WO2020108071A1 - 一种量子点发光二极管及其制备方法 - Google Patents
一种量子点发光二极管及其制备方法 Download PDFInfo
- Publication number
- WO2020108071A1 WO2020108071A1 PCT/CN2019/108337 CN2019108337W WO2020108071A1 WO 2020108071 A1 WO2020108071 A1 WO 2020108071A1 CN 2019108337 W CN2019108337 W CN 2019108337W WO 2020108071 A1 WO2020108071 A1 WO 2020108071A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- quantum dot
- dot light
- emitting diode
- layer
- light emitting
- Prior art date
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 58
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 48
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002347 injection Methods 0.000 claims abstract description 26
- 239000007924 injection Substances 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 158
- 239000000758 substrate Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 30
- 230000005525 hole transport Effects 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000000903 blocking effect Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 239000002346 layers by function Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003574 free electron Substances 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- 230000037230 mobility Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000053 physical method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- HIIGGQNLPWIVAG-UHFFFAOYSA-L nickel(2+);diacetate;hydrate Chemical compound O.[Ni+2].CC([O-])=O.CC([O-])=O HIIGGQNLPWIVAG-UHFFFAOYSA-L 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Polymers C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- -1 HgSe Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012678 divergent method Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002110 nanocone Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/157—Hole transporting layers between the light-emitting layer and the cathode
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Definitions
- the present disclosure relates to the field of quantum dot light-emitting diodes, in particular to a quantum dot light-emitting diode and a preparation method thereof.
- Quantum dot light-emitting diode is an important new display technology in the future. There are still many technical problems in the commercialization of quantum dot display technology, such as unstable device efficiency and poor life, etc. The main factor affecting these devices is the unbalanced charge injection of the device resulting in.
- quantum dots with different structural systems For example, when using quantum dots with different structural systems to prepare light-emitting diodes (QLEDs) under the same device structure, the device efficiency and life will be different. The reason is that the quantum dots of different structural systems have different requirements for the balance of electron hole injection, so Adjust and optimize the charge injection balance of the device.
- QLEDs quantum dot light-emitting diodes
- the purpose of the present disclosure is to provide a quantum dot light emitting diode and a preparation method thereof, aiming to solve the problem of the imbalance of charge injection of the existing quantum dot light emitting diode, resulting in its low luminous efficiency.
- a quantum dot light-emitting diode includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode, and an electron transport layer is further provided between the cathode and the quantum dot light-emitting layer, wherein the electron transport
- the layer material is a mixed material composed of PAMAM dendrimers and nano metal oxides.
- a preparation method of quantum dot light-emitting diode which includes the steps of:
- An anode substrate is provided, a quantum dot light emitting layer is prepared on the anode substrate, an electron transport layer is prepared on the quantum dot light emitting layer, and a cathode is prepared on the electron transport layer to produce the quantum dot light emitting diode;
- a cathode substrate prepares an electron transport layer on the cathode substrate, prepare a quantum dot light emitting layer on the electron transport layer, prepare an anode on the quantum dot light emitting layer, and manufacture the quantum dot light emitting diode ;
- the electron transport layer material is a mixed material composed of PAMAM dendrimer and nano metal oxide.
- the quantum dot light emitting diode provided by the present disclosure includes an electron transport layer, and the material of the electron transport layer is a mixed material composed of PAMAM dendrimers and nano metal oxides. Since PAMAM dendrimers are both ⁇ donors and ⁇ donors, this makes PAMAM dendrimers have certain electron transport capabilities, but because PAMAM dendrimers do not have free electrons, their electron transport capabilities are relatively higher than those of metal oxides. The words are weak.
- the present disclosure uses a mixed material composed of PAMAM dendrimers and nano metal oxides as the electron transport layer material, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby balancing the electron hole injection rate of the quantum dot light-emitting diode, and further Improve the luminous efficiency of quantum dot light-emitting diodes.
- FIG. 1 is a schematic structural diagram of a preferred embodiment of a quantum dot light emitting diode of the present disclosure.
- FIG. 2 is a schematic structural diagram of another preferred embodiment of a quantum dot light emitting diode of the present disclosure.
- FIG. 3 is a flow chart of a method for preparing a positive-type quantum dot light-emitting diode of the present disclosure.
- FIG. 4 is a flow chart of a method for manufacturing an inverse structure quantum dot light emitting diode of the present disclosure.
- the present disclosure provides a quantum dot light emitting diode and a manufacturing method thereof.
- a quantum dot light emitting diode and a manufacturing method thereof.
- the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
- the quantum dot light-emitting diodes are divided into a formal structure and a trans structure.
- the trans-structure quantum dot light-emitting diodes may include a substrate, a cathode, and an electron transmission layered from bottom to top. Layer, quantum dot light emitting layer and anode.
- the quantum dot light-emitting diode of the formal structure shown in FIG. 1 will be mainly used as an example for introduction. Specifically, as shown in FIG.
- the full-structure quantum dot light-emitting diode includes a substrate 10, an anode 20, a quantum dot light-emitting layer 30, an electron transport layer 40, and a cathode 50 stacked from bottom to top.
- the electron transport layer material is a mixed material composed of PAMAM dendrimers and nano metal oxides.
- holes such as a hole transport layer, a hole injection layer, and an electron blocking layer may also be provided between the anode and the quantum dot light emitting layer Functional layer; in addition to the electron transport layer, an electron functional layer such as an electron injection layer and a hole blocking layer may be provided between the cathode and the quantum dot light emitting layer.
- the present disclosure uses a composite material composed of PAMAM dendrimers and nano metal oxides as an electron transport layer material, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby balancing the electron hole injection rate of the quantum dot light-emitting diode, and further Improve the luminous efficiency of quantum dot light-emitting diodes.
- the mechanism for achieving the above effects is as follows:
- PAMAM (polyamide-amine) dendrimers are both ⁇ donors and ⁇ donors, which makes PAMAM dendrimers have certain electron transport capabilities, but because PAMAM dendrimers do not have free electrons, their electron transport capabilities Weak compared to metal oxides. Compared with the nano metal oxide under the same conditions, the electron mobility of the mixed material composed of the PAMAM dendrimer and the nano metal oxide adopted in the present disclosure has been reduced, the main reason is that the PAMAM dendrimer can Effectively hinder the electronic conductivity of nano metal oxides.
- the present disclosure uses the mixed material composed of the PAMAM dendrimer and nano metal oxide as the electron transport layer material of the quantum dot light-emitting diode, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby making the electrons of the quantum dot light-emitting diode
- the hole injection rate is balanced, thereby improving the luminous efficiency of quantum dot light-emitting diodes.
- the PAMAM dendrimer is selected from the first generation PAMAM dendrimer (G1), the second generation PAMAM dendrimer (G2), the third generation PAMAM dendrimer (G3), the fourth generation PAMAM dendrimer (G4), fifth generation PAMAM dendrimer (G5), sixth generation PAMAM dendrimer (G6), seventh generation PAMAM dendrimer (G7), eighth generation PAMAM dendrimer (G8) ), one or more of the ninth generation PAMAM dendrimer (G9) and the tenth generation PAMAM dendrimer (G10), etc., but not limited thereto.
- PAMAM (polyamide-amine) dendrimers are obtained by reacting different molecular units A (ethylenediamine) and molecular units B (methyl acrylate).
- the PAMAM dendrimers can be synthesized by a divergent method. In one step, ethylenediamine and methyl acrylate are reacted to form carboxylic acid ester. In the second step, the resulting carboxylic acid ester is reacted with excess ethylenediamine. After the above two steps, the first generation of PAMAM dendrimer can be prepared. , Repeat the above two steps to get higher algebraic PAMAM dendrimer.
- the general formulas of molecular unit A and molecular unit B contained in PAMAM dendrimers of different algebras are: A(2 n +2 n-1 +...+2 n-3 )+B(2 n+1 +2 n + ....+2 n-1 ), where the value of n is 3-10; in addition, the general formula of the first generation PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B, the second generation PAMAM dendrimer The general formula of the molecule containing molecular unit A and molecular unit B is 5A+8B.
- the mixed materials are used as electron transport layer materials of quantum dot light-emitting diodes to achieve quantum The electron transmission performance of the point light-emitting diode is adjusted to meet the needs of different devices.
- the electron-transporting capacity is greater than that of the electron-transport layer prepared using the second-generation PAMAM dendrimer and nano-zinc oxide.
- the nano metal oxide is selected from one or more of ZnO, NiO, W 2 O 3 , Mo 2 O 3 , TiO 2 , SnO, ZrO 2 and Ta 2 O 3 , but not Limited to this.
- the particle size of the nano metal oxide is 1-20 nm.
- the mass ratio of PAMAM dendrimer to nano metal oxide is 1-10:10.
- the present disclosure also provides a trans-structure quantum dot light-emitting diode, as shown in FIG. 2, which includes a substrate 101, a cathode 102, an electron transport layer 103, and quantum dots stacked in this order from bottom to top
- the present disclosure is not limited to the quantum dot light-emitting diode of the above structure, and may further include an interface function layer or an interface modification layer, including but not limited to an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer One or more.
- the quantum dot light emitting diode of the present disclosure may be partially encapsulated, fully encapsulated, or unencapsulated.
- the material of the anode is selected from doped metal oxides; wherein, the doped metal oxides include but are not limited to indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), Antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), aluminum-doped magnesium oxide One or more of (AMO).
- ITO indium-doped tin oxide
- FTO fluorine-doped tin oxide
- ATO Antimony-doped tin oxide
- AZO aluminum-doped zinc oxide
- GZO gallium-doped zinc oxide
- IZO indium-doped zinc oxide
- MZO magnesium-doped zinc oxide
- AMO aluminum-doped magnesium oxide
- AMO aluminum-doped magnesium oxide
- the material of the hole transport layer is selected from organic materials with good hole transport capabilities, such as but not limited to poly(9,9-dioctylfluorene-CO-N-(4- (Butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) ( Poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4”-tri(carb Azole-9-yl) triphenylamine (TCTA), 4,4'-bis(9-carbazole) biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methyl Phenyl)-1,1'-biphenyl-4,4'
- the material of the quantum dot light-emitting layer is selected from one or more of red quantum dots, green quantum dots, and blue quantum dots, and may also be selected from yellow light quantum dots.
- the material of the quantum dot light emitting layer is selected from CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS , CuInSe, and one or more of various core-shell structure quantum dots or alloy structure quantum dots.
- the quantum dots in the present disclosure may be selected from cadmium-containing or cadmium-free quantum dots.
- the quantum dot light-emitting layer of the material has the characteristics of wide excitation spectrum and continuous distribution, and high stability of emission spectrum.
- the material of the cathode is selected from one or more of conductive carbon materials, conductive metal oxide materials and metal materials; wherein the conductive carbon materials include but are not limited to doped or undoped carbon nanotubes , One or more of doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber and porous carbon; conductive metal oxide materials include but are not limited to ITO, FTO, ATO And one or more of AZO; metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or their alloys; wherein, among the metal materials, their morphologies include but are not limited to dense thin films, nanowires, One or more of nanospheres, nanorods, nanocones and hollow nanospheres.
- the present disclosure also provides a method for manufacturing a quantum dot light-emitting diode with a formal structure as shown in FIG. 1, wherein, as shown in FIG. 3, it includes the steps of:
- An electron transport layer is prepared on the quantum dot light-emitting layer, wherein the electron transport layer material is a mixed material composed of PAMAM dendrimers and nano metal oxides;
- quantum dot light-emitting diodes are divided into a positive structure and an inverse structure.
- the positive structure includes an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode.
- the anode of the positive structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light emitting layer.
- the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the inversion structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
- the cathode of the inversion structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light-emitting layer.
- the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the bottom electrode provided on the substrate is an anode.
- the anode substrate may be provided with a bottom electrode on the substrate; in another embodiment of the present disclosure
- the anode substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a hole transport layer stacked on the surface of the substrate; in yet another embodiment of the present disclosure, the anode substrate may include A substrate, a bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the substrate, and a hole transport layer stacked on the surface of the hole injection layer; in still another embodiment of the present disclosure,
- the anode substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the substrate, a hole transport layer stacked on the surface of the hole injection layer, and a layer stacked on the hole An electron blocking layer on the surface of the transport layer.
- the bottom electrode provided on the substrate is a cathode.
- the cathode substrate may be provided with a bottom electrode on the substrate; in another embodiment of the present disclosure
- the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and an electron injection layer stacked on the surface of the substrate.
- the preparation method of the above layers may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-precipitation method or A variety of; physical methods include but are not limited to physical coating method or solution method, wherein the solution method includes but not limited to spin coating method, printing method, blade coating method, dipping method, dipping method, spraying method, roll coating method, casting Method, slot coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, One or more of atomic layer deposition and pulsed laser deposition.
- the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-pre
- the method for preparing the mixed material includes the steps of: providing a PAMAM dendrimer; adding the PAMAM dendrimer to the nano metal oxide in a mass ratio of 1-10:10 to the electrode A colloidal solution is obtained by mixing in a sexual solvent, and the colloidal solution is dried to prepare the mixed material.
- PAMAM dendrimers contain a large number of functional groups, most of these functional groups have strong polarity and electronegativity, which makes PAMAM dendrimers have better steric hindrance effect in polar solvents. It can effectively avoid the agglomeration of PAMAM dendrimer and nano metal oxide mixed in polar solvent.
- the polar solvent is selected from one of water, ethanol, and methanol, but is not limited thereto. More preferably, the polar solvent is ethanol.
- the concentration of PAMAM dendrimers is 10-40 mg/ml.
- the concentration of the nano metal oxide is 20-80 mg/ml.
- the nano metal oxide is selected from one or more of ZnO, NiO, W 2 O 3 , Mo 2 O 3 , TiO 2 , SnO, ZrO 2 and Ta 2 O 3 , but not Limited to this.
- the particle size of the nano metal oxide is 1-20 nm.
- the colloidal solution is prepared into a film by coating or printing, and annealed to obtain an electron transport layer formed of PAMAM dendrimers and nano metal oxides. Because the PAMAM dendrimer has a certain viscosity, it is favorable for film formation when it is mixed with nano metal oxide to form a colloidal solution.
- the film layer is annealed at 60-150°C. In some embodiments, the annealing treatment time is 15-60 min. Through the annealing treatment, an electron transport layer formed of PAMAM dendrimers and nano metal oxides can be produced.
- PAMAM dendrimers are both ⁇ donors and ⁇ donors, this makes PAMAM dendrimers have certain electron transport capabilities, but because PAMAM dendrimers do not have free electrons, their electron transport capabilities are relatively higher than those of metal oxides. The words are weak.
- the present disclosure uses a mixed material composed of PAMAM dendrimers and nano metal oxides as the electron transport layer material of the quantum dot light-emitting diode, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby making the electron hole injection rate of the quantum dot light-emitting diode Achieve balance, thereby improving the luminous efficiency of quantum dot light-emitting diodes.
- the present disclosure also provides a method for preparing a QLED with a hole-transporting layer in a trans structure, as shown in FIG. 4, including the following steps:
- the material of the electron transport layer is a mixed material composed of PAMAM dendrimers and nano metal oxides.
- the preparation method of the above layers may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-precipitation method or A variety of; physical methods include but are not limited to physical coating method or solution method, wherein the solution method includes but not limited to spin coating method, printing method, blade coating method, dipping method, dipping method, spraying method, roll coating method, casting Method, slot coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, One or more of atomic layer deposition and pulsed laser deposition.
- the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-pre
- a quantum dot light-emitting diode comprising an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode stacked from bottom to top, wherein the electron transport layer material is made of the fifth generation PAMAM A mixture of dendritic molecules and nano-zinc oxide.
- the preparation method of the quantum dot light-emitting diode includes the following steps:
- nano-zinc oxide Disperse 0.5 mol of zinc acetate hydrate in 25 ml of dimethyl sulfoxide to completely disperse it, and disperse 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of ethanol to make it completely Disperse, mix and stir the two mixtures at room temperature for 1h for centrifugal cleaning to prepare nano zinc oxide;
- a 150 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to produce the quantum dot light-emitting diode.
- a quantum dot light-emitting diode which includes an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode that are stacked from bottom to top, wherein the electron transport layer is composed of the second generation PAMAM tree Shaped molecules and nano-nickel oxide mixed materials.
- the preparation method of the quantum dot light-emitting diode includes the following steps:
- nano-nickel oxide Disperse 0.5 mol of nickel acetate hydrate in 25 ml of dimethyl sulfoxide to make it completely dispersed, and 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of ethanol to make it completely Disperse, mix and stir the two mixtures at room temperature for 1h for centrifugal cleaning to prepare nano nickel oxide;
- a 100 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to prepare the quantum dot light-emitting diode.
- a quantum dot light-emitting diode comprising an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode stacked from bottom to top, wherein the electron transport layer is composed of the first generation PAMAM tree Shaped molecules, fourth-generation PAMAM dendrimers and nano-nickel oxide mixed materials.
- the preparation method of the quantum dot light-emitting diode includes the following steps:
- nano-nickel oxide Disperse 0.5 mol of nickel acetate hydrate in 25 ml of dimethyl sulfoxide to make it completely dispersed, and 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of ethanol to make it completely Disperse, mix and stir the two mixtures at room temperature for 1h for centrifugal cleaning to prepare nano nickel oxide;
- a 100 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to prepare the quantum dot light-emitting diode.
- the quantum dot light emitting diode includes an electron transport layer, and the material of the electron transport layer is a mixed material composed of PAMAM dendrimers and nano metal oxides. Since PAMAM dendrimers are both ⁇ donors and ⁇ donors, this makes PAMAM dendrimers have certain electron transport capabilities, but because PAMAM dendrimers do not have free electrons, their electron transport capabilities are relatively higher than metal oxide The words are weak.
- the present disclosure uses a mixed material composed of PAMAM dendrimers and nano metal oxides as the electron transport layer material, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby balancing the electron hole injection rate of the quantum dot light-emitting diode, and further Improve the luminous efficiency of quantum dot light-emitting diodes.
Abstract
一种量子点发光二极管及其制备方法，其中，所述量子点发光二极管包括阴极（50）、阳极（20）以及设置在所述阴极（50）和阳极（20）之间的量子点发光层（30），所述阴极（50）和量子点发光层（30）之间还设置有电子传输层（40），所述电子传输层（40）材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料。由于PAMAM树形分子既是σ给予体又是π给予体，这使得PAMAM树形分子具有一定的电子传输能力，但是由于PAMAM树形分子本身不具有自由电子，因此其电子传输能力相对金属氧化物而言较弱。采用由PAMAM树形分子和纳米金属氧化物组成的混合材料作为电子传输层（40）材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
Description
本公开涉及量子点发光二极管领域，尤其涉及一种量子点发光二极管及其制备方法。
量子点发光二极管是未来重要的新型显示技术，量子点显示技术的商业化仍然存在很多技术问题，比如器件效率不稳定，寿命不好等，影响这些器件的主要因素是器件的电荷注入不平衡所导致。
比如同一种器件结构下利用不同结构体系的量子点制备发光二极管(QLED)时，器件效率和寿命都会不一样，其原因是不同结构体系的量子点对电子空穴注入平衡的需求不同，因此需要对器件的电荷注入平衡做调整和优化。
再比如同一种结构体系的量子点利用不同的器件结构制备量子点发光二极管(QLED)时，因不同器件结构造成的器件效率和寿命不同，其原因是不同的器件结构造成的电子空穴注入平衡不一致，因此针对不同的器件结构也需要对电荷注入平衡做调整和优化。
针对同一种器件结构下不同结构体系的量子点和同一种结构体系的量子点不同的器件结构所存在的电荷注入不平衡的问题，相应的技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点发光二极管及其制备方法，旨在解决现有量子点发光二极管的电荷注入不平衡，导致其发光效率较低的问题。
本公开的技术方案如下：
一种量子点发光二极管，包括阴极、阳极以及设置在所述阴极和阳极之间的量子点发光层，所述阴极和量子点发光层之间还设置有电子传输层，其中，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料。
一种量子点发光二极管的制备方法，其中，包括步骤：
提供一阳极基板，在所述阳极基板上制备量子点发光层，在所述量子点发光层上制备电子传输层，在所述电子传输层上制备阴极，制得所述量子点发光二极管；
或者，提供一阴极基板，在所述阴极基板上制备电子传输层，在所述电子传输层上制备量子点发光层，在所述量子点发光层上制备阳极，制得所述量子点发光二极管；
其中，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料。
有益效果：本公开提供的量子点发光二极管包括电子传输层，所述电子传输层材料为为由PAMAM树形分子和纳米金属氧化物组成的混合材料。由于PAMAM树形分子既是σ给予体又是π给予体，这使得PAMAM树形分子具有一定的电子传输能力，但是由于PAMAM树形分子本身不具有自由电子，因此其电子传输能力相对金属氧化物而言较弱。本公开采用由PAMAM树形分子和纳米金属氧化物组成的混合材料作为电子传输层材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
图1为本公开一种量子点发光二极管较佳实施例的结构示意图。
图2为本公开另一种量子点发光二极管较佳实施例的结构示意图。
图3为本公开一种正型结构的量子点发光二极管的制备方法流程图。
图4为本公开一种反型结构的量子点发光二极管的制备方法流程图。
本公开提供一种量子点发光二极管及其制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
量子点发光二极管有多种形式，且所述量子点发光二极管分为正式结构和反式结构， 所述反式结构的量子点发光二极管可包括从下往上层叠设置的基板、阴极、电子传输层、量子点发光层以及阳极。而本公开的具体实施方式中将主要以如图1所示的正式结构的量子点发光二极管为实施例进行介绍。具体地，如图1所示，所述正式结构的量子点发光二极管包括从下往上层叠设置的基板10、阳极20、量子点发光层30、电子传输层40以及阴极50，其中，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料。
需说明的是，对于所述正式结构和反式结构的量子点发光二极管，在所述阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层；在所述阴极和量子点发光层之间除了设置所述电子传输层之外，还可以设置电子注入层和空穴阻挡层等电子功能层。
本公开采用由PAMAM树形分子和纳米金属氧化物组成的复合材料作为电子传输层材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。实现上述效果的机理具体如下：
PAMAM(聚酰胺-胺)树形分子既是σ给予体又是π给予体，这使得PAMAM树形分子具有一定的电子传输能力，但是由于PAMAM树形分子本身不具有自由电子，因此其电子传输能力相对金属氧化物而言较弱。相对于同等条件下的纳米金属氧化物而言，本公开采用的由所述PAMAM树形分子与纳米金属氧化物组成的混合材料的电子迁移率有所降低，其主要原因是PAMAM树形分子能够有效阻碍纳米金属氧化物的电子传导能力。因此，本公开将由所述PAMAM树形分子与纳米金属氧化物组成的混合材料作为量子点发光二极管的电子传输层材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
在一些实施方式中，所述PAMAM树形分子选自第一代PAMAM树形分子(G1)、第二代PAMAM树形分子(G2)、第三代PAMAM树形分子(G3)、第四代PAMAM树形分子(G4)、第五代PAMAM树形分子(G5)、第六代PAMAM树形分子(G6)、第七代PAMAM树形分子(G7)、第八代PAMAM树形分子(G8)、第九代PAMAM树形分子(G9)和第十代 PAMAM树形分子(G10)等中的一种或多种，但不限于此。
具体来讲，PAMAM(聚酰胺-胺)树形分子是由不同的分子单元A(乙二胺)和分子单元B(丙烯酸甲酯)反应得到，所述PAMAM树形分子可由发散法合成，第一步由乙二胺和丙烯酸甲酯反应生成羧酸酯，第二步将得到的羧酸酯与过量的乙二胺反应，经过上述两步反应后即可制得第一代PAMAM树形分子，重复上述两步反应即可得到更高代数的PAMAM树形分子。不同代数的PAMAM树形分子所含有的分子单元A和分子单元B的通式为：A(2
n+2
n-1+…+2
n-3)+B(2
n+1+2
n+….+2
n-1)，其中n的取值为3-10；另外，第一代PAMAM树形分子含有分子单元A和分子单元B的通式为A+4B，第二代PAMAM树形分子含有分子单元A和分子单元B的通式为5A+8B。随着PAMAM树形分子的代数变大，其分子体积也越大，且其分子内腔体也变多，导致其电子传输能力相应的变弱。也就是说，所述PAMAM树形分子随着代数的增加其电子传输能力逐渐减弱，即G1>G2>G3>G4>G5>G6>G7>G8>G9>G10。
本实施例通过采用不同代数的PAMAM树形分子与纳米金属氧化物混合，可得到具有不同电子迁移率的混合材料，将所述混合材料作为量子点发光二极管的电子传输层材料，可实现对量子点发光二极管的电子传输性能进行调节，从而满足不同器件的需求。作为举例，当采用第一代PAMAM树形分子与纳米氧化锌制备电子传输层时，其电子传输能力大于采用第二代PAMAM树形分子与纳米氧化锌制备的电子传输层的电子传输能力。
在一些实施方式中，所述纳米金属氧化物选自ZnO、NiO、W
2O
3、Mo
2O
3、TiO
2、SnO、ZrO
2和Ta
2O
3中的一种或多种，但不限于此。在一些实施方式中，所述纳米金属氧化物的粒径为1-20nm。
在一些实施方式中，所述混合材料中，PAMAM树形分子与纳米金属氧化物的质量比为1-10:10。
在一些实施方式中，本公开还提供一种反式结构的量子点发光二极管，如图2所示，其包括从下往上依次层叠设置的基板101，阴极102、电子传输层103、量子点发光层104、空穴传输层105和阳极106，其中，所述电子传输层材料为由PAMAM树形分子 和纳米金属氧化物组成的混合材料。
需说明的是，本公开不限于上述结构的量子点发光二极管，还可进一步包括界面功能层或界面修饰层，包括但不限于电子阻挡层、空穴阻挡层、电极修饰层、隔离保护层中的一种或多种。本公开所述量子点发光二极管可以部分封装、全封装或不封装。
在一些实施方式中，所述阳极的材料选自掺杂金属氧化物；其中，所述掺杂金属氧化物包括但不限于铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)、铝掺杂氧化锌(AZO)、镓掺杂氧化锌(GZO)、铟掺杂氧化锌(IZO)、镁掺杂氧化锌(MZO)、铝掺杂氧化镁(AMO)中的一种或多种。
在一些实施方式中，所述空穴传输层的材料选自具有良好空穴传输能力的有机材料，例如可以为但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4’,4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)、掺杂石墨烯、非掺杂石墨烯和C60中的一种或多种。
在一些实施方式中，所述量子点发光层的材料选自红量子点、绿量子点、蓝量子点中的一种或多种，也可选自黄光量子点。具体的，所述量子点发光层的材料选自CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、以及各种核壳结构量子点或合金结构量子点中的一种或多种。本公开所述量子点可以选自含镉或者不含镉量子点。该材料的量子点发光层具有激发光谱宽并且连续分布，发射光谱稳定性高等特点。
在一些实施方式中，所述阴极的材料选自导电碳材料、导电金属氧化物材料和金属材料中的一种或多种；其中导电碳材料包括但不限于掺杂或非掺杂碳纳米管、掺杂或非掺杂石墨烯、掺杂或非掺杂氧化石墨烯、C60、石墨、碳纤维和多孔碳中的一种或多种；导电金属氧化物材料包括但不限于ITO、FTO、ATO和AZO中的一种或多种；金属材料包括但不限于Al、Ag、Cu、Mo、Au、或它们的合金；其中所述金属材料中，其形态 包括但不限于致密薄膜、纳米线、纳米球、纳米棒、纳米锥和纳米空心球中的一种或多种。
进一步地，本公开还提供一种如图1所示正式结构量子点发光二极管的制备方法，其中，如图3所示，包括步骤：
S10、提供一阳极基板；
S20、在所述阳极基板上制备量子点发光层；
S30、在所述量子点发光层上制备电子传输层，其中，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料；
S40、在所述电子传输层上制备阴极，制得所述量子点发光二极管。
具体的，量子点发光二极管分正型结构和反型结构。正型结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，正型结构的阳极设置在衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层，在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。反型结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，反型结构的阴极设置在衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层，在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。
对于正型器件而言，设置在衬底上的底电极为阳极，在本公开的一种实施方式中，所述阳极基板可以为衬底上设置底电极；在本公开的又一种实施方式中，所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极和层叠设置在衬底表面的空穴传输层；在本公开的又一种实施方式中，所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的空穴注入层和层叠设置在空穴注入层表面的空穴传输层；在本公开的还一种实施方式中，所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的空穴注入层、层叠设置在空穴注入层表面的空穴传输层和层叠设置在空穴传输层表面的电子阻挡层。
对于反型器件而言，设置在衬底上的底电极为阴极，在本公开的一种实施方式中， 所述阴极基板可以为衬底上设置底电极；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的电子注入层。
上述各层的制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于物理镀膜法或溶液法，其中溶液法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
在一些实施方式中，所述混合材料的制备方法包括步骤：提供一种PAMAM树形分子；将所述PAMAM树形分子与纳米金属氧化物按照质量比为1-10:10的比例加入到极性溶剂中混合得到胶体溶液，对所述胶体溶液进行干燥处理制得所述混合材料。
在本实施例中，由于PAMAM树形分子外围含有大量的官能团，这些官能团大都具有较强的极性和负电性，这使得PAMAM树形分子在极性溶剂中具有较好的空间位阻效应，可有效避免PAMAM树形分子与纳米金属氧化物在极性溶剂中混合后发生团聚。
在一些实施方式中，所述极性溶剂选自水、乙醇和甲醇中的一种，但不限于此。更优选的，所述极性溶剂为乙醇。
在一些实施方式中，本实施例制备的胶体溶液中，PAMAM树形分子的浓度为10-40mg/ml。所述纳米金属氧化物的浓度为20-80mg/ml。
在一些实施方式中，所述纳米金属氧化物选自ZnO、NiO、W
2O
3、Mo
2O
3、TiO
2、SnO、ZrO
2和Ta
2O
3中的一种或多种，但不限于此。
在一些实施方式中，所述纳米金属氧化物的粒径为1-20nm。
在一些实施方式中，采用涂布或印刷的方式将所述胶体溶液制备成膜，并进行退火处理，得到由PAMAM树形分子和纳米金属氧化物形成的电子传输层。由于PAMAM树形分子具有一定的粘度，其与纳米金属氧化物混合形成胶体溶液后有利于成膜。
在一些实施方式中，所述胶体溶液制备成膜后，在60-150℃的条件下对所述膜层进行退火处理。在一些实施方式中，退火处理时间为15-60min。通过所述退火处理，可制 得由PAMAM树形分子和纳米金属氧化物形成的电子传输层。
由于PAMAM树形分子既是σ给予体又是π给予体，这使得PAMAM树形分子具有一定的电子传输能力，但是由于PAMAM树形分子本身不具有自由电子，因此其电子传输能力相对金属氧化物而言较弱。本公开将由PAMAM树形分子与纳米金属氧化物组成的混合材料作为量子点发光二极管的电子传输层材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
本公开还提供一种反式结构的含空穴传输层的QLED的制备方法，如图4所示，包括如下步骤：
S100、提供一基板，在所述基板上制备阴极；
S200、在所述阴极上制备电子传输层，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料；
S300、在电子传输层上制备量子点发光层；
S400、在量子点发光层上制备空穴传输层；
S500、在空穴传输层上制备阳极，得到QLED。
上述各层的制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于物理镀膜法或溶液法，其中溶液法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
下面通过实施例对本公开量子点发光二极管及其制备方法进行详细说明：
实施例1
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层材料为由第五代PAMAM树形分子和纳米氧化锌组成的混合材料。所述量子点发光二极管的制备方法包括步骤：
1)、纳米氧化锌的制备：将0.5mol的水合醋酸锌分散在25ml的二甲基亚砜中使其完全分散，将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散，将两种混合液进行室温混合搅拌1h进行离心清洗，制得纳米氧化锌；
2)胶体溶液的制备：将20mg的第五代PAMAM树形分子和50mg的纳米氧化锌加入到1ml乙醇中，混合制得胶体溶液；
3)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂PVK，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤2)中制得的胶体溶液，旋涂60s后以120℃退火处理30min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积150nm的铝电极，制得所述量子点发光二极管。
实施例2
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层为由第二代PAMAM树形分子和纳米氧化镍组成的混合材料。所述量子点发光二极管的制备方法包括步骤：
1)、纳米氧化镍的制备：将0.5mol的水合醋酸镍分散在25ml的二甲基亚砜中使其完全分散，将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散，将两种混合液进行室温混合搅拌1h进行离心清洗，制得纳米氧化镍；
2)胶体溶液的制备：将30mg的第二代PAMAM树形分子和70mg的纳米氧化镍加入到1ml乙醇中，混合制得胶体溶液；
3)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂TFB，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤2)中制得的胶体溶液，旋涂60s后以100℃退火处理40min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积100nm的铝电极，制得所述量子点发光二极管。
实施例3
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层为由第一代PAMAM树形分子、第四代PAMAM树形分子和纳米氧化镍组成的混合材料。所述量子点发光二极管的制备方法包括步骤：
1)、纳米氧化镍的制备：将0.5mol的水合醋酸镍分散在25ml的二甲基亚砜中使其完全分散，将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散，将两种混合液进行室温混合搅拌1h进行离心清洗，制得纳米氧化镍；
2)胶体溶液的制备：将10mg的第一代PAMAM树形分子、20mg的第四代PAMAM树形分子和60mg的纳米氧化镍加入到1ml乙醇中，混合制得胶体溶液；
3)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂TFB，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤2)中制得的胶体溶液，旋涂60s后以100℃退火处理40min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积100nm的铝电极，制得所述量子点发光二极管。
综上所述，本公开提供的量子点发光二极管包括电子传输层，所述电子传输层材料 为由PAMAM树形分子和纳米金属氧化物组成的混合材料。由于PAMAM树形分子既是σ给予体又是π给予体，这使得PAMAM树形分子具有一定的电子传输能力，但是由于PAMAM树形分子本身不具有自由电子，因此其电子传输能力相对金属氧化物而言较弱。本公开采用由PAMAM树形分子和纳米金属氧化物组成的混合材料作为电子传输层材料，可降低量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。
Claims (20)
- 一种量子点发光二极管，包括阴极、阳极以及设置在所述阴极和阳极之间的量子点发光层，所述阴极和量子点发光层之间还设置有电子传输层，其特征在于，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材料。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述PAMAM树形分子选自第一代至第十代PAMAM树形分子中的一种或多种。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述纳米金属氧化物选自ZnO、NiO、W 2O 3、Mo 2O 3、TiO 2、SnO、ZrO 2和Ta 2O 3中的一种或多种。
- 根据权利要求3所述的量子点发光二极管，其特征在于，所述纳米金属氧化物的粒径为1-20nm。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述混合材料中，所述PAMAM树形分子与纳米金属氧化物的质量比为1-10:10。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述阳极和量子点发光层之间设置有空穴功能层。
- 根据权利要求6所述的量子点发光二极管，其特征在于，所述空穴功能层包括空穴传输层、空穴注入层和电子阻挡层中的一种或多种。
- 根据权利要求7所述的量子点发光二极管，其特征在于，所述空穴传输层材料选自TFB、PVK、Poly-TPD、PFB、TCTA、CBP、TPD、NPB、掺杂石墨烯、非掺杂石墨烯和C60中的一种或多种。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述阴极和电子传输层之间还设置有电子注入层。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述阳极的材料选自ITO、FTO、ATO、AZO、GZO、IZO、MZO和AMO中的一种或多种。
- 根据权利要求1所述的量子点发光二极管，其特征在于，所述阴极的材料选自导电碳材料、导电金属氧化物材料和金属材料中的一种或多种。
- 一种量子点发光二极管的制备方法，其特征在于，包括步骤：提供一阳极基板，在所述阳极基板上制备量子点发光层，在所述量子点发光层上制备电子传输层，在所述电子传输层上制备阴极，制得所述量子点发光二极管；或者，提供一阴极基板，在所述阴极基板上制备电子传输层，在所述电子传输层上制备量子点发光层，在所述量子点发光层上制备阳极，制得所述量子点发光二极管；其中，所述电子传输层材料为由PAMAM树形分子和纳米金属氧化物组成的混合材 料。
- 根据权利要求12所述量子点发光二极管的制备方法，其特征在于，所述混合材料的制备方法包括步骤：提供一种PAMAM树形分子；将所述PAMAM树形分子与纳米金属氧化物加入到极性溶剂中混合得到胶体溶液，对所述胶体溶液进行干燥处理制得所述混合材料。
- 根据权利要求13所述量子点发光二极管的制备方法，其特征在于，所述PAMAM树形分子与纳米金属氧化物的质量比为1-10:10。
- 根据权利要求13所述量子点发光二极管的制备方法，其特征在于，所述极性溶剂选自水、乙醇和甲醇中的一种或多种。
- 根据权利要求13所述量子点发光二极管的制备方法，其特征在于，所述胶体溶液中，PAMAM树形分子的浓度为10-40mg/ml。
- 根据权利要求13所述量子点发光二极管的制备方法，其特征在于，所述胶体溶液中，纳米金属氧化物的浓度为20-80mg/ml。
- 根据权利要求12所述量子点发光二极管的制备方法，其特征在于，在所述量子点发光层上制备电子传输层的步骤包括：在所述量子点发光层上沉积所述胶体溶液，并进行退火处理，形成电子传输层；或者，在所述阴极基板上制备电子传输层的步骤包括：在所述阴极基板上沉积所述胶体溶液，并进行退火处理，形成电子传输层。
- 根据权利要求18所述量子点发光二极管的制备方法，其特征在于，所述退火处理的步骤中，退火温度为60-150℃。
- 根据权利要求18所述量子点发光二极管的制备方法，其特征在于，所述退处理的步骤中，退火时间为15-60min。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811432412.7 | 2018-11-28 | ||
| CN201811432412.7A CN111244295B (zh) | 2018-11-28 | 2018-11-28 | 一种量子点发光二极管及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020108071A1 true WO2020108071A1 (zh) | 2020-06-04 |
Family
ID=70853771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2019/108337 WO2020108071A1 (zh) | 2018-11-28 | 2019-09-27 | 一种量子点发光二极管及其制备方法 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN111244295B (zh) |
| WO (1) | WO2020108071A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349856A (zh) * | 2020-11-30 | 2021-02-09 | 河南工程学院 | 一种基于电晕放电界面修饰的量子点发光二极管及其制备方法 |
| WO2022227680A1 (zh) * | 2021-04-26 | 2022-11-03 | Tcl科技集团股份有限公司 | 发光器件及其制作方法、显示面板 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116981283A (zh) * | 2022-04-14 | 2023-10-31 | Tcl科技集团股份有限公司 | 发光器件、发光器件的制备方法以及显示装置 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060177376A1 (en) * | 2003-07-21 | 2006-08-10 | Dendritic Nanotechnologies, Inc. | Stabilized and chemically functionalized nanoparticles |
| CN103840048A (zh) * | 2014-03-14 | 2014-06-04 | 东南大学 | 反式全无机纳米氧化物量子点发光二极管及其制备方法 |
| CN103904178A (zh) * | 2014-04-11 | 2014-07-02 | 浙江大学 | 量子点发光器件 |
| CN106257703A (zh) * | 2015-06-18 | 2016-12-28 | 潘才法 | 一种包含有金属纳米团簇的电致发光器件 |
| CN107359264A (zh) * | 2017-08-03 | 2017-11-17 | 青岛海信电器股份有限公司 | 一种qled、制备方法及显示装置 |
| CN107492587A (zh) * | 2017-08-10 | 2017-12-19 | 青岛海信电器股份有限公司 | 一种qled显示器件、制备方法及应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006134666A (ja) * | 2004-11-04 | 2006-05-25 | Dainippon Printing Co Ltd | 分散液、薄膜および有機エレクトロルミネッセンス素子 |
| CN105449110B (zh) * | 2015-12-28 | 2018-11-20 | Tcl集团股份有限公司 | 基于有机无机复合传输层的量子点发光二极管及制备方法 |
| KR101794082B1 (ko) * | 2016-06-03 | 2017-11-06 | 고려대학교 산학협력단 | 아민기를 갖는 덴드리머로 리간드 치환된 양자점 발광층을 포함하는 양자점 발광소자 및 이의 제조방법 |
-
2018
- 2018-11-28 CN CN201811432412.7A patent/CN111244295B/zh active Active
-
2019
- 2019-09-27 WO PCT/CN2019/108337 patent/WO2020108071A1/zh active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060177376A1 (en) * | 2003-07-21 | 2006-08-10 | Dendritic Nanotechnologies, Inc. | Stabilized and chemically functionalized nanoparticles |
| CN103840048A (zh) * | 2014-03-14 | 2014-06-04 | 东南大学 | 反式全无机纳米氧化物量子点发光二极管及其制备方法 |
| CN103904178A (zh) * | 2014-04-11 | 2014-07-02 | 浙江大学 | 量子点发光器件 |
| CN106257703A (zh) * | 2015-06-18 | 2016-12-28 | 潘才法 | 一种包含有金属纳米团簇的电致发光器件 |
| CN107359264A (zh) * | 2017-08-03 | 2017-11-17 | 青岛海信电器股份有限公司 | 一种qled、制备方法及显示装置 |
| CN107492587A (zh) * | 2017-08-10 | 2017-12-19 | 青岛海信电器股份有限公司 | 一种qled显示器件、制备方法及应用 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349856A (zh) * | 2020-11-30 | 2021-02-09 | 河南工程学院 | 一种基于电晕放电界面修饰的量子点发光二极管及其制备方法 |
| CN112349856B (zh) * | 2020-11-30 | 2022-05-20 | 河南工程学院 | 一种基于电晕放电界面修饰的量子点发光二极管及其制备方法 |
| WO2022227680A1 (zh) * | 2021-04-26 | 2022-11-03 | Tcl科技集团股份有限公司 | 发光器件及其制作方法、显示面板 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111244295B (zh) | 2021-10-22 |
| CN111244295A (zh) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020108071A1 (zh) | 一种量子点发光二极管及其制备方法 | |
| CN111384273B (zh) | 一种量子点发光二极管及其制备方法 | |
| CN111384256B (zh) | 量子点发光二极管及其制备方法 | |
| RU2726713C2 (ru) | Легированный титанат | |
| Zhu et al. | All-solution-processed high-performance quantum dot light emitting devices employing an inorganic thiocyanate as hole injection layer | |
| JP2023517364A (ja) | ナノ材料、その製造方法及び量子ドット発光ダイオード | |
| CN113540368A (zh) | 复合材料及其制备方法和量子点发光二极管 | |
| KR102077534B1 (ko) | 용액 공정 기반 광 소자용 투명 상부전극의 제조 방법 및 이로부터 제조된 광 소자용 투명 상부전극 | |
| JP6156797B2 (ja) | 有機電子デバイス | |
| US20070236138A1 (en) | Organic light-emitting diodes with nanostructure film electrode(s) | |
| CN114039002B (zh) | 电子传输墨水、电子传输薄膜、电致发光二极管及显示器件 | |
| CN112531123B (zh) | 电子传输膜层的制备方法和量子点发光二极管的制备方法 | |
| WO2020108087A1 (zh) | 一种量子点发光二极管及其制备方法 | |
| WO2020108072A1 (zh) | 一种纳米金属氧化物及其制备方法、量子点发光二极管 | |
| WO2020108069A1 (zh) | 一种纳米金属氧化物及其制备方法、量子点发光二极管 | |
| CN111244297B (zh) | 一种量子点发光二极管及其制备方法 | |
| WO2023093494A1 (zh) | 电致发光器件及其制备方法、光电装置 | |
| TWI734564B (zh) | 鈣鈦礦太陽能電池及其製作方法 | |
| CN113130811B (zh) | 一种量子点发光二极管及其制备方法 | |
| WO2023051317A1 (zh) | 氧化钨纳米材料及其制备方法、光电器件 | |
| WO2022121802A1 (zh) | 复合纳米颗粒、量子点发光二极管及制备方法 | |
| WO2020108079A1 (zh) | 一种量子点的制备方法 | |
| WO2022252608A1 (zh) | 一种量子点发光二极管及其制备方法 | |
| CN115915887A (zh) | 氧化钼纳米材料及制备方法、空穴功能薄膜及光电器件 | |
| CN114203940A (zh) | 薄膜的制备方法和发光二极管 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19889586 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19889586 Country of ref document: EP Kind code of ref document: A1 |