Perovskite film based on calixarene modification and preparation method and application thereof
By introducing 4-sulfothiacalix[4] aromatics into the perovskite film, the problems of ion migration and defects in perovskite solar cells were solved, and the photoelectric conversion efficiency was improved.
Patent Information
- Application Number
- CN202410714539.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-03
- Publication Date
- 2025-12-12
AI Technical Summary
Perovskite solar cells suffer from ion migration and thin film defects in the perovskite material during application, which limits the improvement of device open-circuit voltage and fill factor.
Perovskite films modified with calixarene were used. By introducing 4-sulfothiacalixarene[4] at the perovskite grain boundaries, the crystallization process was regulated, ion migration was suppressed and defects were reduced by utilizing its multiple interactions with perovskite components.
It significantly improves the photoelectric conversion efficiency of perovskite solar cells, enhances the thin film grain morphology and grain boundary characteristics, and promotes carrier transport.
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Figure CN121127102A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of optoelectronic materials technology, and in particular to a perovskite thin film modified with calixarene, its preparation method and application. Background Technology
[0002] With the continuous development of solar cell technology, perovskite solar cells have attracted much attention due to their high efficiency conversion and low cost.
[0003] However, perovskite solar cells face several challenges in their application, such as the ion migration inherent in perovskite materials. Furthermore, the fabrication of perovskite thin films is prone to the formation of vacancies and defects at grain boundaries, increasing nonradiative recombination energy loss and limiting the improvement of device open-circuit voltage and fill factor.
[0004] Therefore, it is particularly important to provide a solution to suppress ion migration in perovskite thin films and reduce defects in perovskite thin films in order to improve the photoelectric conversion efficiency of perovskite solar cells. Summary of the Invention
[0005] In view of this, this application provides a perovskite thin film modified with calixarene, its preparation method and application, to solve the problem of how to improve the photoelectric conversion efficiency of perovskite solar cells by inhibiting ion migration in perovskite thin films and reducing defects in perovskite thin films.
[0006] To achieve the above technical objectives, this application adopts the following technical solution:
[0007] In a first aspect, this application provides a perovskite thin film modified with calixarene, comprising perovskite grains and 4-sulfothiacalixarene [4]arene (CAS: 211561-04-5) distributed at the perovskite interface and / or grain boundaries; the structure of 4-sulfothiacalixarene [4]arene is shown in formula (I):
[0008]
[0009] Secondly, this application provides a method for preparing perovskite thin films modified with calixarene, comprising the following steps:
[0010] S1. Using lead iodide and formamidine iodide as raw materials, a perovskite precursor solution was prepared. 4-sulfothiacalix[4] aromatic hydrocarbon was added to the perovskite precursor solution and stirred to react, resulting in a mixed solution.
[0011] S2. Spin-coating the mixture onto the hole transport layer on the surface of the conductive substrate;
[0012] S3. Annealing treatment yields the perovskite thin film.
[0013] Preferably, in step S1, the concentration of the perovskite precursor solution is 1.5-2 mmol / ml, the concentration of 4-sulfothiacalix[4] aromatic hydrocarbon is 3-4 mg / ml, the temperature of the stirring reaction is 0-4℃, and the stirring reaction time is 4-6 h.
[0014] Preferably, in step S2, the spin coating conditions are as follows: first spin coating at 1000-1500 rpm for 10 seconds, then spin coating at 5000-6000 rpm for 20 seconds, then add ether, and then spin coating at 5000-6000 rpm for another 10 seconds.
[0015] Preferably, in step S3, the annealing temperature is 110-140℃ and the annealing time is 20-30 min.
[0016] Thirdly, this application provides a method for preparing a perovskite solar cell, comprising the following steps:
[0017] A hole transport layer is fabricated on a conductive substrate;
[0018] Prepare perovskite thin films on hole transport layers;
[0019] A first electron transport layer is prepared on a perovskite thin film;
[0020] A second electron transport layer is fabricated in the first electron transport layer;
[0021] A hole-blocking layer is fabricated on the second electron transport layer;
[0022] An electrode layer is fabricated on a hole-blocking layer.
[0023] Preferably, the hole transport layer is prepared as follows: an IPA solution of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz, CAS: 20999-38-6) is spin-coated onto the surface of a conductive substrate, and then annealed at 100-110°C for 10-20 min to obtain the hole transport layer.
[0024] Preferably, the preparation method of the first electron transport layer is as follows: a chlorobenzene solution of (6,6)-phenylcarbon-61-butyrate (PCBM, CAS: 160848-22-6) is spin-coated onto the surface of the hole transport layer to obtain the electron transport layer.
[0025] The preparation method of the second electron transport layer is as follows: Fullerene (C 60 (CAS: 99685-96-8) Vacuum evaporation is applied to the surface of the first electron transport layer to obtain the second electron transport layer.
[0026] Preferably, the hole blocking layer is prepared by vacuum evaporation of 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline (BCP, CAS: 4733-39-5) onto the surface of the second electron transport layer to obtain the hole blocking layer; the electrode layer is prepared by vacuum evaporation of Ag onto the surface of the hole blocking layer to obtain the electrode layer.
[0027] Fourthly, this application provides a perovskite solar cell.
[0028] The beneficial effects of this application are as follows:
[0029] This application introduces 4-sulfothiacalix[4] aromatics into the perovskite film, so that the 4-sulfothiacalix[4] aromatics are located at the perovskite grain boundaries. Multiple functional groups in the 4-sulfothiacalix[4] aromatics molecules can interact with the perovskite components through hydrogen bonds, CH…π, π-π, halogen…π and heteroatoms through various interactions. On the one hand, it assists the growth of the perovskite film, promotes its crystallization process, and achieves the effect of regulating the directional growth of crystals in the perovskite light absorption layer and controlling the grain boundary defects of the perovskite material. This improves the morphology of the film grains and the characteristics of the grain boundaries. On the other hand, through various interactions, it is beneficial to the extraction and transport of charge carriers, constrains the components of the perovskite, and inhibits the migration of ions and the generation of vacancies in the perovskite film, ultimately achieving a significant improvement in the photoelectric conversion efficiency of the perovskite solar cell. Attached Figure Description
[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.
[0031] Figure 1 This is a structural diagram of the solar cell device of the present invention;
[0032] Figure 2 The image shows the JV curve of the photoelectric conversion efficiency of the device prepared in Example 2.
[0033] Figure 3 This is a comparison chart of PL between Example 2 and Comparative Example 1. Detailed Implementation
[0034] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.
[0035] This application provides a perovskite film modified with calixarene, which includes perovskite grains and 4-sulfothiacalixarene distributed at the perovskite interface and / or grain boundaries[4].
[0036] The introduced 4-sulfothiacalix[4] aromatic hydrocarbon is located at the perovskite grain boundary. Multiple functional groups in the molecule can interact with the perovskite components, assist the growth of the perovskite film, promote its crystallization process, and improve the morphology of the film grains and the characteristics of the grain boundary; reduce the formation of defects, which is conducive to the extraction and transport of charge carriers, and finally achieve a significant improvement in the efficiency of perovskite solar cells.
[0037] This application provides a method for preparing a perovskite thin film, comprising the following steps:
[0038] S1. Using lead iodide and formamidine iodide as raw materials, a perovskite precursor solution was prepared. 4-sulfothiacalix[4] aromatic hydrocarbon was added to the perovskite precursor solution and stirred to react, resulting in a mixed solution.
[0039] S2. Spin-coating the mixture onto the hole transport layer on the surface of the conductive substrate;
[0040] S3. Annealing treatment yields the perovskite thin film.
[0041] In step S1, 4-sulfothiacalix[4]arene is used as an additive in the perovskite precursor solution to passivate defects in the perovskite as a Lewis base. It is used to regulate the crystallization of the perovskite film and suppress ion migration. It reduces the non-radiative recombination loss caused by defects at the perovskite interface and / or grain boundaries. Through the interaction between 4-sulfothiacalix[4]arene and the perovskite components, the crystallization process is regulated, ion migration is significantly suppressed, and defects are reduced.
[0042] In step S1, the perovskite precursor solution is prepared by dissolving lead iodide and formamidine iodide in a mixed solvent of DMF and DMSO at a molar ratio of 1:1-2.
[0043] In step S1, the concentration of the perovskite precursor solution is 1.5-2 mmol / ml, and the concentration of 4-sulfothiacalix[4]arene is 3-4 mg / ml. Within this range, 4-sulfothiacalix[4]arene can be successfully introduced into the perovskite grain boundaries and / or interfaces. If the amount of 4-sulfothiacalix[4]arene is lower or higher than this range, the effect of introducing perovskite grain boundaries and / or interfaces will be poor. The temperature of the stirring reaction is 0-4℃, and the stirring reaction time is 4-6 h.
[0044] In step S2, the spin coating conditions are as follows: spin coating at 1000-1500 rpm for 10 seconds, then spin coating at 5000-6000 rpm for 20 seconds, then add ether, and then spin coating at 5000-6000 rpm for another 10 seconds; in some embodiments, the conductive substrate is an ITO conductive substrate; the hole transport layer is 2PACz.
[0045] In step S3, the annealing temperature is 110-140℃ and the annealing time is 20-30 min.
[0046] like Figure 1 As shown, this application provides a method for preparing a perovskite solar cell, comprising the following steps:
[0047] A hole transport layer is fabricated on a conductive substrate;
[0048] Prepare perovskite thin films on hole transport layers;
[0049] A first electron transport layer is prepared on a perovskite thin film;
[0050] A second electron transport layer is fabricated in the first electron transport layer;
[0051] A hole-blocking layer is fabricated on the second electron transport layer;
[0052] An electrode layer is fabricated on a hole-blocking layer.
[0053] The hole transport layer is prepared as follows: 2 PACz IPA solution is spin-coated onto the surface of ITO conductive substrate, and then annealed at 100-110℃ for 10-20 min to obtain the hole transport layer; the spin-coating rate is 4000-5000 rpm and the spin-coating time is 30-40 s.
[0054] The preparation method of the first electron transport layer is as follows: spin-coating a chlorobenzene solution of PCBM onto the surface of the hole transport layer, with a spin-coating rate of 3000-4000 rpm and a spin-coating time of 30-40 s. The concentration of the chlorobenzene solution of PCBM is 1-2 mg / ml, which is obtained by dissolving 1-2 mg of PCBM in 1 ml of chlorobenzene and stirring for 12-24 h.
[0055] The preparation method of the second electron transport layer is as follows: C60 The second electron transport layer is obtained by vacuum evaporation on the surface of the first electron transport layer; the vacuum evaporation rate is 0.1-0.2 Å / s, and the thickness of the second electron transport layer is 20-30 nm.
[0056] The hole blocking layer is prepared as follows: BCP is vacuum-deposited onto the surface of the second electron transport layer to obtain the hole blocking layer. The vacuum deposition rate is 0.1-0.2 Å / s, and the thickness of the hole blocking layer is 7-10 nm. The electrode layer is prepared as follows: Ag is vacuum-deposited onto the surface of the hole blocking layer at a rate of 1-2 Å / s to obtain the electrode layer. The thickness of the electrode layer is 150-200 nm.
[0057] This application provides a perovskite solar cell, which is used in the photovoltaic field to improve photoelectric conversion efficiency and stability.
[0058] The following detailed implementation method further illustrates this solution.
[0059] Example 1
[0060] 2. A perovskite thin film modified with calixarene, comprising perovskite grains and 4-sulfothiacalix[4]arene distributed at the perovskite interface and / or grain boundaries; the structure of the 4-sulfothiacalix[4]arene is shown in formula (I):
[0061]
[0062] The preparation method of perovskite thin films based on calixarene modification includes the following steps:
[0063] S1. In a 1:1 molar ratio, 0.82 g of lead iodide, 0.2648 g of formamidine, 0.03713 g of methylamine chloride, and 0.003 g of 4-sulfothiacalix[4] aromatic hydrocarbon were weighed and dissolved in 1000 μL of a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio 9:1). The mixture was stirred on a cold plate for 4 hours to completely dissolve it. The solution was then filtered through a 0.22 μm filter membrane to obtain the mixed solution.
[0064] S2. ITO conductive glass with dimensions of 1.5×2.5 was ultrasonically treated for 30 min each in ethanol, ultrapure water with cleaning agent, ultrapure water, and ethanol, and then purged with a nitrogen gun. This was used as a conductive substrate. The cleaned ITO substrate was treated with a UV ozone cleaner for 20 min. 2 PACz (1 mg / ml, IPA dissolved) was spin-coated at 4000 rpm for 30 s, and then annealed at 100℃ for 10 min to obtain a hole transport layer. The mixture was then spin-coated using a two-step spin-coating method. The specific experimental procedure was as follows: first spin-coating at 1000 rpm for 10 s; then spin-coating at 5000 rpm for 30 s. 800 μL of diethyl ether was added 20 s before the end of the spin-coating.
[0065] S3. After spin coating, anneal at 110℃ for 20 minutes to obtain the perovskite film.
[0066] Example 2
[0067] A perovskite solar cell, the preparation method of which is as follows:
[0068] (1). Weigh out 0.82 g of lead iodide, 0.2648 g of iodoformin, 0.03713 g of methylamine chloride, and 3 mg of lead iodide and formamidine in a 1:1 molar ratio. 4-Sulfothiacalix[4]arene was dissolved in 1000 μL of a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio 9:1), and stirred on a cold stage for 4 hours to completely dissolve it. It was then filtered with a 0.22 μm filter membrane to obtain a mixed solution. ITO conductive glass with a size of 1.5×2.5 was ultrasonically treated in ethanol, ultrapure water with cleaning agent, ultrapure water and ethanol for 30 min each, and then purged with a nitrogen gun as a conductive substrate. The cleaned ITO substrate was treated with an ultraviolet ozone cleaner for 20 min. 2PACz (1 mg / ml, IPA dissolved) was spin-coated at 4000 rpm for 30 s, and then annealed at 100 °C for 10 min to obtain a hole transport layer.
[0069] (2) The mixture was spin-coated in two steps. The specific experimental operation was as follows: first spin-coated at 1000 rpm for 10 s; then spin-coated at 5000 rpm for 30 s. 800 μL of ether was added 20 s before the end of spin-coating. After spin-coating, the film was annealed at 110 °C for 20 min to obtain the perovskite film.
[0070] (3) Using PCBM as the first electron transport layer (10 mg / ml, dissolved in CB), spin-coated on the perovskite layer at 3000 rpm for 30 s.
[0071] (4) After spin-coating the first electron transport layer of the PCBM, vacuum-deposit 20 nm of C at a speed of 0.1 Å / s. 60 As a second electron transport layer;
[0072] (5) Use a crucible to vapor deposit BCP material at a temperature of 100°C. After the rate stabilizes, open the baffle and vapor deposit a 7nm thick BCP as a hole blocking layer at a rate of 0.1 Å / s.
[0073] (6) Continue to use vacuum evaporation to deposit silver (150 nm) onto the above sample at a rate of 1 angstrom / second to obtain perovskite solar cells.
[0074] Example 3
[0075] A perovskite battery is the same as in Example 2 except that the amount of 4-sulfothiacalix[4] aromatic hydrocarbon added is 2 mg.
[0076] Example 4
[0077] A perovskite battery is the same as in Example 2 except that the amount of 4-sulfothiacalix[4] aromatic hydrocarbon added is 4 mg.
[0078] Comparative Example 1
[0079] A perovskite battery is the same as in Example 2 except that 4-sulfothiacalix[4] aromatics are not added.
[0080] Comparative Example 2
[0081] A perovskite battery is the same as in Example 2 except that 4-sulfothiacalix[4]arene is replaced with 4-sulfonic acid calixarene (CAS: 137407-62-6).
[0082] Testing and Evaluation
[0083] The photovoltaic performance of the solar cells was tested in a nitrogen glove box using an Enlitech SS-F5-3A system (Enlitech Ltd.) under AM 1.5G illumination, with the light intensity calibrated using NREL standard silicon cells. The open-circuit voltage, short-circuit current, fill factor, and energy conversion efficiency of the perovskite cells in the examples and comparative examples are shown in Table 1. Figure 2 The JV curve represents the photoelectric conversion efficiency of the perovskite solar cell device prepared in Example 2. Figure 3 This is a comparison chart of PL between Example 2 and Comparative Example 1.
[0084] Table 1 Test Results
[0085]
[0086] The above results show that by introducing 4-sulfothiacalix[4] aromatics into the perovskite film, the 4-sulfothiacalix[4] aromatics are located at the perovskite grain boundaries. Multiple functional groups in the 4-sulfothiacalix[4] aromatics molecules can interact with the perovskite components through hydrogen bonds, CH…π, π-π, halogen…π and heteroatoms through various interactions. On the one hand, this assists the growth of the perovskite film, promotes its crystallization process, and achieves the effect of regulating the directional growth of crystals in the perovskite light absorption layer and controlling the grain boundary defects of the perovskite material. This improves the morphology of the film grains and the characteristics of the grain boundaries. On the other hand, through various interactions, it is beneficial to the extraction and transport of charge carriers, constrains the components of the perovskite, and inhibits the migration of ions and the generation of vacancies in the perovskite film, ultimately achieving a significant improvement in the photoelectric conversion efficiency of the perovskite solar cell.
[0087] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A perovskite thin film based on calixarene modification, characterized in that, It includes perovskite grains, and 4-sulfothiacalix[4] aromatics distributed at the perovskite interfaces and / or grain boundaries; the structure of the 4-sulfothiacalix[4] aromatics is shown in formula (I):
2. A method for preparing a perovskite thin film based on calixarene modification as described in claim 1, characterized in that, Includes the following steps: S1. Using lead iodide and formamidine iodide as raw materials, a perovskite precursor solution was prepared. 4-sulfothiacalix[4] aromatic hydrocarbon was added to the perovskite precursor solution and stirred to react, resulting in a mixed solution. S2. Spin-coating the mixture onto the hole transport layer on the surface of the conductive substrate; S3. Annealing treatment, to obtain the perovskite film.
3. The preparation method according to claim 2, characterized in that, In step S1, the concentration of the perovskite precursor solution is 1.5-2 mmol / ml, the concentration of the 4-sulfothiacalix[4] aromatic hydrocarbon is 3-4 mg / ml, the temperature of the stirring reaction is 0-4℃, and the stirring reaction time is 4-6 h.
4. The preparation method according to claim 2, characterized in that, In step S2, the spin coating conditions are as follows: first spin coating at 1000-1500 rpm for 10 seconds, then spin coating at 5000-6000 rpm for 20 seconds, then add ether, and then spin coating at 5000-6000 rpm for another 10 seconds.
5. The preparation method according to claim 2, characterized in that, In step S3, the annealing temperature is 110-140℃ and the annealing time is 20-30 minutes.
6. A method for preparing a perovskite solar cell, characterized in that, Includes the following steps: A hole transport layer is fabricated on a conductive substrate; A perovskite thin film as described in claim 1 is prepared on the hole transport layer; A first electron transport layer is prepared on the perovskite thin film; A second electron transport layer is fabricated in the first electron transport layer; A hole blocking layer is fabricated on the second electron transport layer; An electrode layer is prepared on the hole-blocking layer.
7. The method for preparing a perovskite solar cell according to claim 6, characterized in that, The hole transport layer is prepared as follows: an IPA solution of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid is spin-coated onto the surface of the conductive substrate, and then annealed at 100-110°C for 10-20 min to obtain the hole transport layer.
8. The method for preparing a perovskite solar cell according to claim 6, characterized in that, The first electron transport layer is prepared as follows: a chlorobenzene solution of methyl (6,6)-phenylcarbon-61-butyrate is spin-coated onto the surface of the hole transport layer to obtain the electron transport layer. The preparation method of the second electron transport layer is as follows: Fullerene (C 60 The second electron transport layer is obtained by vacuum evaporation onto the surface of the first electron transport layer.
9. The method for preparing a perovskite solar cell according to claim 6, characterized in that, The hole blocking layer is prepared as follows: 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline (BCP) is vacuum-deposited onto the surface of the second electron transport layer to obtain the hole blocking layer; the electrode layer is prepared as follows: Ag is vacuum-deposited onto the surface of the hole blocking layer to obtain the electrode layer.
10. A perovskite solar cell obtained by the preparation method according to any one of claims 6-9.