CN118307750A - A polycyclic phosphoric acid polymer material and its preparation method and application - Google Patents

Abstract

The invention discloses a polycyclic phosphoric acid polymer material, a preparation method and application thereof, and belongs to the field of new energy material preparation. The polycyclic phosphoric acid polymer material provided by the invention has excellent stability, and the problems of poor compactness, easy diffusion and the like of the traditional small phosphoric acid molecules can be effectively solved by the favorable film forming property and the interaction between macromolecular chains, so that a stable photoelectric device based on the polycyclic phosphoric acid polymer is realized. The synthetic method of the polycyclic phosphoric acid polymer is simple and quick, the reaction condition is mild, the obtained polycyclic phosphoric acid polymer material is dissolved in single or mixed solvents such as toluene, chlorobenzene, chloroform, dichloromethane, methanol, ethanol, isopropanol and the like, and the polycyclic phosphoric acid polymer material is processed into a film through processes such as spin coating, knife coating, slit coating, dip coating, spray coating and the like, so that the photoelectric device based on the polycyclic phosphoric acid polymer material is prepared. The invention has important scientific significance and extremely high industrial value.

Description

A polycyclic phosphoric acid polymer material and its preparation method and application

Technical Field

The invention belongs to the field of new energy material preparation, and specifically relates to a polycyclic phosphoric acid polymer material and a preparation method and application thereof.

Background technique

Small molecule polycyclic phosphoric acid is a hole transport material developed in recent years. It has the advantage of being processable in solution. It can form a monolayer on a conductive substrate (ITO and FTO). Compared with the PTAA-type polytriphenylamine hole transport layer material, the perovskite film has better wettability on small molecule polycyclic phosphoric acid, which is conducive to the large-area coating of the perovskite film and the realization of efficient hole transport in the trans-perovskite photovoltaic. Nowadays, small molecule polycyclic phosphoric acid has become a commonly used hole transport material for trans-structured perovskite solar cells. Although small molecule polycyclic phosphoric acid has excellent hole transport performance, its own density and stability have always been a problem. Small molecule polycyclic phosphoric acid needs to form a dense and uniform monolayer on a conductive substrate to achieve efficient hole transport, but in the actual solution processing process, small molecule polycyclic phosphoric acid will form a multi-molecular layer locally, increasing the resistance to hole extraction. Small molecule polycyclic phosphoric acid will also diffuse into the perovskite active layer under photothermal conditions. In addition, on some rough conductive substrates, such as FTO, small molecule polycyclic phosphoric acid cannot completely cover the entire conductive substrate, causing the perovskite film to be in direct contact with the conductive substrate. This situation causes local leakage on the one hand, and on the other hand, the conductive substrate induces the decomposition of perovskite, causing the attenuation of perovskite solar cells (Science 2020, 370, 1300-1309; Nature 2023, Nature 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). Therefore, developing new hole transport layer materials to solve the problems of current small molecule polycyclic phosphoric acid is an important step to improve the stability of trans-perovskite photovoltaic devices and promote their industrialization.

Summary of the invention

In view of the above problems existing in the prior art, the first technical problem to be solved by the present invention is to provide a polycyclic phosphoric acid for preparing a polycyclic phosphoric acid polymer material, which is a repeating unit of the material. The second technical problem to be solved by the present invention is to provide a polycyclic phosphoric acid polymer material, which has the characteristics of good film-forming property, excellent stability and not easy to diffuse. The third technical problem to be solved by the present invention is to provide a method for preparing a polycyclic phosphoric acid polymer material, which is simple and convenient, and the prepared polycyclic phosphoric acid polymer material is stable. The fourth technical problem to be solved by the present invention is to provide an application of a polycyclic phosphoric acid polymer material in the preparation of a photoelectric device structure, which solves the problems of high hole resistance, poor coverage, diffusion, etc. existing in the application of small molecule polycyclic phosphoric acid on a conductive substrate.

In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

A polycyclic phosphoric acid with the following structural formula:

In the formula, the benzene ring on the polycyclic phosphoric acid unit may or may not contain a substituent; the substituent is selected from: a halogen group, a cyano group, an alkyl group, an aromatic group, and a cyclic group; the value ranges of _m1 , _m2 and _m3 are all 1 to 40, and the value of m here can be 1, 2, 3, 5, 10, 15, 20, or a parameter range formed by any integers in the range.

Furthermore, the halogen group is F, Cl, Br or I; the alkyl group is a (C1-C40) straight-chain alkyl group, a (C3-C40) branched alkyl group or a (C3-C40) cycloalkyl group; the aromatic group is one or more of an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylcarbonyl group, a heteroarylcarbonyl group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, an aryloxycarbonyl group and a heteroaryloxycarbonyl group; and the annular group is used to annulate the benzene ring into a macrocyclic naphthalene or anthracene.

A polycyclic phosphoric acid polymer material obtained by polymerizing polycyclic phosphoric acid, the general structural formula of which is as follows:

The polymerization site of polycyclic phosphate is at any position on the benzene ring, and the value of n ranges from 2 to 10,000,000;

In the polycyclic phosphoric acid structure of the present invention, as long as the small molecule polycyclic phosphoric acid can be polymerized to a certain extent and the molecular weight is increased, the film-forming property of the coating after coating can be effectively improved. The number of repeating units in the polymer material can be 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 it can also be a parameter range composed of any integers in the range.

The polycyclic phosphoric acid used in the present invention is polymerized from small molecule polycyclic phosphoric acid, and the number of rings is greater than 3. The small molecule polycyclic phosphoric acid here can adopt the structure disclosed in the prior art. In the present invention, the molecular weight is increased by polymerizing it. As long as it is a small molecule polycyclic phosphoric acid with certain hole transport properties, the purpose of the present invention can be achieved. It can also be modified by some substituents to adjust and improve its performance.

R ₁ , R ₂ , R ₃ and R ₄ are selected from the group consisting of: H, a halogen group, a cyano group, an alkyl group, an aromatic group, and a cyclic group.

Further, the halogen group is F, Cl, Br or I;

The alkyl group is a (C1-C40) straight chain alkyl group, a (C3-C40) branched chain alkyl group or a (C3-C40) cycloalkyl group;

In the alkyl group, one or more non-adjacent C atoms are optionally replaced by -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -CR ⁰ ＝CR ⁰⁰ -, or -C≡C-, wherein R ⁰ and R ⁰⁰ are independently linear alkyl, branched alkyl or cycloalkyl;

In the alkyl group, one or more H atoms are optionally replaced by F, Cl, Br, I or CN;

The aromatic group is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl, and has 4 to 30 ring atoms;

The annulation group is used to annulate the benzene ring to form a macrocyclic naphthalene or anthracene.

The polycyclic phosphoric acid material with or without substituents provided in the present invention is obtained by polymerizing small molecule polycyclic phosphoric acid esters and hydrolyzing ester groups, and the polymerization site is at any position on the benzene ring. In order to realize the synthesis of the polymer material, the present invention provides the following synthesis idea, that is, polymerization is realized by catalytic polymerization reaction of small molecule polycyclic phosphoric acid esters, and halogenated small molecule polycyclic phosphoric acid esters can be used for condensation polymerization in the reaction, wherein the halogenated groups can be at any position on the polycyclic ring, and in this case, polycyclic phosphoric acid esters modified with some substituents can also be used for reaction; in addition, corresponding halogenated compounds can be added to copolymerize with polycyclic phosphoric acid esters during the condensation reaction, and then halogenated silanes and alcohol compounds are added to hydrolyze the polycyclic phosphoric acid esters into polycyclic phosphoric acid.

The preparation method of the polycyclic phosphoric acid polymer material comprises the following specific steps:

1) Grafting a phosphate functional group onto the reaction site of N of polycyclic phosphoric acid to obtain a polycyclic phosphate molecule, and then adding a halogenated compound to perform halogenation substitution to obtain a halogenated polycyclic phosphate;

Or, a phosphate functional group is grafted onto the reaction site of N of the halogenated polycyclic molecule to obtain a halogenated polycyclic phosphate; wherein the mass ratio of the polycyclic phosphate to the halogenated compound is 1:0.01-1000;

2) adding or not adding other halogenated compounds to the halogenated polycyclic phosphate prepared in step 1), and then adding a solvent and a catalyst to carry out a polymerization reaction, wherein the reaction time is less than 72 hours and the reaction temperature is less than 300° C.;

3) After the polymerization reaction in step 2) is completed, halogenated silane and alcohol are added for hydrolysis to obtain a polycyclic phosphoric acid polymer material.

Furthermore, in step 2), the other halogenated compound is a halogenated aromatic hydrocarbon or a halogenated thiophene with or without a substituent;

Furthermore, the aromatic group of the halogenated aromatic hydrocarbon is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl.

Furthermore, the yield of the hydrolysis reaction is between 1% and 100%.

Furthermore, the catalyst is selected from a nickel-based catalyst or a palladium catalyst.

The halogenated polycyclic phosphates polymerize by themselves without the addition of halogenated compounds;

When other halogenated compounds are added, the halogenated polycyclic phosphate and the other halogenated compounds are randomly copolymerized or alternately copolymerized.

In one embodiment, dibromoindolecarbazole phosphate is used as a raw material, and polyindolecarbazole phosphate is obtained by catalytic polymerization; polyindolecarbazole phosphate and trimethylsilyl bromide are stirred in a solvent for reaction, and then excess methanol is added for hydrolysis to obtain a polyindolecarbazole phosphate material; the reaction equation is as follows:

In the formula, n ranges from 2 to 10,000,000, m ranges from 1 to 40, and R is a (C1-C40) straight chain alkyl group, a (C3-C40) branched chain alkyl group, or a (C3-C40) cycloalkyl group.

In one embodiment, dibromoindole indole phosphate is used as a raw material, and polyindole indole phosphate is obtained by catalytic polymerization; polyindole indole phosphate and trimethylsilyl bromide are stirred in a solvent for reaction, and then excess methanol is added for hydrolysis to obtain a polyindole indole phosphate material; the reaction equation is as follows:

In the formula, n ranges from 2 to 10,000,000, m ranges from 1 to 40, and R is a (C1-C40) straight chain alkyl group, a (C3-C40) branched chain alkyl group, or a (C3-C40) cycloalkyl group.

In one embodiment, dibromoindole indole phosphate and aromatic groups are used as raw materials, and a polyindole indole phosphate copolymer is obtained by catalytic reaction; the polyindole indole phosphate copolymer and trimethylsilyl bromide are stirred in a solvent for reaction, and then excess methanol is added for hydrolysis to obtain a polyindole indole phosphate copolymer polymer; the reaction equation is as follows:

In the formula, n ranges from 2 to 10,000,000, m ranges from 1 to 40, R is a (C1-C40) straight chain alkyl, (C3-C40) branched chain alkyl or (C3-C40) cycloalkyl, and Ar is an aromatic group.

Furthermore, the polycyclic phosphoric acid polymer material is used in the preparation of optoelectronic device structures.

Furthermore, the optoelectronic device structure is a solar cell, a field effect transistor, a photodetector, a radiation detector and a light emitting diode.

Furthermore, the structure of the solar cell is as follows:

The polycyclic phosphoric acid polymer material is used as a hole transport layer material or an electron blocking material in an organic solar cell or a perovskite solar cell or an organic light emitting diode or a perovskite light emitting diode, or is used for interface modification on the basis of an original hole transport layer.

The perovskite light absorbing layer includes a metal halide perovskite, and its chemical formula is ABX ₃ , wherein A includes but is not limited to methylamine ion, formamidine ion, cesium, rubidium, potassium, sodium, ammonium ion, ethylamine, propylamine, butylamine, aniline, benzylamine, phenylethylamine, or a combination of the above components; B includes lead, tin, cadmium, germanium, zinc, nickel, or a combination of the above components. X is fluorine, chlorine, bromine, iodine anion or a combination of the above components.

Specifically, the solar cell electrode contains one or more of gold, silver, copper, aluminum, carbon, and chromium. The hole transport layer includes PTAA, Spiro-OMeTAD, PEDOT:PSS, NiO, MoO ₃ , V ₂ O ₅ , Poly-TPD, EH44, P3HT or a combination of the above materials. The electron transport layer includes C ₆₀ , BCP, TiO ₂ , SnO ₂ , PCBM, ICBA, ZnO, ZrAcac, LiF, TPBi, PFN, Nb ₂ O ₅ or a combination of the above materials.

Specifically, perovskite solar cells have a photoelectric conversion efficiency of 1% to 35%, and organic solar cells have a photoelectric conversion efficiency of 1% to 25%.

Beneficial effects: Compared with the prior art, the advantages of the present invention are:

(1) The polycyclic phosphate polymer material prepared by the present invention has excellent stability and film-forming properties, and the interactions between its polymer chains can effectively solve the problems of poor compactness and easy diffusion of traditional small molecule polycyclic phosphates, thereby realizing stable optoelectronic devices based on polycyclic phosphate polymers.

(2) The method for preparing the polycyclic phosphoric acid polymer material of the present invention is simple and convenient, and the reaction conditions are mild. The present invention dissolves the obtained polycyclic phosphoric acid polymer material in a single or mixed solvent such as toluene, chlorobenzene, chloroform, dichloromethane, methanol, ethanol and isopropanol, and processes it into a thin film through spin coating, scraping, slit coating, dip coating and spraying, etc., to prepare optoelectronic devices based on polycyclic phosphoric acid polymer materials, including perovskite solar cells, organic solar cells, field effect transistors, light-emitting diodes, photodetectors and radiation detectors.

(3) The present invention polymerizes small molecule polycyclic phosphoric acid to increase the molecular weight, which can effectively improve the film-forming property of the polycyclic phosphoric acid polymer material on the surface of the conductive substrate and form a stable hole transport layer with a suitable thickness.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a current-voltage curve of a perovskite solar cell based on DCPA and P-DCPA of the present invention;

FIG. 2 is a perovskite solar current-voltage curve of D4CPA and P-D4CPA of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described below in conjunction with specific embodiments.

Example 1

The preparation steps of P-DCPA are as follows:

1) Dissolve 3.98 g of 4-bromophenylhydrazine hydrochloride and 1.46 g of sodium acetate in 40 mL of ethanol, add 20 mL of 0.05 g/mL 1,4-cyclohexanedione ethanol solution, stir at 30°C for 30 min, then cool to 0°C, filter, and wash with cold water to obtain 3.4 g of 1,4-bis(2-(4-bromophenyl)hydrazineylidene)cyclohexane, the structural formula of which is shown below:

2) 3.4 g of 1,4-bis(2-(4-bromophenyl)hydrazineylidene)cyclohexane was dissolved in a mixed solution of 85 mL of acetic acid and 21 mL of concentrated sulfuric acid, reacted at 0°C for 5 min, then heated to 30°C for 1 h, and then heated to 65°C for 1 h, cooled to room temperature, added with ice water, filtered, and washed with water and ethanol three times respectively until neutral to obtain 1.35 g of 2,8-dibromoindolo(3,2-b)carbazole (2,8-dibromoindole(3,2-b)carbazole), the structural formula of which is shown below:

¹ H NMR (400 MHz, DMSO-d ₆ ) δ 11.29 (s, 2H), 8.47 (d, J=2.0 Hz, 2H), 8.22 (s, 2H), 7.50 (dd, J=8.6, 2.0 Hz, 2H), 7.42 (d, J=8.6 Hz, 2H).

3) Dissolve 500 mg of 2,8-dibromoindolo(3,2-b)carbazole in 5 mL of DMSO, slowly add 106.2 mg of NaH, react at room temperature for 30 min, slowly drop 0.48 mL of 4-bromobutyl diethyl phosphate, react for 30 min, then heat to 60 °C and react for 20 h. After cooling to room temperature, add 25 mL of ice water to the reaction solution, acidify with 1 M hydrochloric acid to pH = 2, and extract with ethyl acetate to obtain 559 mg of tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phos phonate)(tetraethyl((2,8-dibromoindole[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphate)), the structural formula is as follows:

¹ H NMR (400 MHz, Chloroform-d) δ 8.30 (d, J = 1.9 Hz, 2H), 7.93 (s, 2H), 7.56 (dd, J = 8.7, 1.9 Hz, 2H), 7.28 (d, J = 8.6 Hz, 2H), 4.38 (t, J = 7.1 Hz, 4H), 4.09–3.97 (m, 8H), 2.04 (p, J = 7.1 Hz, 4H), 1.74 (d, J = 3.5 Hz, 4H), 1.26 (q, J = 6.9 Hz, 16H).

4) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 500 mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 4 mL DMF and the activated catalyst (activated Ni(COD) ₂ ) was added. , bipyridine, COD and DMF), react at 80°C for 12h, cool to room temperature, add 2mL of 1M hydrochloric acid, stir for 10min, extract with dichloromethane, take the organic phase, and obtain 295mg of polyindole and carbazole phosphate, the structural formula of which is shown below:

5) Dissolve 50 mg of polyindole and carbazole phosphate in 10 mL of dichloromethane, add 100 μL of trimethylsilyl bromide, react at room temperature for 12 h, add excess methanol, stir for 4 h, add ether to precipitate, filter to obtain 38 mg of polyindole and carbazole phosphate (P-DCPA), and determine its structural formula as follows through characterization:

Example 2

The preparation steps of P-D4CPA are as follows:

1) Dissolve 1.39g NaH in 100mL anhydrous tetrahydrofuran, add 4g methyl 5-bromoaminobenzoate in batches, gradually heat the reaction solution to 60°C, and stir for 12h. Cool to room temperature, slowly pour into 0.1M hydrochloric acid, filter and collect the precipitate, wash with deionized water, and then dry at 50°C to obtain 2g 2,8-dibromodibenzo[b,f][1,5]diazocine-6,12(5H,11H)-dione (2,8-dibromodibenzo[b,f][1,5]diazocine-6,12(5H,11H)-dione), the structural formula of which is as follows:

¹ H NMR (400 MHz, DMSO-d ₆ , ppm): 10.37 (s, 1H), 7.57 (dd, J=8.5, 2.4 Hz, 1H), 7.51 (d, J=2.3 Hz, 1H), 7.06 (d, J=8.5 Hz, 1H). ¹³ C NMR (101 MHz, DMSO, ppm): 167.81, 135.63, 134.33, 134.00, 131.10, 128.49, 120.36.

2) Dissolve 3g of 2,8-dibromodibenzo[b,f][1,5]diazocine-6,12(5H,11H)-dione in 50mL of chloroform, add 6g of phosphorus pentachloride in batches, gradually heat the reaction solution to 50°C, stir for 4h, cool to room temperature, and remove the reaction solution by vacuum distillation. Dissolve the obtained solid in 200mL of tetrahydrofuran, add 5.94g of zinc powder, then add 13.5mL of trifluoroacetic acid, stir at room temperature for 12h, add saturated ammonium chloride solution to quench the reaction, extract the reaction solution with ethyl acetate, collect the organic phase, vacuum distill, and purify by column to obtain 1.2g of 3,8-dibromo-5,10-dihydroindolo[3,2-b]indole (3,8-dibromo-5,10-dihydroindole[3,2-b]indole), the structural formula is as follows:

¹ H NMR (400 MHz, DMSO-d ₆ , ppm): 11.38 (s, 1H), 7.92 (d, J=2.0 Hz, 1H), 7.50 (d, J=8.7 Hz, 1H), 7.31 (dd, J=8.7, 2.0 Hz, 1H). ¹³ C NMR (101 MHz, DMSO, ppm): 139.51, 125.89, 124.74, 120.45, 116.17, 114.68, 110.59.

3) Dissolve 3g 3,8-dibromo-5,10-dihydroindolo[3,2-b]indole in 20mL 1.4-dibromobutane, add 1.07g tetrabutylammonium bromide, then add 12.4mL 50% potassium hydroxide, and stir at 60°C for 12h. After cooling to room temperature, concentrate under reduced pressure, filter to obtain the product, and purify it through a column to obtain 3.6g 3,8-dibromo-5,10-bis(4-bromobutyl)-5,10-dihydroindolo[3,2-b]indole (3,8-dibromo-5,10-bis(4-bromobutyl)-5,10-dihydroindolo[3,2-b]indole), the structural formula of which is as follows:

¹ H NMR (400 MHz, Chloroform-d, ppm): 7.91 (d, J = 2.0 Hz, 1H), 7.40 (dd, J = 8.8, 1.9 Hz, 1H), 7.32 (d, J = 8.9 Hz, 1H), 4.48 (t, J = 6.8 Hz, 2H), 3.36 (t, J = 6.4 Hz, 2H), 2.18-2.08 (m, 2H), 1.94-1.85 (m, 2H). ¹³ C NMR (101 MHz, CDCl ₃ )δ139.29,125.59,125.11,120.26,115.58,111.51,111.21,77.34,77.02,76.70,44.57,32.98,29.95,28.79.

4) 4 g of 3,8-dibromo-5,10-bis(4-bromobutyl)-5,10-dihydroindolo[3,2-b]indole was dissolved in 20 mL of triethyl phosphite and heated and stirred at 140°C for 12 h. The triethyl phosphite was removed by vacuum distillation and purified by column to obtain 3.9 g of tetraethyl((3,8-dibromoindolo[3,2-b]indole-5,10-diyl)bis(butane-4,1-diyl))bis(phosphonate) with the following structural formula:

¹ H NMR (400 MHz, Chloroform-d, ppm): 7.88 (d, J = 1.8 Hz, 1H), 7.38 (dd, J = 8.8, 1.9 Hz, 1H), 7.31 (d, J = 8.9 Hz, 1H), 4.43 (t, J = 6.9 Hz, 2H), 4.01 (tt, J = 8.1, 6.3 Hz, 4H), 2.09-2.00 (m, 2H), 1.77-1.62 (m, 4H), 1.24 (t, J = 7.1 Hz, 6H). ¹³ CNMR (101 MHz, CDCl ₃ ,ppm):139.32,125.62,125.00,120.18,115.57,111.38,111.22,61.53,44.95,26.12,24.71,20.33,16.38.

5) Dissolve 0.176g Ni(Cod) ₂ , 0.1g bipyridine and 0.082mL 1,5-cyclooctadiene in 5mL DMF, heat and stir at 80°C for half an hour; dissolve 0.5g tetraethyl((3,8-dibromoindolo[3,2-b]indole-5,10-diyl)bis(butane-4,1-diyl))bis(phosphonate) in 10mL DMF, slowly dropwise add to the reaction system, and continue stirring at 80°C for 24h. After the reaction is completed, cool to room temperature, slowly dropwise add dilute hydrochloric acid under stirring, extract the organic phase with dichloromethane, spin dry, and the final product is a gray polyindole and indole phosphate powder with the following structural formula:

6) 0.12g polyindole and indole phosphate was dissolved in 20mL dichloromethane, 1.5mL 0.1g/mL trimethyl bromosilane was added dropwise, and stirred at room temperature for 24h. After the reaction was completed, excess methanol was added dropwise to the anti-system to remove excess trimethyl bromosilane. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was polyindole phosphate powder (P-D4CPA), with a number average molecular weight of about 79267 and a weight average molecular weight of about 95248. By characterization, its structural formula was determined to be as follows:

Example 3

The preparation steps of indolecarbazole polyphosphate are as follows:

1) Dissolve 500 mg of 3,8-dibromo-11,12-dihydroindolo[2,3-a]carbazole in 5 mL of DMSO, slowly add 106.2 mg of NaH, react at room temperature for 30 min, slowly drop 0.48 mL of 4-bromobutyl diethyl phosphate, react for 30 min, then heat to 60 °C and react for 20 h. After cooling to room temperature, add 25 mL of ice water to the reaction solution, acidify with 1 M hydrochloric acid to pH = 2, and extract with ethyl acetate to obtain 559 mg Tetraethyl((3,8-dibromoindolo[2,3-a]carbazole-11,12-diyl)bis(butane-4,1-diyl))bis(phosphonate) has the following structural formula:

2) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 500 mg tetraethyl((3,8-dibromoindolo[2,3-a]carbazole-11,12-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 4 ml DMF and added to the activated catalyst. The reaction was carried out at 80°C for 12 h. The mixture was cooled to room temperature, 2 mL of 1 M hydrochloric acid was added, and the mixture was stirred for 10 min. The mixture was extracted with dichloromethane and the organic phase was taken to obtain 295 mg of diethyl polyphosphate indolecarbazole with the following structural formula:

3) Dissolve 50 mg of polyphosphoric acid diethyl indolecarbazole in 10 mL of dichloromethane, add 100 μL of trimethylsilyl bromide, react at room temperature for 12 h, add excess methanol, stir for 4 h, add ether to precipitate, filter to obtain 38 mg of polyphosphoric acid indolecarbazole, and determine its structural formula as follows through characterization:

Example 4

The preparation steps of indolecarbazole polyphosphate are as follows:

1) Dissolve 500 mg of 3,9-dibromo-5,12-dihydroindolo[3,2-a]carbazole in 5 mL of DMSO, slowly add 106.2 mg of NaH, react at room temperature for 30 min, slowly drop 0.48 ml of 4-bromobutyl diethyl phosphate, react for 30 min, then heat to 60 °C and react for 20 h. After cooling to room temperature, add 25 mL of ice water to the reaction solution, acidify with 1 M hydrochloric acid to pH = 2, and extract with ethyl acetate to obtain 559 mg Tetraethyl((3,9-dibromoindolo[3,2-a]carbazole-5,12-diyl)bis(butane-4,1-diyl))bis(phosphonate) has the following structural formula:

2) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 500 mg tetraethyl((3,9-dibromoindolo[3,2-a]carbazole-5,12-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 4 mL DMF and added to the activated catalyst. The reaction was carried out at 80°C for 12 h. The mixture was cooled to room temperature, 2 mL of 1 M hydrochloric acid was added, and the mixture was stirred for 10 min. The mixture was extracted with dichloromethane and the organic phase was taken to obtain 295 mg of polyphosphodiethyl indolecarbazole with the following structural formula:

3) Dissolve 50 mg of polyphosphoric acid diethyl indolecarbazole in 10 mL of dichloromethane, add 100 μL of trimethylsilyl bromide, react at room temperature for 12 h, add excess methanol, stir for 4 h, add ether to precipitate, filter to obtain 38 mg of polyphosphoric acid indolecarbazole, and determine its structural formula as follows through characterization:

Example 5

The preparation steps of indolecarbazole polyphosphate are as follows:

1) Dissolve 500 mg of 2,10-dibromo-5,7-dihydroindolo[2,3-b]carbazole in 5 mL of DMSO, slowly add 106.2 mg of NaH, react at room temperature for 30 min, slowly drop 0.48 mL of 4-bromobutyl diethyl phosphate, react for 30 min, then heat to 60 °C and react for 20 h. After cooling to room temperature, add 25 mL of ice water to the reaction solution, acidify with 1 M hydrochloric acid to pH = 2, and extract with ethyl acetate to obtain 559 mg Tetraethyl((2,10-dibromoindolo[2,3-b]carbazole-5,7-diyl)bis(butane-4,1-diyl))bis(phosphonate) has the following structural formula:

2) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 500 mg tetraethyl((2,10-dibromoindolo[2,3-b]carbazole-5,7-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 4 mL DMF and added to the activated catalyst. The reaction was carried out at 80°C for 12 h. The mixture was cooled to room temperature, 2 mL of 1 M hydrochloric acid was added, and the mixture was stirred for 10 min. The mixture was extracted with dichloromethane and the organic phase was taken to obtain 295 mg of polyphosphodiethyl indolecarbazole with the following structural formula:

3) Dissolve 50 mg of polyphosphoric acid diethyl indolecarbazole in 10 mL of dichloromethane, add 100 μL of trimethylsilyl bromide, react at room temperature for 12 h, add excess methanol, stir for 4 h, add ether to precipitate, filter to obtain 38 mg of polyphosphoric acid indolecarbazole, and determine its structural formula as follows through characterization:

Example 6

The preparation steps of polypyrrolodicarbazole phosphate are as follows:

1) Dissolve 4g of 3,8-dibromo-5,10-dihydroindolo[3,2-b]indole in 20mL of 1.4-dibromobutane, add 1.07g of tetrabutylammonium bromide, then add 12.4mL of 50% potassium hydroxide, and stir at 60°C for 12h. After cooling to room temperature, concentrate under reduced pressure, filter to obtain the product, and purify it through a column to obtain 3.6g of 2,11-dibromo-5,8,14-tris(4-bromobutyl)-8,14-dihydro-5H-pyrrolo[3,2-b:4,5-b']dicarb azole (2,11-dibromo-5,8,14-tris(4-bromobutyl)-8,14-dihydro-5H-pyrrolo[3,2-b:4,5-b']dicarbazole), the structural formula of which is as follows:

2) 4 g of 2,11-dibromo-5,8,14-tris(4-bromobutyl)-8,14-dihydro-5H-pyrrolo[3,2-b:4,5-b']dicarbazole was dissolved in 20 mL of triethyl phosphite and heated and stirred at 140°C for 12 h. The triethyl phosphite was removed by vacuum distillation and purified by column to obtain 3.9 g of tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole) ']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate)(tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate)), the structural formula is as follows:

3) 0.176g Ni(Cod) ₂ , 0.1g bipyridine, and 0.082mL 1,5-cyclooctadiene were dissolved in 5mL DMF, heated and stirred at 80°C for half an hour, 0.7g tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 15mL DMF, slowly added dropwise to the reaction system, and continued to stir at 80°C for 24h. After the reaction was completed, cooled to room temperature, diluted hydrochloric acid was slowly added dropwise under stirring, the organic phase was extracted with dichloromethane, and dried by rotation. The final product was a gray polyphosphate pyrrolodicarbazole powder with the following structural formula:

4) 0.12g polyphosphate pyrrolodicarbazole was dissolved in 20mL dichloromethane, 2.25mL of 0.1g/mL trimethylsilyl bromide was added dropwise, and stirred at room temperature for 24h. After the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylsilyl bromide. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was polyphosphate pyrrolodicarbazole powder, and its structural formula was determined as follows by characterization:

Example 7

The preparation steps of polyphosphate pyrrolodicarbazole-triphenylamine are as follows:

1) Dissolve 0.25g Ni(Cod) ₂ , 0.14g bipyridine, and 0.117mL 1,5-cyclooctadiene in 5mL DMF, heat and stir at 80℃ for half an hour, dissolve 0.5g tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 0.2g N,N-bis(4-bromophenyl)-2,4,6-trimethylanil ine in 15mL DMF, slowly dropwise add to the reaction system, and continue stirring at 80℃ for 24h. After the reaction is completed, the mixture is cooled to room temperature, and dilute hydrochloric acid is slowly added dropwise under stirring. The organic phase is extracted with dichloromethane and dried by spin drying. The final product is a gray polyphosphate pyrrolodicarbazole-triphenylamine powder with the following structural formula:

2) 0.12g polyphosphate pyrrolodicarbazole-triphenylamine was dissolved in 20mL dichloromethane, 1.73mL of 0.1g/ml trimethylsilyl bromide was added dropwise, and stirred at room temperature for 24h. After the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylsilyl bromide. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was polyphosphate pyrrolodicarbazole-triphenylamine powder, and its structural formula was determined as follows by characterization:

Example 8

The preparation steps of the indolecarbazole phosphate and thiophene mixed polymer are as follows:

1) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 250 mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 76 mg 2,5-dibromothiophene were dissolved in 4 mL Add the activated catalyst to DMF, react at 80°C for 12h, cool to room temperature, add 2mL of 1M hydrochloric acid, stir for 10min, extract with dichloromethane, take the organic phase, and obtain 195mg of diethyl phosphate indolecarbazole and thiophene mixed polymer, the structural formula is as follows:

2) Dissolve 50 mg in 10 mL of dichloromethane, add 889 μL of trimethylsilyl bromide, react at room temperature for 12 h, add excess methanol, stir for 4 h, then add ether to precipitate, filter to obtain 36 mg of indolecarbazole phosphate and thiophene mixed polymer, and determine its structural formula through characterization as follows:

Example 9

1) Dissolve 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD in 2 mL DMF and activate at 80°C for 30 min. Dissolve 250 mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 94 mg 5,7-dibromo-2,3dihydrothien o[3,4-b][1,4]dioxine in 4 mL Add the activated catalyst to DMF, react at 80°C for 12h, cool to room temperature, add 2mL of 1M hydrochloric acid, stir for 10min, extract with dichloromethane, take the organic phase, and obtain 195mg of a mixed polymer with the following structural formula:

2) 50 mg of the mixed polymer was dissolved in 10 mL of dichloromethane, 823 μL of trimethylsilyl bromide was added, and the mixture was reacted at room temperature for 12 h. Excess methanol was added, and ether was added for precipitation after stirring for 4 h. 36 mg of the mixed polymer was obtained by filtration. The structure of the mixed polymer was determined to be as follows through characterization:

Example 10

1) 172 mg Ni(COD) ₂ , 97.9 mg bipyridine and 81 μL COD were dissolved in 2 mL DMF and activated at 80°C for 30 min. 250 mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 109 mg 6,8-dibromo-3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (6,8-dibromo-3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dithiophene ether) was dissolved in 4 mL of DMF and added to the activated catalyst. The mixture was reacted at 80°C for 12 h, cooled to room temperature, 2 mL of 1M hydrochloric acid was added, stirred for 10 min, extracted with dichloromethane, and the organic phase was taken to obtain 205 mg of a mixed polymer with the following structural formula:

2) 50 mg of the mixed polymer was dissolved in 10 mL of dichloromethane, 661 μL of trimethylsilyl bromide was added, and the mixture was reacted at room temperature for 12 h. Excess methanol was added, and ether was added for precipitation after stirring for 4 h. 38 mg of the mixed polymer was obtained by filtration. The structure of the mixed polymer was determined to be as follows through characterization:

Embodiment 11

1) Dissolve 0.176g Ni(Cod) ₂ , 0.1g bipyridine, and 0.082mL 1,5-cyclooctadiene in 5mL DMF, heat and stir at 80°C for half an hour, dissolve 0.350g tetraethyl((3,8-dibromoind olo[3,2-b]indole-5,10-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 0.250g N,N-bis(4-bromophenyl)-2,4,6-trimethylaniline in 15mL DMF, slowly dropwise add to the reaction system, and continue stirring at 80°C for 24h. After the reaction is completed, cool to room temperature, slowly dropwise add dilute hydrochloric acid under stirring, extract the organic phase with dichloromethane, spin dry, and the final product is a gray powder with the following structural formula:

2) 0.12 g of the product was dissolved in 20 mL of dichloromethane, 2.25 mL of 0.1 g/mL trimethylsilyl bromide was added dropwise, and the mixture was stirred at room temperature for 24 h. After the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylsilyl bromide. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was a brown powder, and its structural formula was determined to be as follows through characterization:

Example 12

1) Dissolve 0.25g Ni(Cod) ₂ , 0.14g bipyridine, and 0.117mL 1,5-cyclooctadiene in 5mL DMF, heat and stir at 80°C for half an hour, dissolve 0.3g tetraethyl((3,8-dibromoindolo[3,2-b]indole-5,10-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 0.2g 2,6-dibromobenz o[1,2-b:4,5-b']dithiophene in 15mL DMF, slowly dropwise add to the reaction system, and continue stirring at 80°C for 24h. After the reaction is completed, cool to room temperature, slowly dropwise add dilute hydrochloric acid under stirring, extract the organic phase with dichloromethane, spin dry, and the final product is a gray powder with the following structural formula:

2) 0.12g of the above product was dissolved in 20mL of dichloromethane, 1.73mL of 0.1g/mL trimethylsilyl bromide was added dropwise, and stirred at room temperature for 24h. After the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylsilyl bromide. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was a brown powder. Through characterization, its structural formula was determined as follows:

Example 13

1) Dissolve 0.25g Ni(Cod) ₂ , 0.14g bipyridine, and 0.117mL 1,5-cyclooctadiene in 5mL DMF, heat and stir at 80°C for half an hour, dissolve 0.3g tetraethyl((3,8-dibromoindolo[3,2-b]indole-5,10-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 0.2g 1,4-dibromobenzene in 15mL DMF, slowly dropwise add to the reaction system, and continue stirring at 80°C for 24h. After the reaction is completed, cool to room temperature, slowly dropwise add dilute hydrochloric acid under stirring, extract the organic phase with dichloromethane, spin dry, and the final product is a gray powder with the following structural formula:

2) 0.12g of the product was dissolved in 20mL of dichloromethane, 1.73mL of 0.1g/mL trimethylsilyl bromide was added dropwise, and the mixture was stirred at room temperature for 24h. After the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylsilyl bromide. The solution was concentrated by vacuum distillation, precipitated in ether, and filtered and rinsed with ether. The final product was a brown powder, and its structural formula was determined to be as follows through characterization:

Embodiment 14

1. Preparation of perovskite solar energy

The ITO conductive glass was placed in a UV ozone cleaning machine for 15 minutes, and then a small molecule polycyclic phosphoric acid (DCPA) or poly-polycyclic phosphoric acid (P-DCPA) was scraped on it and annealed at 100°C. Then, a MA _0.7 FA _0.3 PbI ₃ perovskite polycrystalline film was scraped, and after thermal annealing of the film, 25nm C ₆₀ , 5nm BCP and 100nm copper electrode were evaporated on its surface to prepare a perovskite solar cell. Among them, P-DCPA uses the poly-polycyclic phosphoric acid polymer prepared in Example 1; the structure of DCPA is as follows:

2. Perovskite solar cell efficiency test

The prepared perovskite solar cell was placed under a 3A-level solar simulator, the solar intensity of the simulator was 100mW/ ^cm2 , the current-voltage curve of the perovskite solar cell was scanned and recorded, and the maximum value of the product of 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 spectrum intensity. The results are shown in Figure 1 and Table 1.

Table 1 Comparison of DCPA and P-DCPA device performances Perovskite solar cell device parameters

Hole transport layer V _oc (V) J _sc (mA·cm ^-2 ) FF(%) PCE(%) DCPA 1.107 25.01 79.4 22.00 P-DCPA 1.163 25.84 80.2 24.10

Figure 1 is the current-voltage curve of the perovskite solar cell based on DCPA and P-DCPA of the present invention, and Table 1 is the perovskite solar cell device parameters of the comparison of the performance of DCPA and P-DCPA devices. It can be seen from Figure 1 and Table 1 that the small molecule polycyclic phosphoric acid (DCPA) and the polycyclic phosphoric acid polymer (P-DCPA) are scraped on the ITO conductive glass. The small molecule polycyclic phosphoric acid has poor coverage on ITO, with multi-layer accumulation locally and large resistance. In contrast, the polycyclic phosphoric acid P-DCPA has good coverage and film-forming properties on ITO, with low resistance, which is conducive to the extraction of holes. Therefore, the polycyclic phosphoric acid (P-DCPA) material achieves better photovoltaic performance than the small molecule (DCPA) material, and the prepared perovskite solar cell has a photoelectric conversion efficiency of 1% to 35%.

Embodiment 15

1. Preparation of perovskite solar energy

The ITO conductive glass was placed in a UV ozone cleaning machine for 15 minutes, and then a small molecule polycyclic phosphoric acid (D4CPA) or poly-polycyclic phosphoric acid (P-D4CPA) was scraped on it and annealed at 100°C. Subsequently, a MA _0.7 FA _0.3 PbI ₃ perovskite polycrystalline film was scraped, and after thermal annealing of the film, 25nm C ₆₀ , 5nm BCP and 100nm copper electrode were evaporated on its surface to prepare a perovskite solar cell. Among them, P-D4CPA uses the poly-polycyclic phosphoric acid polymer prepared in Example 2; the structure of D4CPA is as follows:

2. Perovskite solar cell efficiency test

The prepared perovskite solar cell was placed under a 3A-level solar simulator, the solar intensity of the simulator was 100mW/ ^cm2 , the current-voltage curve of the perovskite solar cell was scanned and recorded, and the maximum value of the product of 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 spectrum intensity. The results are shown in Figure 2 and Table 2.

Table 2 Comparison of D4CPA and P-D4CPA device performances Perovskite solar cell device parameters

Hole transport layer V _oc (V) J _sc (mA·cm ^-2 ) FF(%) PCE(%) D4CPA 1.152 25.06 76.6 22.11 P-D4CPA 1.176 25.82 81.3 24.69

Figure 2 is the perovskite solar current-voltage curve of D4CPA and P-D4CPA of the present invention; Table 2 is the perovskite solar cell device parameters of D4CPA and P-D4CPA device performance comparison. It can be seen from Figure 2 and Table 2 that the small molecule polycyclic phosphoric acid (D4CPA) and the poly-polycyclic phosphoric acid polymer (P-D4CPA) are scraped on the ITO conductive glass. The small molecule polycyclic phosphoric acid has poor coverage on ITO, with multi-layer accumulation locally and large resistance. In contrast, the poly-polycyclic phosphoric acid P-D4CPA has good coverage and film-forming properties on ITO, with low resistance, which is conducive to the extraction of holes. Therefore, the poly-polycyclic phosphoric acid (P-D4CPA) material achieves better photovoltaic performance than the small molecule (D4CPA) material, and the perovskite solar cell has a photoelectric conversion efficiency of 1% to 35%.

Example 16

The method for preparing a perovskite solar cell using the materials obtained in Examples 3 to 13 is as follows:

The ITO conductive glass was placed in a UV ozone cleaning machine for 15 minutes, and then 1 mg/mL of the polymer material prepared in Examples 3 to 13 was scraped on it. Subsequently, the MA _0.7 FA _0.3 PbI ₃ perovskite polycrystalline film was scraped, and after the film was thermally annealed, 25 nm C ₆₀ , 5 nm BCP and 100 nm copper electrodes were evaporated on its surface to complete the preparation of the perovskite solar cell. The efficiency of the perovskite solar cell was tested using the same solar cell test method as in Examples 14 and 15 above, and the obtained solar cell performance parameter results are shown in Table 3.

Table 3 Perovskite solar cell device parameters prepared from materials obtained in Examples 3 to 13

V _oc (V) J _sc (mA·cm ^-2 ) FF(%) PCE(%) Example 3 1.12 24.5 0.83 22.8 Example 4 1.14 25.1 0.82 23.5 Example 5 1.17 24.8 0.84 24.4 Example 6 1.16 25.2 0.83 24.3 Example 7 1.15 25.3 0.84 24.4 Example 8 1.18 25.1 0.84 24.9 Example 9 1.17 25.5 0.83 24.8 Example 10 1.13 25.3 0.83 23.7 Embodiment 11 1.18 25.6 0.84 25.4 Example 12 1.15 25.7 0.82 24.2 Example 13 1.19 25.7 0.84 25.7

Table 3 shows the parameters of the perovskite solar cell device prepared by the materials obtained in Examples 3 to 13. It can be seen from the table that the open circuit voltage, short circuit current, fill factor and final efficiency of the perovskite solar cell can be regulated by regulating the structure of polycyclic phosphoric acid. In addition, the materials prepared by the copolymerization strategy achieve better photoelectric conversion efficiency than the self-polymerized materials.

Claims (10)

1. A polycyclic phosphoric acid, characterized in that the structural formula is as follows: In the formula, the benzene ring may or may not contain a substituent; the substituent is selected from: a halogen group, a cyano group, an alkyl group, an aromatic group, and a cyclic group; the values of m ₁ , m ₂ and m ₃ are all in the range of 1 to 40. 2. The polycyclic phosphoric acid according to claim 1, characterized in that the halogen group is F, Cl, Br or I; the alkyl group is a (C1-C40) straight-chain alkyl group, a (C3-C40) branched-chain alkyl group or a (C3-C40) cycloalkyl group; the aromatic group is one or more of an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylcarbonyl group, a heteroarylcarbonyl group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, an aryloxycarbonyl group and a heteroaryloxycarbonyl group; and the annulation group is used to annulate the benzene ring into a macrocyclic naphthalene or anthracene. 3. A polycyclic phosphoric acid polymer material obtained by polymerizing the polycyclic phosphoric acid according to claim 1, characterized in that the general structural formula is as follows: The polymerization site of the polycyclic phosphoric acid is at any position on the benzene ring, and the value of n ranges from 2 to 10,000,000; R ₁ , R ₂ , R ₃ and R ₄ are selected from: H, halogen group, cyano group, alkyl group, aromatic group, and cyclic group. 4. The polycyclic phosphoric acid polymer material according to claim 3, characterized in that the halogen group is F, Cl, Br or I; the alkyl group is a (C1-C40) straight chain alkyl group, a (C3-C40) branched chain alkyl group or a (C3-C40) cycloalkyl group; in the alkyl group, one or more non-adjacent C atoms are optionally replaced by -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -CR ⁰ ＝CR ⁰⁰ - or -C≡C-, wherein R ⁰ and R ⁰⁰ is independently a straight-chain alkyl, a branched alkyl or a cycloalkyl; in the alkyl, one or more H atoms are optionally replaced by F, Cl, Br, I or CN; the aromatic group is one or more of an aryl, a heteroaryl, an aryloxy, a heteroaryloxy, an arylcarbonyl, a heteroarylcarbonyl, an arylcarbonyloxy, a heteroarylcarbonyloxy, an aryloxycarbonyl and a heteroaryloxycarbonyl, and has 4 to 30 ring atoms; the annular group is used to annulate the benzene ring to form a macrocyclic naphthalene or anthracene. 5. The method for preparing the polycyclic phosphoric acid polymer material according to claim 3 or 4, characterized in that the specific steps are as follows: 1) Grafting a phosphate functional group onto the reaction site of N of polycyclic phosphoric acid to obtain a polycyclic phosphate molecule, and then adding a halogenated compound to perform halogenation substitution to obtain a halogenated polycyclic phosphate; Or, a phosphate functional group is grafted onto the reaction site of N of the halogenated polycyclic molecule to obtain a halogenated polycyclic phosphate; wherein the mass ratio of the polycyclic phosphate to the halogenated compound is 1:0.01-1000; 2) adding or not adding other halogenated compounds to the halogenated polycyclic phosphate prepared in step 1), and then adding a solvent and a catalyst to carry out a polymerization reaction, wherein the reaction time is less than 72 hours and the reaction temperature is less than 300° C.; 3) After the polymerization reaction in step 2) is completed, halogenated silane and alcohol are added for hydrolysis to obtain a polycyclic phosphoric acid polymer material. 6 . The method for preparing a polycyclic phosphoric acid polymer material according to claim 5 , wherein the other halogenated compound in step 2) is a halogenated aromatic hydrocarbon or a halogenated thiophene with or without a substituent. 7. The method for preparing a polycyclic phosphate polymer material according to claim 6 is characterized in that the aromatic group of the halogenated aromatic hydrocarbon is one or more of an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylcarbonyl group, a heteroarylcarbonyl group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, an aryloxycarbonyl group and a heteroaryloxycarbonyl group. 8. Use of the polycyclic phosphoric acid polymer material according to claim 3 or 4 in the preparation of optoelectronic device structures. 9. Use of the polycyclic phosphate polymer material according to claim 8 in the preparation of a photoelectric device structure, characterized in that the photoelectric device structure is a solar cell, a field effect transistor, a photodetector, a radiation detector and a light emitting diode. 10. The use of the polycyclic phosphoric acid polymer material according to claim 9 in preparing a photovoltaic device structure, wherein the structure of the solar cell is as follows: