Polymer, composite material, film, photoelectric device and display device

Abstract

The invention discloses a polymer, a composite material, a film, a photoelectric device and a display device, and relates to the technical field of display. The structural formula of the polymer is shown in the specification. The polymer provided by the invention can improve the electron transmission performance of inorganic nanoparticles.

Description

Technical Field

[0001] This application relates to the field of display technology, and more particularly to a polymer, composite material, thin film, optoelectronic device, and display apparatus. Background Technology

[0002] In related technologies, modifiers are often used to modify inorganic nanoparticles to improve their performance, such as carrier mobility. However, existing modifiers have limited effect on improving the performance of inorganic nanoparticles, and the carrier mobility of inorganic nanoparticles is low, which still needs further improvement. Summary of the Invention

[0003] In view of this, this application provides a polymer, a composite material, a thin film, an optoelectronic device, and a display device.

[0004] The embodiments of this application are implemented as follows: a polymer, the structural formula of which is shown below:

[0005]

[0006] Among them, L1 and L2 are each independently selected from single bonds, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-,

[0007]

[0008] One or more of the following;

[0009] R1 and R2 are each independently selected from one or more of the following: H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted aryl with 6-60 ring atoms, and substituted or unsubstituted heteroaryl with 5-60 ring atoms.

[0010] R3, R4, R5, and R6 are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, aryl with 6 to 60 substituted or unsubstituted ring atoms, and heteroaryl with 5 to 60 substituted or unsubstituted ring atoms.

[0011] When R1, R2, R3, R4, R5, and R6 are substituted by substituents, each substituent is independently selected from one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C30 alkyl, C1-C30 alkoxy, and aryl with 6-30 ring atoms.

[0012] Accordingly, embodiments of this application also provide a composite material comprising inorganic nanoparticles and a polymer; the polymer has the following structural formula:

[0013]

[0014] Among them, L1 and L2 are each independently selected from single bonds, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-,

[0015]

[0016] One or more of the following;

[0017] R1 and R2 are each independently selected from one or more of the following: H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted aryl with 6-60 ring atoms, and substituted or unsubstituted heteroaryl with 5-60 ring atoms.

[0018] R3, R4, R5, and R6 are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, aryl with 6 to 60 substituted or unsubstituted ring atoms, and heteroaryl with 5 to 60 substituted or unsubstituted ring atoms.

[0019] When R1, R2, R3, R4, R5, and R6 are substituted by substituents, each substituent is independently selected from one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C30 alkyl, C1-C30 alkoxy, and aryl with 6-30 ring atoms.

[0020] Accordingly, this application also provides a thin film, the material of which includes the above-mentioned composite material.

[0021] Accordingly, this application also provides an optoelectronic device, comprising an anode, an active layer, an electronic functional layer, and a cathode stacked sequentially; wherein the material of the electronic functional layer includes the aforementioned composite material.

[0022] Accordingly, this application also provides a display device, which includes the above-mentioned optoelectronic device.

[0023] The polymer provided in this application can improve the electron transport performance of inorganic nanoparticles. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a flowchart of the polymer preparation method provided in the embodiments of this application;

[0026] Figure 2 This is a schematic diagram of the structure of the optoelectronic device provided in the embodiments of this application.

[0027] Figure label:

[0028] Optoelectronic devices 100;

[0029] Anode 10; Light-emitting layer 20; Electron functional layer 30; Cathode 40; Hole functional layer 50. Detailed Implementation

[0030] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0031] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0032] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0033] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0034] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical 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 range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0035] In this application, aromatic groups, aromatic families, and aromatic ring systems have the same meaning and can be used interchangeably.

[0036] In this application, heteroaromatic groups, heteroaromatic families, and heteroaromatic ring systems have the same meaning and can be used interchangeably.

[0037] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. It is understood that when the group is substituted by a substituent, the number of substituents may be one, two, three or more, and when the number of substituents is two or more, the substituents may be the same or different.

[0038] In this application, "ring atom number" refers to the number of ring atoms constituting the ring itself in a cyclic compound (e.g., a monocyclic or polycyclic compound) obtained by atomic bonding, i.e., the number of atoms forming the ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atom count. The same applies to the "ring atom number" described below unless otherwise specified. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0039] In this application, "aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl, and for polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" means an aryl containing 6 to 40 ring atoms, and the aryl may optionally be further substituted. Preferably, it is a substituted or unsubstituted aryl having 6 to 30 ring atoms; more preferably, it is a substituted or unsubstituted aryl having 6 to 18 ring atoms; particularly preferably, it is a substituted or unsubstituted aryl having 6 to 14 ring atoms, and the aryl may optionally be further substituted. Suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives. Understandably, multiple aryl groups can 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, and diaryl ether systems should also be included in the definition of aryl.

[0040] In this application, "heteroaryl or heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, Si atom, P atom, etc. For example, "substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms" refers to a heteroaryl group having 5 to 60 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 5 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, and the heteroaryl group may optionally be further substituted; suitable examples include, but are not limited to: thiophene, furanyl, pyrrole, diazolyl, triazolyl, imidazole, pyridyl, bipyridyl, pyrimidinyl, etc. Triazinyl, acridineyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidineyl, pyridinylpyrazinyl, benzothiopheneyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrololyl, thienopyrrololyl, thienopyrrololyl, furanolololyl, furanolofuranyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridineyl, primidyl, quinazolinoneyl, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0041] In this application, "alkyl" can mean straight-chain, branched, and / or cyclic alkyl. The number of carbon atoms in an alkyl group can be 1 to 30, 1 to 25, 1 to 20, 1 to 15, 1 to 10, or 1 to 6. Phrases containing this term, such as "C 1-9"Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each time it appears, it can independently be a C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, etc. tert-amyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl The compounds include 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-hepta ...

[0042] In this application, "-C" n H 2n+1 "Unless otherwise specified or limited, it indicates a straight-chain alkyl group. For example, -C4H9 indicates n-butyl."

[0043] In this application, amino represents -NR 1 R 2 , where R 1 R 2 Each can independently represent H or alkyl, that is, amino can refer to -NH2, -NH (alkyl), or -N alkyl (alkyl).

[0044] In this application, "halogen" represents -Cl, -Br, -F, or -I; hydroxyl represents -OH; carboxyl represents -COOH; nitro represents -NO2; sulfonic acid represents -SO3H; mercapto represents -SH; and cyano represents...

[0045] In this application, L is a linking group with two points at both ends. When L is formed by multiple combinations, the linking order can be changed, and all possible linking combinations fall within the protection scope of L in this application.

[0046] Currently, electron transport layers in optoelectronic devices often use N-type nanoparticle materials such as oxides. N-type nanoparticles have surface defects and are prone to aggregation. The prepared films are often uneven, with rough surfaces and poor density, which increases interface defects. These interface defects can lead to interface delamination or interface charge accumulation during the use of optoelectronic devices, affecting the light-emitting performance and lifespan of the optoelectronic devices.

[0047] The technical solution of this application is as follows:

[0048] In a first aspect, embodiments of this application provide a polymer, the polymer having the following structural formula:

[0049]

[0050] Among them, L1 and L2 are each independently selected from single bonds, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-,

[0051]

[0052] One or more of the following;

[0053] R1 and R2 are each independently selected from one or more of the following: H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted aryl with 6-60 ring atoms, and substituted or unsubstituted heteroaryl with 5-60 ring atoms.

[0054] R3, R4, R5, and R6 are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, aryl with 6 to 60 substituted or unsubstituted ring atoms, and heteroaryl with 5 to 60 substituted or unsubstituted ring atoms.

[0055] When R1, R2, R3, R4, R5, and R6 are substituted by substituents, each substituent is independently selected from one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C30 alkyl, C1-C30 alkoxy, and aryl with 6-30 ring atoms.

[0056] The polymer provided in this application is suitable for modifying inorganic nanoparticles. The polymer backbone includes linked benzo[1,2-B:5,4-B']dithiophene (BDT) and dioxane, giving the polymer good chemical and thermal stability. The -L1-R1 and -L2-R2 side chains help improve the solubility of inorganic nanoparticles in organic solvents and increase electron transport performance. The BDT backbone in the polymer provides additional electron transport channels, lowers the electron transport barrier, and makes electron transport easier. The dioxane in the polymer can further increase the solubility of inorganic nanoparticles and improve their thermal stability. The polymer backbone provided in this application is itself a conjugated system, forming an extended conjugated structure through the delocalization of π electrons. This conjugated structure is conducive to electron transport within the molecule, further improving electron mobility.

[0057] In some embodiments, the heteroatom in the heteroaryl group is selected from one or more of O, P, N, and S.

[0058] In some embodiments, the C1-C30 alkyl group can be selected from C2-C28 alkyl, C5-C25 alkyl, C8-C20 alkyl, C10-C15 alkyl, C12-C15 alkyl, etc., specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, pentadecyl, etc.

[0059] In some embodiments, the C2-C30 alkenyl group can be selected from C3-C28 alkenyl, C5-C25 alkenyl, C8-C20 alkenyl, C10-C15 alkenyl, C12-C15 alkenyl, etc., specifically vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, pentadecenyl, octadecenyl, eicosene, icosene, etc.

[0060] In some embodiments, the aryl group having 6 to 60 ring atoms can be selected from aryl groups having 8 to 50 ring atoms, aryl groups having 10 to 40 ring atoms, aryl groups having 20 to 30 ring atoms, etc., specifically phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, etc.

[0061] In some embodiments, the heteroaryl group having 5 to 60 ring atoms can be selected from heteroaryl groups having 8 to 50 ring atoms, heteroaryl groups having 10 to 40 ring atoms, heteroaryl groups having 20 to 30 ring atoms, etc., specifically thiazolyl, thiophenel, furanyl, pyrrolel, pyridinyl, pyrimidinyl, imidazolyl, azole, pyrazinyl, indolyl, quinolinyl, pteridinyl, acridinel, etc.

[0062] In some embodiments, the C1-C30 alkoxy group can be selected from C2-C28 alkoxy, C5-C25 alkoxy, C8-C20 alkoxy, C10-C15 alkoxy, C12-C15 alkoxy, etc., specifically methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, dodecoxy, pentadecoxy, octadecoxy, eicosoxy, pentadecoxy, etc.

[0063] In some embodiments, the aryl group having 6 to 30 ring atoms can be selected from aryl groups having 8 to 25 ring atoms, aryl groups having 10 to 20 ring atoms, aryl groups having 12 to 18 ring atoms, etc., specifically phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, etc.

[0064] In some embodiments, L1 and L2 may be the same or different.

[0065] In some embodiments, L1 and L2 are each independently selected from single bonds, -O-, -S-,

[0066] In some embodiments, R1 and R2 are each independently selected from one or more of hydroxyl, carboxyl, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl, and substituted or unsubstituted aryl with 6 to 30 ring atoms.

[0067] In some embodiments, R3, R4, R5, and R6 may be the same or different.

[0068] In some embodiments, R3, R4, R5, and R6 are each independently selected from aryl groups having 6 to 30 substituted or unsubstituted cyclic atoms, such as phenyl.

[0069] In some embodiments, n is an integer from 10,000 to 50,000, such as 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or any range between two values. It should be noted that n represents the degree of polymerization of the polymer; within the range of the stated degree of polymerization, the polymer exhibits higher stability.

[0070] In some embodiments, R1 and R2 may be the same or different.

[0071] In some embodiments, the polymer is selected from one or more compounds of formulas M1 to M12:

[0072]

[0073]

[0074] Please see Figure 1 This application also provides a method for preparing a polymer, the synthetic route of which is as follows:

[0075]

[0076] The specific steps involved in preparing the polymer are as follows:

[0077] S11. Provide compound a and a metal salt, mix them, react them, and obtain an intermediate product;

[0078] The structural formula of compound a is shown below: X1 and X2 are each independently selected from halogens;

[0079] The structural formula of the metal salt includes R1-A1 and R2-A2, where A1 and A2 are selected from metal ions;

[0080] The structural formula of the intermediate product is shown below:

[0081] S12. Dioxane is provided, and the dioxane and the intermediate product are mixed and reacted to obtain a polymer; the polymer has the following structural formula:

[0082]

[0083] Among them, L1 and L2 are each independently selected from single bonds, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-,

[0084]

[0085] One or more of the following;

[0086] R1 and R2 are each independently selected from one or more of the following: H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted aryl with 6-60 ring atoms, and substituted or unsubstituted heteroaryl with 5-60 ring atoms.

[0087] R3, R4, R5, and R6 are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, aryl with 6 to 60 substituted or unsubstituted ring atoms, and heteroaryl with 5 to 60 substituted or unsubstituted ring atoms.

[0088] When R1, R2, R3, R4, R5, and R6 are substituted by substituents, each substituent is independently selected from one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C30 alkyl, C1-C30 alkoxy, and aryl with 6-30 ring atoms.

[0089] In S11:

[0090] In some embodiments, the halogen is selected from F, Cl, Br, and I.

[0091] In some embodiments, the metal ion is selected from sodium ions, lithium ions, potassium ions, and magnesium ions.

[0092] The selection of L1, L2, R1, R2, R3, R4, R5, and R6 is as described above and will not be repeated here.

[0093] For example, the metal salt includes one or more of sodium phenyl (CAS: 1623-99-0), lithium formate monohydrate (CAS: 6108-23-2), magnesium formate (CAS: 6150-82-9), potassium formate (CAS: 590-29-4), potassium cyanide (CAS: 151-50-8), sodium benzoate (CAS: 532-32-1), sodium butyrate (CAS: 156-54-7), sodium pyruvate (CAS: 113-24-6), sodium tert-butoxide (CAS: 865-48-5), sodium acrylate (CAS: 7446-81-3), sodium isooctanoate (CAS: 19766-89-3), sodium salicylate (CAS: 54-21-7), sodium tetraphenylborate (CAS: 143-66-8), and sodium dodecyl sulfate (CAS: 151-21-3).

[0094] It should be noted that compound a can be obtained by bromination of benzo[1,2-B:5,4-B']dithiophene (CAS: 267-61-8) with sodium bromide.

[0095] In some embodiments, the molar ratio of compound a to the metal salt is 1:(2-4), for example, it can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, or any range between two ratios. Within the range of the molar ratio, it is beneficial to promote the alkylation reaction between compound a and the metal salt.

[0096] In some embodiments, the reaction temperature of the mixture of compound a and the metal salt is 60°C to 80°C, for example, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, or any range between two values; the reaction time is 20 min to 30 min, for example, 22 min, 24 min, 25 min, 26 min, 28 min, or any range between two values. This facilitates the substitution of halogens in compound a by R1 and R2.

[0097] In S12:

[0098] In some embodiments, the molar ratio of the intermediate product to the dioxane is 1:(1-2), for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, or any range between two ratios. Within the range of the molar ratio, it is advantageous to increase the yield of the reaction between the intermediate product and the dioxane.

[0099] In some embodiments, the reaction temperature of the dioxane and the intermediate product is 60°C to 80°C, for example, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, or any range between two values; the reaction time is 2 hours to 3 hours, for example, 2.2 hours, 2.5 hours, 2.8 hours, or any range between two values. This facilitates the copolymerization reaction of the dioxane and the intermediate product.

[0100] In some embodiments, the mixing of dioxane and the intermediate product further includes the addition of a catalyst.

[0101] Furthermore, the catalyst includes a Pd catalyst, a Pd / Cu co-catalytic system, and a Pd / Ag2CO3 co-catalytic system.

[0102] The mass ratio of dioxane to the intermediate and to the catalyst is 100:(1-15), for example, it can be 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, or any range between two such ratios. The catalyst is beneficial for increasing the reaction rate between dioxane and the intermediate.

[0103] Secondly, this application also provides a composite material comprising inorganic nanoparticles and the aforementioned polymer.

[0104] In the composite material provided in this application, inorganic nanoparticles are modified with polymers. Polymers can provide better steric hindrance, prevent the aggregation of inorganic nanoparticles, and improve stability. Polymers can also improve the solubility and dispersibility of inorganic nanoparticles. Polymers can also reduce surface defects of inorganic nanoparticles and improve the carrier migration performance of inorganic nanoparticles.

[0105] In some embodiments, the average particle size of the inorganic nanoparticles is 7 nm to 10 nm, for example, it can be 7.5 nm, 8 nm, 8.5 nm, 9 nm, 9.5 nm, or any range between two values. It should be noted that in this application, the particle size of the inorganic nanoparticles is measured by transmission electron microscopy (TEM).

[0106] In some embodiments, the inorganic nanoparticles include N-type inorganic nanoparticles.

[0107] Further, the N-type inorganic nanoparticles include one or more of the following: first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The first undoped metal oxide particles include one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxides in the first doped metal oxide particles include one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping elements in the first doped metal oxide particles include one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga. The IIB-VIA group semiconductor materials include one or more of ZnS, ZnSe, and CdS. The IIIA-VA group semiconductor materials include one or more of InP and GaP. The IB-IIIA-VIA group semiconductor materials include one or more of CuInS and CuGaS. Furthermore, in the first doped metal oxide particle, the molar ratio of the dopant element to the metal in the metal oxide particle is (10-20):100, for example, it can be 11:100, 12:100, 13:100, 14:100, 15:100, 16:100, 17:100, 18:100, 19:100 or any range between two ratios.

[0108] In some embodiments, the mass ratio of the inorganic nanoparticles to the polymer is (90–99):(1–10), for example, it can be 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, or any range between two ratios. Within the range of the stated mass ratio, the polymer is beneficial for improving the stability, dispersibility, and carrier mobility of the inorganic nanoparticles.

[0109] In some embodiments, the inorganic nanoparticles have active groups, and at least a portion of the inorganic nanoparticles are linked to the polymer through these active groups. The connection between the polymer and the active groups can modify the defect states of the inorganic nanoparticles.

[0110] Furthermore, the active group includes one or more of hydroxyl, carboxyl, amino, and methoxy groups.

[0111] Thirdly, embodiments of this application also provide a thin film, the material of which includes the aforementioned composite material.

[0112] The thin film provided in this application uses the above-mentioned composite material. The polymer helps to improve the density of the thin film, improve the unevenness of the film surface, and further promote the transport of charge carriers.

[0113] In some embodiments, the surface roughness of the thin film is 0.5 nm to 1.5 nm, for example, it can be 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.1 nm, 1.2 nm, 1.3 nm, 1.4 nm, or any range between two values. Within the range of surface roughness, the thin film has high density and good film-forming properties, which is beneficial to the continuity of conductivity and promotes the transport of charge carriers. It should be noted that in this application, the surface roughness of the thin film is measured by atomic force microscopy (AFM).

[0114] In some embodiments, the thickness of the film is 20nm to 60nm, for example, it can be 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm or any range between two values.

[0115] Fourthly, please refer to Figure 2 This application also provides an optoelectronic device 100, including an anode 10, an electronic functional layer 30 and a cathode 40 stacked sequentially; wherein the material of the electronic functional layer 30 includes the aforementioned composite material.

[0116] In the optoelectronic device 100 provided in this application, the application of polymer-modified inorganic nanoparticles to the electronic functional layer 30 of the optoelectronic device 100 can promote electron injection and transport, and improve the compactness of the electronic functional layer 30. This is beneficial to improving the interface contact between the electronic functional layer 30 and other functional layers, thereby improving the stability and luminous efficiency of the optoelectronic device 100 and extending the service life of the optoelectronic device 100.

[0117] The electronic functional layer 30 includes one or more of the following: an electron injection layer and an electron transport layer.

[0118] In some embodiments, the anode 10 and the cathode 40 each independently comprise one or more of a metal, a carbon material, and a metal oxide; the metal comprises one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb, and Mg; the carbon material comprises one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide comprises a metal oxide electrode or a composite electrode in which a metal is disposed between doped or undoped transparent metal oxides, the material of the metal oxide electrode comprising one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, MoO3, and AMO; the composite electrode comprises one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2. In this context, " / " indicates a stacked structure. For example, AZO / Ag / AZO represents a composite electrode consisting of sequentially stacked AZO, Ag, and AZO layers.

[0119] In some embodiments, the optoelectronic device 100 includes a light-emitting diode.

[0120] In some embodiments, the optoelectronic device further includes a light-emitting layer 20 located between the anode and the electronic functional layer, wherein the material of the light-emitting layer includes one or more of organic light-emitting materials and quantum dots.

[0121] The organic light-emitting material may be selected from, but is not limited to, one or more of the following: CBP:Ir(mppy)3(4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridinium(III)]), TCTX:Ir(mmpy)(4,4',4”-tris(carbazole-9-yl)triphenylamine:tris[2-(p-tolyl)pyridinium(III)]), diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, TADF (thermally activated delayed) materials, polymers containing BN covalent bonds, HLCT (hybrid local charge transfer excited state) materials, and Exciplex (excitoplex) light-emitting materials.

[0122] The quantum dot luminescent material may be selected from, but is not limited to, one or more of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials.

[0123] The materials for the single-structure quantum dots, the core material of the core-shell quantum dots, and the shell material of the core-shell quantum dots can be selected from, but are not limited to, one or more of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds. The shell of the core-shell quantum dots may include one or more layers. The group II-VI compounds may be selected from, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. The IV-VI group compounds may be selected from, 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 group III-V compounds may be selected from, 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 group I-III-VI compounds may be selected from, but are not limited to, one or more of CuInS2, CuInSe2, and AgInS2.

[0124] As an example, the core-shell structured quantum dots can be selected from, but are not limited to, one or more of CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS, and InP / ZnSe / ZnS. In the above descriptions of CdSe / ZnS, etc., the " / " indicates that the material after the " / " (as the shell) covers the material before the " / " (as the core).

[0125] The perovskite semiconductor material can be selected from, but is not limited to, doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors. The general structural formula of the inorganic perovskite semiconductor is AMX3, where A is Cs. + Ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ One or more of them, where X is a halide anion selected from Cl. - ,Br - I - One or more of the following. The general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, where B is an organic amine cation selected from CH3(CH2). n-2 NH3 + Or [NH3(CH2)] n NH3] 2+ Where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ One or more of them, where X is a halide anion selected from Cl. - ,Br - I -One or more of them.

[0126] In some embodiments, the optoelectronic device 100 further includes a hole functional layer 50 located between the anode 10 and the light-emitting layer 20.

[0127] The hole functional layer 50 includes one or more of the following: a hole injection layer and a hole transport layer.

[0128] In some embodiments, the material of the hole functional layer 50 includes an organic p-type semiconductor material or an inorganic p-type semiconductor material, wherein the organic p-type semiconductor material includes 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'- bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(carbazol-9-yl)triphenylamine, trichloroisocyanuric acid, terbium-doped phosphate-based green luminescent materials, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4, 4'-(N-(4-sec-butylphenyl)diphenylamine)], poly(4-butylphenyl-diphenylamine), poly[bis(4-phenyl)(4-butylphenyl)amine], polyaniline, polypyrrole, poly(p-)phenylenevinylene, poly(phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1, 1'-Biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT, PEDOT:PSS and its derivatives, PEDOT:PSS derivatives doped with s-MoO3, poly(N-vinylcarbazole) and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine, spiron NPB, nanocrystalline diamond, microcrystalline cellulose and tetracyanoquinone dimethane, doped graphene, undoped graphene;The inorganic P-type semiconductor material comprises one or more of the following: second-doped metal oxide particles, second-undoped metal oxide particles, metal sulfides, metal selenides, and metal nitrides. The metal oxides in the second-doped and second-undoped metal oxide particles each independently comprise one or more of MoO3, WO3, NiO, CrO3, CuO, and V2O5. The doping element in the second-doped metal oxide particles comprises one or more of Mo, W, Ni, Cr, Cu, and V. The metal sulfide comprises one or more of CuS, MoS3, and WS3. The metal selenide comprises one or more of MoSe3 and WSe3. The metal nitride comprises P-type gallium nitride.

[0129] Fifthly, embodiments of this application also provide a display device, the display device including the above-described optoelectronic device 100.

[0130] The display device can be any electronic product with display function, including but not limited to smartphones, tablets, laptops, digital cameras, digital camcorders, smart wearable devices, smart weighing scales, in-vehicle displays, televisions, or e-book readers. Among them, smart wearable devices can be, for example, smart bracelets, smartwatches, virtual reality (VR) headsets, etc.

[0131] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0132] Example 1

[0133] This embodiment provides a polymer, a composite material containing the polymer, and a film prepared from the composite material;

[0134] The polymer is prepared as follows:

[0135] Provide compound a Compound a is mixed with sodium phenyl metal salt at a molar ratio of 1:2 and reacted at 70°C for 25 min to obtain an intermediate product.

[0136] The intermediate product and dioxane were mixed in a 1:1 molar ratio, and a Pd catalyst was added. The mixture was reacted at 70°C for 2.5 h to obtain polymer M4.

[0137] The preparation method of the composite material is as follows:

[0138] N-type inorganic nanoparticles ZnO containing hydroxyl groups are provided. ZnO, the above-mentioned polymer, and ethanol are mixed to obtain a mixture with a mass ratio of ZnO to polymer of 95:5 and a molar concentration of polymer of 0.04 mmol / L in the mixture. The reaction is carried out to obtain a composite material.

[0139] The thin film is prepared as follows:

[0140] The above composite material was dispersed in ethanol to form a composite material dispersion of 20 mg / mL. The composite material dispersion was spin-coated at 4000 r / min for 30 s, and then annealed at 100 °C for 15 min to obtain a film with a thickness of 40 nm.

[0141] Example 2

[0142] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with magnesium formate and the polymer is M3.

[0143] Example 3

[0144] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with potassium cyanide; the polymer is M1.

[0145] Example 4

[0146] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium benzoate and the polymer is M8.

[0147] Example 5

[0148] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium butyrate; the polymer is M6.

[0149] Example 6

[0150] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium tert-butoxide; the polymer is M2.

[0151] Example 7

[0152] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium acrylate; the polymer is M5.

[0153] Example 8

[0154] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium isooctanoate; the polymer is M10.

[0155] Example 9

[0156] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium salicylate and the polymer is M9.

[0157] Example 10

[0158] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium pyruvate and the polymer is M7.

[0159] Example 11

[0160] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium tetraphenylborate; the polymer is M11.

[0161] Example 12

[0162] This embodiment is basically the same as Embodiment 1, except that the metal salt is replaced with sodium dodecyl sulfate; the polymer is M12.

[0163] Example 13

[0164] This embodiment is basically the same as Embodiment 1, except that the inorganic nanoparticles ZnO are replaced with TiO2 in this embodiment.

[0165] Example 14

[0166] This embodiment is basically the same as Embodiment 1, except that the inorganic nanoparticles ZnO are replaced with ZnMgO (magnesium-doped zinc oxide, with a molar ratio of magnesium to zinc of 10:100).

[0167] Example 15

[0168] This embodiment is basically the same as Embodiment 1, except that the mass ratio of ZnO to polymer in this embodiment is 99:1.

[0169] Example 16

[0170] This embodiment is basically the same as Embodiment 1, except that the mass ratio of ZnO to polymer in this embodiment is 90:10.

[0171] Comparative Example 1

[0172] This comparative example is basically the same as Example 1, except that the composite material in this comparative example does not contain polymer.

[0173] Comparative Example 2

[0174] This comparative example is basically the same as Example 13, except that the composite material in this comparative example does not contain polymer.

[0175] Comparative Example 3

[0176] This comparative example is basically the same as Example 14, except that the composite material in this comparative example does not contain polymer.

[0177] Comparative Example 4

[0178] This comparative example is basically the same as Example 1, except that dioxane was not added in this comparative example; the intermediate product was directly polymerized to obtain the polymer.

[0179] The electron mobility and surface roughness of the thin films of Examples 1-16 and Comparative Examples 1-4 were tested respectively, and the results are shown in Table 1.

[0180] The electron mobility test method involves measuring the current density-voltage curve of the optoelectronic device (single carrier transport thin-film device, EOD). The EOD structure is an anode / quantum dot emitting layer / electron transport layer / cathode, with the electron transport layer being the thin film of Examples 1-16 and Comparative Examples 1-4. The space charge confinement current (SCLC) region in the current density-voltage curve is obtained, and then the electron mobility is measured using the formula J = (9 / 8)ε. r ε0μ e V 2 / d 3 Calculate the electron mobility; where J represents the current density in mA / cm². -2 ;ε r ε₀ represents the relative permittivity, and μ represents the vacuum permittivity. e Electron mobility is expressed in cm. 2 V - 1 s -1 V represents the driving voltage, with units of V; d represents the film thickness, with units of m.

[0181] Surface roughness was measured using atomic force microscopy (AFM).

[0182] Table 1

[0183]

[0184]

[0185] As shown in Table 1:

[0186] As can be seen from Examples 1-12 and Comparative Example 1, using the polymer modified inorganic nanoparticles provided in this application can improve the surface defects of inorganic nanoparticles and effectively improve the electron mobility of inorganic nanoparticles; moreover, the polymer improves the compactness of the film, reduces the surface roughness of the film, and further promotes the electron migration efficiency.

[0187] As can be seen from Examples 1, 13-16 and Comparative Examples 1-4, the polymer provided in this application has a good modification effect on a variety of inorganic nanoparticles and has wide applicability. Within the dosage range of the polymer and inorganic nanoparticles provided in this application, the inorganic nanoparticles and polymer are bonded together to effectively improve the electron mobility of the inorganic nanoparticles and reduce the surface roughness of the film, making the film smoother and more uniform.

[0188] Device Example 1

[0189] This embodiment provides an optoelectronic device, the fabrication method of which is as follows:

[0190] The ITO conductive glass was cleaned with a cleaning agent to initially remove the stains on the surface. Then, it was ultrasonically cleaned for 20 minutes each in deionized water, acetone, anhydrous ethanol, and deionized water to remove the impurities on the surface. Finally, it was dried with high-purity nitrogen to form an ITO anode with a thickness of 100 nm.

[0191] In air, a layer of PEDOT:PSS was spin-coated on the surface of the ITO anode at a speed of 5000 r / min for 30 s to obtain a hole injection layer with a thickness of 50 nm. After annealing, the layer was transferred to a glove box filled with nitrogen atmosphere.

[0192] TFB was spin-coated on the surface of the hole injection layer at a speed of 3000 r / min for 30 s to obtain a hole transport layer with a thickness of 30 nm.

[0193] CdSe quantum dots were dissolved in n-octane solvent and spin-coated onto the hole transport layer at a speed of 2000 rpm for 30 s. The mixture was then annealed at 80 °C for 10 min to form a light-emitting layer with a thickness of 20 nm.

[0194] The electron transport layer was prepared on the light-emitting layer according to the method of thin film preparation in Example 1;

[0195] Ag is deposited on the electron transport layer by thermal evaporation, with a vacuum level not exceeding 3 x 10⁻⁶. -4 Pa, velocity of 1 angstrom / second, time of 1000s, forming a cathode with a thickness of 20nm;

[0196] Packaging yields optoelectronic devices.

[0197] Device Examples 2-16

[0198] Device Examples 2-16 are basically the same as Device Example 1, except that the electron transport layer in Device Examples 2-16 is prepared by referring to the preparation method of the thin film in Examples 2-16 respectively.

[0199] Device Comparison Examples 1-4

[0200] The devices in Comparative Examples 1 to 4 are basically the same as those in Device Example 1, except that the electron transport layer in Comparative Examples 1 to 4 is prepared by the same method as the thin film in Comparative Examples 1 to 4.

[0201] The external quantum efficiency and lifetime (T95@1000nit) of the optoelectronic devices in Device Examples 1-16 and Device Comparative Examples 1-4 were tested respectively, and the results are shown in Table 2.

[0202] The external quantum efficiency (EQE) is measured as the ratio of electron-hole pairs injected into a quantum dot to emitted photons, expressed as a percentage (%). It is a crucial parameter for evaluating the quality of electroluminescent devices and can be obtained using an EQE optical testing instrument. The specific calculation formula is as follows:

[0203]

[0204] Where, η e For optical output coupling efficiency, η r χ is the ratio of recombination carriers to injected carriers, and K is the ratio of excitons producing photons to the total number of excitons. R K is the radiation process rate. NR This represents the rate of a non-radiative process.

[0205] Test conditions: Conducted at room temperature with an air humidity of 30-60%.

[0206] The measurement method for lifetime T95@1000nit is as follows: Under constant current or voltage drive, the time required for the brightness of the device to decrease to a certain percentage of its maximum brightness is defined as T95. This lifetime is the measured lifetime. To shorten the testing cycle, device lifetime testing is usually performed at high brightness by accelerating device aging, and the lifetime at high brightness is obtained by fitting an extended exponential decay brightness decay fitting formula. For example, the lifetime at 1000nit is measured as T95@1000nit. The specific calculation formula is as follows:

[0207]

[0208] Among them, T95 L For longer lifespan at low brightness, T95 HFor the measured lifetime under high brightness, L H To accelerate the device to its maximum brightness, L L The value is 1000 nits, and A is the acceleration factor. In this experiment, the lifetime of several groups of QLED devices under rated brightness was measured, and the value of A was found to be 1.7.

[0209] Table 2

[0210]

[0211] As shown in Table 2:

[0212] As can be seen from Device Examples 1-12 and Device Comparative Example 1, using the polymer-modified inorganic nanoparticle composite material provided in this application as the material of the electronic functional layer in the optoelectronic device can improve the external quantum efficiency of the optoelectronic device by promoting electron migration, and the polymer can improve the stability of the composite material, thereby improving the stability of the optoelectronic device and extending the service life of the optoelectronic device.

[0213] As can be seen from Device Examples 1, 13-16 and Device Comparative Examples 1-4, for the same inorganic nanoparticles, the performance of the optoelectronic device in Device Example 1 is significantly improved compared to Device Comparative Example 1, Device Example 13 compared to Device Comparative Example 2, and Device Example 14 compared to Device Comparative Example 3. Within the range of the amount of polymer and inorganic nanoparticles provided in this application, the optoelectronic device has high external quantum efficiency and long service life.

[0214] The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A polymer, characterized in that, The structure of the polymer is as follows: L1, L2 are each independently selected from a single bond, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-, one or more of the following: R1, R2 are each independently selected from one or more of H, D, amino group, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, mercapto group, cyano group, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted aryl group with 6-60 ring atoms, substituted or unsubstituted heteroaryl group with 5-60 ring atoms; R3, R4, R5, R6 are each independently selected from one or more of H, D, amino group, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, mercapto group, cyano group, substituted or unsubstituted aryl group with 6-60 ring atoms, substituted or unsubstituted heteroaryl group with 5-60 ring atoms; When R1, R2, R3, R4, R5, R6 are substituted, each occurrence of the substituent is independently selected from one or more of amino group, halogen, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, mercapto group, cyano group, C1-C30 alkyl group, C1-C30 alkoxy group, aryl group with 6-30 ring atoms.

2. The polymer of claim 1, wherein n is any integer from 10000 to 50000; and / or The C1-C30 alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, pentacosyl; and / or The C2-C30 alkenyl group is selected from vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, pentadecenyl, octadecenyl, eicosenyl, pentacosenyl; and / or The aryl group with 6-60 ring atoms is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl; and / or The heteroaryl group with 5-60 ring atoms is selected from thiazolyl, thienyl, furanyl, pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, pyrazinyl, indolyl, quinolyl, pteridinyl, acridinyl; and / or The C1-C30 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decoxy, dodecoxy, pentadecoxy, octadecoxy, eicosa-oxy, pentacosa-oxy; and / or The aryl group with 6-30 ring atoms is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl.

3. The polymer of claim 1, wherein n is any integer from 20000 to 40000; and / or L1 and L2 are the same or different; and / or R1 and R2 are the same or different; and / or R1, R2 are each independently selected from one or more of hydroxyl group, carboxyl group, cyano group, -BR3R4R5R6, substituted or unsubstituted C1-C15 alkyl group, substituted or unsubstituted C2-C15 alkenyl group, substituted or unsubstituted aryl group with 6-30 ring atoms; and / or L1, L2are each independently selected from the group consisting of a single bond, -0-, -S-, and / or R3, R4, R5, R6 are the same or different; and / or ​ ​ R3, R4, R5, R6are each independently selected from one or more of substituted or unsubstituted aryl having 6 to 30 ring atoms; and / or the heteroatom in the heteroaryl is selected from one or more of O, P, N, S.

4. The polymer of claim 1, wherein the polymer is selected from one or more of compounds of formulae M1 to M12:

5. A composite material, characterized by, comprising inorganic nanoparticles and a polymer; the polymer has a structural formula as shown in the following formula: wherein, L1, L2are each independently selected from a single bond, -O-, -S-, -NH-, -CH=N-, -N=N-, -C≡C-, one or more of the following: R1, R2are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic, mercapto, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted aryl having 6 to 60 ring atoms, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms; R3, R4, R5, R6are each independently selected from one or more of H, D, amino, hydroxyl, carboxyl, nitro, sulfonic, mercapto, cyano, substituted or unsubstituted aryl having 6 to 60 ring atoms, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms; R1, R2, R3, R4, R5, R6when substituted with a substituent, each occurrence of the substituent is independently selected from one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic, mercapto, cyano, C1-C30 alkyl, C1-C30 alkoxy, aryl having 6 to 30 ring atoms.

6. The composite material of claim 5, wherein, n is any integer from 10000 to 50000; and / or L1and L2are the same or different; and / or L1, L2are each independently selected from the group consisting of a single bond, -0-, -S-, and / or R1and R2are the same or different; and / or R1, R2are each independently selected from one or more of hydroxyl, carboxyl, cyano, -BR3R4R5R6, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted aryl having 6 to 30 ring atoms; and / or R3, R4, R5, R6are the same or different; and / or R3, R4, R5, R6are each independently selected from substituted or unsubstituted aryl having 6 to 30 ring atoms; and / or the heteroatom in the heteroaryl is selected from one or more of O, P, N, S.

7. The composite material of claim 5, wherein, the polymer is selected from one or more of compounds of formulae M1 to M12:

8. The composite material of claim 5, wherein, the mass ratio of the inorganic nanoparticles to the polymer is (90-99):(1-10); and / or the inorganic nanoparticles have active groups, and at least part of the inorganic nanoparticles are connected to the polymer through the active groups; the active groups include one or more of hydroxyl, carboxyl, amino, methoxyl; and / or the average particle size of the inorganic nanoparticles is 7 nm to 10 nm; and / or the average particle size of the inorganic nanoparticles is 7 nm to 10 nm; and / or The inorganic nanoparticles comprise N-type inorganic nanoparticles; the N-type inorganic nanoparticles comprise one or more of first doped metal oxide particles, first non-doped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials and IB-IIIA-VIA group semiconductor materials, the material of the first non-doped metal oxide particles comprises one or more of ZnO, TiO2, SnO2, ZrO2 and Ta2O5, the metal oxide in the first doped metal oxide particles comprises one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5 and Al2O3, the doping element in the first doped metal oxide particles comprises one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In and Ga, the IIB-VIA group semiconductor materials comprise one or more of ZnS, ZnSe and CdS, the IIIA-VA group semiconductor materials comprise one or more of InP and GaP, and the IB-IIIA-VIA group semiconductor materials comprise one or more of CuInS and CuGaS; the molar ratio of the doping element to the metal in the first doped metal oxide particles is (10-20):

100.

9. A film, characterized by, The material of the thin film comprises the composite material according to any one of claims 5-8.

10. The thin film according to claim 9, wherein, the surface roughness of the thin film is 0.5-1.5 nm; and / or the thickness of the thin film is 20-60 nm.

11. An optoelectronic device, characterized in that The photoelectric device comprises an anode, an electronic functional layer and a cathode which are sequentially stacked; the material of the electronic functional layer comprises the composite material according to any one of claims 7-8.

12. The photoelectric device according to claim 11, wherein, the anode and the cathode each independently comprise one or more of a metal, a carbon material and a metal oxide; the metal comprises one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb and Mg; the carbon material comprises one or more of graphite, carbon nanotube, graphene and carbon fiber; the metal oxide comprises a metal oxide electrode or a composite electrode with a metal arranged between a doped or non-doped transparent metal oxide, the material of the metal oxide electrode comprises one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, MoO3 and AMO, and the composite electrode comprises one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2 and TiO2 / Al / TiO2; and / or The photoelectric device further comprises a light-emitting layer between the anode and the electron functional layer, the material of the light-emitting layer comprising one or more of organic light-emitting materials and quantum dots; the organic light-emitting materials are selected from one or more of 4,4'-bis(N-carbazole)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine iridium (III)], 4,4',4"-tris(carbazole-9-yl) triphenylamine: tris[2-(p-tolyl)pyridine iridium], diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, TADF materials, polymers containing B-N covalent bonds, HLCT materials, Exciplex light-emitting materials; the quantum dots are selected from one or more of single-structure quantum dots, core-shell structure quantum dots and perovskite quantum dots; the material of the single-structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots are respectively selected from one or more of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the shell of the core-shell structure quantum dots comprises one or more layers; the II-VI group compounds are selected from one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compounds are selected from one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe.The III-V 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; the I-III-VI compound is selected from one or more of CuInS2, CuInSe2, and AgInS2; the core-shell quantum dot is selected from one or more of CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS, and InP / ZnSe / ZnS; the material of the perovskite quantum dot is selected from a doped or undoped inorganic perovskite semiconductor, or an organic-inorganic hybrid perovskite semiconductor; the inorganic perovskite semiconductor has a general structure of AMX3, where A is Cs; + ion, M is a divalent metal cation selected from one or more of Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ , and X is a halide anion selected from one or more of Cl - , Br - , I - ; the organic-inorganic hybrid perovskite semiconductor has a general structure of BMX3, where B is an organic amine cation selected from CH3(CH2) n-2 NH3 + , or [NH3(CH2) n NH3] 2+ , where n > 2, and M is a divalent metal cation selected from one or more of Pb 2+ , Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ Ge 2+ Yb 2+ Eu 2+ one or more of Cl - Br - I - ; and / or The photoelectric device further comprises a hole functional layer between the anode and the light-emitting layer; the material of the hole functional layer comprises an organic P-type semiconductor material or an inorganic P-type semiconductor material, wherein the organic P-type semiconductor material comprises 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-di(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(carbazol-9-yl)triphenylamine, trichloroisocyanuric acid, terbium-doped phosphate-based green light-emitting material, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butyphenyl)diphenylamine)], poly(4-butylphenyl-diphenylamine), poly[bi(4-phenyl)(4-butylphenyl)amine], polyaniline, polypyrrole, poly(p)phenylenevinylene, poly(phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene], copper phthalocyanine, aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraarylbiphenylamine, PEDOT, PEDOT:PSS and derivatives thereof, derivatives of PEDOT:PSS doped with s-MoO3, poly(N-vinylcarbazole) and derivatives thereof, polymethacrylate and derivatives thereof, poly(9,9-octylfluorene) and derivatives thereof, poly(spirofluorene) and derivatives thereof, N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine, spiro NPB, nanopolycrystalline diamond, microcrystalline cellulose and tetracyanoquinodimethane, doped graphene, non-doped graphene;The inorganic P-type semiconductor material includes one or more of second doped metal oxide particles, second undoped metal oxide particles, metal sulfides, metal selenides, and metal nitrides, the metal oxide in the second doped metal oxide particles and the metal oxide in the second undoped metal oxide particles each independently including one or more of MoO3, WO3, NiO, CrO3, CuO, V2O5, the dopant element in the second doped metal oxide particles including one or more of Mo, W, Ni, Cr, Cu, V, the metal sulfides including one or more of CuS, MoS3, WS3, the metal selenides including one or more of MoSe3, WSe3, and the metal nitrides including P-type gallium nitride.

13. A display device comprising: The photoelectric device comprises the photoelectric device according to any one of claims 11-12.

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