CN114203940B - Method for preparing film and light-emitting diode - Google Patents
Method for preparing film and light-emitting diode Download PDFInfo
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- CN114203940B CN114203940B CN202010977460.5A CN202010977460A CN114203940B CN 114203940 B CN114203940 B CN 114203940B CN 202010977460 A CN202010977460 A CN 202010977460A CN 114203940 B CN114203940 B CN 114203940B
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- 238000000034 method Methods 0.000 title claims abstract description 51
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- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims description 35
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910016001 MoSe Inorganic materials 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
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- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims description 4
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- GYPAGHMQEIUKAO-UHFFFAOYSA-N 4-butyl-n-[4-[4-(n-(4-butylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(CCCC)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC(CCCC)=CC=1)C1=CC=CC=C1 GYPAGHMQEIUKAO-UHFFFAOYSA-N 0.000 claims description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
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- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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- FAPCZAUMFXUDMS-UHFFFAOYSA-N 4-bromo-3-(dibromomethyl)-2-hydroxy-2h-furan-5-one Chemical group OC1OC(=O)C(Br)=C1C(Br)Br FAPCZAUMFXUDMS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 239000007850 fluorescent dye Substances 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
- H10K50/155—Hole transporting layers comprising dopants
-
- 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The application relates to the technical field of display, and provides a preparation method of a film and a light-emitting diode. The preparation method of the film provided by the application comprises the following steps: providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film; and (3) carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film under an inert atmosphere. By the method, the aromatic compound can further dissolve and disperse large granular substances on the surface of the dry film in the infiltration process, so that the uniformity of particles on the surface of the film is improved, the roughness of the surface of the film is reduced, and the film with a flat surface is obtained. When the light-emitting diode is applied to the hole functional layer of the light-emitting diode, the film morphology of the hole functional layer is improved, the interface resistance of the hole functional layer and the light-emitting layer is reduced, the hole transmission efficiency of the device is improved, the hole transmission efficiency and the electron transmission efficiency of the device are effectively balanced, and therefore the photoelectric performance and the service life of the device are improved.
Description
Technical Field
The application belongs to the technical field of display, and particularly relates to a preparation method of a film and a light-emitting diode.
Background
QLED (Quantum Dots Light-emission Diode) is an emerging display device, which has a structure similar to OLED (Organic Light-emission Diode), i.e. a sandwich structure mainly composed of a hole transport layer, a Light Emitting layer and an electron transport layer. This is a novel technology between liquid crystal and OLED, the core technology of QLED is "Quantum Dot", which is a particle with particle diameter less than 10nm, often composed of zinc, cadmium, selenium and sulfur atoms. As early as 1983, scientists in the bell laboratories in the united states conducted intensive studies, and after a few years, the physicist mark-reed at the university of us formally named "quantum dots". This material has an extremely specific property: when the quantum dot is stimulated by photoelectricity, colored light is emitted, the color is determined by the material composing the quantum dot and the size and shape of the quantum dot, and by utilizing the characteristic, the color of the light emitted by the light source can be changed. The light-emitting wavelength range of the quantum dots is very narrow, the color is pure, and the color can be adjusted, so that the picture of the quantum dot display is clearer and brighter than that of the liquid crystal display.
Compared with OLED, QLED has the characteristic that the luminescent material adopts inorganic quantum dots with more stable performance. The unique quantum size effect, macroscopic quantum tunneling effect, quantum size effect and surface effect of quantum dots make them exhibit excellent physical properties, especially their optical properties. Compared with organic fluorescent dye, the quantum dot prepared by the colloid method has the advantages of adjustable spectrum, high luminous intensity, high color purity, long fluorescence life, capability of exciting multicolor fluorescence by a single light source, and the like. In addition, the QLED has long service life, simple packaging process or no need of packaging, and is expected to become a next-generation flat panel display, thereby having wide development prospect. QLED is electroluminescent based on inorganic semiconductor quantum dots, which theoretically have higher stability than small organic molecules and polymers; on the other hand, due to the quantum confinement effect, the light-emitting line width of the quantum dot material is smaller, so that the quantum dot material has better color purity. Currently, the light emitting efficiency of QLEDs has substantially reached the commercial demand.
However, the service life of the QLED device prepared in the actual current stage is far less than the theoretical due length, and the phenomenon of fluorescence quenching often occurs in the testing process, so that the development and development progress of the quantum dot light-emitting device are greatly restricted. The above problems are mainly caused by imbalance of the transport rates of hole carriers and electron carriers of the device. Therefore, how to solve the problem of unbalance between the hole transmission efficiency and the electron transmission rate of the device is the focus of the research and development of quantum dots at the present stage.
Disclosure of Invention
The present application is directed to a method for preparing a thin film, a method for preparing a light emitting diode, and aims to solve the problem that the hole transport efficiency and the electron transport rate of the existing light emitting diode are unbalanced.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a film, comprising the steps of:
providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
and carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in the inert atmosphere to obtain the film.
In a second aspect, the present application provides a method for preparing a light emitting diode, including the steps of:
providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
and carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in the inert atmosphere to obtain the hole functional layer.
In a third aspect, the present application provides a light emitting diode comprising: an anode and a cathode disposed opposite each other, a light emitting layer disposed between the anode and the cathode, and a hole function layer disposed between the anode and the light emitting layer;
wherein the hole functional layer comprises a film prepared by the preparation method.
According to the preparation method of the film, the inert atmosphere is doped with the aromatic compound capable of dissolving the dry film, the dry film is subjected to standing treatment under the inert atmosphere doped with the aromatic compound, so that the aromatic compound can further dissolve and disperse large granular substances on the surface of the dry film in the process of soaking the dry film, the uniformity of particles on the surface of the film is improved, the roughness of the surface of the film is reduced, and the film with a flat surface is obtained. In the light-emitting diode, roughness is one of key factors influencing the hole transmission efficiency of the hole functional layer, when the film prepared by the method is applied to the hole functional layer of the light-emitting diode, the film morphology of the hole functional layer is improved, on one hand, the surface defect of the hole functional layer is reduced, the recombination probability of carriers at the interface of the hole functional layer is reduced, on the other hand, the interface contact performance between the hole functional layer and the light-emitting layer is improved, and the interface resistance between the hole functional layer and the light-emitting layer is reduced.
The preparation method of the hole functional layer of the light-emitting diode provided by the application utilizes the preparation method of the film, is favorable for preparing the hole functional layer with a smooth surface, improves the appearance of the film of the hole functional layer, and is favorable for improving the hole transmission efficiency of a device, so that the hole transmission efficiency and the electron transmission efficiency of the device are effectively balanced, and the photoelectric performance and the service life of the device are further improved.
The light-emitting diode provided by the application has the advantages that the hole functional layer comprises the thin film prepared by the preparation method, and the light-emitting diode has excellent photoelectric performance and service life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a thin film according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a light emitting diode according to an embodiment of the present disclosure;
fig. 3 is a schematic structural diagram of a light emitting diode according to another embodiment of the present disclosure;
FIG. 4 is a schematic view showing a method of stationary treatment in a closed vessel in example 1 of the present application;
FIG. 5 is a schematic view of a heat treatment method in a closed vessel in example 3 of the present application;
FIG. 6 is a schematic view of the ultraviolet irradiation treatment method in a closed container in example 4 of the present application;
fig. 7 is a roughness comparison graph of TFB layers of the light emitting diodes of example 1 and comparative example 1;
fig. 8 is a comparison of electrical properties of the light emitting diodes of examples 1 to 5 and example 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, "at least one" means one or more, meaning any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c," or "at least one of a, b, and c," may each denote: a. b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c.
As shown in fig. 1, the embodiment of the application provides a method for preparing a film, which includes the following steps:
s01, providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
s02, carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in an inert atmosphere to obtain the film.
According to the preparation method of the film, the inert atmosphere is doped with the aromatic compound capable of dissolving the dry film, the dry film is subjected to standing treatment under the inert atmosphere doped with the aromatic compound, so that the aromatic compound can further dissolve and disperse large granular substances on the surface of the dry film in the process of soaking the dry film, the uniformity of particles on the surface of the film is improved, the roughness of the surface of the film is reduced, and the film with a flat surface is obtained. In the light-emitting diode, roughness is one of key factors influencing the hole function layer, when the film prepared by the method is applied to the hole function layer of the light-emitting diode, the film morphology of the hole function layer is improved, on one hand, the surface defect of the hole function layer is reduced, the recombination probability of carriers at the interface of the hole function layer is reduced, on the other hand, the interface contact performance between the hole function layer and the light-emitting layer is improved, and the interface resistance between the hole function layer and the light-emitting layer is reduced.
Specifically, in step S01, the dry film is a hole function layer material, so as to be applied to preparing a hole function layer of a light emitting diode.
The inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the hole functional layer material, so that the aromatic compound can make the surface of the dry film flat by soaking the dry film in the process of standing treatment, heating treatment or ultraviolet irradiation treatment of the dry film under the inert atmosphere. Wherein the inert gas is inert gas to the aromatic compound and the dry film, and does not affect the dissolution of the dry film by the aromatic compound. In some embodiments, the inert atmosphere is selected from at least one of argon, helium, nitrogen, neon, xenon, and krypton.
Aromatic compounds are a class of organic compounds containing aromatic rings including benzene rings, naphthalene rings, anthracene rings, and the like. The specific types of the aromatic compounds can be flexibly adjusted according to the material of the hole functional layer, in some embodiments, the aromatic compounds are at least one selected from chlorobenzene, bromobenzene and iodobenzene, and the aromatic compounds have larger polarity and have large polarity difference with the material of the light-emitting layer, so that the appearance of the hole functional layer can be effectively prevented from being damaged in the process of forming the light-emitting layer on the hole functional layer. In a specific embodiment, the aromatic compound is selected to be chlorobenzene.
The dry film in the present specification refers to a film containing no solvent or only a trace amount of solvent with respect to a wet film containing a solvent, and may be selected from commercially available products or dry films prepared by conventional means in the art.
In some embodiments, the method of preparing a dry film includes the steps of:
s011, providing a dispersion liquid in which the hole function layer material is dispersed;
s012, providing a matrix, and performing film forming treatment on the dispersion liquid on the matrix to form a dry film.
The method is a method for preparing the film by adopting a solution method, and compared with a film formed by a physical vapor deposition method, the film prepared by adopting the solution method has high surface roughness, so that the dry film prepared by adopting the solution method has a remarkable effect of reducing the surface roughness by adopting the method of the embodiment of the application.
In step S011, the composition of the dispersion liquid mainly consists of the hole function layer material and the solvent, and the hole function layer material is uniformly dispersed or dissolved in the solvent.
The hole function layer material is used as a function material of the film, and the specific hole function layer material can be flexibly selected by referring to the performance of the light-emitting diode to be prepared. In some embodiments, the hole-functional layer material is selected from PEDOT PSS, cuPc, F-TCNQ, HATCN, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine, poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, 15N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, graphene, C60, niO x 、MoO x 、WO x 、CrO x 、CuO、MoS x 、MoSe x 、WS x 、WSe x And at least one of CuS. In one embodiment, the thin film to be prepared is used as a hole injection layer and a hole functional layer material of the light emitting diodeSelected from PEDOT PSS, cuPc, F4-TCNQ, HATCN, niO x 、MoO x 、WO x 、CrO x 、CuO、MoS x 、MoSe x 、WS x 、WSe x Or CuS. In another embodiment, the thin film to be prepared is used as a hole transport layer of a light emitting diode, and the hole functional layer material is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, 15N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, graphene, C60, niO x 、MoO x 、WO x 、CrO x 、CuO、MoS x 、MoSe x 、WS x 、WSe x Or CuS.
The solvent can be selected from organic solvents conventional in the art, so that the hole-function layer material can be dissolved or uniformly dispersed in the solvent, the dispersion liquid is ensured to have good stability, and the hole-function layer material can be volatilized in the subsequent solvent removal process. In some embodiments, the solvent of the dispersion is selected to be an aromatic compound, which is a compound that is capable of dissolving or dispersing the hole-function layer material, and has a polarity opposite to or substantially different from that of the light-emitting layer material, so as to avoid damaging the morphology of the hole-function layer during formation of the light-emitting layer on the hole-function layer.
In step S012, the step of performing film formation treatment of the dispersion on the substrate may be performed by referring to a conventional operation in the art, for example, a method such as spin coating, blade coating, inkjet printing, evaporation, or magnetron sputtering, so that the dispersion forms a dry film on the substrate.
The substrate as a carrier for the film formation treatment of the dispersion may be selected with reference to a specific light-emitting device to be produced, and for example, a conventional electrode, an anode having a hole injection layer formed thereon, or a cathode having a light-emitting layer formed thereon may be selected. In some embodiments, the substrate is selected as the anode and the material forming the anode includes conductive metals and conductive metal oxides, and the like, such as indium tin oxide, tin antimony oxide, indium gallium zinc oxide, and magnesium zinc oxide.
In an embodiment of the present application, the step of performing a film forming process on a substrate includes: a step of forming a wet film on the substrate from the dispersion liquid, and a step of forming a dry film from the wet film. In some embodiments, the step of subjecting the dispersion to a film forming process on the substrate comprises: the dispersion was formed into a wet film on a substrate and annealed. Through annealing treatment, the solvent in the wet film can be promoted to volatilize, and the hole function layer materials in the dispersion liquid film are promoted to be orderly arranged, so that a dry film with a compact and flat surface is formed. In a further embodiment, the annealing treatment is performed at a temperature of 80-100 ℃ for 5-10 minutes to meet the basic requirement of film annealing, so that a film with a compact and flat surface is formed, and meanwhile, the annealing is performed at the temperature and the time, so that the structure of other film layers in the substrate can be prevented from being damaged due to overhigh temperature, and the internal structure of the device is further optimized.
In some embodiments, the step of film forming the dispersion on the substrate is performed under an inert atmosphere doped with the aromatic compound described above. Therefore, in the film forming process, the aromatic compound doped in the inert atmosphere can play a role of a cosolvent to promote the large-particle substances on the surface of the wet film to be further dispersed, so that the uniformity of particles on the surface of the dry film is improved, the roughness of the surface of the dry film is reduced, and the dry film with a flat surface is obtained. In a further embodiment, the aromatic compound is present in the inert gas at a concentration of 0.5% to 1% by volume. If the volume concentration of the aromatic compound is less than 0.5%, the effect of reducing the roughness of the dry film surface is not obvious; if the volume concentration of the aromatic compound is more than 1%, the dry film on the substrate is in a wet film state before the annealing treatment is finished, and the excessive volume concentration of the aromatic compound can dilute the hole function layer material in the wet film, so that the formation of a thin dry film with compact surface is not facilitated, and the stability is reduced.
In a specific embodiment, the step of subjecting the dispersion to a film forming process on a substrate comprises: the dispersion is spin-coated onto a substrate under an inert atmosphere doped with an aromatic compound and annealed. By combining the process characteristics of the spin coating method, the surface performance of the film can be obviously improved, so that the surface roughness of the film is lower, and the film is smoother and more uniform.
In step S02, the dry film is subjected to standing treatment, heating treatment or ultraviolet irradiation treatment under an inert atmosphere doped with an aromatic compound, so that the aromatic compound dissolves the hole function layer material on the surface of the dry film in the process of soaking the dry film, thereby reducing the roughness of the surface of the film.
In the embodiment of the application, the inert atmosphere is composed of inert gas and aromatic compound, and the volume concentration of the aromatic compound in the inert atmosphere can be flexibly adjusted according to the performance of the light emitting diode to be prepared and the actual process condition.
In some embodiments, the dry film is subjected to a standing treatment under an inert atmosphere, wherein the inert atmosphere has a volume concentration of the aromatic compound of 2% to 5%. By subjecting the dry film to a static treatment under an inert atmosphere doped with the aromatic compound at the volume concentration, it is ensured that large particulate matters remaining on the surface of the dry film are further dispersed under the infiltration of the aromatic compound, thereby preparing a film having low surface roughness. In a specific embodiment, the time for the standing treatment is 30 to 60 minutes.
In some embodiments, in the step of heat treating the dry film under an inert atmosphere, the volume concentration of the aromatic compound in the inert atmosphere is 1% to 1.5%. The dry film is heated in the inert atmosphere doped with the aromatic compound with the volume concentration, so that the production efficiency is improved, the roughness of the surface of the film is further reduced, the use amount of the aromatic compound is reduced, and the environment-friendly and safe effects are realized. In addition, the specific embodiment of heat-treating the dry film under an inert atmosphere may use a heating plate or an oven for heat-treating the dry film with reference to the conventional operation in the art. In addition, the temperature and time for performing the heat treatment may be referred to as specific types of dry films and substrates, and it should be premised on that the overall structures of the films and substrates are not damaged, and in the specific embodiment, the heat treatment includes: heating at 150-200 deg.c for 3-5 min. In a specific embodiment, the heat treatment comprises: heating at 150-200 deg.c for 3-5 min.
In some embodiments, in the step of subjecting the dry film to ultraviolet light irradiation under an inert atmosphere, the volume concentration of the aromatic compound in the inert atmosphere is 1% to 1.5%. The ultraviolet light has high photon energy, and the dry film is subjected to ultraviolet light irradiation treatment under inert atmosphere, so that the intrinsic defect of the film can be further reduced on the basis of reducing the surface roughness of the film, the stability of the film is improved, the crystallinity of the film is improved, the hole transmission rate of the device is improved, and the photoelectric performance and the service life of the device are further improved. Meanwhile, because ultraviolet light only acts on the film, and the acting time is short, side effects caused by long-time heat treatment are avoided, diffusion of chemical components in the matrix to the dry film is inhibited, and the stability of the device is greatly improved. On the basis, the dry film is subjected to ultraviolet irradiation treatment under the inert atmosphere doped with the aromatic compound with the volume concentration, so that the roughness of the surface of the film is further reduced, the use amount of the aromatic compound is reduced, and the environment-friendly and safe effects are realized. In a specific embodiment, the ultraviolet light irradiation treatment includes: the dry film is irradiated by ultraviolet light with the power of 2-3W, the frequency of 0.8-1.2Hz, the pulse width of 18-22nm, the laser energy of 4.4-5.5eV and the irradiation time of 50-70 seconds. The ultraviolet light is adopted to irradiate the dry film, so that the irradiation time is shortened while the basic requirement of annealing is met, a film with compact and smooth surface is formed, and meanwhile, the ultraviolet light is adopted to anneal, so that other film structures in a matrix can be prevented from being damaged, and the internal structure of the device is further optimized.
In summary, by the preparation method, the purpose of reducing the surface roughness of the film and enabling the surface of the film to be flat and compact can be achieved, when the film is applied to a hole function layer of a light-emitting diode, the hole transmission rate of the device can be greatly improved, the hole transmission rate and the electron transmission rate are effectively balanced, and hole injection is promoted, so that the light-emitting diode device has excellent photoelectric performance and service life.
On the basis of the technical scheme, the embodiment of the application provides a preparation method of a light-emitting diode and the light-emitting diode.
Correspondingly, the preparation method of the light-emitting diode comprises the following steps of:
providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
and carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in the inert atmosphere to obtain the hole functional layer.
According to the preparation method of the light-emitting diode, the preparation of the hole functional layer is beneficial to preparing the hole functional layer with a smooth surface, improving the appearance of the film of the hole functional layer and being beneficial to improving the hole transmission efficiency of a device, so that the hole transmission efficiency and the electron transmission efficiency of the device are effectively balanced, and the photoelectric performance and the service life of the device are further improved.
Accordingly, a light emitting diode, as shown in fig. 2, includes: 1 an anode and 5 a cathode disposed opposite to each other, a light emitting layer 3 disposed between the anode 1 and the cathode 5, and a hole function layer 2 disposed between the anode 1 and the light emitting layer 3;
wherein the hole function layer 2 comprises the film prepared by the preparation method.
The light-emitting diode provided by the embodiment of the application has the advantages that the hole functional layer comprises the thin film prepared by the preparation method, and the light-emitting diode has excellent photoelectric performance and service life.
The hole-functional layer is generally referred to as a hole-injecting layer and/or a hole-transporting layer, and in the embodiments herein, the hole-functional layer is a hole-transporting layer. In the light-emitting diode, the hole transmission layer is connected with the light-emitting layer, the surface morphology of the hole transmission layer is improved, and the interface resistance of the hole transmission layer and the light-emitting layer can be directly reduced, so that the hole transmission efficiency of the device is improved, the purposes of effectively balancing the hole transmission efficiency and the electron transmission efficiency of the device are achieved, the photoelectric performance of the device is improved, and the service life of the device is prolonged.
The structure of the light emitting diode can refer to the conventional technology in the field, and in some embodiments, the light emitting diode is in a positive structure, and the anode is connected with the substrate to serve as a bottom electrode; in other embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as the bottom electrode. Further, in addition to the above-described basic functional film layers such as the cathode, anode, light-emitting layer, and hole functional layer, an electron functional layer such as an electron injection layer, an electron transport layer, and an electron blocking layer may be provided between the light-emitting layer and the cathode.
In some embodiments, as shown in fig. 3, the light emitting diode includes: anode 1, hole injection layer 21, hole transport layer 22, light emitting layer 3, electron transport layer 4 and cathode 5, wherein anode 1 connects the substrate as the bottom electrode, hole injection layer 21 is disposed between anode 1 and light emitting layer 3, hole transport layer 22 is disposed between hole injection layer 21 and light emitting layer 3, and electron transport layer 4 is disposed between light emitting layer 3 and cathode 5.
In the light emitting diode, the hole transport layer is a thin film prepared by the preparation method, and the thickness of the thin film is preferably 10-150nm. In addition, materials of the substrate, anode, hole injection layer, light emitting layer, electron transport layer and cathode and thicknesses thereof may be referred to as conventional techniques in the art, and methods of preparing the substrate, anode, hole injection layer, light emitting layer, electron transport layer and cathode are the same.
The substrate comprises a rigid substrate and a flexible substrate, and in some embodiments, the substrate is selected from at least one of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyethersulfone.
The anode comprises a conductive metal including, but not limited to, nickel, platinum, vanadium, chromium, copper, zinc, gold, and the like, or alloys thereof, and/or a conductive metal oxide including, but not limited to, zinc oxide, indium oxide, tin oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), fluorine doped tin oxide, and the like.
The material of the hole injection layer includes, but is not limited to, PEDOT: PSS, cuPc, F4-TCNQ, HATCN, transition metal oxides, transition metal thio compounds, and the like. Wherein the transition metal oxide includes, but is not limited to, niO x 、MoO x 、WO x 、CrO x CuO, etc., metal-sulfur compounds including but not limited to MoS x 、MoSe x 、WS x 、WSe x And CuS, etc.
The material of the light emitting layer is selected from direct band gap compound semiconductors with light emitting capability, including but not limited to II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds, IV simple substances, etc. In some embodiments, the material of the light emitting layer is selected to be nanocrystals of II-VI semiconductors, including but not limited to CdS, cdSe, cdTe, znS, znSe, znTe, hgS, hgSe, hgTe, pbS, pbSe, pbTe, and the like. In some embodiments, the material of the light emitting layer is selected to be a nanocrystal of a III-V semiconductor, including but not limited to GaP, gaAs, inP, inAs, and the like. In addition, the material of the light emitting layer may be selected from doped or undoped inorganic perovskite type semiconductors and/or organic-inorganic hybrid perovskite type semiconductors. Wherein, the structural general formula of the inorganic perovskite semiconductor is AMX 3 A is Cs + Ions; m is a divalent metal cation including but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2 + Etc.; x is a halogen anion including but not limited to Cl - 、Br - 、I - Etc. The structural general formula of the organic-inorganic hybridization perovskite type semiconductor is BMX 3 M is a divalent metal cation including, but not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2 + 、Ge 2+ 、Yb 2+ 、Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the X is a halogen anion, including but not limited to Cl-, br-, I; b is an organic amine ion including but not limited to CH 3 (CH 2 ) n-2 NH 3+ (n.gtoreq.2) or NH 3 (CH 2 ) n NH 3 2+ (n.gtoreq.2), when n=2, inorganic metal halide octahedral MX 64 - M is positioned in the body centers of halogen octahedrons, and B is filled in gaps among the octahedrons to form an infinitely-extending three-dimensional structure; when n > 2, co-roof connected MX 64 - Extending in two-dimensional direction to form a layered structure, and inserting an organic amine cation bilayer (protonated monoamine) or an organic amine cation monolayer (protonated diamine) between the layers, wherein the organic layer and the inorganic layer are mutually overlapped to form a stable two-dimensional layered structure.
The material of the electron transport layer is selected to have good electron transport properties and a band gap greater than that of the light emitting layer, including but not limited to ZnO, tiO 2 、SnO 2 、Ta 2 O 3 ZrO, niO, tiLiO, znAlO, znMgO, znSnO, znLiO, inSnO, etc. The thickness of the electron transport layer is preferably 10 to 100nm.
The cathode may be selected from metals, carbon materials, metal oxides, etc., wherein the metals include, but are not limited to Al, ag, cu, mo, au, ba, ca, mg, etc.; carbon materials include, but are not limited to, graphite, carbon nanotubes, graphene, carbon fibers, and the like; the metal oxide includes doped or undoped metal oxide such as ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, etc., and may also include a composite electrode such as AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO, etc., sandwiching metal between doped or undoped transparent metal oxide 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 The thickness of the metal part should not exceed 20nm and the transmittance to visible light should not be lower than 90%.
The following examples illustrate the practice of the invention.
Example 1
The embodiment provides a top-emission positive quantum dot light emitting diode, and a preparation method thereof comprises the following steps:
(1) Spin-coating PEDOT on an ITO substrate: PSS, rotation speed 5000, time 30 seconds, then heating at 150 ℃ for 15 minutes;
(2) At PEDOT: TFB (8 mg/mL) was spin coated on the PSS layer at 3000 rpm for 30 seconds followed by heating at 80℃for 10 minutes;
(3) Placing the device prepared in the step (2) into a closed container, standing for 50min, wherein the atmosphere environment in the closed container is Ar atmosphere (the volume concentration is 95%) and gaseous chlorobenzene (the volume concentration is 5%), as shown in fig. 4;
(4) Transferring the device prepared in the step (3) into a glove box filled with Ar atmosphere;
(5) Spin-coating quantum dots (20 mg/mL) on the TFB layer at a rotation speed of 2000 and for 30 seconds;
(6) ZnO (30 mg/mL) is spin-coated on the quantum dot layer, the rotating speed is 3000, the time is 30 seconds, and then the quantum dot layer is heated for 30 minutes at 80 ℃;
(7) Evaporating Al by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 100 seconds, and the thickness is 10nm;
(8) Evaporating Ag on Al layer by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 200 seconds, the thickness is 20nm, and the top-emission positive quantum dot light emitting diode is obtained.
Example 2
The present embodiment provides a top-emitting positive quantum dot light emitting diode, which is prepared by the same method as that of embodiment 1, except that: in step (2), in a glove box filled with a mixed atmosphere of gaseous chlorobenzene and Ar gas, in PEDOT: TFB was spin-coated on the PSS layer, wherein the volume concentration of gaseous chlorobenzene in the mixed atmosphere was 0.5%.
Example 3
The present embodiment provides a top-emitting positive quantum dot light emitting diode, which is prepared by the same method as that of embodiment 2, except that: the step (3) is as follows: the device prepared in step (2) was placed in a closed container and heated by using a heating plate at 150℃for 5 minutes, and the atmosphere in the closed container was Ar atmosphere (95% by volume) and gaseous chlorobenzene (1.5% by volume), as shown in FIG. 5.
Example 4
The present embodiment provides a top-emitting positive quantum dot light emitting diode, which is prepared by the same method as that of embodiment 2, except that: the step (3) is as follows: the device prepared in the step (2) was placed in a closed container and the TFB layer of the device was irradiated with ultraviolet light at a power of 2.5W, an irradiation frequency of 1Hz, a pulse width of 20nm, a laser energy of 5eV, and an atmosphere environment in the closed container was Ar (95% by volume) and gaseous chlorobenzene (1.5% by volume), as shown in fig. 6.
Example 5
The embodiment provides a top-emission positive quantum dot light emitting diode, and a preparation method thereof comprises the following steps:
(1) Spin-coating PEDOT on an ITO substrate: PSS, rotation speed 5000, time 30 seconds, then heating at 150 ℃ for 15 minutes;
(2) Doping gaseous chlorobenzene in a glove box environment filled with Ar gas atmosphere, enabling the volume concentration of the gaseous chlorobenzene to be 0.5%, and then placing the device prepared in the step (1) into the glove box;
(3) At PEDOT: TFB (8 mg/mL) was spin coated on the PSS layer at 3000 rpm for 30 seconds followed by heating at 80℃for 10 minutes;
(4) Placing the device prepared in the step (3) into a vacuum container, and then replacing the gas atmosphere in the glove box with Ar atmosphere again;
(5) Spin-coating quantum dots (20 mg/mL) on the TFB layer at a rotation speed of 2000 and for 30 seconds;
(6) ZnO (30 mg/mL) is spin-coated on the quantum dot layer, the rotating speed is 3000, the time is 30 seconds, and then the quantum dot layer is heated for 30 minutes at 80 ℃;
(7) Evaporating Al by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 100 seconds, and the thickness is 10nm;
(8) Evaporating Ag on Al layer by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 200 seconds, the thickness is 20nm, and the top-emission positive quantum dot light emitting diode is obtained.
Comparative example 1
The comparative example provides a top-emission positive quantum dot light emitting diode, the preparation method of which comprises:
(1) Spin-coating PEDOT on an ITO substrate: PSS, rotation speed 5000, time 30 seconds, then heating at 150 ℃ for 15 minutes;
(2) At PEDOT: TFB (8 mg/mL) was spin coated on the PSS layer at 3000 rpm for 30 seconds followed by heating at 80℃for 10 minutes;
(3) Spin-coating quantum dots (20 mg/mL) on the TFB layer at a rotation speed of 2000 and for 30 seconds;
(4) ZnO (30 mg/mL) is spin-coated on the quantum dot layer, the rotating speed is 3000, the time is 30 seconds, and then the quantum dot layer is heated for 30 minutes at 80 ℃;
(5) Evaporating Al by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 100 seconds, and the thickness is 10nm;
(6) Evaporating Ag on Al layer by thermal evaporation to vacuum degree of not higher than 3×10 -4 Pa, the evaporation speed is 1 angstrom/second, the time is 200 seconds, the thickness is 20nm, and the top-emission positive quantum dot light emitting diode is obtained.
1. The light emitting diodes prepared in example 1 and comparative example 1 were taken and the surface morphology of the TFB layer of each light emitting diode was observed. Fig. 7 is a graph comparing the roughness of the TFB layers of the light emitting diodes of example 1 and comparative example 1, and as shown in the results, the TFB layer prepared in example 1 has smaller surface roughness and smoother and denser surface than the TFB layer prepared in comparative example 1, which indicates that the method provided in this example can effectively improve the surface morphology of the thin film.
2. The light emitting diodes prepared in examples 1 to 5 and comparative example 1 were tested for JVR data, respectively, and when the device was powered on, the smaller the current density was, the smaller the leakage current of the device was, the more stable the device was, and as shown in fig. 8, the current densities of comparative example 1, example 5, example 1, example 2, example 3 and example 4 were sequentially decreased when the voltage was 1V, indicating that the stability of comparative example 1, example 5, example 1, example 2, example 3 and example 4 was sequentially increased.
3. The working life of each device was measured using constant current driving of 2mA using the light emitting diodes prepared in examples 1 to 5 and comparative example 1, and the results are shown in table 1.
In Table 1, L (cd/m) 2 ) Representing the highest brightness of the device; t95 (h) and T80 (h) respectively represent the time for the brightness of the device to decay to 95% and 80% under the constant current drive of 2 mA; t95_1k (h) and t80_1k (h) represent the time required for the luminance to decay to 95% and 80% at a luminance of 1000 nit.
TABLE 1
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (11)
1. A method for preparing a film, comprising the steps of:
providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in the inert atmosphere to obtain the film;
wherein the aromatic compound is selected from at least one of chlorobenzene, bromobenzene and iodobenzene;
the dry film material is selected from PEDOT PSS, cuPc, F-TCNQ, HATCN, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, 15N, N '-diphenyl-N, N' - (1-naphthalene)Radical) -1,1 '-biphenyl-4, 4' -diamine, graphene, C60 and NiO x 、MoO x 、WO x 、CrO x 、CuO、MoS x 、MoSe x 、WS x 、WSe x And at least one of CuS.
2. The method according to claim 1, wherein in the step of subjecting the dry film to a standing treatment under the inert atmosphere, the volume concentration of the aromatic compound in the inert atmosphere is 2% to 5%.
3. The method according to claim 2, wherein the time of the standing treatment is 30 to 60 minutes.
4. The method according to claim 1, wherein in the step of subjecting the dry film to heat treatment under the inert atmosphere, the volume concentration of the aromatic compound in the inert atmosphere is 1% to 1.5%.
5. The method of manufacturing according to claim 4, wherein the heat treatment comprises: heating at 150-200 deg.c for 3-5 min.
6. The method according to claim 1, wherein in the step of subjecting the dry film to ultraviolet irradiation under the inert atmosphere, the volume concentration of the aromatic compound in the inert atmosphere is 1% to 1.5%.
7. The method of manufacturing according to claim 6, wherein the ultraviolet light irradiation treatment comprises: and (3) carrying out irradiation treatment on the dry film by using ultraviolet light, wherein the power of the ultraviolet light is 2-3W, the frequency is 0.8-1.2Hz, the pulse width is 18-22nm, the laser energy is 4.4-5.5eV, and the irradiation treatment time is 50-70 seconds.
8. The method of any one of claims 1 to 7, wherein the inert atmosphere is selected from at least one of argon, helium, nitrogen, neon, xenon, and krypton.
9. A method for manufacturing a light emitting diode, comprising the steps of:
providing a dry film and an inert atmosphere, wherein the inert atmosphere is doped with an aromatic compound, and the aromatic compound can dissolve the dry film;
carrying out standing treatment, heating treatment or ultraviolet irradiation treatment on the dry film in the inert atmosphere to obtain the hole functional layer;
wherein the aromatic compound is selected from at least one of chlorobenzene, bromobenzene and iodobenzene;
the dry film material is selected from PEDOT PSS, cuPc, F-TCNQ, HATCN, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine, poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, 15N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, graphene, C60, niO x 、MoO x 、WO x 、CrO x 、CuO、MoS x 、MoSe x 、WS x 、WSe x And at least one of CuS.
10. A light emitting diode, comprising: an anode and a cathode disposed opposite each other, a light emitting layer disposed between the anode and the cathode, and a hole function layer disposed between the anode and the light emitting layer;
wherein the hole function layer comprises the film produced by the production method according to any one of claims 1 to 8.
11. The light-emitting diode according to claim 10, wherein the hole-functional layer is a hole-transporting layer.
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