Hole transport polymer material, preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a hole transport polymer material, a preparation method therefor, and a use thereof. The hole transport polymer material comprises at least one of a compound represented by formula 1, a compound represented by formula 2, a compound represented by formula 3, and a compound represented by formula 4. The hole transport polymer material has excellent hole extraction and anchoring effects and good wettability for a perovskite precursor solution, so that the efficiency and stability of a device are significantly improved.

Description

Hole transport polymer material and preparation method and application TECHNICAL FIELD

[0001] The present application belongs to the technical field of perovskite, and particularly relates to a hole transport polymer material and a preparation method and application thereof. BACKGROUND

[0002] With the development of society, the demand for energy by human beings is increasing, and the energy structure based on fossil energy such as oil, coal and natural gas cannot fully meet the needs of human beings. In addition, fossil energy is a non-renewable energy source, and has limited reserves, high development cost and causes environmental pollution during use, which is not suitable for the current environmental protection concept trend. In order to better solve the energy problem, people have developed many clean energy sources, such as wind energy, tidal energy, geothermal energy, biomass energy, nuclear energy and solar energy. Among them, due to the reasons of technical complexity and cost-effectiveness, solar energy is considered to be the most potential and valuable new clean energy, and the use of solar cells to generate electricity is considered to be one of the most promising methods.

[0003] Since perovskite solar cells were discovered by Japanese scientists in 2009, the photoelectric conversion efficiency thereof has rapidly increased in the past decade. At present, the efficiency of perovskite solar cells of laboratory size has exceeded 26%, which is only less than 1% of the efficiency of single crystal silicon cells, so perovskite solar cells are expected to be industrialized as soon as possible.

[0004] An excellent hole transport layer is crucial for improving the performance and stability of perovskite solar cells, and therefore many different kinds of hole materials have been developed. In recent years, small molecule hole materials for inverted structure cells have developed rapidly, and the efficiency of inverted structure cells has been improved to more than 26%, and the efficiency is still rising, so they have very good prospects. However, small molecule hole materials also have the disadvantages of poor film forming property and poor material stability, which limits large-scale commercial application. SUMMARY

[0005] The present application aims to at least partially solve one of the technical problems in the related art. To this end, one object of the present application is to provide a hole transport polymer material and a preparation method and application thereof. The hole transport polymer material has excellent hole extraction and anchoring effects, and good wettability to perovskite precursor solution, thereby significantly improving the efficiency and stability of the device.

[0006] In one aspect of the present application, a hole transport polymer material is provided. According to embodiments of the present application, the hole transport polymer material comprises at least one of a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3 and a compound represented by Formula 4;

[0007] According to the hole transport polymer material of the above-mentioned embodiments of the present application, including at least one of the compounds shown in Formula 1, the compounds shown in Formula 2, the compounds shown in Formula 3 and the compounds shown in Formula 4, firstly, the carbazole structure, the phenothiazine structure, the acridine structure and the diphenylamine structure in the compounds shown in Formula 1, the compounds shown in Formula 2, the compounds shown in Formula 3 and the compounds shown in Formula 4 can effectively extract holes, thereby improving the device efficiency; secondly, the phosphonic acid group in the compounds shown in Formula 1, the compounds shown in Formula 2, the compounds shown in Formula 3 and the compounds shown in Formula 4 has strong anchoring performance, mainly because the hydroxyl group in the phosphonic acid group can form a covalent bond with the hydroxyl group on the surface of the conductive glass (FTO, ITO), so that the hole transport polymer material can form a firm action with the conductive glass, not only can completely cover the conductive glass to avoid the current loss problem caused by the hole transport layer forming a hole, but also the polymer material is firmly fixed on the conductive glass, which is conducive to charge transport, so that the device efficiency and stability are improved. At the same time, the lower end of the polymer material can not only be anchored to the surface of the conductive glass or other metal oxides, but also the polymer material has good wettability to the perovskite precursor solution, which can make the perovskite precursor solution form a good spread, improve the film forming quality of the perovskite, and further improve the device efficiency. Therefore, the hole transport polymer material has excellent hole extraction and anchoring effect, and good wettability to the perovskite precursor solution, thereby significantly improving the efficiency and stability of the device.

[0008] In addition, the hole transport polymer material according to the above-mentioned embodiments of the present application can also have the following additional technical features:

[0009] In some embodiments of the present application, a1 is an integer of 100-1000, and b1 is an integer of 2-10.

[0010] In some embodiments of the present application, a2 is an integer of 100-1000, b2 is an integer of 2-10, and b3 is an integer of 2-10.

[0011] In some embodiments of the present application, a3 is an integer of 100-1000, b4 is an integer of 2-10, and b5 is an integer of 2-10.

[0012] In some embodiments of the present application, a4 is an integer of 100-1000, b6 is an integer of 2-10, and b7 is an integer of 2-10.

[0013] In some embodiments of the present application, a1 is an integer of 100-1000, and b1 is an integer of 2-4.

[0014] In some embodiments of the present application, a2 is an integer of 100-1000, b2 is an integer of 2-4, and b3 is an integer of 2-4.

[0015] In some embodiments of the present application, a3 is an integer from 100 to 1000, b4 is an integer from 2 to 4, and b5 is an integer from 2 to 4.

[0016] In some embodiments of the present application, a4 is an integer from 100 to 1000, b6 is an integer from 2 to 4, and b7 is an integer from 2 to 4.

[0017] In another aspect of the present application, the present application provides a method for preparing the hole-transporting polymer material described above. According to embodiments of the present application, the method comprises:

[0018] (1) 2,7-dihalocarbazole, 2,7-dihalo-9,9-dimethylacridine, 3,6-dihalophenothiazine, and 4,4-dihalodiphenylamine, respectively, are reacted with halogenated alkane in the presence of a first strong base and a phase transfer catalyst, so as to obtain 2,7-dihalo-9-halogenated alkylcarbazole, 2,7-dihalo-9,9-dimethyl-10-halogenated alkylacridine, 3,6-dihalo-10-halogenated alkylphenothiazine, and N-halogenated alkyl-4,4-dihalodiphenylamine, respectively;

[0019] (2) 2,7-dihalo-9-halogenated alkylcarbazole is reacted with bis(pinacolato)diboron in the presence of a second strong base and a first catalyst in a first solvent, so as to obtain 9-halogenated alkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole;

[0020] (3) 2,7-dihalo-9-halogenated alkylcarbazole, 2,7-dihalo-9,9-dimethyl-10-halogenated alkylacridine, 3,6-dihalo-10-halogenated alkylphenothiazine, N-halogenated alkyl-4,4-dihalodiphenylamine, and 9-halogenated alkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, respectively, are reacted with triethyl phosphite, so as to obtain product A, product B, product C, product D, and product E,

[0021] (4) the product A, the product B, the product C, the product D, respectively, are reacted with the product E in the presence of a second catalyst in a second solvent, so as to obtain carbazole-phosphodiethyl ester polymer, carbazole-acridine-phosphodiethyl ester polymer, carbazole-phenothiazine-phosphodiethyl ester polymer, and carbazole-diphenylamine-phosphodiethyl ester polymer, respectively;

[0022] (5) subjecting the carbazole phosphoric acid diethyl ester polymer, the carbazole-acridine phosphoric acid diethyl ester polymer, the carbazole-phenothiazine phosphoric acid diethyl ester polymer and the carbazole-diphenylamine phosphoric acid diethyl ester polymer to an ester hydrolysis reaction to obtain a compound shown in formula 1, a compound shown in formula 2, a compound shown in formula 3 and a compound shown in formula 4, respectively.

[0023] Thus, the method can be used to prepare the compound shown in formula 1, the compound shown in formula 2, the compound shown in formula 3 and the compound shown in formula 4 with excellent hole extraction and anchoring effect.

[0024] In addition, the method for preparing the hole transport polymer material according to the above-mentioned embodiments of the present application can further have the following technical features:

[0025] In some embodiments of the present application, in step (1), the halogen in the 2,7-dihalogenated carbazole, the halogen in the 2,7-dihalogenated-9,9-dimethyl acridine, the halogen in the 3,6-dihalogenated phenothiazine and the halogen in the 4,4-dihalogenated diphenylamine independently include at least one of chlorine, bromine and iodine.

[0026] In some embodiments of the present application, in step (1), the halogenated alkane has a carbon atom number of 2-10, and one hydrogen on each of the two carbon atoms in the halogenated alkane is replaced by halogen, and the halogen includes at least one of chlorine, bromine and iodine.

[0027] In some embodiments of the present application, in step (1), the first strong base includes at least one of potassium hydroxide, sodium hydroxide and potassium tert-butoxide.

[0028] In some embodiments of the present application, in step (1), the phase transfer catalyst includes at least one of tetrabutylammonium bromide and tetrabutylammonium iodide.

[0029] In some embodiments of the present application, in step (1), the reaction conditions include 25-70℃ under inert gas for 20-30h.

[0030] In some embodiments of the present application, in step (2), the second strong base includes at least one of potassium acetate and potassium carbonate.

[0031] In some embodiments of the present application, in step (2), the first catalyst includes at least one of 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride and bis(triphenylphosphine) palladium dichloride.

[0032] In some embodiments of the present application, in step (2), the first solvent includes at least one of 1,4-dioxane, dichloromethane, toluene and xylene.

[0033] In some embodiments of the present application, in step (2), the reaction conditions include refluxing under inert gas for 20-30 hours.

[0034] In some embodiments of the present application, in step (3), n1, n2, n3, n4, n5 are independently an integer from 2 to 10.

[0035] In some embodiments of the present application, in step (3), the reaction conditions include reacting at 160-165°C under inert gas for 20-30 hours.

[0036] In some embodiments of the present application, in step (4), the second catalyst includes at least one of tetrakis(triphenylphosphine)palladium, palladium acetate and palladium chloride.

[0037] In some embodiments of the present application, in step (4), the second solvent includes at least one of a mixture of toluene and aqueous potassium carbonate, a mixture of toluene and aqueous sodium carbonate and a mixture of xylene and aqueous potassium carbonate.

[0038] In some embodiments of the present application, in step (4), the reaction conditions include reacting at 75-85°C under inert gas for 70-75 hours.

[0039] In some embodiments of the present application, in step (5), the solvent used in the ester hydrolysis reaction includes at least one of dichloromethane and 1,4-dioxane.

[0040] In some embodiments of the present application, in step (5), the reactants of the ester hydrolysis reaction include at least one of trimethylsilyl bromide, concentrated hydrochloric acid and concentrated sulfuric acid.

[0041] In a third aspect of the present application, the present application provides use of the above-mentioned hole-transporting polymer material or the hole-transporting polymer material obtained by the above-mentioned method in a perovskite solar cell, a perovskite LED or a perovskite sensor.

[0042] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0043] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings.

[0044] FIG. 1 is a hydrogen spectrum of a compound shown in formula 1 according to an embodiment of the present application;

[0045] FIG. 2 is a hydrogen spectrum of a compound shown in formula 2 according to an embodiment of the present application;

[0046] Figure 3 is a hydrogen spectrum of the compound shown in Formula 3 according to an embodiment of the present application;

[0047] Figure 4 is a hydrogen spectrum of the compound shown in Formula 4 according to an embodiment of the present application;

[0048] Figure 5 is a diagram of the contact angle test results of the materials of Examples 2-4 and Comparative Examples 1-2 according to the present application;

[0049] Figure 6 is a diagram of the perovskite solar stability test results of Examples 1-4 and Comparative Examples 1-2 according to the present application. DETAILED DESCRIPTION

[0050] The embodiments of the present application are described in detail below with the aim of explaining the present application, and cannot be understood as a limitation of the present application.

[0051] In one aspect of the present application, a hole transport polymer material is provided. According to an embodiment of the present application, the hole transport polymer material includes at least one of a compound shown in Formula 1, a compound shown in Formula 2, a compound shown in Formula 3, and a compound shown in Formula 4;

[0052] According to the hole transport polymer material of the above-mentioned embodiments of the present application, including at least one of the compound shown in Formula 1, the compound shown in Formula 2, the compound shown in Formula 3, and the compound shown in Formula 4, first, the carbazole structure, the phenothiazine structure, the acridine structure, and the diphenylamine structure in the compound shown in Formula 1, the compound shown in Formula 2, the compound shown in Formula 3, and the compound shown in Formula 4 can effectively perform hole extraction, thereby improving device efficiency; second, the phosphonic acid group in the compound shown in Formula 1, the compound shown in Formula 2, the compound shown in Formula 3, and the compound shown in Formula 4 has strong anchoring performance, mainly because the hydroxyl group in the phosphonic acid group can form a covalent bond with the hydroxyl group on the surface of the conductive glass (FTO, ITO), so that the hole transport polymer material can form a firm action with the conductive glass, not only can completely cover the conductive glass, avoid the current loss problem caused by the hole transport layer forming a hole, and the polymer material is firmly fixed on the conductive glass, which is conducive to charge transport, so that the device efficiency and stability are improved. At the same time, the lower end of the polymer material not only can be anchored with the surface of the conductive glass or other metal oxides, but also has good wettability to the perovskite precursor solution, which can make the perovskite precursor solution form a good spread, improve the film forming quality of the perovskite, and further improve the device efficiency. Therefore, the hole transport polymer material has excellent hole extraction and anchoring effect, and good wettability to the perovskite precursor solution, thereby significantly improving the efficiency and stability of the device.

[0053] According to embodiments of the present application, a1 is an integer from 100 to 1000, and b1 is an integer from 2 to 10. Preferably, a1 is an integer from 100 to 1000, and b1 is an integer from 2 to 4. The inventors have found that a1 and b1 in the above ranges can form a polymer, which is beneficial for film formation.

[0054] According to embodiments of the present application, a2 is an integer from 100 to 1000, b2 is an integer from 2 to 10, and b3 is an integer from 2 to 10. Preferably, a2 is an integer from 100 to 1000, b2 is an integer from 2 to 4, and b3 is an integer from 2 to 4. The inventors have found that a2, b2 and b3 in the above ranges can form a polymer, which is beneficial for film formation.

[0055] According to embodiments of the present application, a3 is an integer from 100 to 1000, b4 is an integer from 2 to 10, and b5 is an integer from 2 to 10. Preferably, a3 is an integer from 100 to 1000, b4 is an integer from 2 to 4, and b5 is an integer from 2 to 4. The inventors have found that a3, b4 and b5 in the above ranges can form a polymer, which is beneficial for film formation.

[0056] According to embodiments of the present application, a4 is an integer from 100 to 1000, b6 is an integer from 2 to 10, and b7 is an integer from 2 to 10. Preferably, a4 is an integer from 100 to 1000, b6 is an integer from 2 to 4, and b7 is an integer from 2 to 4. The inventors have found that a4, b6 and b7 in the above ranges can form a polymer, which is beneficial for film formation.

[0057] In another aspect of the present application, the present application provides a method for preparing the hole-transporting polymer material described above. According to embodiments of the present application, the method comprises:

[0058] S100: preparing 2,7-dihalo-9-haloalkylcarbazole, 2,7-dihalo-9,9-dimethyl-10- haloalkylacridine, 3,6-dihalo-10-haloalkylphenothiazine and N-haloalkyl-4,4- dihalodiphenylamine

[0059] In this step, 2,7-dihalocarbazole, 2,7-dihalo-9,9-dimethylacridine, 3,6-dihalophenothiazine, 4,4-dihalodiphenylamine respectively react with halogenated alkane in the presence of a first strong base and a phase transfer catalyst, thereby obtaining 2,7-dihalo-9-haloalkylcarbazole, 2,7-dihalo-9,9-dimethyl-10-haloalkylacridine, 3,6-dihalo-10-haloalkylphenothiazine and N-haloalkyl-4,4-dihalodiphenylamine respectively. Further, the halogen in 2,7-dihalocarbazole, the halogen in 2,7-dihalo-9,9-dimethylacridine, the halogen in 3,6-dihalophenothiazine and the halogen in 4,4-dihalodiphenylamine respectively independently include at least one of chlorine, bromine and iodine. For example, the reaction equation is as follows:

[0060] For example, 2,7-dihalocarbazole includes 2,7-dibromocarbazole, 2,7-dichlorocarbazole or 2,7-diiodocarbazole; 2,7-dihalo-9,9-dimethylacridine includes 2,7-dibromo-9,9-dimethylacridine, 2,7-dichloro-9,9-dimethylacridine or 2,7-diiodo-9,9-dimethylacridine; 3,6-dihalophenothiazine includes 3,6-dibromophenothiazine, 3,6-dichlorophenothiazine or 3,6-diiodophenothiazine; 4,4-dihalodiphenylamine includes 4,4-dibromodiphenylamine, 4,4-dichlorodiphenylamine or 4,4-diiododiphenylamine.

[0061] For example, 2,7-dihalo-9-haloalkylcarbazole includes but is not limited to 2,7-dibromo-9-bromoethylcarbazole, 2,7-dibromo-9-bromopropylcarbazole, 2,7-dibromo-9-bromobutylcarbazole and the like; 2,7-dihalo-9,9-dimethyl-10-haloalkylacridine includes but is not limited to 2,7-dibromo-9,9-dimethyl-10-bromoethylacridine, 2,7-dibromo-9,9-dimethyl-10-bromopropylacridine, 2,7-dibromo-9,9-dimethyl-10-bromobutylacridine and the like; 3,6-dihalo-10-haloalkylphenothiazine includes but is not limited to 3,6-dibromo-10-bromoethylphenothiazine, 3,6-dibromo-10-bromopropylphenothiazine, 3,6-dibromo-10-bromobutylphenothiazine and the like; N-haloalkyl-4,4-dihalodiphenylamine includes but is not limited to N-bromoethyl-4,4-dibromodiphenylamine, N-bromopropyl-4,4-dibromodiphenylamine, N-bromobutyl-4,4-dibromodiphenylamine and the like.

[0062] According to the embodiment of the present application, the first strong base includes but is not limited to at least one of potassium hydroxide, sodium hydroxide and potassium tert-butoxide. The phase transfer catalyst includes but is not limited to at least one of tetrabutylammonium bromide and tetrabutylammonium iodide. It should be noted that the first strong base is dissolved in water to participate in the reaction, and specifically, the concentration of the aqueous solution of the first strong base is about 50wt%.

[0063] According to embodiments of the present application, the halogenated alkane has a number of carbon atoms between 2 and 10, and one hydrogen on each of the two carbon atoms in the halogenated alkane is replaced by a halogen, which includes at least one of chlorine, bromine and iodine. For example, the halogenated alkane includes, but is not limited to, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,2-diiodoethane, 1,3-diiodopropane, or 1,4-diiodobutane, etc.

[0064] According to embodiments of the present application, the reaction conditions include a temperature between 25°C and 70°C under an inert gas for a time period between 20h and 30h. The inventors have found that controlling the temperature and time period of the reaction within the above ranges can substantially complete the reaction of the starting materials and control the occurrence of side reactions. It is noted that the inert gas includes, but is not limited to, nitrogen, argon, etc.

[0065] S200: preparing 9-haloalkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole

[0066] In this step, 2,7-dihalo-9-haloalkylcarbazole and bis(pinacolato)diboron react in a first solvent in the presence of a second strong base and a first catalyst to obtain 9-haloalkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole. Further, the first catalyst includes at least one of 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium and dichlorobistriphenylphosphine palladium; the first solvent includes at least one of 1,4-dioxane, dichloromethane, toluene and xylene; and the second strong base includes at least one of potassium acetate and potassium carbonate. The specific reaction process can be referred to the following reaction equation:

[0067] As an example, 9-haloalkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole includes, but is not limited to, 9-bromoethyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, 9-bromopropyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, etc.

[0068] According to an embodiment of the present application, the reaction condition includes refluxing the reaction under inert gas for 20-30 hours. The inventor finds that the reaction can be as complete as possible when the reaction time is controlled within the above range. It should be noted that different reaction materials have different refluxing temperatures, and those skilled in the art can control the refluxing temperature according to the different materials.

[0069] S300: preparing product A, product B, product C, product D and product E

[0070] In this step, 2,7-dihalogen-9-halogenalkylcarbazole, 2,7-dihalogen-9,9-dimethyl-10-halogenalkylacridine, 3,6-dihalogen-10-halogenalkylphenothiazine, N-halogenalkyl-4,4-dihalogen-diphenylamine and 9-halogenalkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole react with triethyl phosphite respectively to obtain product A. product B product C product D and product E Preferably, n1, n2, n3, n4 and n5 are independently integers from 2 to 10. Further, the reaction condition includes reacting the materials at 160-165°C under inert gas for 20-30 hours so as to make the materials react completely.

[0071] The specific reaction process can refer to the following reaction equation:

[0072] S400: preparing carbazole-phosphoric acid diethyl ester polymer, carbazole-acridine-phosphoric acid diethyl ester polymer, carbazole-phenothiazine-phosphoric acid diethyl ester polymer and carbazole-diphenylamine-phosphoric acid diethyl ester polymer

[0073] In this step, product A, the product B, the product C and the product D react with the product E respectively in a second solvent under the action of a second catalyst to obtain carbazole-phosphoric acid diethyl ester polymer, carbazole-acridine-phosphoric acid diethyl ester polymer, carbazole-phenothiazine-phosphoric acid diethyl ester polymer and carbazole-diphenylamine-phosphoric acid diethyl ester polymer respectively. Further, the second catalyst includes at least one of tetrakis(triphenylphosphine)palladium, palladium acetate and palladium chloride; and the second solvent includes at least one of a mixture of toluene and potassium carbonate aqueous solution, a mixture of toluene and sodium carbonate aqueous solution and a mixture of xylene and potassium carbonate aqueous solution. The specific reaction process can refer to the following reaction process:

[0074] According to an embodiment of the present application, the reaction condition includes reacting at 75-85°C under inert gas protection for 70-75 hours so as to make the reaction complete.

[0075] S500: preparing the compound shown in formula 1, the compound shown in formula 2, the compound shown in formula 3 and the compound shown in formula 4

[0076] In this step, the carbazole phosphoric acid diethyl ester polymer, the carbazole-acridine phosphoric acid diethyl ester polymer, the carbazole-phenothiazine phosphoric acid diethyl ester polymer and the carbazole-diphenylamine phosphoric acid diethyl ester polymer undergoes ester hydrolysis reaction, thereby obtaining the compound shown in formula 1, the compound shown in formula 2, the compound shown in formula 3 and the compound shown in formula 4 respectively. Further, the solvent used in the ester hydrolysis reaction includes at least one of dichloromethane and 1.4-dioxane. The reactant of the ester hydrolysis reaction includes at least one of trimethylsilyl bromide, concentrated hydrochloric acid and concentrated sulfuric acid. The specific reaction process can refer to the following reaction process:

[0077] Specifically, the hydrogen spectrum of the compound represented by Formula 1 is shown in FIG. 1, and it can be seen from FIG. 1 that1H NMR (300 MHz, DMSO-d6) δ 8.15 (dd, J = 7.5, 1.5 Hz, 2H), 7.75 (dd, J = 7.5, 1.5 Hz, 1H), 7.65 (dd, J = 7.5, 1.5 Hz, 1H), 7.24 (ddd, J = 7.5, 7.4, 1.5 Hz, 2H), 4.8 (s, 2H), 4.16 (d, J = 7.1 Hz, 2H), 1.74 (m, 2H), 1.66 (d, J = 7.1 Hz, 2H), 1.26 (m, 2H). The hydrogen spectrum of the compound represented by Formula 2 is shown in FIG. 2, and it can be seen from FIG. 2 that1H NMR (300 MHz, DMSO-d6) δ 8.31 (d, J = 7.5 Hz, 1H), 7.96 (dd, J = 7.5, 1.5 Hz, 1H), 7.91 (dd, J = 7.5, 1.5 Hz, 1H), 7.76 (d, J = 1.5 Hz, 1H), 7.74 (d, J = 1.5 Hz, 1H), 7.64 (dd, J = 7.5, 1.5 Hz, 1H), 7.45 (dd, J = 7.5, 1.5 Hz, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.33 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.19 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.17 (dd, J = 7.5, 1.5 Hz, 1H), 7.14 (dd, J = 7.5, 1.5 Hz, 1H), 4.16 (t, J = 7.1 Hz, 2H), 3.93 (t, J = 7.1 Hz, 2H), 1.74 (m, 2H), 1.69 (s, 6H), 1.66 (m, 4H), 1.49 (m, 2H) 1.26 (m, 4H).The hydrogen spectrum of the compound shown in formula 3 is shown in Figure 3. As can be seen from Figure 3, 1H NMR (300 MHz, DMSO-d6) δ 8.32 (d, J = 7.5 Hz, 1H), 7.96 (dd, J = 7.5, 1.5 Hz, 1H), 7.91 (dd, J = 7.5, 1.5 Hz, 1H), 7.74 (d, J = 1.5 Hz, 1H), 7.64 (dd, J = 7.5, 1.5 Hz, 1H), 7.39 (d, J = 7.5 Hz, 1H), 7.33 (m, 2H), 7.25 (d, J = 1.5 Hz, 1H), 7.21 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.16 (dd, J = 7.5, 1.5 Hz, 1H), 7.06 (dd, J = 7.5, 1.5 Hz, 1H), 4.16 (t, J = 7.1 Hz, 2H), 3.93 (t, J = 7.1 Hz, 2H), 1.74 (m, 2H), 1.66 (m, 4H), 1.49 (m, 2H) 1.26 (m, 4H). The hydrogen spectrum of the compound shown in formula 4 is shown in Figure 4. As can be seen from Figure 4, 1H NMR (300 MHz, DMSO-d6) δ 8.31 (d, J = 7.5 Hz, 1H), 7.96 (dd, J = 7.5, 1.5 Hz, 1H), 7.91 (dd, J = 7.5, 1.5 Hz, 1H), 7.74 (d, J = 1.5 Hz, 1H), 7.64 (dd, J = 7.5, 1.5 Hz, 1H), 7.55 (dd, J = 7.5, 1.5 Hz, 2H), 7.40 (ddd, J = 7.5, 7.5, 1.5 Hz, 2H), 7.37 (d, J = 7.5, 1.5 Hz, 2H), 7.33 (m, 3H), 4.16 (t, J = 7.1 Hz, 2H), 3.93 (t, J = 7.1 Hz, 2H), 1.74 (m, 2H), 1.66 (m, 4H), 1.49 (m, 2H) 1.26 (m, 4H). The above four polymer structures are consistent with nuclear magnetic resonance.

[0078] In a third aspect of the present application, the present application provides the use of the above-mentioned hole transport polymer material or the hole transport polymer material obtained by the above-mentioned method in a perovskite solar cell, a perovskite LED or a perovskite sensor.

[0079] According to an embodiment of the present application, a method for preparing a hole transport layer comprises: dissolving the hole transport polymer material in an organic solvent, and then applying and annealing on a conductive substrate to form a hole transport layer on the conductive substrate. Further, the concentration of the hole transport polymer material in the organic solvent is 0.1 mg / mL to 1 mg / mL. It should be noted that the organic solvent and the conductive substrate are conventional materials in the art, and a person skilled in the art can select them according to actual needs. For example, the organic solvent includes but is not limited to methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methyl pyrrolidone; and the conductive substrate includes but is not limited to FTO conductive glass, ITO conductive glass, FTO conductive plastic, and ITO conductive plastic. The application method and the annealing condition are also conventional processes in the art. For example, the application method includes spin coating, spraying, doctor blading, coating, or soaking; and the annealing temperature is 100°C to 120°C.

[0080] According to an embodiment of the present application, a perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, and an electrode which are sequentially stacked, and the hole transport layer is prepared by the above method. Further, the thickness of the conductive substrate is 300 nm to 600 nm; the thickness of the hole transport layer is 10 nm to 200 nm; the thickness of the perovskite layer is 300 nm to 1000 nm; the thickness of the electron transport layer is 10 nm to 50 nm; and the thickness of the electrode is 100 nm to 200 nm. It should be noted that the perovskite layer, the electron transport layer, and the electrode are prepared by using conventional materials and processes in the art, and a person skilled in the art can select them according to actual needs.

[0081] The present application will be described below with reference to specific examples. It should be noted that these examples are merely descriptive and do not limit the present application in any way.

[0082] Example 1

[0083] A carbazole butyl phosphonic acid polymer is prepared, and the structure is as follows: wherein a is 100 to 1000.

[0084] (1) 2,7-dibromo carbazole and 1,4-dibromo butane are reacted under the action of 50% potassium hydroxide aqueous solution and tetrabutylammonium bromide under inert gas at 50-70°C for 24 h to generate 2,7-dibromo-9-bromobutyl carbazole;

[0085] (2) 2,7-dibromo-9-bromobutyl carbazole is refluxed with bis(pinacolato)diboron under the action of potassium acetate and palladium catalyst 1,1'-bis(diphenylphosphino) ferrocene dichloride for 25 h to obtain 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole;

[0086] (3) 2,7-dibromo-9-bromobutylcarbazole and 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole are reacted with triethyl phosphite at 160°C under inert gas for 25h to form [4-(3,6-dibromocarbazol-9-yl)butyl]diethyl phosphonate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphonate, respectively;

[0087] (4) [4-(3,6-dibromocarbazol-9-yl)butyl]diethyl phosphonate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphonate are reacted with tetrakis(triphenylphosphine)palladium as catalyst in a mixture of toluene and aqueous potassium carbonate at 80°C under inert gas for 70h to form carbazol diethyl phosphonate polymer;

[0088] (5) carbazol butyl diethyl phosphonate polymer is hydrolyzed with trimethylsilyl bromide at room temperature to form carbazol butyl phosphonic acid polymer.

[0089] Example 2

[0090] Carbazol-acridine butyl phosphonic acid polymer is prepared, structure: wherein a is 100-1000.

[0091] (1) 2,7-dibromocarbazole and 2,7-dibromo-9,9-dimethylacridine are reacted with 1,4-dibromobutane in the presence of 50% aqueous potassium hydroxide and tetrabutylammonium bromide at 50-70°C under inert gas for 24h to form 2,7-dibromo-9-bromobutylcarbazole and 2,7-dibromo-9,9-dimethyl-10-bromobutylacridine;

[0092] (2) 2,7-dibromo-9-bromobutylcarbazole is reacted with bis(pinacolato)diboron in the presence of potassium acetate and palladium catalyst 1,1'-bis(diphenylphosphino)ferrocene dichloride at reflux for 25h to form 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole;

[0093] (3) 2,7-dibromo-9,9-dimethyl-10-bromobutylacridine and 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole are reacted with triethyl phosphite at 162°C under inert gas for 25h to form [4-(2,7-dibromo-9,9-dimethylacridin-10-yl)butyl]diethyl phosphonate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphonate, respectively;

[0094] (4) [4-(2,7-dibromo-9,9-dimethylacridin-10-yl)butyl] diethyl phosphate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphate are reacted with the catalysis of tetrakis(triphenylphosphine)palladium in a mixture of toluene and aqueous potassium carbonate under inert gas protection at 82°C for 75h to form carbazole-acridine butyl diethyl phosphate polymer;

[0095] (5) The carbazole-acridine butyl diethyl phosphate polymer is hydrolyzed to form carbazole-acridine butyl phosphonic acid polymer under the action of trimethyl bromosilane at room temperature.

[0096] Example 3

[0097] Carbazole-phenothiazine butyl phosphonic acid polymer is prepared, and the structure is as follows: wherein a is 100-1000.

[0098] (1) 2,7-dibromocarbazole and 3,6-dibromophenothiazine are reacted with 1,4-dibromobutane under the action of 50% aqueous potassium hydroxide and tetrabutylammonium bromide at 50-70°C under inert gas for 24h to form 2,7-dibromo-9-bromobutylcarbazole and 3,6-dibromo-10-bromobutylphenothiazine;

[0099] (2) 2,7-dibromo-9-bromobutylcarbazole is reacted with bis(pinacolato)diboron under the catalysis of potassium acetate and 1,1'-bisdiphenylphosphinyl ferrocene dichloropalladium at reflux for 25h to obtain 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole;

[0100] (3) 3,6-dibromo-10-bromobutylphenothiazine and 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole are respectively reacted with triethyl phosphite under inert gas at 160°C for 25h to form [4-(3,6-dibromophenothiazine-10-yl)butyl] diethyl phosphate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphate;

[0101] (4) [4-(3,6-dibromophenothiazine-10-yl)butyl] diethyl phosphate and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanecarbazole]-butyl diethyl phosphate are reacted with the catalysis of tetrakis(triphenylphosphine)palladium in a mixture of toluene and aqueous potassium carbonate under inert gas protection at 80°C for 70h to form carbazole-phenothiazine butyl diethyl phosphate polymer;

[0102] (5) The carbazole-diphenylamine butyl phosphonic acid diethyl ester polymer is hydrolyzed to carbazole-diphenylamine butyl phosphonic acid polymer under the action of trimethyl bromosilane at room temperature.

[0103] Example 4

[0104] The carbazole-diphenylamine butyl phosphonic acid polymer is prepared, and the structure is as follows: wherein a is 100-1000.

[0105] (1) 2,7-dibromo carbazole and 4,4-dibromo diphenylamine are reacted with 1,4-dibromo butane under the action of 50% potassium hydroxide aqueous solution and tetrabutyl ammonium bromide under inert gas at 50-70°C for 24h to generate 2,7-dibromo-9-bromobutyl carbazole and N-bromobutyl-4,4-dibromo diphenylamine;

[0106] (2) 2,7-dibromo-9-bromobutyl carbazole is reacted with bis(pinacolato)diboron under the action of potassium acetate and 1,1'-bis(diphenylphosphino) ferrocene palladium dichloride catalyst under reflux for 25h to obtain 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole;

[0107] (3) N-bromobutyl-4,4-dibromo diphenylamine and 9-bromobutyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole are respectively reacted with triethyl phosphite under inert gas at 160°C for 25h to generate 4,4-dibromo diphenylamine-N-butyl phosphonic acid diethyl ester and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan carbazole]-butyl phosphonic acid diethyl ester;

[0108] (4) 4,4-dibromo diphenylamine-N-butyl phosphonic acid diethyl ester and 4-[2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan carbazole]-butyl phosphonic acid diethyl ester are reacted under the catalysis of tetrakis(triphenylphosphine) palladium in a mixture of toluene and potassium carbonate aqueous solution under inert gas protection at 80°C for 70h to generate carbazole-diphenylamine butyl phosphonic acid diethyl ester polymer;

[0109] (5) The carbazole-diphenylamine butyl phosphonic acid diethyl ester polymer is hydrolyzed to carbazole-diphenylamine butyl phosphonic acid polymer under the action of trimethyl bromosilane at room temperature.

[0110] Comparative Example 1

[0111] The hole transport layer material 4PACz is used, and the structure is as follows:

[0112] Comparative Example 2

[0113] The hole transport layer material PTAA has the structure of:

[0114] (1) The contact angle of the materials of Examples 2-4 and Comparative Examples 1-2 was tested. Specifically, the five hole transport materials of the examples and comparative examples were dissolved in N,N-dimethylformamide (DMF) to prepare solutions with the same concentration (0.5 mg / mL). The solutions were spin-coated on a transparent conductive glass (FTO), and a hole transport layer was prepared by annealing at 100°C for 10 min. The contact angle of the DMF solution on the hole transport layer was measured using a contact angle measuring instrument.

[0115] The contact angle test results of the materials of Examples 2-4 and Comparative Examples 1-2 are shown in FIG. 5. As can be seen from FIG. 5, the contact angles from large to small are 4PACz, PTAA, carbazole-diphenylamine butyl phosphonic acid polymer, carbazole-acridine butyl phosphonic acid polymer, and carbazole-phenothiazine butyl phosphonic acid polymer. The introduction of acridine, diphenylamine, and phenothiazine polymers significantly reduces the contact angle, which is more conducive to the coverage of the perovskite precursor solvent and improves the film quality of the perovskite film.

[0116] (2) Perovskite solar cells were prepared using the materials of Examples 1-4 and Comparative Examples 1-2, and the performance of the perovskite solar cells was measured.

[0117] The preparation process of the perovskite solar cell is as follows: The FTO conductive glass was cleaned with acetone, ethanol, and pure water three times and dried. The hole transport material solutions of the above examples and comparative examples with the same concentration (0.5 mg / mL) were spin-coated on the surface of the FTO (3000 rpm / min for 30 s), and a hole transport layer was prepared by annealing and drying at 100°C for 10 min. A 1M perovskite solution was spin-coated on the hole transport layer, and a perovskite layer was prepared by annealing at 150°C for 30 min. An electron transport layer was prepared by spin-coating a PCBM (15 mg / mL) solution on the perovskite layer and annealing and drying at 100°C for 10 min. Finally, a 100 nm Ag electrode was evaporated using a vacuum coating method to complete the preparation of the perovskite cell device.

[0118] The test method for the perovskite solar cell is as follows: The perovskite cell device was placed in an AM1.5G simulated sunlight emitter calibrated by a standard silicon cell to test the V-I curve.

[0119] The performance test results of the perovskite solar cells prepared using the materials of Examples 1-4 and Comparative Examples 1-2 are shown in Table 1.

[0120] Table 1

[0121] As can be seen from Table 1, the perovskite solar cells of Examples 1-4 have higher efficiency than the common small molecule hole transport materials (Comparative Examples 1-2). The main reason is that the polymer hole transport materials with anchoring groups of Examples 1-4 can completely cover the conductive glass, and the hole transport layer will not form holes to cause current loss. On the other hand, the polymer hole transport materials with anchoring groups of Examples 1-4 have anchoring groups that can interact with the conductive glass, and can firmly fix the polymer bulk on the conductive glass, which is conducive to charge transport, so the efficiency of the battery is higher than that of the common polymer.

[0122] (3) Perovskite solar cell stability test, the specific method is: the perovskite solar cell devices prepared by the hole transport materials of the examples and comparative examples are kept under the same waterless and oxygen-free conditions, and the device efficiency is tested at the same time and multiple times within 0-500h, and the efficiency change is compared.

[0123] The perovskite solar cell stability test results of Examples 1-4 and Comparative Examples 1-2 are shown in Figure 6. As can be seen from Figure 6, the efficiency of the batteries prepared by the common small molecule and common polymer hole transport materials (4PACz, PTAA) decreases rapidly with time, and the remaining efficiency after time test is significantly lower than that of the batteries prepared by the polymer hole transport materials with anchoring function of the examples 1-4 of the present application.

[0124] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0125] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A hole transporting polymer material, characterized by, The hole-transporting polymer material includes at least one of a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, and a compound represented by Formula 4. wherein a1 is an integer ≥ 2, b1 is an integer ≥ 1; and / or a2 is an integer ≥ 2, b2 is an integer ≥ 1, b3 is an integer ≥ 1; and / or a3 is an integer ≥ 2, b4 is an integer ≥ 1, b5 is an integer ≥ 1; and / or a4 is an integer ≥ 2, b6 is an integer ≥ 1, b7 is an integer ≥ 1.

2. The hole-transporting polymer material according to claim 1, wherein a1 is an integer 100-1000, b1 is an integer 2-10; and / or a2 is an integer 100-1000, b2 is an integer 2-10, b3 is an integer 2-10; and / or a3 is an integer 100-1000, b4 is an integer 2-10, b5 is an integer 2-10; and / or a4 is an integer 100-1000, b6 is an integer 2-10, b7 is an integer 2-10.

3. The hole transporting polymer material according to claim 2, wherein a1 is an integer 100-1000, b1 is an integer 2-4; and / or a2 is an integer 100-1000, b2 is an integer 2-4, b3 is an integer 2-4; and / or a3 is an integer 100-1000, b4 is an integer 2-4, b5 is an integer 2-4; and / or a4 is an integer 100-1000, b6 is an integer 2-4, b7 is an integer 2-4.

4. A method of preparing the hole transporting polymer material of any one of claims 1 to 3, characterized in that, comprising: (1) 2,7-dihalocarbazole, 2,7-dihalo-9,9-dimethylacridine, 3,6-dihalophenothiazine, 4,4-dihalodianiline respectively react with halogenated alkane in the presence of a first strong base and a phase transfer catalyst, so as to obtain 2,7-dihalo-9-halogenated alkylcarbazole, 2,7-dihalo-9,9-dimethyl-10-halogenated alkylacridine, 3,6-dihalo-10-halogenated alkylphenothiazine and N-halogenated alkyl-4,4-dihalodianiline respectively; (2) 2,7-dihalo-9-halogenated alkylcarbazole and bis(pinacolato)diboron react in a first solvent in the presence of a second strong base and a first catalyst, so as to obtain 9-halogenated alkyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole; (3) 2,7-dihalo-9-haloalkylcarbazole, 2,7-dihalo-9,9-dimethyl-10-haloalkylacridine, 3,6-dihalo-10-haloalkylphenothiazine, N-haloalkyl-4,4-dihalodiphenylamine, and 9-haloalkyl-2,7-bis(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)carbazole, respectively, are reacted with triethyl phosphite to give Product A, Product B, Product C, Product D, and Product E, respectively, (4) the product A, the product B, the product C, the product D respectively react with the product E in the presence of a second catalyst in a second solvent, so as to obtain carbazole phosphoric acid diethyl ester polymer, carbazole-acridine phosphoric acid diethyl ester polymer, carbazole-phenothiazine phosphoric acid diethyl ester polymer and carbazole-dianiline phosphoric acid diethyl ester polymer respectively; (5) the carbazole phosphoric acid diethyl ester polymer, the carbazole-acridine phosphoric acid diethyl ester polymer, the carbazole-phenothiazine phosphoric acid diethyl ester polymer and the carbazole-dianiline phosphoric acid diethyl ester polymer undergo ester hydrolysis reaction, so as to obtain the compound shown in formula 1, the compound shown in formula 2, the compound shown in formula 3 and the compound shown in formula 4 respectively.

5. The method of claim 4, wherein, In step (1), the halogen in the 2,7-dihalocarbazole, the halogen in the 2,7-dihalo-9,9-dimethylacridine, the halogen in the 3,6-dihalophenothiazine and the halogen in the 4,4-dihalodianiline independently comprise at least one of chlorine, bromine and iodine; Optionally, the halogenated alkane has a carbon number of 2-10, and one hydrogen on each of the two carbon atoms in the halogenated alkane is replaced by halogen, the halogen including at least one of chlorine, bromine and iodine; Optionally, the first strong base includes at least one of potassium hydroxide, sodium hydroxide and potassium tert-butoxide; Optionally, the phase transfer catalyst includes at least one of tetrabutylammonium bromide and tetrabutylammonium iodide; Optionally, the reaction conditions include 20-30 h of reaction at 25-70 °C under inert gas.

6. The method of claim 4, wherein, In step (2), the second strong base includes at least one of potassium acetate and potassium carbonate; Optionally, the first catalyst includes at least one of 1,1'-bis(diphenylphosphino) ferrocene palladium dichloride, 1,1'-bis(diphenylphosphino) ferrocene palladium dichloride and bis(triphenylphosphine) palladium dichloride; Optionally, the first solvent includes at least one of 1,4-dioxane, dichloromethane, toluene and xylene; Optionally, the reaction conditions include 20-30 h of reaction at reflux under inert gas.

7. The method of claim 4, wherein, In step (3), n1, n2, n3, n4 and n5 are independently an integer of 2-10; Optionally, the reaction conditions include 20-30 h of reaction at 160-165 °C under inert gas.

8. The method of claim 4, wherein, In step (4), the second catalyst includes at least one of tetrakis(triphenylphosphine) palladium, palladium acetate and palladium chloride; Optionally, the second solvent includes at least one of a mixture of toluene and aqueous potassium carbonate, a mixture of toluene and aqueous sodium carbonate, and a mixture of xylene and aqueous potassium carbonate; Optionally, the reaction conditions include 70-75 h of reaction at 75-85 °C under inert gas protection.

9. The method of claim 4, wherein, In step (5), the solvent used in the ester hydrolysis reaction includes at least one of dichloromethane and 1,4-dioxane; Optionally, the reactants of the ester hydrolysis reaction include at least one of trimethylsilyl bromide, concentrated hydrochloric acid and concentrated sulfuric acid.

10. Use of the hole transport polymer material of any one of claims 1-3 or the hole transport polymer material obtained by the method of any one of claims 4-9 in a perovskite solar cell, a perovskite LED or a perovskite sensor.

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