CN113707777A - Composite material, preparation method thereof and light-emitting device - Google Patents
Composite material, preparation method thereof and light-emitting device Download PDFInfo
- Publication number
- CN113707777A CN113707777A CN202010434605.7A CN202010434605A CN113707777A CN 113707777 A CN113707777 A CN 113707777A CN 202010434605 A CN202010434605 A CN 202010434605A CN 113707777 A CN113707777 A CN 113707777A
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- Prior art keywords
- gas
- metallized
- metal
- composite material
- metal compound
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 112
- 239000000243 solution Substances 0.000 claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 claims abstract description 77
- 239000002184 metal Substances 0.000 claims abstract description 77
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000002096 quantum dot Substances 0.000 claims description 77
- 229910021645 metal ion Inorganic materials 0.000 claims description 59
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 47
- -1 amine sulfide Chemical class 0.000 claims description 37
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000011787 zinc oxide Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 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
- 238000003756 stirring Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-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
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-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
- 150000002505 iron 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
- 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
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 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
- 229910052697 platinum Inorganic materials 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 55
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- 230000006798 recombination Effects 0.000 abstract description 9
- 238000005215 recombination Methods 0.000 abstract description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
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- 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
- H01L33/14—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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
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- 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
- H01L33/0083—Processes for devices with an active region comprising only II-VI compounds
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table
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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 graphyne and a first metal salt, mixing a reducing agent with the mixed solution, and then carrying out hydrothermal reaction to obtain metallized graphyne; obtaining a metal compound solution and an organic solution of metallized graphdiyne, and mixing the organic solution of metallized graphdiyne with the metal compound solution to obtain the metallized graphdiyne doped metal compound composite material. The preparation method of the composite material provided by the invention is simple to operate, is suitable for industrial large-scale production and application functions, and the metallized graphite alkyne-doped metal compound composite material improves the electron transport capability of an electron transport layer, promotes the effective recombination of electrons and holes in a luminescent layer, reduces the influence of exciton accumulation on the performance of a device, and further improves the photoelectric performance of the luminescent 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, people can realize the required light emission with specific wavelength by regulating and controlling the size of the quantum dots, and the tuning range of the light emission wavelength 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 recombined in a light emitting layer to form excitons for light emission.
In recent years, inorganic semiconductors have been studied as an electron transport layer in a relatively hot manner. Semiconductor materials such as nano ZnO, ZnS and the like are wide bandgap semiconductor materials, and attract the attention 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 forbidden band of 3.37eV and a low work function of 3.7eV, and the structural characteristics of the energy band determine that ZnO can be used as a proper electron transport layer material. In addition, ZnS is a II-VI semiconductor material, has two different structures of sphalerite and wurtzite, and has the characteristics of stable chemical property of forbidden bandwidth (3.62eV), abundant resources, low price and the like. Therefore, in the last ten years, ZnO, ZnS II-VI and other conductor nano materials have shown great development potential in the research of fields such as photocatalysis, sensors, transparent electrodes, fluorescent probes, diodes, solar cells, lasers and the like.
At present, ZnO, ZnS and other semiconductor materials are poor in crystallinity, and a large number of active groups and surface defect states exist on the surface, so that loss of photocurrent is easily caused, and the performance of a device is reduced; meanwhile, the active groups can also cause bonding effect among the nanoparticles, which not only causes agglomeration among the particles to influence the dispersibility of the nanoparticles, but also reduces the injection efficiency of electrons and influences the electron and hole recombination efficiency in the quantum dot light-emitting layer. Therefore, the application performance of the semiconductor materials such as ZnO, ZnS and the like in the electron transport layer of the photoelectric device needs to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a composite material, aiming at improving the electron transmission performance of the existing semiconductor materials such as ZnO, ZnS and the like to a certain extent and improving 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 purpose of the invention, the technical scheme adopted by the invention is as follows:
a method of making a composite material comprising the steps of:
obtaining a mixed solution of graphyne and a first metal salt, mixing a reducing agent with the mixed solution, and then carrying out hydrothermal reaction to obtain metallized graphyne;
obtaining a metal compound solution and an organic solution of metallized graphdiyne, and mixing the organic solution of metallized graphdiyne with the metal compound solution to obtain the metallized graphdiyne doped metal compound composite material.
Accordingly, a composite material comprising: a metallized graphdiyne and a metal compound bonded to the metallized graphdiyne.
Correspondingly, the light-emitting device 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 electronic function layer arranged between the cathode and the quantum dot light-emitting layer; the electronic functional layer comprises a composite material prepared as described above, or comprises a composite material as described above.
Firstly, mixing a reducing agent with the mixed solution, and then carrying out hydrothermal reaction to obtain the metallized graphdiyne doped with metal atoms. Reducing the first metal ions into first metal atoms by a reducing agent, doping the first metal atoms in the graphyne material, and transferring electrons to sp of the graphyne through outer-layer electrons rich in the metal atoms2And n-type doping is formed on the benzene ring, so that the electron transmission performance of the graphdiyne is improved. Then, after obtaining a metal compound solution, mixing the organic solution of the metallized graphdiyne with the metal compound solution for treatment, and obtaining the metallized stone through stronger adsorption between metal atoms in the metallized graphdiyne and metal atoms in the metal compoundA composite of an inkyne doped with a metal compound. According to the composite material prepared by the invention, on one hand, the metallized graphdiyne provides a two-dimensional network structure with a special electronic structure and a hole structure for the metal compound, so that the metal compound is effectively prevented from agglomerating in the application process, and the stability of an electron transmission film is improved; on the other hand, through the doping of the metallized graphdiyne, the hybridization effect between the pz orbit of the graphdiyne and the 3d orbit of metal ions in the metal compound is realized, the electronic interaction can be generated between the graphdiyne and the metal compound, and the electronic transmission capability of the composite material is improved. On the other hand, in the metallized graphdiyne doped metal compound composite material, the work function of the graphdiyne is about 5.0eV and is between the electrode and an electron transport material such as a metal compound and the like, 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 effective recombination of electron-hole in the luminescent layer is promoted, and the influence of exciton accumulation on the performance of the device is reduced, so that the photoelectric performance of the luminescent device is improved.
The present invention provides a composite material comprising: the metallized graphite alkyne is a graphite alkyne material combined with metal atoms and has a special electronic structure and a two-dimensional network structure with a hole structure, so that the agglomeration of the metal compound in the application process is effectively prevented, and the stability of the electron transmission film is improved. In addition, the metal compound is combined on the metallized graphdiyne, so that the hybridization between the pz orbit of the graphdiyne and the 3d orbit of metal ions in the metal compound is realized, the electronic interaction can be generated between the graphdiyne and the metal compound, and the electronic transmission capability of the composite material is improved. In addition, in the composite material of the metallized graphdiyne doped metal compound, the work function of the graphdiyne is about 5.0eV, and the work function is between an electrode and an electron transport material such as the metal compound, so that the transport barrier of electrons is reduced, the energy level matching of an electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer is improved, the effective recombination of electron-hole in a luminescent layer is promoted, the influence of exciton accumulation on the performance of the device is reduced, and the photoelectric performance of the luminescent 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 metal compound. Therefore, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capability 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 light-emitting device of a positive type configuration according to an embodiment of the present invention.
Fig. 3 is an inverted light emitting device according to an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present 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.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a composite material, including the following steps:
s10, obtaining a mixed solution of graphite alkyne and a first metal salt, mixing a reducing agent with the mixed solution, and then carrying out hydrothermal reaction to obtain metallized graphite alkyne;
s20, obtaining a metal compound solution and an organic solution of metallized graphdiyne, and mixing the organic solution of metallized graphdiyne with the metal compound solution to obtain the metallized graphdiyne doped metal compound composite material.
According to the preparation method of the composite material provided by the embodiment of the invention, firstly, a reducing agent and a mixed solution are mixed and then subjected to hydrothermal reaction to obtain the metallized grapyne doped with metal atoms. Reducing the first metal ions into first metal atoms by a reducing agent, doping the first metal atoms in the graphyne material, and transferring electrons to sp of the graphyne through outer-layer electrons rich in the metal atoms2And n-type doping is formed on the benzene ring, so that the electron transmission performance of the graphdiyne is improved. Then, after obtaining the metal compound solution, mixing the organic solution of the metallized graphdiyne with the metal compound solution, and obtaining the metallized graphdiyne doped metal compound composite material through stronger adsorption between metal atoms in the metallized graphdiyne and metal atoms in the metal compound. According to the composite material prepared by the embodiment of the invention, on one hand, the metallized graphdiyne provides a two-dimensional network structure with a special electronic structure and a hole structure for the metal compound, so that the metal compound is effectively prevented from being agglomerated in the application process, and the stability of an electron transmission film is improved; on the other hand, the hybridization between the pz orbit of the graphyne and the 3d orbit of the metal ion in the metal compound is realized by doping the metallized graphyne, and the product can be produced between the graphyne and the metal compoundThe electron generation interaction improves the electron transmission capability of the composite material. On the other hand, in the metallized graphdiyne doped metal compound composite material, the work function of the graphdiyne is about 5.0eV and is between the electrode and an electron transport material such as a metal compound and the like, 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 effective recombination of electron-hole in the luminescent layer is promoted, and the influence of exciton accumulation on the performance of the device is reduced, so that the photoelectric performance of the luminescent device is improved.
Specifically, in the above example S10, a mixed solution of graphyne and the first metal salt was obtained, and a reducing agent was mixed with the mixed solution and subjected to a hydrothermal reaction, thereby obtaining a metallized graphyne. According to the embodiment of the invention, a reducing agent and a mixed solution are mixed and then subjected to hydrothermal reaction, first metal ions are reduced into first metal atoms through the reducing agent and doped in a graphite alkyne material, and electrons are transferred to sp of the graphite alkyne through outer-layer electrons rich in the metal atoms2And n-type doping is formed on the benzene ring, so that the electron transmission performance of the graphdiyne is improved. Meanwhile, the graphite alkyne doped with the first metal atom has stronger adsorption effect with 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 favorable for obtaining the composite material by doping the metal compound with the metallized graphite alkyne.
The present invention has the structure represented by sp and sp2A novel carbon allotrope-graphite alkyne formed by hybridization is used as a base material, and is a two-dimensional plane hyperconjugated structure which is formed by conjugating and connecting benzene rings by 1, 3-diyne bonds and has rich carbon chemical bonds and a huge conjugated system, thereby not only becoming a good electron acceptor due to the huge highly conjugated structure, but also having good electron donating property due to the self-owned mass of free electrons, and having special electronic structure and hole structure, excellent chemical and thermal stability, semiconductor performance and other properties. When the metal compound is applied to the composite material, not only an attachment carrier is provided for the metal compound, the dispersion stability of the metal compound is improved, but also the electron transmission performance of the metal compound can be effectively improved, and the electron-hole is promotedEffectively recombine in the luminous layer, thereby improving the photoelectric performance of the luminous device.
In some embodiments, the step of obtaining the mixed solution of the graphdiyne and the first metal salt may include, but is not limited to, dissolving the first metal salt in deionized water, adding the graphdiyne, and stirring to fully disperse the graphdiyne into the solution system to form the mixed solution of the graphdiyne and the first metal salt.
In some embodiments, the molar ratio of graphdine to first metal ion in the mixed solution is 1: (0.05-0.2), the first metal ions in the molar ratio have a good doping metallization effect on the graphyne, and the electron transport performance of the graphyne can be better improved. When the doping molar ratio of the first metal atom is more than 0.2, the first metal ion reacts with a reducing agent added subsequently to form a metal atom, agglomeration is easily formed on the surface of the graphite alkyne, the dispersibility is poor, and the electron transport performance of the graphite alkyne cannot be improved well; when the doping molar ratio of the first metal atoms is less than 0.05, the first metal ions are lost in the reaction process, and effective doping cannot be realized. In a further embodiment, the molar ratio of graphdine to first metal ion in the mixed solution is 1: (0.05-0.15), the molar ratio of the graphite alkyne to the first metal ions in the mixed solution has the optimal metallization doping effect on the graphite alkyne, and after the first metal ions are reduced into first metal atoms by a reducing agent and doped in the graphite alkyne material, the graphite alkyne and the metal compound have better electronic interaction, so that the electronic transmission capability of the composite material is improved. In some embodiments, the molar ratio of graphdiyne to first metal ion in the mixed solution may 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 sufficiently ensures the content of the first metal ions in the mixed solution, so that the first metal ions are sufficiently adsorbed in the graphite alkyne, and the subsequent sufficient metallization of the graphite alkyne is facilitated. In some embodiments, the concentration of the first metal salt in the mixed solution is 0.2-1 mol/L; the molar ratio of graphyne 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. In the embodiment of the invention, the first metal salt is at least one transition metal salt selected from iron salt, cobalt salt and platinum salt, and after the transition metal salts are reduced by a reducing agent, the obtained transition metal atoms can be very firmly adsorbed on vacant sites of alkyne rings of graphite, and stable structures can be formed between alkyne chains of graphite alkyne through bonding with sp hybridized carbon on two adjacent alkyne chains. And, these transition metal atoms have rich outer electrons by transferring external electrons to sp of graphyne2And n-type doping is formed on the benzene ring, so that the electron transmission performance of the graphdiyne can be effectively improved.
In some embodiments, the step of mixing the reducing agent with the mixed solution and then performing the hydrothermal reaction includes: and mixing the reducing agent with the mixed solution, mixing for 18-24 hours at the temperature of 130-150 ℃, and separating to obtain the metallized graphdiyne. According to the embodiment of the invention, the first metal ions are fully reduced into the first metal atoms doped in the graphdiyne material by the reducing agent after mixing treatment for 18-24 hours at the temperature of 130-150 ℃, the first metal ions have the optimal reduction rate under the reaction condition, so that the reduced metal atoms are uniformly doped in the graphdiyne to obtain the metallized graphdiyne, and the problem that the metal atoms are aggregated into larger particles due to the excessively high reduction rate of the first metal ions and the graphdiyne cannot be effectively doped is avoided.
In some embodiments, in the system after the reducing agent is mixed with the mixed solution, the molar ratio of the first metal ion to the reducing agent is 1: (0.2-0.5). When the molar ratio of the first metal ions to the reducing agent is less than 1:0.2, the reduction effect on the first metal ions is poor, and the doping effect of metal atoms on the graphdiyne is influenced; when the molar ratio of the first metal ion to the reducing agent is less than 1:0.5, the reducing agent is excessive, resulting in waste of raw materials and difficulty in removal in subsequent cleaning. Therefore, the molar ratio of the first metal ion to the reducing agent is controlled to be 1: (0.2-0.5) is most preferable.
In some embodiments, the reducing agent is selected from: and at least one of sodium borohydride and hydrazine hydrate, wherein the reducing agents have better reduction characteristics on the first metal salt in the hydrothermal reaction, so that the first metal ions are reduced into metal atoms and combined on the graphite alkyne, and the metallized graphite alkyne material is obtained.
Specifically, in step S20, a metal compound solution and an organic solution of the metalized graphine alkyne are obtained, and the organic solution of the metalized graphine alkyne and the metal compound solution are mixed to obtain the composite material of the metalized graphine alkyne-doped metal compound. After the metal compound solution and the organic solution of the metallized graphdiyne are obtained, the organic solution of the metallized graphdiyne and the metal compound solution are mixed, and the composite material of the metallized graphdiyne doped metal compound is obtained through the strong adsorption effect between the metal atoms in the metallized graphdiyne and the metal atoms in the metal compound. The composite material has good dispersion stability, realizes the hybridization between the pz orbit of the graphite alkyne and the 3d orbit of metal ions in a metal compound by doping the metallized graphite alkyne, can generate electronic interaction between the graphite alkyne and the metal compound, and improves the electronic transmission capability of the composite material. And the graphdiyne can reduce the transmission barrier of electrons, is beneficial to the energy level matching of the electron transmission layer and an electrode, improves the electron transmission capability of the 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 the light-emitting device.
In some embodiments, the step of obtaining a metal compound solution comprises: and mixing and dissolving a second metal salt and an alkaline substance or a sulfur source in a first organic solvent at the temperature of 60-90 ℃, and then mixing and treating for 4-6 hours to obtain a metal compound solution. In the embodiment of the invention, under the condition that the temperature is 60-90 ℃, the second metal salt and the alkaline substance or the sulfur source are mixed and dissolved in the first organic solvent, then the mixture is treated for 4-6 hours, the second metal salt and the alkaline substance react to generate hydroxide, then the condensation polymerization reaction is carried out, and the second metal oxide is generated by dehydration, or the second metal salt and the sulfur source react to generate the second metal sulfide. After the reaction or cooling, a metal compound of the second metal oxide or the second metal sulfide is precipitated by using weak polar and nonpolar solvents such as ethyl acetate, heptane, octane and the like as a precipitating agent, and the metal compound solution is obtained by washing and extracting for many times. The metal compound solution can be directly used for subsequent reaction with the metallized graphdine without drying, and if the metal compound is dried, some active groups on the surface of the material can be damaged, so that the subsequent doping combination reaction with the metallized graphdine is not facilitated.
In some embodiments, the second metal salt and the alkaline substance are mixed and dissolved in the first organic solvent, and the pH value is 12-13. In some embodiments, the second metal salt and the alkaline substance are mixed and dissolved in 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, and the molar ratio of the second metal ion to the basic species is 1: (1.8-3). In some embodiments, the second metal ion is a tetravalent metal ion, and the molar ratio of the second metal ion to the basic species is 1: (3-4.5). In the embodiment of the invention, the second metal salt and the alkaline substance react to prepare the metal compound of the second metal oxide, 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, when the H value in the system is less 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 more than 12, the pH value is too high, so that the hydrolysis and polycondensation speed of the sol in the system is reduced, and the preparation of the second metal oxide semiconductor material is not facilitated. Similarly, when the second metal ion is Zn2+When the divalent metal is equal, the molar ratio of the second metal ion to the basic substance is 1: (1.8-3) when the second metal ion is Ti4+、Sn4+When the tetravalent metal is used, the mole ratio of the second metal ions to the alkaline substance is 1: (3-4.5), if the alkaline substance is excessive, the hydrolysis and polycondensation speed of the sol in the system can be reduced, and the preparation of the second metal oxide semiconductor material is not facilitated; if the amount of the alkaline substance is too small, the amount of the second metal salt is excessive, and the reaction is not sufficient。
In some embodiments, the second metal salt and the sulfur source are mixed and dissolved in the first organic solvent, and the molar ratio of the second metal ion to the sulfur source is 1: (1-1.5). In the embodiment of the invention, a second metal salt and a sulfur source react to prepare a metal compound of a second metal sulfide, and the molar ratio of a second metal ion to the sulfur source is 1: (1-1.5), the method is favorable for preparing the second metal sulfide semiconductor material with small and uniform particle size, and when the molar ratio of the second metal ions to the sulfur source is less than 1:1, excessive zinc salt and less sulfur source are generated, so that the zinc sulfide is not sufficiently generated; 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, and the impurity compound is easily formed and is not easily removed.
In some embodiments, the step of treating the organic solution of metallized graphdine in combination with the metal compound solution comprises: and adding the organic solution of the metallized graphdiyne into the metal compound solution under the stirring condition of the temperature of 60-80 ℃, reacting for 1-2 hours, and separating to obtain the metallized graphdiyne doped metal compound composite material. In the embodiment of the invention, under the stirring condition of the temperature of 60-80 ℃, after the organic solution of the metallized graphdine is added into the metal compound solution in a dropping mode or the like, the added metallized graphdine can be rapidly and uniformly combined with the metal compound, and the composite material of the metallized graphdine doped metal compound is obtained through the stronger adsorption action between the metal atoms in the metallized graphdine and the metal atoms in the metal compound. The metallized graphdiyne provides a two-dimensional network structure with a special electronic structure and a hole structure for the metal compound, effectively prevents the metal compound from agglomerating in the application process, and improves the stability of the electron transmission film. Meanwhile, through the doping of the metallized graphdiyne, the hybridization effect between the pz orbit of the graphdiyne and the 3d orbit of metal ions in the metal compound is realized, the electronic interaction can be generated between the metallized graphdiyne and the metal compound, and the electronic transmission capability of the metal compound is improved.
In some embodiments, the organic solution of the metallized graphdine is added to the system after the metal compound solution is added dropwise, and the molar ratio of the metallized graphdine to the metal compound is (0.1-0.3): 1. when the molar ratio of the metallized graphdine to the metal compound is less than 0.1:1, the metal compound is excessive, the metal compound cannot be well dispersed, and the improvement effect on the conductivity is small; when the molar ratio of the metallized graphdine to the metal compound is greater than 0.3:1, excessive metallized graphdine can not generate hybridization with metal ions in the gold nano material, and the electronic transmission performance of the composite transmission material is not obviously improved. In some embodiments, the molar ratio of metallized graphdiyne to metal compound may be 0.1:1, 0.15:1, 0.2:1, 0.25:1, or 0.3:1, and the like.
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 adopted in the embodiment of the invention can react with alkaline substances or sulfur sources to generate metal compounds with electron transport characteristics.
In some embodiments, the alkaline material is selected from: at least one of ammonia water, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine and ethylenediamine, wherein the alkaline substances can react with a second metal salt such as zinc salt, titanium salt, tin salt and the like to generate hydroxide, and then the hydroxide is subjected to 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, wherein the sulfur source can react with a second metal salt 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: the organic solvents have better solubility to the second metal salt, the alkaline substance and the sulfur source, 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 the metallized graphdine is selected from the group consisting of: the organic solvents have good dispersion characteristics on the metallized graphite alkyne, and are beneficial to mutual doping reaction between the metallized graphite alkyne and a metal compound, so that the metallized graphite alkyne-doped metal compound composite material is obtained.
Correspondingly, the embodiment of the invention also provides a composite material, which comprises: metallized graphdiynes and metal compounds bound to the metallized graphdiynes.
The composite material provided by the embodiment of the invention comprises: the metallized graphdiyne is a graphdiyne material combined with metal atoms and has a special two-dimensional network structure with an electronic structure and a hole structure, so that the agglomeration of the metal compound in the application process is effectively prevented, and the stability of the electron transmission film is improved. In addition, the metal compound is combined on the metallized graphdiyne, so that the hybridization between the pz orbit of the graphdiyne and the 3d orbit of metal ions in the metal compound is realized, the electronic interaction can be generated between the graphdiyne and the metal compound, and the electronic transmission capability of the composite material is improved. In addition, in the composite material of the metallized graphdiyne doped metal compound, the work function of the graphdiyne is about 5.0eV, and the work function is between an electrode and an electron transport material such as the metal compound, so that the transport barrier of electrons is reduced, the energy level matching of an electron transport layer and the electrode is facilitated, the electron transport capacity of the electron transport layer is improved, the effective recombination of electron-hole in a luminescent layer is promoted, the influence of exciton accumulation on the performance of the device is reduced, and the photoelectric performance of the luminescent device is improved.
In some embodiments, the composite material comprises a metallized graphdiyne comprising a graphdiyne and a first metal atom bonded to the graphdiyne, and a metal compound bonded to the metallized graphdiyne, wherein the molar ratio of graphdiyne to first metal ion in the metallized graphdiyne is 1: (0.05-0.2).
In some embodiments, the first metal ion bound to the graphdine is selected from: at least one of iron ions, cobalt ions and platinum ions.
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 graphdine to metal compound is (0.1-0.3): 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 transmission 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 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 materials such as metal compounds. Therefore, the energy level matching of the electron transport layer and the electrode is facilitated, the electron transport capability 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, light emitting devices of embodiments of the present invention are divided into positive and negative structures.
In one embodiment, a light emitting device of a positive type structure includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, and the anode is disposed on a substrate. Further, a hole functional layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the light-emitting layer; an electron-transporting layer, an electron-injecting layer, a hole-blocking layer, and other electron-functional layers may also be provided between the cathode and the light-emitting layer, as shown in fig. 2. In some embodiments of positive-type structure devices, a 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 inversion 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. Further, a hole functional layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the light-emitting layer; an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer may be further provided between the cathode and the light emitting layer, as shown in fig. 3. In some embodiments of the device having an inverted structure, 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 or ZTO, etc.;
the hole injection layer includes PEODT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid)), WoO3、MoO3、NiO、V2O5HATCN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene), CuS, etc.;
the hole transport layer can be a micromolecular organic matter or a macromolecule conducting polymer, and comprises the following components: 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), peot: PSS, MoO3、WoO3、NiO、CuO、V2O5CuS, and the like or a mixture of any combination thereof, and can also be other high-performance hole transport materials.
The luminescent layer is a quantum dot luminescent layer, wherein the quantum dot is one of red, green and blue. Including but not limited to: at least one of the semiconductor compounds of II-IV group, II-VI group, II-V group, III-VI group, IV-VI group, I-III-VI group, II-IV-VI group and II-IV-V group of the periodic table of the elements, or at least two of the semiconductor compounds. In some embodiments, the quantum dot light emitting layer material is selected from: at least one semiconductor nanocrystal compound of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe and CdZnSe, or at least two semiconductor nanocrystal compounds with mixed type, gradient mixed type, core-shell structure type or combined type structures. In other embodiments, the quantum dot light emitting layer material is selected from: at least one semiconductor nanocrystal compound of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe and ZnCdSe, or a semiconductor nanocrystal compound with a mixed type, a gradient mixed type, a core-shell structure type or a combined type of at least two components. In other embodiments, the quantum dot light emitting layer material is selected from: at least one of a perovskite nanoparticle material (in particular a luminescent perovskite nanoparticle material), a metal nanoparticle material, a metal oxide nanoparticle material. The quantum dot materials have the characteristics of quantum dots, and have good photoelectric properties;
the electron transport layer comprises the composite material;
the cathode includes: al, Ag, Au, Cu, Mo, or an alloy thereof.
In some embodiments, the fabrication of a light emitting device of 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 light-emitting layer on the hole transport layer;
and S60, finally depositing an electron transmission layer on the quantum dot light-emitting layer, and depositing a cathode on the electron transmission layer to obtain the light-emitting device.
In some embodiments, in step S30, in order to obtain a high-quality zinc oxide nanomaterial film, the ITO substrate needs to undergo a pretreatment process. The specific treatment steps of the substrate comprise: and cleaning the ITO conductive glass with a cleaning agent to primarily remove stains on the surface, then 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 anode.
In some embodiments, in step S40, the step of growing the hole transport layer includes: depositing a prepared solution of the hole transport material on an ITO substrate to form a film in modes of spin coating and the like; the film thickness is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then a thermal annealing process is performed at an appropriate temperature.
In some embodiments, the step of depositing the quantum dot light-emitting layer on the hole transport layer in step S50 includes: and depositing the prepared luminescent material solution with a certain concentration on the hole transport layer in a spin coating mode and other modes, controlling the thickness of the luminescent layer to be about 20-60 nm by adjusting the concentration of the solution, the spin coating speed and the spin coating time, and drying at a proper temperature to form the quantum dot luminescent layer.
In some embodiments, the step of depositing an electron transport layer on the quantum dot light emitting layer in step S60 includes: the electron transmission layer is a zinc oxide nano material (a/c-ZnO) film with a mixed crystalline phase and an amorphous phase, a prepared zinc oxide composite material solution with a certain concentration is deposited on the quantum dot light emitting layer in a spin coating mode and other modes, the thickness of the electron transmission layer is controlled by adjusting the concentration of the solution, the spin coating speed (preferably, the rotating speed is 2000-6000 rpm) and the spin coating time to be about 20-60 nm, and then the electron transmission layer film is formed by annealing at the temperature of 200-250 ℃.
In some embodiments, in step S60, the step of preparing the cathode includes: the substrate deposited with the functional layers 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 Cu wire is used, so that a carrier can be smoothly injected due to the small resistance.
Further, the obtained photoelectric device is subjected to packaging treatment, and the packaging treatment can adopt common machine packaging or manual packaging. Preferably, the oxygen content and the water content are both lower than 0.1ppm in the packaging treatment environment to ensure the stability of the device.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the advanced performance of the composite material, the preparation method thereof and the photoelectric device of the embodiments of the present invention obviously manifest, the above technical solutions are exemplified by a plurality of embodiments.
Example 1
An Fe @ graphite alkyne-doped ZnS electron transport film comprises the following steps:
firstly, dissolving a proper amount of ferric chloride in 30ml of deionized water to form a solution with the total concentration of 0.5M, adding the graphdiyne, and uniformly stirring (molar ratio, C: Fe)3+1: 0.2). Adding sodium borohydride solution (molar ratio, Fe)3+Sodium borohydride is 1:0.5), then the mixture is poured into a hydrothermal kettle with a polytetrafluoroethylene inner container for hydrothermal reaction, the mixture is reacted for 24 hours at 150 ℃, obtained black precipitates are clarified by deionized water and ethanol for a plurality of times, and then the black precipitates are placed into a vacuum drying oven to be dried for one night at 60 ℃ to obtain Fe @ graphite alkyne.
② adding proper amount of zinc chloride into 50ml of ethanol to form solution with total concentration of 0.5M, stirring and dissolving at 70 ℃. A solution of sodium sulfide dissolved in 10ml of ethanol (molar ratio, S) was added2-：Zn2+1.2: 1). Stirring was continued at 70 ℃ for 4h to give a homogeneous ZnS solution.
And thirdly, slowly dripping Fe @ graphite alkyne into the ZnS solution, dispersing the Fe @ graphite alkyne in 10ml of ethanol solution (the molar ratio of Fe @ graphite alkyne: ZnS is 0.2:1), and continuously stirring at 70 ℃ for 1.5h to obtain the Fe @ graphite alkyne doped ZnS solution.
Fourthly, after the solution is cooled, depositing on the processed ITO by a spin coater and annealing at 200 ℃ to obtain the Fe @ graphite alkyne doped ZnS electron transport film.
Example 2
A Pt @ graphite alkyne-doped ZnO electron transport film comprises the following steps:
dissolving a proper amount of platinum nitrate in 30ml of deionized water to form a solution with the total concentration of 0.5M, adding the graphdiyne, and uniformly stirring (molar ratio, C: Pt)2+1: 0.05). Sodium borohydride solution (molar ratio, Pt) was added2+: sodium borohydride is 1:0.2), then the obtained solution is poured into a hydrothermal kettle with a polytetrafluoroethylene inner container for hydrothermal reaction, the reaction is carried out for 20 hours at 130 ℃, the obtained black precipitate is clarified by deionized water and ethanol for a plurality of times, and then the obtained black precipitate is placed into a vacuum drying oven for drying at 60 ℃ for one night to obtain Pt @ graphite alkyne.
② adding proper amount of zinc nitrate into 50ml of propanol to form solution with total concentration of 0.5M, stirring and dissolving at 80 ℃. A solution of sodium hydroxide dissolved in 10ml of propanol (molar ratio, OH) was added-：Zn2+2: 1). Stirring was continued at 80 ℃ for 4h to give a homogeneous ZnO solution.
③ slowly dripping Pt @ graphite alkyne into the ZnO solution to disperse in 10ml of propanol solution (molar ratio, Pt @ graphite alkyne: ZnO is 0.3:1), and continuously stirring for 2h at 80 ℃ to obtain the Pt @ graphite alkyne doped ZnO solution.
Fourthly, after the solution is cooled, spin-coating the solution on the treated ITO by a spin coater and annealing the solution at 150 ℃ to obtain the Pt @ graphite alkyne-doped ZnO electron transport film.
Example 3
Co @ graphite alkyne doped TiO2The electron transport film of (1), comprising the steps of:
dissolving a proper amount of platinum nitrate in 30ml of deionized water to form a solution with the total concentration of 0.5M, adding the graphdiyne, and uniformly stirring (molar ratio, C: Co)2+1: 0.1). Adding hydrazine hydrate solution (molar ratio, Co)2+: hydrazine hydrate 1:0.3) and then pouring the mixture into a hydrothermal kettle with a polytetrafluoroethylene inner container for hydrothermal reaction, reacting for 24 hours at 130 ℃, and putting the obtained black precipitate into a vacuum drying oven for drying at 60 ℃ for one night after being clarified by deionized water and ethanol for several times to obtain the Co @ graphite alkyne.
② adding a proper amount of titanium sulfate into 50ml of methanol to form a solution with the total concentration of 0.5M, and stirring and dissolving at 60 ℃. Adding hydrogenSolution of potassium oxide dissolved in 10ml of methanol (molar ratio, OH)-：Ti4+4: 1). Stirring at 60 deg.C for 4 hr to obtain uniform TiO2And (3) solution.
③ to TiO2Slowly dropwise adding Co @ graphite alkyne into the solution, dispersing the Co @ graphite alkyne into 10ml of methanol solution (the molar ratio is Co @ graphite alkyne: ZnO is 0.1:1), and continuously stirring for 1h at 60 ℃ to obtain Co @ graphite alkyne doped TiO2And (3) solution.
Fourthly, after the solution is cooled, the solution is sprayed on the treated ITO by a spin coater and annealed at 200 ℃ to obtain Co @ graphite alkyne doped TiO2The electron transport film of (1).
Example 4
A positive 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission layer is arranged between the anode and the quantum dot light-emitting layer, and the anode is arranged on the substrate. 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 Fe @ graphite alkyne doped ZnS nano material obtained by the method in the embodiment 1, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dot CdXZn1-XS/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 5
A positive 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission layer is arranged between the anode and the quantum dot light-emitting layer, and the anode is arranged on the substrate. 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 the Pt @ graphite alkyne-doped ZnO nanomaterial obtained by the method in the embodiment 2, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; in the amount of blue lightSub-dot CdXZn1-XS/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 6
A positive 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission 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 material, and the electron transport layer is made of TiO doped Co @ graphite alkyne obtained by the method in the embodiment 32The nano material is annealed at the temperature of 250 ℃ to prepare an electron transport layer, and the cathode is made of Al; with blue light quantum dot CdXZn1-XS/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 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission layer is arranged between the anode and the quantum dot light-emitting layer, and the anode is arranged on the substrate. 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 Fe @ graphite alkyne doped ZnS nano material obtained by the method in the embodiment 1, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dot CdXZn1-XS/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 inverse structure comprises 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission layer is arranged between the anode and the quantum dot light-emitting layer, andan anode is disposed on the substrate. 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 the Pt @ graphite alkyne-doped ZnO nanomaterial obtained by the method in the embodiment 2, the electron transport layer is prepared by annealing at 250 ℃, and the material of the cathode is Al; with blue light quantum dot CdXZn1-XS/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Example 9
The quantum dot light-emitting diode comprises 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 transmission layer is arranged between the cathode and the quantum dot light-emitting layer, a hole transmission 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 material, and the electron transport layer is made of TiO doped Co @ graphite alkyne obtained by the method in the embodiment 32The nano material is annealed at the temperature of 250 ℃ to prepare an electron transport layer, and the cathode is made of Al; with blue light quantum dot CdXZn1-XS/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 comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. 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, and the material of the cathode is Al; with blue light quantum dot CdXZn1-XS/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 comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light emitting layer arranged between the anode and the cathode, and a quantum dot light emitting layer arranged on the cathodeAn electron transport layer between the anode and the quantum dot light emitting layer, a hole transport layer disposed between the anode and the quantum dot light emitting layer, and a cathode disposed on the substrate. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of a TFB (thin film transistor), the electron transport layer is made of a commercial ZnO material, and the cathode is made of Al; with blue light quantum dot CdXZn1-XS/ZnS is used as a material of the luminescent layer, wherein X is more than 0 and less than 1.
Comparative example 3
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of commercial TiO2The material of the cathode is Al; with blue light quantum dot CdXZn1-XS/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 advancement of the electron transport film and the quantum dot light emitting diode prepared by the embodiment of the invention, the embodiment of the invention is subjected to performance test.
The performance of the electron transport film prepared in the embodiment 1-3, the electron transport film prepared in the comparative example 1-3, the quantum dot light-emitting diode prepared in the embodiment 4-9 and the comparative example 1-3 is tested, and the test indexes and the test method are as follows:
(1) electron mobility: testing the current density (J) -voltage (V) of the quantum dot light-emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) region in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3(ii) a Wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant;μedenotes the electron mobility in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and resistivity were tested as single layer thin film structure devices, namely: cathode/electron transport film/anode. QLED device for external quantum efficiency test, 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
From the above test results, it can be seen that the electron transport films of the metallized graphdiyne doped metal compounds prepared in examples 1-3 of the present invention have resistivity significantly lower than that of the electron transport films made of the metal compound nanomaterial in comparative examples 1-3, and have electron mobility significantly higher than that of the electron transport films made of the metal compound nanomaterial in comparative examples 1-3.
The external quantum efficiency of the quantum dot light-emitting diodes (the electron transport layer is made of the metallized graphite alkyne doped metal compound) prepared in the embodiments 4 to 9 of the invention is obviously higher than that of the quantum dot light-emitting diodes in the comparative examples 1 to 3, which shows that the quantum dot light-emitting diodes obtained in the embodiments 4 to 9 have better luminous efficiency.
It is noted that the embodiments provided by the present invention all use blue light quantum dots CdXZn1-XS/ZnS as a material for a light-emitting layer isThe blue light emitting system is a system which is used more (besides, the manufacturing of the light emitting diode based on the blue light quantum dot is relatively difficult, so the light emitting diode is of more reference value), and the invention is not only used for the blue light emitting system.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A preparation method of a composite material is characterized by comprising the following steps:
obtaining a mixed solution of graphyne and a first metal salt, mixing a reducing agent with the mixed solution, and then carrying out hydrothermal reaction to obtain metallized graphyne;
obtaining a metal compound solution and an organic solution of metallized graphdiyne, and mixing the organic solution of metallized graphdiyne with the metal compound solution to obtain the metallized graphdiyne doped metal compound composite material.
2. The method for 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: and mixing a reducing agent with the mixed solution, mixing for 18-24 hours at the temperature of 130-150 ℃, and separating to obtain the metallized graphdiyne.
3. The method for preparing the composite material according to claim 1 or 2, wherein the concentration of the first metal salt in the mixed solution is 0.2 to 1 mol/L; and/or the presence of a gas in the gas,
in the mixed solution, the molar ratio of the graphdiyne to the first metal ions is 1: (0.05-0.2); and/or the presence of a gas in the gas,
in a system in which a reducing agent is mixed with the mixed solution, the molar ratio of the first metal ion to the reducing agent is 1: (0.2 to 0.5); and/or the presence of a gas in the gas,
the first metal salt is selected from: at least one of iron salt, cobalt salt and platinum salt; and/or the presence of a gas in the gas,
the reducing agent is selected from: at least one of sodium borohydride and hydrazine hydrate.
4. The method of preparing a composite material of claim 1, wherein the step of obtaining a solution of a metal compound comprises: mixing and dissolving a second metal salt and an alkaline substance or a sulfur source in a first organic solvent at the temperature of 60-90 ℃, and then mixing and treating for 4-6 hours to obtain a metal compound solution; and/or the presence of a gas in the gas,
the step of mixing the organic solution of metallized graphdine with the metal compound solution comprises: and adding the organic solution of the metallized graphdiyne into the metal compound solution under the stirring condition of the temperature of 60-80 ℃, reacting for 1-2 hours, and separating to obtain the composite material of the metallized graphdiyne doped metal compound.
5. The method for preparing the composite material according to claim 4, wherein the second metal salt and the alkaline substance are mixed and dissolved in a system formed by the first organic solvent, and the pH value is 12-13; and/or the presence of a gas in the gas,
mixing and dissolving a second metal salt and an alkaline substance in a system formed by dissolving the second metal salt and the alkaline substance in a first organic solvent, wherein the molar ratio of a second metal ion to the alkaline substance is 1: (1.8-4.5); or
Mixing and dissolving a second metal salt and a sulfur source in a system formed by dissolving the second metal salt and the sulfur source in a first organic solvent, wherein the molar ratio of second metal ions to the sulfur source is 1: (1-1.5); and/or the presence of a gas in the gas,
adding the organic solution of the metallized grapyne into the system after the metal compound solution is added, wherein the molar ratio of the metallized grapyne to the metal compound is (0.1-0.3): 1.
6. the method of claim 5, wherein the second metal ion is a divalent metal ion, and the molar ratio of the second metal ion to the basic substance is 1: (1.8-3); or
The second metal ion is a tetravalent metal ion, and the molar ratio of the second metal ion to the basic substance is 1: (3-4.5).
7. A method of preparing a composite material as claimed in any one of claims 4 to 6, wherein the second metal salt is selected from: at least one of zinc salt, titanium salt and tin salt; and/or the presence of a gas in the gas,
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 presence of a gas in the gas,
the sulfur source is selected from: at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; and/or the presence of a gas in the gas,
the first organic solvent is selected from: at least one of isopropanol, ethanol, propanol, butanol, and methanol; and/or the presence of a gas in the gas,
the organic solvent in the organic solution of the metallized graphdine 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 presence of a gas in the gas,
the titanium salt is selected from: at least one of titanium nitrate, titanium chloride, titanium sulfate and titanium bromide; and/or the presence of a gas in the gas,
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, comprising: a metallized graphdiyne and a metal compound bonded to the metallized graphdiyne.
10. The composite material of claim 9, wherein the metallized graphdine comprises a graphdine and a first metal atom bonded to the graphdine; and/or the presence of a gas in the gas,
the metal compound includes: at least one of zinc oxide, titanium oxide, tin oxide, zinc sulfide, titanium sulfide, and tin sulfide; and/or the presence of a gas in the gas,
in the composite material, the molar ratio of the metallized graphdiyne to the metal compound is (0.1-0.3): 1.
11. the composite material of claim 10, wherein the metallized graphdine has a molar ratio of graphdine to the first metal ion of 1: (0.05-0.2); and/or the presence of a gas in the gas,
the first metal ion is selected from: at least one of iron ions, cobalt ions and platinum ions.
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 by the method of any one of claims 1 to 8, or comprises a composite material of any one of claims 9 to 11.
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