Carbazole polyphosphate material, manufacturing method and application to photoelectric devices

Abstract

The present invention discloses a carbazole polyphosphate material and its manufacturing method and application, which belongs to the field of material manufacturing. [Solution] The polycarbazole phosphate material provided by the present invention has better stability, and its excellent film-forming properties and interactions with polymer chains effectively solve the problems of traditional carbazole phosphate small molecules, such as weak compactness and easy diffusion, thereby realizing stable photoelectric devices based on polycarbazole phosphate. The synthesis method of this polycarbazole phosphate is simple and rapid, and the reaction conditions are mild. The resulting polycarbazole phosphate material can be dissolved in a single or mixed solvent, such as toluene, chlorobenzene, chloroform, methylene chloride, methanol, ethanol, or isopropanol, and processed into a film by processes such as spin coating, blade coating, slit coating, dip coating, or spray coating, and then used to fabricate photoelectric devices based on the polycarbazole phosphate material. This application is of great scientific significance and is of great industrial value.

Description

[Technical Field]

[0001] The present invention is in the field of materials manufacturing, and more particularly relates to carbazole polyphosphate materials and their manufacturing methods and applications. [Background technology]

[0002] Small molecule phosphate carbazole (PACz) is a recently developed hole transport material. It has the advantage of being solution-processable and can form monolayers on conductive substrates (ITO and FTO). Compared with PTAA (Poly(triarylamine)-based polytriphenylamine) hole transport layer materials, PACz exhibits superior wettability of perovskite films on PACz, which is beneficial for large-area coating of perovskite films and enables efficient hole transport in trans-perovskite solar cells. Currently, PACz has become the commonly used hole transport material in trans-perovskite solar cells. While PACz has excellent hole transport properties, its compactness and stability have always been issues. To achieve efficient hole transport, PACz needs to form a dense, uniform monolayer on conductive substrates. However, in actual solution processing, PACz forms local multilayers, increasing resistance to hole extraction. The carbazole phosphate small molecules can also diffuse into the perovskite active layer under photothermal conditions. Furthermore, on some rough conductive substrates, such as FTO, the carbazole phosphate small molecules cannot completely cover the entire conductive substrate, resulting in direct contact between the perovskite film and the conductive substrate. This situation can lead to localized leakage and, on the one hand, the conductive substrate can induce perovskite decomposition, resulting in decay of the perovskite solar cell (Science 2020, 370, 1300-1309; Nature 2023, https: / / doi.org / 10.1038 / s41586-41023-05992-y; Joule 2020, 4, 850-864; Nature Energy 2023, https: / / doi.org / 10.1038 / s41560-41023-01227-41566). Developing novel hole transport layer materials to solve the current problems of small-molecule carbazole phosphate is an important step to improve the stability of trans-perovskite photovoltaics and promote their industrialization. Summary of the Invention [Problem to be solved by the invention]

[0003] The technical problem solved by the present invention is that when carbazole phosphate small molecules are applied to conductive substrates, they have high hole resistance, insufficient coverage, and may diffuse. The present invention provides a polycarbazole phosphate material that has excellent film-forming properties, excellent stability, and is less likely to diffuse. Another technical problem solved by the present invention is to provide a method for producing the polycarbazole phosphate material. Another technical problem solved by the present invention is to provide the application of the polycarbazole phosphate material to organic solar cells and perovskite solar cells. [Means for solving the problem]

[0004] During the research process of this patent, it was discovered that by polymerizing small molecule carbazole phosphate to increase its molecular weight, it is possible to effectively improve the film formation properties on the surface of a conductive substrate and form a stable hole transport layer with an appropriate thickness.

[0005] The carbazole polyphosphate material comprises a plurality of repeating units, the repeating units having the structure: [ka] wherein the benzene ring in the carbazole phosphate unit contains no or no substituents; In the polycarbazole phosphate structure of the present invention, if the small molecular weight carbazole phosphate can be polymerized to a certain extent to increase the molecular weight, the coating film forming properties after application can be effectively improved. The number of repeating units in the polymerized material can be 2 to 10,000,000, and preferably the number of repeating units can be more than 5, 8, 10, 15, 20, 25, 30, 50, 80, 100, 200, 500, 1,000, 2,000, 5,000, etc., or can be within a parameter range consisting of any integer within the range.

[0006] The polycarbazole phosphate used in this patent is polymerized from small molecules. The small molecule carbazole phosphate used here can adopt the structure disclosed in the prior art, and in this patent, by polymerizing it to increase the molecular weight, the objective of the present invention can be achieved as long as it is a small molecule carbazole phosphate with a certain degree of hole transport property, and its performance can also be adjusted and improved by modifying it with some substituents.

[0007] When no substituents are present, the benzene ring contains one or more independent substituents, and these independent substituents are: 1) H, 2) halogen groups, 3) a cyano group, 4) alkyl groups, 5) aromatic group, 6) Ring-fused group The value of n is selected from the group consisting of 1 to 40, the polymerization site of the carbazole polyphosphate is located at any position on the benzene ring, and the molecular weight ranges from 300 to 10,000,000. Here, the value of n may be 1, 2, 3, 5, 10, 15, or 20, or may be within a parameter range formed from any integer within the range, and the molecular weight increases after polymerization and can exceed 500, 800, 1,000, 1,500, 2,000, 3,000, 5,000, 8,000, 10,000, 15,000, 20,000, 30,000, 50,000, 100,000, or 200,000, or may be within a parameter range formed from any integer within the range.

[0008] The alkyl is selected from (C1-C40) straight chain alkyl, (C3-C40) branched chain alkyl, or (C3-C40) cyclic alkyl.

[0009] The ring condensing groups described above are used to condense a benzene ring to a larger ring such as naphthalene or anthracene.

[0010] The halogen group is F, Cl, Br or I.

[0011] The aromatic group is one or more selected from aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, or heteroaryloxycarbonyl.

[0012] The structure of the repeating unit is one of the following structural formulas: [ka] In the formula, m ranges from 2 to 10,000,000, and R1, R2, and R3 are H or the above-mentioned substituents.

[0013] The polyphosphate carbazole material provided in this patent, with or without substituents, can be obtained by polymerizing a small molecule phosphate ester carbazole and hydrolyzing the ester group, with the polymerization site located at any position on the benzene ring. To synthesize the polymerized material, the present invention provides the following synthesis idea: the polymerization is achieved by catalytic polycondensation of phosphate carbazole. In the reaction, a halogenated phosphate ester carbazole can be used for polycondensation, and the halogen group can be located at any position on the benzene ring. In this case, a phosphate ester carbazole modified with several substituents can also be used in the reaction. Alternatively, a corresponding halogenated compound can be added during the polycondensation reaction to copolymerize with the phosphate ester carbazole, and then a halogenated silane or an alcohol compound can be added to hydrolyze the polyphosphate ester carbazole into polyphosphate carbazole.

[0014] The method for producing the carbazole polyphosphate material includes the steps of: Step 1: copolymerizing a halogenated phosphate ester carbazole in a solvent with or without the addition of other halogenated compounds; and Step 2 includes adding a halogenated silane and an alcohol system and hydrolyzing the mixture to obtain a carbazole polyphosphate material.

[0015] The halogenated compound is selected from halogenated arenes or halogenated thiophenes, with or without substituents.

[0016] The aromatic group in the halogenated arene is one or more selected from aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, or heteroaryloxycarbonyl.

[0017] Halogenated phosphate ester carbazoles self-polymerize without the addition of other halogenated compounds.

[0018] When other halogenated compounds are added, the halogenated phosphate ester carbazole polymerizes with the other halogenated compounds, the mass ratio of the phosphate ester carbazole to the halogenated compounds is 1:0.01-10.0, the polymerization reaction time is 0.1-72 hours, and the reaction temperature is 0-300°C.

[0019] The catalyst used in the above catalytic polymerization reaction is selected from nickel-based catalysts.

[0020] The phosphate ester carbazole may include one or more of the following structural units: [ka] The value of n ranges from 1 to 40.

[0021] Rx independently 1) H, 2) halogen groups, 3) a cyano group, 4) alkyl groups, 5) aromatic group, 6) Ring-fused group wherein the halogen group is F, Cl, Br or I.

[0022] The alkyl is selected from (C1-C40) straight chain alkyl, (C3-C40) branched chain alkyl, or (C3-C40) cyclic alkyl.

[0023] In the above alkyl, one or more non-adjacent C atoms may optionally be -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -CR 0 =CR 00 - or -C≡C-, where R 0 and R 00 is independently a straight chain alkyl, a branched chain alkyl, or a cyclic alkyl.

[0024] In the above alkyl, one or more H atoms may optionally be replaced by F, Cl, Br, I or CN.

[0025] The aromatic group is selected from aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, or heteroaryloxycarbonyl, each having 4 to 30 ring members.

[0026] In one embodiment, dibromophosphate carbazole is used as raw material to undergo catalytic polymerization to obtain polycarbazole phosphate, and polycarbazole phosphate and trimethylbromosilane are stirred in a solvent to react with each other, and then excess methanol is added for hydrolysis to obtain polycarbazole phosphate material, the reaction formula is as follows: [ka]

[0027] In one embodiment, dibromophosphate carbazole and aromatic group are used as raw materials to undergo catalytic reaction to obtain polycarbazole phosphate, and polycarbazole phosphate and trimethylbromosilane are stirred in a solvent to react with each other, and then excess methanol is added for hydrolysis to obtain polycarbazole phosphate material. The reaction formula is as follows: [ka] In the formula, n is an integer of 40 or less, m is an integer of 2 to 10,000,000, and Ar is an aromatic group.

[0028] Application of carbazole polyphosphate materials to the fabrication of photovoltaic device structures.

[0029] The above-mentioned photoelectric device structures include solar cells, field effect transistors, photoelectric detectors, radiation detectors, and light-emitting diodes, and the above-mentioned solar cells include organic solar cells and perovskite solar cells.

[0030] The above carbazole polyphosphate materials are used as hole transport layer materials in organic solar cells or perovskite solar cells, or for interface modification based on the original hole transport layer.

[0031] In the above application, the battery structure is [Table 0] It is one of the following.

[0032] The perovskite light-absorbing layer includes a metal halide perovskite having the chemical formula ABX3, where A is, but is not limited to, a methylamine ion, a formamidine ion, cesium, rubidium, potassium, sodium, ammonium ion, ethylamine, propylamine, butylamine, aniline, benzylamine, phenethylamine, or a combination of the above components, B is, but is not limited to, a lead, tin, cadmium, germanium, zinc, nickel, or a combination of the above components, and X is an anion of fluorine, chlorine, bromine, or iodine, or a combination of the above components.

[0033] Specifically, the solar cell electrode may include one or more of gold, silver, copper, aluminum, carbon, and chromium. The hole transport layer may include PTAA, Spiro-OMeTAD (2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonic acid)), NiO, MoO3, VO5, Poly-TPD (N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine), EH44 (9-(2-ethylhexyl)-N,N,N,N-tetra(4-methoxyphenyl)-9H-carbazole-2,7-diamine), P3HT (poly(3-hexylthiophene)), or a combination of the above materials. The electron transport layer may include C 60 , BCP (Bathocuproine), TiO2, SnO2, PCBM (Phenyl-C61-hydrochloric acid methyl ester), ICBA (Indene-C60 diadduct), ZnO, ZrAcac (Zirconium acetylacetonate), LiF, TPBi (1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl), PFN (Poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]), Nb2O5, or a combination of the above materials.

[0034] Specifically, perovskite solar cells have a photoelectric conversion efficiency of 1% to 30%.

[0035] Organic solar cells have a photoelectric conversion efficiency of 1% to 20%. [Effects of the Invention]

[0036] 1) The polycarbazole phosphate polymer material provided by the present invention has better stability and film-forming properties. Due to the interaction between polymer chains, it can effectively solve the problems of traditional carbazole phosphate small molecules, such as weak compactness and easy diffusion, and realize stable photoelectric devices based on polycarbazole phosphate. 2) The synthesis method of the carbazole polyphosphate is simple and rapid, and the reaction conditions are mild. The obtained carbazole polyphosphate material can be dissolved in a single or mixed solvent such as toluene, chlorobenzene, chloroform, methylene chloride, methanol, ethanol, isopropanol, etc., and processed into a film by processes such as spin coating, blade coating, slit coating, dip coating, and spray coating to manufacture optoelectronic devices based on the carbazole polyphosphate material. The optoelectronic devices include perovskite solar cells, organic solar cells, field effect transistors, light-emitting diodes, photoelectric detectors, and radiation detectors. 3) The present invention has great scientific significance and is of great industrial value. [Brief explanation of the drawings]

[0037] [Figure 1] Stacking morphology of small molecule carbazole phosphate (left) and carbazole polyphosphate (right) materials on conductive ITO and current distribution diagrams obtained by conductive atomic force microscopy. [Figure 2] FIG. 1 shows the current-voltage curves of carbazole polyphosphate perovskite solar cells with varying annealing temperature. [Figure 3] Figure 1 shows the current-voltage curves of carbazole phosphate small molecule perovskite solar cells with varying annealing temperature. [Figure 4] FIG. 1 shows the current-voltage curves of carbazole polyphosphate perovskite solar cells with varying concentrations. [Figure 5] Figure 1 shows the current-voltage curves of carbazole phosphate small molecule perovskite solar cells with varying concentrations. [Figure 6] Figure 1 shows the current-voltage curves of an optimized perovskite solar cell using carbazole polyphosphate on an ITO / FTO substrate. [Figure 7] FIG. 1 shows the curves of long-term stability studies. DETAILED DESCRIPTION OF THE INVENTION [Example]

[0038] 3.25g of 3,6-dibromocarbazole and 2.1g of potassium carbonate were dissolved in 20mL of 1,4-dibromobutane, and 0.485g of tetrabutylammonium bromide was added, followed by 5.2mL of 50% potassium hydroxide, and the mixture was stirred at 60°C for 12 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure and filtered to obtain the product, which was purified through a column to obtain 4.1g of 3,6-dibromo-9-(4-bromobutyl)-9-hydrocarbazole. The structural formula is as follows: [ka] 1 H NMR(400MHz,CDCl3,ppm):8.15(d,J=1.9Hz,2H),7.55(dd,J=8.6Hz,2.0Hz,2H),7.25(d,2.1Hz 2H),4.30(t,7.3Hz,2H),3.37(t,6.4Hz,2H),2.07-1.99(m,2H),1.91-1.85(m,2H). 13 C NMR(400MHz, CDCl3, ppm):139.21,129.21,123.58,123.41,112.25,110.28,42.52,32.84,30.06. [Example]

[0039] 1 g of 3,6-dibromo-9-(4-bromobutyl)-9-hydrocarbazole was dissolved in 10 mL of triethyl phosphite, and the mixture was heated and stirred at 140°C for 12 hours. The triethyl phosphite was removed by distillation under reduced pressure, and the mixture was purified through a column to obtain dimethyl (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate. The structural formula is as follows: [ka] 1 H NMR(400MHz,CDCl3,ppm):8.12(d,2.1Hz,2H),7.54(dd,J=8.7Hz,1.9Hz,2H),7.25(d,8.9H z,2H),4.25(t,J=7.9Hz,2H),3.96-4.06(m,4H),1.61-1.96(m,6H),1.25(t,J=7.1Hz,6H). 13 C NMR(400MHz,CDCl3,ppm):139.22,129.13,123.53,123.33,112.15,110.33,61.63,42.68,26.12,24.78,20.46,16.46. [Example]

[0040] 0.8g of Ni(Cod)2, 0.286g of bipyridine, and 0.23mL of 1,5-cyclooctadiene were dissolved in 10mL of DMF and stirred at 80°C for 0.5 hours. 0.5g of diethyl (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate was dissolved in 10mL of DMF and slowly added dropwise to the reaction system. The mixture was stirred at 80°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, and dilute hydrochloric acid was slowly added dropwise with stirring until a clear green solution was formed. The suspended solid was filtered and collected. The final product was a brown polyphosphate ester carbazole powder. The structural formula is as follows: [ka] [Example]

[0041] 0.12g of polyphosphate ester carbazole was dissolved in 20mL of methylene chloride, 2mL of 0.1g / mL trimethylbromosilane was added dropwise, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, excess methanol was added dropwise to the reaction mixture to remove the excess trimethylbromosilane. The solution was concentrated by vacuum distillation, precipitated in ethyl ether, and filtered and rinsed with ethyl ether. The final product was polyphosphate carbazole powder with a number-average molecular weight of about 1800 and a weight-average molecular weight of about 2300. The structural formula is as follows: [ka] [Example]

[0042] The ITO conductive glass was placed in an ultraviolet ozone cleaning device and treated for 15 minutes, then blade-coated with small molecule phosphate carbazole or polyphosphate carbazole at different concentrations (0.3 mg / ml to 3 mg / ml) and annealed at 100 °C, 150 °C, and 200 °C, respectively. 0.7 FA 0.3 PbI3 perovskite polycrystalline films were blade coated, and after thermal annealing of the films, 25 nm of C was deposited on the surface. 60 The fabrication of the perovskite solar cell was completed by depositing 5 nm of BCP and a 100 nm copper electrode.

[0043] Comparative experiment: To compare the performance of polycarbazole phosphate, the small molecule carbazole phosphate (Me-4PACz) shown in the following figure was used for comparison, and the carbazole phosphate prepared in Example 2 was used. [ka]

[0044] Small molecule carbazole phosphate (Me-4PACz) and polycarbazole phosphate (Poly-4PACz) were blade-coated onto ITO conductive glass. As shown in Figure 1, the small molecule carbazole phosphate on ITO had poor coverage, resulting in localized deposition of multiple layers, resulting in low current and high electrical resistance in conductive atomic force microscopy tests. In contrast, polycarbazole phosphate had good coverage and film-forming properties on ITO, resulting in high current and low electrical resistance in conductive atomic force microscopy tests, contributing to hole extraction.

[0045] The research results on the annealing temperature of small molecule carbazole phosphate (Me-4PACz) or polycarbazole phosphate (Poly-PACz) are shown in Figure 2, Figure 3 and Table 1. Figure 2 shows the current-voltage curves of polycarbazole phosphate perovskite solar cells with varying annealing temperatures, and Figure 3 shows the current-voltage curves of small molecule carbazole phosphate perovskite solar cells with varying annealing temperatures. It is clear that small molecule carbazole phosphate is sensitive to the annealing temperature, while polycarbazole phosphate material is less sensitive to the annealing temperature.

[0046] Table 1. Device parameters of polycarbazole phosphate and small molecule carbazole phosphate perovskite solar cells at different annealing temperatures. [Table 1]

[0047] The research results on the concentration / thickness of small molecule carbazole phosphate or carbazole polyphosphate are shown in Figure 4, Figure 5 and Table 2. Figure 4 shows the current-voltage curves of a perovskite solar cell using carbazole polyphosphate as the concentration changes, and Figure 5 shows the current-voltage curves of a perovskite solar cell using carbazole small molecule phosphate as the concentration changes. Small molecule carbazole phosphate is easily affected by the concentration / thickness, while polycarbazole phosphate material is not easily affected by the concentration / thickness.

[0048] Table 2. Perovskite solar cell device parameters for different concentrations of carbazole polyphosphate and carbazole phosphate small molecules. [Table 2]

[0049] The polycarbazole phosphate-based perovskite solar cell achieved a photoelectric conversion efficiency of 22.64%, exceeding that of the control group based on small molecule carbazole phosphate, and it was found that the polycarbazole phosphate-based perovskite solar cell was less sensitive to the polycarbazole phosphate concentration and annealing temperature. [Example]

[0050] The ITO conductive glass was placed in an ultraviolet ozone cleaning device and treated for 15 minutes, after which a 5-10 nm thick layer of carbazole polyphosphate was spin-coated on it, followed by a PM6:Y6 active layer, and finally a 5 nm layer of PDINN was spin-coated and a 100 nm layer of silver electrode was deposited to complete the fabrication of the organic solar cell. [Example]

[0051] The FTO conductive glass was placed in an ultraviolet ozone cleaning device and treated for 15 minutes, then 1 mg / ml of carbazole polyphosphate was blade-coated on it and annealed at 150°C. 0.7 FA 0.3 PbI3 perovskite polycrystalline films were blade coated, and after thermal annealing of the films, 25 nm of C was deposited on the surface. 60 The fabrication of the perovskite solar cell was completed by depositing a 5 nm BCP and a 100 nm copper electrode. Figure 6 shows the current-voltage curves of the optimal polycarbazole phosphate perovskite solar cell on an ITO / FTO substrate, and Table 3 lists the parameters of the polycarbazole phosphate perovskite solar cell based on ITO and FTO. It was clearly observed that polycarbazole phosphate achieved good photoelectric conversion efficiency on both ITO and FTO substrates.

[0052] Table 3. Parameters of ITO and FTO-based carbazole polyphosphate perovskite solar cell devices. [Table 3] [Example]

[0053] After packaging, perovskite solar cells based on carbazole phosphate small molecule (Me-4PACz) and carbazole polyphosphate (Poly-4PACz) were placed under a solar simulator to test the stability of the solar cells at their maximum power point. After testing for over 100 hours (Figure 7), the perovskite solar cells based on carbazole phosphate small molecule showed no obvious efficiency decline, while the perovskite solar cells based on carbazole phosphate small molecule showed a clear decline, indicating that the carbazole polyphosphate material has better light stability than the carbazole phosphate small molecule.

Claims

1. A polycarbazole phosphate material comprising a plurality of repeating units, the repeating units having the structure: 【Chemistry 11】 wherein the benzene ring in the carbazole phosphate unit contains no or no substituents; When no substituents are present, the benzene ring contains one or more independent substituents, and these independent substituents are: 1) H, 2) a halogen group, 3) a cyano group, 4) alkyl groups, 5) aromatic group, 6) Ring-fused group wherein n is selected from the group consisting of 1 to 40, the polymerization site of the carbazole polyphosphate is located at any position on the benzene ring, and the molecular weight of the carbazole polyphosphate is in the range of 300 to 10,000,000.

2. 2. The polycarbazole phosphate material of claim 1, wherein the alkyl is selected from a (C1-C40) linear alkyl, a (C3-C40) branched alkyl, or a (C3-C40) cyclic alkyl group; the cyclic fusion group is used to condense the benzene ring to a larger ring such as naphthalene or anthracene; the halogen group is F, Cl, Br, or I; the aromatic group is one or more selected from aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, and heteroaryloxycarbonyl; and the number of repeating units is 2 to 10,000,000.

3. The structure of the repeating unit is one of the following structural formulas: 【Chemistry 12】 In the formula, m ranges from 2 to 10,000,000, and R １ , R ２ , R ３ 2. The carbazole polyphosphate material of claim 1, wherein is H or the aforementioned substituent.

4. Step 1: copolymerizing a halogenated phosphate ester carbazole in a solvent with or without the addition of other halogenated compounds; Step 2: Adding halogenated silane and alcoholic system and hydrolyzing to obtain polyphosphate carbazole material The method for producing the carbazole polyphosphate material of claim 1 , comprising:

5. 5. The method of claim 4, wherein the halogenated compound refers to a halogenated arene or halogenated thiophene, which may or may not have a substituent; the aromatic group in the halogenated arene is one or more selected from the group consisting of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, and heteroaryloxycarbonyl; the halogenated phosphate ester carbazole self-polymerizes without the addition of other halogenated compounds, but polymerizes with other halogenated compounds when other halogenated compounds are added; the mass ratio of the phosphate ester carbazole to the halogenated compounds is 1:0.01-10.0; the polymerization reaction time is 0.1-72 hours; and the reaction temperature is 0-300°C.

6. The phosphate ester carbazole may include one or more of the following structural units: 【Chemistry 13】 The value of n ranges from 1 to 40.

5. The method for producing the carbazole polyphosphate material according to claim 4.

7. Rx is independently 1) H, 2) a halogen group, 3) a cyano group, 4) alkyl groups, 5) aromatic group, 6) Ring-fused group wherein the halogen group is F, Cl, Br or I; The alkyl is selected from a (C1-C40) linear alkyl, a (C3-C40) branched alkyl, or a (C3-C40) cyclic alkyl; In the above alkyl, one or more non-adjacent C atoms may optionally be -O-, -S-, -C(O)-, -C(O-)-O-, -O-C(O)-, -OC(O)-O-, -CR ０ =CR ００ - or -C≡C-, wherein R ０ and R ００ are independently a straight chain alkyl, branched chain alkyl, or cyclic alkyl group; wherein one or more H atoms may be optionally replaced by F, Cl, Br, I, or CN; The aromatic group is selected from aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl, or heteroaryloxycarbonyl having 4 to 30 ring members.

7. The method for producing the carbazole polyphosphate material according to claim 6.

8. Application of carbazole polyphosphate materials to the fabrication of photovoltaic device structures.

9. The photoelectric device structure is a solar cell, a field effect transistor, a photoelectric detector, a radiation detector, or a light emitting diode, and the solar cell includes an organic solar cell and a perovskite solar cell; 9. The application according to claim 8, characterized in that the carbazole polyphosphate material is used as a hole transport layer material in organic solar cells or perovskite solar cells, or is used for interface modification based on the original hole transport layer.

10. The battery structure is Table 4 10. The application according to claim 9, characterized in that it is one of the following:

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