Organic compounds or their salts, organic hole transport compositions and their applications

Abstract

This invention provides an organic compound or its salt, a hole transport composition thereof, and its applications. The organic compound has the structure shown in Formula I: Formula I. The organic compound or its salt, as a dopant in a hole transport material, can effectively improve the stability of the hole transport material, thereby enhancing the stability of the assembled perovskite solar cell device.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and more specifically to an organic compound or its salt, an organic hole transport composition, and their applications. Background Technology

[0002] Energy issues have become one of the major concerns of the international community in recent years. The long-term and large-scale use of fossil fuels has led to problems such as energy security, the greenhouse effect, and environmental pollution. Solar energy, as a long-term, stable, clean, and renewable energy source, has attracted much attention, and photovoltaic power generation is one of the most effective ways to utilize solar energy. Among many new types of solar cells, perovskite solar cells have shown great development potential due to their high photoelectric conversion efficiency and astonishing development speed, attracting widespread attention.

[0003] After more than a decade of development, the photoelectric conversion efficiency of perovskite solar cells has rapidly increased from the initial 3.8% to 26%, comparable to commercially available monocrystalline silicon cells. Perovskite solar cells possess advantages such as readily available materials, simple fabrication processes, low cost, and the ability to fabricate flexible devices, making them highly promising for commercial applications. However, their long-term operational instability limits their commercial development. Hygroscopic lithium salts are commonly used as dopants to improve cell efficiency in hole transport materials, but the hygroscopic nature of lithium salts is detrimental to device stability. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an organic compound or its salt, an organic hole transport composition and its application.

[0005] In a first aspect, the present invention provides an organic compound or a salt thereof, said organic compound having the structure shown in Formula I:

[0006]

[0007] Wherein, ring A is selected from the following groups:

[0008]

[0009] Wherein, M is selected from metal ions;

[0010] B1, B2, B3, and B4 are each independently selected from...

[0011]

[0012] R1, R2, and R3 may be the same or different, and each is independently selected from C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-S-, C1-C3 alkyl-O-C1-C3 alkylene, and C1-C3 alkyl-S-C1-C3 alkylene.

[0013] n1 is selected from 0, 1, 2, 3, 4 or 5;

[0014] n2 is selected from 0, 1, 2, 3, 4 or 5;

[0015] n3 is selected from 0, 1, 2, 3 or 4.

[0016] In some embodiments, the salt is a TFSI salt.

[0017] In some implementations, the TFSI - for

[0018] In some implementations, M is a divalent metal ion.

[0019] In some implementations, M is any one of cobalt, nickel, copper, or zinc.

[0020] In some embodiments, R1, R2, and R3 are each independently selected from C1-C3 alkyl-O-, C1-C3 alkyl-S-, C1-C3 alkyl-O-C1-C3 alkylene, and C1-C3 alkyl-S-C1-C3 alkylene.

[0021] In some embodiments, R1, R2, and R3 are each independently selected from one or more of -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -O-CH2-, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH(CH3)2, or -S-CH2-.

[0022] In some implementations, R1, R2, and R3 are the same.

[0023] In some implementations, n1, n2, and n3 are all 1.

[0024] In some embodiments, the organic compound or a salt thereof is selected from the following structures:

[0025]

[0026]

[0027]

[0028] In a second aspect, the present invention provides an organic hole transport composition comprising the organic compound or a salt thereof described in the first aspect of the present invention, and an organic hole transport material.

[0029] In a third aspect, the present invention provides the use of an organic compound or a salt thereof as a dopant in an organic hole transport layer.

[0030] In some embodiments, the organic hole transport layer further comprises an organic hole transport material.

[0031] In some embodiments, the organic hole transport layer is used to fabricate a solar cell.

[0032] In some embodiments, the organic hole transport layer is used to fabricate perovskite solar cells.

[0033] In some embodiments, the organic hole transport material is 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene.

[0034] In some embodiments, the organic compound or its salt constitutes 0.01%-25% of the total mass of the organic compound or its salt and the organic hole transport material, for example, 0.01%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.8%, 0.9%, 1.0%, 5.0%, 10.0%, 15.0%, 20%, and 25% by mass percentage.

[0035] In some embodiments, the organic compound or its salt accounts for 0.1% to 20% of the total mass of the organic compound or its salt and the organic hole transport material, by mass percentage.

[0036] In some embodiments, the organic compound or its salt accounts for 0.01% to 5% of the total mass of the organic compound or its salt and the organic hole transport material, by mass percentage.

[0037] In some embodiments, the organic compound or its salt accounts for 0.1% to 1% of the total mass of the organic compound or its salt and the organic hole transport material, by mass percentage.

[0038] In some embodiments, the organic compound or its salt accounts for 0.2% to 0.8% of the total mass of the organic compound or its salt and the organic hole transport material, by mass percentage.

[0039] Fourthly, the present invention provides an organic hole transport layer comprising the organic compound described in the first aspect of the present invention or a salt thereof, or the composition described in the second aspect of the present invention.

[0040] Fifthly, the present invention provides a method for preparing a hole transport layer for a perovskite solar cell device, comprising spin-coating an organic solution containing the composition described in the present invention onto the surface of a perovskite thin film.

[0041] In some embodiments, the spin coating rate is 3000-6000 rpm, for example 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm, 5500 rpm, 6000 rpm.

[0042] In some embodiments, the spin coating time is 20-30 seconds, for example, 20 seconds, 22 seconds, 24 seconds, 26 seconds, 28 seconds, or 30 seconds.

[0043] In some embodiments, the solvent in the organic solution is selected from chlorobenzene and chloroform.

[0044] In some embodiments, the concentration of the composition in the organic solution is 10-50 mg / mL, for example, 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL, 45 mg / mL, or 50 mg / mL.

[0045] In a sixth aspect, the present invention provides a perovskite solar cell device comprising an organic hole transport layer prepared using the method described in the third aspect of the present invention or a hole transport layer prepared using the method described in the fourth aspect of the present invention.

[0046] Porphyrin and phthalocyanine complexes can replace lithium salts and volatile 4-tert-butylpyridine as dopants in hole transport materials, which can not only improve their photoelectric conversion efficiency but also enhance the stability of perovskite solar cells. Using the organic compounds or their salts as dopants in hole transport materials can effectively improve the stability of the hole transport materials, thereby improving the stability of the assembled perovskite solar cell devices. Attached Figure Description

[0047] Figure 1 Voltage and current density plots of perovskite solar cells fabricated using Spiro-OMeTAD as hole transport material (without dopants);

[0048] Figure 2 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeS-CuPc-TFSI as Spiro-OMeTAD dopant.

[0049] Figure 3 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeS-H2Pc-TFSI as Spiro-OMeTAD dopant.

[0050] Figure 4Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeS-NiPc-TFSI as Spiro-OMeTAD dopant.

[0051] Figure 5 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-H2Pc-TFSI as Spiro-OMeTAD dopant.

[0052] Figure 6 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-NiPc-TFSI as Spiro-OMeTAD dopant.

[0053] Figure 7 Voltage and current density diagrams of perovskite solar cells fabricated using different concentrations (0.3%, 0.5%, 1%) of MeS-CuPc-TFSI as dopants in the Spiro-OMeTAD hole transport layer.

[0054] Figure 8 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-H2P-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0055] Figure 9 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-CoP-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0056] Figure 10 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-NiP-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0057] Figure 11 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-CuP-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0058] Figure 12 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeO-ZnP-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0059] Figure 13 Voltage and current density plots of perovskite solar cells fabricated using 0.5% MeS-H2P-TFSI as a dopant in the Spiro-OMeTAD hole transport layer.

[0060] Figure 14 Voltage and current densities of perovskite solar cells prepared by doping with different concentrations (0.3%, 0.5%, 1%) of MeO-CuP-TFSI as dopants for the hole transport layer of Spiro-OMeTAD. Detailed Implementation

[0061] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and techniques have also been described in many publications.

[0062] Experimental instruments and materials:

[0063] All reagents used in this invention can be purchased commercially or prepared by the methods described in this invention.

[0064] TiO2 slurry (Dyesol DSL 18NR-T)

[0065] Spin coater (KW-4A model, Institute of Microelectronics, Chinese Academy of Sciences)

[0066] Matrix-assisted laser desorption / resorption mass spectrometry (SHIMADZU)

[0067] Sunlight Simulator (Newport)

[0068] Vacuum Coating System (Micro-Nano Vacuum VZZ-300)

[0069] Pinacol diboronate (Bide Pharmaceuticals)

[0070] 4-Bromophthalonitrile (Alpha)

[0071] 4-Bromoaniline (Alpha)

[0072] Tetraisopropyl titanate (Ti(Oi-Pr)4)

[0073] Example 1: Synthesis of Phthalocyanine Metal Complexes

[0074] Triphenylamine-substituted phthalocyanine complexes were synthesized according to the following formula.

[0075]

[0076] Synthesis of triphenylamine 1:

[0077] Under an Ar atmosphere, Pd₂(dba)₃ (74 mg, 0.33 mmol) and P(t-Bu)₃ (1 M in toluene, 0.53 mL) were added separately to dry toluene (1 mL) in a three-necked flask at room temperature for 30 minutes to obtain the catalyst. The deep red solution was injected into a Schlenk tube containing 4-methoxyiodobenzene (4-iodoanisole) (2.2 eq.), 4-bromoaniline (1 eq), t-BuOK (3 eq), and toluene (15 mL), and stirred under reflux overnight. After cooling to room temperature, the toluene was removed, followed by extraction with water / dichloromethane (3 x 20 mL), drying over magnesium sulfate, filtration, and solvent removal. The crude product was purified by rapid column chromatography (silica gel) to obtain a grayish-white solid.

[0078] Synthesis of borate ester 2:

[0079] A triphenylamine compound (1 eq.), pinacol diborate (1.5 eq.), potassium acetate (3 eq.), and 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (2%) were added to a round-bottom flask, purged with nitrogen three times, followed by the addition of 1,4-dioxane, and refluxed for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The resulting solid was extracted with water and dichloromethane (4 × 15 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The product was purified by rapid column chromatography (silica gel) to obtain a white solid.

[0080] Synthesis of compound 3:

[0081] Boric acid compound (1 eq.), 4-bromophthalonitrile (1.5 eq.), potassium carbonate (3 eq.), tetrahydrofuran (30 mL) / water (10 mL), and tetra-triphenylphosphine palladium (5%) were added to a round-bottom flask, and the reaction was carried out under N2 protection. After reflux for 12 hours, the mixture was cooled to room temperature, and THF was removed by vacuum distillation. The resulting solid was extracted with water and dichloromethane (4 × 15 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The product was purified by rapid column chromatography (silica gel) to give a yellow-green solid.

[0082] Synthesis of compound 4:

[0083] Compound 3 (1 eq), DBU (1,8-diazabicyclo-[5.4.0]-undecyl-7-ene), n-pentanol, and M(OAc)2 were added to a round-bottom flask and the reaction was carried out under Ar protection. After reflux for 36 hours and cooling to room temperature, n-pentanol was removed by vacuum distillation, DBU was eluted with ethanol, and the product was purified by alumina chromatography to obtain a blue solid.

[0084]

[0085]

[0086]

[0087] Synthesis of Compound 5:

[0088] Under a nitrogen atmosphere, the synthesized compound 4 (1 eq.) and 20 mL of chloroform were added to a dry 50 mL flask with stirring. Silver(I)-bis(trifluoromethanesulfonyl)imide (Ag-TFSI) (2 eq.) was added over 5 minutes at room temperature. The mixture was stirred at room temperature for 24 hours. The reaction mixture was diluted with chloroform. The gray silver(O) precipitate was filtered off using a non-porous inorganic membrane to remove the solvent, leaving a solid. The solid was dissolved in a minimal amount of chloroform and precipitated in dry diethyl ether. The resulting fine, dark powder was collected by filtration through an inorganic membrane.

[0089] Example 2: Synthesis of Porphyrin Metal Complexes

[0090] Triphenylamine-substituted porphyrin metal complexes were synthesized according to the following formula.

[0091]

[0092] Synthesis of triphenylamine porphyrin 1:

[0093] According to the literature method, porphyrin 1 can be prepared by refluxing 4-[bis(4-methoxyphenyl)amino]benzaldehyde and pyrrole in propionic acid.

[0094] Synthesis of triphenylamine metalloporphyrin 2:

[0095] The porphyrins prepared above can be refluxed overnight in CHCl3 / CH3OH with excess cobalt acetate, copper acetate and zinc acetate respectively to prepare CoP, CuP and ZnP porphyrin complexes.

[0096] The NiP porphyrin complex can be prepared by refluxing the porphyrin prepared above with excess nickel acetate in DMF overnight.

[0097] Synthesis of porphyrin compound 3:

[0098] Compound 2 (1 eq.) synthesized above and 20 mL of chloroform were added to a 50 mL dry flask. The mixture was stirred under a nitrogen atmosphere, and silver(I)-bis(trifluoromethanesulfonyl)imide (Ag-TFSI) (2 eq.) was added over 5 minutes at room temperature. The mixture was stirred at room temperature for 24 hours. The reaction mixture was diluted with chloroform. The gray silver(O) precipitate was filtered off using a non-porous inorganic membrane to remove the solvent, leaving a solid. The solid was dissolved in a minimal amount of chloroform and precipitated in dry diethyl ether. The resulting fine, dark powder was collected by filtration through an inorganic membrane.

[0099] The synthesis of MeS-substituted triphenylamine metalloporphyrins is similar to that of MeO-substituted triphenylamine metalloporphyrins described above; only the following steps are required: The methoxy group can be replaced with a thiomethyl group.

[0100] Example 3: Device Fabrication

[0101] Laser etching was used to etch FTO glass (2.0 × 2.0 cm). 2 Etching was performed to obtain a specific electrode pattern, followed by ultrasonic cleaning with acetone, ultrapure water, and ethanol for 10 min each. The substrate was then dried and treated with UV ozone for 15 min. An electron transport layer precursor solution (169 mg zinc acetate and 49.3 mg magnesium acetate dissolved in 2.5 mL methoxyethanol and 60 μL ethanolamine) was spin-coated onto an FTO substrate (2800 rpm, 25 s), and then annealed at 500 °C for 30 min. After cooling to room temperature, the FTO substrate was heated in a 1 M TiCl4 solution at 70 °C for 12 min. After drying, a TiO2 slurry in isopropanol (1:8, mass ratio) was spin-coated at 5000 rpm for 25 s and annealed at 500 °C for 30 min to obtain a mesoporous TiO2 layer. 167.03 mg FAI, 22.28 mg MABr, and 599.31 mg... PbI₂ was dissolved in a mixed solution of DMF and DMSO (743 μL: 186 μL), and then 47.8 μL (1.5 M) of CsI in DMSO solution and 46.9 μL (1.5 M) of RbI in DMSO solution were added to prepare a perovskite precursor solution. The perovskite layer was deposited on a mesoporous TiO₂ layer using a spin coater in a nitrogen-filled glove box at 800 rpm for 10 s and 4000 rpm for 30 s. Chlorobenzene was used as the antisolvent, and after annealing, a dense black perovskite film was obtained. Finally, the obtained porphyrin and phthalocyanine complexes were doped at different concentrations in a chlorobenzene solution (or an organic solvent such as chloroform) of hole transport materials such as Spiro-OMeTAD or phthalocyanine, and deposited on the perovskite surface by spin coating (4000 rpm, 25 s). Finally, 80 nm gold was deposited using a vacuum deposition system, and the cell efficiency was tested under a solar simulator.

[0102] Example 4: Battery Efficiency Test

[0103] Study on the efficiency of batteries doped with different ligands:

[0104] The cell efficiency of Spiro-OMeTAD doped with triphenylamine-substituted porphyrin complexes and / or phthalocyanine complexes with different central coordination sites was tested, as well as the cell efficiency under different doping concentrations. Current-voltage (IV) curves were performed on equipment (Newport) equipped with a Keithley 2400 source meter and an LSH-7320ABA LED lamp simulator. Before testing, the light intensity was calibrated to 100 mW·cm using a standard silicon cell. -2This refers to AM 1.5G sunlight conditions. The test results are as follows... Figure 1-14 .

[0105] In this invention, the doping amount of the dopant is all expressed as a mass percentage.

[0106] Perovskite solar cells fabricated using Spiro-OMeTAD as a hole transport material showed an efficiency of 20.17% under a solar simulator. Figure 1 As shown.

[0107] Using 0.5% MeS-CuPc-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.82%. Figure 2 As shown.

[0108] Using 0.5% MeS-H2Pc-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 20.82%. Figure 3 As shown.

[0109] Using 0.5% MeS-NiPc-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.48%. Figure 4 As shown.

[0110] Using 0.5% MeO-H2Pc-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 20.96%. Figure 5 As shown.

[0111] Using 0.5% MeO-NiPc-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.26%. Figure 6 As shown.

[0112] Study on dopant concentration:

[0113] The cell efficiency was tested using MeS-CuPc-TFSI doped with different concentrations (0.3%, 0.5%, 1%) as the hole transport layer dopant in Spiro-OMeTAD, such as... Figure 7 As shown. According to Figure 7 When the doping concentration is 0.3%, the battery efficiency is 21.31%; when the doping concentration is 0.5%, the current efficiency is 21.82%; and when the doping concentration is 1%, the current efficiency is 20.47%. It can be seen that the battery efficiency is relatively high when the doping concentration is 0.5%.

[0114] Using 0.5% MeO-H2P-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.02%. Figure 8 As shown.

[0115] Using 0.5% MeO-CoP-TFSI as a Spiro-OMeTAD dopant, the tested battery device efficiency was 19.58%. Figure 9 As shown.

[0116] Using 0.5% MeO-NiP-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.47%. Figure 10 As shown.

[0117] Using 0.5% MeO-CuP-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.57%. Figure 11 As shown.

[0118] Using 0.5% MeO-ZnP-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 20.34%. Figure 12 As shown.

[0119] Using 0.5% MeS-H2P-TFSI as a Spiro-OMeTAD dopant, the tested battery device achieved an efficiency of 21.17%. Figure 13 As shown.

[0120] Study on dopant concentration:

[0121] The cell efficiency was tested using MeO-CuP-TFSI doped with different concentrations (0.3%, 0.5%, 1%) as the hole transport layer dopant in Spiro-OMeTAD, such as... Figure 14 As shown. From Figure 14 It can be seen that when the doping concentration is 0.3%, the battery efficiency is 21.29%; when the doping concentration is 0.5%, the current efficiency is 21.57%; when the doping concentration is 1%, the current efficiency is 20.53%; and the battery efficiency is relatively high when the doping concentration is 0.5%.

[0122] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A salt of an organic compound having the structure shown in Formula I: in, Ring A is selected from the following groups: Wherein, M is selected from metal ions; B1, B2, B3, and B4 are each independently selected from... R1, R2, and R3 may be the same or different, and each is independently selected from C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-S-, C1-C3 alkyl-O-C1-C3 alkylene, and C1-C3 alkyl-S-C1-C3 alkylene. n1 is selected from 0, 1, 2, 3, 4 or 5; n2 is selected from 0, 1, 2, 3, 4 or 5; n3 is selected from 0, 1, 2, 3 or 4; The salt is a TFSI salt.

2. The salt of the organic compound according to claim 1, characterized in that, M is a divalent metal ion.

3. The salt of the organic compound according to claim 1, characterized in that, M can be any one of cobalt, nickel, copper, or zinc.

4. The salt of the organic compound according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from C1-C3 alkyl-O-, C1-C3 alkyl-S-, C1-C3 alkyl-O-C1-C3 alkylene, and C1-C3 alkyl-S-C1-C3 alkylene.

5. The salt of the organic compound according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from one or more of -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -O-CH2-, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH(CH3)2, or -S-CH2-.

6. The salt of the organic compound according to claim 1, characterized in that, R1, R2, and R3 are the same; And / or, n1, n2, and n3 are all 1.

7. The salt of the organic compound according to claim 1, characterized in that, The salts of the organic compounds are selected from the following structures:

8. An organic hole transport composition comprising a salt of the organic compound according to any one of claims 1-7, and an organic hole transport material.

9. Use of a salt of the organic compound according to any one of claims 1-7 as a dopant in an organic hole transport layer.

10. The use according to claim 9, characterized in that, The organic hole transport layer also includes organic hole transport material.

11. The use according to claim 9, characterized in that, The organic hole transport layer is used to fabricate solar cells.

12. The use according to claim 9, characterized in that, The organic hole transport layer is used to fabricate perovskite solar cells.

13. The use according to claim 9, characterized in that, The organic hole transport material is 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene.

14. The composition according to claim 8 or the use according to any one of claims 9-13, characterized in that, The salt of the organic compound accounts for 0.01%-25% of the total mass of the salt of the organic compound and the organic hole transport material, by mass percentage.

15. The composition according to claim 8 or the use according to any one of claims 9-13, characterized in that, The salt of the organic compound accounts for 0.1% to 20% of the total mass of the salt of the organic compound and the organic hole transport material, by mass percentage.

16. The composition according to claim 8 or the use according to any one of claims 9-13, characterized in that, The salt of the organic compound accounts for 0.01%-5% of the total mass of the salt of the organic compound and the organic hole transport material, by mass percentage.

17. The composition according to claim 8 or the use according to any one of claims 9-13, characterized in that, The salt of the organic compound accounts for 0.1% to 1% of the total mass of the salt of the organic compound and the organic hole transport material, by mass percentage.

18. The composition according to claim 8 or the use according to any one of claims 9-13, characterized in that, The salt of the organic compound accounts for 0.2%-0.8% of the total mass of the salt of the organic compound and the organic hole transport material, by mass percentage.

19. An organic hole transport layer comprising a salt of the organic compound of any one of claims 1-7 or the composition of claim 8.

20. A method for preparing a hole transport layer for a perovskite solar cell device, comprising spin-coating a salt comprising any one of the organic compounds of claims 1-7 or an organic solution comprising the composition of claim 8 onto the surface of a perovskite thin film.

21. The preparation method according to claim 20, characterized in that, The spin coating rate is 3000-6000 rpm, and / or The spin coating time is 20-30 seconds, and / or The solvent in the organic solution is selected from chlorobenzene, chloroform; and / or In the organic solution, the concentration of the composition is 10-50 mg / mL.

22. A perovskite solar cell device, comprising an organic hole transport layer as described in claim 19 or a hole transport layer prepared by the preparation method according to claim 20 or 21.

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