Random copolymer containing carbazole polyphosphate as well as preparation method and application of random copolymer

Abstract

The invention provides a random copolymer containing polyphosphoric acid carbazole and a preparation method and application thereof, and belongs to the technical field of new energy materials, the random copolymer containing polyphosphoric acid carbazole contains a structural unit A, a structural unit B and a structural unit C. The structural unit A is of a structure as shown in a formula (1), the structural unit B is of a structure as shown in a formula (2), and the structural unit C is of a structure as shown in a formula (3). And the structural unit C has a structure as shown in a formula (3) or a formula (4). The prepared random copolymer containing carbazole polyphosphate has the characteristics of good film-forming property, excellent stability, difficulty in diffusion and the like. The interaction among macromolecular chains can effectively solve the problems of poor compactness, easy diffusion and the like of traditional carbazole phosphate micromolecules, so that a stable photoelectric device based on polyphosphocarbazole is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new energy materials, in particular to a random copolymer containing poly-carbazole phosphate and a preparation method and application thereof. BACKGROUND

[0002] Small molecule polycyclic phosphoric acid is a hole transport material developed in recent years, which has the advantage of solution processing. It can form a monolayer on conductive substrates (ITO and FTO). Compared with PTAA type polytriphenylamine hole transport layer material, the perovskite film has better wettability on small molecule polycyclic phosphoric acid, which is beneficial to the large-area coating of the perovskite film. It can realize efficient hole transport in trans-perovskite photovoltaic devices. Nowadays, small molecule polycyclic phosphoric acid has become a commonly used hole transport material for trans-structure perovskite solar cells. Although the phosphoric acid carbazole small molecule has excellent hole transport performance, its own compactness and stability have always been a problem. The phosphoric acid carbazole small molecule needs to form a dense and uniform monolayer on the conductive substrate to realize efficient hole transport. However, in the actual solution processing process, the phosphoric acid carbazole small molecule will form a multilayer in some local areas, which will increase the resistance of hole extraction. The phosphoric acid carbazole small molecule will also diffuse to the perovskite active layer under the condition of light and heat. In addition, on some rough conductive substrates such as FTO, the phosphoric acid carbazole small molecule cannot completely cover the entire conductive substrate, so that the perovskite film directly contacts the conductive substrate. This situation will cause local leakage on one hand, and the conductive substrate will induce the decomposition of the perovskite on the other hand, which will cause the degradation of the perovskite solar cell.

[0003] At present, poly-carbazole phosphate is used to improve the stability of polycyclic phosphoric acid. However, the existing poly-carbazole phosphate has the problems of poor solubility and poor wettability, which will affect the hole transport efficiency. Therefore, developing a new hole transport layer material to solve the current problems of polycyclic phosphoric acid is an important step to improve the stability of trans-perovskite photovoltaic devices and promote the industrialization process. SUMMARY

[0004] In view of the technical problems in the background art, the present application provides a random copolymer containing poly-carbazole phosphate and a preparation method and application thereof, which aims to solve the technical problems of poor solubility and wettability of the existing poly-carbazole phosphate.

[0005] In a first aspect, the embodiments of the present application provide a random copolymer containing poly-carbazole phosphate, which contains structural unit A, structural unit B and structural unit C. The structural unit A is a structure shown in formula (1), the structural unit B is a structure shown in formula (2), and the structural unit C is a structure shown in formula (3) or formula (4). Formula (1); Formula (2); Equation (3); Equation (4); Where m ranges from 2 to 40, and M ranges from 2 to 1000; The value of n ranges from 2 to 40, and the value of N ranges from 2 to 1000. The value of x ranges from 2 to 40, and the value of X ranges from 2 to 1000. The value of y ranges from 2 to 40, and the value of Y ranges from 2 to 1000.

[0006] Secondly, embodiments of this application provide a method for preparing a random copolymer containing polyphosphate carbazole, comprising the following steps: subjecting compound I, compound II and compound III to a Yamamoto coupling reaction in a solvent to obtain a random copolymer containing polyphosphate carbazole. Compound I is ; Compound II is ; Compound III is or ; Where n ranges from 2 to 40, m ranges from 2 to 40, x ranges from 2 to 40, and y ranges from 2 to 40; R1, R1', R2, R2', R3, R3', R4, and R4' are each independently selected from halogen groups; A random copolymer containing polyphosphate carbazole is reacted with a halosilane to generate a polyphosphate carbazole derivative. A random copolymer containing polycarbazole was obtained by alcoholysis of a polyphosphoric acid carbazole derivative and an alcohol compound.

[0007] Thirdly, embodiments of this application provide an application of a random copolymer containing carbazole polyphosphate in the structure of an optoelectronic device.

[0008] The advantages of this application, which differ from existing technical solutions, include: The random copolymer containing carbazole polyphosphate prepared in this invention exhibits excellent film-forming properties, superior stability, and resistance to diffusion. The interactions between its polymer chains effectively address the problems of poor compactness and easy diffusion inherent in traditional small-molecule carbazole polyphosphate, thereby enabling stable optoelectronic devices based on carbazole polyphosphate. The addition of phenylalkoxy groups (structural unit C) effectively enhances the wettability of the carbazole polyphosphate molecule, forming a high-quality, uniform, and dense carbazole polyphosphate layer. Structural units A and B give the molecule tunable energy levels, which can be adjusted by varying the proportions of the added molecules.

[0009] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Detailed Implementation

[0010] The embodiments of the technical solution of this application will be described in detail below. The following embodiments are only used to illustrate the technical solution of this application more clearly, and are therefore only examples, and should not be used to limit the scope of protection of this application.

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion.

[0012] To address the technical problems of poor solubility and wettability of existing polycarbazole polyphosphate, this application provides a random copolymer containing polycarbazole polyphosphate, its preparation method, and its application. The random copolymer containing polycarbazole polyphosphate prepared in this invention exhibits good film-forming properties, excellent stability, and resistance to diffusion. The interactions between its polymer chains can effectively solve the problems of poor compactness and easy diffusion of traditional small-molecule polycarbazole phosphate, thereby realizing stable optoelectronic devices based on polycarbazole polyphosphate.

[0013] In the first aspect, embodiments of this application provide a random copolymer containing carbazole polyphosphate, wherein the random copolymer containing carbazole polyphosphate contains structural unit A, structural unit B and structural unit C, structural unit A is the structure shown in formula (1), structural unit B is the structure shown in formula (2), and structural unit C is the structure shown in formula (3) or formula (4). Equation (1); Equation (2); Equation (3); Equation (4); Where m ranges from 2 to 40, and M ranges from 2 to 1000; The value of n ranges from 2 to 40, and the value of N ranges from 2 to 1000. The value of x ranges from 2 to 40, and the value of X ranges from 2 to 1000. The value of y ranges from 2 to 40, and the value of Y ranges from 2 to 1000.

[0014] Furthermore, in some embodiments, the random copolymer containing carbazole polyphosphate is selected from one or more of the following structural formulas:

[0015]

[0016]

[0017]

[0018] .

[0019] Secondly, embodiments of this application provide a method for preparing a random copolymer containing polyphosphate carbazole, comprising the following steps: subjecting compound I, compound II and compound III to a Yamamoto coupling reaction in a solvent to obtain a random copolymer containing polyphosphate carbazole; Compound I is ; Compound II is ; Compound III is or ; Where n ranges from 2 to 40, m ranges from 2 to 40, x ranges from 2 to 40, and y ranges from 2 to 40; R1, R1', R2, R2', R3, R3', R4, and R4' are each independently selected from halogen groups; A random copolymer containing polyphosphate carbazole is reacted with a halosilane to generate a polyphosphate carbazole derivative. A random copolymer containing polycarbazole was obtained by alcoholysis of a polyphosphoric acid carbazole derivative and an alcohol compound.

[0020] Furthermore, in some embodiments, the Yamamoto coupling reaction in step S1 includes the following steps: S11. Ni(Cod)2, bipyridine and 5-cyclooctadiene are dissolved in DMF, heated and stirred to obtain a reaction solution; Compound I, compound II and compound III were dispersed in DMF to obtain a mixture; S12. Add the mixture dropwise to the reaction solution and stir the reaction at a temperature of 20~100℃. After the reaction is completed, cool to room temperature, add dilute hydrochloric acid dropwise, and after purification and drying, obtain a random copolymer containing polyphosphate carbazole.

[0021] Furthermore, the reaction of the random copolymer containing polyphosphate carbazole with the halosilane in step S2 includes the following steps: A random copolymer containing polyphosphate carbazole was dissolved in dichloromethane, and a halosilane was added dropwise to the solution. The mixture was stirred to obtain a polyphosphate carbazole derivative.

[0022] Furthermore, in some embodiments, the alcoholysis reaction in step S3 includes the following steps: An alcohol compound was added to a carbazole phosphate derivative, the mixture was stirred and reacted, and after the reaction was completed, it was concentrated by vacuum distillation, purified and dried to obtain a random copolymer containing carbazole polyphosphate.

[0023] Furthermore, in some embodiments, the molar ratio of compound I, compound II and compound III is (1~1000):1:(1~1000).

[0024] Thirdly, embodiments of this application provide an application of a random copolymer containing carbazole polyphosphate in the structure of an optoelectronic device.

[0025] Furthermore, in some embodiments, the optoelectronic device structure includes a solar cell, a field-effect transistor, a photodetector, a radiation detector, and a light-emitting diode, wherein the solar cell includes organic solar cells and perovskite solar cells.

[0026] Furthermore, in some embodiments, random copolymers containing carbazole polyphosphate are used as hole transport layer materials in organic solar cells or perovskite solar cells, or as interface modifications on the basis of existing hole transport layers.

[0027] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0028] I. Preparation Method Example 1 Step 1: Dissolve 3.25 g of 3,6-dibromocarbazole and 2.1 g of potassium carbonate in 20 mL of 1,4-dibromobutane, add 0.485 g of tetrabutylammonium bromide, followed by 5.2 mL of 50% potassium hydroxide. Stir at 60 °C for 12 hours. After cooling to room temperature, concentrate under reduced pressure, filter to obtain the product, and purify by column chromatography to obtain 4.1 g of 3,6-dibromo-9-(4-bromobutyl)-9H-carbazole (3,6-dibromo-9-(4-bromobutyl)-9-hydro-carbazole), with the following structural formula:

[0029] 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, 2.1Hz2H), 4.30(t, 7.3Hz, 2H), 3.37(t ,6.4Hz ,2H),2.07–1.99(m ,2H) ,1.91,1.85 (m ,2H) .

[0030] 13 CNMR (400MHz, CDCl3, ppm): 139.21, 129.21, 123.58, 123.41, 112.25, 110.28, 42.52, 32.84, 30.06.

[0031] Step 2: Dissolve 1g of 3,6-dibromo-9-(4-bromobutyl)-9H-carbazole in 10mL of triethyl phosphite and heat and stir at 140℃ for 12 hours. Remove triethyl phosphite by vacuum distillation and purify by column chromatography to obtain diethyl(4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate(4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate, with the following structural formula:

[0032] 1 HNMR(400MHz,CDCl3,ppm):8.12(d,2.1Hz,2H),7.54(dd,J=8.7Hz,1.9Hz,2H) ,7.25(d,8.9Hz,2H),4.25(t,J=7.9Hz,2H),3.9-4.06(m,4H),1.61-1.96(m,6H) ,1.25(t,J=7.1Hz,6H). 13 CNMR (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. Step 3: Dissolve 4.25 g of 5,9-dibromo-7H-dibenzo[C,G]carbazole and 2.1 g of potassium carbonate in 20 mL of 1,4-dibromobutane, add 0.485 g of tetrabutylammonium bromide, followed by 5.2 mL of 50% potassium hydroxide, and stir at 60 °C for 12 hours. After cooling to room temperature, concentrate under reduced pressure, filter to obtain the product, and purify by column chromatography to obtain 5.1 g of 5,9-dibromo-7-(4-bromobutyl)-7H-dibenzo[C,G]carbazole (5,9-dibromo-7-(4-bromobutyl)-7H-dibenzo[C,G]carbazole), with the following structural formula:

[0033] 1 H NMR (400MHz, CDCl3, δ): 8.88 (d,J=9.0Hz,2H) ,8.14(d,J=2.3Hz, 2H) ,7.77 (d, J=8.8Hz,2H) ,7.67 (t,J=8.9Hz,4H) ,4.51 (t,J=7.2Hz, 2H) ,3.36 (t,J =6.4Hz, 2H), 2.08 (dd J= 15.2,7.7Hz, 2H), 1.90(t,J = 7.6Hz,2H) Step 4: Dissolve 1g of 5,9-dibromo-7-(4-bromobutyl)-7H-dibenzo[c,g]carbazole in 10mL of triethyl phosphite and heat and stir at 140℃ for 12 hours. Remove triethyl phosphite by vacuum distillation and purify by column chromatography to obtain diethyl(4-(5,9-dibromo-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonate((4-(5,9-dibromo-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonate), with the following structural formula:

[0034] 1H NMR (400MHz, CDCl3, δ): 8.89 (d, J =8.9Hz, 2H), 8.14 (d, J = 2.5Hz, 2H), 7.78 (d, J = 8.8Hz, 2H), 7.68 (dd J =8.9, 2.4Hz, 4H), 4.51 (t, J = 7. OHz, 2H) ,3.99(p,J=7.9,7.2Hz,4H) , 2.03 (s, 2H) ,1.71(d J=14.9Hz,2H) ,1.25(d,J=6.7Hz,2H) , 1.20(q,J =7.0,6.OHz,6H). Step 5: Add 8g Ni(Cod)2, 2.86g bipyridine, and 2.3mL 1,5 Cyclooctadiene was dissolved in 100 mL of DMF and heated and stirred at 80 °C for half an hour. 6 g of (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate((4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate was then added. 2g diethyl(4-(5,9-dibromo-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonate((4-(5,9-dibromo-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonate), 2g 1,4-Dibromo-2,5-dipropoxybenzene was dissolved in 100 mL of DMF and slowly added dropwise to the reaction system. The mixture was stirred at 80 °C for 24 hours. After the reaction was completed and cooled to room temperature, dilute hydrochloric acid was slowly added dropwise while stirring until the solution dissolved and became a transparent green solution. The suspended solid was filtered off, and the final product was a yellow random copolymer powder containing polyphosphate carbazole, with the following structural formula: .

[0035] Step Six: Dissolve 1.2g of the random copolymer containing polyphosphate carbazole in 200mL of dichloromethane, add 20mL of 0.1g / mL trimethylbromosilane dropwise, and stir at room temperature for 24 hours. After the reaction is complete, add excess methanol dropwise to the reaction system to remove excess trimethylbromosilane. Concentrate the solution by vacuum distillation, precipitate in diethyl ether, and filter and wash with diethyl ether. The final product is a random copolymer containing polyphosphate carbazole, with a number average molecular weight of approximately 8000 and a weight average molecular weight of approximately 10000. The structural formula is as follows: .

[0036] Comparative Example 1 8g Ni(Cod)2, 2.86g bipyridine, and 2.3mL 1,5 Cyclooctadiene was dissolved in 100 mL of DMF and heated and stirred at 80 °C for half an hour. 6 g of (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate((4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate was then added. (2-butyl)-diethyl phosphate was dissolved in 100 mL of DMF and slowly added dropwise to the reaction system. The mixture was stirred at 80 °C for 24 hours. After the reaction was completed and cooled to room temperature, dilute hydrochloric acid was slowly added dropwise while stirring until the solution dissolved and became a transparent green solution. The suspended solid was filtered off, and the final product was polyphosphate carbazole powder. 1.2 g of a random copolymer containing polyphosphate carbazole was dissolved in 200 mL of dichloromethane, and 20 mL of 0.1 g / mL trimethylbromosilane was added dropwise. The mixture was stirred at room temperature for 24 hours. After the reaction was complete, excess methanol was added dropwise to the reaction system to remove excess trimethylbromosilane. The solution was concentrated by vacuum distillation, precipitated in diethyl ether, and filtered and washed with diethyl ether. The final product was polyphosphate carbazole (poly-4PACz) powder, with the following structural formula: .

[0037] Example 2 ITO conductive glass was treated in a UV ozone cleaner for 15 minutes, then coated with 1 mg / L of the polyphosphate carbazole prepared in Example 1, and annealed at 100°C. Subsequently, MA was coated... 0.7 FA 0.3 A 25nm C200PbI3 perovskite polycrystalline thin film was deposited on its surface after thermal annealing. 60 The fabrication of perovskite solar cells was completed using 5nm BCP and 100nm copper electrodes.

[0038] Example 3 The difference between Example 3 and Example 2 is that the annealing temperature is 150°C.

[0039] Example 4 The difference between Example 4 and Example 2 is that the annealing temperature is 200°C.

[0040] Example 5 The ITO conductive glass was treated in an ultraviolet ozone cleaner for 15 minutes, then a 1 nm thick layer of polyphosphate carbazole was spin-coated, followed by a PM6:Y6 active layer, and finally a 5 nm PDINN was spin-coated and a 100 nm silver electrode was deposited by evaporation to complete the fabrication of the organic solar cell.

[0041] Example 6 FTO conductive glass was treated in a UV ozone cleaner for 15 minutes, then coated with a random copolymer containing 1 mg / ml of carbazole polyphosphate, and annealed at 150°C. Subsequently, MA was coated. 0.7 FA 0.3 A polycrystalline PbI3 perovskite film was thermally annealed, and then 25 nm C60, 5 nm BCP, and 100 nm copper electrodes were deposited on its surface to complete the fabrication of a perovskite solar cell. The resulting perovskite solar cell exhibited a photoelectric conversion efficiency of 18.68%, indicating that the random copolymer containing carbazole polyphosphate can achieve good photoelectric conversion efficiency on both ITO and FTO substrates.

[0042] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that the ITO conductive glass was treated in an ultraviolet ozone cleaner for 15 minutes, and then the polyphosphate carbazole prepared in Comparative Example 1 was coated onto it and annealed at 100°C. Subsequently, MA was coated onto it. 0.7 FA 0.3 A 25nm C200PbI3 perovskite polycrystalline thin film was deposited on its surface after thermal annealing. 60 The fabrication of perovskite solar cells was completed using 5nm BCP and 100nm copper electrodes.

[0043] Comparative Example 3 The difference between Comparative Example 3 and Comparative Example 2 is that the annealing temperature is 150℃.

[0044] Comparative Example 4 The difference between Comparative Example 4 and Comparative Example 2 is that the annealing temperature is 200℃.

[0045] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that the ITO conductive glass was treated in a UV ozone cleaner for 15 minutes, then coated with a small molecule carbazole phosphate, and annealed at 100°C. Subsequently, MA was coated... 0.7 FA 0.3 A 25nm C200PbI3 perovskite polycrystalline thin film was deposited on its surface after thermal annealing. 60 The fabrication of perovskite solar cells was completed using 5nm BCP and 100nm copper electrodes.

[0046] Comparative Example 6 The difference between Comparative Example 6 and Comparative Example 5 is that the annealing temperature is 150℃.

[0047] Comparative Example 7 The difference between Comparative Example 7 and Comparative Example 5 is that the annealing temperature is 200℃.

[0048] II. Testing Methods 1. JV curve: Recorded using a Keithley 2400 source measurement unit and a solar simulator (Oriel, model 9119) equipped with an AM1.5G spectral line, with a black mask having an effective area of ​​0.0556 square centimeters.

[0049] 2. Light Intensity: Calibrated using a reference silicon solar cell (KG3, Enlitech). The scan speed for both forward and reverse scans was 0.02Vs~1.

[0050] III. Analysis of Test Results for Each Embodiment and Comparative Example (1) The performance of the perovskite solar cells prepared in Examples 2-4 and Comparative Examples 2-7 was tested, and the test results are shown in Table 1 below.

[0051] Table 1 Performance test results of perovskite solar cells

[0052] The results of the study on annealing temperature showed that small molecule carbazole phosphate is more sensitive to annealing temperature, while random copolymers containing carbazole polyphosphate are not sensitive to annealing temperature.

[0053] Perovskite solar cells based on random copolymers containing carbazole polyphosphate can achieve a photoelectric conversion efficiency of 24.56%, which exceeds that of comparative examples 2-4 based on carbazole polyphosphate and comparative examples 5-7 based on small molecule carbazole phosphate.

[0054] (2) Small molecule carbazole phosphate and polycarbazole phosphate have poor coverage on ITO, with local multilayer stacking. The current is small and the resistance is large in the conductive atomic force microscopy test. Random copolymers containing polycarbazole phosphate have good coverage and film-forming properties on ITO, with large current and small resistance, which is beneficial for hole extraction.

[0055] (3) Perovskite solar cells based on small molecule carbazole phosphate and random copolymers containing carbazole polyphosphate were encapsulated and placed under a solar simulator for stability testing at the maximum power point. After more than 100 hours of testing, no significant efficiency degradation was found in the perovskite solar cells based on random copolymers containing carbazole polyphosphate, while the perovskite solar cells based on small molecule carbazole phosphate showed severe degradation, indicating that the random copolymers containing carbazole polyphosphate have better light stability.

[0056] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A random copolymer containing carbazole polyphosphate, characterized in that, The random copolymer containing carbazole polyphosphate contains structural unit A, structural unit B and structural unit C, wherein the molar ratio of structural unit A, structural unit B and structural unit C is (1~1000):(1~1000):1, structural unit A is the structure shown in formula (1), structural unit B is the structure shown in formula (2), and structural unit C is the structure shown in formula (3) or formula (4). Equation (1); Equation (2); Equation (3); Equation (4); Where m ranges from 2 to 40, and M ranges from 2 to 1000; The value of n ranges from 2 to 40, and the value of N ranges from 2 to 1000. The value of x ranges from 2 to 40, and the value of X ranges from 2 to 1000. The value of y ranges from 2 to 40, and the value of Y ranges from 2 to 1000.

2. The random copolymer containing carbazole polyphosphate according to claim 1, characterized in that, The random copolymer containing carbazole polyphosphate includes one or more of the following structural formulas: 。 3. A method for preparing a random copolymer containing carbazole polyphosphate as described in claim 1 or 2, characterized in that, Includes the following steps: S1. Compounds I, II and III undergo a Yamamoto coupling reaction in DMF to obtain a random copolymer containing polyphosphate carbazole. Compound I is ; Compound II is ; Compound III is or ; Where n ranges from 2 to 40, m ranges from 2 to 40, x ranges from 2 to 40, and y ranges from 2 to 40; R1, R1', R2, R2', R3, R3', R4, and R4' are each independently selected from halogen groups; S2. The random copolymer containing polyphosphate carbazole is reacted with a halosilane to generate a polyphosphate carbazole derivative. S3. The polyphosphate carbazole derivative and an alcohol compound are subjected to an alcoholysis reaction to obtain a random copolymer containing polyphosphate carbazole.

4. The method for preparing the random copolymer containing carbazole polyphosphate according to claim 3, characterized in that, The Yamamoto coupling reaction described in step S1 includes the following steps: S11. Ni(Cod)2, bipyridine and 5-cyclooctadiene are dissolved in DMF, heated and stirred to obtain a reaction solution; Compound I, compound II and compound III were dispersed in DMF to obtain a mixture; S12. The mixture is added dropwise to the reaction solution, and the reaction is stirred at a temperature of 20~100℃. After the reaction is completed, the mixture is cooled to room temperature, dilute hydrochloric acid is added dropwise, and after purification and drying, a random copolymer containing polyphosphate carbazole is obtained.

5. The method for preparing the random copolymer containing carbazole polyphosphate according to claim 3, characterized in that, The reaction of the random copolymer containing polyphosphate carbazole with the halosilane in step S2 includes the following steps: A random copolymer containing polyphosphate carbazole was dissolved in dichloromethane, and a halosilane was added dropwise to the solution. The mixture was stirred to obtain a polyphosphate carbazole derivative.

6. The method for preparing the random copolymer containing carbazole polyphosphate according to claim 3, characterized in that, The alcoholysis reaction in step S3 includes the following steps: An alcohol compound was added to a carbazole phosphate derivative, the mixture was stirred and reacted, and after the reaction was completed, it was concentrated by vacuum distillation, purified and dried to obtain a random copolymer containing carbazole polyphosphate.

7. The method for preparing the random copolymer containing carbazole polyphosphate according to claim 3, characterized in that, The molar ratio of compound I, compound II and compound III is (1~1000):(1~1000):

1.

8. The application of a random copolymer containing carbazole polyphosphate as described in claim 1 or 2 in the structure of an optoelectronic device.

9. The application according to claim 8, characterized in that, The optoelectronic device structure includes a solar cell, a field-effect transistor, a photodetector, a radiation detector, and a light-emitting diode. The solar cell includes organic solar cells and perovskite solar cells.

10. The application according to claim 9, characterized in that, The random copolymer containing carbazole polyphosphate can be used as a hole transport layer material in organic solar cells or perovskite solar cells, or as an interface modification of the existing hole transport layer.

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