Photoelectric conversion device containing carbazole polyphosphate and high polymer material

Abstract

The invention discloses a carbazole polyphosphate-containing photoelectric conversion device and a polymer material, the carbazole polyphosphate material adopted by an electron transport layer in the photoelectric conversion device in the patent takes an aromatic ring except carbazole as a polymerization site, the molecular weight is higher, and the film-forming property, the conductivity and the stability are better; therefore, a stable photoelectric device based on novel carbazole polyphosphate is realized. The synthesis method of the carbazole polyphosphate high polymer material is simple and rapid, the reaction condition is mild, the obtained carbazole polyphosphate high polymer material is dissolved in a solvent and processed into a film, and then a photoelectric device based on the carbazole polyphosphate high polymer material is prepared.

Description

Technical Field

[0001] The present invention belongs to the field of solar cells, and particularly relates to a photoelectric conversion device and a polymer material containing polyphosphine carbazole. Background Art

[0002] Small molecule phosphine carbazole (PACz) is a hole transport material developed in recent years and has the advantage of solution processability. It can form a monolayer on conductive substrates (ITO and FTO). Compared with PTAA-based poly(triphenylamine) hole transport layer materials, the perovskite film has better wettability on phosphine carbazole, which is beneficial to the large-area coating of the perovskite film and realizes efficient hole transport in inverted perovskite photovoltaics. Nowadays, phosphine carbazole has become a commonly used hole transport material for inverted perovskite solar cells. Although the small molecule of phosphine carbazole has excellent hole transport performance, its own compactness and stability have always been problematic. The small molecule of phosphine carbazole needs to form a dense and uniform monolayer on the conductive substrate to achieve efficient hole transport. However, in the actual solution process, the small molecule of phosphine carbazole will form a multi-layer locally, increasing the resistance of hole extraction. The small molecule of phosphine carbazole will also diffuse into the perovskite active layer under light and heat conditions. In addition, on some rough conductive substrates, such as FTO, the small molecule of phosphine carbazole cannot completely cover the entire conductive substrate, making the perovskite film in direct contact with the conductive substrate. This situation causes local leakage on the one hand, and on the other hand, the conductive substrate will induce the decomposition of perovskite, resulting in the attenuation of perovskite solar cells (Science 2020, 370, 1300-1309; Nature 2023, 618, 80-86; Joule 2020, 4, 850-864; Nature Energy 2023, 8, 462-472). Developing new hole transport layer materials to solve the problems existing in the current small molecule of phosphine carbazole is an important step to improve the stability of inverted perovskite photovoltaic devices and promote their industrialization process.

[0003] To solve the problems of traditional small molecule phosphine carbazole, polyphosphine carbazole polymers have been developed in the field of perovskite photovoltaics (Joule 2023, 7, 2894-2904). This polymer uses carbazole as the polymerization site. Although its performance has been improved compared with small molecule phosphine carbazole, the polymerization of carbazole is difficult to achieve high molecular weight, thus limiting the molecular weight and conductivity of polyphosphine carbazole. Therefore, it is necessary to develop new polyphosphine carbazole polymer structures and polymerization methods. Summary of the Invention

[0004] The technical problems to be solved by the present invention are the problems of low conductivity, poor coverage, diffusion in the application of carbazole phosphate small molecules on a conductive substrate, and low molecular weight of existing poly(carbazole phosphate) polymers. The present invention provides a poly(carbazole phosphate) polymer material and a polymerization method, which have the characteristics of high molecular weight, good film-forming property, excellent stability, and difficult diffusion. Another technical problem to be solved by the present invention is to provide a preparation method of the above poly(carbazole phosphate) polymer material. The technical problem to be solved by the present invention is also to provide an application of the above poly(carbazole phosphate) polymer material in organic solar cells and perovskite solar cells.

[0005] During the research process of this patent, it was found that: by polymerizing the grafted carbazole and aromatic monomers of phosphoric acid, the molecular weight is increased, effectively improving the film-forming property on the surface of the conductive substrate, and a stable hole transport layer with a suitable thickness can be formed.

[0006] A photoelectric conversion device comprising poly(carbazole phosphate) has at least an electron transport layer, a perovskite material layer, and a hole transport layer; the photoelectric conversion device is a normal structure or an inverted structure; the hole transport layer contains or has on its surface a poly(carbazole phosphate) polymer material, and the poly(carbazole phosphate) polymer material contains a plurality of repeating units, and the structure of the repeating unit is as follows:

[0007]

[0008] In the formula, the benzene ring on the carbazole unit does not contain or contains substituents; Ar is an aryl group or a heteroaryl group;

[0009] The polymerization site is in the Ar unit, and Ar is selected from a monocyclic aryl group, a bicyclic aryl group, a polycyclic aryl group, a monocyclic heteroaryl group, a bicyclic heteroaryl group, or a polycyclic heteroaryl group, or a group obtained by fusing or connecting two or more of them, and each Ar may contain 1 to 5 aryl groups or heteroaryl groups.

[0010] In the structure of the poly(carbazole phosphate) of this patent, as long as the halogenated aromatic monomers (which can be dihalogenated or polyhalogenated) grafted with carbazole and phosphoric acid can be polymerized to a certain extent to increase the molecular weight, the film-forming property of the coated layer can be effectively improved. In the structure of the halogenated aromatic monomers grafted with carbazole and phosphoric acid, the halogenated aromatic monomer is directly substituted at any position of the benzene ring in carbazole, and the phosphoric acid group is connected to any position of the benzene ring on the halogenated aromatic monomer or any position of the benzene ring in carbazole.

[0011] The number of repeating units n in the polymer material can be from 2 to 10,000,000, preferably the number of repeating units is greater than 5, 8, 10, 15, 20, 25, 30, 50, 80, 100, 200, 500, 1000, 2000, 5000, etc., and can also be a parameter range composed of any integers within this range.

[0012] The poly(phosphinocarbazole) used in this patent is polymerized from small molecules. The small molecule carbazole here can adopt the structures disclosed in the prior art. In this patent, its molecular weight is increased after polymerization. As long as the small molecule carbazole has certain hole-transporting properties, the object of the present invention can be achieved. It can also be modified by some substituents to adjust and improve its performance.

[0013] When containing substituents, the benzene ring contains one or more independent substituents, and these independent substituents are selected from:

[0014] 1) H;

[0015] 2) Halogen groups;

[0016] 3) Cyano group;

[0017] 4) Alkyl groups;

[0018] 5) Aromatic groups;

[0019] 6) Fused-ring groups;

[0020] The value range of m is 0 - 40. The polymerization site of the poly(phosphinocarbazole) is at any position on Ar, and the value range of its molecular weight is 300 - 10,000,000. The value of m here can be 0, 1, 2, 3, 4, 5, 6, 10, 15, 20, etc., and can also be a parameter range composed of any integers within this range; the molecular weight is increased after polymerization, and the value can also be greater than 500, 800, 1000, 1500, 2000, 3000, 5000, 8000, 10000, 15000, 20000, 30000, 50000, 100000, 200000, etc., and can also be a parameter range composed of any integers within this range.

[0021] The alkyl groups mentioned above are selected from (C1 - C40) linear alkyl groups, (C3 - C40) branched alkyl groups or (C3 - C40) cycloalkyl groups.

[0022] The fused-ring groups are used to fuse the benzene ring into large rings such as naphthalene and anthracene.

[0023] The halogen groups mentioned above are F, Cl, Br or I.

[0024] The aromatic group is selected from one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl.

[0025] The repeating unit structure is one of the following structural formulas:

[0026]

[0027] Wherein the range of n is 2 - 10000000, and the independent value ranges of a and b are 0 - 40.

[0028] The polyphosphazene carbazole material with or without substituents provided in this patent is obtained by polymerizing small molecule phosphoester carbazole and hydrolyzing the ester group. Its polymerization site is at any position on non-carbazole. To realize the synthesis of this polymer material, the present invention gives the following synthesis idea. Polymerization is achieved through the catalytic reaction of phosphoester carbazole. In the reaction, halogenated phosphoester carbazole can be used for polycondensation, and the halogenated group can be at any position on non-carbazole. In this case, some phosphoester carbazole modified with substituents can also be used for the reaction; in addition, during the polymerization reaction, corresponding aromatic ring compounds can be added to copolymerize with phosphoester carbazole, and then halogenated silane and alcohol compounds are added to hydrolyze the polyphosphoester carbazole into polyphosphazene carbazole.

[0029] The preparation method of the above-mentioned polyphosphazene carbazole polymer material includes the following steps:

[0030] Step 1, grafted carbazole and the halogenated Ar unit of phosphoester are polymerized in a solvent with or without other polymerizable aromatic ring compounds.

[0031] Step 2, after adding halogenated silane and alcohol for hydrolysis, a polyphosphazene carbazole material is obtained.

[0032] In the grafted carbazole and the halogenated aromatic ring monomer of phosphoester, the benzene ring in the halogenated aromatic ring monomer is connected to any position on carbazole (such as any position on the benzene ring or N), and the P on the phosphoester is connected to any position on the benzene ring of the halogenated aromatic ring monomer, or is connected to the N on carbazole through or without an alkyl group.

[0033] Other polymerizable aromatic ring compounds refer to other halogenated aromatic ring compounds, arylstannanes, aryl borate esters; the other halogenated aromatic ring compounds are selected from halogenated aromatic hydrocarbons or halogenated thiophenes with or without substituents.

[0034] The aromatic group in the halogenated aromatic hydrocarbon is selected from one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl.

[0035] In the case of not adding other polymerizable aromatic ring compounds, the halogenated phosphate carbazole polymerizes by itself.

[0036] When other polymerizable aromatic ring compounds are added, polymerization occurs between the halogenated phosphate carbazole and other polymerizable aromatic ring compounds; the molar ratio of the phosphate carbazole to other polymerizable aromatic ring compounds is 1:0.01 - 10.0.

[0037] The polymerization reaction is carried out for 0.1 - 72 hours, and the reaction temperature is 0 - 300 °C.

[0038] The catalyst used in the catalytic polymerization reaction is selected from nickel-based catalysts or palladium catalysts.

[0039] Its preparation method can be any one of the following two reaction methods:

[0040] The halogenated compound shown in formula (I) undergoes self-polymerization under the action of a catalyst to obtain a polyaromatic ring phosphate carbazole compound shown in formula (II), and then halogenated silane and alcohols are further added for hydrolysis to obtain a polyphosphate carbazole material; among them, the benzene ring on the carbazole unit in the halogenated compound shown in formula (I) does not contain or contains substituents;

[0041]

[0042] Or, the halogenated compound shown in formula (I) and other polymerizable aromatic ring compounds shown in formula (III) carry out copolymerization under catalyst conditions to obtain a polyaromatic ring phosphate carbazole compound shown in formula (IV), and then halogenated silane and alcohols are further added for hydrolysis to obtain a polyphosphate carbazole material;

[0043]

[0044] X refers to a halogen, F, Cl, Br or I;

[0045] Ar’ also refers to an aromatic ring group, and its defined range is the same as that of the Ar unit, and the two can be the same or different;

[0046] R refers to a stannyl group or a borate group or a halogen.

[0047] In one embodiment, using dibromoaromatic ring phosphate carbazole as a raw material, catalytic reaction polymerization is carried out to obtain polyaromatic ring phosphate carbazole; polyaromatic ring phosphate carbazole and trimethylbromosilane are stirred and reacted in a solvent, and then excessive methanol is added for hydrolysis to obtain a polyphosphate carbazole polymer material, and the reaction equation is as follows:

[0048]

[0049] In the formula, n is an integer from 2 to 10000000, and Ar is an independent aromatic group.

[0050] In one embodiment, using dibromoaromatic ring phosphate carbazole and an aromatic group as raw materials, a catalytic reaction is carried out to obtain polycarbazole phosphate; the polycarbazole phosphate and trimethylbromosilane are stirred and reacted in a solvent, and then an excess of methanol is added for hydrolysis to obtain a polyphosphate carbazole polymer material. The reaction equation is as follows:

[0051]

[0052] In the formula, n is an integer from 2 to 10000000, and Ar and Ar' are independent aromatic groups.

[0053] In one embodiment, the compound of formula (I) is synthesized through the following steps:

[0054]

[0055] Application of the polyphosphate carbazole polymer material in the preparation of optoelectronic device structures.

[0056] The optoelectronic device structure is a solar cell, a field-effect transistor, a photodetector, a radiation detector, a light-emitting diode. The solar cell includes an organic solar cell and a perovskite solar cell.

[0057] The polyphosphate carbazole polymer material is used as a hole transport layer material in an organic solar cell or a perovskite solar cell, or is used for interface modification on the basis of the original hole transport layer.

[0058] In the above application, the battery structure is selected from one of the following:

[0059]

[0060] The perovskite light-absorbing layer includes metal halide perovskite with the chemical formula ABX3, where A includes but is not limited to methylamine ion, formamidine ion, cesium, rubidium, potassium, sodium, ammonium ion, ethylamine, propylamine, butylamine, aniline, benzylamine, phenethylamine or a combination of the above components; B includes lead, tin, cadmium, germanium, zinc, nickel or a combination of the above components. X is a fluoride, chloride, bromide, iodide anion or a combination of the above components.

[0061] Specifically, the solar cell electrode contains one or several of gold, silver, copper, aluminum, carbon, chromium. The hole transport layer includes PTAA, Spiro-OMeTAD, PEDOT:PSS, NiO, MoO3, V2O5, Poly-TPD, EH44, P3HT or a combination of the above materials. The electron transport layer includes C 60, BCP, TiO2, SnO2, PCBM, ICBA, ZnO, ZrAcac, LiF, TPBi, PFN, Nb2O5, or combinations of the above materials.

[0062] Specifically, the perovskite solar cell has a photoelectric conversion efficiency of 1% to 35%.

[0063] The organic solar cell has a photoelectric conversion efficiency of 1% to 25%.

[0064] Beneficial effects:

[0065] 1) The polyphosphazene carbazole polymer material provided by the present invention has a higher molecular weight, better stability and film-forming property. The interaction between its polymer chains can effectively solve the problems of poor compactness and easy diffusion of traditional phosphazene carbazole small molecules, thus realizing stable optoelectronic devices based on polyphosphazene carbazole.

[0066] 2) The synthesis method of the polyphosphazene carbazole is simple and fast, and the reaction conditions are mild. The obtained polyphosphazene carbazole material is dissolved in single or mixed solvents such as toluene, chlorobenzene, chloroform, dichloromethane, methanol, ethanol, isopropanol, etc., and processed into a film by processes such as spin coating, blade coating, slot coating, dip coating, spray coating, etc., to prepare optoelectronic devices based on polyphosphazene carbazole materials, including perovskite solar cells, organic solar cells, field effect transistors, light emitting diodes, photodetectors, radiation detectors, etc.

[0067] 3) The present invention has both important scientific significance and extremely high industrial value. Description of the drawings

[0068] Figure 1 is the current-voltage curve graph of a perovskite solar cell based on Me-4PACz, Poly-4PACz and novel Polymer-1 polymer. Figure 2 is the stability test graph of a perovskite solar cell based on phosphazene carbazole small molecules, traditional polyphosphazene carbazole and novel polyphosphazene carbazole. Detailed implementation manners

[0069] Example 1

[0070]

[0071] Compound 2: Dissolve 2,6-dibromo-4-fluorobenzaldehyde (2 g, 7.1 mmol) in 50 mL of anhydrous ethanol. Add sodium borohydride (1 g, 26.4 mmol) under stirring at 0 °C for 4 hours. Quench the reaction with dilute hydrochloric acid (1 M, 15 mL). Extract with ethyl acetate (3 × 50 mL). Dry the ethyl acetate phase with anhydrous sodium sulfate and remove ethyl acetate by rotary evaporation under reduced pressure to obtain the crude product. Purify by silica gel column chromatography (eluting with petroleum ether / ethyl acetate in a ratio of 50:1 - 20:1) to obtain 1.5 g of white solid 2,6-dibromo-4-fluorobenzyl alcohol (yield 75%). The structural formula is as follows:

[0072]

[0073] Compound 3: Dissolve 2,6-dibromo-4-fluorobenzyl alcohol (1.5 g, 5.3 mmol) in 20 mL of dichloromethane. Slowly drop phosphorus tribromide (0.72 g, 2.65 mmol) into the 2,6-dibromo-4-fluorobenzyl alcohol solution at 0 °C and slowly heat to reflux for 6 hours. Cool to room temperature and add 20 mL of water to quench the reaction. Take the dichloromethane phase, dry it with anhydrous sodium sulfate, and remove dichloromethane by rotary evaporation under reduced pressure to obtain the crude product. Purify by silica gel column chromatography (eluting with petroleum ether) to obtain 1.47 g of white solid 1,3-dibromo-4-fluorobenzyl bromide (yield 80%). The structural formula is as follows:

[0074]

[0075] Compound 4: Dissolve 3.46 g of 1,3-dibromo-2-methylbromo-5-fluorobenzene in 100 mL of triethyl phosphite and heat with stirring at 140 °C for 12 hours. Remove triethyl phosphite by distillation under reduced pressure to obtain the crude product. Purify by silica gel column chromatography using dichloromethane and ethyl acetate as mobile solvents to obtain 3.2 g of 1,3-dibromo-2-methylphosphate-5-fluorobenzene. The structural formula is as follows:

[0076]

[0077] Compound 5: Take 1,3-dibromo-2-methylphosphate-5-fluorobenzene (2.42 g, 6 mmol), carbazole (0.25 g, 1.5 mmol), and cesium carbonate (2.0 g, 6 mmol). Then add 10 mL of dimethylacetamide (DMAC) and reflux with stirring at 170 °C for 24 hours. After the reaction is completed, wait for the reaction solution to cool to room temperature, dilute it with a small amount of dichloromethane solution, pour it into a separatory funnel, and extract with water multiple times. Take the dichloromethane phase and remove the dichloromethane solvent by rotary evaporation to obtain the crude product. Purify the crude product by silica gel column chromatography using dichloromethane and petroleum ether as the mobile phase to obtain 0.27 g of the target product as a white solid with a yield of 33%. The structural formula is as follows:

[0078]

[0079] Compound 6: Dissolve 1 g of Ni(cod)2, 0.567 g of bipyridine, and 0.5 mL of 1,5-cyclooctadiene in 10 mL of DMF, heat and stir at 80 °C for half an hour. Dissolve 1.67 g in 10 mL of DMF and dissolve 1.67 g of Compound 5 in 10 mL of DMF, slowly add dropwise to the reaction system, and continue stirring at 80 °C for 12 hours. After the reaction is completed, cool to room temperature, slowly add dropwise dilute hydrochloric acid under stirring until the solution becomes a transparent green solution, filter to obtain the suspended solid, and the final product is a brown polymer 6 (0.87 g, yield 75%), and the structural formula is as follows:

[0080]

[0081] Compound 7: Dissolve 0.1 g of polymer 6 in 20 mL of dichloromethane, add 0.12 g of trimethylbromosilane dropwise, stir at room temperature for 12 hours. After the reaction is completed, add dropwise excessive methanol to the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate in diethyl ether, and filter and wash with diethyl ether. The final product is a brown polyphosphoric carbazole powder (Polymer-1), and the structural formula is as follows:

[0082]

[0083] Example 2

[0084]

[0085] Synthesize the above poly(3-phosphate-4-carbazolethiophene) according to a similar method, add trimethylbromosilane dropwise, stir at room temperature for 12 hours. After the reaction is completed, add dropwise excessive methanol to the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate in diethyl ether, and filter and wash with diethyl ether. The final product is poly(3-phosphate-4-carbazolethiophene) powder (Polymer-2).

[0086] Example 3

[0087]

[0088] Synthesize the above polyphosphate carbazole benzene according to a similar method, add trimethylbromosilane dropwise, stir at room temperature for 12 hours. After the reaction is completed, add dropwise excessive methanol to the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate in diethyl ether, and filter and wash with diethyl ether. The final product is polyphosphate carbazole benzene powder (Polymer-3).

[0089] Example 4

[0090]

[0091] Synthesize the above poly(p-phenylenediphosphonate)carbazolebenzene by a similar method. Drop trimethylbromosilane and stir at room temperature for 12 hours. After the reaction is completed, drop excessive methanol into the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate it in diethyl ether, and filter and wash it with diethyl ether. The final product is poly(p-phenylenediphosphonate)carbazolebenzene powder (Polymer-4).

[0092] Example 5

[0093]

[0094] Synthesize the above poly(phosphonate)carbazolethiophene by a similar method. Drop trimethylbromosilane and stir at room temperature for 12 hours. After the reaction is completed, drop excessive methanol into the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate it in diethyl ether, and filter and wash it with diethyl ether. The final product is poly(phosphonate)carbazolethiophene powder (Polymer-5).

[0095] Example 6

[0096]

[0097] Synthesize the above poly(diphenylenediphosphonate)carbazolethiophene by a similar method. Drop trimethylbromosilane and stir at room temperature for 12 hours. After the reaction is completed, drop excessive methanol into the reaction system to react and remove the excessive trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate it in diethyl ether, and filter and wash it with diethyl ether. The final product is poly(diphenylenediphosphonate)carbazolethiophene powder (Polymer-6).

[0098] Example 7

[0099] Place the ITO conductive glass in an ultraviolet ozone cleaning machine for 15 minutes, and then spin-coat different concentrations (0.3 mg / mL to 3 mg / mL) of small molecule phosphonate carbazole or the above poly(phosphonate)carbazole on it and perform annealing treatment at 100 °C. Subsequently, spin-coat MA 0.7 FA 0.3 PbI3 perovskite polycrystalline thin film. After thermal annealing of the thin film, deposit 25 nm of C 60 , 5 nm of BCP and 100 nm of copper electrode on its surface to complete the preparation of the perovskite solar cell.

[0100] Comparative experiment: To compare the performance of poly(phosphonate)carbazole, a small molecule phosphonate carbazole (Me-4PACz) and a hole transporting poly(phosphonate)carbazole (Poly-4PACz) were used for comparison.

[0101]

[0102] The prepared perovskite solar cell was placed under a 3A-class solar simulator with a solar light intensity of 100 mW / cm 2 . The current-voltage curve of the perovskite solar cell was scanned and recorded. The maximum value of the product of the current and voltage in the current-voltage curve was used as the maximum output power of the perovskite solar cell. The photoelectric conversion efficiency of the perovskite solar cell was obtained by dividing the maximum output power per unit area of the perovskite solar cell by the solar spectral intensity. The results are shown in Table 1 and Figure 1 as follows.

[0103] Table 1 Device parameters of perovskite solar cells prepared from the materials obtained in Examples 1-6

[0104]

[0105] Table 1 shows the device parameters of perovskite solar cells prepared from the materials obtained in Examples 1-6. It can be seen from Table 1 that the perovskite solar cells based on the novel polyphosphazene carbazole all achieved higher photoelectric conversion efficiencies than the small molecule phosphazene carbazole and the traditional polyphosphazene carbazole.

[0106] Example 8

[0107] After encapsulating the perovskite solar cells based on the small molecule phosphazene carbazole (Me-4PACz), the traditional polyphosphazene carbazole (Poly-4PACz), and the novel polyphosphazene carbazole (Polymer-1), they were placed under the solar simulator for stability testing at the maximum power point of the solar cell. After more than 100 hours of testing, the results are shown in Figure 1 .

[0108] As Figure 2 can be seen, no obvious efficiency decay was found in the perovskite solar cells based on the novel polyphosphazene carbazole, while the perovskite solar cells based on the small molecule phosphazene carbazole decayed severely, indicating that the polyphosphazene carbazole material has better light stability compared to the small molecule phosphazene carbazole and the traditional polyphosphazene carbazole.

Claims

1. A photoelectric conversion device comprising polyphosphazene carbazole, which at least has an electron transport layer, a perovskite material layer, and a hole transport layer; the photoelectric conversion device is a normal structure or an inverted structure; a polyphosphazene carbazole polymer material is included in or on the surface of the hole transport layer, and the polyphosphazene carbazole polymer material comprises a plurality of repeating units, characterized in that, The repeating unit structure is as follows: In the formula, the benzene ring on the carbazole unit does not contain or contains substituents; Ar is an aryl group or a heteroaryl group; When containing substituents, the benzene ring contains a single or multiple independent substituents, and these independent substituents are selected from: 1)H； 2) Halogen groups; 3) Cyano groups; 4) Alkyl groups; 5) Aromatic groups; 6) Fused-ring groups; The value range of m is 0 - 40, and the polymerization site of polyphosphoric acid carbazole is at any position on Ar, and the value range of n is 2 - 100000000.

2. The optoelectronic conversion device according to claim 1, wherein The value range of the molecular weight of the polymer material is 300 - 10000000; the alkyl group is selected from (C1 - C40) linear alkyl groups, (C3 - C40) branched alkyl groups or (C3 - C40) cycloalkyl groups; the fused-ring group is used to fuse the benzene ring into large rings such as naphthalene and anthracene; the halogen group is F, Cl, Br or I; the aromatic group is selected from one or more of aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, arylcarbonyl groups, heteroarylcarbonyl groups, arylcarbonyloxy groups, heteroarylcarbonyloxy groups, aryloxycarbonyl groups or heteroaryloxycarbonyl groups.

3. The optoelectronic conversion device according to claim 1, wherein Ar is selected from monocyclic aryl groups, bicyclic aryl groups, polycyclic aryl groups, monocyclic heteroaryl groups, bicyclic heteroaryl groups or polycyclic heteroaryl groups, or groups obtained by fusing or connecting two or more of them, and each Ar may contain 1 - 5 aryl groups or heteroaryl groups.

4. The optoelectronic conversion device according to claim 1, characterized in that, The repeating unit structure is one of the following structural formulas: Wherein the value range of n is 2 - 10000000, and the independent value ranges of a and b are 0 - 40.

5. The optoelectronic conversion device according to claim 1, characterized in that, The preparation method of the polyphosphoric acid carbazole polymer material includes the following steps: Step 1: The grafted carbazole and the halogenated Ar unit of the phosphate ester undergo self-polymerization or copolymerization in a solvent with or without the addition of other polymerizable aromatic ring compounds; Step 2: After adding halogenated silane and alcohols for hydrolysis, a polyphosphoric acid carbazole material is obtained; In the grafted carbazole and the halogenated aromatic ring monomer of the phosphate ester, the benzene ring in the halogenated aromatic ring monomer is connected to any position on the carbazole, and the P on the phosphate ester is connected to any position on the benzene ring in the halogenated aromatic ring monomer, or is connected to the N on the carbazole through or without an alkyl group.

6. The optoelectronic conversion device according to claim 5, characterized in that, Other polymerizable aromatic ring compounds refer to other halogenated aromatic ring compounds, arylstannanes, arylboronic esters; the other halogenated aromatic ring compounds refer to halogenated aromatic hydrocarbons or halogenated thiophenes with or without substituents; the aromatic group in the halogenated aromatic hydrocarbon is selected from one or more of aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, arylcarbonyl groups, heteroarylcarbonyl groups, arylcarbonyloxy groups, heteroarylcarbonyloxy groups, aryloxycarbonyl groups or heteroaryloxycarbonyl groups; in the case of not adding other polymerizable aromatic ring compounds, the grafted carbazole and the halogenated Ar of the phosphate ester polymerize by themselves; when adding other polymerizable aromatic ring compounds, the grafted carbazole and the halogenated Ar of the phosphate ester polymerize with other polymerizable aromatic ring compounds; the mass ratio of halogenated Ar to other polymerizable aromatic ring compounds is 1:0.01 - 10.0, the polymerization reaction is 0.1 - 72 hours, and the reaction temperature is 0 - 300 °C.

7. The optoelectronic conversion device according to claim 5, characterized in that, It is any one of the following two reaction methods: The first: The halogenated compound shown in formula (I) undergoes self-polymerization under the action of a catalyst to obtain a polyaryl phosphate carbazole compound shown in formula (II), and then a halogenated silane and an alcohol are further added for hydrolysis to obtain a polyphosphate carbazole material, and the degree of hydrolysis is from 1% to 100%; wherein, the benzene ring on the carbazole unit in the halogenated compound shown in formula (I) does not contain or contains substituents; The second method: The halogenated compound shown in formula (I) and other polymerizable aromatic ring compounds shown in formula (III) are copolymerized under the condition of a catalyst to obtain a polyaryl phosphate carbazole compound shown in formula (IV), and then a halogenated silane and an alcohol are further added for hydrolysis to obtain a polyphosphate carbazole material; X refers to a halogen, F, Cl, Br or I; Ar' also refers to an aromatic ring group, and its defined range is the same as that of the Ar unit, and the two can be the same or different; R refers to a stannyl group or a borate group or a halogen.

8. The optoelectronic conversion device according to claim 1, characterized in that, Its structure is a solar cell, a field effect transistor, a photodetector, a radiation detector or a light emitting diode, and the solar cell includes an organic solar cell and a perovskite solar cell; The polyphosphate carbazole material is used as a hole transport layer material in an organic solar cell or a perovskite solar cell, or is used for interface modification on the basis of an original hole transport layer.

9. The structure of the optoelectronic conversion device according to claim 7, wherein, The battery structure is selected from one of the following:

10. A polycarbazole polyphosphoric acid polymer material, characterized in that, It contains a plurality of repeating units, and is characterized in that the repeating unit structure is as follows: In the formula, the benzene ring on the carbazole unit does not contain or contains substituents; Ar is an aryl group or a heteroaryl group; When containing substituents, the benzene ring contains single or multiple independent substituents, and these independent substituents are selected from: 1)H； 2) a halogen group; 3) a cyano group; 4) an alkyl group; 5) an aromatic group; 6) a fused ring group; The value range of m is 0-40, and the polymerization site of the polyphosphate carbazole is at any position on Ar, and the value range of n is 2-100000000.

Images