Composite material, thin film, preparation method of thin film and photoelectric device

Abstract

The invention discloses a composite material, a thin film, a preparation method of the thin film and a photoelectric device, the composite material comprises a first metal oxide material and an organic phosphonic acid compound, the organic phosphonic acid compound is bonded with the first metal oxide material, the structural general formula of the organic phosphonic acid compound is # imgabs0 #, R1 and R2 are not selected from hydroxyl groups at the same time, and R2 is selected from hydroxyl groups at the same time. And at least one of R1 and R2 comprises a halogen group, so that the hydrophobicity of the first metal oxide material is effectively improved.

Description

Technical Field

[0001] The present application relates to the field of optoelectronic technologies, and particularly relates to a composite material, a thin film, a method for preparing the thin film, and an optoelectronic device. Background Art

[0002] Metal oxides refer to compounds formed by the combination of metal elements and oxygen elements. Metal oxides are widely used in technical fields such as light-emitting devices, photovoltaic cells, supercapacitors, and photodetectors due to their good electrical conductivity. Metal oxides can be used as carrier functional materials or electrode materials.

[0003] In some application scenarios, it is required that metal oxides have hydrophobicity. Therefore, how to improve the hydrophobic performance of metal oxides is the technical problem to be solved by the present application. Summary of the Invention

[0004] Based on this, the present application provides a composite material, a thin film, a method for preparing the thin film, and an optoelectronic device.

[0005] The technical solution of the present application is as follows:

[0006] In a first aspect, the present application provides a composite material, which includes a first metal oxide material and an organic phosphonic acid compound. The organic phosphonic acid compound is bonded to the first metal oxide material, and the organic phosphonic acid compound has a structure represented by the following general formula (I):

[0007]

[0008] In the general formula (I), R1 and R2 are each independently selected from a hydroxyl group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon oxy group, an unsubstituted or at least one first group-substituted C3-C30 aliphatic cycloalkyl group, an unsubstituted or at least one first group-substituted aliphatic heterocyclic hydrocarbon group having 3-30 ring atoms, an unsubstituted or at least one first group-substituted aryl group having 6-30 ring atoms, an unsubstituted or at least one first group-substituted aryloxy group having 6-30 ring atoms, an unsubstituted or at least one first group-substituted heteroaryl group having 5-30 ring atoms, or an unsubstituted or at least one first group-substituted heteroaryloxy group having 5-30 ring atoms, or a combination of these groups; the heteroatoms in the aliphatic heterocyclic hydrocarbon group, the heteroaryl group or the heteroaryloxy group are selected from one or more of N, S, O, P, and Si, and the number of the heteroatoms is selected from 1-20; each occurrence of the first group is independently selected from deuterium, -X, an amino group, a hydroxyl group, a carboxyl group, a nitro group, a sulfonic acid group, an aldehyde group, a mercapto group, a cyano group or a phosphonic acid group, and X is selected from a halogen atom;

[0009] R1 and R2 are not simultaneously selected from hydroxyl groups, and at least one of R1 and R2 includes -X.

[0010] In a second aspect, the present application provides a thin film, and the material of the thin film includes the composite material as described in the first aspect.

[0011] In a third aspect, the present application provides a method for preparing a thin film, including the following steps:

[0012] Providing a cured film layer including the first metal oxide material and a solution including the organic phosphonic acid compound; and

[0013] Placing the cured film layer in the solution so that the organic phosphonic acid compound reacts with the first metal oxide material to undergo a bonding reaction to obtain the thin film.

[0014] In a fourth aspect, the present application provides an optoelectronic device, and the optoelectronic device includes the thin film as described in the second aspect, or the thin film prepared by the method for preparing a thin film as described in the third aspect.

[0015] The present application provides a composite material, a thin film, a method for preparing a thin film, and an optoelectronic device, having the following technical effects:

[0016] In the composite material, the first metal oxide material is modified with an organic phosphonic acid compound, and the organic phosphonic acid compound includes a halogen group, so that the organic phosphonic acid compound easily reacts with oxygen atoms on the surface of the first metal oxide material and is anchored on the surface of the first metal oxide material, effectively improving the hydrophobicity of the first metal oxide material. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The following, in conjunction with the drawings, through a detailed description of the specific embodiments of the present application, will make the technical solutions and other beneficial effects of the present application obvious.

[0018] Figure 1 It is a schematic diagram of the bonding reaction between the first metal oxide material and the organic phosphonic acid compound in the embodiment of the present application.

[0019] Figure 2 It is a schematic diagram of the structure of a thin film provided by the embodiment of the present application.

[0020] Figure 3 It is a schematic flow diagram of a method for preparing a thin film provided by the embodiment of the present application.

[0021] Figure 4 It is a schematic diagram of the structure of an optoelectronic device provided by the embodiment of the present application.

[0022] Figure 5Schematic diagram of a optoelectronic device provided for Comparative Example 2 of the device in this application.

[0023] The reference numerals are as follows:

[0024] 10: Optoelectronic device, 100: Thin film, 101: Anode, 102: Cathode, 103: Functional layer, 1001: First film layer, 1002: Second film layer, 1031: Light-emitting layer, 1032: Hole functional layer, 1033: Electron functional layer, 10011: First surface, 10321: Hole injection layer, 10322: Hole transport layer.

[0025] 1031: Electron functional layer, 1032: Auxiliary layer, 1033: Light-emitting layer, 1034: Hole functional layer, 10341: Hole injection layer, 10342: Hole transport layer. Detailed implementation manners

[0026] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application.

[0027] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred methods and materials described herein are only for illustrative purposes and do not limit the content of the present application.

[0028] It should be noted that the description order of the following embodiments does not limit the preferred order of the embodiments. The various embodiments of the present application can exist in a range form; it should be understood that the description in a range form is only for convenience and brevity and should not be construed as a rigid limitation on the scope of the present invention; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that the range description 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., and single numbers within the counted range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0029] In the description of the present application, the term "including" means "including but not limited to".

[0030] The term "at least one" means one or more, "multiple" and "plural" means two or more. The term "at least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b or c" or "at least one of a, b and c" can be expressed as: a, b, c, ab (i.e. a and b), ac, bc or abc, where a, b and c can be single or plural, respectively.

[0031] The selection scope of the term "and / or" includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, and the said any and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. For example, "A and / or B" includes three parallel solutions of A, B and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four items of A, B, C, and D (that is, the technical solution connected by "logical and").

[0032] In the present application, “layer A is formed on one side of layer B”, “layer A is formed on the side of layer B away from layer C” or similar descriptions can be expressed as layer A is directly formed on one side of layer B or on the side of layer B away from layer C, that is, layer A is in direct contact with layer B, or as layer A is indirectly formed on one side of layer B or on the side of layer B away from layer C, that is, other spacing structure layers can be formed between layer A and layer B. Similarly, “layer A is arranged on one side of layer B”, “layer A is arranged on the side of layer B away from layer C” can be expressed as layer A is in direct contact with layer B, or as other spacing structure layers are arranged between layer A and layer B; “layer A is arranged between layer B and layer C” can be expressed as layer A is in direct contact with layer B and layer A is in direct contact with layer C, or layer A is in direct contact with layer B and one or more spacing structure layers are arranged between layer A and layer C, or one or more spacing structure layers are arranged between layer A and layer B and one or more spacing structure layers are arranged between layer A and layer C, or one or more spacing structure layers are arranged between layer A and layer B and layer A is in direct contact with layer C.

[0033] The term "particle size" refers to the diameter of a nanoparticle.

[0034] The term "chain hydrocarbon group" refers to an aliphatic straight chain hydrocarbon group or an aliphatic branched chain hydrocarbon group, and the "C1-C30 chain hydrocarbon group" may be, for example, a straight chain alkyl group having 1 to 30 carbon atoms, a straight chain alkenyl group having 2 to 30 carbon atoms, a straight chain alkynyl group having 2 to 30 carbon atoms, a branched chain alkyl group having 3 to 30 carbon atoms, a branched chain alkenyl group having 4 to 30 carbon atoms, or a branched chain alkynyl group having 4 to 30 carbon atoms. The number of carbon atoms in the chain hydrocarbon group may be, for example, 1 to 3, 1 to 5, 1 to 8, 1 to 10, 1 to 20, 2 to 5, 2 to 10, 3 to 6, 3 to 10, 4 to 8, or 4 to 10, exemplified by 1, 2, 5, 8, 10, 20, 30, or a value between any two of the foregoing values.

[0035] The term "alkoxy" refers to a group of the general formula *-O-alkoxy, where * represents the attachment site and O represents an oxygen atom.

[0036] The term "aliphatic cycloalkyl" refers to a cyclic hydrocarbon group belonging to the aliphatic group. The number of carbon atoms in the "C3-C30 aliphatic cycloalkyl" can be, for example, 3 to 5, 3 to 8, 3 to 10, 3 to 14, 3 to 20, or 5 to 10, exemplified by 3, 5, 6, 8, 10, 14, 20, 24, 28, 30, or a value between any two of the foregoing values. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or adamantyl.

[0037] The term "aliphatic heterocyclic hydrocarbon group" means that at least one carbon atom in the aliphatic cyclic hydrocarbon group is replaced by a heteroatom, the heteroatom is selected from one or more of N, S, O, P and Si, and the number of heteroatoms is selected from 1 to 20. The number of ring atoms in the "aliphatic heterocyclic hydrocarbon group having 3 to 30 ring atoms" can be, for example, 3 to 5, 3 to 8, 3 to 10, 3 to 14, 3 to 20, or 5 to 10, exemplified by 3, 5, 6, 8, 10, 14, 20, 24, 28, 30, or a value between any two of the foregoing values.

[0038] The term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which may be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For a polycyclic ring, at least one is an aromatic ring system. "Aryl having 6 to 30 ring atoms" may be an aromatic group having 6 to 20 ring atoms, an aromatic group having 6 to 18 ring atoms, an aromatic group having 6 to 16 ring atoms, an aromatic group having 6 to 14 ring atoms, or an aromatic group having 6 to 10 ring atoms. The number of ring atoms may be, for example, 6, 10, 12, 14, 16, 18, 20, 24, 26, 28, 30 or a value between any two of the foregoing values. Suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthylene, fluorenyl, perylene, acenaphthene and derivatives thereof. It is understandable that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g. <10% non-H atoms, such as C, N or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aromatic groups.

[0039] The term "aryloxy" refers to a group of the general formula *-O-aryl.

[0040] The term "heteroaryl" means that at least one carbon atom is replaced by a heteroatom based on an aryl group, the heteroatom is selected from one or more of N, S, O, P and Si, and the number of heteroatoms is selected from 1 to 20. "Heteroaryl having 5 to 30 ring atoms" may be a heteroaryl having 5 to 20 ring atoms, a heteroaryl having 5 to 18 ring atoms, a heteroaryl having 5 to 16 ring atoms, a heteroaryl having 5 to 14 ring atoms, a heteroaryl having 5 to 12 ring atoms, or a heteroaryl having 5 to 10 ring atoms, and the number of ring atoms may be, for example, 5, 10, 12, 14, 18, 20, 24, 26, 28, 30 or a value between any two of the foregoing values. Suitable examples include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primidyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, or carbazolyl.

[0041] The term "heteroaryloxy" refers to a group of the general formula *-O-heteroaryl.

[0042] The term "amino" refers to a group of the general formula -NR'R", wherein R' and R" are independently selected from, but not limited to, a hydrogen atom, a deuterium atom, a cyano group, an isocyano group, a nitro group, a halogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aliphatic cycloalkyl group having 3 to 10 ring atoms, an aliphatic heterocycloalkyl group having 3 to 10 ring atoms, an aromatic group having 6 to 14 ring atoms, and a heteroaryl group having 5 to 14 ring atoms.

[0043] The term "phosphonic acid group" refers to a group having the structural formula The group.

[0044] The embodiment of the present application provides a composite material, which includes a first metal oxide material and an organic phosphonic acid compound, wherein the organic phosphonic acid compound is bonded to the first metal oxide material, and the organic phosphonic acid compound has a structure shown in the following general formula (I):

[0045]

[0046] In the general formula (I), R1 and R2 are independently selected from hydroxyl, unsubstituted or substituted by at least one first group C1-C30 chain hydrocarbon group, unsubstituted or substituted by at least one first group C1-C30 chain hydrocarbonoxy group, unsubstituted or substituted by at least one first group C3-C30 aliphatic cycloalkyl group, unsubstituted or substituted by at least one first group aliphatic heterocycloalkyl group with 3-30 ring atoms, unsubstituted or substituted by at least one first group aryl group with 6-30 ring atoms, unsubstituted or substituted by at least one first group aryl group with 6-30 ring atoms ~30 aryloxy groups, unsubstituted or substituted by at least one first group with 5 to 30 ring atoms, or unsubstituted or substituted by at least one first group with 5 to 30 heteroaryloxy groups, or a combination of these groups; the heteroatoms in the aliphatic heterocyclic hydrocarbon group, the heteroaryl group or the heteroaryloxy group are selected from one or more of N, S, O, P and Si, and the number of heteroatoms is selected from 1 to 20; each occurrence of the first group is independently selected from deuterium, -X, amino, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano or phosphonic acid, and X is selected from halogen atoms.

[0047] In the composite material of the embodiment of the present application, an organic phosphonic acid compound is used to modify the first metal oxide material, and the organic phosphonic acid compound includes a halogen group, so that the organic phosphonic acid compound can easily react with oxygen atoms on the surface of the first metal oxide material and anchor to the surface of the first metal oxide material, thereby effectively improving the hydrophobicity of the first metal oxide material.

[0048] In order to improve the hydrophobicity and work function of the first metal oxide material, in some embodiments of the present application, R1 and R2 are independently selected from hydroxyl, C1-C20 chain hydrocarbon group substituted by at least one first group, C1-C20 chain hydrocarbonoxy group substituted by at least one first group, aryl group with 6-14 ring atoms substituted by at least one first group, aryloxy group with 6-14 ring atoms substituted by at least one first group, heteroaryl group with 5-14 ring atoms substituted by at least one first group, or heteroaryloxy group with 5-14 ring atoms substituted by at least one first group, or a combination of these groups; each time the first group appears, it is independently selected from -X, hydroxyl or phosphonic acid group, and X is selected from F, Cl, Br or I.

[0049] In order to further improve the hydrophobicity and work function of the first metal oxide material, in some embodiments of the present application, one of R1 and R2 is selected from hydroxyl, and the other is selected from C1-C20 chain hydrocarbon group substituted by at least one fluorine group, C1-C20 chain hydrocarbonoxy group substituted by at least one fluorine group, aryl group with 6-14 ring atoms substituted by at least one fluorine group, aryloxy group with 6-14 ring atoms substituted by at least one fluorine group, heteroaryl group with 5-14 ring atoms substituted by at least one fluorine group, or heteroaryloxy group with 5-14 ring atoms substituted by at least one fluorine group, or a combination of these groups. As an example, one of R1 and R2 is selected from a hydroxyl group, and the other is selected from an aromatic group having 6 to 14 ring atoms (such as a phenyl group or a naphthyl group) substituted by at least one fluorine group. Based on the strong electron-pulling effect of the fluorine group, the electron cloud in the organic phosphonic acid compound molecule can be shifted toward the aromatic group where the aromatic group is located, thereby reducing the constraint on the hydrogen atoms in the hydroxyl group, thereby enhancing the acidity of the organic phosphonic acid compound, and then it is easier to react with the oxygen atoms on the surface of the first metal oxide material and anchor to the surface of the first metal oxide material, thereby increasing the content of the organic phosphonic acid compound on the surface of the first metal oxide material.

[0050] In some embodiments of the present application, the organic phosphonic acid compound is selected from one or more of 2,3,4,5,6-pentafluorobenzylphosphonic acid (CAS No. 137174-84-6), 3,4,5-trifluorobenzyl phosphoric acid (CAS No. 1160299-58-0), (4-trifluoromethyl-phenyl)-phosphoric acid (CAS No. 1869-27-8), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicofluorododecyl phosphoric acid (CAS No. 252237-39-1) and (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid (CAS No. 80220-63-9).

[0051] In some embodiments of the present application, the composite material consists of a first metal oxide material and an organic phosphonic acid compound.

[0052] In some embodiments of the present application, the organic phosphonic acid compound is bonded to the surface of the first metal oxide material, for example, the first metal oxide material and the organic phosphonic acid compound are bonded via *-O-#, wherein * represents a site connected to a phosphorus atom and / or a carbon atom in the organic phosphonic acid compound, and # represents a site connected to a metal atom in the first metal oxide. It is understood that the organic phosphonic acid compound can react with the hydroxyl group on the surface of the first metal oxide material, and can react with the bridging oxygen bond on the surface of the first metal oxide material, and the general formula of the bridging oxygen bond is M1-O-M2, and M1 and M2 are independently a metal atom in the first metal oxide material, so that the organic phosphonic acid compound is bonded to the surface of the first metal oxide material via *-O-#.

[0053] In some embodiments of the present application, the first metal oxide material includes one or more doped first metal oxides, and the doped first metal oxides include but are not limited to nanoparticles, nanosheets, nanoneedles or nanorods. The doping element of the doped first metal oxide is selected from one or more of In, F, Sb, Al, Ga and Mg, and the molar amount of the doping element accounts for no more than 50% of the total molar amount of the doped first metal oxide; the main material of the doped first metal oxide is selected from tin oxide, zinc oxide or magnesium oxide. The first metal oxide material is selected from one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO) and magnesium-doped zinc oxide (MZO).

[0054] Taking ITO as the first metal oxide material, the selection range of R is the same as that of R1 (R2), and the bonding reaction between the first metal oxide material and the organic phosphonic acid compound is as follows: Figure 1 shown.

[0055] In order to further improve the conductivity of the composite material, in some embodiments of the present application, the mass ratio of the organic phosphonic acid compound to the first metal oxide material in the composite material is 1:(1000-1500), for example, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400, 1:1500 or a value between any two of the foregoing values.

[0056] An embodiment of the present application further provides a film, the material of which includes any one of the composite materials described above, and the film has good electrical conductivity and hydrophobicity.

[0057] In some embodiments of the present application, Figure 2 As shown, the film 100 includes a first film layer 1001 and a second film layer 1002, the first film layer 1001 includes a first surface 10011, and the second film layer 1002 at least covers the first surface 10011 to improve the surface flatness of the first surface 10011. The material of the first film layer 1001 is a first metal oxide material, and the material of the second film layer 1002 is an organic phosphonic acid compound.

[0058] In some embodiments of the present application, the average thickness of the first film layer 1001 is 10nm to 100nm, for example, it can be 10nm, 30nm, 50nm, 70nm, 100nm or a value between any two of the aforementioned values; and / or, the average thickness of the second film layer 1002 is 1nm to 10nm, for example, it can be 1nm, 3nm, 5nm, 7nm, 10nm or a value between any two of the aforementioned values.

[0059] The present application also provides a method for preparing a thin film, which can be used to prepare any of the above-mentioned thin films, such as Figure 3 As shown, the following steps are included:

[0060] S1, providing a cured film layer including a first metal oxide material and a solution including an organic phosphonic acid compound;

[0061] S2. Contacting the surface of the cured film layer with the solution obtained in step S1, so that the organic phosphonic acid compound and the first metal oxide material undergo a bonding reaction to obtain a thin film.

[0062] In step S1, the preparation method of the solidified film layer including the first metal oxide material includes but is not limited to chemical method and / or physical method. Among them, the chemical method includes but is not limited to one or more of chemical vapor deposition, continuous ion layer adsorption and reaction method, anodization method, electrolytic deposition method and coprecipitation method. The physical method includes but is not limited to physical plating method and solution method. The physical plating method includes but is not limited to one or more of thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion plating method, physical vapor deposition method, atomic layer deposition method and pulsed laser deposition method. The solution method includes but is not limited to spin coating, printing method, inkjet printing method, scraping method, printing method, dip pulling method, immersion method, spraying method, roll coating method, casting method, slit coating method and strip coating method. When the solidified film layer including the first metal oxide material is prepared by the solution method, a drying process can be added, and the drying process includes but is not limited to one or more of heat treatment and vacuum drying process.

[0063] The solvent of the solution including the organic phosphonic acid compound is a first solvent, and the first solvent includes but is not limited to one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds, amide compounds and sulfone compounds. Wherein, the alkane includes but is not limited to one or more of nonane, decane, dodecane, terpene, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane and cyclopentane, and / or the aromatic hydrocarbon includes but is not limited to one or more of diethylbenzene, trimethylbenzene, propylbenzene, isopropylbenzene, p-toluene isopropylbenzene, butylbenzene and 1-methylnaphthalene or indene, and / or the halogenated hydrocarbon includes but is not limited to one or more of dichloromethane, chloroform and carbon tetrachloride, and / or the alcohol compound includes but is not limited to one or more of methanol, ethanol, propanol, butanol, ethylene glycol and glycerol, and / or the ether compound includes but is not limited to one or more of ethylene glycol monomethyl ether, ethyl ether and propylene oxide, and / or the furan compound includes but is not limited to one or more of tetrahydrofuran and 2-methylfuran, and / or the pyridine compound includes but is not limited to pyridine, and / or the amide compound includes but is not limited to N,N-dimethylformamide, and / or the sulfone compound includes but is not limited to dimethyl sulfoxide.

[0064] In step S1, the method of contacting the surface of the cured film layer with the solution prepared in step S1 includes but is not limited to immersing the cured film layer in the solution or coating the solution on the surface of the cured film layer.

[0065] In order to further improve the conductivity and hydrophobicity of the film, in some embodiments of the present application, the thickness of the cured film layer is 10nm to 100nm; and / or, in the solution comprising the organic phosphonic acid compound, the concentration of the organic phosphonic acid compound is 0.01mmol / L to 10mmol / L, for example, 0.01mmol / L, 0.05mmol / L, 0.1mmol / L, 0.5mmol / L, 1mmol / L, 5mmol / L, 10mmol / L or a value between any two of the foregoing values; and / or, the bonding reaction in step S2 is carried out at a temperature of 50°C to 80°C, for example, 50°C, 60°C, 70°C, 80°C or a value between any two of the foregoing values, so as to promote the aggregation of the organic phosphonic acid compound on the surface of the first metal oxide material and improve the reaction efficiency; and / or, the time for which the cured film layer in step S2 is placed in the solution is 1h to 6h, for example, 1h, 3h, 6h or a value between any two of the foregoing values. It should be noted that the cured film layer can also be placed in a solution and left to stand at room temperature for bonding reaction, and then the cured film layer can be taken out and heated in air environment, but the process is more complicated, time-consuming and the performance of the film is not as good as the above method.

[0066] In order to further improve the conductivity of the film, in some embodiments of the present application, after the step of placing the cured film layer in the solution obtained in step S1 and before the step of obtaining the film, the film preparation method further includes the step of: using a second solvent to wash and remove the organic phosphonic acid compounds that have not undergone a bonding reaction, and then drying. Wherein, the second solvent includes, for example, one or more of water, C1-C10 aliphatic hydrocarbon compounds and C1-C10 aliphatic alcohol compounds, optionally, C1-C10 aliphatic hydrocarbon compounds are selected from one or more of propane, butane, pentane, hexane, heptane and octane, and / or C1-C10 aliphatic alcohol compounds are selected from one or more of ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol, and the second solvent is exemplified as a mixture of ethanol and water; the drying treatment is, for example, selected from one or more of heat treatment and vacuum drying treatment, and the temperature of the heat treatment is exemplified as 40°C to 200°C.

[0067] The present application also provides an optoelectronic device, which includes any of the above-mentioned thin films or a thin film prepared by any of the above-mentioned thin film preparation methods. The optoelectronic device includes but is not limited to a light-emitting device, a solar cell or a photodetector.

[0068] Specifically, Figure 4 As shown, the optoelectronic device 10 includes a bottom electrode 101, a top electrode 102 and a functional layer 103, wherein the functional layer 103 is disposed between the bottom electrode 101 and the top electrode 102. At least one of the bottom electrode 101 and the top electrode 102 includes a thin film as described in any one of the above texts, or a thin film prepared by any one of the thin film preparation methods described in the above texts, which can improve the surface hydrophobicity of the bottom electrode 101 and / or the top electrode 102, optimize the interface between the bottom electrode 101 and the functional layer 103 and / or the interface between the top electrode 102 and the functional layer 103, effectively improve the problem of film corrosion, and improve the device life and performance stability of the optoelectronic device 10.

[0069] In some embodiments of the present application, one of the bottom electrode 101 and the top electrode 102 is an anode, and the other is a cathode; the anode includes a thin film as described in any one of the foregoing, or a thin film obtained by any one of the thin film preparation methods described in the foregoing, so as to improve the work function of the anode and enhance the hydrophobicity of the anode surface; and / or, the material of the cathode is selected from one or more of a metal, a carbon material and a second metal oxide, the metal is selected from one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni and Mg, the carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber, and the second metal oxide 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, aluminum-doped magnesium oxide, SnO2, ZnO and In2O3.

[0070] In some embodiments of the present application, when the anode includes a first film layer 1001 and a second film layer 1002, the first surface 10011 is a side of the first film layer 1001 close to the functional layer 103, and the second film layer 1002 at least covers the first surface 10011 to optimize the interface between the anode and the functional layer 103, which is beneficial to further improve the photoelectric performance and device life of the photoelectric device 10.

[0071] In some embodiments of the present application, the bottom electrode 101 or the top electrode 102 may also be a composite electrode, the composite electrode having a structure similar to a "sandwich", the materials of the upper layer and the bottom layer are respectively doped or undoped second metal oxides, the material of the middle layer is a metal, for example, it may be 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 TiO2 / Al / TiO2, and the thickness of the middle layer does not exceed 35nm. The thickness of the bottom electrode 101 may be, for example, 20nm to 100nm, and the thickness of the top electrode 102 may be, for example, 20nm to 100nm.

[0072] In some embodiments of the present application, the optoelectronic device 10 is a light emitting device. Figure 4The functional layer 103 includes a light-emitting layer 1031, and the material of the light-emitting layer 1031 includes one or more of organic light-emitting materials and light-emitting quantum dots, wherein the organic light-emitting material includes but is 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, exciplex light-emitting materials, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives. One or more.

[0073] The luminescent quantum dots include, but are not limited to, one or more of red quantum dots, green quantum dots, and blue quantum dots, and the luminescent 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, and the shell layer of the core-shell structure quantum dots is one or more. The average particle size of the luminescent quantum dots can be, for example, 5nm to 20nm, exemplified by 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 15nm, 20nm, or a value between any two of the foregoing values.

[0074] For single-component quantum dots and core-shell structured quantum dots, the material of the single-component quantum dots, the material of the core of the core-shell structured quantum dots, or the material of the shell of the core-shell structured quantum dots includes but is not limited to at least one of II-VI group compounds, III-V group compounds, IV-VI group compounds, or I-III-VI group compounds. Among them, the II-VI group compounds include but are not limited to one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe. The III-VI compounds include, but are not limited to, one or more of In2S3, In2Se3, InGaS3, and InGaSe3. The III-V compounds include, but are not limited to, 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 IV-VI group compounds include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe. The I-III-VI group compounds include, but are not limited to, one or more of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2 and CuInGaS2.

[0075] For inorganic perovskite quantum dots, the general structural formula of inorganic perovskite quantum dots is AMX3, where A is Cs + , M is a divalent metal cation, including but not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - Br - or I - .

[0076] For organic perovskite quantum dots, the general structural formula of organic perovskite quantum dots is CMX3, wherein C is a carboxamidine group, and M is a divalent metal cation, and M includes but is not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - Br - or I - .

[0077] For organic-inorganic hybrid perovskite quantum dots, the general structural formula of organic-inorganic hybrid perovskite quantum dots is BMX3, wherein B is selected from organic amine cations, and the organic amine cations include but are not limited to CH3(CH2) n-2 NH 3+ (n≥2) or NH3(CH2) n NH3 2+ (n≥2), M is a divalent metal cation, including but not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - Br - or I - .

[0078] When the material of the light-emitting layer 1031 includes quantum dots, in order to improve the solution processing performance of the quantum dots and further improve the luminous efficiency of the optoelectronic device 10, in some embodiments of the present application, the surface of the quantum dots is also connected with a ligand. The ligand can be a common ligand in the art, including but not limited to C1~C 30 Fatty carboxylic acid ligands, C6~C 30 Aromatic carboxylic acid ligands, C1~C 30 Aliphatic thiol ligands, C6~C 30 Thiol aromatic ligands, C1~C 30 Fatty amine ligands, C6~C 30 Aromatic amine ligands, C1~C 30 Aliphatic phosphine ligands, C6~C 30 Aromatic phosphine ligands and C6~C 30 One or more of aromatic phosphate ligands and halogen ligands.

[0079] Among them, C1~C 30 The fatty carboxylic acid ligands include, but are not limited to, one or more of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, lignoceric acid, hexacosanoic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, erucic acid and docosahexaenoic acid; C6-C 30 The aromatic carboxylic acid ligands include, but are not limited to, one or more of benzoic acid, bibenzoic acid, and 1-naphthoic acid. 30 The fatty thiol ligands include, but are not limited to, one or more of hexyl mercaptan, octyl mercaptan, nonyl mercaptan, decanyl mercaptan, undecanyl mercaptan, dodecanyl mercaptan, hexadecanyl mercaptan and octadecanyl mercaptan, C6-C 30 The thiol aromatic ligands include, but are not limited to, one or more of benzenethiol, triphenylmethylthiol, and p-terphenyl-4,4"-dithiol. 30 The fatty amine ligands include, but are not limited to, one or more of hexylamine, octylamine, dioctylamine, trioctylamine, nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine and oleylamine, C6-C 30 The aromatic amine ligands include, but are not limited to, one or more of aniline, indenepropylamine, 4-octylaniline and benzidine. 30The aliphatic phosphine ligands include, but are not limited to, one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide and tridecylphosphine oxide, C6-C 30 The aromatic phosphine ligands include, but are not limited to, one or more of bis(2-diphenylphosphinoethyl)phenylphosphine and triphenylphosphine oxide, C6~C 30 The aromatic phosphate ligands include, but are not limited to, one or more of tetraethyl p-xylene diphosphate and diphenyl ethyl phosphate. The halogen ligands include, but are not limited to, -Cl, -F, -I or -Br.

[0080] In some embodiments of the present application, the functional layer 103 further includes a hole functional layer 1032. When the optoelectronic device 10 includes a light-emitting layer 1031, the hole functional layer 1032 is disposed between the anode and the light-emitting layer 1031. Taking the optoelectronic device 10 as an upright structure as an example, continue to refer to Figure 4 The hole function layer 1032 is disposed between the bottom electrode 101 and the light emitting layer 1031. The thickness of the hole function layer 1032 is, for example, 10 nm to 100 nm. The material of the hole function layer 1032 includes, for example, one or more of an organic compound, a first inorganic compound material, and a second inorganic compound material.

[0081] The organic compounds include, but are not limited to, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (abbreviated as PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (CAS No. 105598-27-4), polyaniline (CAS No. 25233-30-1), polypyrrole (CAS No. 30604-33-1), and poly(ethylenedioxythiophene):poly(styrene sulfonic acid) (CAS No. 155090-83-8). -81-0), 3-hexyl substituted polythiophene (CAS No. 104934-50-1), poly (9-vinyl carbazole) (abbreviated as PVK, CAS No. 25067-59-8), 4,4'-bis (9-carbazole) biphenyl (abbreviated as CBP, CAS No. 58328-31-7), poly [bis (4-phenyl) (4-butylphenyl) amine], 4,4'-cyclohexyl bis [N,N-bis (4-methylphenyl) aniline] (abbreviated as TAPC, CAS No. 58473-78-2), poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4'- (N- (4-sec-butylphenyl) diphenylamine)] (abbreviated as TFB, CAS No. 220797-16-0), Poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-dioctylfluorenyl-2,7-diyl)](CAS No. 223569-31-1), 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine(CAS No. 124729-98-2), 4,4',4"-tri(carbazol-9-yl)triphenylamine(abbreviated as TCTA, CAS No. 139092-78-7), 4,4',4'-tri(2-naphthylphenylamino)triphenylamine(CAS No. 185690-41-9), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'- diamine (abbreviated as NPB, CAS No. 123847-85-8), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as TPD, CAS No. 65181-78-4), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine (CAS No. 209980-53-0), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirobifluorene-2,7-diamine (abbreviated as Spiro-TPD, CAS No. 1033035-83-4), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine (CAS No. 932739-76-9), poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTTA, CAS No. 1333317-99-9) and 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-omeTAD, CAS No. 207739-72-8) one or more; and / or, the first inorganic compound material includes but is not limited to one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide; and / or, the second inorganic compound material includes but is not limited to one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide; The compound material includes one or more doped second inorganic compounds, the main material of the doped second inorganic compound is selected from graphene, C60, nickel oxide (such as NiO), molybdenum oxide (such as MoO3), tungsten oxide (such as WO3), vanadium oxide (such as V2O5), P-type gallium nitride, chromium oxide (such as Cr2O3), copper oxide (such as CuO or Cu2O), copper sulfide (such as CuS), molybdenum sulfide (such as MoS2) or tungsten sulfide (such as WS2), the doping element of the doped second inorganic compound is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper and platinum group metal elements, and the molar amount of the doping element accounts for no more than 50% of the total molar amount of the doped second inorganic compound. ,

[0082] It should be noted that there is a large hole injection barrier between the anode and the light-emitting layer of some light-emitting devices, especially quantum dot light-emitting diodes, which leads to an imbalance in electron-hole transmission and has an adverse effect on the optoelectronic performance and device life of the light-emitting device. In order to improve the hole injection level of the light-emitting device, a hole functional layer is usually set between the anode and the light-emitting layer. The hole functional layer of the quantum dot light-emitting diode generally includes a stacked hole injection layer and a hole transport layer. The hole injection layer is closer to the anode than the hole transport layer. PEDOT:PSS is often used as a material for the hole injection layer, which can effectively reduce the injection barrier between the anode and the hole transport layer to increase hole injection and improve the smoothness of the anode surface. However, PEDOT:PSS has strong acidity and hygroscopicity, which will cause "corrosion" of the anode and the adjacent functional layer, seriously reducing the device life of the optoelectronic device.

[0083] In some embodiments of the present application, the bottom electrode 101 is an anode, and the anode includes a thin film as described in any one of the above, or a thin film prepared by any one of the above thin film preparation methods, which can improve the work function of the anode and increase the hydrophobicity of the anode surface, thereby reducing the injection barrier between the anode and the light-emitting layer 1031 (hole transport layer), and can improve the adhesion of the light-emitting layer 1031 (hole transport layer) on the anode surface to improve the hole injection ability, and can ensure that the optoelectronic device 10 has good optoelectronic performance and device life under the premise of omitting the hole injection layer, that is: continue to refer to Figure 2 and Figure 4 The hole functional layer 1032 is a single-layer structure, the hole functional layer 1032 is a hole transport layer, the anode includes a first film layer 1001 and a second film layer 1002, the first film layer 1001 includes a first surface 10011, the second film layer 1002 at least covers the first surface 10011, the first surface 10011 is a side of the first film layer 1001 close to the hole functional layer 1032, that is, the second film layer 1002 is located between the first film layer 1001 and the functional layer, wherein the material of the first film layer 1001 is a first metal oxide material, and the material of the second film layer 1002 is an organic phosphonic acid compound.

[0084] In some embodiments of the present application, the functional layer 103 further includes an electronic functional layer 1033. When the optoelectronic device 10 includes a light-emitting layer 1031, the electronic functional layer 1033 is disposed between the cathode and the light-emitting layer 1031. Taking the optoelectronic device 10 as an upright structure as an example, continue to refer to Figure 4 , the electronic functional layer 1033 is disposed between the top electrode 102 and the light-emitting layer 1031 .

[0085] The electronic functional layer 1033 may be a single-layer structure or a multi-layer structure, and the thickness of the electronic functional layer 1033 is, for example, 10 nm to 100 nm. When the electronic functional layer 1033 is a multi-layer structure, the electronic functional layer 1033 includes, for example, one or more of an electron injection layer, an electron transport layer, and a hole blocking layer. For the electronic functional layer 1033 including the electron injection layer, the electron transport layer, and the hole blocking layer, the electron transport layer is located between the electron injection layer and the hole blocking layer, and the electron injection layer is closer to the top electrode 102 than the hole blocking layer; for the electronic functional layer 1033 including the electron transport layer and the hole blocking layer, the electron transport layer is closer to the top electrode 102 than the hole blocking layer; for the electronic functional layer 1033 including the electron injection layer and the electron transport layer, the electron injection layer is closer to the top electrode 102 than the electron transport layer.

[0086] In some embodiments of the present application, the material of the electronic functional layer 1033 includes one or more of a second metal oxide material, a third metal oxide material, a IIB-VIA group semiconductor material, a IIIA-VA group semiconductor material, and a IB-IIIA-VIA group semiconductor material. Among them, the second metal oxide material includes, but is not limited to, one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, and ZrO2, and / or the IIB-VIA group semiconductor material includes, but is not limited to, one or more of ZnS, ZnSe, and CdS, and / or the IIIA-VA group semiconductor material includes, but is not limited to, one or more of InP and GaP, and / or the IB-IIIA-VIA group semiconductor material includes, but is not limited to, one or more of CuInS and CuGaS; and / or, the third metal oxide material includes one or more doped third metal oxides, and the doping elements of the doped third metal oxides are selected from one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In, and Sn, and the main material of the doped third metal oxides is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, or ZrO2. The doped third metal oxides are, for example, selected from one or more of magnesium zinc oxide, calcium zinc oxide, zirconium zinc oxide, gallium zinc oxide, aluminum zinc oxide, lithium zinc oxide, titanium zinc oxide, yttrium zinc oxide, indium tin oxide, and lithium titanium oxide, and are exemplified by ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O, In (1-x) Sn x O and Ti (1-x) Li x One or more of O, where 0 < x ≤ 0.5. It can be understood that when the electronic functional layer 1033 includes multiple materials and the electronic functional layer 1033 is a multi-layer structure, the multiple materials can all be in the same layer, or in different layers respectively, or part of them in the same layer.

[0087] It should be noted that the preparation methods of the respective film layers in the optoelectronic device include, but are not limited to, chemical methods and / or physical methods. Among them, the chemical methods include, but are not limited to, one or more of chemical vapor deposition, sequential ionic layer adsorption and reaction, anodic oxidation, electrolytic deposition, and coprecipitation. The physical methods include, but are not limited to, physical coating methods and solution methods. The physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. The solution methods include, but are not limited to, one or more of spin coating, printing, inkjet printing, blade coating, printing, dip coating, immersion, spraying, roll coating, casting, slot die coating, and bar coating. After the respective film layers of the optoelectronic device are prepared, a packaging treatment process is also required. The packaging treatment can be carried out by using common machine packaging or manual packaging. In the environment of the packaging treatment, the oxygen content and the water content are both lower than 0.1 ppm to ensure the stability of the optoelectronic device.

[0088] The embodiment of the present application also provides an electronic device, which includes any one of the optoelectronic devices described above, or an optoelectronic device prepared by the preparation method of any one of the optoelectronic devices described above. The electronic device can be, for example, any electronic product with a display function, including, but not limited to, a smartphone, a tablet personal computer, a mobile phone, a videophone, an e-book reader, a laptop PC, a netbook computer, a workstation, a server, a personal digital assistant, a portable multimedia player, an MP3 player, a mobile medical device, a camera, a game console, a digital camera, a car navigator, an electronic billboard, an automated teller machine, a smart bracelet, a smart watch, a Virtual Reality (VR) device, or a wearable device.

[0089] The technical solutions and technical effects of the present application will be described in detail below through specific examples, comparative examples, and experimental examples. The following examples are only partial examples of the present application and do not specifically limit the present application.

[0090] Material Example 1

[0091] This embodiment provides a thin film and a preparation method thereof. The material of the thin film includes ITO and 2,3,4,5,6-pentafluorobenzylphosphonic acid, and 2,3,4,5,6-pentafluorobenzylphosphonic acid is bonded to the metal atoms (In atoms and / or Sn atoms) in ITO.

[0092] The preparation method of the thin film includes the following steps:

[0093] S1.1. Provide a glass substrate (with an average thickness of 2 mm), sputter ITO on one side of the glass substrate to obtain an ITO layer (with an average thickness of 80 nm). The side of the ITO layer away from the glass substrate is the first surface, and the surface area of the first surface is 0.04 cm 2 , ultrasonically clean the glass substrate including the ITO layer for 15 min successively with an aqueous surfactant solution (composed of 15% by volume of nonylphenol polyoxyethylene ether and 85% by volume of deionized water), ultrasonically clean with deionized water for 15 min, ultrasonically clean with toluene for 15 min, ultrasonically clean with acetone for 15 min, and ultrasonically clean with ethanol for 15 min, then place it in ethanol and heat it to slightly boiling, and then dry it with an argon gas flow, and then perform oxygen plasma cleaning treatment for 10 min (oxygen plasma cleaner, power is 80 W) to obtain a cured film layer including ITO;

[0094] S1.2. Immerse the glass substrate including the cured film layer in a 2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (the solvent is toluene), then heat it to 50 °C and keep it at 50 °C unchanged, let it stand for 6 h, then take out the glass substrate including the cured film layer, and then rinse it 3 - 5 times with an aqueous ethanol solution (the volume percentage of ethanol is 99.5%), and then dry it with an argon gas flow to obtain the thin film.

[0095] Material Example 2

[0096] This embodiment provides a thin film and a preparation method thereof. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that: in step S1.2, "let it stand for 6 h" is replaced by "let it stand for 1 h".

[0097] Material Example 3

[0098] This embodiment provides a thin film and a preparation method thereof. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that: in step S1.2, "a 2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (the solvent is toluene)" is replaced by "a 2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 0.01 mmol / L (the solvent is toluene)".

[0099] Material Example 4

[0100] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "3,4,5-trifluorobenzylphosphoric acid".

[0101] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (toluene as the solvent)" in step S1.2 is replaced by "3,4,5-trifluorobenzylphosphoric acid solution with a concentration of 2 mmol / L (toluene as the solvent)".

[0102] Material Example 5

[0103] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "(4-trifluoromethyl-phenyl)-phosphoric acid".

[0104] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (toluene as the solvent)" in step S1.2 is replaced by "(4-trifluoromethyl-phenyl)-phosphoric acid solution with a concentration of 2 mmol / L (toluene as the solvent)".

[0105] Material Example 6

[0106] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecylphosphoric acid".

[0107] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (toluene as the solvent)" in step S1.2 is replaced by "3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecylphosphoric acid solution with a concentration of 2 mmol / L (toluene as the solvent)".

[0108] Material Example 7

[0109] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "(1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid".

[0110] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: in step S1.2, "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (the solvent is toluene)" is replaced by "(1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid solution with a concentration of 2 mmol / L (the solvent is toluene)".

[0111] Material Example 8

[0112] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "ITO" in the thin film is replaced by "antimony-doped tin oxide (CAS No. 128221-48-7)".

[0113] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: in step S1.1, all "ITO" is replaced by "antimony-doped tin oxide (CAS No. 128221-48-7)".

[0114] Material Example 9

[0115] This embodiment provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this embodiment is that: "ITO" in the thin film is replaced by "aluminum-doped zinc oxide (model: HN-J50L)".

[0116] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: in step S1.1, all "ITO" is replaced by "aluminum-doped zinc oxide (model: HN-J50L)".

[0117] Material Example 10

[0118] This embodiment provides a thin film and a preparation method thereof. Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this embodiment is that: in step S1.2, "heating to 50 °C and maintaining at 50 °C unchanged, standing for 6 h" is replaced by "standing for 6 h at room temperature (25 °C)".

[0119] Material Comparative Example 1

[0120] This comparative example provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this comparative example lies in that the material of the thin film is ITO.

[0121] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this comparative example lies in that step S1.2 is omitted, and the cured film layer including ITO obtained in step S1.1 is the thin film.

[0122] Material Comparative Example 2

[0123] This comparative example provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this comparative example lies in that "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "n-dodecylphosphoric acid".

[0124] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this example lies in that "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (solvent: toluene)" in step S1.2 is replaced by "n-dodecylphosphoric acid solution with a concentration of 2 mmol / L (solvent: toluene)".

[0125] Material Comparative Example 3

[0126] This comparative example provides a thin film and a preparation method thereof. Compared with the thin film in Material Example 1, the difference of the thin film in this comparative example lies in that "2,3,4,5,6-pentafluorobenzylphosphonic acid" in the thin film is replaced by "didodecylphosphinic acid (CAS No.: 6196-71-0)".

[0127] Compared with the preparation method of the thin film in Material Example 1, the difference of the preparation method of the thin film in this example lies in that "2,3,4,5,6-pentafluorobenzylphosphonic acid solution with a concentration of 2 mmol / L (solvent: toluene)" in step S1.2 is replaced by "didodecylphosphinic acid solution with a concentration of 2 mmol / L (solvent: toluene)".

[0128] Device Example 1

[0129] This example provides an optoelectronic device and a preparation method thereof. The optoelectronic device is a quantum dot light-emitting diode with a normal structure, and the light-emitting mode is bottom emission type, as Figure 1As shown, in the direction from bottom to top, the optoelectronic device 10 includes a bottom electrode 101, a functional layer 103, and a top electrode 102 that are sequentially stacked. The bottom electrode 101 is an anode and the top electrode 102 is a cathode. The functional layer 103 includes a hole functional layer 1032, a light-emitting layer 1031, and an electron functional layer 1033 that are sequentially stacked. Among them, the hole functional layer 1032 is a single-layer structure, and the hole functional layer 1032 is a hole transport layer; the electron functional layer 1033 is a single-layer structure, and the electron functional layer 1033 is an electron transport layer. The light-emitting area of the optoelectronic device 10 is 0.04 cm 2 .

[0130] The structural compositions of the respective layers in the optoelectronic device 10 are as follows:

[0131] The bottom electrode 101 is a thin film prepared according to Material Example 1;

[0132] The material of the top electrode 102 is Ag, and the average thickness of the top electrode 102 is 100 nm;

[0133] The material of the light-emitting layer 1031 is a light-emitting quantum dot having a core-shell structure. The material of the core of the light-emitting quantum dot is CdSe, the material of the shell of the light-emitting quantum dot is ZnS, the average particle size of the light-emitting quantum dot is 6 nm, the emission color of the light-emitting quantum dot is red, and the average thickness of the light-emitting layer 1031 is 30 nm;

[0134] The material of the hole functional layer 1032 is TFB, and the average thickness of the hole functional layer 1032 is 30 nm;

[0135] The material of the electron functional layer 1033 is nano-ZnO (average particle size: 5 nm), and the average thickness of the electron functional layer 1033 is 35 nm.

[0136] The preparation method of the optoelectronic device in this embodiment includes the following steps:

[0137] S10.1. Prepare a glass substrate including a bottom electrode with reference to the thin film preparation method in Material Example 1;

[0138] S10.2. Under a nitrogen environment at normal temperature and pressure, spin-coat a TFB-chlorobenzene solution with a concentration of 8 mg / mL on the side of the bottom electrode away from the substrate, and then place it in a constant-temperature heat treatment at 150 °C under a nitrogen atmosphere to cure into a film to obtain a hole functional layer;

[0139] S10.3. Under a nitrogen environment at normal temperature and pressure, spin-coat a light-emitting quantum dot-n-hexane solution with a concentration of 25 mg / mL on the side of the hole functional layer away from the bottom electrode, and then place it in a constant-temperature heat treatment at 100 °C under a nitrogen atmosphere to cure into a film to obtain a light-emitting layer;

[0140] S10.4. Under the nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO-ethanol solution with a concentration of 30 mg / mL on the side of the light-emitting layer away from the hole functional layer, and then place it in a constant-temperature heat treatment at 100 °C under a nitrogen atmosphere to cure into a film, obtaining an electron functional layer;

[0141] S10.5. Place the stacked structure completed in step S10.4 in a vacuum coating machine, evacuate to 4×10 -6 mbar, evaporate Ag on the side of the electron functional layer away from the light-emitting layer through a mask plate to obtain a cathode, and finally encapsulate it with an ultraviolet curable adhesive to obtain an optoelectronic device.

[0142] Device Example 2

[0143] This example provides an optoelectronic device and its preparation method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this example is that the bottom electrode is replaced with the thin film prepared in Material Example 2.

[0144] Compared with the preparation method of the optoelectronic device in Device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Example 2".

[0145] Device Example 3

[0146] This example provides an optoelectronic device and its preparation method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this example is that the bottom electrode is replaced with the thin film prepared in Material Example 3.

[0147] Compared with the preparation method of the optoelectronic device in Device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Example 3".

[0148] Device Example 4

[0149] This example provides an optoelectronic device and its preparation method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this example is that the bottom electrode is replaced with the thin film prepared in Material Example 4.

[0150] Compared with the preparation method of the optoelectronic device in Device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Example 4".

[0151] Device Example 5

[0152] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 5.

[0153] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 5".

[0154] Device Embodiment 6

[0155] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 6.

[0156] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 6".

[0157] Device Embodiment 7

[0158] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 7.

[0159] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 7".

[0160] Device Embodiment 8

[0161] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 8.

[0162] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 8".

[0163] Device Embodiment 9

[0164] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 9.

[0165] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 9".

[0166] Device Embodiment 10

[0167] This embodiment provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the bottom electrode is replaced with the thin film prepared in Material Embodiment 10.

[0168] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this embodiment is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Embodiment 10".

[0169] Device Comparative Example 1

[0170] This comparative example provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this comparative example is that the bottom electrode is replaced with the thin film prepared in Material Comparative Example 1.

[0171] Compared with the method for manufacturing the optoelectronic device in Device Embodiment 1, the difference of the method for manufacturing the optoelectronic device in this comparative example is that step S10.1 is replaced with "preparing a glass substrate including a bottom electrode with reference to the method for manufacturing the thin film in Material Comparative Example 1".

[0172] Device Comparative Example 2

[0173] This comparative example provides an optoelectronic device and a method for manufacturing the same. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this comparative example is that the bottom electrode is replaced with the thin film prepared in Material Comparative Example 1, and as Figure 4 shown, the hole functional layer 1032 is composed of a hole injection layer 10321 and a hole transport layer 10322 which are stacked; wherein, the material of the hole injection layer 10321 is PEDOT:PSS, and the average thickness of the hole injection layer 10321 is 40 nm; the material of the hole transport layer 10322 is TFB, and the average thickness of the hole transport layer 10322 is 30 nm.

[0174] Compared with the preparation method of the optoelectronic device in Device Example 1, the differences in the preparation method of the optoelectronic device in this comparative example are as follows: Step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Comparative Example 1", and a step "spin-coating a PEDOT:PSS aqueous solution on the side of the bottom electrode away from the substrate under an air environment at normal temperature and pressure, and then placing it in a constant temperature heat treatment at 150°C under a nitrogen atmosphere to form a solid film to obtain a hole injection layer" is added between Step S10.1 and Step S10.2, and "spin-coating a TFB-chlorobenzene solution with a concentration of 8 mg / mL on the side of the bottom electrode away from the substrate" in Step S10.2 is replaced with "spin-coating a TFB-chlorobenzene solution with a concentration of 8 mg / mL on the side of the hole injection layer away from the anode".

[0175] Device Comparative Example 3

[0176] This comparative example provides an optoelectronic device and its preparation method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the bottom electrode is replaced with the thin film prepared in Material Comparative Example 2.

[0177] Compared with the preparation method of the optoelectronic device in Device Example 1, the differences in the preparation method of the optoelectronic device in this comparative example are as follows: Step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Comparative Example 2".

[0178] Device Comparative Example 4

[0179] This comparative example provides an optoelectronic device and its preparation method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the bottom electrode is replaced with the thin film prepared in Material Comparative Example 3.

[0180] Compared with the preparation method of the optoelectronic device in Device Example 1, the differences in the preparation method of the optoelectronic device in this comparative example are as follows: Step S10.1 is replaced with "preparing a glass substrate including a bottom electrode by referring to the preparation method of the thin film in Material Comparative Example 3".

[0181] Experimental Example 1

[0182] The work functions of the thin films in Material Examples 1 to 10 and Material Comparative Examples 1 to 3 were detected respectively. The work functions of each thin film were detected using a photoelectron spectrometer, and the detection results are shown in Table 1 below:

[0183] Table 1

[0184]

[0185] As can be seen from Table 1, compared with the thin films in Material Comparative Examples 1 to 3, the thin films in Material Examples 1 to 7 and Material Example 10 have a higher work function, indicating that modifying ITO with an organophosphonic acid compound and the organophosphonic acid compound including a halogen group can increase the work function of the thin film. Among them, the reason for the lower work function of the thin films in Material Examples 8 and 9 is that the first metal oxide material of the thin film in Material Example 8 is antimony-doped tin oxide, and the first metal oxide material of the thin film in Material Example 9 is aluminum-doped zinc oxide, and the work functions of both are lower than that of ITO.

[0186] Experimental Example 2

[0187] The performances of the optoelectronic devices in the state of being encapsulated for 1 h in Device Examples 1 to 10 and Device Comparative Examples 1 to 4 were respectively detected. The performance test was carried out in an environment with a temperature of 25 °C and a relative humidity of 40%.

[0188] The detection of the optoelectronic performance was carried out using a FushiDa FPD optical property measurement device (an efficiency test system built with components such as Ocean Optics USB2000, LabView-controlled QE-PRO spectrometer, Keithley 2400, high-precision digital source meter Keithley 6485, optical fiber with an inner diameter of 50 μm, device test probe and fixture, various relevant connecting wires and data cards, efficiency test dark box and data acquisition system, etc.) to obtain parameters such as the turn-on voltage, current, brightness, and emission spectrum of each optoelectronic device, and then calculate key parameters such as the external quantum efficiency and power efficiency.

[0189] Among them, the detection method of the current efficiency includes the steps of: intermittently collecting the brightness values of the light-emitting device within the range of a driving voltage from 0 V to 8 V, and the collected light-emitting area is 0.04 cm 2 , the voltage value of the initially collected brightness is 3 V, and it is collected every 0.2 V. The brightness value collected each time is divided by the corresponding current density to obtain the current efficiency of the light-emitting device under the collection conditions of this time, obtain the current efficiency (C.E1, cd / A) at a brightness of 1000 nit, and obtain the maximum brightness (L max , cd / m 2 ) during the current efficiency test.

[0190] The test method for device lifetime includes the steps of: under the drive of a constant current (2 mA), using a 128-channel QLED lifetime test system to perform electroluminescence lifetime analysis on each light-emitting device, recording the time (T95,h) required for each light-emitting device to decay from the maximum brightness to 95%, and calculating the time (T95@1000nit,h) required for the brightness of each light-emitting device to decay from 100% to 95% at a brightness of 1000 nit through the decay fitting formula.

[0191] The detection method for device efficiency stability includes the steps of: after placing the packaged optoelectronic device in an environment with a temperature of 35 °C and a relative humidity of 70% for 30 days, intermittently collecting the brightness values of the optoelectronic device in the voltage range of 0 V to 8 V, collecting once every 0.2 V, and dividing the brightness value collected each time by the corresponding current density to obtain the current efficiency of the optoelectronic device under the collection conditions of that time, obtaining the current efficiency (C.E2, cd / A) at a brightness of 1000 nit, and calculating A(%) according to the following formula:

[0192] A(%) = |1 - C.E2 / C.E1| × 100%;

[0193] Among them, the larger A% is, the higher the stability of the device efficiency of the optoelectronic device is; on the contrary, the smaller A% is, the lower the stability of the device efficiency of the optoelectronic device is.

[0194] The performance detection data of each optoelectronic device are shown in Table 2 below:

[0195] Table 2

[0196]

[0197] As can be seen from Table 2, compared with the comprehensive performance of the optoelectronic devices in Device Comparative Example 1, Device Comparative Example 3, and Device Comparative Example 4, the comprehensive performance of the optoelectronic devices in Device Examples 1 to 10 is more advantageous, specifically manifested as: the maximum brightness and device efficiency of the optoelectronic devices in Device Examples 1 to 10 are higher, the device lifetime of the optoelectronic devices in Device Examples 1 to 10 is longer, and the performance stability of the optoelectronic devices in Device Examples 1 to 10 is better.

[0198] Taking the optoelectronic devices in Device Example 1 and Device Comparative Example 1 as an example, the L of the optoelectronic device in Example 1 max is the L of the optoelectronic device in Comparative Example 1 max1.6 times that of Comparative Example 1, and C.E1 of the optoelectronic device in Example 1 is 1.4 times that of the optoelectronic device in Comparative Example 1, and T95@1000nit of the optoelectronic device in Example 1 is 1.67 times that of the optoelectronic device in Comparative Example 1, and A of the optoelectronic device in Example 1 is 11% higher than that of the optoelectronic device in Comparative Example 2. It can be seen that the material of the anode is the first metal oxide material modified by an organic phosphonic acid compound, and at least one of R1 and R2 of the organic phosphonic acid compound includes a halogen group, which can improve the work function and surface hydrophobicity of the anode, thereby optimizing the interface between the anode and the hole functional layer, reducing the injection barrier between the anode and the hole functional layer, and further improving the hole injection ability of the optoelectronic device, and enhancing the optoelectronic performance and device life of the optoelectronic device.

[0199] In addition, the comprehensive performance of the optoelectronic devices in Device Examples 1 to 10 has a small difference from the comprehensive performance of the optoelectronic devices in Device Comparative Example 2. It can be seen that the material of the anode is the first metal oxide material modified by an organic phosphonic acid compound, and at least one of R1 and R2 of the organic phosphonic acid compound includes a halogen group, which can ensure that the optoelectronic device has good optoelectronic performance and device life on the premise of omitting the hole injection layer.

[0200] The above has introduced in detail a composite material, a thin film, a preparation method of the thin film, and an optoelectronic device provided by the embodiments of the present application. Specific examples are used herein to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the technical solution and its core idea of the present application; those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A composite material, characterized in that, The composite material includes a first metal oxide material and an organic phosphonic acid compound. The organic phosphonic acid compound is bonded to the first metal oxide material, and the organic phosphonic acid compound has a structure represented by the following general formula (I): In general formula (I), R1 and R2 are each independently selected from a hydroxyl group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon oxy group, an unsubstituted or at least one first group-substituted C3-C30 aliphatic cycloalkyl group, an unsubstituted or at least one first group-substituted aliphatic heterocyclic hydrocarbon group having 3 to 30 ring atoms, an unsubstituted or at least one first group-substituted aryl group having 6 to 30 ring atoms, an unsubstituted or at least one first group-substituted aryloxy group having 6 to 30 ring atoms, an unsubstituted or at least one first group-substituted heteroaryl group having 5 to 30 ring atoms, or an unsubstituted or at least one first group-substituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups; the heteroatoms in the aliphatic heterocyclic hydrocarbon group, the heteroaryl group or the heteroaryloxy group are selected from one or more of N, S, O, P and Si, and the number of the heteroatoms is selected from 1 to 20; Each occurrence of the first group is independently selected from deuterium, -X, an amino group, a hydroxyl group, a carboxyl group, a nitro group, a sulfonic acid group, an aldehyde group, a mercapto group, a cyano group or a phosphonic acid group, and X is selected from a halogen atom; R1 and R2 are not simultaneously selected from a hydroxyl group, and at least one of R1 and R2 includes -X.

2. The composite material according to claim 1, wherein R1 and R2 are each independently selected from a hydroxyl group, a C1-C20 hydrocarbon group substituted by at least one first group, a C1-C20 hydrocarbon oxy group substituted by at least one first group, an aryl group having 6 to 14 ring atoms substituted by at least one first group, an aryloxy group having 6 to 14 ring atoms substituted by at least one first group, a heteroaryl group having 5 to 14 ring atoms substituted by at least one first group, or a heteroaryloxy group having 5 to 14 ring atoms substituted by at least one first group, or a combination of these groups; each occurrence of the first group is independently selected from -X, a hydroxyl group or a phosphonic acid group, and X is selected from F, Cl, Br or I; and / or The composite material is composed of the first metal oxide material and the organic phosphonic acid compound; and / or The first metal oxide material includes one or more doped first metal oxides, the doping elements of the doped first metal oxides are selected from one or more of In, F, Sb, Al, Ga and Mg, and the doped first metal oxides are selected from tin oxide, zinc oxide or magnesium oxide; and / or In the composite material, the mass ratio of the organic phosphonic acid compound to the first metal oxide material is 1:(1000-1500); and / or The first metal oxide material and the organic phosphonic acid compound are bonded through *-O-#, where * represents a site connected to a phosphorus atom and / or a carbon atom in the organic phosphonic acid compound, and # represents a site connected to a metal atom in the first metal oxide.

3. The composite material according to claim 2, wherein, The first metal oxide material 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; and / or One of R1 and R2 is selected from a hydroxyl group, and the other is selected from a C1-C20 hydrocarbon group substituted with at least one fluorine group, a C1-C20 hydrocarbon oxy group substituted with at least one fluorine group, an aryl group having 6-14 ring atoms substituted with at least one fluorine group, an aryloxy group having 6-14 ring atoms substituted with at least one fluorine group, a heteroaryl group having 5-14 ring atoms substituted with at least one fluorine group, or a heteroaryloxy group having 5-14 ring atoms substituted with at least one fluorine group, or a combination of these groups; and / or The organic phosphonic acid compound is selected from one or more of 2,3,4,5,6-pentafluorobenzylphosphonic acid, 3,4,5-trifluorobenzylphosphoric acid, (4-trifluoromethyl-phenyl)-phosphoric acid, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecylphosphoric acid, and (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid.

4. A film, characterized in that, The material of the thin film includes the composite material described in any one of claims 1 to 3.

5. The thin film according to claim 4, characterized in that, The thin film includes a first film layer and a second film layer. The first film layer includes a first surface, and the second film layer covers at least the first surface; the material of the first film layer is the first metal oxide material, and the material of the second film layer is the organic phosphonic acid compound.

6. The thin film according to claim 5, characterized in that, The average thickness of the first film layer is 10 nm to 100 nm; and / or The average thickness of the second film layer is 1 nm to 10 nm.

7. A method for preparing a thin film, characterized in that, Comprising the following steps: Providing a cured film layer including the first metal oxide material and a solution including the organic phosphonic acid compound; and Bringing the surface of the cured film layer into contact with the solution so that the organic phosphonic acid compound reacts with the first metal oxide material to obtain the thin film.

8. The method for preparing the thin film according to claim 7, wherein, The thickness of the cured film layer is 10 nm to 100 nm; and / or The solvent of the solution is a first solvent, and the first solvent is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds, amide compounds, and sulfone compounds; the alkanes are selected from one or more of nonane, decane, dodecane, terpane, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane, and cyclopentane, and / or the aromatic hydrocarbons are selected from one or more of diethylbenzene, mesitylene, propylbenzene, isopropylbenzene, p-cumene, butylbenzene, and 1-methylnaphthalene or indene, and / or the halogenated hydrocarbons are selected from one or more of dichloromethane, chloroform, and carbon tetrachloride, and / or the alcohol compounds are selected from one or more of methanol, ethanol, propanol, butanol, ethylene glycol, and glycerol, and / or the ether compounds are selected from one or more of ethylene glycol monomethyl ether, diethyl ether, and propylene oxide, and / or the furan compounds are selected from one or more of tetrahydrofuran and 2-methylfuran, and / or the pyridine compounds are selected from pyridine, and / or the amide compounds are selected from N,N-dimethylformamide, and / or the sulfone compounds are selected from dimethyl sulfoxide; and / or In the solution, the concentration of the organic phosphonic acid compound is 0.01 mmol / L to 10 mmol / L; and / or The bonding reaction is carried out at a temperature of 50°C to 80°C, and / or the time for which the cured film layer is placed in the solution is 1 h to 6 h; and / or After the step of placing the cured film layer in the solution and before the step of obtaining the thin film, the method for preparing the thin film further includes the steps of: washing and removing the organic phosphonic acid compound that has not undergone the bonding reaction with a second solvent, and then drying; and / or The organic phosphonic acid compound has a structure represented by the following general formula (I): In the general formula (I), R1 and R2 are each independently selected from a hydroxyl group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon group, an unsubstituted or at least one first group-substituted C1-C30 hydrocarbon oxy group, an unsubstituted or at least one first group-substituted C3-C30 aliphatic cycloalkyl group, an unsubstituted or at least one first group-substituted aliphatic heterocyclic alkyl group having 3 to 30 ring atoms, an unsubstituted or at least one first group-substituted aryl group having 6 to 30 ring atoms, an unsubstituted or at least one first group-substituted aryloxy group having 6 to 30 ring atoms, an unsubstituted or at least one first group-substituted heteroaryl group having 5 to 30 ring atoms, or an unsubstituted or at least one first group-substituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups; the heteroatoms in the aliphatic heterocyclic alkyl group, the heteroaryl group, or the heteroaryloxy group are selected from one or more of N, S, O, P, and Si, and the number of the heteroatoms is selected from 1 to 20; Each occurrence of the first group is independently selected from deuterium, -X, amino, hydroxyl, carboxyl, nitro, sulfonic acid group, aldehyde group, mercapto group, cyano group or phosphonic acid group, and X is selected from halogen atoms; R1 and R2 are not simultaneously selected from hydroxyl groups, and at least one of R1 and R2 includes -X; and / or The first metal oxide material includes one or more doped first metal oxides, and the doping elements of the doped first metal oxides are selected from one or more of In, F, Sb, Al, Ga and Mg, and the doped first metal oxides are selected from tin oxide, zinc oxide or magnesium oxide.

9. The method for preparing the thin film according to claim 8, wherein, The drying treatment is selected from one or more of heat treatment and vacuum drying treatment, and the temperature of the heat treatment is selected from 40°C to 200°C; and / or The second solvent includes one or more of water, C1-C10 aliphatic hydrocarbon compounds and C1-C10 aliphatic alcohol compounds; optionally, the C1-C10 aliphatic hydrocarbon compounds are selected from one or more of propane, butane, pentane, hexane, heptane and octane, and / or the C1-C10 aliphatic alcohol compounds are selected from one or more of ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol.

10. An optoelectronic device, characterized in that, The optoelectronic device includes the thin film described in any one of claims 4 to 6, or the thin film prepared by the preparation method of the thin film described in any one of claims 7 to 9.

11. The optoelectronic device according to claim 10, characterized in that, Comprising: A bottom electrode and a top electrode arranged opposite to each other; And A functional layer disposed between the bottom electrode and the top electrode; Wherein, at least one of the bottom electrode and the top electrode includes the thin film described in any one of claims 4 to 6, or the thin film prepared by the preparation method of the thin film described in any one of claims 7 to 9.

12. The optoelectronic device according to claim 11, wherein One of the bottom electrode and the top electrode is an anode, and the other is a cathode; wherein, the anode includes the thin film described in any one of claims 4 to 6, or the thin film prepared by the preparation method of the thin film described in any one of claims 7 to 9; and / or, the material of the cathode is selected from one or more of metals, carbon materials and second metal oxides, the metals are selected from one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni and Mg, the carbon materials are selected from one or more of graphite, carbon nanotubes, graphene and carbon fibers, and the second metal oxides are 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, aluminum-doped magnesium oxide, SnO2, ZnO and In2O3; optionally, the bottom electrode is the anode; and / or The functional layer includes a light-emitting layer, and the material of the light-emitting layer includes one or more of an organic light-emitting material and a light-emitting quantum dot; the organic light-emitting material is selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescence material, TTA material, thermally activated delayed material, a polymer containing a B-N covalent bond, a hybrid local charge transfer excited state material, an exciplex luminescent material, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives; and / or, the light-emitting quantum dot is selected from one or more of a single-component quantum dot, a core-shell structure quantum dot, an inorganic perovskite quantum dot, an organic perovskite quantum dot, and an organic-inorganic hybrid perovskite quantum dot, the core-shell structure quantum dot includes one or more shells, and the material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are each independently selected from one or more of II-VI group compounds, III-VI group compounds, III-V group compounds, IV-VI group compounds, and I-III-VI group compounds;Optionally, the II-VI group compound is selected from one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; and / or the III-VI group compound is selected from one or more of In2S3, In2Se3, InGaS3, and InGaSe3; and / or the III-V group compound is 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 / or the IV-VI group compound is 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 / or the I-III-VI group compound is selected from one or more of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2, and CuInGaS2; and / or the structural general formula of the inorganic perovskite quantum dot is AMX3, where A is Cs; + , M is a divalent metal cation, and M is selected from Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ and Eu 2+ one or more of; X is a halogen anion; and / or, the general structural formula of the organic perovskite quantum dots is CMX3, where C is formamidinium; and / or, the general structural formula of the organic-inorganic hybrid perovskite quantum dots is BMX3, where B is an organic amine cation; and / or The functional layer includes an electronic functional layer, and the material of the electronic functional layer includes one or more of a second metal oxide material, a third metal oxide material, a IIB-VIA group semiconductor material, a IIIA-VA group semiconductor material, and a IB-IIIA-VIA group semiconductor material; the second metal oxide material is selected from one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, and ZrO2, and / or the IIB-VIA group semiconductor material is selected from one or more of ZnS, ZnSe, and CdS, and / or the IIIA-VA group semiconductor material is selected from one or more of InP and GaP, and / or the IB-IIIA-VIA group semiconductor material is selected from one or more of CuInS and CuGaS; and / or, the third metal oxide material includes one or more doped third metal oxides, the doping element of the doped third metal oxide is selected from one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In, and Sn, and the main material of the doped third metal oxide is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, or ZrO2.

13. The optoelectronic device according to claim 11 or 12, characterized in that, The functional layer includes a hole functional layer, and the material of the hole functional layer includes one or more of an organic compound, a first inorganic compound material, and a second inorganic compound material; Wherein, the organic compound is selected from one or more of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium oxyphthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, polypyrrole, polyaniline, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazolyl)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-din-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4''-tris(carbazol-9-yl)triphenylamine, 4,4',4'-tris(2-naphthylphenylamino)triphenylamine, N,N'-diphenyl-N,N'-(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[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirobifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene; and / or, the first inorganic compound material is selected from one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, p-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide; and / or, the second inorganic compound material includes one or more doped second inorganic compounds, the host material of the doped second inorganic compound is selected from graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, p-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide, or tungsten sulfide, and the doping element of the doped second inorganic compound is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper, and platinum group metal elements; and / or, the hole functional layer is a single-layer structure, and the hole functional layer is a hole transport layer; and / or, the anode includes a first film layer and a second film layer, and the second film layer is located between the first film layer and the functional layer; the material of the first film layer is the first metal oxide material, and the material of the second film layer is the organic phosphonic acid compound.

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