CN118284276A

CN118284276A - Composite material, light-emitting device comprising composite material, and electronic device

Info

Publication number: CN118284276A
Application number: CN202211738045.XA
Authority: CN
Inventors: 张天朔
Original assignee: Guangdong Juhua New Display Research Institute; TCL Technology Group Co Ltd
Current assignee: Guangdong Juhua New Display Research Institute; TCL Technology Group Co Ltd
Filing date: 2022-12-30
Publication date: 2024-07-02

Abstract

The application discloses a composite material, a light-emitting device and an electronic device comprising the composite material, wherein the composite material comprises a first metal oxide and a first organic compound, the first metal oxide and the first organic compound are connected through chemical bonds, the composite material has ideal stability and conductivity, and the preparation method of the composite material comprises the following steps: the preparation method has the advantages that the preparation process is simple, and the preparation method is suitable for large-scale industrial production, and the material of the electronic functional layer in the light-emitting device comprises the composite material or the composite material prepared by the preparation method of the composite material, so that the current efficiency and the brightness of the light-emitting device are improved, and the resistance of the light-emitting device to the aging of water and oxygen is improved.

Description

Composite material, light-emitting device comprising composite material, and electronic device

Technical Field

The application relates to the technical field of photoelectricity, in particular to a composite material, a light-emitting device containing the composite material and electronic equipment.

Background

The metal oxide is a compound formed by combining metal elements and oxygen elements, and after the metal oxide is nanocrystallized, the metal oxide has small-size effect, surface and interface effect, quantum dot size effect and macroscopic quantum tunnel effect due to the characteristics of small size, large specific surface area and many surface active centers, so that the metal oxide is widely applied to high-efficiency catalysts, batteries, light-emitting devices, super capacitors, energy storage devices, magnetic devices and optical devices.

Currently, there are many defect states on the surface of the metal oxide, such as oxygen vacancy defects, and the environmental condition is one of the influencing factors of the number of defect states, and the stability of the metal oxide is negatively influenced by the excessive number of defect states. Therefore, how to improve the stability of the metal oxide is of great importance for the application and development of the metal oxide.

Disclosure of Invention

The application provides a composite material, a light-emitting device and an electronic device containing the composite material, so as to improve the stability of metal oxide.

The technical scheme of the application is as follows:

In a first aspect, the present application provides a composite material comprising a first metal oxide and a first organic compound, the first metal oxide being chemically bonded to the first organic compound, the first organic compound having a structure represented by the following general formula (i):

In the general formula (I), R ₁ is- (CH ₂)_s -, s is selected from positive integers of 1-10, R ₂ is- (CH ₂)_t -, t is selected from positive integers of 1-10, and n is more than 0.

Optionally, s is a positive integer from 1 to 7, and t is a positive integer from 1 to 7; and/or

The first organic compound is coordinately bound to the first metal oxide; and/or

The metal element in the first metal oxide is selected from one or more of group IA metal, group IIA metal, group IIIA metal, group IVA metal, group VA metal and transition metal, preferably, the first metal oxide is selected from one or more of zinc oxide, titanium oxide, tin oxide, barium oxide, tantalum oxide, aluminum oxide, zirconium oxide, zinc magnesium oxide, zinc calcium oxide, zinc zirconium oxide, zinc gallium oxide, zinc aluminum oxide, zinc lithium oxide, zinc titanium oxide, yttrium zinc oxide, indium tin oxide and titanium lithium oxide.

Optionally, the mass of the first organic compound is no more than 15% of the total mass of the composite material.

In a second aspect, the present application provides a method of preparing a composite material, comprising the steps of: providing a mixture comprising a second organic compound and a first metal oxide, and subjecting the mixture to a heat treatment to obtain the composite material;

Wherein the second organic compound has a structure represented by the following general formula (II):

In the general formula (II), R ₁ is- (CH ₂)_s -, s is a positive integer from 1 to 10, R ₂ is- (CH ₂)_t -, and t is a positive integer from 1 to 10).

Optionally, in the mixture, the mass of the first metal oxide is at least six times the mass of the second organic compound; and/or

The mixture is a dispersion liquid, and the solvent of the dispersion liquid is one or more selected from alkane, aromatic hydrocarbon, halogenated alkane, alcohol compound, ether compound, furan compound, pyridine compound and amide compound.

Optionally, the temperature of the heat treatment is 140-180 ℃; and/or

The time of the heat treatment is 20 min-60 min.

In a third aspect, the present application provides a light emitting device comprising:

An anode;

A cathode disposed opposite the anode;

A light-emitting layer disposed between the anode and the cathode; and

An electron functional layer disposed between the cathode and the light emitting layer;

Wherein the material of the electronic functional layer comprises the composite material according to any one of the first aspects, or the material of the electronic functional layer comprises the composite material prepared by the preparation method of the composite material according to any one of the second aspects.

Optionally, the material of the light emitting layer is selected from organic light emitting materials or quantum dots;

Wherein the organic luminescent material is selected from one or more of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonding, hybrid local charge transfer excited state materials and exciplex luminescent materials;

the quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots;

The material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compounds, group III-V compounds, group IV-VI compounds, or group I-III-VI compounds, independently of each other, wherein the group II-VI compounds are selected from one or more of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe and HgZnSTe, the group III-V compounds are selected from one or more of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs and InAlPSb, the group IV-VI compounds are selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, and the group I-III-VI compounds are selected from one or more of CuInS, cuInSe, and AgInS;

The structural general formula of the inorganic perovskite quantum dot is AMX ₃, wherein A is Cs ⁺ ion, M is divalent metal cation, M is selected from one or more of Pb²⁺、Sn²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Cr²⁺、Mn²⁺、Co²⁺、Fe²⁺、Ge²⁺、Yb²⁺ and Eu ²⁺, and X is halogen anion;

The structural general formula of the organic perovskite quantum dot is CMX ₃, and C is formamidino;

The organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX ₃, and B is selected from organic amine cations; and/or

The light-emitting device further comprises a hole functional layer, wherein the hole functional layer is arranged between the light-emitting layer and the anode, and the material of the hole functional layer is selected from poly (3, 4-ethylenedioxythiophene) such as poly (styrenesulfonic acid), copper phthalocyanine, titanylphthalocyanine, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl-substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N ' -bis (4-butylphenyl) -N, N ' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), Poly (4, 4 '-tris (2-naphthylphenylamino) triphenylamine), 2,3,5, 6-tetrafluoro-7, 7',8 '-tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, poly (4, 4' -N, N '-dicarbazolyl-biphenyl), poly (N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine), poly (4, 4 '-bis (9-carbazole) biphenyl), poly (4, 4',4" -tris (carbazole-9-yl) triphenylamine), poly (N, N '-diphenyl-N, N' -bis (3-methylphenyl) - (1, 1 '-biphenyl) -4,4' -diamine), Poly (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro), poly (N, N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine), poly (4, 4' -tris (N-carbazolyl) -triphenylamine), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], poly (4-butylphenyl-diphenylamine), polyaniline, polypyrrole, Poly (p-phenylenevinylene), poly (2-methoxy-5- (2-ethylhexyl oxy) -1, 4-phenylenevinylene), poly (2-methoxy-5- (3 ',7' -dimethyloctyl oxy) -1, 4-phenylenevinylene), aromatic tertiary amine, 4' -bis (p-carbazolyl) -1,1' -biphenyl compound, N ' -tetraarylbenzidine, poly (N-vinylcarbazole) and derivatives thereof, polymethacrylate and derivatives thereof, poly (9, 9-octylfluorene) and derivatives thereof, poly (spirofluorene) and derivatives thereof, poly (N, N ' -bis (naphthalen-1-yl) -N, N ' -diphenylbenzidine) and derivatives thereof, one or more of doped or undoped graphene, C60, doped or undoped nickel oxide, doped or undoped molybdenum oxide, doped or undoped tungsten oxide, doped or undoped vanadium oxide, doped or undoped P-type gallium nitride, doped or undoped chromium oxide, doped or undoped copper oxide, transition metal sulfides, and transition metal selenides; And/or

The materials of the anode and the cathode are independently selected from one or more of a metal selected from one or more of Al, ag, cu, mo, au, ba, pt, ca and Mg, a carbon material selected from one or more of graphite, carbon nanotubes, graphene and carbon fibers, and a second metal oxide selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide.

In a fourth aspect, the present application also provides a method for manufacturing a light emitting device, the method comprising the steps of:

providing a bottom electrode, and forming a light-emitting layer on one side of the bottom electrode; and

Forming a top electrode on one side of the light-emitting layer away from the bottom electrode;

When the light emitting device is in a positive structure, the bottom electrode is an anode and the top electrode is a cathode, after the step of forming a light emitting layer on one side of the bottom electrode, and before the step of forming a top electrode on one side of the light emitting layer away from the bottom electrode, the preparation method of the light emitting device further comprises the steps of: applying a dispersion liquid containing a second organic compound and a first metal oxide to a side of the light-emitting layer away from the bottom electrode, and then performing heat treatment on the dispersion liquid positioned on a side of the light-emitting layer away from the bottom electrode to obtain an electronic functional layer;

when the light emitting device is in an inverted structure, the bottom electrode is a cathode and the top electrode is an anode, and before the step of forming the light emitting layer, the method for manufacturing the light emitting device further includes the steps of: applying a dispersion liquid containing a second organic compound and a first metal oxide on one side of the bottom electrode, and then performing heat treatment on the dispersion liquid on one side of the bottom electrode to obtain an electronic functional layer;

Optionally, in the dispersion, the mass of the first metal oxide is at least six times the mass of the second organic compound; and/or

The metal element in the first metal oxide is selected from one or more of group IA metal, group IIA metal, group IIIA metal, group IVA metal, group VA metal and transition metal, preferably, the first metal oxide is selected from one or more of zinc oxide, titanium oxide, tin oxide, barium oxide, tantalum oxide, aluminum oxide, zirconium oxide, zinc magnesium oxide, zinc calcium oxide, zinc zirconium oxide, zinc gallium oxide, zinc aluminum oxide, zinc lithium oxide, zinc titanium oxide, yttrium zinc oxide, indium tin oxide and titanium lithium oxide; and/or

The temperature of the heat treatment is 140-180 ℃; and/or

The time of the heat treatment is 20 min-60 min.

In a fifth aspect, the present application provides an electronic device comprising the light-emitting device according to any one of the third aspects, or the electronic device comprising the light-emitting device manufactured by the manufacturing method of the light-emitting device according to any one of the fourth aspects.

The application provides a composite material, a light-emitting device and electronic equipment containing the composite material, and the light-emitting device and the electronic equipment have the following advantages:

the composite material comprises a first metal oxide and a first organic compound, wherein the first metal oxide and the first organic compound are connected through chemical bonds, for example, the first organic compound is connected to a dangling bond on the surface of the first metal oxide through-OH coordination, so that the defect state on the surface of the first metal oxide is effectively passivated, the defect state quantity of the first metal oxide is reduced, and the stability of the first metal oxide is improved.

In the light-emitting device of the embodiment of the application, the material of the electronic functional layer contains the composite material or the composite material prepared by the preparation method of the composite material, and compared with the electronic functional layer of which the material is the first metal oxide, the electronic functional layer containing the composite material has better performance stability and conductivity, thereby improving the current efficiency and the brightness of the light-emitting device; in addition, the whole electronic functional layer has a cross-linking structure, so that the electronic functional layer has ideal stability, the performance stability of the light-emitting device is improved, and the anti-aging capacity of the light-emitting device against oxygen is effectively improved.

Drawings

The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.

Fig. 1 is a schematic structural diagram of a first light emitting device according to an embodiment of the present application;

fig. 2 is a schematic structural diagram of a second light emitting device according to an embodiment of the present application;

fig. 3 is a schematic structural diagram of a second light emitting device according to an embodiment of the present application.

The reference numerals are as follows:

1: light emitting device, 10: substrate, 11: anode, 12: cathode, 13: light emitting layer, 14: electronic functional layer, 15: hole functional layer, 151: hole injection layer, 152: and a hole transport layer.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.

The following description of the embodiments is not intended to limit the preferred embodiments. Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.

In the description of the present application, the term "comprising" means "including but not limited to".

The term "at least one" means one or more, and "plurality" means two or more. The terms "at least one," "at least one of," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c" or "at least one (individual) of a, b, and c" may each be expressed as: a. b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c, respectively, may be single or multiple.

In the present application, the description of "the a layer is formed on the side of the B layer" or "the a layer is formed on the side of the B layer away from the C layer" may mean that the a layer is directly formed on the side of the B layer or the side of the B layer away from the C layer, that is, the a layer is in direct contact with the B layer; it may also mean that the grounding between layers a is formed on one side of layer B or on one side of layer B away from layer C, i.e. other film layers may also be formed between layers a and B.

The scope of the term "and/or" includes any one of the two or more items listed in relation to each other as well as any and all combinations of items listed in relation to each other, including any two items listed in relation to each other, any more items listed in relation to each other, or all combinations of items listed in relation to each other. For example, "a and/or B" includes A, B and three parallel schemes a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical schemes of all "logical or" connections), also include any and all combinations of A, B, C, D, i.e., the combinations of any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical schemes of all "logical and" connections).

The embodiment of the application provides a composite material, which comprises a first metal oxide and a first organic compound, wherein the first metal oxide is connected with the first organic compound through a chemical bond, and the first organic compound has a structure shown in the following general formula (I):

In the general formula (I), n is more than 0, R ₁ is- (CH ₂)_s -, s is a positive integer from 1 to 10, s is selected from 1 to 3, 1 to 4, 1 to 5,1 to 6, 1 to 7, 1 to 8, or 1 to 9, s is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.R ₂ is- (CH ₂)_t -, t is a positive integer from 1 to 10, and t is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, for example.

In the composite material of the embodiment of the application, the first metal oxide and the first organic compound are connected through chemical bonds, for example, the first organic compound is connected to the dangling bond on the surface of the first metal oxide through-OH coordination, so that the defect state on the surface of the first metal oxide is effectively passivated, the defect state quantity of the first metal oxide is reduced, and the stability of the first metal oxide is improved.

In some embodiments of the present application, the metal element in the first metal oxide is selected from one or more of group IA metals, group IIA metals, group IIIA metals, group IVA metals, group VA metals, and transition metals. The first metal oxide may be doped or undoped, the undoped first metal oxide being selected from one or more of ZnO, tiO ₂、SnO₂、BaO、Ta₂O₃、Al₂O₃ and ZrO ₂, for example, the doped first metal oxide being selected from one or more of Zn_(1-x)Mg_xO、Zn_(1-x)Ca_xO、Zn_(1-x)Zr_xO、Zn_(1-x)Ga_xO、Zn_(1-x)Al_xO、Zn_(1-x)Li_xO、Al_(1-x)Zn_xO、Zn_(1-x)Ti_xO、Zn_(1-x)Y_xO、In_(1-x)Sn_xO and Ti _(1-x)Li_x O, wherein 0 < x.ltoreq.0.5.

In some embodiments of the application, the first metal oxide has an average particle size of 2nm to 40nm, which may be, for example, 2nm to 5nm, 5nm to 10nm, 10nm to 15nm, 15nm to 20nm, 20nm to 25nm, 25nm to 30nm, 30nm to 35nm, or 35nm to 40nm.

To further enhance the conductive properties of the composite, in some embodiments of the application, the mass of the first organic compound comprises no more than 15%, such as no more than 14%, no more than 13%, no more than 12%, no more than 11%, no more than 10%, no more than 9%, no more than 8%, no more than 7%, no more than 6%, no more than 5%, no more than 4%, no more than 3%, no more than 2%, or no more than 1% of the total mass of the composite.

The embodiment of the application also provides a preparation method of the composite material, which can be used for preparing the composite material according to any one of the above, and comprises the following steps: providing a mixture comprising a second organic compound and a first metal oxide, and heat treating the mixture to obtain the composite material. Wherein the first metal oxide is described with reference to the foregoing.

The second organic compound has a structure represented by the following general formula (II):

In the general formula (II), R ₁ is- (CH ₂)_s -, s is a positive integer from 1 to 10, R ₂ is- (CH ₂)_t -, and t is a positive integer from 1 to 10. R ₁ and R ₂ can refer to the description.

In the preparation method of the composite material, the alkenyl in the second organic compound is subjected to cross-linking polymerization reaction in a heat treatment mode to form the first organic compound, and in the heat treatment process, hydroxyl can be coordinately connected to dangling bonds on the surface of the first metal oxide, so that the defect state of the surface of the first metal oxide is effectively passivated, the defect state quantity of the first metal oxide is reduced, and the stability of the first metal oxide is improved.

To further enhance the electrical conductivity of the composite material, in some embodiments of the application, the mass of the first metal oxide is at least six times, such as at least seven times, at least eight times, at least ten times, at least eleven times, at least twelve times, at least ten times, at least fifteen times, at least sixteen times, at least seventy times, at least twenty times, at least thirty times, at least forty times, at least fifty times, or at least one hundred times the mass of the second organic compound in the mixture.

To facilitate the preparation of the composite material, in some embodiments of the application, the mixture is a dispersion, and the solvent of the dispersion is selected from one or more of alkanes, aromatic hydrocarbons, haloalkanes, alcohols, ethers, furans, pyridines, and amides, and the solvent is selected from one or more of cyclohexane, toluene, methanol, ethanol, n-propanol, isopropanol, butanol, t-butanol, pentanol, glycerol, ethylene glycol, diethylene glycol, and dipropylene glycol, for example cyclohexane and/or toluene. The concentration of the first metal oxide in the dispersion is, for example, 20mg/mL to 50mg/mL.

In some embodiments of the application, "providing a mixture comprising a second organic compound and a first metal oxide" comprises the steps of: providing a first solution comprising a first metal oxide, dispersing a second organic compound in the first solution, obtaining a mixture. It will be appreciated that "providing a mixture comprising a second organic compound and a first metal oxide" may further comprise the steps of: providing a second solution comprising a second organic compound, dispersing the first metal oxide in the second solution to obtain a mixture; or "providing a mixture comprising the second organic compound and the first metal oxide" may further comprise the steps of: providing a first solution comprising a first metal oxide and a second solution comprising a second organic compound, and mixing the first solution and the second solution to obtain a mixture. Solvents for the first solution and the second solution are described above with respect to the solvents.

In order to enhance the crosslinking effect of the second organic compound and the coordination effect of the hydroxyl group, in some embodiments of the present application, the temperature of the heat treatment is 140 to 180 ℃, for example, may be 140 to 150 ℃, 150 to 160 ℃, 160 to 170 ℃, or 170 to 180 ℃; and/or the heat treatment time is 20 to 60 minutes, for example, 20 to 30 minutes, 30 to 40 minutes, 40 to 50 minutes, or 50 to 60 minutes.

It should be noted that the composite material may be in a film form, and the preparation method of the corresponding composite material is as follows: providing a substrate, applying a dispersion liquid containing a second organic compound and a first metal oxide on one side of the substrate, and then performing heat treatment on the dispersion liquid on one side of the substrate to obtain a composite material in a thin film form. Wherein the application is a solution process including, but not limited to, one or more of spin coating, printing, ink jet printing, knife coating, printing, dip-coating, dipping, spray coating, roll coating, casting, slot coating, and bar coating, "heat treatment" is described above. Since the alkenyl group in the second compound reacts to form the first organic compound, the composite material in the form of a thin film has a crosslinked structure as a whole, and thus has desired stability.

The embodiment of the present application further provides a light emitting device, as shown in fig. 1, where the light emitting device 1 includes an anode 11, a cathode 12, a light emitting layer 13, and an electronic functional layer 14, the anode 11 is disposed opposite to the cathode 12, the light emitting layer 13 is disposed between the anode 11 and the cathode 12, and the electronic functional layer 14 is disposed between the cathode 12 and the light emitting layer 13, where a material of the electronic functional layer 14 includes any one of the composite materials described in the foregoing, or a material of the electronic functional layer 14 includes a composite material manufactured by a method for manufacturing any one of the composite materials described in the foregoing.

In the light emitting device 1 according to the embodiment of the present application, the material of the electronic functional layer 14 includes any one of the above-mentioned composite materials, or the material of the electronic functional layer 14 includes any one of the above-mentioned composite materials manufactured by the method for manufacturing the composite material, the electronic functional layer including the composite material has better performance stability and conductivity than the electronic functional layer including the first metal oxide, thereby improving the current efficiency and the brightness of the light emitting device 1. Because the first organic compound is of a cross-linked structure, the electronic functional layer 14 is of a cross-linked structure as a whole, so that the electronic functional layer 14 has ideal stability, the performance stability of the light-emitting device 1 is improved, and the resistance of the light-emitting device 1 to water and oxygen aging is effectively improved. In addition, the first organic compound has an ideal light transmittance, does not adversely affect the light emission characteristics of the light emitting device 1, and can satisfy the optical model required for the light emitting device 1.

In the light emitting device 1 of the embodiment of the present application, materials of the anode 11, the cathode 12, and the light emitting layer 13 may be common in the art, for example:

The materials of the anode 11 and the cathode 12 are independently selected from one or more of a metal, a carbon material, and a second metal oxide, wherein the metal includes, but is not limited to, one or more of Al, ag, cu, mo, au, ba, pt, ca and Mg; the carbon material includes, but is not limited to, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the second metal oxide may be a doped or undoped metal oxide including, but not limited to, one or more of Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), tin antimony oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), indium doped zinc oxide (IZO), and magnesium doped zinc oxide (MZO). The anode 11 or the cathode 12 can also be a composite electrode, the composite electrode has a sandwich-like structure, the upper layer and the bottom layer are respectively doped or undoped transparent metal oxide, the middle layer is made of metal, for example, one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO₂/Ag/TiO₂、TiO₂/Al/TiO₂、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO₂/Ag/TiO₂ and TiO ₂/Al/TiO₂, and the thickness of the middle layer is not more than 35nm. The thickness of the anode 11 may be, for example, 20nm to 300nm, and the thickness of the cathode 12 may be, for example, 20nm to 300nm.

It is understood that when the light emitting mode of the light emitting device 1 is the top emission type, the transmittance of the top electrode 12 to visible light is not less than 90%, for example, not less than 91%, not less than 92%, not less than 93%, not less than 94%, not less than 95%, not less than 96%, not less than 97%, not less than 98%, not less than 99%, or not less than 100%. When the light emitting mode of the light emitting device 1 is bottom emission, the transmittance of the bottom electrode 11 to visible light is not less than 90%, for example, not less than 91%, not less than 92%, not less than 93%, not less than 94%, not less than 95%, not less than 96%, not less than 97%, not less than 98%, not less than 99%, or not less than 100%.

The material of the light emitting layer 13 may be selected from organic light emitting materials or quantum dots, and the thickness of the light emitting layer 13 may be, for example, 10nm to 100nm, corresponding to the light emitting device 1 being an OLED or QLED. The light-emitting layer 13 may have a single-layer structure or a multilayer structure, and for example, the light-emitting layer 13 may have two or more layers.

Wherein the organic luminescent material comprises, but is not limited to, one or more of 4,4' -bis (N-carbazole) -1,1' -biphenyl tris [2- (p-tolyl) pyridine iridium (III), 4' -tris (carbazole-9-yl) triphenylamine tris [2- (p-tolyl) pyridine iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonding, hybrid local charge transfer excited state materials and exciplex luminescent materials.

The quantum dots include, but are not limited to, one or more of red, green, and blue quantum dots, and the quantum dots include, but are not limited to, one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, the average particle size of the quantum dots may be, for example, 5nm to 10nm, with the average particle size of the quantum dots exemplified by 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm.

For single component quantum dots and core-shell structured quantum dots, the material of the single component quantum dot, the material of the core-shell structured quantum dot, or the material of the shell of the core-shell structured quantum dot includes, but is not limited to, at least one of a group II-VI compound selected from one or more of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe and HgZnSTe, a group III-V compound selected from one or more of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs and InAlPSb, and a group IV-VI compound selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe and SnPbSTe, a group IV-VI compound selected from one or more of CuInS, cuInSe and AgInS. The chemical formula provided for the material of the single component quantum dot, the material of the core of the quantum dot of the core-shell structure, or the material of the shell of the quantum dot of the core-shell structure shows only the elemental composition, and the content of each element is not shown, for example: cdZnSe is only composed of three elements Cd, zn and Se, and if the content of each element is expressed, the corresponding value is Cd _xZn_1-x Se,0< x <1.

For inorganic perovskite quantum dots, the structural formula of the inorganic perovskite quantum dots is AMX ₃, wherein A is Cs ⁺ ion, M is divalent metal cation, M comprises, but is not limited to, Pb²⁺、Sn²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Cr²⁺、Mn²⁺、Co²⁺、Fe²⁺、Ge²⁺、Yb²⁺ or Eu ²⁺, and X is halogen anion, including, but not limited to, cl ^-、Br^- or I ^-.

For organic perovskite quantum dots, the structural formula hey CMX ₃ of the organic perovskite quantum dots, wherein C is a formamidino group, M is a divalent metal cation, M includes but is not limited to Pb²⁺、Sn²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Cr²⁺、Mn²⁺、Co²⁺、Fe²⁺、Ge²⁺、Yb²⁺ or Eu ²⁺, and X is a halogen anion, including but not limited to Cl ^-、Br^- or I ^-.

For the organic-inorganic hybrid perovskite quantum dots, the structural general formula of the organic-inorganic hybrid perovskite quantum dots is BMX ₃, wherein B is selected from organic amine cations, the organic amine cations comprise but are not limited to CH ₃(CH₂)_n-2NH³⁺ (n is more than or equal to 2) or NH ₃(CH₂)_nNH₃ ²⁺ (n is more than or equal to 2), M is a divalent metal cation, M comprises but is not limited to Pb²⁺、Sn²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Cr²⁺、Mn²⁺、Co²⁺、Fe²⁺、Ge²⁺、Yb²⁺ or Eu ²⁺, and X is a halogen anion, including but not limited to Cl ^-、Br^- or I ^-.

It is understood that when the material of the light emitting layer comprises quantum dots, the material of the light emitting layer further comprises a ligand attached to the surface of the quantum dots, the ligand comprises, but is not limited to, at least one of an amine ligand, a carboxylic acid ligand, a thiol ligand, (oxy) phosphine ligand, a phospholipid, a soft phospholipid or a polyvinylpyridine, the amine ligand is, for example, at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, tributylamine or trioctylamine, the carboxylic acid ligand is, for example, at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, dodecylic acid, hexadecanoic acid, octadecanoic acid, oleic acid or benzoic acid, the thiol is, for example, at least one of methyl mercaptan, ethyl mercaptan, butanethiol, pentanethiol, hexanethiol, hexadecane, hexadecanethiol, octadecanethiol or benzylphosphine, (the ligand is, for example, methyl phosphine, n-octyl phosphine, trioctylphosphine or trioctylphosphine).

In the light emitting device 1 of the embodiment of the present application, the electron functional layer 14 may have a single-layer structure or a multi-layer structure, and the thickness of the electron functional layer 14 is, for example, 10nm to 100nm. When the electron functional layer 14 is a multilayer structure, the electron functional layer 14 includes, for example, an electron injection layer and an electron transport layer, the electron injection layer is closer to the cathode than the electron transport layer, and the electron transport layer is closer to the light emitting layer than the electron injection layer. The material of the electron transport layer comprises the composite material described in any one of the foregoing, or the material of the electron transport layer comprises the composite material prepared by the preparation method of any one of the foregoing. The material of the electron injection layer includes, but is not limited to, one or more of alkali metal halides, alkali metal organic complexes, and organic phosphine compounds, and the material of the electron injection layer is, for example, one or more selected from the group consisting of lithium 8-hydroxyquinoline, cesium carbonate, cesium fluoride, cesium azide, lithium fluoride, organic phosphorus oxide, organic thiophosphine compounds, and organic selenophosphine compounds.

In order to further enhance the overall performance of the light emitting device, in some embodiments of the present application, as shown in fig. 2, the light emitting device 1 further includes a hole function layer 15, and the hole function layer 15 is disposed between the light emitting layer 13 and the anode 11. The hole function layer 15 may have a single-layer structure or a multilayer structure, and the thickness of the hole function layer 15 may be, for example, 10nm to 100nm. The hole function layer 15 includes, for example, a hole injection layer and/or a hole transport layer, and for a hole function layer including a hole injection layer and a hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light-emitting layer than the hole injection layer.

Materials for the hole-functional layer include, but are not limited to, poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonic acid), copper phthalocyanine, titanylphthalocyanine, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl-substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), poly (4, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly (4, 4' -tris (2-naphthylphenylamino) triphenylamine), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, poly (4, 4' -N, N ' -dicarbazolyl-biphenyl), poly (N, N ' -diphenyl-N, N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine), poly (4, 4' -bis (9-carbazole) -biphenyl), poly (4, 4',4" -tris (carbazole-9-yl) triphenylamine), poly (N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine), Poly (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro), poly (N, N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine), poly (4, 4' -tris (N-carbazolyl) -triphenylamine), poly (4, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], poly (4-butylphenyl-diphenylamine), polyaniline, polypyrrole, poly (p-phenylenevinylene), poly (2-methoxy-5- (2-ethylhexyl oxy) -1, 4-phenylenevinylene), poly (2-methoxy-5- (3 ',7' -dimethyloctyl oxy) -1, 4-phenylenevinylene), aromatic tertiary amine, 4 '-bis (p-carbazolyl) -1,1' -biphenyl compound, N, N, N ', N' -tetraarylbenzidine, poly (N-vinylcarbazole) and its derivatives, polymethacrylate and its derivatives, poly (9, 9-octylfluorene) and its derivatives, 3-hexyl-substituted polythiophene, poly (spirofluorene) and its derivatives, poly (N, N '-di (naphthalen-1-yl) -N, N' -diphenyl benzidine), doped or undoped graphene, C60, doped or undoped nickel oxide, doped or undoped molybdenum oxide, doped or undoped tungsten oxide, doped or undoped vanadium oxide, doped or undoped P-type gallium nitride, doped or undoped chromium oxide, doped or undoped copper oxide, doped or undoped transition metal sulfide, and one or more of transition metal selenides, wherein the transition metal sulfide includes, but is not limited to, one or more of molybdenum sulfide, tungsten sulfide, and copper sulfide, and the transition metal selenide includes, but is not limited to, one or more of molybdenum selenide and tungsten selenide. Wherein, the doped or undoped nickel oxide is exemplified by NiO; an example of doped or undoped molybdenum oxide is MoO ₃; an example of doped or undoped tungsten oxide is WO ₃; an example of doped or undoped vanadium oxide is V ₂O₅; an example of doped or undoped chromium oxide is CrO ₃; Examples of doped or undoped copper oxide are one or more of CuO and Cu ₂ O.

The embodiment of the application also provides a preparation method of the light-emitting device, which can be used for preparing any one of the light-emitting devices in the embodiment of the application, and the preparation method of the light-emitting device comprises the following steps:

S10, providing a bottom electrode, and forming a light-emitting layer on one side of the bottom electrode;

and S20, forming a top electrode on one side of the light-emitting layer away from the bottom electrode.

When the light emitting device is in a positive structure, the bottom electrode is an anode and the top electrode is a cathode, after the step of forming the light emitting layer on one side of the bottom electrode and before the step of forming the top electrode on one side of the light emitting layer far away from the bottom electrode, the preparation method of the light emitting device further comprises the steps of: and applying a dispersion liquid containing a second organic compound and a first metal oxide on the side of the light-emitting layer away from the bottom electrode, and then performing heat treatment on the dispersion liquid on the side of the light-emitting layer away from the bottom electrode to obtain the electronic functional layer.

When the light emitting device is of an inverted structure, the bottom electrode is a cathode and the top electrode is an anode, and before the step of forming the light emitting layer, the method for manufacturing the light emitting device further comprises the steps of: a dispersion liquid containing a second organic compound and a first metal oxide is applied to one side of the bottom electrode, and then the dispersion liquid located on one side of the bottom electrode is subjected to heat treatment to obtain an electron functional layer.

It should be noted that, the preparation method of the electronic functional layer may refer to the description of the preparation method of the composite material. The preparation methods of the bottom electrode, the top electrode, and the light-emitting layer may be accomplished using conventional techniques in the art, including but not limited to solution methods and deposition methods, including but not limited to one or more of spin coating, printing, inkjet printing, doctor blading, printing, dip-coating, dipping, spray coating, roll coating, casting, slot coating, and bar coating; the deposition method includes a chemical method including, but not limited to, one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation, and a physical method including, but not limited to, one or more of thermal vapor deposition, electron beam vapor deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and laser deposition. When the film layer is prepared by the solution method, a drying process is added to obtain higher energy for the wet film formed by the solution method to be converted into a cured film, and the drying process includes, but is not limited to, a vacuum drying process or a heating process.

It will be appreciated that the method of manufacturing a light emitting device may also include other steps, such as: forming a hole function layer between the anode and the light emitting layer, the hole function layer forming method including but not limited to a solution method and a deposition method; another example is: after each film layer of the light emitting device is prepared, the light emitting device needs to be packaged.

The embodiment of the application also provides electronic equipment, which comprises the light-emitting device according to any one of the embodiments of the application, or the electronic equipment comprises the light-emitting device manufactured by the manufacturing method of any one of the light-emitting devices according to the embodiments of the application. The electronic device may be, for example, any electronic product with display function, including but not limited to, a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle display, a television set, or an electronic book reader, where the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, or the like.

The technical solutions and effects of the present application will be described in detail by way of specific examples, comparative examples and experimental examples, which are only some examples of the present application, and are not intended to limit the present application in any way.

Example 1

The present embodiment provides a composite material including a first organic compound having a structure represented by the following formula (1.1) and TiO ₂, and a method of producing the composite material:

the preparation method of the composite material comprises the following steps:

S1.1, dispersing TiO ₂ (with an average particle size of 5 nm) in toluene to prepare a TiO ₂ -toluene solution with a concentration of 30mg/mL, and dispersing 3mg of a second organic compound in 10mL of the TiO ₂ -toluene solution to obtain a dispersion;

s1.2, providing a substrate, and spin-coating the dispersion liquid prepared in the step S1.1 on one side of the substrate in a nitrogen environment at normal temperature and normal pressure;

s1.3, performing heat treatment on the mixture positioned on one side of the substrate, wherein the heat treatment temperature is 160 ℃, the heat treatment time is 60 minutes, and a composite material in a film form is formed on the 5 substrate, and the thickness is 40nm.

Wherein the second organic compound has a structure represented by the following formula (1.2):

The preparation method of the second organic compound with the structure shown in the formula (1.2) comprises the following steps: 10g of 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-diol was dissolved in 30mL of ethanol and dispersed uniformly to obtain a mixed solution; then, transferring the mixed solution into a single-neck flask with a magnetic stirrer, adding 30mL of 3-amino-1-propanol (CAS number 156-87-6) into the single-neck flask, continuously stirring for 1h at 100 ℃, and separating and purifying to obtain 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-dipropanol; next, in an atmosphere at a pressure of 10 ^-1 Pa and a temperature of 330 ℃,3,6,10,11-tetrakis (n-pentyloxy) triphenylene-2, 7-dipropyl alcohol is subjected to a cracking reaction to produce a second organic compound having a structure represented by formula (1.2).

Example 2

The present embodiment provides a composite material including a first organic compound having a structure represented by the following formula (2.1) and TiO ₂, and a method of producing the composite material:

compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: the second organic compounds are different. The second organic compound in this embodiment has a structure represented by the following formula (2.2):

the preparation method of the second organic compound with the structure shown in the formula (2.2) comprises the following steps: 10g of 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-diol was dissolved in 30mL of ethanol and dispersed uniformly to obtain a mixed solution; then, transferring the mixed solution into a single-neck flask with a magnetic stirrer, adding 30mL of 6-amino-1-hexanol (CAS number 4048-33-3), continuously stirring for 1h at 140 ℃, and separating and purifying to obtain 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-dihexanol; next, in an atmosphere having a pressure of 10 ^-1 Pa and a temperature of 330 ℃,3,6,10,11-tetrakis (n-pentyloxy) triphenylene-2, 7-dihexanol is subjected to a cracking reaction to produce a second organic compound having a structure represented by formula (2.2).

Example 3

The present embodiment provides a composite material including a first organic compound having a structure represented by the following formula (3.1) and TiO ₂, and a method of producing the composite material:

compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: the second organic compounds are different. The second organic compound in this embodiment has a structure represented by the following formula (3.2):

The preparation method of the second organic compound with the structure shown in the formula (3.2) comprises the following steps: 10g of 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-diol was dissolved in 30mL of ethanol and dispersed uniformly to obtain a mixed solution; then transferring the mixed solution into a single-neck flask with a magnetic stirrer, adding 30mL of 8-amino-1-octanol (CAS number 19008-71-0) into the single-neck flask, continuously stirring for 1h at 160 ℃, and separating and purifying to obtain 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-dioctanol; next, in an atmosphere having a pressure of 10 ^-1 Pa and a temperature of 330 ℃,3,6,10,11-tetrakis (n-pentyloxy) triphenylene-2, 7-dioctanol is subjected to a cracking reaction to produce a second organic compound having a structure represented by formula (3.2).

Example 4

The present embodiment provides a composite material including a first organic compound having a structure represented by the following formula (4.1) and TiO ₂, and a method of producing the composite material:

Compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: the second organic compounds are different. The second organic compound in this embodiment has a structure represented by the following formula (4.2):

The preparation method of the second organic compound with the structure shown in the formula (4.2) comprises the following steps: 10g of 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-diol was dissolved in 30mL of ethanol and dispersed uniformly to obtain a mixed solution; then, the mixed solution was transferred to a single-neck flask with a magnetic stirrer, 30mL of 10-amino-1-decanol (CAS number 23160-46-5) was added thereto, stirring was continued at 180℃for 1 hour, and 3,6,10,11-tetrakis (n-pentyloxy) triphenylene-2, 7-didecyl alcohol was obtained by separation and purification; next, in an atmosphere at a pressure of 10 ^-1 Pa and a temperature of 330 ℃,3,6,10,11-tetrakis (n-pentoxy) triphenylene-2, 7-didecyl alcohol is subjected to a cracking reaction to produce a second organic compound having a structure represented by formula (4.2).

Example 5

The present embodiment provides a composite material including a first organic compound having a structure represented by the following formula (5.1) and TiO ₂, and a method of producing the composite material:

Compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: the second organic compounds are different. The second organic compound in this embodiment has a structure represented by the following formula (5.2):

The preparation method of the second organic compound with the structure shown in the formula (4.2) comprises the following steps: 10g of 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-diol was dissolved in 30mL of ethanol and dispersed uniformly to obtain a mixed solution; then transferring the mixed solution into a single-neck flask with a magnetic stirrer, adding 30mL of 12-amino-1-dodecanol (CAS number 67107-87-3) into the single-neck flask, continuously stirring for 1h at 200 ℃, and separating and purifying to obtain 3,6,10,11-tetra (n-pentyloxy) triphenylene-2, 7-didodecyl alcohol; next, in an atmosphere having a pressure of 10 ^-1 Pa and a temperature of 330 ℃,3,6,10,11-tetrakis (n-pentyloxy) triphenylene-2, 7-didodecyl alcohol is subjected to a cracking reaction to produce a second organic compound having a structure represented by formula (5.2).

Example 6

The present embodiment provides a composite material including a first organic compound having a structure represented by formula (1.1) and ZnO, and a method of manufacturing the composite material.

Compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: step S1.1 was replaced with "ZnO (average particle diameter: 5 nm) was dispersed in toluene to obtain a ZnO-toluene solution having a concentration of 30mg/mL, and 3mg of the second organic compound having the structure represented by formula (1.2) was dispersed in 10mL of ZnO-toluene solution to obtain a dispersion liquid.

Example 7

The present embodiment provides a composite material including a first organic compound having a structure represented by formula (1.1) and TiO ₂, and a method of manufacturing the composite material.

Compared with the preparation method of the composite material in example 1, the preparation method of the composite material in this example is different in that: the temperature of the heat treatment in step S1.3 was replaced with "120 ℃.

Example 8

The embodiment provides a light emitting device and a preparation method thereof, the light emitting device is a quantum dot light emitting diode with a forward structure, the light emitting mode is a top emission type, as shown in fig. 3, in a bottom-up direction, the light emitting device 1 includes a substrate 10, an anode 11, a hole functional layer 15, a light emitting layer 13, an electron functional layer 14 and a cathode 12 which are sequentially stacked, wherein the hole functional layer 15 is composed of a hole injection layer 151 and a hole transport layer 152 which are stacked, the hole injection layer 151 is closer to the anode 11 than the hole transport layer 152, and the hole transport layer 152 is closer to the light emitting layer 13 than the hole injection layer 151.

The materials and thicknesses of the respective layers in the light emitting device 1 are as follows:

the material of the substrate 10 is glass, and the thickness of the substrate 10 is 2mm;

the anode 11 is made of ITO, and the thickness of the anode 11 is 20nm;

the cathode 12 is made of Ag, and the thickness of the cathode 12 is 130nm;

The material of the luminescent layer 13 is CdSe (core)/ZnS (shell) quantum dots, the luminescent color is blue, the average particle size of the quantum dots is 7nm, and the thickness of the luminescent layer 13 is 70nm;

The hole injection layer 151 is made of PEDOT PSS, and the thickness of the hole injection layer 151 is 80nm;

The material of the hole transport layer 152 is Poly-TPD, and the thickness of the hole transport layer 152 is 30nm;

The material of the electronic functional layer 14 was the composite material prepared in example 1, and the thickness of the electronic functional layer 14 was 40nm.

The preparation method of the light-emitting device in the embodiment comprises the following steps:

S8.1, providing a substrate, sputtering ITO on one side of the substrate to obtain an ITO layer, dipping a small amount of soapy water on the surface of the ITO layer by using a cotton swab to wipe the surface of the ITO layer so as to remove impurities visible to the naked eyes on the surface, sequentially ultrasonically cleaning the substrate comprising the ITO by using deionized water, acetone for 15min, ethanol for 15min and isopropanol for 15min, and performing ultraviolet-ozone surface treatment for 15min after drying to obtain the substrate comprising an anode;

s8.2, spin-coating PEDOT (polyether-ether-ketone) PSS aqueous solution (PEDOT: PSS mass percent is 20%) on one side of the anode far away from the substrate in an air environment at normal temperature and normal pressure, and then performing constant-temperature heat treatment at 160 ℃ to solidify the aqueous solution into a film to obtain a hole injection layer;

S8.3, spin-coating a (Poly-TPD) -chlorobenzene solution with the concentration of 8mg/mL on one side of the hole injection layer far away from the anode in a nitrogen environment at normal temperature and normal pressure, and then placing the solution in a constant-temperature heat treatment mode at 125 ℃ to solidify the solution into a film to obtain a hole transport layer;

S8.4, spin-coating CdSe/ZnS quantum dot-n-octane solution with the concentration of 20mg/mL on one side of the hole transport layer far away from the hole injection layer in a nitrogen environment at normal temperature and normal pressure, and then placing the solution in a constant-temperature heat treatment mode at 60 ℃ to solidify the solution into a film to obtain a light-emitting layer;

s8.5, forming an electron function layer on one side of the light-emitting layer far away from the hole transport layer according to the preparation method of the composite material in the reference example 1;

S8.6, placing the prefabricated device containing the electronic functional layer in an evaporation bin with the vacuum degree not higher than 3 multiplied by 10 ^-4 Pa, thermally evaporating Ag on one side of the electronic functional layer, which is far away from the light-emitting layer, through a mask plate to obtain a cathode, and then packaging by adopting epoxy resin glue and a cover glass to obtain the light-emitting device.

Example 9

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 2".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 2 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Example 10

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 3".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 3 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Example 11

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 4".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 4 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Example 12

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 5".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 5 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Example 13

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 6".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 6 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Example 14

The present embodiment provides a light emitting device and a method for manufacturing the same, and compared with the light emitting device in embodiment 8, the light emitting device in this embodiment is different in that: the material of the electronic functional layer was replaced with "composite material produced in example 7".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the preparation method of the composite material in reference example 7 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Comparative example 1

The comparative example provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing the composite material in example 1, the method for preparing the composite material in the comparative example is characterized in that: the step S1.3 is replaced by "the substrate containing the dispersion is placed under 10 ^-2 MPa for 15min, and a composite material in a film form is formed on the substrate.

Comparative example 2

The comparative example provides a film and a preparation method thereof, wherein the material of the film in the comparative example is TiO ₂ (the average grain diameter is 5 nm), and the preparation method of the film comprises the following steps: tiO ₂ (average particle size 5 nm) was dispersed in toluene to prepare a TiO ₂ -toluene solution having a concentration of 30 mg/mL; providing a substrate, spin-coating TiO ₂ -toluene solution on one side of the substrate in a nitrogen environment at normal temperature and normal pressure, and then placing the substrate at a constant temperature of 160 ℃ for heat treatment for 60min to obtain a film.

Comparative example 3

The present comparative example provides a light emitting device and a method of manufacturing the same, which is different from the light emitting device of example 8 in that: the material of the electron functional layer was replaced with "composite material in comparative example 1".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the method for producing a composite material in comparative example 1 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Comparative example 4

The present comparative example provides a light emitting device and a method of manufacturing the same, which is different from the light emitting device of example 8 in that: the material of the electronic functional layer is replaced with "TiO ₂".

The manufacturing method of the light emitting device in this embodiment differs from that of embodiment 8 in that: step S8.5 was replaced with "the method for producing a thin film in reference comparative example 2 forms an electron functional layer on the side of the light-emitting layer remote from the hole transport layer".

Experimental example

The light emitting devices of examples 8 to 14, comparative example 3 and comparative example 4 were subjected to performance detection, and parameters such as the turn-on voltage, current, brightness, light emission spectrum and the like of each light emitting device in the first state to the fourth state were obtained by detecting using a frieda FPD optical characteristic measuring device (including a marine optical USB2000, a LabView control QE-PRO spectrometer, a Keithley 2400, a high-precision digital source table Keithley6485, an optical fiber with an inner diameter of 50 μm, a device test probe and fixture, and an efficiency test system built by various connecting wires and data cards, an efficiency test cassette, a data acquisition system and the like), and then key parameters such as external quantum efficiency, power efficiency and the like were calculated and obtained to obtain the maximum brightness (L _max, nit). The first state is a state of the light emitting device on the same day as the packaging, the second state is a state of the light emitting device after the packaging is completed and placed in an environment with a temperature of 25 ℃ and a humidity of 75% for 10 days, the third state is a state of the light emitting device after the packaging is completed and placed in an environment with a temperature of 25 ℃ and a humidity of 75% for 30 days, and the fourth state is a state of the light emitting device after the packaging is completed and placed in an environment with a temperature of 25 ℃ and a humidity of 75% for 60 days.

The current efficiency testing method comprises the following steps: the luminance value of the light emitting device in the range of 0V to 8V is intermittently collected by setting the light emitting area to be 2mm multiplied by 2 mm=4mm ², the voltage value of the initial collected luminance is 3V, the luminance value collected every 0.2V is divided by the corresponding current density to obtain the current efficiency of the light emitting device under the condition of the collection, and the maximum current efficiency (C.E _max, cd/A) is obtained.

The performance test data of each light emitting device is shown in table 1 below:

Table 1a list of performance test data for light emitting devices in examples 8 to 14, comparative example 3 and comparative example 4

As can be seen from the performance test data of the light emitting devices in table 1, the light emitting devices in examples 8 to 14 were better in photoelectric performance and better in performance stability than the light emitting devices in comparative examples 3 and 4. Taking the light emitting devices of example 10 and comparative example 4 as examples, C.E _max of the light emitting device of example 10 was 1.8 times as large as C.E _max of the light emitting device of comparative example 4 and L _max of the light emitting device of example 10 was 2 times as large as L _max of the light emitting device of comparative example 4 on the day of packaging; at 60 days of standing, C.E _max times the light-emitting device in example 10 was 9.9 times the light-emitting device C.E _max in comparative example 4, and L _max times the light-emitting device in example 10 was 5.2 times the light-emitting device L _max in comparative example 4.

For the light emitting device in example 10, C.E _max and L _max of the light emitting device did not change much during the period from the packaging day to 60 days of placement, and C.E _max and L _max of the light emitting device placed for 60 days of placement were slightly improved compared to the packaging day. For the light emitting device in comparative example 4, C.E _max and L _max of the light emitting device slightly rose during the period from the packaging day to the placement for 10 days, C.E _max and L _max of the light emitting device significantly decreased during the period from the placement for 10 days to the placement for 60 days, C.E _max of the light emitting device placed for 60 days was only 18.4% of C.E _max of the light emitting device on the packaging day, and L _max of the light emitting device placed for 60 days was only 38.2% of L _max of the light emitting device on the packaging day. The following is explained: compared with the electronic functional layer made of TiO ₂, the electronic functional layer containing the composite material has better performance stability and conductivity, so that the current efficiency and the brightness of the light-emitting device are improved, and the anti-aging property of the light-emitting device is improved.

For the luminescent device with the electronic functional layer made of composite material, the luminescent device can not generate positive/negative aging phenomenon due to permeated water oxygen at least within 60 days after encapsulation, and has ideal performance stability; for the light emitting device with the material of the electronic functional layer being TiO ₂, a negative aging phenomenon occurs within 30 days after the encapsulation, which may be due to: the composite material is of a cross-linked structure, so that the whole electronic functional layer is of the cross-linked structure, and the performance stability of the electronic functional layer is effectively improved, thereby improving the performance stability of the light-emitting device; in addition, at least part of surface defect states of the first metal oxide in the composite material are passivated by hydroxyl groups of the first organic compound, so that the defect state quantity of the first metal oxide is reduced, the performance stability of the electronic functional layer is further improved, and the electron transmission performance of the electronic functional layer is improved.

In addition, the light emitting device of comparative example 3 is inferior in photoelectric properties and stability because: in the preparation process of the electronic functional layer, the vacuum drying treatment is adopted to replace the heating treatment, so that the second organic compound cannot undergo a crosslinking reaction to generate the first organic compound with a crosslinking structure, the coordination effect of the hydroxyl group in the second organic compound is poor, the stability improvement degree of the electronic functional layer is limited, and the improvement degree of the anti-oxidative aging capability of the light-emitting device is limited.

The above describes in detail a composite material, a light emitting device including the composite material, and an electronic device provided by the embodiment of the application. The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is only for aiding in the understanding of the technical solution of the present application and its core ideas; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the scope of the corresponding technical solutions of the embodiments of the present application.

Claims

1. A composite material comprising a first metal oxide and a first organic compound, the first metal oxide being chemically bonded to the first organic compound, the first organic compound having a structure represented by the following general formula (i):

2. The composite material according to claim 1, wherein s is selected from positive integers from 1 to 7 and t is selected from positive integers from 1 to 7; and/or

3. The composite material according to claim 1 or 2, wherein the mass of the first organic compound is not more than 15% of the total mass of the composite material.

4. A method of preparing a composite material, comprising the steps of: providing a mixture comprising a second organic compound and a first metal oxide, and subjecting the mixture to a heat treatment to obtain the composite material;

5. The method of producing a composite material according to claim 4, wherein in the mixture, the mass of the first metal oxide is at least six times the mass of the second organic compound; and/or

6. The method of producing a composite material according to claim 4, wherein the temperature of the heat treatment is 140 ℃ to 180 ℃; and/or

The time of the heat treatment is 20 min-60 min.

7. A light emitting device, comprising:

An anode;

A cathode disposed opposite the anode;

A light-emitting layer disposed between the anode and the cathode; and

Wherein the material of the electronic functional layer comprises the composite material as claimed in any one of claims 1 to 3, or the material of the electronic functional layer comprises the composite material produced by the method for producing a composite material as claimed in any one of claims 4 to 6.

8. The light-emitting device according to claim 7, wherein the material of the light-emitting layer is selected from an organic light-emitting material or quantum dots;

9. A method of manufacturing a light emitting device, comprising the steps of:

10. The method for producing a light-emitting device according to claim 9, wherein, in the dispersion liquid, the mass of the first metal oxide is at least six times the mass of the second organic compound; and/or

The temperature of the heat treatment is 140-180 ℃; and/or

The time of the heat treatment is 20 min-60 min.

11. An electronic apparatus comprising the light-emitting device according to claim 7 or 8, or the electronic apparatus comprising the light-emitting device manufactured by the manufacturing method of the light-emitting device according to claim 9 or 10.