Materials for polyphosphate hole transport layers with UV resistance and their preparation methods; methods for fabricating perovskite devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-07
- Publication Date
- 2026-08-14
AI Technical Summary
[0003]SAM材料虽然可以为钙钛矿器件提供优秀的光电转换效率，但是基于SAM材料的钙钛矿器件很难获得良好的稳定性，尤其是热稳定性
[0038]与现有技术相比，本发明的具有抗紫外的多磷酸空穴传输层材料及其制备方法、钙钛矿器件的制备方法，所述多磷酸空穴传输层材料的结构中存在的多个磷酸基团，将合成的多磷酸空穴传输层材料溶解在乙醇、异丙醇、氯仿、DMSO、DMF中的一种或多种溶剂中，旋涂或刮涂在TCO玻璃或者NiOx上作为空穴传输层使用，可以更加紧密地与基底上的金属氧化物结合。同时，由于其连接基团摒弃了传统的C-N键，而选取键合作用更强的C-C键进行连接，使得分子在紫外作用下不易分解，从而增加了稳定性。并且，通过苯环作为桥接基团，连接两个咔唑单元作为母核，使得材料能级与钙钛矿以及TCO适配，提升了钙钛矿组件的能量转换效率和紫外稳定性。
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Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of perovskite devices, and specifically relates to a polyphosphate hole transport layer material with UV resistance, its preparation method, and a method for preparing perovskite devices. Background Technology
[0002] Perovskite devices (i.e., perovskite solar cells) have developed rapidly in recent years, with laboratory efficiencies reaching 26.7%, comparable to commercial crystalline silicon cells. Furthermore, the emergence of self-assembled small molecule materials (SAMs) has led to a rapid increase in the efficiency of inversion devices, making them a mainstream research direction. Inversion devices also offer advantages such as good stability, simple fabrication processes, and compatibility with traditional solar cells, making them a promising area for future development.
[0003] While SAM materials can provide excellent photoelectric conversion efficiency for perovskite devices, perovskite devices based on SAM materials struggle to achieve good stability, especially thermal stability. Currently, the bonding between common SAM materials and TCO glasses relies solely on a single phosphate group in the molecule, which is easily detached under heat or ultraviolet light. This prevents proper charge transfer to the TCO and creates defects at the interface, leading to carrier recombination. Summary of the Invention
[0004] The technical problem this invention aims to solve is to provide a polyphosphate hole transport layer material with UV resistance, its preparation method, and a method for fabricating perovskite devices. Due to the multiple phosphate groups present in the structure of the polyphosphate hole transport layer material, it can bond more tightly to the metal oxide on the substrate. Simultaneously, because its connecting groups abandon the traditional CN bond and select the stronger CC bond for connection, the molecule is less prone to decomposition under UV radiation, thereby increasing stability. Furthermore, by using a benzene ring as a bridging group to connect two carbazole units as the parent core, the material's energy levels are adapted to perovskite and TCO, improving the energy conversion efficiency and UV stability of the perovskite device.
[0005] This invention is achieved by providing a polyphosphate hole transport layer material with UV resistance, the general chemical formula of which is shown below:
[0006]
[0007] This invention is implemented as follows, and also provides a method for preparing the aforementioned UV-resistant polyphosphate hole transport layer material, the preparation method comprising the following steps:
[0008] Step 1: Synthesis of intermediate Z1:
[0009] 3.25 g and 10 mmol of 3,6-dibromocarbazole, 1.64 g and 5 mmol of p-diiodobenzene, 190 mg and 1 mmol of cuprous iodide, and 12.74 g and 60 mmol of potassium phosphate were mixed in a double-necked flask. The atmosphere inside the flask was replaced with N2 and the flask was sealed. 456 mg and 4 mmol of 1,2-cyclohexanediamine and 100 mL of toluene were added sequentially using a syringe. The reaction apparatus was placed in an oil bath at 120 °C and heated with stirring for 12 h. After the reaction was completed, the apparatus was cooled to room temperature, the reaction was quenched with water, and the organic phase was extracted with dichloromethane (DCM). The collected organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product. Finally, the crude product was purified by silica gel column chromatography to obtain 2.67 g of intermediate Z1 in 74% yield.
[0010] The structure of intermediate Z1 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0011] 1 H NMR (400MHz, DMSO-d6ppm): δ = 8.13 (s, 4H), 7.70-7.7.72 (d, 4H), 7.61-7.63 (d, 4H), 7.51-7.53 (d, 4H).
[0012] Step 2: Synthesis of intermediate Z2:
[0013] 2.67 g and 3.7 mmol of intermediate Z1 were mixed with 57 mg and 0.11 mmol of catalyst bis(tri-tert-butylphosphine)palladium in a double-necked flask. The atmosphere inside the flask was replaced with N2 and sealed. 1.92 g and 18.5 mmol of vinyl phosphoric acid were dissolved in 100 mL of ultra-dry dioxane and bubbled with oxygen for 20 min. Then, 8.79 g and 45 mmol of dioxane and N-methyldicyclohexylamine were added sequentially to the reaction flask using a syringe. Finally, the reaction was heated in an oil bath at 80 °C with stirring for 12 h. After the reaction was complete and cooled to room temperature, the product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried with anhydrous magnesium sulfate and then the solvent was removed using a rotary evaporator to obtain a gray-green precipitate. The precipitate was washed with water several times and then dried to obtain 2.0 g of intermediate Z2 in 65% yield.
[0014] The structure of intermediate Z2 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0015] 1H NMR (400MHz, DMSO-d6ppm): δ = 8.15 (s, 4H), 7.74-7.7.76 (d, 4H), 7.63-7.65 (d, 4H), 7.51-7.53 (d, 4H), 7.22 (t, 4H), 6.51 (t, 4H).
[0016] Step 3: Synthesis of the final product, polyphosphate hole transport layer material Z3:
[0017] 2.0 g (2.4 mmol) of intermediate Z2 was mixed with 518.4 mg (0.48 mmol) of palladium / carbon in a double-necked flask. The atmosphere inside the flask was replaced with N2 and the flask was sealed. 60 mL of tetrahydrofuran was mixed with 10 mL of ethanol and bubbled with nitrogen for 1 h to remove dissolved oxygen from the solvent. The deoxygenated mixed solvent was added to the reaction system using a syringe, followed by dropwise addition of 3.8 mL (24 mmol) of triethylsilane using a syringe. The reaction was stirred at room temperature for 20 h. After the reaction was completed, the reaction was quenched with water. The product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried with anhydrous magnesium sulfate and then the solvent was removed using a rotary evaporator to obtain a gray precipitate. The precipitate was washed with water several times and then dried to obtain 1.35 g of the final product, polyphosphate hole transport layer material Z3, with a yield of 67%.
[0018] The structure of the final product Z3 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0019] 1 H NMR (400MHz, DMSO-d6ppm): δ = 8.10 (s, 4H), 7.65-7.7.68 (d, 4H), 7.53-7.55 (d, 4H), 7.51-7.53 (d, 4H), 4.63-4.67 (m, 8H), 2.95-2.99 (m, 8H);
[0020] 1 C NMR (100MHz, DMSO-d6ppm): δ = 139.7, 136.8, 135.9, 126.4, 126.2, 124.3, 120.9, 111.8, 29.5, 25.4.
[0021] The present invention is implemented as follows, and also provides a perovskite device, the perovskite device including a hole transport layer, the hole transport layer comprising a polyphosphate hole transport layer material with UV resistance as described above.
[0022] This invention is implemented as follows, and also provides a method for fabricating a perovskite device, comprising the following steps:
[0023] Step 1, ITO cleaning: Clean the ITO glass substrate sequentially with ITO cleaner, deionized water, acetone and isopropanol, each ultrasonically for 30 minutes. After cleaning, place the substrate in a 70℃ oven and bake for 2 hours. Treat the dried ITO glass substrate with oxygen plasma for 10 minutes to remove residual organic matter on the surface and increase surface wettability.
[0024] Step 2, Hole transport layer preparation: Dissolve 0.5 mg of the polyphosphate hole transport layer material Z3 prepared by the method of preparing the UV-resistant polyphosphate hole transport layer material as described in claim 2 in 1 mL of ethanol solution, and shake to dissolve it; spin-coat it on an ITO glass substrate at 4000 rpm for 30 s, and anneal it at a hot stage of 100°C for 10 min to obtain the hole transport layer.
[0025] Step 3, perovskite layer preparation: perovskite precursor solution preparation: Weigh 3.8 mg of MABr, 12.9 mg of PbBr2, 15.0 mg of MACl, 22.5 mg of CsI, 277.0 mg of FAI and 720.0 mg of PbI2, add 1 mL of a mixed solvent of DMF:DMSO with a volume ratio of 4:1 and dissolve.
[0026] In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of chlorobenzene (CB) antisolvent was added, and then the mixture was transferred to a hot plate at 120 °C for annealing for 20 min to obtain the perovskite layer.
[0027] Step 4: Preparation of electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain the PCBM solution; spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the electron transport layer.
[0028] Step 5: Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir to dissolve; spin-coat the BCP solution over the electron transport layer at 4000 rpm for 30 s, and dry to obtain the electron transport layer.
[0029] Step 6: Electrode layer preparation: Transfer the prepared electron transport layer substrate to a thermal evaporation apparatus and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.
[0030] This invention is implemented as follows, and also provides a method for fabricating a perovskite device, comprising the following steps:
[0031] Step 1, ITO cleaning: Clean the ITO glass substrate sequentially with ITO cleaner, deionized water, acetone and isopropanol, each ultrasonically for 30 minutes. After cleaning, place the substrate in a 70℃ oven and bake for 2 hours. Treat the dried ITO glass substrate with oxygen plasma for 10 minutes to remove residual organic matter on the surface and increase surface wettability.
[0032] Step 2, Hole transport layer preparation: Dissolve 0.5 mg of intermediate Z2 prepared by the method of preparing polyphosphate hole transport layer material with anti-ultraviolet properties as described in claim 2 in 1 mL of ethanol solution and shake to dissolve; spin-coat on ITO glass substrate at 4000 rpm for 30 s, and anneal at 100°C for 10 min to obtain hole transport layer.
[0033] Step 3, perovskite layer preparation: perovskite precursor solution preparation: Weigh 3.8 mg of MABr, 12.9 mg of PbBr2, 15.0 mg of MACl, 22.5 mg of CsI, 277.0 mg of FAI and 720.0 mg of PbI2, add 1 mL of a mixed solvent of DMF:DMSO with a volume ratio of 4:1 and dissolve.
[0034] In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of CB antisolvent was added, and then the mixture was transferred to a hot plate at 120 °C for annealing for 20 min to obtain the perovskite layer.
[0035] Step 4: Preparation of electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain a PCBM solution; spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the PCBM layer.
[0036] Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir until dissolved; spin-coat the BCP solution over the PCBM layer at 4000 rpm for 30 s to complete the preparation of the electron transport layer.
[0037] Step 5, Electrode layer preparation: Transfer the substrate with the prepared electron transport layer to a thermal evaporation device, and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.
[0038] Compared with the prior art, the present invention provides a polyphosphate hole transport layer material with UV resistance, a method for preparing the same, and a method for preparing perovskite devices. The polyphosphate hole transport layer material contains multiple phosphate groups in its structure. The synthesized polyphosphate hole transport layer material is dissolved in one or more solvents selected from ethanol, isopropanol, chloroform, DMSO, and DMF, and then spin-coated or blade-coated onto TCO glass or NiO. x Using it as a hole transport layer allows for tighter bonding with the metal oxides on the substrate. Furthermore, because its connecting groups abandon the traditional CN bond and instead use the stronger CC bond, the molecule is less prone to decomposition under UV light, thus increasing its stability. Moreover, by using a benzene ring as a bridging group to connect two carbazole units as the core, the material's energy levels are adapted to perovskite and TCO, improving the energy conversion efficiency and UV stability of the perovskite module. Attached Figure Description
[0039] Figure 1 This is a schematic diagram showing the comparison curves of the ultraviolet aging test results of the perovskite devices prepared in Examples 4, 5 and the comparative examples of the present invention. Detailed Implementation
[0040] To make the technical problems to be solved, the technical solutions, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
[0041] Example 1
[0042] A preferred embodiment of the present invention has a polyphosphate hole transport layer material with UV resistance, wherein the general chemical structural formula of the polyphosphate hole transport layer material is shown below:
[0043]
[0044] Example 2
[0045] This invention also discloses a method for preparing a polyphosphate hole transport layer material with UV resistance as described above, the preparation method comprising the following steps:
[0046] Step 1: Synthesis of intermediate Z1:
[0047] 3.25 g and 10 mmol of 3,6-dibromocarbazole, 1.64 g and 5 mmol of p-diiodobenzene, 190 mg and 1 mmol of cuprous iodide, and 12.74 g and 60 mmol of potassium phosphate were mixed in a double-necked flask. The atmosphere inside the flask was purged with nitrogen (N2), and the flask was sealed. 456 mg and 4 mmol of 1,2-cyclohexanediamine and 100 mL of toluene were added sequentially using a syringe. The reaction apparatus was heated in an oil bath at 120 °C with stirring for 12 h. After the reaction was complete, the apparatus was cooled to room temperature, the reaction was quenched with water, and the organic phase was extracted with dichloromethane (DCM). The collected organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product. Finally, the crude product was purified by silica gel column chromatography to give 2.67 g of intermediate Z1 in 74% yield.
[0048] The structure of intermediate Z1 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0049] 1 H NMR (400MHz, DMSO-d6ppm): δ = 8.13 (s, 4H), 7.70-7.7.72 (d, 4H), 7.61-7.63 (d, 4H), 7.51-7.53 (d, 4H).
[0050] Step 2: Synthesis of intermediate Z2:
[0051] 2.67 g (3.7 mmol) of intermediate Z1 and 57 mg (0.11 mmol) of catalyst bis(tri-tert-butylphosphine)palladium were mixed in a double-necked flask. The atmosphere inside the flask was purged with nitrogen (N2) and sealed. 1.92 g (18.5 mmol) of vinylphosphoric acid was dissolved in 100 mL of ultra-dry dioxane and bubbled with oxygen for 20 min. Then, 8.79 g (45 mmol) of dioxane and N-methyldicyclohexylamine were added sequentially to the reaction flask using a syringe. Finally, the reaction was heated in an oil bath at 80 °C with stirring for 12 h. After the reaction was complete and cooled to room temperature, the product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a gray-green precipitate. The precipitate was washed several times with water and dried to obtain 2.0 g (65% yield) of intermediate Z2.
[0052] The structure of intermediate Z2 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0053] 1H NMR (400MHz, DMSO-d6ppm): δ = 8.15 (s, 4H), 7.74-7.7.76 (d, 4H), 7.63-7.65 (d, 4H), 7.51-7.53 (d, 4H), 7.22 (t, 4H), 6.51 (t, 4H).
[0054] Step 3: Synthesis of the final product, polyphosphate hole transport layer material Z3:
[0055] 2.0 g (2.4 mmol) of intermediate Z2 was mixed with 518.4 mg (0.48 mmol) of palladium / carbon in a double-necked flask. The atmosphere inside the flask was purged with N2 and the flask was sealed. 60 mL of tetrahydrofuran was mixed with 10 mL of ethanol, and nitrogen was bubbled through the mixture for 1 h to remove dissolved oxygen from the solvent. The deoxygenated solvent mixture was added to the reaction system using a syringe, followed by dropwise addition of 3.8 mL (24 mmol) of triethylsilane using a syringe. The reaction was stirred at room temperature for 20 h. After the reaction was complete, water was added to quench the reaction, and the product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a gray precipitate. The precipitate was washed several times with water and then dried to obtain 1.35 g of the final product, polyphosphate hole transport layer material Z3, with a yield of 67%.
[0056] The structure of the final product Z3 was determined by 400MHz NMR, and the proton NMR data were obtained as follows:
[0057] 1 H NMR (400MHz, DMSO-d6ppm): δ = 8.10 (s, 4H), 7.65-7.7.68 (d, 4H), 7.53-7.55 (d, 4H), 7.51-7.53 (d, 4H), 4.63-4.67 (m, 8H), 2.95-2.99 (m, 8H).
[0058] 1 C NMR (100MHz, DMSO-d6ppm): δ = 139.7, 136.8, 135.9, 126.4, 126.2, 124.3, 120.9, 111.8, 29.5, 25.4.
[0059] Example 3
[0060] The present invention also discloses a perovskite device, the perovskite device comprising a hole transport layer, the hole transport layer comprising a polyphosphate hole transport layer material with UV resistance as described above.
[0061] Example 4
[0062] This invention discloses a first embodiment of a method for fabricating a perovskite device, comprising the following steps:
[0063] Step 1: ITO Cleaning: Clean the ITO glass substrate sequentially with ITO cleaner, deionized water, acetone, and isopropanol, using ultrasonic cleaning for 30 minutes each. After cleaning, bake the substrate in a 70℃ oven for 2 hours. Treat the dried ITO glass substrate with oxygen plasma for 10 minutes to remove residual organic matter on the surface and increase surface wettability.
[0064] Step 2: Hole transport layer preparation: Dissolve 0.5 mg of the polyphosphate hole transport layer material Z3, prepared by the method described above for preparing UV-resistant polyphosphate hole transport layer material, in 1 mL of ethanol solution and shake to dissolve. Spin-coat the solution onto an ITO glass substrate at 4000 rpm for 30 s, and anneal at 100°C for 10 min to obtain the hole transport layer.
[0065] Step 3, perovskite layer preparation: perovskite precursor solution preparation: Weigh 3.8 mg of MABr, 12.9 mg of PbBr2, 15.0 mg of MACl, 22.5 mg of CsI, 277.0 mg of FAI and 720.0 mg of PbI2, add 1 mL of a mixed solvent of DMF:DMSO with a volume ratio of 4:1 and dissolve.
[0066] In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of chlorobenzene (CB) antisolvent was added, and then the mixture was transferred to a hot plate at 120 °C and annealed for 20 min to obtain the perovskite layer.
[0067] Step 4: Preparation of the electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain the PCBM solution. Spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the electron transport layer.
[0068] Step 5: Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir until dissolved. Spin-coat the BCP solution over the electron transport layer at 4000 rpm for 30 seconds, and dry to obtain the electron transport layer.
[0069] Step 6: Electrode layer preparation: Transfer the prepared electron transport layer substrate to a thermal evaporation apparatus and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.
[0070] Example 5
[0071] This invention also discloses a second embodiment of a method for fabricating a perovskite device, comprising the following steps:
[0072] Step 1, ITO Cleaning: The ITO glass substrate was sequentially cleaned using ITO cleaner, deionized water, acetone, and isopropanol, each ultrasonically for 30 minutes. After cleaning, the substrate was baked in a 70°C oven for 2 hours. The dried ITO glass substrate was then treated with oxygen plasma for 10 minutes to remove residual organic matter and increase surface wettability.
[0073] Step 2, Hole transport layer preparation: Dissolve 0.5 mg of intermediate Z2, prepared by the method for preparing the UV-resistant polyphosphate hole transport layer material as described in claim 2, in 1 mL of ethanol solution and shake to dissolve. Spin-coat the solution onto an ITO glass substrate at 4000 rpm for 30 s, and anneal at 100°C for 10 min to obtain the hole transport layer.
[0074] Step 3, perovskite layer preparation: perovskite precursor solution preparation: Weigh 3.8 mg of MABr, 12.9 mg of PbBr2, 15.0 mg of MACl, 22.5 mg of CsI, 277.0 mg of FAI and 720.0 mg of PbI2, add 1 mL of a mixed solvent of DMF:DMSO with a volume ratio of 4:1 and dissolve.
[0075] In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of CB antisolvent was added, and then the mixture was transferred to a hot plate at 120 °C and annealed for 20 min to obtain the perovskite layer.
[0076] Step 4, Preparation of the electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain a PCBM solution. Spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the PCBM layer.
[0077] Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir until dissolved. Spin-coat the BCP solution over the PCBM layer at 4000 rpm for 30 s to complete the preparation of the electron transport layer.
[0078] Step 5, Electrode layer preparation: Transfer the substrate with the prepared electron transport layer to a thermal evaporation device, and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.
[0079] Comparative Example
[0080] The difference between this comparative example and Example 4 is that compound 2PACz is used instead of polyphosphate hole transport layer material Z3. The other steps are the same as in Example 1 and will not be repeated.
[0081] The chemical molecular structure of compound 2PACz is shown below:
[0082]
[0083] The perovskite devices prepared in Examples 4, 5 and the comparative example were subjected to performance tests, and the data comparison is shown in Table 1 below.
[0084] Table 1. Performance comparison of perovskite devices prepared in Examples 4, 5, and the comparative examples.
[0085] Example 4 25.34 1.18 84.34 25.21 Example 5 24.47 1.13 81.23 22.46 Comparative Example 25.21 1.15 83.44 24.19
[0086] Table 1 shows that the photovoltaic performance parameters of perovskite devices based on the polyphosphate hole transport material Z3 of this invention are compared with those of its intermediate Z2 and the commercially available hole transport material 2PACz. The results show that the performance of the perovskite device based on Z3 is significantly better than that based on Z2 and 2PACz. Its open-circuit voltage (Voc) and fill factor (FF) are significantly improved, which proves that the interfacial contact between the hole transport layer and the perovskite is improved.
[0087] The perovskite devices prepared in Examples 4, 5, and the comparative example were subjected to ultraviolet aging tests, and the results were as follows: Figure 1 The comparison curves shown are shown.
[0088] from Figure 1 It can be observed that the polyphosphate hole transport material Z3 exhibits excellent stability under ultraviolet irradiation, maintaining an initial efficiency of 95.8% even at an irradiation value of 90 kWh, while the efficiency of Z2-based and 2PACz-based materials has decreased to 81% and 53%, respectively. This demonstrates that the polyphosphate hole transport material Z3 of this invention uses C-C bonds with stronger bonding to connect molecules, making the molecules less prone to decomposition under ultraviolet light, thereby increasing the ultraviolet stability of perovskite devices.
[0089] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A polyphosphate hole transport layer material with UV resistance, characterized in that, The general chemical structural formula of the polyphosphate hole transport layer material is shown below:
2. A method for preparing a polyphosphate hole transport layer material with UV resistance as described in claim 1, characterized in that, The preparation method includes the following steps: Step 1: Synthesis of intermediate Z1: 3.25 g and 10 mmol of 3,6-dibromocarbazole, 1.64 g and 5 mmol of p-diiodobenzene, 190 mg and 1 mmol of cuprous iodide, and 12.74 g and 60 mmol of potassium phosphate were mixed in a double-necked flask. The atmosphere inside the flask was replaced with N2 and the flask was sealed. 456 mg and 4 mmol of 1,2-cyclohexanediamine and 100 mL of toluene were added sequentially using a syringe. The reaction apparatus was placed in an oil bath at 120 °C and heated with stirring for 12 h. After the reaction was completed, the apparatus was cooled to room temperature, the reaction was quenched with water, and the organic phase was extracted with dichloromethane. The collected organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product. Finally, the crude product was purified by silica gel column chromatography to obtain 2.67 g of intermediate Z1 in 74% yield. The structure of intermediate Z1 was determined by 400MHz NMR, and the proton NMR data were obtained as follows: 1 H NMR(400MHz,DMSO-d6ppm):δ=8.13(s,4H),7.70-7.7.72(d,4H),7.61-7.63(d,4H),7.51-7.53(d,4H); Step 2: Synthesis of intermediate Z2: 2.67 g and 3.7 mmol of intermediate Z1 were mixed with 57 mg and 0.11 mmol of catalyst bis(tri-tert-butylphosphine)palladium in a double-necked flask. The atmosphere inside the flask was replaced with N2 and sealed. 1.92 g and 18.5 mmol of vinyl phosphoric acid were dissolved in 100 mL of ultra-dry dioxane and bubbled with oxygen for 20 min. Then, 8.79 g and 45 mmol of dioxane and N-methyldicyclohexylamine were added sequentially to the reaction flask using a syringe. Finally, the reaction was heated in an oil bath at 80 °C with stirring for 12 h. After the reaction was complete and cooled to room temperature, the product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried with anhydrous magnesium sulfate and then the solvent was removed using a rotary evaporator to obtain a gray-green precipitate. The precipitate was washed with water several times and then dried to obtain 2.0 g of intermediate Z2 in 65% yield. The structure of intermediate Z2 was determined by 400MHz NMR, and the proton NMR data were obtained as follows: 1 H NMR(400MHz,DMSO-d6ppm):δ=8.15(s,4H),7.74-7.7.76(d,4H),7.63-7.65(d,4H),7.51-7.53(d,4H),7.22(t,4H),6.51(t,4H); Step 3: Synthesis of the final product, polyphosphate hole transport layer material Z3: 2.0 g and 2.4 mmol of intermediate Z2 were mixed with 518.4 mg and 0.48 mmol of palladium / carbon in a double-necked flask. The atmosphere inside the flask was replaced with N2 and the flask was sealed. 60 mL of tetrahydrofuran and 10 mL of ethanol were mixed and bubbled with nitrogen for 1 h to remove dissolved oxygen from the solvent. The deoxygenated mixed solvent was added to the reaction system using a syringe, followed by dropwise addition of 3.8 mL and 24 mmol of triethylsilane using a syringe. The reaction was stirred at room temperature for 20 h. After the reaction was completed, the reaction was quenched with water. The product was extracted with ethyl acetate containing 5% hydrochloric acid. The collected organic phase was dried with anhydrous magnesium sulfate and then the solvent was removed using a rotary evaporator to obtain a gray precipitate. The precipitate was washed with water several times and then dried to obtain 1.35 g of the final product, polyphosphate hole transport layer material Z3, with a yield of 67%. The structure of the final product Z3 was determined by 400MHz NMR, and the proton NMR data were obtained as follows: 1 H NMR(400MHz,DMSO-d6ppm):δ=8.10(s,4H),7.65-7.7.68(d,4H),7.53-7.55(d,4H),7.51-7.53(d,4H),4.63-4.67(m,8H),2.95-2.99(m,8H); 1 C NMR(100MHz,DMSO-d6ppm):δ=139.7,136.8,135.9,126.4,126.2,124.3,120.9,111.8,29.5,25.4。 3. A perovskite device, said perovskite device comprising a hole transport layer, characterized in that, The hole transport layer comprises the UV-resistant polyphosphate hole transport layer material as described in claim 1.
4. A method for fabricating a perovskite device, characterized in that, Includes the following steps: Step 1, ITO cleaning: Clean the ITO glass substrate sequentially with ITO cleaning agent, deionized water, acetone and isopropanol, each ultrasonically for 30 minutes. After cleaning, place the substrate in a 70℃ oven and bake for 2 hours. Treat the dried ITO glass substrate with oxygen plasma for 10 minutes to remove residual organic matter on the surface and increase surface wettability. Step 2, Hole transport layer preparation: Dissolve 0.5 mg of the polyphosphate hole transport layer material Z3 prepared by the method of preparing the UV-resistant polyphosphate hole transport layer material as described in claim 2 in 1 mL of ethanol solution, and shake to dissolve it; spin-coat it on an ITO glass substrate at 4000 rpm for 30 s, and anneal it at a hot table at 100°C for 10 min to obtain the hole transport layer; Step 3, perovskite layer preparation: Perovskite precursor solution preparation: Weigh 3.8 mg of methylammonium bromide (MABr), 12.9 mg of lead bromide (PbBr2), 15.0 mg of methylammonium chloride (MACl), 22.5 mg of cesium iodide (CsI), 277.0 mg of formamidinium hydroiodate (FAI), and 720.0 mg of lead iodide (PbI2), and dissolve them in 1 mL of a mixed solvent with a volume ratio of N,N-dimethylformamide (DMF):dimethyl sulfoxide (DMSO) of 4:
1. In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of chlorobenzene antisolvent was added, and then the mixture was transferred to a hot plate at 120 °C and annealed for 20 min to obtain the perovskite layer. Step 4: Preparation of electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain the PCBM solution; spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the electron transport layer. Step 5: Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir to dissolve; spin-coat the BCP solution over the electron transport layer at 4000 rpm for 30 s, and dry to obtain the electron transport layer. Step 6: Electrode layer preparation: Transfer the prepared electron transport layer substrate to a thermal evaporation apparatus and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.
5. A method for fabricating a perovskite device, characterized in that, Includes the following steps: Step 1, ITO cleaning: Clean the ITO glass substrate sequentially with ITO cleaning agent, deionized water, acetone and isopropanol, each ultrasonically for 30 minutes. After cleaning, place the substrate in a 70℃ oven and bake for 2 hours. Treat the dried ITO glass substrate with oxygen plasma for 10 minutes to remove residual organic matter on the surface and increase surface wettability. Step 2, Hole transport layer preparation: Dissolve 0.5 mg of intermediate Z2 prepared by the method of preparing polyphosphate hole transport layer material with anti-ultraviolet properties as described in claim 2 in 1 mL of ethanol solution and shake to dissolve; spin-coat on ITO glass substrate at 4000 rpm for 30 s and anneal at 100°C for 10 min to obtain hole transport layer. Step 3, perovskite layer preparation: perovskite precursor solution preparation: Weigh 3.8 mg of MABr, 12.9 mg of PbBr2, 15.0 mg of MACl, 22.5 mg of CsI, 277.0 mg of FAI and 720.0 mg of PbI2, add 1 mL of a mixed solvent of DMF:DMSO with a volume ratio of 4:1 and dissolve. In a nitrogen glove box, 100 μL of perovskite precursor solution was dropped onto the surface of the hole transport layer and spin-coated at 5000 rpm for 30 s. 12 s before the end of spin-coating, 160 μL of CB antisolvent was added, and then the mixture was transferred to a hot stage at 120 °C and annealed for 20 min to obtain the perovskite layer. Step 4, Preparation of electron transport layer: Dissolve 23 mg of methyl [6,6]-phenyl-C61-butyrate (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain a PCBM solution; spin-coat the PCBM solution onto the perovskite layer at 1500 rpm for 20 s, and then anneal on a hot plate at 100 °C for 1 min to obtain the PCBM layer. Dissolve 0.5 mg of BCP in 1 mL of isopropanol and stir until dissolved; spin-coat the BCP solution over the PCBM layer at 4000 rpm for 30 s to complete the preparation of the electron transport layer. Step 5, Electrode layer preparation: Transfer the substrate with the prepared electron transport layer to a thermal evaporation device, and deposit 100 nm of copper at a vacuum level of 3E-4 MPa to complete the preparation of the electrode layer.