CN118234350A - Composite material, preparation method thereof and light-emitting device - Google Patents
Composite material, preparation method thereof and light-emitting device Download PDFInfo
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- CN118234350A CN118234350A CN202211643693.7A CN202211643693A CN118234350A CN 118234350 A CN118234350 A CN 118234350A CN 202211643693 A CN202211643693 A CN 202211643693A CN 118234350 A CN118234350 A CN 118234350A
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- composite material
- organic framework
- metal
- inorganic particles
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- 239000002131 composite material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 206
- 239000010954 inorganic particle Substances 0.000 claims abstract description 131
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 109
- 238000002347 injection Methods 0.000 claims abstract description 50
- 239000007924 injection Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000010410 layer Substances 0.000 claims description 283
- 230000005525 hole transport Effects 0.000 claims description 62
- 239000002243 precursor Substances 0.000 claims description 62
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 45
- 239000002096 quantum dot Substances 0.000 claims description 41
- 239000011787 zinc oxide Substances 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000002346 layers by function Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 229910002601 GaN Inorganic materials 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013175 zeolitic imidazolate framework-11 Substances 0.000 claims description 8
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 8
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 8
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 7
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000013132 MOF-5 Substances 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 239000011257 shell material Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- AJGDITRVXRPLBY-UHFFFAOYSA-N aluminum indium Chemical compound [Al].[In] AJGDITRVXRPLBY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 claims description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 4
- 229910017115 AlSb Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 3
- 229910005542 GaSb Inorganic materials 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- 229910004262 HgTe Inorganic materials 0.000 claims description 3
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 3
- 229910007709 ZnTe Inorganic materials 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 3
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 3
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910004611 CdZnTe Inorganic materials 0.000 claims description 2
- 241000764773 Inna Species 0.000 claims description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002665 PbTe Inorganic materials 0.000 claims description 2
- 229910005642 SnTe Inorganic materials 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000003220 pyrenes Chemical class 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910017083 AlN Inorganic materials 0.000 claims 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 125000004556 carbazol-9-yl group Chemical group C1=CC=CC=2C3=CC=CC=C3N(C12)* 0.000 claims 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 42
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 33
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- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 10
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 2
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Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The application discloses a composite material, a preparation method thereof and a light-emitting device, and belongs to the technical field of display. The composite material comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles. The composite material of the application has the advantages that the metal organic frame is coated outside the inorganic particles, so that the metal organic frame has the effect of reducing the electron injection efficiency of the inorganic particles; meanwhile, the thickness of the inorganic particles coated by the metal organic frame material can be controlled according to the requirement, so that the uniformity of the particle size of the composite material is ensured, and the process stability of the composite material in application is improved.
Description
Technical Field
The application relates to the technical field of display, in particular to a composite material, a preparation method thereof and a light-emitting device.
Background
Quantum dot electroluminescence is a novel solid-state lighting technology, has the advantages of low cost, light weight, high response speed, high color saturation and the like, has a wide development prospect, and becomes one of important research directions of the new generation of LED lighting. The nano inorganic particles have the advantages of high electron mobility, easy preparation, high electron injection efficiency and the like, but the high electron injection rate of the nano inorganic particles also easily causes the problem of unbalanced charge injection.
Disclosure of Invention
The application aims to provide a composite material, which can overcome the defects in the prior art.
The present application provides a composite material comprising inorganic particles and metal organic framework Materials (MOFs) encapsulated outside the inorganic particles.
Correspondingly, the application also provides a preparation method of the composite material, which comprises the following steps:
Providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles.
In addition, the application also provides a light-emitting device, which comprises a laminated first electrode, a light-emitting layer and a second electrode, and further comprises a first carrier functional layer, wherein the first carrier functional layer is positioned between the first electrode and the light-emitting layer, and the first carrier functional layer comprises the composite material or the composite material prepared by the preparation method.
The application has the beneficial effects that:
The composite material comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles, wherein the metal organic framework is wrapped outside the inorganic particles, so that the metal organic framework has the effect of reducing the electron injection efficiency of the inorganic particles; meanwhile, the thickness of the inorganic particles coated by the metal organic frame material can be controlled according to the requirement, so that the uniformity of the particle size of the composite material is ensured, and the process stability of the composite material in application is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of a light emitting device according to an embodiment of the present application;
Fig. 2 is a schematic diagram of a second structure of a light emitting device according to an embodiment of the present application;
Fig. 3 is a schematic diagram of a light emitting device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction. Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as1, 2, 3,4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the course of research and practice of the technology, the inventors of the present application found that the hole injection efficiency of the Hole Transport Layer (HTL) is generally much lower than that of the Electron Transport Layer (ETL) formed by inorganic particles, which results in unbalanced carrier injection of the QLED device, thus resulting in low luminous efficiency of the device and poor lifetime of the device. In order to solve the problem of unbalanced carrier injection, an insulating layer PMMA with the thickness of about 6nm can be inserted between the nano zinc oxide and the quantum dot layer to block excessive electron injection so as to optimize the problem of balanced carrier injection in the device. However, the performance of the device prepared by the method is greatly influenced by the PMMA thickness of the insulating layer, and when the variation of the PMMA average thickness is as small as +/-1 nm, the device efficiency is obviously reduced, so that the thickness error of the insulating layer is difficult to control in the prior art, thereby causing the fluctuation of the device performance, and the prior art needs to be improved. The embodiment of the application provides a composite material, a preparation method thereof and a light-emitting device. The following will describe in detail. The following description of the embodiments is not intended to limit the preferred embodiments.
The embodiment of the application provides a composite material, which comprises inorganic particles and metal-organic frame Materials (MOFs) wrapped outside the inorganic particles. The metal organic frame material can play a role in reducing the electron injection efficiency of inorganic particles and can play a role in blocking electrons to the inorganic particles.
Further, the composite material is composed of inorganic particles and a metal-organic framework material wrapped outside the inorganic particles. Further, the metal organic framework material is coordinately bound to the inorganic particles.
The inorganic particles are wrapped by the metal organic framework material in the composite material, the particle size is consistent due to the shape, and the composite material formed by wrapping the inorganic particles by the metal organic framework material and the inorganic particles have similar application methods and are more advantageous in process stability.
In some embodiments, the inorganic particles include at least one of metal oxides, P-type semiconductors.
In some embodiments, the P-type semiconductor is selected from at least one of gallium nitride, aluminum indium gallium nitride, and indium gallium nitride.
In some embodiments, the metal element in the metal oxide is selected from at least one of zinc (Zn), titanium (Ti), aluminum (Al), zirconium (Zr), vanadium (V), molybdenum (Mo), and nickel (Ni). For example, the metal oxide is selected from at least one of zinc oxide (ZnO), zinc titanate (ZnTiO 3), aluminum oxide (Al 2O3), titanium oxide, zirconium oxide, vanadium oxide, molybdenum oxide, and nickel oxide. The method can achieve the effect of reducing the electron injection rate of the inorganic particles. For example, when the inorganic particles are zinc oxide (ZnO), the composite material may be denoted as zno@mofs. In the embodiment of the application, the composite material can be used as a carrier transmission material; the composite material comprising inorganic particles containing Zn, ti, al, zr or other metal elements can be used as an electron transport material.
In some embodiments, the metal organic framework Materials (MOFs) are selected from at least one of ZIF-series metal organic framework materials, IRMOF-type metal organic framework materials. Wherein the ZIF series metal organic framework material is selected from at least one of ZIF-8, ZIF-7 and ZIF-11. The IRMOF type metal organic framework material is at least one selected from IRMOF-1, IRMOF-3, IRMOF-8 and IRMOF-9. In the embodiment of the application, metal organic framework Materials (MOFs) can be selected according to actual requirements.
In some embodiments, the average particle size of the inorganic particles may be 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
In some embodiments, the composite material has an average particle size of 15 to 100 nanometers. Further, the average particle size of the composite material is 15 to 30 nanometers. For example, the average particle size of the composite material may be 15 nm, 16 nm, 18 nm, 20 nm, 25 nm, 28 nm, 30 nm, 35 nm, 40 nm, 50 nm, 55 nm, 60 nm, 70 nm, 80 nm, 90 nm, 95 nm, or 100 nm.
In some embodiments, the mass fraction of inorganic particles in the composite material may be 1 to 2wt%. That is, the mass ratio of the inorganic particles to the composite material in the composite material is 1% to 2%. For example, in the composite material, the mass fraction of inorganic particles may be 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt% or 2wt%.
In the embodiment of the application, the surface of the inorganic particles in the composite material is coated with metal organic frame Materials (MOFs), and the MOFs can act as an electron blocking layer for reducing the electron injection efficiency of the inorganic particles. In the application of the composite material in the light-emitting device, the composite material can also isolate water and oxygen and prevent the bad phenomenon that inorganic particles and quantum dot interfaces and/or cathode metal contact to generate chemical reaction so as to cause fluctuation of the device performance.
In the embodiment of the application, the shell gap of the metal organic framework material can be only several to tens of(Abbreviation/>(Angstrom), which is a length measurement unit, 1 angstrom=0.1 nm), the inorganic particles are not easily embedded in the gaps. In the actual reaction, even though inorganic particles which are not coated by the metal organic framework material are possibly connected to the shell, the residual part after the purification and other processes is few, and the influence on the finally obtained composite material is small and negligible.
The embodiment of the application also provides a preparation method of the composite material, which comprises the following steps:
Providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles.
According to the composite material, the metal organic framework material is generated on the surface of the inorganic particles, the concentration and time of the MOFs precursor added can be controlled to control the thickness of the shell, and the consistency of the particle size can be maintained in the later generation stage through centrifugal washing and other methods.
Further, the preparation method of the composite material comprises the following steps:
And mixing the inorganic particle dispersion liquid with a precursor solution of metal organic framework Materials (MOFs), and carrying out coordination reaction, wherein the metal organic framework materials are coated outside the inorganic particles, so as to obtain the composite material.
In some embodiments, the method of mixing comprises: a precursor solution of metal organic framework Materials (MOFs) is added dropwise to the inorganic particle dispersion and stirred to mix them uniformly. Further, the rate of the dropwise addition of the precursor solution may be 1 to 10mL/h. For example, the rate of addition is 1mL/h, 2mL/h, 3mL/h, 4mL/h, 5mL/h, 6mL/h, 7mL/h, 8mL/h, 9mL/h, or 10mL/h. Further, the reaction system was continuously stirred during the dropping. Further, stirring was continued during the reaction. The stirring speed may be 100 to 500 rpm. For example, the stirring speed may be 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350rpm, 400 rpm, 450 rpm, or 500 rpm.
In some embodiments, the reaction time is 4 to 24 hours, preferably 4 to 8 hours. For example, the reaction time may be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, or 24h.
In some embodiments, the inorganic particles include at least one of metal oxides, P-type semiconductors. Further, the P-type semiconductor is at least one selected from gallium nitride, aluminum indium gallium nitride, and indium gallium nitride. The metal oxide is at least one selected from zinc oxide, titanium oxide, zinc titanate, aluminum oxide, zirconium oxide, vanadium oxide, molybdenum oxide and nickel oxide.
In some embodiments, the metal-organic framework material may be selected from, but is not limited to, at least one of a ZIF-series metal-organic framework material, an IRMOF-type metal-organic framework material. Further, the ZIF-series metal organic framework material is selected from at least one of ZIF-8, ZIF-7 and ZIF-11; the IRMOF type metal organic framework material is at least one selected from IRMOF-1, IRMOF-3, IRMOF-8 and IRMOF-9.
In some embodiments, the precursor solution of the metal-organic framework material includes a metal-organic framework material, and the metal-organic framework material is at least one selected from the group consisting of a ZIF series metal-organic framework material and an IRMOF type metal-organic framework material.
Further, the precursor solution of the metal organic frame material comprises a connecting agent, and the metal organic frame material is connected to the surface of the inorganic particles through the connecting agent, so that the metal organic frame material is coated outside the inorganic particles. For example, when the metal organic framework material is IRMOF-3, the linker may be (NEt 3H)2BDC-NH2. In embodiments of the application, the linker is one of the components of MOFs, constituting the MOFs structural body to form a structural backbone.
In embodiments of the present application, the linking agent needs to be selected according to the type of metal-organic framework material specifically used. In general, the binder is also one of the components of the metal-organic framework material, and in addition to the structural body constituting the metal-organic framework material, the binder undergoes a ligand in-situ exchange reaction with the ligand of the inorganic particle, and the ligand on the surface of the inorganic particle is replaced with the component of the binder, so that the metal-organic framework material can grow on the surface of the nanoparticle through the binder.
In some embodiments, when the metal organic framework material is ZIF-8, the precursor of the metal organic framework material comprises: zn (NO 3)2·6H2 O and 2-methylimidazole further, zn (NO 3)2·6H2 O concentration is 0.5-2 mM) in the precursor solution, 2-methylimidazole concentration is 5-20 mM in the precursor solution further, zn (NO 3)2·6H2 O and 2-methylimidazole molar ratio is 1:10. For example, in a specific embodiment, zn (NO 3)2·6H2 O and 2-methylimidazole both are dissolved in methanol, zn (NO 3)2·6H2 O concentration is 1-4 mM, 2-methylimidazole concentration is 10-40 mM), and the volume ratio is 1:1 when mixed).
In some embodiments, when the metal organic framework material is IRMOF-3, the precursors of the metal organic framework material include Zn (OAc) 2·2H2 O and (NEt 3H)2BDC-NH2.(NEt3H)2BDC-NH2) are products that can be obtained by reacting 2-amino terephthalic acid (H 2BDC-NH2) and triethylamine (TEA, N-diethyl ethylamine).
In some embodiments, when the metal organic framework material is ZIF-7, the precursor of the metal organic framework material comprises Zn (NO 3)2·6H2 O and benzimidazole, specifically, the precursor materials are Zn (NO 3)2·6H2 O and benzimidazole, where the molar ratio of Zn (NO 3)2·6H2 O and benzimidazole is 1:0.75), both of which are dissolved in DMF, the Zn (NO 3)2·6H2 O concentration range is 2-4 mM, the 2-methylimidazole concentration range is 1.5-3 mM, and the volume ratio is 1:1 when mixed).
In some embodiments, when the metal organic framework material is ZIF-11, the precursors of the metal organic framework material include Zn (OAc) 2·2H2 O, benzimidazole, and ammonia. The precursor materials used are Zn (OAc) 2·2H2 O, benzimidazole and ammonia water (NH 3·H2 O), the precursor solution needs pretreatment, wherein Zn (OAc) 2·2H2 O is marked as precursor liquid 1 in a mixed solvent of toluene and ethanol (the molar ratio is 1:3), benzimidazole and ammonia water are also marked as precursor liquid 2 in a mixed solvent of toluene and ethanol (the molar ratio is 1:3), and two bottles of precursor solutions need ultrasonic treatment for 10min for reuse, and the molar ratio of each material is Zn (OAc) 2·2H2 O: benzimidazole: NH 3·H2 o=1:1.5:2.5, the volume ratio of two bottles of precursor solution when mixed is 1:2 (precursor liquid 1: precursor liquid 2).
In some embodiments, when the metal organic framework material is IRMOF-1, the precursors of the metal organic framework material include Zn (OAc) 2·2H2 O, terephthalic acid, and triethylamine. Specifically, the precursor materials used were Zn (OAc) 2·2H2 O, terephthalic acid and triethylamine, respectively, the precursor solutions required pretreatment, wherein Zn (OAc) 2·2H2 O was labeled precursor solution 1 in DMF, terephthalic acid and triethylamine were also labeled precursor solution 2 in DMF, the molar ratios of the materials were Zn (OAc) 2·2H2 O: terephthalic acid: triethylamine = 77.4:30.5:60, the volume ratio of two bottles of precursor solution is about 5:4 (precursor liquid 1: precursor liquid 2).
In some embodiments, the mass fraction of inorganic particles in the composite is 1 to 2wt%. The average particle size of the composite material may be 15 nm, 20 nm, 30 nm, 40 nm, 50nm, 60nm, 70nm, 80 nm, 90nm or 100 nm.
In some embodiments, the average particle size of the inorganic particles may be 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
In some embodiments, the inorganic particles have surface ligands. The surface ligands may include pyridine and/or 4-tert-butylpyridine. For example, the zinc oxide surface ligand may be pyridine and/or 4-tert-butylpyridine. Further, if the surface ligand of the inorganic particle used is pyridine or 4-t-butylpyridine, it may be used as it is, but if other ligands are used, the surface ligand of the inorganic particle may be changed to pyridine or 4-t-butylpyridine by a ligand exchange method. In the present application, the surface ligands of the inorganic particles help to attach the metal organic framework material to the surface of the nanoparticles, thereby achieving coating of the nanoparticles with the metal organic framework material. In detail, the surface ligand can perform in-situ exchange reaction with the connecting agent in the metal organic frame material, so that the metal organic frame material can grow on the surface of the inorganic particles, which is equivalent to providing growth points for the metal organic frame material.
In some embodiments, the solvent of the precursor solution includes a first solvent that employs a polar solvent. Further, the first solvent may include, but is not limited to, at least one of methanol, DMF.
In some embodiments, the solvent of the inorganic particle dispersion includes a second solvent, the second solvent being a polar solvent. Further, the second solvent may include, but is not limited to, at least one of methanol, DMF.
Further, the first solvent and the second solvent are the same solvent.
In some embodiments, the speed of agitation may be 100 revolutions per minute, 200 revolutions per minute, 300 revolutions per minute, 400 revolutions per minute, or 500 revolutions per minute.
In the embodiment of the application, the components in the precursor solution of the metal-organic framework material are adjusted according to the selection of the corresponding metal-organic framework material.
In the embodiment of the application, the molar quantity of the precursor material of the metal organic framework material is required to be far greater than that of the added nano particles (calculated by particles), and the nano zinc oxide particles to be treated are supposed to be 0.5nmol, at this time, the nano particles can be dispersed in 25-100 mL of methanol solution, and Zn (NO 3)2·6H2 O and 2-methylimidazole with 10mM concentration) with 1mM concentration are added dropwise.
For example, the method of preparing the composite material comprises the steps of: adding nano zinc oxide particles dispersed in a solvent into a clean glass container, slowly dropwise adding a precursor solution of MOFs into the container by using a syringe or a needle tube, continuously stirring the reaction solution after the dropwise adding process is finished, extracting part of reactants at intervals for testing until the size of the generated reactants meets the requirement, stopping stirring at the moment, and carrying out the whole reaction under the room temperature condition. And after the reaction is finished, washing the reaction product, centrifuging and the like to purify the reaction product, wherein the purified product can be used for preparing films on other functional layers of the light-emitting device by adopting methods of spin coating, printing and the like. The ligand on the surface of the nano zinc oxide particles can be pyridine and/or 4-tert-butylpyridine; the solvent for dispersing the nano zinc oxide particles can be polar solvents such as methanol, DMF and the like.
The preparation method of the application utilizes the metal organic framework material to coat the inorganic particles to form the nano crystallization characteristic. Specifically, MOFs with certain thickness are grown around the nano zinc oxide serving as a core, so that the method for inserting an ultrathin electron barrier layer between the nano zinc oxide and quantum dots in the prior art is replaced.
In the composite material, the metal organic frame material can function as an electronic barrier layer, and the metal organic frame material can isolate water and oxygen to a certain extent and prevent the problem that the performance of the device fluctuates due to chemical reaction between inorganic particles and quantum dot interfaces and/or cathode metal contact. By further purifying the product prepared by the method, the problem of non-uniform thickness of the electron blocking layer caused by unstable process when an ultrathin electron blocking layer is inserted between inorganic particles and quantum dots can be avoided. In addition, the application method of the composite material is similar to that of the material (such as ZnO) for the electron transport layer in the prior art, the film can be prepared by using the same process, the reaction condition is mild, and the composite material has better practicability.
According to the application, a layer of metal organic frame Material (MOFs) is generated on the surface of the nano zinc oxide particles to serve as an insulating layer, and the metal organic frame material can still serve as an electron blocking layer in function, but compared with a method for inserting an ultrathin insulating layer film between the nano zinc oxide and the quantum dot layer. In addition, the method for preparing the film after generating the nano particles is similar to the method for preparing the common nano zinc oxide film, such as spin coating, printing and the like, and has great advantages in process stability.
The embodiment of the application provides a light-emitting device, which comprises a first electrode, a light-emitting layer and a second electrode which are laminated, wherein the light-emitting device further comprises a first carrier functional layer, the first carrier functional layer is positioned between the first electrode and the light-emitting layer, and the first carrier functional layer comprises the composite material or the composite material prepared by the preparation method.
Further, the light emitting device further includes a second carrier functional layer located between the light emitting layer and the second electrode.
Further, the first electrode is a cathode, the second electrode is an anode, the first carrier functional layer is an electron functional layer, and the second carrier functional layer is a hole functional layer;
The electron functional layer comprises an electron transmission layer, wherein the electron transmission layer is arranged between the cathode and the light-emitting layer, and the material forming the electron transmission layer is a composite material; the hole function layer includes a hole transport layer disposed between the anode and the light emitting layer.
Further, the electron functional layer further comprises an electron injection layer, and the electron injection layer is arranged between the cathode and the electron transport layer; the hole function layer further includes a hole injection layer disposed between the anode and the hole transport layer.
In some embodiments, the light emitting layer is an organic light emitting layer or a quantum dot light emitting layer. Wherein the material of the organic light emitting layer is at least one selected from the group consisting of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials.
In some embodiments, the material of the quantum dot light emitting layer is selected from at least one of group II-VI quantum dots, group IV-VI quantum dots, group III-V quantum dots, and group I-III-VI quantum dots. Wherein the II-VI group quantum dots are selected from at least one of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe and HgZnSTe. The IV-VI group quantum dot is selected from at least one of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe. The III-V quantum dot is selected from at least one of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs and InAlPSb. The I-III-VI group quantum dot is selected from at least one of CuInS 2、CuInSe2 and AgInS 2.
In some embodiments, the material of the quantum dot light emitting layer is selected from at least one of single structure quantum dots and core-shell structure quantum dots. The core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS.
In some embodiments, the first electrode and the second electrode are each independently selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode. For example, the first electrode is an anode, and the second electrode is a cathode; otherwise, one electrode is a cathode, and the second electrode is an anode.
Further, the material of the metal electrode is selected from at least one of Al, ag, cu, mo, au, ba, ca and Mg. The material of the carbon electrode is at least one selected from graphite, carbon nanotubes, graphene and carbon fibers. The material of the doped or undoped metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO. The composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2.
In one embodiment, referring to fig. 1, a light emitting device 100 includes: anode 101, light-emitting layer 104, electron transport layer 105, cathode 107.
Further, the light emitting device 100 includes:
An anode 101 and a cathode 107 disposed opposite to each other;
a light emitting layer 104 disposed between the anode 101 and the cathode 107;
an electron transport layer 105 disposed between the cathode 107 and the light emitting layer 104.
The material forming the electron transport layer 105 includes the composite material as described above or a composite material prepared by the preparation method as described above. The composite material is described in detail above and is not described here. For example, the material of the electron transport layer may use the aforementioned zno@mofs particles.
In some embodiments, referring to fig. 2, the light emitting device further includes: a hole injection layer 102 and/or a hole transport layer 103 provided between the anode 101 and the light-emitting layer 104. Further, a hole transport layer 103 is provided between the hole injection layer 102 and the light emitting layer 104.
Further, the quantum dots used in the light emitting layer include, but are not limited to, at least one of CdSe、CdS、CdTe、ZnO、ZnSe、ZnS、ZnTe、HgS、HgSe、HgTe、CdZnS、CdZnSe、InAs、InP、InN、GaN、InSb、InAsP、InGaAs、GaAs、GaP、GaSb、AlP、AlN、AlAs、AlSb、CdSeTe.
Further, the material of the anode includes, but is not limited to, at least one of Al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, AZO and FTO. The material of the cathode includes, but is not limited to, at least one of Al, au, ag, ca, ba, mg, cu, fe, co, ni, mn, pd, pt and ITO.
Further, the material of the hole injection layer 102 is selected from poly (ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS), poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine) (TFB), polyarylamine, poly (N-vinylcarbazole), polyaniline, polypyrrole, N, N, N ', N ' -tetra (4-methoxyphenyl) -benzidine (TPD), 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl (. Alpha. -NPD), 4', 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA), 4' -tris (N-carbazolyl) -triphenylamine (TCTA), 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC), 4' -tris (diphenylamino) triphenylamine (TDATA) doped with tetrafluoro-tetracyano-quinone dimethane (F4-TCNQ), p-doped phthalocyanine, F4-TCNQ doped N, N ' -diphenyl-N, at least one of N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (alpha-NPD) and hexaazabenzophenanthrene-hexa-nitrile (HAT-CN).
Further, the material of the hole transport layer 103 is selected from 4,4'-N, N' -dicarbazolyl-biphenyl (CBP), N '-diphenyl-N, N' -bis (1-naphthyl) -1,1 '-biphenyl-4, 4 "-diamine (α -NPD), N' -diphenyl-N, N '-bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4 '-diamine (TPD), N' -bis (3-methylphenyl) -N, N '-bis (phenyl) -spiro (spiro-TPD), N' -bis (4- (N, N '-diphenyl-amino) phenyl) -N, N' -diphenylbenzidine (DNTPD), 4 '-tris (N-carbazolyl) -triphenylamine (TCTA), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), poly [ (9, 9 '-dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ] (TFB), poly (4-butylphenyl-diphenylamine) (poly-TPD), polyaniline, polypyrrole, poly (phenylene vinylene) (PPV), at least one of poly [ 2-methoxy-5- (2-ethylhexyl oxy) -1, 4-phenylenevinylene ] (MEH-PPV), poly [ 2-methoxy-5- (3 ',7' -dimethyloctyl oxy) -1, 4-phenylenevinylene ] (MOMO-PPV), copper phthalocyanine, aromatic or polynuclear aromatic tertiary amine, 4' -bis (p-carbazolyl) -1,1' -biphenyl compound, N ' -tetraarylbenzidine, PEDOT: PSS, poly (N-vinylcarbazole) (PVK), polymethacrylate, poly (9, 9-octylfluorene), N ' -bis (naphthalen-1-yl) -N, N ' -diphenyl benzidine (NPB), and spiro NPB.
In one embodiment, referring to fig. 2, a light emitting device 100 includes: an anode 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, and a cathode 107. Further, the anode 101 is disposed on a substrate, the hole injection layer 102 is disposed on a side of the anode 101 facing away from the substrate, the hole transport layer 103 is disposed on a side of the hole injection layer 102 facing away from the anode 101, the light emitting layer 104 is disposed on a side of the hole transport layer 103 facing away from the hole injection layer 102, the electron transport layer 105 is disposed on a side of the light emitting layer 104 facing away from the hole transport layer 103, and the cathode 107 is disposed on a side of the electron transport layer 105 facing away from the electron transport layer 105.
Further, the quantum dot material in the light emitting layer 104 includes, but is not limited to, at least one of group II-IV semiconductor nanocrystals, group III-V semiconductor nanocrystals, group II-V semiconductor nanocrystals, group III-VI semiconductor nanocrystals, group IV-VI semiconductor nanocrystals, and core-shell structures thereof.
Further, the anode 101 may be a transparent conductive film. The light emitting device may emit light from the anode side. Further, the material of anode 101 includes, but is not limited to, at least one of Al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, AZO and FTO; for example, transparent indium doped tin oxide (ITO).
Further, the material of cathode 107 includes, but is not limited to, at least one of Al, au, ag, ca, ba, mg, cu, fe, co, ni, mn, pd, pt and ITO. Still further, the material of the cathode 107 includes at least one of Al, ag, pt.
Referring to fig. 3, in some embodiments, the light emitting device 100 may further include an electron injection layer 106. An electron injection layer 106 is disposed between the cathode 107 and the electron transport layer 105.
With continued reference to fig. 3, the light emitting device 100 includes: an anode 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, an electron injection layer 106, and a cathode 107.
The application has been tested several times in succession, and the application will now be described in further detail with reference to a few test results, which are described in detail below in connection with specific examples.
Example 1
The embodiment provides a composite material, which comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles. The composite material consists of inorganic particles and a metal organic framework material coated outside the inorganic particles. The metal organic framework material is coordinately connected with the inorganic particles. The metal organic framework material is ZIF-8. The inorganic particles include zinc oxide.
The preparation method of the composite material of the embodiment comprises the following steps: providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting for 4h to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles. The step of mixing includes: the precursor solution of the metal-organic framework material is added dropwise to the inorganic particle dispersion liquid and stirred.
The precursor solution of the metal organic framework material (ZIF-8) comprises: the precursor of the metal organic frame material is Zn (NO 3)2·6H2 O, connecting agent is 2-methylimidazole and solvent is DMF).
Example 2
The embodiment provides a composite material, which comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles. The composite material consists of inorganic particles and a metal organic framework material coated outside the inorganic particles. The metal organic framework material is coordinately connected with the inorganic particles. The metal organic framework material is ZIF-7. The inorganic particles include alumina.
The preparation method of the composite material of the embodiment comprises the following steps: providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting for 4h to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles. The step of mixing includes: the precursor solution of the metal-organic framework material is added dropwise to the inorganic particle dispersion liquid and stirred.
The precursor solution for the metal organic framework material (ZIF-7) comprises: the precursor of the metal organic frame material is Zn (NO 3)2·6H2 O, connecting agent is benzimidazole and solvent is DMF).
Example 3
The embodiment provides a composite material, which comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles. The composite material consists of inorganic particles and a metal organic framework material coated outside the inorganic particles. The metal organic framework material is coordinately connected with the inorganic particles. The metal organic framework material is ZIF-11. The inorganic particles include titanium oxide.
The preparation method of the composite material of the embodiment comprises the following steps: providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting for 4h to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles. The step of mixing includes: the precursor solution of the metal-organic framework material is added dropwise to the inorganic particle dispersion liquid and stirred.
The precursor solution of the metal organic framework material (ZIF-11) comprises: the precursor of the metal organic framework material comprises Zn (OAc) 2·2H2 O, a connecting agent, benzimidazole and a solvent, namely DMF.
Example 4
The embodiment provides a composite material, which comprises inorganic particles and a metal organic framework material wrapped outside the inorganic particles. The composite material consists of inorganic particles and a metal organic framework material coated outside the inorganic particles. The metal organic framework material is coordinately connected with the inorganic particles. The metal organic framework material is IRMOF-3. The inorganic particles include zinc titanate.
The preparation method of the composite material of the embodiment comprises the following steps: providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting for 4h to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles. The step of mixing includes: the precursor solution of the metal-organic framework material is added dropwise to the inorganic particle dispersion liquid and stirred.
The precursor solution for the metal organic framework material (IRMOF-3) comprises: the precursor of the metal organic framework material is Zn (OAc) 2·2H2 O, a connecting agent (NEt 3H)2BDC-NH2) and a solvent DMF.
Example 5
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer was made of the composite material of example 1; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Depositing and preparing an electron transport layer (the average particle size of the composite material is 22+/-2 nm) on the light-emitting layer, and the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Example 6
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer was made of the composite material of example 2; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Depositing and preparing an electron transport layer (the average particle size of the composite material is 26+/-2 nm) on the light-emitting layer, and the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Example 7
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer was made of the composite material of example 3; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
depositing and preparing an electron transport layer (ZnO@MOFs is adopted as a material, and the average particle size is 24+/-2 nm) on the light-emitting layer, wherein the thickness is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Example 8
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer was made of the composite material of example 4; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Depositing and preparing an electron transport layer (the average particle size of the composite material is 20+/-2 nm) on the light-emitting layer, and the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 1
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transmission layer, a light-emitting layer, an insulating layer, an electron transmission layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the insulating layer is PMMA; the electron transport layer is ZnO; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
spin-coating an insulating layer PMMA on the light-emitting layer, wherein the thickness is 6nm;
Depositing and preparing an electron transport layer on the PMMA of the insulating layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 2
The present comparative example provides a light emitting device of a front structure including an anode, a hole transport layer, a light emitting layer, an insulating layer, an electron transport layer, and a cathode sequentially disposed on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the insulating layer is PMMA; the electron transport layer is alumina; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
spin-coating an insulating layer PMMA on the light-emitting layer, wherein the thickness of the insulating layer PMMA is 7nm;
Depositing and preparing an electron transport layer on the PMMA of the insulating layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 3
The present comparative example provides a light emitting device of a front structure including an anode, a hole transport layer, a light emitting layer, an insulating layer, an electron transport layer, and a cathode sequentially disposed on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the insulating layer is PMMA; the electron transport layer is titanium oxide; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
spin-coating an insulating layer PMMA on the light-emitting layer, wherein the thickness is 9nm;
Depositing and preparing an electron transport layer on the PMMA of the insulating layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 4
The present comparative example provides a light emitting device of a front structure including an anode, a hole transport layer, a light emitting layer, an insulating layer, an electron transport layer, and a cathode sequentially disposed on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the insulating layer is PMMA; the electron transport layer is zinc titanate; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Spin-coating an insulating layer PMMA on the light-emitting layer, wherein the thickness is 12nm;
Depositing and preparing an electron transport layer on the PMMA of the insulating layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 5
The embodiment provides a light-emitting device with a positive structure, which comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are sequentially arranged on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer is ZnO; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Depositing and preparing an electron transport layer on the light-emitting layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Comparative example 6
The present comparative example provides a light emitting device of a front structure including an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode sequentially disposed on a substrate. The device emits light from the anode. Wherein the substrate material is a glass sheet, the anode material is an ITO base plate, and the hole transport layer is PVK; the luminescent layer material is CdZnS/ZnS semiconductor nanocrystalline; the electron transport layer is alumina; the cathode is Ag.
The preparation method of the light-emitting device of the embodiment comprises the following steps:
providing a clean anode substrate ITO, and depositing and preparing a hole injection layer PEDOT on the anode substrate: PSS with the thickness of 35nm;
spin-coating a hole transport layer PVK on the hole injection layer, wherein the thickness of the hole transport layer PVK is 35nm;
Spin-coating a luminescent layer with the thickness of 10nm on the hole transport layer;
Depositing and preparing an electron transport layer on the light-emitting layer, wherein the thickness of the electron transport layer is 150nm;
Anode Ag is evaporated on the electron transport layer, and the thickness is 100nm.
Test example 1
The composite materials prepared in examples 1 to 4 were subjected to particle size testing during a reaction time of 4 hours, and the results are shown in Table 1. The specific particle size testing process comprises the following steps: when the inorganic particle dispersion liquid and the precursor solution of the metal organic framework material are mixed for reaction, partial reactants are extracted at intervals to carry out particle size test, the test method comprises TEM, SEM, AFM and other methods, the time interval for detecting the extracted products can be 10-120 min, in the test example, the interval time is 60min until the average particle size of the generated material meets the requirement, at the moment, the stirring is stopped, and the whole reaction process is carried out under the room temperature condition.
TABLE 1
As shown in table 1, as the reaction time increases, the average particle size of the obtained composite material is also increased compared with that of the inorganic particles, which indicates that the surface of the inorganic particles is successfully coated with the metal organic framework material, and the metal organic framework material is coated outside the inorganic particles, so that the metal organic framework has the effect of reducing the electron injection efficiency of the inorganic particles; meanwhile, the thickness of the inorganic particles coated by the metal organic frame material can be controlled according to the reaction time, so that the uniformity of the particle size of the composite material is ensured, the process stability of the composite material in application is improved, and the problem that the thickness of the electron blocking layer is not uniform due to unstable process when the electron blocking layer is arranged between the electron transmission layer and the luminescent layer is avoided.
Test example 2
The performance of the light emitting devices in examples 5 to 8 and comparative examples 1 to 6 was examined, and the comparison of the performances is shown in Table 1. Table 1 shows the performance test results of the light emitting device.
TABLE 1
In table 1, luminance L * is the luminance detected by lighting the light-emitting device under the condition of 2 mA; VT is the device start-up voltage; t95 is life time data when the device luminance decreases from the highest point to 95% of the highest luminance.
According to the data in Table 1, it can be found that the brightness of the devices of the device embodiments 5 to 8 of the present application can be as high as 3089Cd/m 2, the luminous efficiency can be as high as 16%, the starting voltage can be as low as 1.4V, and T95 can be 7h; while the performance of comparative examples 1-6 is significantly worse than that of device examples 1-4. Therefore, the performance of the light-emitting device of the embodiment of the application is better than that of the device of the comparative example, and the electron transport layer formed by adopting the composite material of MOFs coated with inorganic particles of the application can improve the light-emitting efficiency and the service life of the device.
In summary, the composite material of the present application achieves the coverage of nanoparticles by attaching MOFs to the surface of inorganic particles. Because metal organic frame Materials (MOFs) are novel microporous crystal materials formed by self-assembly of metal ions and organic connectors, nano inorganic particles are used as cores to generate Metal Organic Frames (MOFs) around the metal organic frame materials, and the generated materials are composite nano crystals formed by wrapping one or a small cluster of nano inorganic particles by the metal organic frame materials. The composite material has the particle size consistent with the size, can be prepared into a film to be used as an Electron Transport Layer (ETL) of a light-emitting device, and the preparation process can be spin coating or printing, so that the process stability is high, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and for parts of one embodiment that are not described in detail, reference may be made to related descriptions of other embodiments.
The above description of the composite material, the preparation method thereof and the light-emitting device provided by the embodiment of the application has been presented in detail, and specific examples are applied to the description of the principle and the implementation of the application, and the description of the above examples is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (19)
1. A composite material, characterized in that the composite material comprises inorganic particles and a metal-organic framework material wrapped outside the inorganic particles.
2. The composite material of claim 1, wherein the composite material consists of the inorganic particles and the metal-organic framework material encapsulated outside the inorganic particles.
3. The composite material of claim 1 or 2, wherein the metal-organic framework material is coordinately bound to the inorganic particles.
4. The composite material according to claim 1 or 2, wherein the inorganic particles comprise at least one of metal oxide, P-type semiconductor.
5. The composite material according to claim 4, wherein the metal element in the metal oxide is at least one selected from the group consisting of zinc, titanium, aluminum, zirconium, vanadium, molybdenum and nickel; and/or
The P-type semiconductor is at least one selected from gallium nitride, aluminum indium gallium nitride and indium gallium nitride.
6. The composite material according to claim 1 or 2, wherein the metal-organic framework material is selected from at least one of a ZIF series metal-organic framework material, IRMOF type metal-organic framework material; wherein,
The ZIF series metal organic framework material is selected from at least one of ZIF-8, ZIF-7 and ZIF-11;
The IRMOF metal organic framework material is at least one selected from IRMOF-1, IRMOF-3, IRMOF-8 and IRMOF-9.
7. The composite material according to claim 1 or 2, wherein the inorganic particles have an average particle diameter of 1 to 10 nm; and/or
The average grain diameter of the composite material is 15-100 nanometers; and/or
In the composite material, the mass fraction of the inorganic particles is 1-2 wt%.
8. The preparation method of the composite material is characterized by comprising the following steps:
Providing inorganic particle dispersion liquid and precursor solution of metal organic frame material, mixing and reacting to obtain the composite material, wherein the composite material comprises inorganic particles and metal organic frame material coated outside the inorganic particles.
9. The method of preparing a composite material according to claim 8, wherein the step of mixing comprises: and adding the precursor solution of the metal organic framework material into the inorganic particle dispersion liquid and stirring.
10. The method of producing a composite material according to claim 8, wherein the inorganic particles include at least one of a metal oxide and a P-type semiconductor.
11. The method for producing a composite material according to claim 10, wherein the metal oxide is at least one selected from zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, vanadium oxide, molybdenum oxide, and nickel oxide; and/or
The P-type semiconductor is at least one selected from gallium nitride, aluminum indium gallium nitride and indium gallium nitride.
12. The method for producing a composite material according to claim 8, wherein the precursor solution of the metal-organic framework material includes a metal-organic framework material selected from at least one of a ZIF-series metal-organic framework material and an IRMOF-type metal-organic framework material; and/or
The precursor solution of the metal organic framework material comprises a connecting agent, wherein the connecting agent is selected from at least one of 2-methylimidazole, (NEt 3H)2BDC-NH2, benzimidazole and terephthalic acid.
13. The method of preparing a composite material according to claim 12, wherein the ZIF-series metal organic framework material is selected from at least one of ZIF-8, ZIF-7 and ZIF-11; the IRMOF type metal organic framework material is at least one selected from IRMOF-1, IRMOF-3, IRMOF-8 and IRMOF-9;
When the metal organic framework material is ZIF-8, the precursor solution of the metal organic framework material comprises: zn (NO 3)2·6H2 O and 2-methylimidazole;
when the metal organic framework material is ZIF-7, the precursor solution of the metal organic framework material includes Zn (NO 3)2·6H2 O and benzimidazole;
When the metal organic framework material is ZIF-11, the precursor solution of the metal organic framework material comprises Zn (OAc) 2·2H2 O, benzimidazole and ammonia water;
When the metal organic framework material is IRMOF-3, the precursor solution of the metal organic framework material comprises Zn (OAc) 2·2H2 O and (NEt 3H)2BDC-NH2;
When the metal organic framework material is IRMOF-1, the precursor solution of the metal organic framework material comprises Zn (OAc) 2·2H2 O, terephthalic acid and triethylamine.
14. The method for producing a composite material according to claim 9, wherein the mass fraction of the inorganic particles in the composite material is 1 to 2wt%; and/or
The average grain diameter of the composite material is 15-100 nanometers; and/or
The average particle diameter of the inorganic particles is 1-10 nanometers; and/or
The inorganic particles have a surface ligand including at least one of pyridine and 4-tert-butylpyridine; and/or
The precursor solution of the metal organic framework material comprises a first solvent, wherein the first solvent comprises at least one of methanol and DMF; and/or
The inorganic particle dispersion liquid comprises a second solvent, wherein the second solvent comprises at least one of methanol and DMF; and/or
The stirring speed is 100-500 rpm.
15. A light emitting device comprising a first electrode, a light emitting layer, and a second electrode stacked, the light emitting device further comprising a first carrier functional layer between the first electrode and the light emitting layer, characterized in that,
The first carrier functional layer comprises a composite material according to any one of claims 1 to 7 or a composite material produced by the method of producing a composite material according to any one of claims 8 to 14.
16. The light emitting device of claim 15, further comprising a second carrier functional layer positioned between the light emitting layer and the second electrode.
17. The light-emitting device according to claim 16, wherein the first electrode is a cathode, wherein the second electrode is an anode, wherein the first carrier functional layer is an electron functional layer, and wherein the second carrier functional layer is a hole functional layer;
Wherein the electron functional layer comprises an electron transport layer, the electron transport layer is arranged between the cathode and the light emitting layer, and the material of the electron transport layer comprises the composite material; the hole functional layer includes a hole transport layer disposed between the anode and the light emitting layer.
18. The light-emitting device according to claim 17, wherein the electron functional layer further comprises an electron injection layer provided between the cathode and the electron transport layer; and/or
The hole function layer further includes a hole injection layer disposed between the anode and the hole transport layer.
19. The light-emitting device according to claim 15, wherein the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, wherein a material of the organic light-emitting layer is at least one selected from the group consisting of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4',4 "-tris (carbazol-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, and DBP fluorescent materials;
The material of the quantum dot luminescent layer is at least one selected from II-VI group quantum dots, IV-VI group quantum dots, III-V group quantum dots and I-III-VI group quantum dots; wherein the II-VI group quantum dots are selected from at least one of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe and HgZnSTe, the IV-VI group quantum dots are selected from at least one of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, the III-V group quantum dots are selected from at least one of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs and InAlPSb, and the I-III-VI group quantum dots are selected from at least one of CuInS 2、CuInSe2 and AgInS 2;
The material of the quantum dot luminescent layer is at least one of quantum dots with a single structure and quantum dots with a core-shell structure, the core of the quantum dots with the core-shell structure is any one of the quantum dots with the single structure, and the shell material of the quantum dots with the core-shell structure is at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS;
The first electrode and the second electrode are respectively and independently selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2.
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