 ；ε r Represent relative dielectric constant, ε 0 Represents the vacuum dielectric constant; mu (mu) e Expressed in electron mobility in cm 2 V -1 s -1 The method comprises the steps of carrying out a first treatment on the surface of the V represents a driving voltage, unit V; d represents film thickness, unit m.
(2) Resistivity: the same resistivity test instrument is used for measuring the resistivity of the electron transport film.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
And (3) injection: 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 a 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
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From the above test results, it is clear that the electron transport films of the metallized graphite alkyne-doped metal compounds prepared in examples 1 to 3 of the present invention have a resistivity significantly lower than that of the electron transport films of the metal compound nanomaterial in comparative examples 1 to 3, and an electron mobility significantly higher than that of the electron transport films of the metal compound nanomaterial in comparative examples 1 to 3.
The external quantum efficiency of the quantum dot light emitting diode (the electron transport layer material is the metallized graphite alkyne doped metal compound) prepared in the embodiment 4-9 of the invention is obviously higher than that of the quantum dot light emitting diode of the comparative example 1-3, which shows that the quantum dot light emitting diode obtained in the embodiment 4-9 has better light emitting efficiency.
It is worth noting that the specific embodiments provided by the invention all use blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of the light emitting layer, is based on a blue light emitting system, uses more systems (in addition, the light emitting diode based on blue light quantum dots is relatively difficult to manufacture and has more reference value), and does not represent that the invention is only used for the blue light emitting system.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (12)
1. A method of preparing a composite material, comprising the steps of:
obtaining a mixed solution of graphite alkyne and first metal salt, mixing a reducing agent with the mixed solution, and performing hydrothermal reaction to obtain metallized graphite alkyne; wherein the first metal salt is selected from at least one of ferric salt, cobalt salt and platinum salt;
obtaining a metal compound solution and an organic solution of metallized graphite alkyne, mixing the organic solution of metallized graphite alkyne with the metal compound solution, and obtaining a composite material of the metallized graphite alkyne doped metal compound through the adsorption between metal atoms in the metallized graphite alkyne and metal atoms in the metal compound;
Wherein the step of obtaining a metal compound solution comprises: mixing and dissolving a second metal salt and an alkaline substance or a sulfur source in a first organic solvent to obtain a metal compound solution; the second metal salt is selected from at least one of zinc salt, titanium salt and tin salt.
2. The method of preparing a composite material according to claim 1, wherein the step of mixing a reducing agent with the mixed solution and then performing a hydrothermal reaction comprises: mixing the reducer with the mixed solution, mixing the mixed solution for 18 to 24 hours at the temperature of 130 to 150 ℃, and separating to obtain the metallized graphite alkyne.
3. The method for producing a composite material according to claim 1 or 2, wherein the concentration of the first metal salt in the mixed solution is 0.2 to 1mol/L; and/or the number of the groups of groups,
in the mixed solution, the mole ratio of the graphite alkyne to the first metal ion is 1: (0.05-0.2); and/or the number of the groups of groups,
in a system obtained by mixing a reducing agent with the mixed solution, the mol ratio of the first metal ions to the reducing agent is 1: (0.2 to 0.5); and/or the number of the groups of groups,
the reducing agent is selected from: at least one of sodium borohydride and hydrazine hydrate.
4. The method of preparing a composite material according to claim 1, wherein the step of obtaining a metal compound solution comprises: under the condition of 60-90 ℃, mixing and dissolving second metal salt and alkaline substances or sulfur sources in a first organic solvent, and then mixing and treating for 4-6 hours to obtain a metal compound solution; and/or the number of the groups of groups,
The step of mixing the organic solution of the metallized graphite alkyne with the metal compound solution comprises the following steps: and adding the organic solution of the metallized graphite alkyne into the metal compound solution under the stirring condition of 60-80 ℃, reacting for 1-2 hours, and separating to obtain the composite material of the metallized graphite alkyne doped metal compound.
5. The method for preparing a composite material according to claim 4, wherein the second metal salt and the alkaline substance are mixed and dissolved in the system after the first organic solvent, and the pH value is 12-13; and/or the number of the groups of groups,
mixing and dissolving a second metal salt and an alkaline substance in a system after the first organic solvent, wherein the molar ratio of the second metal ion to the alkaline substance is 1: (1.8-4.5); or alternatively
Mixing and dissolving a second metal salt and a sulfur source in a system after the first organic solvent, wherein the molar ratio of the second metal ion to the sulfur source is 1: (1-1.5); and/or the number of the groups of groups,
adding the organic solution of the metallized graphite alkyne into a system after the metal compound solution, wherein the mol ratio of the metallized graphite alkyne to the metal compound is (0.1-0.3): 1.
6. the method for preparing a composite material according to claim 5, wherein the second metal ion is zinc ion, and the molar ratio of the second metal ion to the alkaline substance is 1: (1.8-3); or (b)
The second metal ion is at least one of titanium ion and tin ion, and the molar ratio of the second metal ion to the alkaline substance is 1: (3-4.5).
7. A process for preparing a composite material as claimed in any one of claims 4 to 6,
the alkaline substance is selected from: at least one of ammonia water, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine and ethylenediamine; and/or the number of the groups of groups,
the sulfur source is selected from: at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; and/or the number of the groups of groups,
the first organic solvent is selected from: at least one of isopropanol, ethanol, propanol, butanol, and methanol; and/or the number of the groups of groups,
the organic solvent in the organic solution of the metallized graphite alkyne is selected from the group consisting of: at least one of isopropanol, ethanol, propanol, butanol, and methanol.
8. The method of preparing a composite material according to claim 7, wherein the zinc salt is selected from the group consisting of: at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate; and/or the number of the groups of groups,
the titanium salt is selected from: at least one of titanium nitrate, titanium chloride, titanium sulfate and titanium bromide; and/or the number of the groups of groups,
The tin salt is selected from: at least one of tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate and tin propane sulfonate.
9. A composite material obtainable by the process of any one of claims 1 to 8, wherein the composite material comprises: metallized graphite alkyne and metal compound bonded to the metallized graphite alkyne;
wherein the metallized graphite alkyne comprises graphite alkyne and first metal atoms bonded to the graphite alkyne; the first metal atom is selected from at least one of iron atom, cobalt atom and platinum atom; the metal compound includes: at least one of zinc oxide, titanium oxide, tin oxide, zinc sulfide, titanium sulfide, and tin sulfide.
10. The composite material of claim 9, wherein the composite material comprises,
in the composite material, the molar ratio of the metallized graphite alkyne to the metal compound is (0.1-0.3): 1.
11. the composite material of claim 10, wherein in the metallized graphite alkyne, the molar ratio of the graphite alkyne to the first metal atom is 1: (0.05-0.2).
12. A light emitting device comprising an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, and an electron transport layer disposed between the cathode and the quantum dot light emitting layer;
The electron transport layer comprises a composite material prepared according to the method of any one of claims 1 to 8 or comprises a composite material according to any one of claims 9 to 11.
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