Composite material and preparation method thereof, film, photoelectric device and preparation method thereof, and display device

Abstract

The invention discloses a composite material and a preparation method thereof, a film, a photoelectric device and a preparation method thereof, and a display device, the composite material comprises a hole function material and an additive, the additive comprises a compound having a structure represented by a formula (1), and an X group of the additive is connected with the hole function material through a non-covalent bond; wherein A comprises one or more of an aromatic ring and a heteroaromatic ring; the number of ring carbon atoms with substitutable sites on A is p, n is an integer greater than or equal to 1 and less than or equal to p, m is an integer greater than or equal to 0 and less than or equal to p, and the sum of n and m is less than or equal to p; x is independently selected from one or a combination of more of a halogen group, a hydroxyl group and an amino group when appearing each time; y is independently selected from one or a combination of more of C1-C6 alkyl groups and C1-C6 alkoxy groups when appearing each time. The invention aims to improve the transmission performance of the P-type semiconductor and solve the problem of poor stability of the existing hole function material.

Description

Technical Field

[0001] The present application relates to the field of semiconductors, and in particular to a composite material and a preparation method thereof, a thin film, an optoelectronic device and a preparation method thereof, and a display device. Background Art

[0002] Some organic materials, such as polystyrene sulfonate (PEDOT:PSS), poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl)diphenylamine)] (TFB), etc., usually have hole injection and hole transport properties and are suitable for preparing hole functional films. However, these materials are prone to decomposition or chain segment migration during long-term use, and the stability of the materials is poor, thereby reducing the hole injection and hole performance of the materials. Summary of the invention

[0003] In view of this, the present application provides a composite material and a preparation method thereof, a thin film, a photoelectric device and a preparation method thereof, and a display device. The present application aims to improve the stability of existing hole functional materials.

[0004] The embodiment of the present application is implemented as follows:

[0005] In a first aspect, the present application provides a composite material, comprising a hole functional material and an additive, wherein the additive comprises a compound having a structure shown in formula (1);

[0006]

[0007] Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer;

[0008] X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group at each occurrence;

[0009] Each occurrence of Y is independently selected from a combination of one or more of C1-C6 alkyl, C1-C6 cycloalkyl and C1-C6 alkoxy.

[0010] Optionally, in some embodiments of the present application, A includes one or more of an aromatic ring having 6 to 20 ring carbon atoms and a heteroaromatic ring having 6 to 20 ring atoms; and / or,

[0011] m is 0 to 5; and / or,

[0012] n is 1 to 6.

[0013] Optionally, in some embodiments of the present application, A is selected from one or more of the groups of any structure shown in formula (2) to (8):

[0014]

[0015] and / or,

[0016] n is 1 or 2; and / or,

[0017] m is 0 to 3; and / or,

[0018] In the composite material, the mass percentage of the additive is 5 to 25%; and / or,

[0019] The boiling point of the additive is greater than 230°C; and / or,

[0020] The X group of the additive is connected to the hole functional material via a non-covalent bond.

[0021] Optionally, in some embodiments of the present application, the additive includes one or more compounds having a structure shown in any one of formulas (9) to (15).

[0022]

[0023] Optionally, in some embodiments of the present application, each occurrence of X is independently selected from the halogen group or the hydroxyl group, and the halogen group is selected from -F; and / or,

[0024] When A includes a heteroaromatic ring, the substitution position of X is selected from the ortho or para position of the heteroatom in A.

[0025] Optionally, in some embodiments of the present application, the additive includes one or more compounds having a structure represented by any one of formulas (10) to (14).

[0026]

[0027] Optionally, in some embodiments of the present application, the hole functional material includes a hole transport material or a hole injection material, and the hole transport material is selected from poly [(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly (4-butylphenyl-diphenylamine), poly (triarylamine), polypyrrole, poly [N,N'-bis (4-butylphenyl) -N,N'-bis (phenyl) - benzidine], poly (p-) phenylene vinylene, poly [2-methoxy-5-(2- At least one of poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene) and poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene), PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives; the hole injection material is selected from at least one of PEDOT, PEDOT:PSS and phenolic copper cyanine.

[0028] In a second aspect, the present application provides a method for preparing a composite material, comprising the following steps:

[0029] Providing a hole functional material, an additive and a first solvent;

[0030] Mixing the hole functional material, the additive and the first solvent, and removing the first solvent to obtain a composite material;

[0031] Wherein, the additive includes a compound having a structure shown in formula (1);

[0032]

[0033] Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer;

[0034] X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group at each occurrence;

[0035] Each occurrence of Y is independently selected from a combination of one or more of C1-C6 alkyl, C1-C6 cycloalkyl and C1-C6 alkoxy.

[0036] Optionally, in some embodiments of the present application, in the composite material, the mass percentage of the additive is 5 to 25%; and / or,

[0037] The first solvent includes one or more of C1-C5 alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene; and / or,

[0038] The additive includes one or more compounds having a structure represented by any one of formulas (9) to (15).

[0039]

[0040] In a third aspect, the present application also proposes a film, wherein the material of the film comprises the composite material described above, or comprises the composite material obtained by the preparation method described above.

[0041] In a fourth aspect, the present application also proposes a photoelectric device, comprising a first electrode, a hole functional layer and a second electrode, wherein the hole functional layer comprises one or two layers of a hole injection layer and a hole transport layer, and the material of at least one layer of the hole functional layer comprises the composite material as described above, or a composite material obtained by the preparation method described above; or, at least one layer of the hole functional layer comprises the thin film described above.

[0042] Optionally, in some embodiments of the present application, when the hole functional material in the composite material is selected from at least one of PEDOT, PEDOT:PSS, and phenolic copper, the composite material is a first composite material; the hole functional material in the composite material is selected from poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), poly(triarylamine), polypyrrole, poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl) -benzidine], poly(p-)phenylene vinylene, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, the composite material is the second composite material;

[0043] The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole injection layer is independently selected from the first composite material, and the material of the hole transport layer is independently selected from the second composite material; or

[0044] The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole transport layer is selected from the second composite material, and the material of the hole injection layer is selected from at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, and copper phthalocyanine; or,

[0045] The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole injection layer is selected from the first composite material, and the material of the hole transport layer is selected from 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N '-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(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), poly(triarylamine), polypyrrole, poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine], poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4′-bis(p-carbazolyl) )-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine, spiro NPB, doped graphene, undoped graphene, and at least one of C60.

[0046] Optionally, in some embodiments of the present application, the first electrode and the second electrode are each independently selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is 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, the composite electrode of metal and metal oxide is selected from 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, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or,

[0047] The photoelectric device further comprises a light-emitting layer, wherein the light-emitting layer is arranged between the first electrode and the hole functional layer, or between the second electrode and the hole functional layer, and the material of the light-emitting layer is selected from one or more of organic light-emitting materials and quantum dot light-emitting materials, and the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives , TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescent material, TTA material, thermally activated delayed material, polymer containing BN covalent bond, hybrid localized charge transfer excited state material, exciplex luminescent material or more; the quantum dot luminescent material is selected from at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials; the material of the single structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots are selected from II-VI group compounds, IV-VI group compounds, II At least one of a I-V group compound and a I-III-VI group compound; the II-VI group compound is selected from 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, CdZn At least one of SeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound is at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of; and / or,

[0048] The photoelectric device further comprises an electronic functional layer, the electronic functional layer is arranged between the first electrode and the hole functional layer, the electronic functional layer comprises one or two layers of an electron transport layer and an electron injection layer, and when the electronic functional layer comprises an electron transport layer and an electron injection layer, the electron injection layer is located between the electron transport layer and the first electrode; the material of the electron transport layer is selected from at least one of metal oxides, doped metal oxides, II-VI semiconductor materials, III-V semiconductor materials and I-III-VI semiconductor materials, and the metal oxide is selected from ZnO, BaO, TiO2 , SnO2; the metal oxide in the doped metal oxide is selected from at least one of ZnO, TiO2, SnO2, the doping element is selected from at least one of Al, Mg, Li, In, Ga, the II-VI semiconductor family material is selected from at least one of ZnS, ZnSe, CdS; the III-V semiconductor family material is selected from at least one of InP and GaP; the I-III-VI group semiconductor material is selected from at least one of CuInS and CuGaS; the material of the electron injection layer is selected from at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

[0049] In a fifth aspect, the present application also proposes a method for preparing a photoelectric device, comprising the following steps:

[0050] providing a first electrode;

[0051] Providing a composite material, and disposing the composite material on one side of the first electrode to form a hole functional layer;

[0052] Disposing a second electrode on a side of the hole functional layer away from the first electrode;

[0053] Wherein, the composite material includes the composite material as described above, or the composite material prepared by the preparation method described above.

[0054] Optionally, in some embodiments of the present application, the step of disposing the composite material on one side of the first electrode to form the hole functional layer includes:

[0055] providing a second solvent, dispersing the composite material in the second solvent to obtain a composite material solution;

[0056] Disposing the composite material solution on one side of the first electrode to obtain a hole functional layer;

[0057] Wherein, the second solvent includes one or more of C1-C5 alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene.

[0058] Optionally, in some embodiments of the present application, in the composite material solution, the concentration of the hole functional material is 2 to 15 mg / ml.

[0059] In a sixth aspect, the present application further proposes a display device, comprising the optoelectronic device described above, or the optoelectronic device manufactured by the preparation method described above.

[0060] The present application provides a composite material, which includes a hole functional material and an additive. The additive contains strong polar groups such as halogen groups, hydroxyl groups, and amino groups. These groups form strong intermolecular hydrogen bonds or halogen bonds with the hole functional material. Through this intermolecular interaction, molecular locks are formed, which can regulate the aggregation behavior of the hole functional material, make its chain segment arrangement more regular and orderly, optimize and fix its morphology, and improve the stability of the hole functional material during long-term use. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0062] Figure 1 It is a schematic flow chart of a method for preparing a photoelectric device according to an embodiment of the present application;

[0063] Figure 2 is a schematic structural diagram of an optoelectronic device according to an embodiment of the present application;

[0064] Figure 3 is a schematic structural diagram of an optoelectronic device according to another embodiment of the present application;

[0065] Figure 4 is the AFM image of the control group in Experimental Example 1;

[0066] Figure 5 is the AFM image of the experimental group in Experimental Example 1;

[0067] Reference numerals:

[0068] 100 - photoelectric device; 10 - anode; 20 - light-emitting layer; 30 - electron transport layer; 40 - cathode; 50 - hole transport layer; 60 - hole injection layer. DETAILED DESCRIPTION

[0069] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application. In the present application, unless otherwise specified, the directional words such as "upper" and "lower" used are specifically the directions of the drawings in the accompanying drawings. In addition, in the description of the specification of the present application, the term "including" means "including but not limited to". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and simplicity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, description of a range from 1 to 6 should be considered to have 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 stated range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the stated range.

[0070] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0071] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0072] In a first aspect, the present application provides a composite material, the composite material comprising a hole functional material and an additive, the additive comprising a compound having a structure represented by formula (1), the X group of the additive being connected to the hole functional material via a non-covalent bond;

[0073]

[0074] Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer; X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group each time it appears; Y is independently selected from a combination of one or more of a C1 to C6 alkyl group, a C1 to C6 cycloalkyl group and a C1 to C6 alkoxy group each time it appears.

[0075] In the present application, the "number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) obtained by bonding atoms to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5. The "number of ring carbon atoms" refers to the number of atoms among the carbon atoms constituting the ring itself. For example, the number of ring carbon atoms of a benzene ring is 6, and the number of ring carbon atoms of a pyridine ring is 5.

[0076] In the present application, "a ring carbon atom at a substitutable site" refers to a ring carbon atom in a compound to which a substitutable hydrogen atom is originally connected, and the substitutable hydrogen atom can be substituted by X or Y.

[0077] In the present application, "aromatic ring or aromatic ring" refers to a cyclic compound containing a benzene ring, which can be a single ring or a condensed ring formed by multiple rings. For a polycyclic ring, at least one is an aromatic ring system. For example, "aromatic ring with 6 to 40 ring atoms" refers to an aromatic ring containing 6 to 40 ring atoms, preferably an aromatic ring with 6 to 30 ring atoms, more preferably an aromatic ring with 6 to 18 ring atoms, and particularly preferably an aromatic ring with 6 to 14 ring atoms; suitable examples include, but are not limited to: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, fluorene ring, indene ring, etc.

[0078] In the present application, "heteroaromatic ring or heteroaromatic ring" means that at least one carbon atom on the basis of an aromatic ring is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. Suitable examples include, but are not limited to, thiophene, furan, pyrrole, imidazole, diazole, triazole, pyridine, bipyridine, pyrimidine, triazine, acridine, pyridazine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, benzothiophene, benzofuran, indole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, o-naphthyridine, phenanthridine, primary idine, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and derivatives thereof.

[0079] In the present application, "alkyl" may represent a straight chain alkyl or a branched chain alkyl. C1-6 alkyl refers to an alkyl group containing 1 to 6 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl or C6 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, n-hexyl, etc.

[0080] In the present application, the alkoxy group has the structural characteristics of the formula -OR, wherein R refers to an alkyl group, i.e., a linear alkyl group or a branched alkyl group; an amino group refers to -NH2; a hydroxyl group refers to -OH; and a halogen group refers to -F, -Br, -Cl or -I.

[0081] In this application, -(X) n It means that there are n substitutable sites on the ring of the main structure A connected to a substituent X, that is, n Xs are connected to any substitutable site on the ring one by one, and the X connected to each site can independently select the type of group, and the n Xs can be the same or different; similarly, -(Y) m It means that there are m substitutable sites on the ring of the main structure A, to which a substituent Y is connected. The Y connected to each site can independently select the type of group, and the m Ys can be the same or different.

[0082] The present application provides a composite material, which includes a hole functional material and an additive. The additive contains strong polar groups such as halogen groups, hydroxyl groups, and amino groups. Strong intermolecular hydrogen bonds or halogen bonds are formed between these groups and the hole functional material. Through this intermolecular interaction, molecular locks are formed, which can regulate the aggregation behavior of the hole functional material, make its chain segment arrangement more regular and orderly, optimize and fix its morphology, and improve the stability of the hole functional material during long-term use; at the same time, the crystallinity is improved, thereby improving the hole transport performance of the material.

[0083] In some embodiments, the X group of the additive is connected to the hole functional material via a non-covalent bond.

[0084] In some embodiments, A includes one or more of an aromatic ring having 6 to 20 ring carbon atoms and a heteroaromatic ring having 6 to 20 ring atoms. In other embodiments, A is selected from one or more of benzene, biphenyl, naphthalene, pyridine, pyrimidine, quinoline, and isoquinoline; the structural formulas of the above rings are shown in the following formulas (2) to (8) in sequence:

[0085]

[0086] In some other embodiments, A is selected from one or more of pyridine, pyrimidine, quinoline, and isoquinoline, which have certain electron-withdrawing properties, which help to strengthen hydrogen bonds or halogen bonds and enhance molecular locks.

[0087] In some embodiments, n is 1 to 6, such as 1, 2, 3, 4, 5 or 6; in other embodiments, n is 1 or 2, which helps to fully exert the intermolecular force and improve the steric effect.

[0088] In some embodiments, m is 0-5, such as 0, 1, 2, 3, 4 or 5; in other embodiments, m is 0, 1, 2 or 3.

[0089] In some embodiments, the boiling point of the additive is greater than 230° C. For example, the boiling point may be 230.1° C. to 250° C., 250° C. to 270° C., 260° C. to 300° C., 290° C. to 350° C., or above 350° C., etc. Since the annealing temperature of the hole functional material is usually between 200° C. and 230° C., when the composite material is used to prepare a film, the additive will not be removed during the thermal annealing process, but will be stably combined with the hole functional material, thereby effectively improving the stability of the film.

[0090] In some embodiments, in the composite material, the mass percentage of the additive is 5-25%; for example, it can be 5%, 6%, 7%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 24%, 25% and values ​​between any two of the values ​​listed above. Within this range, the stability and electrical properties of the material can be effectively improved, and the material can be ensured to have good film-forming properties.

[0091] In some specific embodiments, the additives include 3-hydroxymethylpyridine (boiling point 266°C, CAS: 100-55-0; structural formula as shown in formula (9)), 2-hydroxypyridine (boiling point 280-281°C, CAS: 142-08-5; structural formula as shown in formula (10)), 4-hydroxypyridine (boiling point 380.6°C; CAS: 626-64-2; structural formula as shown in formula (11)), 2-hydroxy-4-methylpyridine (boiling point 304.18°C; CAS: 13466-41-6; structural formula as shown in formula (12)), naphthylamine (boiling point 301°C; CAS: 134-32-7; structural formula as shown in formula (13)), 3-fluoroquinoline (CAS: 392-57-4, boiling point 238.4°C; structural formula as shown in formula (14)), and p-diiodobenzene (CAS: 624-38-4, boiling point 285°C; structural formula as shown in formula (15)).

[0092]

[0093] In some embodiments, each time X appears, it is independently selected from the halogen group or the hydroxyl group, and the halogen group is selected from -F; that is, X is selected from -F or -OH, FH...F and OH...O have a strong force, which helps to improve the stability of the material and improve the electrical properties. In other embodiments, when A includes a heteroaromatic ring, the substitution position of X is selected from the ortho or para position of the heteroatom in A. For example, when A is pyridine, X can replace the hydrogen in the para or ortho position to the ring N, which helps to enhance the induction effect. Specifically, the additive includes but is not limited to one or more of 2-hydroxypyridine, 4-hydroxypyridine, 2-hydroxy-4-methylpyridine, naphthylamine, and 3-fluoroquinoline.

[0094] In some embodiments, the hole functional material can be selected from organic materials commonly used in the art for preparing the hole transport layer 50 or the hole injection layer 60. When selected from organic materials used to prepare the hole transport layer 50, the hole functional material is defined as a hole transport material; when selected from organic materials used to prepare the hole injection layer 60, the hole functional material is defined as a hole injection material.

[0095] In a specific embodiment, the hole transport material is selected from poly [(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] (TFB), poly (4-butylphenyl-diphenylamine), poly (triarylamine) (PTAA), polypyrrole, poly [N,N'-bis (4-butylphenyl)-N,N'-bis (phenyl)-benzidine] (polyTPD), poly (p-) phenylene vinylene (PPV), poly [2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] At least one of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) (PVK) and its derivatives, polytrihexylthiophene (P3HT) and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives; in actual application, the composite material obtained by using the hole transport materials listed above can be used to prepare the hole transport layer 50 of the optoelectronic device 100.

[0096] In another embodiment, the hole injection material is selected from at least one of PEDOT, PEDOT:PSS, and copper cyanide. In practical applications, the composite material obtained by using the hole injection materials listed above can be used to prepare the hole injection layer 60 of the optoelectronic device 100.

[0097] The present application also proposes a method for preparing a composite material. The preparation method comprises the following steps:

[0098] S100, providing a hole functional material, an additive and a first solvent;

[0099] S200, mixing the hole functional material, the additive and the first solvent, and removing the first solvent to obtain a composite material;

[0100] The additive comprises a compound having a structure shown in formula (1), and in the composite material, the X group of the additive is connected to the hole functional material via a non-covalent bond;

[0101]

[0102] Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer;

[0103] X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group at each occurrence;

[0104] Each occurrence of Y is independently selected from a combination of one or more of C1-C6 alkyl, C1-C6 cycloalkyl and C1-C6 alkoxy.

[0105] In some embodiments, the first solvent includes one or more of C1-C5 alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene.

[0106] In addition, the present application also proposes a thin film, the material of which includes the composite material described above. The material of the thin film is composed of a hole functional material and an additive; accordingly, the preparation method of the thin film of this embodiment may include: mixing the hole functional material, the additive and a first solvent to obtain a mixed solution, depositing the mixed solution on a substrate and removing the first solvent to obtain a thin film. The method of removing the solvent may include but is not limited to heat treatment to evaporate the solvent, or vacuuming to evaporate the solvent, etc.

[0107] In the second aspect, the present application also proposes a photoelectric device 100, which includes but is not limited to a light emitting device, a photovoltaic cell and a photodetector. The photoelectric device 100 includes a first electrode, a functional layer and a second electrode. The first electrode is one of the cathode 40 and the anode 10, and the second electrode is the other of the cathode 40 and the anode 10. Figure 2The optoelectronic device 100 includes a first electrode, a hole functional layer and a second electrode, the hole functional layer includes one or two layers of a hole injection layer 60 and a hole transport layer 50, and the material of at least one layer of the hole functional layer includes the composite material as described above. One or two layers of the hole injection layer 60 and the hole transport layer 50 are prepared with a composite material, the composite material includes a hole functional material and an additive, and has high stability, thereby helping to improve the stability of the optoelectronic device 100 and extend its life. At the same time, the composite material has a better hole mobility, which helps to improve the carrier balance of the device, thereby improving the performance of the device.

[0108] It can be understood that when the hole transport layer 50 is prepared by a composite material, the hole functional material in the composite material is selected from poly [(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl) diphenylamine))], poly (4-butylphenyl-diphenylamine), poly (triarylamine), polypyrrole, poly [N,N'-bis (4-butylphenyl) -N,N'-bis (phenyl) - benzidine], poly (p-) phenylene vinylene, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene] At least one of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives; when the hole injection layer 60 is prepared using a composite material, the hole functional material in the composite material is selected from at least one of PEDOT and PEDOT:PSS.

[0109] In some embodiments, the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the hole transport layer 50 and the hole injection layer 60 are both prepared using a suitable composite material, that is, the material of the hole injection layer 60 and the material of the hole transport layer 50 are independently selected from the composite material, for example, the material of the hole transport layer 50 is poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] and a first additive; the material of the hole injection layer 60 is PEDOT:PSS and a second additive. It can be understood that the first additive and the second additive are both additives as described above, and are named only to distinguish each other, and the two may be the same or different.

[0110] In other embodiments, the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the material of the hole transport layer 50 is selected from the composite material, and the material of the hole injection layer 60 is selected from the conventional materials used to prepare the hole injection layer 60 in the art, for example, it can be selected from but not limited to at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, and copper phthalocyanine.

[0111] In some other embodiments, the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the material of the hole injection layer 60 is selected from the composite material, and the material of the hole transport layer 50 is selected from the conventional materials for preparing the hole transport layer 50 in the art, for example, it can be selected from but not limited to 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N, N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(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), poly(triarylamine), polypyrrole, poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine], poly(p-)phenylene vinylene, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, At least one of 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine, spiro NPB, doped graphene, undoped graphene, and C60.

[0112] In some embodiments, the anode 10 may be an anode 10 known in the art for use in a photoelectric device 100, for example, may be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of a metal and a metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is 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, the composite electrode of a metal and a metal oxide is selected from 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, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0113] In some embodiments, the cathode 40 can be a cathode 40 for the optoelectronic device 100 known in the art, for example, can be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is 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, the composite electrode of metal and metal oxide is selected from 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, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0114] See also Figure 3 In some embodiments, the optoelectronic device 100 further includes a light-emitting layer 20, and the light-emitting layer 20 is disposed between the first electrode and the hole functional layer. Specifically, the light-emitting layer 20 is located between the cathode 40 and the hole functional layer. The light-emitting layer 20 may be an organic light-emitting layer 20 or a quantum dot light-emitting layer 20. When the light-emitting layer 20 is an organic light-emitting layer 20, the optoelectronic device 100 may be an organic light-emitting device; when the light-emitting layer 20 is a quantum dot light-emitting layer 20, the optoelectronic device 100 may be a quantum dot light-emitting device.

[0115] The material of the organic light-emitting layer 20 is a material known in the art for the organic light-emitting layer 20 of the optoelectronic device 100, for example, it can be selected from but not limited to 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene 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 BN covalent bonds, hybrid localized charge transfer excited state materials, and exciplex luminescent materials. One or more.

[0116] The material of the quantum dot light-emitting layer 20 is a quantum dot material known in the art for the quantum dot light-emitting layer 20 of the optoelectronic device 100, for example, it can be selected from but not limited to at least one of a single structure quantum dot, a core-shell structure quantum dot and a perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO , HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgT e. At least one of HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group The compound is selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V group compound is selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlN P, 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 I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2.

[0117] As an example, the core-shell structured quantum dots may be selected from but not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS and InP / ZnSe / ZnS.

[0118] It should be noted that, for the material of the aforementioned single structure quantum dot, or the material of the core of the core-shell structure quantum dot, or the material of the shell of the core-shell structure quantum dot, the chemical formula provided only indicates the elemental composition, but does not indicate the content of each element. For example, CdZnSe only indicates that it is composed of three elements, Cd, Zn and Se. If the content of each element is indicated, it corresponds to Cd x Zn 1-x Se,0 <x<1。

[0119] The perovskite semiconductor material may be selected from but not limited to doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

[0120] In some embodiments, the photoelectric device 100 also includes an electronic functional layer, which is arranged between the first electrode and the hole functional layer. Specifically, the electronic functional layer is located between the hole functional layer and the cathode 40. When the photoelectric device 100 also includes a light-emitting layer 20, the electronic functional layer is located between the light-emitting layer 20 and the cathode 40.

[0121] The electronic functional layer includes one or two layers of the electron transport layer 30 and the electron injection layer, and when the electronic functional layer includes the electron transport layer 30 and the electron injection layer, the electron injection layer is located between the electron transport layer 30 and the cathode 40. The electronic functional layer can be prepared by using materials with electron transport properties known in the art for the optoelectronic device 100. For example, the material of the electron transport layer 30 includes but is not limited to at least one of metal oxides, doped metal oxides, II-VI semiconductor materials, III-V semiconductor materials and I-III-VI semiconductor materials, the metal oxide is selected from at least one of ZnO, BaO, TiO2, SnO2; the metal oxide in the doped metal oxide is selected from at least one of ZnO, TiO2, SnO2, the doping element is selected from at least one of Al, Mg, Li, In, Ga, the II-VI semiconductor material is selected from at least one of ZnS, ZnSe, CdS; the III-V semiconductor material is selected from at least one of InP and GaP; the I-III-VI semiconductor material is selected from at least one of CuInS and CuGaS. The material of the electron injection layer may be selected from but not limited to at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

[0122] It is understandable that the thickness of each layer in the optoelectronic device 100 is set as needed and is not limited here. In some embodiments, the thickness of the first electrode is 10 to 100 nm, the thickness of the hole injection layer 60 is 30 to 100 nm, the thickness of the hole transport layer 50 is 30 to 100 nm, the thickness of the light emitting layer 20 is 10 to 50 nm, the thickness of the electron transport layer 30 is 20 to 50 nm, and the thickness of the second electrode is 30 to 100 nm.

[0123] When there are multiple film layers between the anode 10 and the cathode 40, and the multiple film layers are selected from the light-emitting layer 20, the electron transport layer 30, the electron injection layer, the hole transport layer 50, and the hole injection layer 60, the film layer stacking order of the photoelectric device 100 is the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30, the electron injection layer and the cathode 40; it can be understood that the photoelectric device 100 can be an upright device or an inverted device. In some embodiments, the photoelectric device 100 is an upright device, and accordingly, the photoelectric device 100 includes an anode 10, a hole injection layer 60, a hole transport layer 50, a light-emitting layer 20, an electron transport layer 30, an electron injection layer and a cathode 40 stacked in sequence from bottom to top; in other embodiments, the photoelectric device 100 is an inverted device, and accordingly, the photoelectric device 100 includes a cathode 40, an electron injection layer, an electron transport layer 30, a light-emitting layer 20, a hole transport layer 50, a hole injection layer 60 and an anode 10 stacked in sequence from bottom to top.

[0124] It is understandable that the optoelectronic device 100 may also be provided with some functional layers conventionally used in optoelectronic devices 100 that help improve the performance of the optoelectronic device 100, such as an electron blocking layer, a hole blocking layer, an interface modification layer, etc.

[0125] It can be understood that the materials of each layer of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100 .

[0126] In a third aspect, the present application also proposes a method for preparing an optoelectronic device 100, see Figure 1 , the preparation method comprises the following steps:

[0127] S10, providing a first electrode;

[0128] S20, providing a composite material, and disposing the composite material on one side of the first electrode to form a hole functional layer; wherein the composite material includes the composite material described above.

[0129] S30, disposing a second electrode on a side of the hole functional layer away from the first electrode.

[0130] The first electrode is selected from one of the anode 10 and the cathode 40, and the second electrode is selected from the other of the two. In actual preparation, the types of the first electrode and the second electrode are adjusted according to the type of the device. For example, when preparing an upright device, the first electrode is the anode 10 and the second electrode is the cathode 40; conversely, when the device is an inverted device, the first electrode is the cathode 40 and the second electrode is the anode 10.

[0131] In some embodiments, the step of disposing the composite material on one side of the first electrode to form a hole functional layer includes:

[0132] providing a solvent, and dispersing the composite material in the solvent to obtain a composite material solution;

[0133] The composite material solution is arranged on one side of the first electrode to obtain a hole functional layer.

[0134] The solvent may be any common solvent capable of dissolving hole functional materials and additives, for example, one or more of alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene. The alcohol solvents include but are not limited to methanol, ethanol, isopropanol, n-butanol, pentanol, and the like.

[0135] In some embodiments, in the composite material solution, the concentration of the hole functional material is 2 to 15 mg / ml, for example, it can be 2 mg / ml, 3 mg / ml, 4 mg / ml, 5 mg / ml, 8 mg / ml, 10 mg / ml, 12 mg / ml, 15 mg / ml and values ​​between any two of the above values.

[0136] It can be understood that when there is only a hole functional layer between the anode 10 and the cathode 40, the hole functional layer can be directly arranged on the first electrode; when the device includes multiple film layers located between the anode 10 and the cathode 40, for example, it also includes an electronic functional layer, a light-emitting layer 20, etc., the film layers between the anode 10 and the cathode 40 can be prepared in sequence according to the film layer stacking order of the upright device. In this way, the hole functional layer can be arranged on the film layer that is located below it in the film layer sequence and in the previous film making process in the preparation process. For example, in an inverted device, the hole functional layer can be arranged on the light-emitting layer 20.

[0137] In the preparation method of the optoelectronic device, the preparation method of the anode 10, the light-emitting layer 20, the electron injection layer, the electron transport layer 30, the hole transport layer 50, the hole injection layer 60 and the cathode 40 can be achieved by conventional techniques in the art, such as chemical methods or physical methods. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, and coprecipitation. The physical method includes physical plating and solution method, among which the physical plating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, blade coating, printing, dip pulling, immersion, spraying, roll coating, casting, slit coating, and strip coating, etc.

[0138] In some embodiments, after the photoelectric device is prepared, the step of packaging the photoelectric device is further included. The packaging process can be performed by a common machine packaging or by manual packaging. Preferably, in the packaging process environment, the oxygen content and the water content are both less than 0.1 ppm to ensure the stability of the light emitting device 100.

[0139] In a fourth aspect, the present application further proposes a display device, which includes the optoelectronic device as described above, or includes an optoelectronic device manufactured using the manufacturing method as described above.

[0140] The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, among which smart wearable devices can be, for example, smart bracelets, smart watches, virtual reality (VR) helmets, etc.

[0141] The technical scheme and technical effects of the present application are described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of the present application and do not specifically limit the present application.

[0142] Material Example 1

[0143] The preparation method of the composite material is as follows:

[0144] (1) A hole functional material and an additive are mixed in a weight ratio of 90:10 to prepare a composite material, wherein the hole functional material is TFB and the additive is 2-hydroxypyridine.

[0145] (2) Add the above composite material into chlorobenzene and stir to mix well to obtain a composite material solution with a composite material concentration of 8 mg / ml for later use.

[0146] Material Example 2

[0147] This material embodiment is basically the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is 4-hydroxypyridine.

[0148] Material Example 3

[0149] This material embodiment is basically the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is 3-hydroxymethylpyridine.

[0150] Material Example 4

[0151] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is naphthylamine.

[0152] Material Example 5

[0153] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is p-diiodobenzene.

[0154] Material Example 6

[0155] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is 3-fluoroquinoline.

[0156] Material Example 7

[0157] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the additive is 1,4-diiodotetrafluorobenzene.

[0158] Material Example 8

[0159] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the weight ratio of the hole functional material to the additive is 95:5.

[0160] Material Example 9

[0161] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the weight ratio of the hole functional material to the additive is 75:25.

[0162] Material Example 10

[0163] This material embodiment is substantially the same as material embodiment 1, with the only difference being that in this material embodiment: the weight ratio of the hole functional material to the additive is 74:26.

[0164] Material Example 11

[0165] This material embodiment is basically the same as material embodiment 1, except that, in this material embodiment:

[0166] The hole functional material is PEDOT:PSS.

[0167] Material Comparative Example 1

[0168] This comparative example is TFB.

[0169] Material Comparative Example 2

[0170] This comparative example is PEDOT:PSS.

[0171] Film Example 1

[0172] The composite material solution prepared in Material Example 1 was taken and the solution was spin-coated on a glass substrate at a rotation speed of 3000 r / min for 30 seconds and annealed at 230° C. for 30 minutes to obtain a thin film with a thickness of 40 nm.

[0173] Film Examples 2 to 11

[0174] The scheme of film embodiment t is basically the same as film embodiment 1, with the only difference being that in film embodiment t, the composite material solution prepared in material embodiment 1 is replaced by the composite material solution prepared in material embodiment t, wherein t is 2 to 11.

[0175] Device Example 1

[0176] The preparation method of the QLED device is as follows:

[0177] (1) The patterned ITO glass substrate was placed in acetone, washing liquid, deionized water, and isopropanol for ultrasonic cleaning in order, and each ultrasonic cleaning time was 20 minutes. After cleaning, it was blown dry with a nitrogen gun. Then, the ITO glass substrate was placed in oxygen plasma for further cleaning for 10 minutes, and then the surface of the ITO glass substrate was treated with ultraviolet-ozone for 15 minutes to obtain an anode with an anode thickness of 10 nm.

[0178] (2) In air, a layer of PEDOT:PSS was spin-coated on the surface of the anode at a speed of 3000 r / min for 30 seconds, and then annealed at 200°C for 20 minutes to obtain a hole injection layer with a thickness of 80 nm. After annealing, the substrate was transferred to a glove box filled with nitrogen atmosphere.

[0179] (3) The composite material solution prepared in Example 1 was spin-coated on the surface of the hole injection layer at a speed of 3000 r / min for 30 s, and then annealed at 230° C. for 30 min to obtain a hole transport layer with a thickness of 40 nm.

[0180] (4) After the semi-finished product obtained in step (3) is cooled, 40 mg / ml of blue quantum dot material CdZnSe / ZnSe / Cd / Cd is spin-coated on the surface of the hole transport layer at a speed of 1500 r / min. 0.6 ZnS2, spin coating time 30s, then annealing treatment, annealing temperature is 100℃, annealing temperature is 5min, to obtain a light-emitting layer with a thickness of 25nm.

[0181] (5) A 40 mg / ml ZnO ethanol solution was spin coated on the surface of the light-emitting layer at a speed of 3000 r / min for 30 s, and then annealed at a temperature of 100° C. for 15 min to obtain an electron transport layer with a thickness of 30 nm.

[0182] (6) The semi-finished product obtained in step (5) is placed in a vacuum chamber, a layer of silver with a thickness of 100 nm is evaporated on the surface of the electron transport layer as a cathode, and encapsulated to obtain a QLED device.

[0183] Device Examples 2 to 10

[0184] The scheme of device embodiment m is basically the same as device embodiment 1, with the only difference being that in device embodiment m, in step (3), the material used to prepare the hole transport layer is changed to the composite material solution prepared in material embodiment m, wherein m is 2 to 10.

[0185] Device Example 11

[0186] The device embodiment scheme is basically the same as device embodiment 1, except that, in the device embodiment:

[0187] 1. In step (3), the material used to prepare the hole transport layer is changed to a chlorobenzene solution of TFB with a concentration of 8 mg / ml;

[0188] 2. In step (2), the material used to prepare the hole injection layer is changed to the composite material solution prepared in Material Example 9.

[0189] Device Example 12

[0190] The device embodiment scheme is basically the same as the device embodiment 1, except that, in the device embodiment, the hole transport layer and the hole injection layer are both made of composite materials:

[0191] In step (2), the material used to prepare the hole injection layer is changed to the composite material solution prepared in Material Example 9.

[0192] Device Comparison Examples 1 and 2

[0193] The device comparative example n is substantially the same as the device embodiment 1, except that in the device comparative example n:

[0194] In step (3), the material used to prepare the hole transport layer is changed to the solution prepared in material comparison example n, wherein n is 1 or 2.

[0195] Experimental Example 1

[0196] The film prepared in Film Example 1 was taken as the experimental group;

[0197] The solution of material comparison example 1 was taken and spin-coated on a glass substrate at a rotation speed of 3000 r / min for 30 seconds and annealed at 230° C. for 30 minutes to obtain a thin film with a thickness of 40 nm, which was used as a control group.

[0198] The films of the experimental group and the control group were observed using an atomic force microscope (AFM). Figure 4 and Figure 5 shown.

[0199] Figure 4 and Figure 5 The root mean square roughness Rq of the experimental group film is 0.64, and the Rq of the control group film is 1.10. Obviously, the film containing solid additives is more uniform, the surface roughness is smaller, and it has a better surface morphology, indicating that the addition of solid additives makes the arrangement of hole transport material molecules more regular, reduces irregular local excessive agglomeration, and thus significantly improves the film morphology.

[0200] Experimental Example 2

[0201] Hole transport performance test: Control QE PRO and Keithley 2400 through LabView to build a QLED efficiency test system. The system tests the current density-voltage curve of the single carrier transport thin film device (HOD / EOD). Compare the current density of the device under the working voltage (6V) and the working voltage in the steady state. The working voltage in the steady state refers to the working voltage of the device in the device balance stage when the device runs for more than 4 hours during the device life test. Among them:

[0202] The preparation method of the single hole device (HOD) is basically the same as the preparation method of its corresponding complete QLED device, the only difference is that the electron transport layer is subtracted.

[0203] In the above tests, the devices used are single-hole devices corresponding to the QLED devices in the above device embodiments 1 to 12 and device comparison examples 1-2.

[0204] Table 1:

[0205]

[0206] manual

[0207]

[0208] It can be seen from Table 1 that compared with device comparison example 1, the single hole devices of device embodiments 1 to 10 and 12 all have higher current density and lower operating voltage. At the same time, compared with device comparison example 2, device embodiments 11 and 12 all have higher current density and lower operating voltage, indicating that the use of composite materials doped with additives to prepare the hole functional layer is helpful to improve the hole mobility of the device and improve the carrier balance of the device, indicating that adding additives to the hole transport material is helpful to improve its hole mobility.

[0209] Experimental Example 3

[0210] The quantum dot light-emitting diodes of device examples 1-12 and device comparative examples 1-2 were subjected to performance tests, and the test results are shown in Table 2. The test method is as follows:

[0211] (1) The detection method of external quantum efficiency EQE is: the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons, the unit is %, which is an important parameter to measure the quality of electroluminescent devices and can be obtained by using EQE optical testing instruments. The specific calculation formula is as follows:

[0212]

[0213] Among them, ηe is the light output coupling efficiency, ηγ is the ratio of the number of recombined carriers to the number of injected carriers, x is the ratio of the number of excitons that generate photons to the total number of excitons, KR is the radiation process rate, and KNR is the non-radiative process rate.

[0214] Test conditions: carried out at room temperature, air humidity is 30-60%.

[0215] (2) The test method for life T95@1000nit is:

[0216] The time required for the device to reduce its brightness to a certain percentage of the maximum brightness when driven by a constant current or voltage. The time it takes for the brightness to drop to 95% of the maximum brightness is defined as T95, and this life is the measured life. In order to shorten the test cycle, the device life test is usually carried out at high brightness by accelerating device aging, and the life under high brightness is obtained by fitting the extended exponential decay brightness attenuation fitting formula. For example, the life under 1000nit is calculated as T95@1000nit. The specific calculation formula is as follows:

[0217]

[0218] Among them, T95 L For lifespan at low brightness, T95 H is the measured lifetime under high brightness, L H To accelerate the device to the highest brightness, L Lis 1000nit, A is the acceleration factor, and this experiment measured the lifespan of several groups of QLED devices at rated brightness and found that the A value was 1.7.

[0219] In the above tests, the devices used in the external quantum efficiency test and the device life test are the QLED devices with complete structures in the above embodiments and comparative examples.

[0220] Table 2:

[0221]

[0222]

[0223] From Table 2 we can see that:

[0224] Compared with device comparison example 1, device embodiments 1 to 10 and 12 all have higher EQE and T95@1000nit. At the same time, compared with device comparison example 2, device embodiments 11 and 12 all have higher EQE and T95@1000nit, indicating that the use of a composite material doped with additives to prepare a hole functional layer helps to improve the carrier balance of the device, thereby improving the luminescence efficiency and service life of the device.

[0225] The composite materials and preparation methods thereof, thin films, optoelectronic devices and preparation methods thereof, and display devices provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the methods and core ideas of the present application. At the same time, for technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A composite material, characterized in that: It includes a hole functional material and an additive, wherein the additive includes a compound having a structure shown in formula (1); Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer; X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group at each occurrence; Each occurrence of Y is independently selected from a combination of one or more of C1-C6 alkyl, C1-C6 cycloalkyl and C1-C6 alkoxy.

2. The composite material according to claim 1, characterized in that A includes one or more of an aromatic ring having 6 to 20 ring carbon atoms and a heteroaromatic ring having 6 to 20 ring atoms; and / or, m is 0 to 5; and / or, n is 1 to 6.

3. The composite material according to claim 2, characterized in that A is one or more selected from the group represented by any one of formulae (2) to (8): and / or, n is 1 or 2; and / or, m is 0 to 3; and / or, In the composite material, the mass percentage of the additive is 5 to 25%; and / or, The boiling point of the additive is greater than 230°C; and / or, The X group of the additive is connected to the hole functional material via a non-covalent bond.

4. The composite material according to claim 1, characterized in that The additive includes one or more compounds having a structure represented by any one of formulas (9) to (15).

5. The composite material according to any one of claims 1 to 4, characterized in that: X is independently selected from the halogen group or the hydroxyl group at each occurrence, and the halogen group is selected from -F; and / or, When A includes a heteroaromatic ring, the substitution position of X is selected from the ortho or para position of the heteroatom in A.

6. The composite material according to claim 5, characterized in that The additive includes one or more compounds having a structure represented by any one of formulae (10) to (14).

7. The composite material according to claim 1, characterized in that The hole functional material comprises a hole transport material or a hole injection material, wherein the hole transport material is selected from poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), poly(triarylamine), polypyrrole, poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine], poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1, At least one of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and derivatives thereof, poly(N-vinylcarbazole) and derivatives thereof, polytrihexylthiophene and derivatives thereof, polymethacrylate and derivatives thereof, poly(9,9-octylfluorene) and derivatives thereof, poly(spirofluorene) and derivatives thereof; the hole injection material is selected from at least one of PEDOT, PEDOT:PSS and phenolic copper cyanine.

8. A method for preparing a composite material, characterized in that: The following steps are involved: Providing a hole functional material, an additive and a first solvent; Mixing the hole functional material, the additive and the first solvent, and removing the first solvent to obtain a composite material; Wherein, the additive includes a compound having a structure shown in formula (1); Wherein, A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, m is an integer greater than or equal to 0, and n is a positive integer; X is independently selected from a combination of one or more of a halogen group, a hydroxyl group and an amino group at each occurrence; Each occurrence of Y is independently selected from a combination of one or more of C1-C6 alkyl, C1-C6 cycloalkyl and C1-C6 alkoxy.

9. The preparation method according to claim 8, characterized in that: In the composite material, the mass percentage of the additive is 5 to 25%; and / or, The first solvent includes one or more of C1-C5 alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene; and / or, The additive includes one or more compounds having a structure represented by any one of formulas (9) to (15).

10. A film, characterized in that: The material of the film includes the composite material according to any one of claims 1 to 7, or includes the composite material prepared by the preparation method according to claim 8 or 9.

11. A photoelectric device, characterized in that: It comprises a first electrode, a hole functional layer and a second electrode, wherein the hole functional layer comprises one or two layers of a hole injection layer and a hole transport layer, and the material of at least one layer of the hole functional layer comprises the composite material according to any one of claims 1 to 7, or the composite material obtained by the preparation method according to claim 8 or 9; or at least one layer of the hole functional layer comprises the thin film according to claim 10.

12. The optoelectronic device according to claim 11, characterized in that: When the hole functional material in the composite material is selected from at least one of PEDOT, PEDOT:PSS, and phenolic copper, the composite material is a first composite material; the hole functional material in the composite material is selected from poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), poly(triarylamine), polypyrrole, poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine], poly( When the composite material is at least one of (p-)phenylene vinylene, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and derivatives thereof, poly(N-vinylcarbazole) and derivatives thereof, polytrihexylthiophene and derivatives thereof, polymethacrylate and derivatives thereof, poly(9,9-octylfluorene) and derivatives thereof, and poly(spirofluorene) and derivatives thereof, the composite material is the second composite material; The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole injection layer is independently selected from the first composite material, and the material of the hole transport layer is independently selected from the second composite material; or The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole transport layer is selected from the second composite material, and the material of the hole injection layer is selected from at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, and copper phthalocyanine; or, The hole functional layer comprises the stacked hole injection layer and the hole transport layer, wherein the material of the hole injection layer is selected from the first composite material, and the material of the hole transport layer is selected from 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N '-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(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), poly(triarylamine), polypyrrole, poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine], poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4′-bis(p-carbazolyl) )-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) and its derivatives, polytrihexylthiophene and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine, spiro NPB, doped graphene, undoped graphene, and at least one of C60.

13. The optoelectronic device according to claim 11, characterized in that: The first electrode and the second electrode are each independently selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode; the material of the doped metal oxide particle electrode is 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; the composite electrode of metal and metal oxide is selected from 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; the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or, The photoelectric device further comprises a light-emitting layer, wherein the light-emitting layer is arranged between the first electrode and the hole functional layer, or between the second electrode and the hole functional layer, and the material of the light-emitting layer is selected from one or more of organic light-emitting materials and quantum dot light-emitting materials, and the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives , TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescent material, TTA material, thermally activated delayed material, polymer containing BN covalent bond, hybrid localized charge transfer excited state material, exciplex luminescent material or more; the quantum dot luminescent material is selected from at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials; the material of the single structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots are selected from II-VI group compounds, IV-VI group compounds, II At least one of a I-V group compound and a I-III-VI group compound; the II-VI group compound is selected from 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, CdZn At least one of SeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound is at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

14. A method for preparing a photoelectric device, characterized in that: The following steps are involved: providing a first electrode; Providing a composite material, and disposing the composite material on one side of the first electrode to form a hole functional layer; Disposing a second electrode on a side of the hole functional layer away from the first electrode; Wherein, the composite material includes the composite material according to any one of claims 1 to 7, or the composite material prepared by the preparation method according to claim 8 or 9.

15. The preparation method according to claim 14, characterized in that: The step of disposing the composite material on one side of the first electrode to form a hole functional layer comprises: providing a second solvent, dispersing the composite material in the second solvent to obtain a composite material solution; Disposing the composite material solution on one side of the first electrode to obtain a hole functional layer; Wherein, the second solvent includes one or more of C1-C5 alcohol solvents, chloroform, chlorobenzene, and dichlorobenzene.

16. The preparation method according to claim 15, characterized in that: In the composite material solution, the concentration of the hole functional material is 2-15 mg / ml.

17. A display device, characterized in that: The photoelectric device comprises the photoelectric device according to any one of claims 11 to 13, or the photoelectric device prepared by the preparation method according to any one of claims 14 to 16.

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