CN116171063A - Electroluminescent device, preparation method thereof and photoelectric device - Google Patents
Electroluminescent device, preparation method thereof and photoelectric device Download PDFInfo
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- 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
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The application discloses electroluminescent device and preparation method thereof, photoelectric device, through doping the photocrosslinker in the material of at least two-layer functional layer, two-layer the functional layer is adjacent setting, and on the one hand photocrosslinker can combine through the mode of chemical bond with each functional layer material, on the other hand, can also form crosslinked structure between the photocrosslinker, makes the laminating between each adjacent functional layer more firm, avoids the condition that the flexible device appearing the rete fracture and the rete is whole to drop in the use to improve the easy inefficacy problem of device.
Description
Technical Field
The application relates to the field of photoelectric devices, in particular to an electroluminescent device, a preparation method thereof and a photoelectric device.
Background
Electroluminescent, also known as electroluminescence, is a physical phenomenon in which electrons excited by an electric field collide with a luminescence center to cause transition, change and recombination of electrons between energy levels to cause luminescence. QLED (Quantum Dots Light-emission Diode) is an emerging electroluminescent device based on inorganic semiconductor quantum dots.
The QLED core technology is Quantum Dot, and the Quantum Dot is composed of zinc, cadmium, selenium and sulfur atoms, and is a particle with particle diameter less than 10 nm. This material has an extremely specific property: when the quantum dot is stimulated by photoelectricity, colored light is emitted, and the color is determined by the materials composing the quantum dot and the size and shape of the quantum dot. Because of this property, it is possible to change the color of the light emitted from the light source. The light-emitting wavelength range of the quantum dots is very narrow, the color is relatively pure and can be adjusted, so that the picture of the quantum dot display is clearer and brighter than that of a liquid crystal display, and the quantum dot display is expected to become a next-generation flat panel display and has wide development prospect.
However, in the development process of the electroluminescent device represented by QLED, there are still many problems, for example, in the field of flexible panels, in order to match with a flexible substrate with a low melting point, each conductive film can only be deposited at a low temperature, and the prepared film has high resistivity, poor transparency, poor adhesion with a functional layer, and is easy to break during bending, so that the device fails. In the working process, the conductive film can be fallen off due to the heating of the device.
Disclosure of Invention
The embodiment of the application provides an electroluminescent device, a preparation method thereof and a photoelectric device, and aims to solve the problem that the device is easy to fail.
In a first aspect, embodiments of the present application provide an electroluminescent device, including: the cathode, the anode and two or more than two functional layers arranged between the cathode and the anode, wherein the functional layers comprise luminous layers, and at least two adjacent functional layers are doped with photocrosslinking agents.
The photocrosslinking agent is selected from: at least one of coumarin, coumarin derivative, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide, wherein the photocrosslinking agent is combined with the material of the functional layer through chemical bonds, and a crosslinking structure is formed between the photocrosslinking agents.
Optionally, the mass ratio of the photocrosslinker to the functional layer material is (1-3): 4.
optionally, the functional layer doped with the photocrosslinker is composed of a material of the functional layer and the photocrosslinker, and the photocrosslinker is mixed and dispersed in the material of the functional layer.
Optionally, the material of each functional layer is doped with the photo-crosslinking agent, each functional layer is composed of the material of the functional layer and the photo-crosslinking agent, and the photo-crosslinking agent is mixed and dispersed in the material of the functional layer.
Optionally, the functional layer further includes a hole functional layer and an electron functional layer, the hole functional layer is disposed between the light emitting layer and the anode, the electron functional layer is disposed between the light emitting layer and the cathode, and the photo-crosslinking agent is mixed and dispersed in the electron functional layer, the hole functional layer and the light emitting layer.
Optionally, one of the functional layers includes a first film layer distant from an adjacent functional layer, and a second film layer and/or a third film layer close to the adjacent functional layer; the second film layer is close to the adjacent lower functional layer, the third film layer is close to the adjacent upper functional layer, and the photo-crosslinking agent is mixed and dispersed in the second film layer and/or the third film layer.
Optionally, the functional layer further includes a hole functional layer and an electron functional layer, the hole functional layer is disposed between the light emitting layer and the anode, and the electron functional layer is disposed between the light emitting layer and the cathode; wherein the photocrosslinker is doped on one side of the hole functional layer close to the light emitting layer, the photocrosslinker is doped on one side of the light emitting layer close to the hole function layer, and/or the photocrosslinker is doped on one side of the electron functional layer close to the light emitting layer, and the photocrosslinker is doped on one side of the light emitting layer close to the electron functional layer.
Optionally, the functional layer further includes a hole functional layer and an electron functional layer, the hole functional layer includes a hole injection layer, the electron functional layer includes an electron injection layer, and a material of the hole injection layer is selected from the group consisting of: poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, polymeric triarylamine, 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-carbazol) 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 or C 60 At least one of (a) and (b); and/or the number of the groups of groups,
the material of the light-emitting layer is selected from the group consisting of: group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV elements; wherein the II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, hgS, hgSe, hgTe, pbS, pbSe or PbTe, and the III-V compound is selected from at least one of GaP, gaAs, inP or InAs; alternatively, the material of the light emitting layer is 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 + An ion, M is a divalent metal cation, X is a halogen anion, said divalent metal cation being selected from the group consisting of: pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、C d2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ Or Eu 2+ The halogen anion is selected from Cl-, br-or I-, and the structural general formula of the organic-inorganic hybridization perovskite semiconductor is BMX 3 Wherein B is an organic amine cation selected from CH 3 (CH 2 ) n-2 NH 3+ (n.gtoreq.2) or NH 3 (CH 2 )nNH 3 2+ (n is more than or equal to 2); and/or the number of the groups of groups,
the material of the electron injection layer is selected from the group consisting of: znO, tiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 At least one of NiO, tiLiO, znAlO, znMgO, znSnO, znLiO or InSnO; and/or the number of the groups of groups,
the anode material is selected from: a metallic or non-metallic material selected from nickel, platinum, gold, silver, iridium or carbon nanotubes; or selected from doped or undoped metal oxides selected from: indium tin oxide, indium zinc oxide, indium tin zinc oxide, indium copper oxide, tin oxide, indium oxide, cadmium zinc oxide, fluorine tin oxide, indium zinc oxide, gallium tin oxide or zinc aluminum oxide; and/or the number of the groups of groups,
the cathode material is selected from one or more of metal materials, carbon materials and metal oxides. Wherein the metal material comprises one or more of Al, ag, cu, mo, au, ba, ca, mg, the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber, the metal oxide is selected from doped/undoped metal oxide or a composite electrode of doped/undoped transparent metal oxide and metal sandwiched between the doped/undoped transparent metal oxide, the doped/undoped metal oxide comprises at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 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 One or more of the following.
In a second aspect, the present application further provides a method for preparing an electroluminescent device, where the method includes:
preparing two or more functional layers on the anode from bottom to top in sequence; and
preparing a cathode on the functional layer to obtain the electroluminescent device;
or sequentially preparing two or more functional layers on the cathode from bottom to top; and
preparing an anode on the functional layer to obtain the electroluminescent device;
the functional layers comprise luminous layers, at least two layers of materials of the functional layers are doped with photo-crosslinking agents, and the two layers of functional layers are adjacently arranged.
Optionally, the preparation method of the two or more functional layers includes:
mixing and heating a cross-linking agent and a material solution of the functional layer to obtain a mixed solution, and preparing the functional layer by using the mixed solution;
sequentially preparing the next functional layers to obtain two or more functional layers; and
and carrying out ultraviolet light irradiation treatment on the two or more functional layers.
Optionally, the preparation method of the two or more functional layers includes:
mixing and heating a cross-linking agent and a material solution of a functional layer to obtain a mixed solution, preparing a first film layer by using the material solution of the functional layer, and preparing a second film layer and/or a third film layer by using the mixed solution to obtain the functional layer; wherein the second film layer is close to the adjacent lower functional layer, and the third film layer is close to the adjacent upper functional layer;
Sequentially preparing the next functional layers to obtain two or more functional layers; and
and carrying out ultraviolet light irradiation treatment on the two or more functional layers.
Optionally, in the mixed solution, the mass ratio of the photocrosslinker to the functional layer material is (1-3): 4.
optionally, the photocrosslinking agent is selected from: at least one of coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide.
The application also provides an optoelectronic device comprising the electroluminescent device described in the first aspect or comprising the electroluminescent device prepared by the preparation method described in the second aspect.
The beneficial effects are that:
according to the method, the photocrosslinking agent is doped in the material of at least two adjacent functional layers, the photocrosslinking agent can be combined with the material of each functional layer in a chemical bond mode, and a crosslinking structure can be formed between the photocrosslinking agents, so that the adjacent functional layers are more firmly bonded, the situation that the membrane layer cracks and the membrane layer integrally fall off in the using process of the flexible device is avoided, and the problem that the device is easy to fail is solved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is a schematic diagram of a positive electroluminescent device according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an electroluminescent device with a positive structure according to another embodiment of the present invention;
FIG. 3 is a schematic view of an electroluminescent device with an inversion structure according to an embodiment of the present invention;
fig. 4 is a schematic flow chart of a method for manufacturing an electroluminescent device with a positive structure according to an embodiment of the present invention;
FIG. 5 is a schematic flow chart of a method for fabricating an electroluminescent device with an inversion structure according to an embodiment of the present invention;
fig. 6 is a view of morphology photographing of each electroluminescent device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
The embodiment of the application provides an electroluminescent device, a preparation method thereof and an optoelectronic device. The following will describe in detail. The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction. Various embodiments of the present application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. Whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the range referred to.
First, an embodiment of the present application provides an electroluminescent device, including: the cathode, the anode and two or more than two functional layers arranged between the cathode and the anode, wherein at least two layers of the functional layers are doped with photocrosslinkers, and the two layers of the functional layers are adjacently arranged.
By doping the photocrosslinking agent in the material of at least two adjacent functional layers, on the one hand, the photocrosslinking agent can be combined with the materials of all the functional layers in a chemical bond mode, and on the other hand, a crosslinking structure can be formed between the photocrosslinking agents, so that the adjacent functional layers are more firmly bonded, the conditions that the film layer cracks and the film layer falls off integrally in the use process of the flexible device are avoided, and the problem that the device is easy to fail is solved.
In some embodiments, the photocrosslinking agent is selected from the group consisting of: at least one of coumarin (2H-1-benzopyran-2-ketone), coumarin derivative, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide, wherein the photocrosslinkers are combined with the material of the functional layer through chemical bonds, and a crosslinked structure is formed between the photocrosslinkers.
When the photocrosslinker is selected from coumarin or derivatives thereof, the coumarin of each functional layer is crosslinked to form a four-membered ring. The chemical bond bonding mode between the materials of each functional layer and coumarin or the derivatives thereof is as follows:
taking carboxyl substituted polymerized triarylamine as an example of a hole injection layer material, using amino substituted coumarin as a cross-linking agent material, and combining the carboxyl substituted polymerized triarylamine and the amino substituted coumarin through an amide bond to obtain the reversible photoresponsive cross-linked hole injection material.
Taking ZnS quantum dots as an example of luminescent layer materials, using a cross-linking agent material as coumarin, and combining carbonyl of the coumarin with ZnS through coordination bonds to obtain the reversible photoresponsive cross-linked QD material.
Taking ZnO as an electron injection layer material as an example, using a cross-linking agent material as coumarin, and combining carbonyl of the coumarin with ZnO through coordination bonds to obtain the reversible photoresponse cross-linked electron injection layer material.
In some embodiments, the mass ratio of the photocrosslinker to the functional layer material is (1-3): 4. if the content of the photo-crosslinking agent is too high, the carrier mobility of the crosslinked layer is lowered, and if the content is too low, crosslinking between the functional layers is not effectively performed. It is understood that the mass ratio of the photocrosslinker to the functional layer material is (1-3): 4, for example 1: 4. 1.5: 4. 2: 4. 2.5: 4. 3:4, etc., or (1 to 3): other values within the range of 4 are not listed.
The present invention is not limited to the distribution of the photocrosslinking agent in the functional layer, and the photocrosslinking agent may be dispersed in the material of the functional layer or may be dispersed at the interface where each functional layer contacts.
For example: in some embodiments, the functional layer incorporating the photocrosslinker is composed of a material of the functional layer and a photocrosslinker mixed and dispersed in the material of the functional layer. In some embodiments, the photocrosslinking agent is doped in the material of each functional layer, and each functional layer is composed of the material of the functional layer and the photocrosslinking agent, and the photocrosslinking agent is mixed and dispersed in the material of the functional layer. Under the structural condition, a cross-linking structure can be formed between the functional layers, the physical deformation capacity of each film layer in the flexible device and the tolerance capacity of water oxygen or solvent are greatly improved, and mechanical stress test experiments of the flexible device of the inventor prove that the device with the structure has obvious effect of improving the service life.
As shown in fig. 1, fig. 1 shows an electroluminescent device comprising a substrate 10, an anode 20 and a cathode 60, and a functional layer between the anode 20 and the cathode 60, the functional layer comprising a hole injection layer 30, a light emitting layer 40 and an electron injection layer 50 stacked in this order from bottom to top, wherein the photo-crosslinking agent is mixed and dispersed in the materials of the hole injection layer 30, the light emitting layer 40 and the electron injection layer 50.
For another example: in some embodiments, the functional layer comprises a first film layer distal to an adjacent functional layer, and a second film layer and/or a third film layer proximal to an adjacent functional layer; the second film layer is close to the adjacent lower functional layer, the third film layer is close to the adjacent upper functional layer, and the photo-crosslinking agent is mixed and dispersed in the second film layer and/or the third film layer. In the preparation process of the structure, the precursor solution of the functional layer material and the precursor solution of the crosslinking material only have the difference of ligands, so that the first film layer, the second film layer or the third film layer can be mutually dissolved to form a relatively stable whole, and the device with the structure can form a crosslinking structure with other functional layers at an interface, and meanwhile, the excellent electrical property of the device can be reserved to the greatest extent.
Specifically, when an adjacent functional layer is located above the functional layer, the functional layer may include a first film layer and a third film layer, where the first film layer is located on a side of the functional layer away from the adjacent functional layer, and the third film layer is located on a side of the functional layer close to the adjacent functional layer.
When an adjacent functional layer is located below the functional layer, the functional layer may include a first film layer and a second film layer, the first film layer being located on a side of the functional layer away from the adjacent functional layer, the second film layer being located on a side of the functional layer near the adjacent functional layer.
When adjacent functional layers are located below and above the functional layers, the functional layers may include a first film layer, a second film layer, and a third film layer, the second film layer being located on a side of the functional layer adjacent to the lower side of the adjacent functional layers, the third film layer being located on a side of the functional layer adjacent to the upper side of the adjacent functional layers, the first film layer being located between the second film layer and the third film layer.
As shown in fig. 2, fig. 2 shows an electroluminescent device comprising a substrate 10, an anode 20 and a cathode 60, and functional layers between the anode 20 and the cathode 60, the functional layers comprising a hole injection layer 30, a light emitting layer 40, and an electron injection layer 50 stacked in this order from bottom to top.
Wherein the hole injection layer 30 in fig. 2 includes a first hole injection layer 31 far from the light emitting layer 40, and a third hole injection layer 32 near the light emitting layer 40, the first hole injection layer 31 being a first film layer, the third hole injection layer 32 being a third film layer; the light emitting layer 40 includes a second light emitting layer 41 adjacent to the hole injecting layer 30, a third light emitting layer 43 adjacent to the electron injecting layer 50, and a first light emitting layer 42 between the second light emitting layer 41 and the third light emitting layer 43, the first light emitting layer 42 being a first film layer, the second light emitting layer 41 being a second film layer, the third light emitting layer 43 being a third film layer; the electron injection layer 50 includes a second electron injection layer 51 adjacent to the light emitting layer 40, and a first electron injection layer 52 remote from the light emitting layer 40, the first electron injection layer 52 being a first film layer, and the second electron injection layer 51 being a second film layer.
In some embodiments, the distribution of photocrosslinkers in the functional layer may be the same as or different from that in the adjacent functional layer. For example: in some embodiments, the photocrosslinkers in the functional layer and the adjacent functional layer are uniformly distributed; in other embodiments, the functional layer is divided into a first film layer, a second film layer, and a third film layer, and the photocrosslinkers in adjacent functional layers are uniformly distributed. The photocrosslinking agent can have a crosslinking effect no matter the distribution of the photocrosslinking agent in the functional layer is the same as or different from that in the adjacent functional layers, so that the bonding between the adjacent functional layers is firmer.
In some embodiments, the functional layer further includes a hole functional layer and an electron functional layer in addition to the light emitting layer, the hole functional layer is disposed between the light emitting layer and the anode, the electron functional layer is disposed between the light emitting layer and the cathode, and the photocrosslinker is mixed and dispersed in the electron functional layer, the hole functional layer, and the light emitting layer.
In other embodiments, the functional layer further includes a hole functional layer and an electron functional layer in addition to the light emitting layer, the hole functional layer is disposed between the light emitting layer and the anode, the electron functional layer is disposed between the light emitting layer and the cathode, the photo-crosslinking agent is doped on a side of the hole functional layer adjacent to the light emitting layer, the photo-crosslinking agent is doped on a side of the light emitting layer adjacent to the hole functional layer, and/or the photo-crosslinking agent is doped on a side of the electron functional layer adjacent to the light emitting layer, and the photo-crosslinking agent is doped on a side of the light emitting layer adjacent to the electron functional layer.
The electroluminescent device in the embodiment of the application may be a positive type structure or an inverse type structure. In an electroluminescent device, the cathode or anode further comprises a substrate on the side remote from the light-emitting layer, the anode being arranged on the substrate in a positive configuration and the cathode being arranged on the substrate in an negative configuration. Whether in a positive type structure or an inverse type structure, a hole functional layer such as a hole transport layer and an electron blocking layer can be further arranged between the anode and the light-emitting layer, and an electron functional layer such as a hole blocking layer can be further arranged between the cathode and the light-emitting layer. For example: in some embodiments, the functional layers further comprise a hole functional layer comprising a hole injection layer and an electron functional layer comprising an electron injection layer.
Fig. 1 shows a schematic diagram of a positive structure of an electroluminescent device according to an embodiment of the present application, as shown in fig. 1, the positive structure quantum dot device includes a substrate 10, an anode 20 disposed on a surface of the substrate 10, a hole injection layer 30 disposed on a surface of the anode 20, a light emitting layer 40 disposed on a surface of the hole injection layer 30, an electron injection layer 50 disposed on a surface of the light emitting layer 40, and a cathode 60 disposed on a surface of the electron injection layer 50, wherein photocrosslinkers are doped in the hole injection layer 30, the light emitting layer 40, and the electron injection layer 50.
Fig. 3 shows a schematic diagram of an inversion structure of the quantum dot device according to the embodiment of the present application, as shown in fig. 3, the inversion structure quantum dot device includes a substrate 10, a cathode 60 disposed on a surface of the substrate 10, an electron injection layer 50 disposed on a surface of the cathode 60, a light emitting layer 40 disposed on a surface of the electron injection layer 50, a hole injection layer 30 disposed on a surface of the light emitting layer 40, and an anode 20, wherein photo-crosslinking agents are doped in the hole injection layer 30, the light emitting layer 40, and the electron injection layer 50.
In some embodiments, the electronic light emitting device is an electroluminescent device (QLED).
In embodiments of the present application, the materials of the respective functional layers may be the following materials, for example:
the substrate may be a rigid substrate or a flexible substrate. Specific materials may include at least one of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone.
The anode material may be: nickel (Ni), platinum (Pt), gold (Au), silver (Ag), iridium (Ir) or Carbon Nanotubes (CNT). May also include doped or undoped metal oxides such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), indium Tin Zinc Oxide (ITZO), indium Copper Oxide (ICO), tin oxide (SnO) 2 ) Indium oxide (In) 2 O 3 ) Cadmium zinc oxide (Cd: znO), fluorine tin oxide (F: snO) 2 ) Indium zinc oxide (In: snO) 2 ) Gallium tin oxide (Ga: snO) 2 ) Or zinc-alumina (Al: znO; AZO).
The hole injection layer is made of a material selected from the group consisting of: poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, polymeric triarylamine, 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-carbazol) 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 or C 60 At least one of them.
The material of the light-emitting layer is selected from the group consisting of: a direct bandgap compound semiconductor having light emitting capability including, but not limited to, one or more of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, or group IV simple substances. Specifically, the semiconductor materials used for the light emitting layer include, but are not limited to, nanocrystals of II-VI semiconductors, such as CdS, cdSe, cdTe, znS, znSe, znTe, hgS, hgSe, hgTe, pbS, pbSe, pbTe and other binary, ternary, and quaternary II-VI compounds; nanocrystals of group III-V semiconductors, such as GaP, gaAs, inP, inAs and other binary, ternary, quaternary III-V compounds; the material for the light emitting layer is not limited to group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV simple substances, and the like. Wherein the luminescent layer material can also be a doped or undoped inorganic perovskite semiconductor and/or an organic-inorganic hybrid perovskite semiconductor; specifically, the structural general formula of the inorganic perovskite semiconductor is AMX 3 Wherein 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+ X is a halogen anion including but not limited to Cl - 、Br - 、I - The method comprises the steps of carrying out a first treatment on the surface of the The structural general formula of the organic-inorganic hybridization perovskite semiconductor is BMX 3 Wherein B is an organic amine cation 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 is not less than 2). When n=2, inorganic metal halide octahedral MX 64 - The metal cations M are positioned in the centers of halogen octahedrons, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely-extending three-dimensional structure; when n > 2, the inorganic metal halide octahedrons MX are connected in a co-topped manner 64 - Extending in two-dimensional direction to form a layered structure, inserting an organic amine cation bilayer (protonated monoamine) or an organic amine cation monomolecular layer (protonated diamine) between the layers, and overlapping the organic layer and the inorganic layer to form a stable two-dimensional layered structure; 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+ 、F e2+ 、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。
The material of the electron injection layer is selected from the group consisting of: znO, tiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 At least one of NiO, tiLiO, znAlO, znMgO, znSnO, znLiO or InSnO.
The cathode material is selected from one or more of metal materials, carbon materials and metal oxides. Wherein the metal material comprises one or more of Al, ag, cu, mo, au, ba, ca, mg, the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber, the metal oxide is selected from doped/undoped metal oxide or a composite electrode of doped/undoped transparent metal oxide and metal sandwiched between the doped/undoped transparent metal oxide, the doped/undoped metal oxide comprises at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 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 One or more of the following.
Correspondingly, the application also provides a preparation method of the electroluminescent device, fig. 4 shows a preparation method of a positive structure of the electroluminescent device according to the embodiment of the application, and as shown in fig. 4, the preparation method of the electroluminescent device of the positive structure comprises the following steps:
s10, sequentially preparing two or more functional layers on the anode from bottom to top; and
s20, preparing a cathode on the functional layer to obtain the electroluminescent device.
Wherein the functional layer comprises a light-emitting layer, and a photocrosslinking agent is doped in the material of at least two adjacent functional layers.
Fig. 5 shows a method for preparing an inversion structure of an electroluminescent device according to an embodiment of the present application, and as shown in fig. 5, the method for preparing an inversion structure electroluminescent device includes the following steps:
s100, sequentially preparing two or more functional layers on a cathode from bottom to top; and
s200, preparing an anode on the functional layer to obtain the electroluminescent device.
Wherein the functional layer comprises a light-emitting layer, and a photocrosslinking agent is doped in the material of at least two adjacent functional layers.
In the embodiment of the present invention, the forming method of each functional layer may be implemented by a method known in the art, and as an exemplary embodiment, each functional layer is prepared by a solution method, by which the production cost can be greatly reduced, for mass production, and the solution method includes a spin coating method, a printing method, an inkjet printing method, a doctor blade method, a printing method, a dip-coating method, a dipping method, a spraying method, a roll coating method, a casting method, a slit coating method, and a bar coating method.
In some embodiments, the method for preparing two or more functional layers in the step S10 or S200 includes:
(1) Mixing and heating a cross-linking agent and a material solution of the functional layer to obtain a mixed solution, and preparing the functional layer by using the mixed solution;
(2) Sequentially preparing the next functional layers to obtain two or more functional layers; and
(3) And carrying out ultraviolet light irradiation treatment on the two or more functional layers.
In other embodiments, the method for preparing the two or more functional layers includes:
(10) Mixing and heating a cross-linking agent and a material solution of a functional layer to obtain a mixed solution, preparing a first film layer by using the material solution of the functional layer, preparing a second film layer and/or a third film layer by using the mixed solution, and obtaining the functional layer; wherein the second film layer is close to the adjacent lower functional layer, and the third film layer is close to the adjacent upper functional layer;
(20) Sequentially preparing the next functional layers to obtain two or more functional layers; and
(30) And carrying out ultraviolet light irradiation treatment on the two or more functional layers.
In some embodiments, in the mixed solution, the mass ratio of the photocrosslinker to the functional layer material is (1 to 3): 4.
In some embodiments, the photocrosslinking agent is selected from the group consisting of: at least one of coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide.
When the photocrosslinker is selected from coumarin or derivatives thereof, double bonds in the coumarin can be chemically crosslinked to form a four-membered ring under the irradiation of 365nm ultraviolet light. The mode of doping coumarin or derivatives thereof into each functional layer is as follows:
taking carboxyl of hole injection material to replace polymerized triarylamine as an example, using cross-linking agent material to replace coumarin, mixing the two materials, and heating to make the two materials produce amidation reaction, as shown in formula 1, to obtain the reversible light response cross-linked hole injection material.
Taking ZnS quantum dots as an example of luminescent layer materials, using a cross-linking agent material as coumarin, mixing the luminescent layer material with the coumarin, and heating the mixture to form coordination bonds between carbonyl groups of the coumarin and ZnS to obtain the reversible photoresponsive cross-linked QD material.
Taking ZnO as an electron injection material as an example, using a cross-linking agent material as coumarin, mixing the two materials, and heating to form coordination bonds between carbonyl groups of the coumarin and ZnO to obtain the reversible photoresponsive cross-linked electron injection material.
The cross-linked structure of the hole injection material and the luminescent layer is shown in formula 1, and the cross-linked structure of the electron injection material and the luminescent layer is shown in formula 2. (Zn in formula 1 represents a luminescent layer material ZnS quantum dot, zn in formula 2 represents an electron injection material ZnO)
From the formulas 1 and 2, it can be seen that the photocrosslinker can be combined with each functional layer material in a chemical bond mode, and double bonds in coumarin can also generate chemical crosslinking to form a four-membered ring under 365nm ultraviolet irradiation, and the structure can enable the adjacent functional layers to be bonded more firmly, so that the conditions of film cracking and film integral falling in the use process of the flexible device are avoided, and the problem that the device is easy to fail is solved.
Correspondingly, the application also provides an optoelectronic device, which comprises the electroluminescent device described in any one of the above, or comprises the electroluminescent device prepared by the preparation method described in any one of the above, and the structure, the implementation principle and the effect are similar, and are not described herein again. In a specific embodiment, the optoelectronic device is a QLED.
Alternatively, the optoelectronic device may be: the lighting lamp and the backlight source are any products or components with display functions, such as mobile phones, tablet computers, televisions, displays, notebook computers, digital photo frames, navigator and the like.
It should be noted that, the drawings relate to only the structures related to the embodiments of the present application, and other structures may refer to the general designs.
The present application is described in detail by examples below.
Example 1:
the embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device comprises the following steps:
(1) Material for preparing cross-linked hole injection layer: amino-substituted coumarin powder (5 mg/mL) was mixed into the carboxyl-substituted polymeric triarylamine (8 mg/mL), and the mixture was heated at 120℃for 10 minutes under an inert gas atmosphere to obtain a crosslinked-polymeric triarylamine.
(2) Materials for preparing the crosslinked luminescent layer: mixing ZnS quantum dot material (20 mg/mL) with amino-substituted coumarin powder (8 mg/mL), and heating at 80deg.C for 10min under inert gas environment to obtain crosslinked-QD.
(3) Material for preparing cross-linked electron injection layer: coumarin powder (10 mg/mL) was mixed with the ZnO precursor solution (30 mg/mL), and the mixture was heated at 120℃for 10 minutes under an inert gas atmosphere to obtain crosslinked ZnO.
(4) A material solution (8 mg/mL) for crosslinking the hole injection layer was spin-coated on the ITO substrate at 3000rpm for 30 seconds, followed by heating at 80℃for 10 minutes, and allowed to stand for cooling for 5 minutes.
(5) The material of the crosslinked luminescent layer (20 mg/mL) was spin-coated at 2000rpm for 30 seconds followed by heating at 80℃for 10 minutes and cooling for 5 minutes.
(6) Spin-coating the material of the crosslinked electron injection layer at 2000rpm for 30 seconds, followed by heating at 80℃for 20 minutes, and standing for cooling for 5 minutes.
(7) Ultraviolet light is used for irradiation, the wavelength is 365nm, the pulse width of ultraviolet laser is 22ns, the power is 5W, the frequency is 1.2Hz, and the time is 90s.
(8) Vacuum degree is not higher than 3×10 by thermal evaporation -4 Pa, evaporating Ag at a speed of 1 angstrom/second for 200 seconds and thickness of 20nm to obtain a top-emitting positive electroluminescent device, and packaging the device.
Example 2:
the embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device comprises the following steps:
(1) Material for preparing cross-linked hole injection layer: carboxyl-substituted polymeric triarylamine (8 mg/mL) was mixed with amino-substituted coumarin powder (5 mg/mL), and the mixture was heated at 120℃for 10 minutes under an inert gas atmosphere to obtain a crosslinked-polymeric triarylamine.
(2) Materials for preparing the crosslinked luminescent layer: the cross-linked-QD was obtained by mixing an amino-substituted coumarin powder (8 mg/mL) with ZnS quantum dot material (20 mg/mL) and heating at 80℃for 10min under an inert gas atmosphere.
(3) Material for preparing cross-linked electron injection layer: coumarin powder (10 mg/mL) was mixed with the ZnO precursor solution (30 mg/mL), and the mixture was heated at 120℃for 10 minutes under an inert gas atmosphere to obtain crosslinked ZnO.
(4) On an ITO substrate, polymerized triarylamine (8 mg/mL) was spin-coated at 4500rpm for 30 seconds, followed by heating at 80℃for 10 minutes, and allowed to stand for cooling for 5 minutes.
(5) The material for the crosslinked hole injection layer (8 mg/mL) was spin-coated on the ITO substrate at 5000rpm for 30 seconds, followed by heating at 80℃for 10 minutes, and left to cool for 5 minutes.
(6) Spin-coating the material of the crosslinked luminescent layer (20 mg/mL), rotating at 5000rpm for 30 seconds, followed by heating at 80℃for 10 minutes, and standing for cooling for 5 minutes.
(7) Quantum dot material (20 mg/mL) was spin coated at 3000rpm for 30 seconds followed by heating at 80℃for 10 minutes and cooling for 5 minutes.
(8) Spin-coating the material of the crosslinked luminescent layer (20 mg/mL), rotating at 5000rpm for 30 seconds, followed by heating at 80℃for 10 minutes, and standing for cooling for 5 minutes.
(9) Spin coating the material of the crosslinked electron injection layer at 5000rpm for 30 seconds, followed by heating at 80 ℃ for 20 minutes, and standing for cooling for 5 minutes.
(10) Spin-coating ZnO, rotating at 3000rpm for 30 seconds, then heating at 80 ℃ for 20 minutes, and standing and cooling for 5 minutes;
(11) Ultraviolet light is used for irradiation, the wavelength is 365nm, the pulse width of ultraviolet laser is 22ns, the power is 5W, the frequency is 1.2Hz, and the time is 90s.
(12) Vacuum degree is not higher than 3×10 by thermal evaporation -4 Pa, evaporating Ag at a speed of 1 angstrom/second for 200 seconds and thickness of 20nm to obtain a top-emitting positive electroluminescent device, and aligningThe part is encapsulated.
Example 3:
this example is substantially the same as example 1, except that the concentration of coumarin in the crosslinked hole transport layer is 2mg/mL; the coumarin concentration in the crosslinked luminescent layer is 5mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 8mg/mL.
Example 4:
this example is substantially the same as example 1, except that the coumarin concentration in the crosslinked hole transport layer is 6mg/mL; the coumarin concentration in the crosslinked luminescent layer is 15mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 20mg/mL.
Example 5:
this example is substantially the same as example 1, except that the coumarin concentration in the crosslinked hole transport layer is 0.2mg/mL; the concentration of coumarin in the crosslinked luminescent layer is 1mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 1mg/mL.
Example 6:
this example is substantially the same as example 1, except that the coumarin concentration in the crosslinked hole transport layer is 12mg/mL; the coumarin concentration in the crosslinked luminescent layer is 30mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 50mg/mL.
Example 7:
this example is substantially the same as example 2, except that the concentration of coumarin in the crosslinked hole transport layer is 2mg/mL; the coumarin concentration in the crosslinked luminescent layer is 5mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 8mg/mL.
Example 8:
this example is substantially the same as example 2, except that the coumarin concentration in the crosslinked hole transport layer is 6mg/mL; the coumarin concentration in the crosslinked luminescent layer is 15mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 20mg/mL.
Example 9:
this example is substantially the same as example 2, except that the coumarin concentration in the crosslinked hole transport layer is 0.2mg/mL; the concentration of coumarin in the crosslinked luminescent layer is 1mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 1mg/mL.
Example 10:
this example is substantially the same as example 2, except that the coumarin concentration in the crosslinked hole transport layer is 12mg/mL; the coumarin concentration in the crosslinked luminescent layer is 30mg/mL; the concentration of coumarin in the cross-linked electron injection layer was 50mg/mL.
Comparative example 1:
the embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device comprises the following steps:
(1) Spin-coating PEDOT on an ITO substrate: PSS, 5000rpm, for 30 seconds, followed by heating at 150℃for 15 minutes and cooling by standing for 5 minutes.
(2) TFB (8 mg/mL) was spin coated at 3000rpm for 30 seconds followed by heating at 80℃for 10 minutes and cooling by standing for 5 minutes.
(3) Quantum dots (20 mg/mL) were spin coated at 2000rpm for 30 seconds followed by heating at 80℃for 10 minutes and cooling for 5 minutes.
(4) ZnO (30 mg/mL) was spin coated at 1500rpm for 30 seconds followed by heating at 80℃for 20 minutes and cooling by standing for 5 minutes.
(5) Vacuum degree is not higher than 3×10 by thermal evaporation -4 Pa, evaporating Ag at a speed of 1 angstrom/second for 200 seconds and thickness of 20nm to obtain a top-emitting positive electroluminescent device, and packaging the device.
In order to illustrate the effect of the cross-linking agent doped in the material of the device functional layer on the electrical property and service life of the device, JVL data of each example and comparative example are tested respectively to determine the electrical property of the device, the service life data of the device is tested, constant current driving of 2mA is used to determine the service life of the device, and the results of the electrical property and service life are shown in Table 1. The electroluminescent morphology (EL) photographs of the devices of example 1, example 2 and comparative example 1 were performed using an optical microscope, and the results are shown in fig. 6.
TABLE 1
Remarks: the data in the table are working life test data of the flexible QLED device after mechanical stress test, and the device film prepared by the process of comparative example 1 is cracked and has no test data. Wherein: l represents the device brightness, and at the same current, a higher device brightness represents a better device efficiency; t95 represents the time taken for the brightness of the device to decay from 100% to 95%, and at the same current, the longer the device T95 time, the better the device performance, the more excellent the stability; T95-1K represents the time taken for the luminance to decay from 100% to 95% when the device is at a luminance of 1000 nit. This value is calculated from the values of L and T95; C.E shows the current efficiency of the device, and the higher C.E the better the device performance on the premise that the area of the light emitting region is consistent with the driving current; C.E-1000nit shows the current efficiency of the device under the brightness of 1000nit, and the higher C.E-1000nit is, the better the device performance is on the premise that the area of the light emitting area is consistent with the driving current.
Comparing the morphology and performance of example 1 and example 2 with those of comparative example 1, it can be seen from fig. 6 that the morphology of example 1 and example 2 is significantly better than that of comparative example, and in table 1, the device of comparative example 1 fails due to cracking of the film layer, which indicates that the doping of the cross-linking agent in the material of the functional layer of the device can avoid cracking of the functional layer, improve the yield of the device, and improve the failure problem of the device. The crosslinking structure is formed between the photocrosslinkers, so that the adjacent functional layers are firmly bonded, and the phenomenon that the film layer of the flexible device is cracked and the film layer is entirely fallen off in the use process is avoided.
Comparing examples 1, 3 to 6 with examples 2, 7 to 10, respectively, it can be seen from table 1 that the device performance and lifetime of examples 2, 7 to 10 are significantly better than those of corresponding examples 1, 3 to 6, demonstrating that the cross-linked structure is formed at the interface where the functional layers are in contact, and that the excellent electrical performance of the device itself is retained to the greatest extent.
In each example in which the crosslinking agent was uniformly dispersed in each film layer, examples 1, 3 and 4 were compared with examples 5 and 6, and the properties of examples 1, 3 and 4 were significantly better than those of other examples 5 and 6, indicating that the mass ratio of the crosslinking agent to the functional layer material was (1 to 3): 4, while the device performance was better, when the crosslinker content was too low, as in example 5, the device was still susceptible to failure, and when the crosslinker content was too high, as in example 6, the device performance improvement was insignificant.
In each example where the cross-linking agent forms a cross-linked structure at the interface where the film layers are in contact, comparing example 2, example 7, example 8 with example 9, example 10, it can be seen that the performance of example 2, example 7, and example 8 is significantly better than other examples, indicating that when the mass ratio of the cross-linking agent to the functional layer material is (1-3): 4, while the device performance is better, when the crosslinker content is too low, as in example 9, the device is still susceptible to failure, and when the crosslinker content is too high, as in example 10, the device performance improvement is insignificant.
The above describes in detail an electroluminescent device, a method for manufacturing the same, and an optoelectronic device provided in the embodiments of the present application, and specific examples are applied herein to illustrate principles and embodiments of the present application, where the above description of the embodiments is only for helping to understand the method and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (14)
1. An electroluminescent device, comprising: the cathode, the anode and two or more than two functional layers arranged between the cathode and the anode, wherein the functional layers comprise luminous layers, at least two layers of materials of the functional layers are doped with photocrosslinkers, and the two layers of functional layers are adjacently arranged.
2. The electroluminescent device of claim 1, wherein the photocrosslinker is selected from the group consisting of: at least one of coumarin, coumarin derivative, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide, wherein the photocrosslinking agent is combined with the material of the functional layer through chemical bonds, and a crosslinking structure is formed between the photocrosslinking agents.
3. The electroluminescent device of claim 1, wherein the mass ratio of photocrosslinker to material of the functional layer is (1-3): 4.
4. the electroluminescent device of claim 1, wherein the functional layer doped with the photocrosslinker consists of a material of the functional layer and the photocrosslinker, the photocrosslinker being mixed and dispersed in the material of the functional layer.
5. The electroluminescent device of claim 4, wherein the functional layer further comprises a hole functional layer and an electron functional layer, the hole functional layer is disposed between the light emitting layer and the anode, the electron functional layer is disposed between the light emitting layer and the cathode, the photo-crosslinking agent is mixed and dispersed in the hole functional layer and the light emitting layer, and/or the photo-crosslinking agent is mixed and dispersed in the light emitting layer and the electron functional layer.
6. An electroluminescent device according to claim 1, characterized in that one of the functional layers comprises a first film layer distant from an adjacent functional layer, and a second film layer and/or a third film layer close to an adjacent functional layer; wherein,,
the second film layer is close to the adjacent lower functional layer, the third film layer is close to the adjacent upper functional layer, and the photo-crosslinking agent is mixed and dispersed in the second film layer and/or the third film layer.
7. The electroluminescent device of claim 6, wherein the functional layers further comprise a hole functional layer and an electron functional layer, the hole functional layer being disposed between the light emitting layer and the anode, the electron functional layer being disposed between the light emitting layer and the cathode; wherein,,
the side of the hole function layer close to the light emitting layer is doped with the photo-crosslinking agent, the side of the light emitting layer close to the hole function is doped with the photo-crosslinking agent, and/or,
the side, close to the light-emitting layer, of the electronic functional layer is doped with the photocrosslinking agent, and the side, close to the electronic functional layer, of the light-emitting layer is doped with the photocrosslinking agent.
8. An electroluminescent device as claimed in claim 5 or 7, characterized in that,
The hole functional layer comprises a hole injection layer, and the electron functional layer comprises an electron injection layer;
the hole injection layer is made of a material selected from the group consisting of: poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, polymeric triarylamine, 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-carbazol) 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 or C 60 At least one of (a) and (b); and/or the number of the groups of groups,
the material of the light-emitting layer is selected from the group consisting of: group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV elements; wherein the II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, hgS, hgSe, hgTe, pbS, pbSe or PbTe, and the III-V compound is selected from at least one of GaP, gaAs, inP or InAs; alternatively, the material of the light emitting layer is 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 + An ion, M is a divalent metal cation, X is a halogen anion, said divalent metal cation being selected from the group consisting of: pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、C d2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ Or Eu 2 + The halogen anion is selected from Cl-, br-or I-, and the structural general formula of the organic-inorganic hybridization perovskite semiconductor is BMX 3 Wherein B is an organic amine cation selected from CH 3 (CH 2 ) n-2 NH 3+ (n.gtoreq.2) or NH 3 (CH 2 )nNH 3 2 + (n is more than or equal to 2); and/or the number of the groups of groups,
the material of the electron injection layer is selected from the group consisting of: znO, tiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 At least one of NiO, tiLiO, znAlO, znMgO, znSnO, znLiO or InSnO; and/or the number of the groups of groups,
the anode material is selected from: a metallic or non-metallic material selected from nickel, platinum, gold, silver, iridium or carbon nanotubes; or selected from doped or undoped metal oxides selected from: indium tin oxide, indium zinc oxide, indium tin zinc oxide, indium copper oxide, tin oxide, indium oxide, cadmium zinc oxide, fluorine tin oxide, indium zinc oxide, gallium tin oxide or zinc aluminum oxide; and/or the number of the groups of groups,
the cathode material is one or more selected from metal materials, carbon materials and metal oxides; wherein the metal material comprises one or more of Al, ag, cu, mo, au, ba, ca, mg, the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber, the metal oxide is selected from doped/undoped metal oxide or a composite electrode of doped/undoped transparent metal oxide and metal sandwiched between the doped/undoped transparent metal oxide, the doped/undoped metal oxide comprises at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 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 One or more of the following.
9. A method of manufacturing an electroluminescent device, the method comprising:
preparing two or more functional layers on the anode from bottom to top in sequence; and
preparing a cathode on the functional layer to obtain the electroluminescent device;
or sequentially preparing two or more functional layers on the cathode from bottom to top; and
preparing an anode on the functional layer to obtain the electroluminescent device;
the functional layers comprise luminous layers, at least two layers of materials of the functional layers are doped with photo-crosslinking agents, and the two layers of functional layers are adjacently arranged.
10. The method of claim 9, wherein the method of producing the two or more functional layers comprises:
mixing and heating a cross-linking agent and a material solution of the functional layer to obtain a mixed solution, and preparing the functional layer by using the mixed solution;
sequentially preparing the next functional layers to obtain two or more functional layers; and
and carrying out ultraviolet light irradiation treatment on the two or more functional layers.
11. The method of claim 9, wherein the method of producing the two or more functional layers comprises:
Mixing and heating a cross-linking agent and a material solution of a functional layer to obtain a mixed solution, preparing a first film layer by using the material solution of the functional layer, and preparing a second film layer and/or a third film layer by using the mixed solution to obtain the functional layer; wherein the second film layer is close to the adjacent lower functional layer, and the third film layer is close to the adjacent upper functional layer;
sequentially preparing the next functional layers to obtain two or more functional layers; and
and carrying out ultraviolet light irradiation treatment on the two or more functional layers.
12. The method according to claim 10 or 11, wherein in the mixed solution, the mass ratio of the photocrosslinker to the functional layer material is (1 to 3): 4.
13. the method of claim 9, wherein the photocrosslinker is selected from the group consisting of: at least one of coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolacrylamide or diacetone acrylamide.
14. An optoelectronic device comprising an electroluminescent device as claimed in any one of claims 1 to 8 or comprising an electroluminescent device produced by the production method as claimed in any one of claims 9 to 13.
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