Phenylphosphine phosphonic acid organic compound, hole transport material, perovskite solar cell and preparation method thereof, electric device

Abstract

The application discloses a phenylphosphinic acid organic compound, a hole transport material, a perovskite solar cell and a preparation method and an electric device thereof, the phenylphosphinic acid organic compound comprises at least one of a compound as shown in formula I and a compound as shown in formula II: wherein R1 comprises a C1-C8 alkyl chain or at least one aryl chain; R2 comprises a C1-C8 alkyl chain or at least one aryl chain, X ‑ comprises a halogen ion, a sulfonate ion, a benzenesulfonate ion, a thiocyanate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a formate ion or an acetate ion. The open-circuit voltage (Voc) and the photoelectric conversion efficiency (PCE) of the perovskite solar cell prepared by using the phenylphosphinic acid organic compound as a hole transport layer are obviously improved.

Description

Technical Field

[0001] This application belongs to the field of perovskite solar cell technology, specifically relating to a phenylphosphine acid organic compound, hole transport materials, perovskite solar cells and their preparation methods, and electrical equipment. Background Technology

[0002] Perovskite solar cells (PSCs), as a novel type of thin-film solar cell, are developing rapidly. PSCs have a wide range of material sources, simple processes, and high photoelectric conversion efficiency, making them a promising technology. Currently, most high-efficiency single-junction or tandem PSCs use self-assembled monolayer (SAM) materials as the hole transport layer. These materials offer advantages such as low material consumption and minimal parasitic absorption.

[0003] However, during the fabrication of perovskite films, the evaporation of solvents and organic salts easily leaves a large number of charge defects at the lower interface and grain boundaries. These defects become centers for nonradiative recombination, reducing the device performance and stability of PSCs. Furthermore, these self-assembled monolayers do not possess defect passivation capabilities, posing a significant obstacle to the rational design of more efficient hole transport layers. Summary of the Invention

[0004] This application aims to at least partially solve one of the technical problems in related technologies. Therefore, the purpose of this application is to provide a phenylphosphine phosphonate organic compound, a hole transport material, a perovskite solar cell, a method for fabricating the same, and an electrical device thereof. The open-circuit voltage (V) of a perovskite solar cell fabricated using the phenylphosphine phosphonate organic compound of this application as the hole transport layer is also discussed. OC The photoelectric conversion efficiency (PCE) has been significantly improved.

[0005] In one aspect of this application, a phenylphosphonic acid organic compound is provided. According to embodiments of this application, the phenylphosphonic acid organic compound includes at least one of the compounds shown in Formula I and Formula II:

[0006]

[0007]

[0008] Wherein, R1 comprises a C1-C8 alkyl chain or at least one aryl chain; R2 comprises a C1-C8 alkyl chain or at least one aryl chain, X - This includes halide ions, sulfonate ions, benzenesulfonate ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, or acetate ions.

[0009] According to the phenylphosphonic acid organic compounds of this application, firstly, the phosphonic acid in the phenylphosphonic acid organic compound is an anchoring group, which can effectively anchor the phenylphosphonic acid organic compound onto the metal oxide substrate, improving the molecular coverage on the metal oxide substrate. Secondly, the phosphoric acid in the phenylphosphonic acid organic compound can chemically bond with the metal oxide in the metal oxide substrate, forming an effective hole transport interface on the metal oxide substrate, while passivating defects on the metal oxide. Thirdly, the phenylphosphonic group in the phenylphosphonic acid organic compound can bridge the perovskite light-absorbing layer and the metal oxide substrate respectively, effectively passivating defects on the interface under the perovskite light-absorbing layer, improving the perovskite crystal quality, enhancing interface stability, and improving the operating stability of the device. Fourthly, the introduction of alkyl chains or aryl groups as intermediate segments in the phenylphosphonic acid organic compound can adjust the molecular flexibility, optimize the band structure, enhance hole transport, and improve the carrier transport performance. Therefore, the open-circuit voltage (V) of the perovskite solar cell prepared using the above-mentioned phenylphosphonic acid organic compound as the hole transport layer is [not specified in the original text]. OC The photoelectric conversion efficiency (PCE) has been significantly improved.

[0010] In addition, the phenylphosphonic acid organic compounds according to the above embodiments of this application may also have the following additional technical features:

[0011] In some embodiments of this application, R1 comprises a C1-C6 alkyl chain, one aryl chain, or two aryl chains; R2 comprises a C1-C4 alkyl chain; X - Including halide ions.

[0012] In some embodiments of this application, the phenylphosphonic acid organic compound includes at least one of the following compounds:

[0013]

[0014]

[0015] In a second aspect, this application proposes a hole transport material. According to embodiments of this application, the hole transport material comprises the phenylphosphonic acid organic compounds described in the above embodiments. Therefore, this hole transport material can effectively anchor onto a metal oxide substrate, increasing the molecular coverage on the metal oxide substrate; it can effectively form a hole transport interface on the metal oxide substrate, while effectively passivating defects on the metal oxide; it can effectively passivate defects on the interface below the perovskite light-absorbing layer, improving the perovskite crystal quality; and it can effectively adjust molecular flexibility, optimize the band structure, enhance hole transport, and improve carrier transport performance.

[0016] In a third aspect, this application proposes a perovskite solar cell. According to an embodiment of this application, the perovskite solar cell includes hole transport, and the hole transport layer comprises the hole transport material described in the above embodiments. Therefore, by introducing phenylphosphonic acid-based organic compounds into the hole transport layer of the perovskite solar cell, the open-circuit voltage (V0.05) of the perovskite solar cell can be effectively improved. OC ) and photoelectric conversion efficiency (PCE).

[0017] In addition, the perovskite solar cells according to the above embodiments of this application may also have the following additional technical features:

[0018] In some embodiments of this application, the thickness of the hole transport layer is 1nm-10nm; and / or, the hole transport layer is a SAM layer.

[0019] In some embodiments of this application, the perovskite solar cell further includes a metal oxide substrate, a perovskite light-absorbing layer, an electron transport layer, and an electrode layer, wherein the metal oxide substrate, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, and the electrode layer are stacked sequentially.

[0020] In some embodiments of this application, the thickness of the perovskite light-absorbing layer is 100 nm-3 μm; and / or, the thickness of the electron transport layer is 1 nm-100 nm.

[0021] In some embodiments of this application, the perovskite light-absorbing layer comprises an ABX3 type perovskite material, wherein A ions include at least one selected from cesium ions, rubidium ions, potassium ions, methylamine ions, formamidinium ions, methylenediamine ions, benzylamidinium cations, and guanidine cations; B ions include at least one selected from divalent lead ions and divalent tin ions; X ions include at least one selected from fluoride ions, chloride ions, bromide ions, iodide ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, and acetate ions; and / or, the electron transport layer comprises tin dioxide, At least one of titanium dioxide, [6,6]-phenyl-C71-butyrate isomethyl ester, C60 and C60 derivatives; and / or, the electrode layer comprises at least one of ITO, IZO, IWO, FTO, ICO, AZO, BZO, gold, silver, copper, aluminum, and carbon; and / or, the metal oxide substrate comprises a transparent conductive oxide layer, the transparent conductive oxide layer comprising at least one of ITO, IZO, IWO, FTO, ICO, AZO, and BZO; optionally, the metal oxide substrate further comprises TiO2 and NiO. x At least one of Al2O3 or SiO2.

[0022] In a fourth aspect, this application discloses a method for fabricating perovskite solar cells. According to embodiments of this application, the method includes:

[0023] The hole transport material described in the above embodiments is mixed with a solvent to form a mixture;

[0024] The above mixture is spin-coated onto the surface of a metal oxide substrate and then heated and annealed to form a hole transport layer on the surface of the metal oxide substrate.

[0025] According to the method for preparing perovskite solar cells in the embodiments of this application, by introducing phenylphosphine acid-based organic compounds into the hole transport layer of the perovskite solar cell, the open-circuit voltage (V) of the perovskite solar cell can be effectively improved. OC ) and photoelectric conversion efficiency (PCE).

[0026] In addition, the method for preparing perovskite solar cells according to the above embodiments of this application may also have the following additional technical features:

[0027] In some embodiments of this application, the concentration of the hole transport material in the mixture is 0.1 mg / mL to 4.0 mg / mL.

[0028] In a fifth aspect, this application proposes an electrical device. According to an embodiment of this application, the electrical device has a perovskite solar cell as described above. Thus, the electrical device possesses all the advantages of the perovskite solar cell, which will not be elaborated further here.

[0029] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0030] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0031] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of this application.

[0032] Figure label:

[0033] 100 - Metal oxide substrate, 200 - Hole transport layer, 300 - Perovskite light-absorbing layer, 400 - Electron transport layer, 500 - Electrode layer. Detailed Implementation

[0034] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain this application, and should not be construed as limiting this application.

[0035] This application was filed by the inventor based on the following questions:

[0036] In related technologies, high-efficiency single-junction or stacked perovskite solar cells (PSCs) often use self-assembled monolayer (SAM) materials as hole transport layers. These materials have advantages such as low material consumption and low parasitic absorption. However, during the fabrication of perovskite films, the evaporation of solvents and organic salts easily leaves a large number of charge defects at the lower interface and grain boundaries. These defects become centers for non-radiative recombination, reducing the device performance and stability of PSCs. Furthermore, these self-assembled monolayers do not possess defect passivation capabilities, which poses a significant obstacle to the rational design of more effective hole transport layers.

[0037] In view of this, in one aspect of this application, a phenylphosphonic acid organic compound is provided. According to embodiments of this application, the phenylphosphonic acid organic compound includes at least one of the compounds shown in Formula I and Formula II:

[0038]

[0039] Wherein, R1 comprises a C1-C8 alkyl chain or at least one aryl chain; R2 comprises a C1-C8 alkyl chain or at least one aryl chain, X - This includes halide ions, sulfonate ions, benzenesulfonate ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, or acetate ions.

[0040] According to the phenylphosphonic acid organic compounds of this application, firstly, the phosphonic acid in the phenylphosphonic acid organic compound is an anchoring group, which can effectively anchor the phenylphosphonic acid organic compound onto the metal oxide substrate, improving the molecular coverage on the metal oxide substrate. Secondly, the phosphonic acid in the phenylphosphonic acid organic compound can chemically bond with the metal oxide in the metal oxide substrate, forming an effective hole transport interface on the metal oxide substrate, while passivating defects on the metal oxide. Thirdly, the phenylphosphonic group in the phenylphosphonic acid organic compound can bridge the perovskite light-absorbing layer and the metal oxide substrate respectively, effectively passivating defects on the interface under the perovskite light-absorbing layer, improving the perovskite crystal quality, enhancing interface stability, and improving the operating stability of the device. Fourthly, the introduction of alkyl chains or aryl groups as intermediate segments into the phenylphosphonic acid organic compound can adjust the molecular flexibility, optimize the band structure, enhance hole transport, and improve the carrier transport performance. Therefore, the open-circuit voltage (V) of the perovskite solar cell prepared using the above-mentioned phenylphosphonic acid organic compound as the hole transport layer is [not specified in the original text]. OC The photoelectric conversion efficiency (PCE) has been significantly improved.

[0041] It should be noted that the aforementioned metal oxide substrate includes a transparent conductive oxide layer, which includes at least one of ITO, IZO, IWO, FTO, ICO, AZO, and BZO.

[0042] According to some specific embodiments of this application, R1 comprises a C1-C6 alkyl chain, one aryl chain, or two aryl chains; R2 comprises a C1-C4 alkyl chain; X - This includes halide ions. The resulting phenylphosphonic acid organic compounds can be more effectively anchored on metal oxide substrates, improving the molecular coverage on the metal oxide substrate; they can more effectively form hole transport interfaces on metal oxide substrates, while also more effectively passivating defects on the metal oxides; they can more effectively passivate defects on the interface below the perovskite light-absorbing layer, improving the crystal quality of the perovskite; and they can more effectively adjust molecular flexibility, optimize the band structure, enhance hole transport, and improve carrier transport performance.

[0043] According to further specific embodiments of this application, the above-mentioned phenylphosphonic acid organic compounds include at least one of the following compounds:

[0044]

[0045]

[0046] The phenylphosphonic acid organic compounds shown in H1, H2, H3, H4, H5, H6, H7, and H8 can be more effectively anchored on metal oxide substrates, increasing the molecular coverage on the metal oxide substrate; they can more effectively form hole transport interfaces on metal oxide substrates, while also more effectively passivating defects on the metal oxide; they can more effectively passivate defects on the interface below the perovskite light-absorbing layer, improving the crystal quality of perovskite; and they can more effectively adjust molecular flexibility, optimize band structure, enhance hole transport, and improve carrier transport performance.

[0047] The preparation method of the above-mentioned phenylphosphonic acid organic compounds is not particularly limited. As a specific example, the preparation method of the phenylphosphonic acid organic compounds shown in Formula I is as follows:

[0048] Step 1: React the diphenylphosphine shown in Formula M1 and the dibromoalkyl or dibromoaryl shown in Formula M2 under strong base and phase transfer catalyst conditions to prepare the compound shown in Formula M3;

[0049] Step 2: React the compound shown in formula M3 and the phosphate ester shown in formula M4 under alkaline conditions to prepare the compound shown in formula M5;

[0050] Step 3: Hydrolyze the compound represented by formula M5 through a hydrolysis reaction to prepare the compound represented by formula I.

[0051] in,

[0052]

[0053] In formula M2, R1 is selected from C1-8 alkyl chains or at least one aryl chain;

[0054]

[0055] According to some specific embodiments of this application, the molar ratio of diphenylphosphine represented by formula M1 and dibromo compound represented by formula M2 can be 1:(2-10).

[0056] According to some specific embodiments of this application, the reaction temperature in step one can be 50 degrees Celsius to 90 degrees Celsius.

[0057] According to some specific embodiments of this application, in step two, the molar ratio of the compound represented by formula M3 and the phosphate ester represented by formula M4 can be 1:(10-40).

[0058] According to some specific embodiments of this application, the reaction temperature in step two can be 120 degrees Celsius to 160 degrees Celsius.

[0059] The preparation method of phenylphosphonic acid organic compounds as shown in Formula II is similar to that of phenylphosphonic acid organic compounds as shown in Formula I, specifically including:

[0060] Step 1: React the triphenylphosphine bromide salt shown in Formula N1 and the phosphate ester shown in Formula N2 under alkaline conditions to prepare the compound shown in Formula N3;

[0061] Step 2: Hydrolyze the compound represented by formula N3 to prepare the compound represented by formula II.

[0062] in, R2 includes a C1-C8 alkyl chain or at least one aryl chain, X - This includes halide ions, sulfonate ions, benzenesulfonate ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, or acetate ions.

[0063]

[0064] In a second aspect, this application proposes a hole transport material. According to embodiments of this application, the hole transport material comprises the phenylphosphonic acid organic compounds described in the above embodiments. Therefore, this hole transport material can effectively anchor onto a metal oxide substrate, increasing the molecular coverage on the metal oxide substrate; it can effectively form a hole transport interface on the metal oxide substrate, while effectively passivating defects on the metal oxide; it can effectively passivate defects on the interface below the perovskite light-absorbing layer, improving the perovskite crystal quality; and it can effectively adjust molecular flexibility, optimize the band structure, enhance hole transport, and improve carrier transport performance.

[0065] In a third aspect, this application proposes a perovskite solar cell. According to embodiments of this application, refer to the appendix... Figure 1 The perovskite solar cell includes a hole transport layer 200, which comprises the hole transport material described in the above embodiments. Therefore, by introducing phenylphosphonic acid-based organic compounds into the hole transport layer of the perovskite solar cell, the open-circuit voltage (V0) of the perovskite solar cell can be effectively improved. OC ) and photoelectric conversion efficiency (PCE).

[0066] According to some specific embodiments of this application, the thickness of the hole transport layer can be 1nm-10nm, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc. By limiting the thickness of the hole transport layer within the above range, the hole transport layer's ability to transport holes can be further enhanced, while also ensuring that it passivates defects on the interface below the perovskite light-absorbing layer, thereby improving the perovskite crystal quality.

[0067] According to some specific embodiments of this application, the hole transport layer is a SAM layer, i.e., a self-assembled monolayer.

[0068] Further, see Appendix Figure 1 The perovskite solar cell further includes a metal oxide substrate 100, a perovskite light-absorbing layer 300, an electron transport layer 400, and an electrode layer 500, wherein the metal oxide substrate 100, the hole transport layer 200, the perovskite light-absorbing layer 300, the electron transport layer 400, and the electrode layer 500 are stacked sequentially.

[0069] The working process of a perovskite solar cell mainly includes: exciton generation and separation, free carrier transport, carrier collection, and current generation. Specifically, in a perovskite solar cell, sunlight is absorbed by the perovskite light-absorbing layer, which absorbs photons and generates excitons. Due to the low Coulomb force binding of the perovskite light-absorbing layer, the excitons subsequently separate into free electrons and holes. The separated free carriers are transported within the perovskite light-absorbing layer and then through the transport layer. The electron transport layer transports electrons while blocking holes, and the hole transport layer transports holes while blocking electrons. The electrons and holes transported through the transport layer are collected by the electrodes to form current and voltage, respectively.

[0070] In the embodiments of this application, the perovskite light-absorbing layer serves as a light-absorbing layer, capable of converting photons into holes and electrons. Its material can be any material conventional in the art and is not limited herein; those skilled in the art can select it according to actual needs. As some specific examples, the material of the aforementioned perovskite light-absorbing layer can be ABX3 type perovskite material, wherein A ion can be at least one of cesium ion, rubidium ion, potassium ion, methylamine ion, formamidinium ion, methylenediamine ion, benzylamidinium cation, and guanidine cation; B ion can be at least one of divalent lead ion and divalent tin ion; and X ion can be at least one of fluoride ion, chloride ion, bromide ion, iodide ion, thiocyanate ion, tetrafluoroborate ion, hexafluorophosphate ion, formate ion, and acetate ion.

[0071] According to some specific embodiments of this application, the thickness of the perovskite light-absorbing layer can be 100nm-3μm, for example, it can be 100nm, 300nm, 500nm, 800nm, 1μm, 1.5μm, 2μm, 2.5μm, 3μm, etc., thereby further ensuring the ability of the perovskite light-absorbing layer to convert photons into holes and electrons.

[0072] In the embodiments of this application, the electron transport layer, as a transport layer, can effectively transport electrons. Its material can be selected from conventional materials in the art, and is not limited thereto. Those skilled in the art can choose according to actual needs. As some specific examples, the material of the electron transport layer includes at least one of tin dioxide, titanium dioxide, isomethyl [6,6]-phenyl-C71-butyrate, C60, and C60 derivatives.

[0073] According to some specific embodiments of this application, the thickness of the electron transport layer can be 1nm-100nm, for example, it can be 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc., thereby further ensuring the electron transport layer's ability to transport electrons.

[0074] In the embodiments of this application, the material of the electrode layer is not particularly limited. As some specific examples, the electrode layer includes at least one of indium tin oxide, indium zinc oxide, zinc aluminum oxide, silver nanowires, gold, silver, copper, aluminum, and carbon.

[0075] According to some specific embodiments of this application, the aforementioned metal oxide substrate includes a transparent conductive oxide layer and a substrate (e.g., glass). The material of the transparent conductive oxide layer is not particularly limited. As some specific examples, the transparent conductive oxide layer includes at least one of ITO, IZO, IWO, FTO, ICO, AZO, and BZO. Optionally, the metal oxide substrate further includes TiO2 and NiO. x At least one of Al2O3 or SiO2.

[0076] In the embodiments of this application, the perovskite solar cell can be a single-layer cell or a tandem cell. When it is a tandem cell, it is preferably any one of the following: perovskite / crystalline silicon tandem cell, all-perovskite tandem cell, perovskite / organic tandem cell, or perovskite / CIGS tandem cell.

[0077] In a fourth aspect, this application discloses a method for fabricating perovskite solar cells. According to embodiments of this application, the method includes:

[0078] The hole transport material described in the above embodiments is mixed with a solvent to form a mixture;

[0079] The above mixture is spin-coated onto the surface of a metal oxide substrate and then heated and annealed to form a hole transport layer on the surface of the metal oxide substrate.

[0080] According to some specific embodiments of this application, the concentration of the hole transport material in the above-mentioned mixture is 0.1 mg / mL-4.0 mg / mL, for example, it can be 0.1 mg / mL, 0.2 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3.5 mg / mL, 4.0 mg / mL, etc. By limiting the concentration of the hole transport material in the above-mentioned mixture within the above range, the hole transport material can be more effectively anchored on the metal oxide substrate, improving the coverage of the hole transport material on the metal oxide substrate; it can further effectively form a hole transport interface on the metal oxide substrate, and at the same time, it can further effectively passivate defects on the metal oxide; it can further effectively passivate defects on the interface under the perovskite light-absorbing layer, improving the crystal quality of the perovskite; it can further effectively adjust the flexibility of the hole transport material, optimize the band structure, enhance hole transport, and improve the transport performance of charge carriers.

[0081] According to some specific embodiments of this application, the above mixture is spin-coated at a speed of 3000rpm-5000rpm for 20s-40s, for example, spin-coated at a speed of 4000rpm for 30s.

[0082] According to some specific embodiments of this application, the metal oxide substrate after spin coating of the mixture is placed on a hot stage at 90°C-110°C and annealed for 5 min-15 min, for example, placed on a hot stage at 100°C and annealed for 10 min.

[0083] In the embodiments of this application, the specific types of solvents are not particularly limited. As some preferred options, the solvents are at least one of chloroform, chlorobenzene, ethyl acetate, tetrahydrofuran, dichloroethane, isopropanol, acetone, ethanol, N,N-dimethylformamide, and 2-methoxyethanol.

[0084] Metal oxide substrates include a transparent conductive oxide layer and a substrate (e.g., glass).

[0085] Furthermore, the above method also includes:

[0086] A perovskite light-absorbing layer is formed on the surface of the hole transport layer that is far from the metal oxide substrate;

[0087] An electron transport layer is formed on the surface of the perovskite light-absorbing layer that is far from the hole transport layer;

[0088] An electrode layer is formed on the surface of the electron transport layer away from the perovskite light-absorbing layer.

[0089] In the embodiments of this application, the preparation method of the perovskite absorber layer is not particularly limited, and conventional preparation methods in the art can be used. Those skilled in the art can choose according to actual needs. As some specific examples, the preparation method of the above-mentioned perovskite absorber layer can be to first prepare a perovskite precursor solution, and then prepare a perovskite thin film by dip coating, spin coating, blade coating, slot coating, bar coating or inkjet printing.

[0090] In the embodiments of this application, the preparation method of the electron transport layer is not particularly limited, and conventional preparation methods in the art can be used. Those skilled in the art can choose according to actual needs. As some specific examples, the electron transport layer can be prepared by vacuum evaporation, magnetron sputtering, atomic layer deposition, electrochemical deposition, molecular beam evaporation, solvent-based dip coating, spin coating, blade coating, slot coating, bar coating, or inkjet printing.

[0091] In a fifth aspect, this application proposes an electrical device. According to an embodiment of this application, the electrical device has the perovskite solar cell described above. Thus, the electrical device possesses all the advantages of perovskite solar cells, which will not be elaborated further here.

[0092] Specifically, electrical equipment can include lighting elements, display elements, mobile devices, etc., specifically including streetlights, signal lights, insect-killing lamps, electric fans, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Among them, electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc.; photovoltaic power generation systems can include large-scale ground photovoltaic power generation systems, distributed photovoltaic power generation and building-integrated photovoltaic power generation systems, etc.

[0093] The embodiments of this application are described in detail below. 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. In addition, unless otherwise specified, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known methods. For reaction conditions not listed, they are also readily available to those skilled in the art.

[0094] Example 1

[0095] (1) A method for preparing a hole transport material H1 is provided, comprising the following steps:

[0096] Synthesis Step 1: 1,2-Dibromoethane (5 mmol), diphenylphosphine (2 mmol), tetrabutylammonium bromide (0.7 mmol), and 50% potassium hydroxide aqueous solution (50 mmol) were added sequentially to a 150 mL dry three-necked round-bottom flask. The reaction mixture was heated and stirred at 70 °C for 24 h under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled to room temperature, and dichloromethane and deionized water were added. The mixture was extracted repeatedly with dichloromethane 3-4 times, and the organic phase was collected in an Erlenmeyer flask. The combined organic layers were dried over anhydrous sodium sulfate, and after rotary evaporation under reduced pressure, the organic phase was purified by silica gel column chromatography (petroleum ether to dichloromethane volume ratio 3:1) to obtain intermediate 2.

[0097] Synthesis Step 2: Intermediate 2 (2 mmol) and triethyl phosphite (10 mL, 60 mmol) were added sequentially to a 100 mL dry three-necked round-bottom flask. The mixture was heated to 140 °C and stirred for 12 h under a N2 atmosphere. After the reaction was complete, the mixture was cooled to room temperature and extracted repeatedly with dichloromethane 3-4 times. The organic phase was collected in an Erlenmeyer flask. The combined organic layers were dried over anhydrous sodium sulfate, and the organic phase was evaporated under reduced pressure. The resulting product was then purified by silica gel column chromatography (dichloromethane to ethyl acetate volume ratio 30:1) to obtain intermediate 3.

[0098] Synthesis Step 3: Intermediate 3 (1.0 mmol) and 20 mL of dichloromethane were added sequentially to a 50 mL dry round-bottom flask for dissolution. 2 mL of trimethylbromosilane was slowly added dropwise, and the mixture was stirred at room temperature for 9 h. After the reaction was complete, the solvent was removed under reduced pressure, and 50 mL of methanol was added. Then, 60 mL of water was added dropwise until the solution became turbid. The mixture was stirred at room temperature for 12 h, filtered, washed with deionized water, and dried to obtain the hole transport material H1.

[0099] By referring to the above method and changing the raw materials, different hole transport materials H2, H3, H4, H5, H6, H7, and H8 can be prepared, which will not be elaborated here.

[0100] (2) The following is a method for preparing a perovskite solar cell, including the following steps:

[0101] Step 1: Spin-coat a 0.5 mg / mL H1 solution (isopropanol as solvent) onto a clean ITO transparent conductive substrate at 4000 rpm for 30 seconds. Place the ITO glass with the H1 solution spin-coated onto a hot plate at 100°C and heat for annealing for 10 minutes to form a hole transport layer with a thickness of approximately 2.5 nm.

[0102] Step 2: Dissolve 622.36 mg lead iodide, 10.73 mg methyl iodide, 17.53 mg cesium iodide and 208.94 mg methyl iodide perovskite material in 1 mL of a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide (4:1 v:v), and stir at room temperature until completely dissolved to obtain a perovskite precursor solution.

[0103] Step 3: In a nitrogen glove box, take 60 μL of perovskite precursor solution and drop it onto a clean ITO conductive glass. Spin coat at 500 rpm and 4000 rpm for 5 s and 35 s respectively. At 25 s, slowly drop 400 μL of anisole. Then place the ITO glass on a hot stage and heat it at 150°C for annealing for 15 min to form a perovskite light-absorbing layer of about 500 nm.

[0104] Step 4: Transfer the ITO conductive glass with the perovskite light-absorbing layer to a vacuum coating instrument, and wait for the vacuum level to reach 3*10. -4 C60 was deposited at Pa to obtain an electron transport layer with a thickness of approximately 30 nm.

[0105] Step 5: Transfer the ITO conductive glass with the hole transport layer, perovskite light-absorbing layer, and electron transport layer formed into a glove box, scrape out the negative electrode area, and then transfer it to a vacuum coating instrument until the vacuum level reaches 6*10. -4 Silver electrodes are deposited by vapor deposition at Pa to form a silver electrode with a thickness of 100 nm, thus obtaining the electrode layer.

[0106] Example 2

[0107] The preparation method of Example 2 is basically the same as that of Example 1, except that:

[0108] Replacing H1 with H2 results in a hole transport layer with a thickness of approximately 3 nm.

[0109] Example 3

[0110] The preparation method of Example 3 is basically the same as that of Example 1, except that H1 is replaced with H3, and the thickness of the hole transport layer is about 4nm.

[0111] Example 4

[0112] The preparation method of Example 4 is basically the same as that of Example 1, except that H1 is replaced with H4, and the thickness of the hole transport layer is about 2.5 nm.

[0113] Example 5

[0114] The preparation method of Example 5 is basically the same as that of Example 1, except that H1 is replaced with H5, and the thickness of the hole transport layer is about 4nm.

[0115] Example 6

[0116] The preparation method of Example 6 is basically the same as that of Example 1, except that H1 is replaced with H6, and the thickness of the hole transport layer is about 2.5 nm.

[0117] Example 7

[0118] The preparation method of Example 7 is basically the same as that of Example 1, except that H1 is replaced with H7, and the thickness of the hole transport layer is about 2.5 nm.

[0119] Example 8

[0120] The preparation method of Example 8 is basically the same as that of Example 1, except that H1 is replaced with H8, and the thickness of the hole transport layer is about 2.5 nm.

[0121] Example 9

[0122] The preparation method of Example 9 is basically the same as that of Example 1, except that the concentration of H1 solution is replaced by 0.1 mg / mL instead of 0.5 mg / mL.

[0123] Example 10

[0124] The preparation method of Example 10 is basically the same as that of Example 1, except that the concentration of H1 solution is replaced by 1 mg / mL instead of 0.5 mg / mL.

[0125] Example 11

[0126] The preparation method of Example 11 is basically the same as that of Example 1, except that the concentration of H1 solution is replaced by 2 mg / mL instead of 0.5 mg / mL.

[0127] Example 12

[0128] The preparation method of Example 12 is basically the same as that of Example 1, except that the concentration of H1 solution is replaced by 4 mg / mL instead of 0.5 mg / mL.

[0129] Comparative Example 1

[0130] The preparation method of this comparative example is basically the same as that of Example 1, except that H1 is replaced with [2-(9H-carbazole-9-yl)ethyl]phosphonic acid.

[0131] The perovskite solar cells prepared in Examples 1-12 and Comparative Example 1 were tested using a simulated light source system. The relevant performance test results are shown in Table 1.

[0132] Table 1

[0133]

[0134]

[0135] As can be seen from Table 1, compared with Comparative Example 1, the open-circuit voltage (V) of Examples 1-8 is... OC The perovskite solar cells of Examples 1-8 showed significantly improved performance and photoelectric conversion efficiency (PCE). Examples 1-8 benefited from the combination of phenylphosphine and uncoordinated lead in the phenylphosphine-phosphonic acid organic compounds, and the bonding of anchoring groups with metal oxides. This allowed the phenylphosphine-phosphonic acid organic compounds in the hole transport layer to bridge the perovskite light-absorbing layer and the metal oxide substrate, respectively, thus improving the hole transport capability of the hole transport layer. Simultaneously, by passivating defects at the perovskite interface, the crystal quality of the perovskite was improved. Therefore, the performance of the perovskite solar cells of Examples 1-8 was significantly improved. Table 1 also shows that the perovskite solar cells of Examples 1 and 10 exhibited superior overall performance compared to Examples 9 and 11-12. It is evident that the preferred concentration of H1 is 0.5 mg / mL-1 mg / mL.

[0136] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0137] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A hole transport material, characterized by, Including phenylphosphonic acid organic compounds, The phenylphosphonic acid organic compounds include at least one of the following compounds: H1H2 H3H4H5 H6H7 H8 。 2. A perovskite solar cell, characterized by, It includes a hole transport layer, wherein the hole transport layer comprises the hole transport material of claim 1.

3. The perovskite solar cell according to claim 2, characterized in that, The thickness of the hole transport layer is 1nm-10nm; And / or, the hole transport layer is a SAM layer.

4. The perovskite solar cell according to claim 2 or 3, characterized in that, It also includes a metal oxide substrate, a perovskite light-absorbing layer, an electron transport layer, and an electrode layer, wherein the metal oxide substrate, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, and the electrode layer are stacked sequentially.

5. The perovskite solar cell according to claim 4, characterized in that, The thickness of the perovskite light-absorbing layer is 100 nm-3 µm; And / or, the thickness of the electron transport layer is 1nm-100nm.

6. The perovskite solar cell according to claim 4, characterized in that, The perovskite light-absorbing layer comprises ABX3 type perovskite material, wherein A ions include at least one of cesium ions, rubidium ions, potassium ions, methylamine ions, formamidinium ions, methylenediamine ions, benzylamidinium cations, and guanidine cations; B ions include at least one of divalent lead ions and divalent tin ions; and X ions include at least one of fluoride ions, chloride ions, bromide ions, iodide ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, and acetate ions. And / or, the electron transport layer comprises at least one of tin dioxide, titanium dioxide, isomethyl [6,6]-phenyl-C71-butyrate, C60 and C60 derivatives; And / or, the electrode layer includes at least one of ITO, IZO, IWO, FTO, ICO, AZO, BZO, gold, silver, copper, aluminum, and carbon; and / or the metal oxide base comprises at least one of ITO, IZO, IWO, FTO, ICO, AZO, BZO, TiO2, NiO x , AI2O3, or SiO2.

7. A method for preparing perovskite solar cells, characterized in that, include: The hole transport material of claim 1 is mixed with a solvent to form a mixture; The mixture is spin-coated and heated for annealing to form a hole transport layer.

8. The method according to claim 7, characterized in that, The concentration of the hole transport material in the mixture is 0.1 mg / mL to 4.0 mg / mL.

9. An electrical appliance, characterized in that, A perovskite solar cell having any one of claims 2-6 or a perovskite solar cell prepared by the method of claim 7 or 8.

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