CN118057939A - Light-emitting device, preparation method thereof and display device - Google Patents
Light-emitting device, preparation method thereof and display device Download PDFInfo
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- CN118057939A CN118057939A CN202211448866.XA CN202211448866A CN118057939A CN 118057939 A CN118057939 A CN 118057939A CN 202211448866 A CN202211448866 A CN 202211448866A CN 118057939 A CN118057939 A CN 118057939A
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- 239000000463 material Substances 0.000 claims abstract description 72
- 238000002347 injection Methods 0.000 claims abstract description 64
- 239000007924 injection Substances 0.000 claims abstract description 64
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- 150000001875 compounds Chemical class 0.000 claims abstract description 60
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- 239000012621 metal-organic framework Substances 0.000 claims abstract description 43
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 12
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 11
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
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- 241000764773 Inna Species 0.000 claims description 3
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The application belongs to the technical field of photoelectric light emitting and display devices and relates to a light emitting device, a preparation method thereof and a display device, wherein the light emitting device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electronic functional layer and a cathode which are sequentially laminated; the light-emitting device further comprises a first interface modification layer arranged between the hole transport layer and the hole injection layer and/or a second interface modification layer arranged between the light-emitting layer and the electronic functional layer; the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide, and the material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds. The technical scheme provided by the application can prevent the corrosion of the acidic substance of the hole injection layer to the hole transport layer, improve the electron injection efficiency, weaken the damage of external moisture to the light-emitting layer, and further improve the stability and efficiency of the quantum dot light-emitting diode.
Description
Technical Field
The application relates to the technical field of photoelectric light emitting and display devices, in particular to a light emitting device, a preparation method thereof and a display device.
Background
In recent years, with the rapid development of display technology, a Quantum Dot LIGHT EMITTING Diodes (QLED) using a semiconductor Quantum Dot material as a light-emitting layer has received attention. The quantum dot light emitting diode has the advantages of high color purity, high luminous efficiency, adjustable luminous color, stable device and the like, and has wide application prospect in the fields of flat panel display, solid state lighting and the like.
The QLED device structure generally comprises an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode, wherein electrons and holes are injected from two ends of the cathode and the anode respectively, and light is emitted in a composite manner at the quantum dot light-emitting layer. The preparation of the QLED screen at the present stage mainly can be prepared by a method of ink-jet printing and vapor deposition of an electrode. In the preparation process of the QLED device, a hole injection layer and a hole transport layer which are commonly used are respectively PEDOT: PSS and TFB, but PEDOT is acidic and can corrode adjacent TFB layers during device application, thereby rendering the device useless. In addition, since the light emission mechanism of the QLED device is that one QD (Quantum Dot) firstly receives one electron to form QD-, and then one hole is received to form QD exciton, in order to improve the light emission efficiency of the QLED device, first, injection of electrons is further improved. Finally, in the preparation or use process of the device, external moisture also permeates into the quantum dot luminescent layer material, so that the performance of the device is reduced, the service life is shortened, and the like.
Disclosure of Invention
The technical problems to be solved by the application are that in the prior art, a hole transport layer is easily corroded by acidic substances of adjacent hole injection layers, the electron injection efficiency of an electron functional layer is low, a light-emitting layer is easily corroded by water penetration and the like.
In order to solve the above technical problems, an embodiment of the present application provides a light emitting device, which adopts the following technical scheme:
Comprises an anode and a cathode;
a light-emitting layer disposed between the anode and the cathode;
An electron functional layer disposed between the light emitting layer and the cathode;
a hole transport layer disposed between the anode and the light emitting layer;
A hole injection layer disposed between the anode and the hole transport layer;
The light-emitting device further comprises a first interface modification layer arranged between the hole transport layer and the hole injection layer and/or a second interface modification layer arranged between the light-emitting layer and the electronic function layer;
wherein the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide;
The material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds.
Further, the metal element in the polyoxometalate comprises at least one of Mo, W and V;
The metal element in the metal-organic framework compound comprises at least one of Cu, zn, fe, co, ni;
the organic ligand in the metal organic framework compound is selected from aromatic polyacid compounds.
Further, the polyoxometalate comprises at least one of phosphomolybdate, phosphotungstate and phosphovanadate;
The aromatic polyacid compound comprises at least one of terephthalic acid, trimesic acid and pyromellitic acid.
Further, the thickness of the hole injection layer is 20-100nm;
And/or the thickness of the first interface modification layer is 5-10nm;
And/or the thickness of the hole transport layer is 30-50nm;
and/or the thickness of the light-emitting layer is 15-60nm;
and/or the thickness of the second interface modification layer is 5-10nm;
And/or the thickness of the electronic functional layer is 20-150nm;
And/or the material of the anode and/or the cathode comprises one or more of a metal material, a carbon material, and a metal oxide, the metal material comprising one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nanotubes, graphene and carbon fibers; the metal oxide comprises doped or undoped metal oxide, the doped metal oxide comprises one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or a composite electrode comprising one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2, wherein metal is sandwiched between the doped or undoped transparent metal oxide;
And/or the light-emitting layer is a quantum dot light-emitting layer; the material of the quantum dot luminescent layer comprises at least one of single-structure quantum dots and core-shell structure quantum dots, wherein the material of the single-structure quantum dots is selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds, wherein the II-VI group compounds 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 compounds 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 compounds 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 or InAlPSb, and the I-III-VI group compounds are selected from at least one of CuInS2, cuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure;
And/or the electron functional layer comprises an electron transport layer and/or an electron injection layer, and the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium;
And/or the material of the hole injection layer comprises an organic material having a hole injection ability or an inorganic material having a hole transport ability, and the material of the hole injection layer comprises at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper polyestercarbonate (CuPc), moO 3、WO3, and other transition metal oxides, transition metal sulfides;
And/or the material of the hole transport layer comprises at least one of an organic hole transport material and an inorganic hole transport material, the organic material with hole transport capability comprises at least one of 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 "-tris (carbazole-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), graphene, C60 and non-doped or non-doped graphene, and at least one of the materials has no doping capability of 3, 3 o and no doping.
In order to solve the above technical problems, the embodiment of the present application further provides a method for manufacturing a light emitting device, which adopts the following technical scheme:
Providing an anode layer;
preparing a hole injection layer on the anode layer;
preparing a hole transport layer on the hole injection layer;
preparing a light emitting layer on the hole transport layer;
preparing an electronic functional layer on the light-emitting layer;
preparing a cathode on the electronic functional layer;
The method also comprises the following steps:
preparing a first interface modification layer on the hole injection layer, and preparing the hole transport layer on the first interface modification layer;
And/or preparing a second interface modification layer on the light-emitting layer, and preparing the electronic functional layer on the second interface modification layer; wherein the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide;
The material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds.
Further, the first interface modification layer is prepared from first interface modification ink;
the preparation steps of the first interface modification ink comprise:
Adding vanadium dioxide into water, adding ascorbic acid, heating and stirring, and then centrifugally washing and drying to obtain ascorbic acid treated vanadium dioxide;
And dissolving the ascorbic acid treated vanadium dioxide in an organic solvent, and performing ultrasonic dispersion to obtain the first interface modification ink.
Further, the mass ratio of the ascorbic acid to the vanadium dioxide powder is 10:9; the preset temperature is 55-65 ℃; the mass fraction of the vanadium dioxide in the ascorbic acid treated vanadium dioxide is 1-5 wt%.
Further, the second interface modification layer is prepared from second interface modification ink;
the preparation steps of the second interface modification ink comprise:
dissolving soluble metal salt and polyoxometalate in deionized water to prepare a solution A;
Dissolving an aromatic polyacid compound in ethanol to prepare a solution B;
Slowly dropwise adding the solution B into the solution A for reaction, and centrifugally drying after the reaction is finished to obtain a composite material consisting of polyoxometallate and a metal organic framework compound, wherein anions in polyoxometallate are anchored on the metal organic framework;
and dissolving the composite material consisting of the polyoxometallate and the metal organic framework compound in a solvent to prepare the second interface modification ink.
Further, the soluble metal salt comprises at least one of a soluble Cu salt, a soluble Zn salt, a soluble Fe salt, a soluble Co salt and a soluble Ni salt;
The metal element in the polyoxometalic acid comprises at least one of Mo, W and V;
The aromatic polyacid compound comprises at least one of terephthalic acid, trimesic acid and pyromellitic acid.
Further, the mass ratio of the soluble metal salt to the polyoxometalate is 10: (10-11);
the polyoxometalic acid comprises at least one of phosphomolybdic acid, phosphotungstic acid and phosphovanadic acid.
In order to solve the above technical problems, embodiments of the present application provide a display apparatus including the light emitting device described above or a light emitting device prepared by the preparation method described above.
Compared with the prior art, the embodiment of the application has the following main beneficial effects:
The light emitting device provided by the application comprises an anode and a cathode; the light-emitting layer is arranged between the anode and the cathode; an electron functional layer arranged between the light-emitting layer and the cathode; the hole transmission layer is arranged between the anode and the light-emitting layer; the hole injection layer is arranged between the anode and the hole transport layer; the light-emitting device further comprises a first interface modification layer arranged between the hole transport layer and the hole injection layer and/or a second interface modification layer arranged between the light-emitting layer and the electronic functional layer; wherein the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide, and the material of the second interface modification layer is selected from composite materials consisting of polyoxometallate and metal organic framework compounds; according to the application, the first interface modification layer is prepared by adopting the vanadium dioxide treated by the ascorbic acid, and is used as the modification layer of the hole injection layer, so that the corrosion of acidic substances of the hole injection layer to the hole transport layer can be prevented, the stability of the light-emitting device is improved, meanwhile, carriers are increased to be transmitted into the hole transport layer from the hole injection layer, and the transmission of the carriers is better promoted; the second interface modification layer is used as a modification layer of the electronic functional layer, the polyoxometallate has good oxidation capability and presents electronegativity, and a large number of naked oxygen atoms are contained on the surface of the polyoxometallate and can better receive electrons of the electronic functional layer, so that the electrons can be better injected into the luminescent layer, the starting voltage of the device is improved, the efficiency of the device is further improved, meanwhile, the skeleton structure of the metal-organic skeleton compound can improve the stability of the polyoxometallate material, and meanwhile, the porous nature of the metal-organic skeleton compound material can absorb moisture, so that the invasion of water molecules is inhibited, the material of the luminescent layer is protected from being invaded by water molecules, the stability of the device is improved, and the luminous efficiency and the service life of the device are further improved.
Drawings
In order to more clearly illustrate the solution of the present application, a brief description will be given below of the drawings required for the description of the embodiments, it being obvious that the drawings in the following description are some embodiments of the present application, and that other drawings may be obtained from 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;
fig. 4 is a flowchart of an embodiment of a method of manufacturing a light emitting device according to the present application;
Fig. 5 is a flowchart of another embodiment of a method of manufacturing a light emitting device according to the present application;
Fig. 6 is a flowchart of still another embodiment of a method of manufacturing a light emitting device according to the present application.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used in the description of the applications herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion. The terms first, second and the like in the description and in the claims or in the above-described figures, are used for distinguishing between different objects and not necessarily for describing a sequential or chronological order.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
An embodiment of the present application provides a light emitting device, as shown in fig. 1, including an anode 10, a cathode 20, a light emitting layer 30, an electron functional layer 40, a hole transporting layer 50, a hole injecting layer 60, and a first interface modification layer 70 and/or a second interface modification layer 80.
Wherein the light emitting layer 30 is disposed between the anode 10 and the cathode 20, the hole transporting layer 50 is disposed between the anode 10 and the light emitting layer 30, the hole injecting layer 60 is disposed between the anode 10 and the hole transporting layer 50, and the first interface modifying layer 70 is disposed between the hole transporting layer 50 and the hole injecting layer 60; the material of the first interface modification layer 70 is selected from ascorbic acid treated vanadium dioxide (VO 2).
VO 2 is a P-type semiconductor, a new V-O-C peak position occurs through VO 2 treated with ascorbic acid (C 6H8O6), and the formation of this peak position provides an effective path for hole carriers of the hole injection layer 20 to be transferred into VO 2, so that the hole carrier transport can be better promoted, whereas VO 2 after ascorbic acid treatment has an acid-resistant principle mainly as follows: VO 2 reacts with acidic substances under the action of a certain excessive hole carrier to generate high oxygen vacancies of HVO 2,HVO2, and does not react with H+, so that the acid-resistant material has a certain acid resistance.
Referring to fig. 2, in the present embodiment, the light emitting device further includes an electron functional layer 40 disposed between the light emitting layer 30 and the cathode 20, and a second interface modification layer 80 disposed between the light emitting layer 30 and the electron functional layer 40; the material of the second interface modification layer 80 is selected from a composite material consisting of a polyoxometalate and a metal organic framework compound.
In this embodiment, the metal element in the polyoxometalate includes at least one of Mo, W, V; the metal element in the metal-organic framework compound comprises at least one of Cu, zn, fe, co, ni; the organic ligand in the metal organic framework compound is selected from aromatic polyacid compounds, and the aromatic polyacid compounds comprise at least one of terephthalic acid, trimesic acid and pyromellitic acid.
The polyoxometallate may be represented by POM, and the metal organic framework compound may be represented by MOF, so that the second interface modification layer 80 is a pom+mof composite material, and the pom+mof composite material is used as an interface modification layer of the electronic functional layer 40, and uses the oxidation capability of high valence state of transition metal (such as Mo, W, V, etc.) in the POM to present electronegativity, so that electrons of the electronic functional layer 40 can be better received, and the transmission of electron carriers to the light emitting layer 30 is increased.
In this embodiment, the POM is anchored on the MOF skeleton, and the MOF skeleton is a multi-layer structure and a porous structure, and meanwhile, the stability of the second interface modification layer 80 can be increased by utilizing the stability of the MOF multi-layer structure and the hygroscopicity of the porous structure, so that the luminescent material is protected from being corroded by water molecules, and the stability of the light emitting device is improved.
The second interface modification layer prepared by the POM+MOF composite material is used for modifying the electronic functional layer 40, and has good oxidation capability to present electronegativity due to the fact that transition metals (such as Mo, W and V) in the POM are usually in a high valence state, and a large number of naked oxygen atoms are contained on the surface of the second interface modification layer and can better receive electrons of the electronic functional layer, so that electrons can be better injected into a light-emitting layer, the starting voltage of a device is improved, the efficiency of the device is further improved, meanwhile, the skeleton structure of the MOF can improve the stability of the POM material, and besides, the porous nature of the MOF material can absorb moisture, so that the invasion of water molecules is restrained, the light-emitting layer material is prevented from being invaded by water molecules, the stability of the device is improved, and the light-emitting efficiency and the service life of the device are further improved.
In this embodiment, the thickness of the hole injection layer 60 is 20 to 100nm, specifically 20-40nm、20-50nm、20-60nm、20-70nm、20-80nm、40-50nm、40-60nm、40-70nm、40-80nm、40-100nm、50-60nm、50-70nm、50-80nm、50-100nm、60-70nm、60-80nm、60-100nm、70-80nm、70-100nm and 80 to 100nm, etc., and for example, the thickness of the hole injection layer 60 may be 20nm, 40nm, 50nm, 60nm, 70nm, 80nm, 100nm, etc.
The thickness of the first interface modification layer 70 is 5 to 10nm, and a specific range may be 5 to 6nm, 5 to 7nm, 5 to 8nm, 5 to 9nm, 6 to 7nm, 6 to 8nm, 6 to 9nm, 6 to 10nm, 7 to 8nm, 7 to 9nm, 7 to 10nm, 8 to 9nm, 8 to 10nm, 9 to 10nm, etc., for example, the thickness of the first interface modification layer 70 may be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc.
The thickness of the hole transport layer 50 is 30 to 50nm, and specific ranges may be 30 to 35nm, 30 to 40nm, 30 to 45nm, 35 to 40nm, 35 to 45nm, 35 to 50nm, 40 to 45nm, 40 to 50nm, 45 to 50nm, etc., and for example, the thickness of the hole transport layer 50 may be 30nm, 35nm, 40nm, 45nm, 50nm, etc.
The thickness of the light emitting layer 30 is 15 to 60nm, and a specific range may be 15-25nm、15-35nm、15-45nm、15-50nm、15-60nm、25-35nm、25-45nm、25-50nm、25-60nm、35-45nm、35-50nm、35-60nm、45-50nm、45-60nm、50-60nm or the like, for example, the thickness of the light emitting layer 30 may be 15nm, 25nm, 35nm, 45nm, 50nm, 60nm or the like.
The thickness of the second interface modification layer 80 is 5 to 10nm, and a specific range may be 5 to 6nm, 5 to 7nm, 5 to 8nm, 5 to 9nm, 6 to 7nm, 6 to 8nm, 6 to 9nm, 6 to 10nm, 7 to 8nm, 7 to 9nm, 7 to 10nm, 8 to 9nm, 8 to 10nm, 9 to 10nm, etc., for example, the thickness of the second interface modification layer 80 may be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc.
The thickness of the electron functional layer 40 is 20 to 150nm, and the specific range may be 20-40nm、20-60nm、20-80nm、20-90nm、20-110nm、20-130nm、20-150nm、40-60nm、40-80nm、40-90nm、40-110nm、40-130nm、40-150nm、60-80nm、60-90nm、60-110nm、60-130nm、60-150nm、80-90nm、80-110nm、80-130nm、80-150nm、90-110nm、90-130nm、90-150nm、110-130nm、110-150nm and 130 to 150nm, etc., for example, the thickness of the electron functional layer 40 may be 20nm, 40nm, 60nm, 80nm, 90nm, 110nm, 130nm, 150nm, etc.
It should be noted that, each layer is selected to have a proper thickness according to the actual situation, so that the device efficiency can be improved.
In some alternative implementations of the present embodiment, the material of anode 10 and/or cathode 20 comprises one or more of a metal material, a carbon material, and a metal oxide, the metal material comprising one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber; the metal oxide includes doped or undoped metal oxide including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or a composite electrode including one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2 with metal sandwiched between doped or undoped transparent metal oxide.
In the present embodiment, the light emitting layer 30 is a quantum dot light emitting layer; the material of the quantum dot luminescent layer comprises at least one of single-structure quantum dots and core-shell structure quantum dots, the material of the single-structure quantum dots is selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds, wherein the II-VI group compounds 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 compounds 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 compounds 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 or InAlPSb, and the I -III- VI group compounds are selected from at least one of CuInS2, cuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
The electron functional layer 40 includes an electron transport layer and/or an electron injection layer, and a material of the electron transport layer and/or the electron injection layer includes an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium.
In this embodiment, the material of the hole injection layer 60 includes an organic material having hole injection capability or an inorganic material having hole injection capability, and the material of the hole injection layer includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper polyestercarbonate (CuPc), moO 3、WO3, and other transition metal oxides, transition metal sulfides.
The material of the hole transport layer 50 includes at least one of an organic hole transport material having a hole transport ability, an inorganic hole transport material, and the organic hole transport material includes at least one of 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 "-tris (carbazole-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60, and a non-doped or non-doped material of WO, and at least one of WO 3、MoO3.
The light emitting principle of the light emitting device is: under the drive of a certain voltage, electrons and holes are injected from the cathode 20 and the anode 10 to the electron functional layer 40 and the hole transport layer 50 respectively, the electrons and the holes migrate to the light emitting layer 30 through the electron functional layer 40 and the hole transport layer 50 respectively and meet in the quantum dot light emitting layer 30 to form excitons and excite light emitting molecules, and the light emitting molecules emit visible light through radiation relaxation.
In this embodiment, the first interface modification layer 70 modifies the interface of the hole injection layer 60, the second interface modification layer 80 modifies the interface of the electron functional layer 40, and the hole and electron transport efficiency are more matched through the first interface modification layer 70 and the second interface modification layer 80, so that the voltage of the quantum dot light emitting diode device can be reduced, and the light emitting efficiency of the quantum dot light emitting diode device can be improved.
Referring to fig. 4, based on the above light emitting device, the present application further provides a method for manufacturing a light emitting device, comprising the steps of:
in step S101, the anode layer 10 is provided.
Specifically, an anode substrate is provided, on which an anode layer 10 is provided.
Step S102, a hole injection layer 60 is prepared on the anode layer 10.
A hole injection material, such as PEDOT: PSS, moO 3、WO3, etc., is prepared on the anode layer 10 to a thickness of 20-100nm, forming a hole injection layer 60.
In step S103, the first interface modification layer 70 is prepared on the hole injection layer 60.
In this embodiment, the material of the first interface modification layer 70 is selected from ascorbic acid treated vanadium dioxide, and the first interface modification layer 70 is prepared from a first interface modification ink, where the preparation step of the first interface modification ink includes:
Adding vanadium dioxide powder into water, adding ascorbic acid, heating and stirring at a preset temperature, and then centrifugally washing and drying to obtain ascorbic acid treated vanadium dioxide;
Dissolving the ascorbic acid treated vanadium dioxide in an organic solvent, and performing ultrasonic dispersion to obtain the first interface modification ink.
Wherein deionized water can be selected as water, the preset temperature is 55-65 ℃, and the mass fraction of the vanadium dioxide in the ascorbic acid treated vanadium dioxide is 1-5 wt%.
The first interface modification ink is printed on the hole injection layer 60 to form a first interface modification layer 70 having a thickness of 5-10 nm.
In step S104, the hole transport layer 50 is prepared on the first interface modification layer 70.
In this embodiment, a hole transport material including, but not limited to, organic transport materials such as poly-TPD, TFB, inorganic transport materials such as NiO, moO 3, and composites of organic transport materials and inorganic transport materials is prepared on the first interface modification layer 70 to form the hole transport layer 50 having a thickness of 30-50 nm.
In step S105, the light-emitting layer 30 is prepared on the hole transport layer 50.
In this embodiment, the light emitting layer 30 is a quantum dot light emitting layer, a light emitting layer 30 having a thickness of 15-60nm is prepared on the hole transport layer 50, and then the light emitting layer 30 is annealed.
In step S106, the electronic function layer 40 is prepared on the light emitting layer 30.
An electron functional material is prepared on the light emitting layer 30 to form an electron functional layer 40. Wherein the electron functional layer 40 includes an electron transport layer and/or an electron injection layer.
Illustratively, the electron functional layer 40 includes an electron transport layer, and an electron transport material is prepared on the light emitting layer 40 to form the electron transport layer with a thickness of 50-150nm. Wherein the electron transport material includes, but is not limited to, at least one of inorganic transport materials such as ZnO, cs 2CO3, etc., and organic transport materials such as AlQ3, etc.
In step S107, the cathode 20 is prepared on the electronic functional layer 40, and the light emitting device is obtained.
Wherein, the cathode 20 is prepared on the electronic functional layer 40 by vacuum evaporation, and the light emitting device is obtained.
Specifically, aluminum (Al) or silver (Ag) is deposited on the electron function layer 40 by vacuum evaporation at an evaporation rate of 0.1-0.3nm/s to form the cathode 20 having a thickness of 50-100nm, thereby manufacturing a light emitting device.
In some optional implementations of this embodiment, referring to fig. 5, the method for manufacturing a light emitting device further includes the following steps:
Step S201, providing an anode layer 10;
Step S202, preparing the hole injection layer 60 on the anode layer 10;
Step S203 of preparing the hole transport layer 50 on the hole injection layer 60;
Step S204 of preparing the light emitting layer 30 on the hole transport layer 50;
Step S205, preparing a second interface modification layer 80 on the light emitting layer 30;
Step S206, preparing the electronic function layer 40 on the second interface modification layer 80;
In step S207, the cathode 20 is prepared on the electronic functional layer 40, and the light emitting device is obtained.
Wherein the material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds. In this embodiment, the second interface modification layer 80 is prepared from a second interface modification ink, and the preparation steps of the second interface modification ink include:
dissolving soluble metal salt and polyoxometalate in deionized water to prepare a solution A;
Dissolving an aromatic polyacid compound in ethanol to prepare a solution B;
slowly dripping the solution B into the solution A for reaction, and centrifugally drying after the reaction is finished to obtain a composite material consisting of polyoxometallate and a metal organic framework compound, wherein anions in polyoxometallate are anchored on the metal organic framework;
and dissolving the composite material consisting of the polyoxometallate and the metal organic framework compound in a solvent to prepare the second interface modification ink.
Wherein the soluble metal salt comprises at least one of soluble Cu salt, soluble Zn salt, soluble Fe salt, soluble Co salt and soluble Ni salt; the metal element in the polyoxometalic acid comprises at least one of Mo, W and V; the aromatic polyacid compound includes at least one of terephthalic acid, trimesic acid, and pyromellitic acid.
Illustratively, the soluble metal salt is soluble Cu salt copper acetate (Cu (OAc) 2), the polyoxometalate is phosphomolybdic acid (H 3PMo12O40) or phosphotungstic acid (H 3PW12O40), the aromatic polyacid compound is trimesic acid (H 3 BTC), the metallo-organic framework is formed by Cu and BTC, and the PMO anionic compound PMo 2O40 3- anionic compound or PW 12O40 3- anionic compound is anchored on the metallo-organic framework.
In this example, the mass ratio of the soluble metal salt to the polyoxometalate is 10: (10-11), printing the prepared second interface modification ink on the electronic function layer 40 to form a second interface modification layer 80 having a thickness of 5-10 nm.
In some alternative implementations, referring to fig. 6, the method for manufacturing a light emitting device further includes the steps of:
Step S301, providing an anode layer 10;
Step S302 of preparing the hole injection layer 60 on the anode layer 10;
step S303, preparing a first interface modification layer 70 on the hole injection layer 60;
step S304, preparing the hole transport layer 50 on the first interface modification layer 70;
Step S305 of preparing the light emitting layer 30 on the hole transport layer 50;
Step S306, preparing a second interface modification layer 80 on the light-emitting layer 30;
step S307, preparing the electronic functional layer 40 on the second interface modification layer 80;
In step S308, the cathode 20 is prepared on the electronic functional layer 40, and the light emitting device is obtained.
The light emitting device prepared by the embodiment of the application comprises the first interface modification layer 70 and the second interface modification layer 80, so that the stability of the light emitting device is improved, and meanwhile, the efficiency of the device is improved.
The application also provides a display device which comprises the light-emitting device or the light-emitting device prepared by the preparation method. The display device has high efficiency and long service life.
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
Example 1
The present embodiment provides an electronic light emitting device including a light emitting device (hereinafter referred to as QLED) and an encapsulation layer for encapsulating the QLED.
The structure of the electronic light emitting device is as follows: ITO substrate (anode 10)/PEDOT: PSS (hole injection layer 60)/AA-VO 2 (first interface modification layer 70)/poly-TPD (hole transport layer 50)/red quantum dot light emitting layer (light emitting layer 30)/phosphomolybdic acid+mof (second interface modification layer 80)/ZnO (electron transport layer 70)/silver electrode (cathode 20)/cap plate package.
Among them, ITO is an N-type oxide semiconductor-indium tin oxide, and an ITO thin film is an N-type indium tin oxide semiconductor transparent conductive film, which has high conductivity, high visible light transmittance, high mechanical hardness, and good chemical stability, and is generally used as an anode.
The PEDOT is PSS which is an aqueous solution of a high-molecular polymer, the conductivity is very high, the aqueous solution with different conductivities can be obtained according to different formulas, the aqueous solution consists of two substances of PEDOT and PSS, wherein the PEDOT is the polymer of EDOT (3, 4-ethylenedioxythiophene monomer), and the PSS is polystyrene sulfonate, and the two substances are combined together to greatly improve the solubility of the PEDOT.
The electronic light-emitting device of the embodiment is prepared according to the following method:
sequentially forming an HIL film layer (hole injection layer) on an ITO substrate according to the QLED structure of the embodiment, and then preparing a first interface modification layer on the HIL film layer, wherein the preparation method of the first interface modification layer is as follows:
Dispersing 0.45g of vanadium dioxide powder in 20ml of deionized water, slowly adding 0.5g of ascorbic acid, stirring for 6 hours at 60 ℃, and then centrifugally washing and drying to obtain ascorbic acid-treated VO 2 powder;
Weighing 3wt% of ascorbic acid-treated VO 2 powder, dissolving in an organic solvent ethanol, performing ultrasonic dispersion for 30min to uniformly disperse the powder to prepare 4mg/ml first interface modification ink, and printing 4 drops of the first interface modification ink on the HIL film layer to prepare a 6nm first interface modification layer;
Sequentially depositing an HTL layer (hole transport layer) and a QD light-emitting layer, and then preparing a second interface modification layer on the surface of the QD light-emitting layer, wherein the preparation method of the second interface modification layer is as follows:
Solution A was prepared by dissolving 0.2g of copper acetate (Cu (OAc) 2 and 0.22g of phosphomolybdic acid (H 3PMo12O40) in 10ml of deionized water;
0.14g of trimesic acid (H 3 BTC) is dissolved in 10ml of ethanol and recorded as a solution B;
Slowly dripping the solution B into the solution A to react for 30min, and centrifugally drying to obtain a MOF framework formed by Cu and BTC and a PMo 12O40 3- anionic compound anchored on the MOF framework;
Preparing MOF skeleton anchored with PMo 12O40 3- anion compound into 5mg/ml second interface modification ink, printing 7 drops of the second interface modification ink to form a film, and preparing a second interface modification layer with the thickness of 10 nm;
preparing a ZnO functional layer (electron transport layer) with the thickness of 30nm on the second interface modification layer by adopting a printing method;
And preparing a silver electrode (top electrode) with the thickness of 70nm on the ZnO functional layer by adopting a silver steaming method, and packaging the silver electrode by a cover plate to obtain the electronic light-emitting device.
Example 2
The embodiment provides an electronic light emitting device, which comprises a QLED and an encapsulation layer for encapsulating the QLED.
The structure of the electronic light emitting device is as follows: ITO substrate (anode 10)/PEDOT: PSS (hole injection layer 60)/AA-VO 2 (first interface modification layer 70)/poly-TPD (hole transport layer 50)/red quantum dot light emitting layer (light emitting layer 30)/phosphomolybdic acid+mof (second interface modification layer 80)/ZnO (electron transport layer 70)/silver electrode (cathode 20)/cap plate package.
The electronic light-emitting device of the embodiment is prepared according to the following method:
sequentially forming an HIL film layer (hole injection layer) on an ITO substrate according to the QLED structure of the embodiment, and then preparing a first interface modification layer on the HIL film layer, wherein the preparation method of the first interface modification layer is as follows:
Dispersing 0.45g of vanadium dioxide powder in 20ml of deionized water, slowly adding 0.5g of ascorbic acid, stirring for 6 hours at 60 ℃, and then centrifugally washing and drying to obtain ascorbic acid-treated VO 2 powder;
Weighing 3wt% of ascorbic acid-treated VO 2 powder, dissolving in an organic solvent ethanol, performing ultrasonic dispersion for 30min to uniformly disperse the powder to prepare 4mg/ml first interface modification ink, and printing 5 drops of the first interface modification ink on the HIL film layer to prepare an 8nm first interface modification layer;
Sequentially depositing an HTL layer (hole transport layer) and a QD light-emitting layer, and then preparing a second interface modification layer on the surface of the QD light-emitting layer, wherein the preparation method of the second interface modification layer is as follows:
Solution A was prepared by dissolving 0.2g of copper acetate (Cu (OAc) 2 and 0.22g of phosphomolybdic acid (H 3PMo12O40) in 10ml of deionized water;
0.14g of trimesic acid (H 3 BTC) is dissolved in 10ml of ethanol and recorded as a solution B;
Slowly dripping the solution B into the solution A to react for 30min, and centrifugally drying to obtain a MOF framework formed by Cu and BTC and a PMo 12O40 3- anionic compound anchored on the MOF framework;
Preparing MOF skeleton anchored with PMo 12O40 3- anion compound into 5mg/ml second interface modification ink, printing 4 drops of the second interface modification ink to form a film, and preparing a second interface modification layer with the thickness of 5 nm;
preparing a ZnO functional layer (electron transport layer) with the thickness of 30nm on the second interface modification layer by adopting a printing method;
And preparing a silver electrode (top electrode) with the thickness of 70nm on the ZnO functional layer by adopting a silver steaming method, and packaging the silver electrode by a cover plate to obtain the electronic light-emitting device.
Example 3
The embodiment provides an electronic light emitting device, which comprises a QLED and an encapsulation layer for encapsulating the QLED.
The structure of the electronic light emitting device is as follows: ITO substrate (anode 10)/PEDOT: PSS (hole injection layer 60)/AA-VO 2 (first interface modification layer 70)/poly-TPD (hole transport layer 50)/red quantum dot light emitting layer (light emitting layer 30)/phosphomolybdic acid+mof (second interface modification layer 80)/ZnO (electron transport layer 70)/silver electrode (cathode 20)/cap plate package.
The electronic light-emitting device of the embodiment is prepared according to the following method:
sequentially forming an HIL film layer (hole injection layer) on an ITO substrate according to the QLED structure of the embodiment, and then preparing a first interface modification layer on the HIL film layer, wherein the preparation method of the first interface modification layer is as follows:
Dispersing 0.45g of vanadium dioxide powder in 20ml of deionized water, slowly adding 0.5g of ascorbic acid, stirring for 6 hours at 60 ℃, and then centrifugally washing and drying to obtain ascorbic acid-treated VO 2 powder;
Weighing 3wt% of ascorbic acid-treated VO 2 powder, dissolving in an organic solvent ethanol, performing ultrasonic dispersion for 30min to uniformly disperse the powder to prepare 4mg/ml first interface modification ink, and printing 4 drops of the first interface modification ink on the HIL film layer to prepare a 6nm first interface modification layer;
Sequentially depositing an HTL layer (hole transport layer) and a QD light-emitting layer, and then preparing a second interface modification layer on the surface of the QD light-emitting layer, wherein the preparation method of the second interface modification layer is as follows:
Solution A was prepared by dissolving 0.2g of copper acetate (Cu (OAc) 2 and 0.2g of phosphotungstic acid (H 3PW12O40) in 10ml of deionized water;
0.14g of trimesic acid (H 3 BTC) is dissolved in 10ml of ethanol and recorded as a solution B;
Slowly dripping the solution B into the solution A to react for 30min, and centrifugally drying to obtain a MOF framework formed by Cu and BTC and PW 12O40 3- anionic compound anchored on the MOF framework;
Preparing MOF skeleton anchored with PMo 12O40 3- anion compound into 5mg/ml second interface modification ink, printing 6 drops of the second interface modification ink to form a film, and preparing a second interface modification layer with the thickness of 10 nm;
preparing a ZnO functional layer (electron transport layer) with the thickness of 30nm on the second interface modification layer by adopting a printing method;
And preparing a silver electrode (top electrode) with the thickness of 70nm on the ZnO functional layer by adopting a silver steaming method, and packaging the silver electrode by a cover plate to obtain the electronic light-emitting device.
Example 4
The embodiment provides an electronic light emitting device, which comprises a QLED and an encapsulation layer for encapsulating the QLED.
The structure of the electronic light emitting device is as follows: ITO substrate-Ag 150nm-ITO substrate (anode 10)/PEDOT: PSS (hole injection layer 60)/AA-VO 2 (first interface modification layer 70)/poly-TPD (hole transport layer 50)/red quantum dot light emitting layer (light emitting layer 30)/phosphomolybdic acid+mof (second interface modification layer 80)/ZnO (electron transport layer 70)/silver electrode (cathode 20)/cap plate package.
The electronic light-emitting device of the embodiment is prepared according to the following method:
sequentially forming an HIL film layer (hole injection layer) on an ITO substrate according to the QLED structure of the embodiment, and then preparing a first interface modification layer on the HIL film layer, wherein the preparation method of the first interface modification layer is as follows:
Dispersing 0.45g of vanadium dioxide powder in 20ml of deionized water, slowly adding 0.5g of ascorbic acid, stirring for 6 hours at 60 ℃, and then centrifugally washing and drying to obtain ascorbic acid-treated VO 2 powder;
Weighing 3wt% of ascorbic acid-treated VO 2 powder, dissolving in an organic solvent ethanol, performing ultrasonic dispersion for 30min to uniformly disperse the powder to prepare 4mg/ml first interface modification ink, and printing 4 drops of the first interface modification ink on the HIL film layer to prepare a 6nm first interface modification layer;
Sequentially depositing an HTL layer (hole transport layer) and a QD light-emitting layer, and then preparing a second interface modification layer on the surface of the QD light-emitting layer, wherein the preparation method of the second interface modification layer is as follows:
Solution A was prepared by dissolving 0.2g of copper acetate (Cu (OAc) 2 and 0.22g of phosphomolybdic acid (H 3PMo12O40) in 10ml of deionized water;
0.14g of trimesic acid (H 3 BTC) is dissolved in 10ml of ethanol and recorded as a solution B;
Slowly dripping the solution B into the solution A to react for 30min, and centrifugally drying to obtain a MOF framework formed by Cu and BTC and a PMo 12O40 3- anionic compound anchored on the MOF framework;
Preparing MOF skeleton anchored with PMo 12O40 3- anion compound into 5mg/ml second interface modification ink, printing 7 drops of the second interface modification ink to form a film, and preparing a second interface modification layer with the thickness of 10 nm;
preparing a ZnO functional layer (electron transport layer) with the thickness of 30nm on the second interface modification layer by adopting a printing method;
And preparing a silver electrode (top electrode) with the thickness of 30nm on the ZnO functional layer by adopting a silver steaming method, and packaging the silver electrode by a cover plate to obtain the electronic light-emitting device.
It should be noted that examples 1 to 3 are bottom light emitting devices, example 4 is a top light emitting device, the bottom light emitting device is a bottom electrode which is ITO, and light is emitted from the bottom, and this structure is generally used for screening materials; the bottom electrode of the top light emitting device is an ITO + metal reflective electrode (typically Ag) +ito so that light is reflected from the bottom and emitted from the top, and this structure is typically a structure for a display screen, and the brightness efficiency of the device is typically high due to the reflection of the light involved.
Embodiment 1 to embodiment 4 illustrate that the above quantum dot light emitting diode has versatility, and can be applied to both a bottom light emitting device and a top light emitting device.
Example 5
Example 5 differs from example 1 in that: the second interface modification layer is not arranged, and the structure is as follows: ITO substrate/PEDOT: PSS (50 nm)/AA-VO 2 (6 nm)/poly-TPD (30 nm)/red quantum dot luminescent layer (20 nm)/ZnO (30 nm)/silver electrode (70 nm)/cover plate package.
Example 6
Example 6 differs from example 1 in that: the structure of the first interface modification layer is not arranged, and the structure is as follows: ITO substrate/PEDOT: PSS (50 nm)/poly-TPD (30 nm)/red quantum dot luminescent layer/(20 nm)/phosphomolybdic acid+MOF (10 nm)/ZnO (30 nm)/silver electrode (70 nm)/cover plate package.
Comparative example
The comparative example differs from example 1 in that: the structure of the first interface modification layer and the second interface modification layer is that: ITO substrate/PEDOT: PSS (50 nm)/poly-TPD (30 nm)/red quantum dot luminescent layer (20 nm)/ZnO (30 nm)/silver electrode (70 nm)/cover plate package.
Experimental test analysis:
Experimental test analysis was performed on the electron-emitting devices in examples 1 to 6 and comparative examples, and the analysis results are shown in table 1.
TABLE 1
EQE is the ratio of device exciton conversion to photon, which is commonly used to characterize the efficiency of a device, the higher the EQE, the higher the device efficiency; lt95@1000nit refers to the time required for the device to decay to 950Nit brightness at an initial brightness of 1000Nit, the longer the time the more stable the device.
As can be seen from the above table, the electronic light emitting device provided with only the first interface modification layer or the second interface modification layer has improved device efficiency and device stability, while the electronic light emitting device provided with the first interface modification layer and the second interface modification layer has high device efficiency, greatly improved device stability, and further improved device lifetime.
It is apparent that the above-described embodiments are only some embodiments of the present application, but not all embodiments, and the preferred embodiments of the present application are shown in the drawings, which do not limit the scope of the patent claims. This application may be embodied in many different forms, but rather, embodiments are provided in order to provide a thorough and complete understanding of the present disclosure. Although the application has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing description, or equivalents may be substituted for elements thereof. All equivalent structures made by the content of the specification and the drawings of the application are directly or indirectly applied to other related technical fields, and are also within the scope of the application.
Claims (11)
1. A light emitting device, comprising:
An anode and a cathode;
a light-emitting layer disposed between the anode and the cathode;
An electron functional layer disposed between the light emitting layer and the cathode;
a hole transport layer disposed between the anode and the light emitting layer;
A hole injection layer disposed between the anode and the hole transport layer;
The light-emitting device further comprises a first interface modification layer arranged between the hole transport layer and the hole injection layer and/or a second interface modification layer arranged between the light-emitting layer and the electronic function layer;
wherein the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide;
The material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds.
2. The light-emitting device according to claim 1, wherein the metal element in the polyoxometalate includes at least one of Mo, W, V;
The metal element in the metal-organic framework compound comprises at least one of Cu, zn, fe, co, ni;
the organic ligand in the metal organic framework compound is selected from aromatic polyacid compounds.
3. The light-emitting device according to claim 2, wherein the polyoxometalate comprises at least one of phosphomolybdate, phosphotungstate, and phosphovanadate;
The aromatic polyacid compound comprises at least one of terephthalic acid, trimesic acid and pyromellitic acid.
4. A light-emitting device according to any one of claims 1 to 3, wherein the thickness of the hole injection layer is 20-100nm;
And/or the thickness of the first interface modification layer is 5-10nm;
And/or the thickness of the hole transport layer is 30-50nm;
and/or the thickness of the light-emitting layer is 15-60nm;
and/or the thickness of the second interface modification layer is 5-10nm;
And/or the thickness of the electronic functional layer is 20-150nm;
And/or the material of the anode and/or the cathode comprises one or more of a metal material, a carbon material, and a metal oxide, the metal material comprising one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nanotubes, graphene and carbon fibers; the metal oxide comprises doped or undoped metal oxide, the doped metal oxide comprises one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or a composite electrode comprising one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2, wherein metal is sandwiched between the doped or undoped transparent metal oxide;
And/or the light-emitting layer is a quantum dot light-emitting layer; the material of the quantum dot luminescent layer comprises at least one of single-structure quantum dots and core-shell structure quantum dots, wherein the material of the single-structure quantum dots is selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds, wherein the II-VI group compounds 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 compounds 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 compounds 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 or InAlPSb, and the I-III-VI group compounds are selected from at least one of CuInS2, cuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure;
And/or the electron functional layer comprises an electron transport layer and/or an electron injection layer, and the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium;
And/or the material of the hole injection layer comprises an organic material having a hole injection ability or an inorganic material having a hole transport ability, and the material of the hole injection layer comprises at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper polyestercarbonate (CuPc), moO 3、WO3, and other transition metal oxides, transition metal sulfides;
And/or the material of the hole transport layer comprises at least one of an organic hole transport material and an inorganic hole transport material, wherein the organic hole transport material comprises 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 "-tris (carbazol-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazol) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60, the inorganic hole transport material comprising at least one of doped or undoped NiO, WO3, moO3, and CuO.
5. A method of fabricating a light emitting device, comprising the steps of:
Providing an anode layer;
preparing a hole injection layer on the anode layer;
preparing a hole transport layer on the hole injection layer;
preparing a light emitting layer on the hole transport layer;
preparing an electronic functional layer on the light-emitting layer;
preparing a cathode on the electronic functional layer;
The method is characterized by further comprising the following steps:
preparing a first interface modification layer on the hole injection layer, and preparing the hole transport layer on the first interface modification layer;
and/or preparing a second interface modification layer on the light-emitting layer, and preparing the electronic functional layer on the second interface modification layer;
wherein the material of the first interface modification layer is selected from ascorbic acid treated vanadium dioxide;
The material of the second interface modification layer is selected from composite materials consisting of polyoxometalate and metal organic framework compounds.
6. The method of manufacturing a light-emitting device according to claim 5, wherein the first interface modification layer is manufactured from a first interface modification ink;
the preparation steps of the first interface modification ink comprise:
Adding vanadium dioxide powder into water, adding ascorbic acid, heating and stirring at a preset temperature, and then centrifugally washing and drying to obtain ascorbic acid treated vanadium dioxide;
And dissolving the ascorbic acid treated vanadium dioxide in an organic solvent, and performing ultrasonic dispersion to obtain the first interface modification ink.
7. The method of manufacturing a light-emitting device according to claim 6, wherein a mass ratio of the ascorbic acid to the vanadium dioxide powder is 10:9; the preset temperature is 55-65 ℃; the mass fraction of the vanadium dioxide in the ascorbic acid treated vanadium dioxide is 1-5 wt%.
8. The method of manufacturing a light-emitting device according to claim 5, wherein the second interface modification layer is manufactured from a second interface modification ink;
the preparation steps of the second interface modification ink comprise:
dissolving soluble metal salt and polyoxometalate in deionized water to prepare a solution A;
Dissolving an aromatic polyacid compound in ethanol to prepare a solution B;
Slowly dropwise adding the solution B into the solution A for reaction, and centrifugally drying after the reaction is finished to obtain a composite material consisting of polyoxometallate and a metal organic framework compound, wherein anions in polyoxometallate are anchored on the metal organic framework;
and dissolving the composite material consisting of the polyoxometallate and the metal organic framework compound in a solvent to prepare the second interface modification ink.
9. The method of manufacturing a light-emitting device according to claim 8, wherein the soluble metal salt includes at least one of a soluble Cu salt, a soluble Zn salt, a soluble Fe salt, a soluble Co salt, and a soluble Ni salt;
The metal element in the polyoxometalic acid comprises at least one of Mo, W and V;
The aromatic polyacid compound comprises at least one of terephthalic acid, trimesic acid and pyromellitic acid.
10. The method of manufacturing a light-emitting device according to claim 8, wherein the mass ratio of the soluble metal salt to the polyoxometalate is 10: (10-11);
the polyoxometalic acid comprises at least one of phosphomolybdic acid, phosphotungstic acid and phosphovanadic acid.
11. A display device comprising the light-emitting device according to any one of claims 1 to 4 or a light-emitting device produced by the production method according to any one of claims 5 to 10.
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