A wide band gap perovskite thin film and perovskite / crystalline silicon tandem solar cell and preparation method thereof
Patent Information
- Application Number
- CN202610979680.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-02
- Publication Date
- 2026-09-25
AI Technical Summary
[0004]为了解决上述技术问题，本发明的目的是提供一种宽带隙钙钛矿薄膜及钙钛矿/晶硅叠层太阳电池及其制备方法，有效解决了现有太阳电池存在的光谱利用不完全、结晶不可控、非辐射复合作用强导致的电池性能差和稳定性差的问题
本发明通过向钙钛矿前驱体中引入多功能有机添加剂（如DBG、TBG或DBTG），其分子中的双叔丁氧羰基、三氟甲磺酰基及胍基协同作用，有效促进了非光活性相向光活性相的结晶转变，调控了薄膜的均匀生长并同步钝化了未配位铅离子与碘空位缺陷。显著抑制了非辐射复合损失，从而大幅提升了载流子寿命与器件开路电压。最终，基于DBTG的钙钛矿/晶硅叠层电池获得了优异的光电转换效率与高开路电压。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of solar cell technology, specifically to a wide-bandgap perovskite thin film and a perovskite / crystalline silicon tandem solar cell and its preparation method. Background Technology
[0002] Perovskite solar cells, due to their excellent photoelectric properties such as high absorption coefficient, high carrier mobility, tunable bandgap, and solution processability, have become one of the most promising next-generation photovoltaic technologies. Since their first report in 2009, the photoelectric conversion efficiency of single-junction perovskite solar cells has rapidly increased from an initial 3.8% to over 27%, approaching the level of commercially available crystalline silicon cells. However, limited by the Shockley-Quisser theoretical limit, single-junction cells have an inherent bottleneck in utilizing the solar spectrum. By combining a wide-bandgap perovskite top cell with a mature crystalline silicon bottom cell to construct a perovskite / crystalline silicon tandem solar cell, this efficiency limit can be broken, achieving a certified efficiency of over 34%, and demonstrating potential in flexible and lightweight applications.
[0003] Wide-bandgap perovskite absorber layers are a key component of tandem solar cells, and their performance directly determines the efficiency and stability of the final device. Effectively controlling the crystallization kinetics of wide-bandgap perovskites and simultaneously passivating bulk and interface defects is a core challenge in achieving high-efficiency and stable tandem solar cells. Additive engineering has proven to be an effective strategy for controlling the perovskite film formation process and optimizing crystal quality and defect state density. Currently, multifunctional molecular additives capable of simultaneously achieving crystallization control, defect passivation, stress mitigation, and energy level matching are still rarely reported. Designing and developing such integrated additives is crucial for further advancing high-performance perovskite / crystalline silicon tandem solar cells. Summary of the Invention
[0004] To address the aforementioned technical problems, the present invention aims to provide a wide-bandgap perovskite thin film and a perovskite / crystalline silicon tandem solar cell and its preparation method, effectively solving the problems of incomplete spectral utilization, uncontrollable crystallization, and poor cell performance and stability caused by strong non-radiative recombination in existing solar cells.
[0005] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: a wide-bandgap perovskite thin film is provided, the thin film being made of multifunctional organic additives and perovskite precursor materials; The multifunctional organic additives are N,N'-di-Boc-guanidine (DBG), N,N′,N′′-tri-tert-butoxycarbonylguanidine (TBG) or 1,3-di-tert-butoxycarbonyl-2-(trifluoromethanesulfonyl)guanidine (DBTG).
[0006] Furthermore, the perovskite precursor material is FA. 0.8 Cs 0.05 MA0.15 Pb(I 0.75 Br 0.25 3. Perovskite; the molar amount of the multifunctional organic additive is 0.1-2% of the molar amount of Pb in the perovskite precursor material.
[0007] The present invention also provides a method for preparing the above-mentioned wide-bandgap perovskite thin film, comprising the following steps: Under nitrogen atmosphere, a multifunctional organic additive is added to the perovskite precursor material, then dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirred to obtain a wide-bandgap perovskite film.
[0008] The present invention also provides the application of the above-mentioned wide-bandgap perovskite thin film in the preparation of solar cells.
[0009] The present invention also provides a perovskite / crystalline silicon tandem solar cell, which uses the above-mentioned wide-bandgap perovskite thin film as the wide-bandgap perovskite absorber layer.
[0010] This invention also provides a method for preparing the above-mentioned perovskite / crystalline silicon tandem solar cell, comprising the following steps: S1. An IZO intermediate interconnect layer is sputtered on a silicon substrate solar cell using radio frequency magnetic sputtering. S2. Nickel oxide is deposited on the intermediate connecting layer by spin coating and then annealed to obtain a nickel oxide hole transport layer. S3. (4-(7H-dibenzo[c,g]carbazole-7-yl)butylphosphonic acid was deposited on the nickel oxide hole transport layer by spin coating, and then annealed to obtain a 4PADCB hole transport layer. S4. Wide-bandgap perovskite thin film was prepared by spin-coating and annealing on hole transport layer using anti-solvent method to obtain wide-bandgap perovskite absorber layer. S5. C is deposited on a wide-bandgap perovskite absorber layer using a thermal evaporation method. 60 Electron transport layer; S6. Using atomic layer deposition in C 60 A tin dioxide electron transport layer is deposited on the electron transport layer; S7. An IZO transparent conductive thin film layer is sputtered on the electron transport layer using radio frequency magnetic sputtering. S8. Silver metal grid electrodes and silver bottom electrodes are deposited on the transparent conductive thin film layer and the silicon bottom cell respectively by thermal evaporation to obtain perovskite / crystalline silicon tandem solar cell.
[0011] Furthermore, in step S2, spin coating is performed at 3000-5000 rpm for 20-40 s, followed by annealing at 80-150 ℃ for 5-20 min.
[0012] Furthermore, in step S3, spin coating is performed at 2000-5000 rpm for 20-50 s, followed by annealing at 80-120 ℃ for 5-20 min.
[0013] Further, in step S4, spin coating is performed at 3000-5000 rpm for 20-40 s, followed by annealing at 80-120 ℃ for 5-20 min.
[0014] Furthermore, the thickness of the nickel oxide hole transport layer is 5-20 nm, the thickness of the 4PADCB hole transport layer is 1-5 nm, the thickness of the wide-bandgap perovskite absorber layer is 300-600 nm, and C... 60 The electron transport layer has a thickness of 15-30 nm, the tin dioxide electron transport layer has a thickness of 15-30 nm, the IZO transparent conductive film layer has a thickness of 30-100 nm, the silver metal gate electrode has a thickness of 100-500 nm, and the silver bottom electrode has a thickness of 50-200 nm.
[0015] The present invention has the following beneficial effects: This invention introduces multifunctional organic additives (such as DBG, TBG, or DBTG) into the perovskite precursor. The synergistic effect of the bis-tert-butoxycarbonyl, trifluoromethanesulfonyl, and guanidine groups in these additives effectively promotes the crystallization transformation from the non-photoactive phase to the photoactive phase, regulates the uniform growth of the thin film, and simultaneously passivates uncoordinated lead ions and iodine vacancy defects. This significantly suppresses non-radiative recombination losses, thereby substantially improving carrier lifetime and device open-circuit voltage. Ultimately, the perovskite / crystalline silicon tandem solar cell based on DBTG achieves excellent photoelectric conversion efficiency and high open-circuit voltage. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the perovskite / crystalline silicon tandem solar cell structure of the present invention; Figure 2 This is a cross-sectional scanning electron microscope image of the perovskite / crystalline silicon tandem solar cell obtained in Example 3; Figure 3 The image shows a cross-sectional scanning electron microscope image of the solar cell obtained in Comparative Example 1. Figure 4 The current density-voltage characteristic curves of the solar cells obtained in Examples 1-3 and Comparative Example 1 are shown. Detailed Implementation
[0017] The principles and features of this invention are described below. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0018] Example 1
[0019] A wide-bandgap perovskite thin film is prepared by a multifunctional organic additive and a perovskite precursor material; the multifunctional organic additive is N,N'-di-Boc-guanidine (DBG), and the perovskite precursor material is FA. 0.8 Cs 0.05 MA 0.15 Pb(I 0.75 Br 0.25 3. Perovskite; the molar amount of the multifunctional organic additive is 0.5% of the molar amount of Pb in the perovskite precursor material.
[0020] The method for preparing this wide-bandgap perovskite thin film includes the following steps: Under nitrogen atmosphere, a multifunctional organic additive is added to the perovskite precursor material, then dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirred to obtain a wide-bandgap perovskite film.
[0021] A perovskite / crystalline silicon tandem solar cell (e.g.) Figure 1 As shown), its preparation method includes the following steps: S1. An IZO intermediate interconnect layer is sputtered on a silicon substrate solar cell using radio frequency magnetic sputtering. S2. Nickel oxide is deposited on the intermediate connecting layer by spin coating and annealed to obtain a nickel oxide hole transport layer; spin coating at 3000-5000 rpm for 20-40 s and annealing at 80-150 ℃ for 5-20 min. S3. (4-(7H-dibenzo[c,g]carbazole-7-yl)butylphosphonic acid was deposited on the nickel oxide hole transport layer by spin coating, followed by annealing to obtain a 4PADCB hole transport layer; spin coating was performed at 2000-5000 rpm for 20-50 s, followed by annealing at 80-120 ℃ for 5-20 min. S4. Wide-bandgap perovskite thin films were prepared by spin-coating and annealing on the hole transport layer using the anti-solvent method to obtain a wide-bandgap perovskite absorber layer; spin-coating was performed at 3000-5000 rpm for 20-40 s, and annealing was performed at 80-120 ℃ for 5-20 min. S5. C is deposited on a wide-bandgap perovskite absorber layer using a thermal evaporation method. 60 Electron transport layer; S6. Using atomic layer deposition in C 60 A tin dioxide electron transport layer is deposited on the electron transport layer; S7. An IZO transparent conductive thin film layer is sputtered on the electron transport layer using radio frequency magnetic sputtering. S8. Silver metal grid electrodes and silver bottom electrodes are deposited on the transparent conductive thin film layer and the silicon bottom cell respectively by thermal evaporation to obtain perovskite / crystalline silicon tandem solar cell.
[0022] Example 2
[0023] A wide-bandgap perovskite thin film is prepared by a multifunctional organic additive and a perovskite precursor material; the multifunctional organic additive is N,N′,N′′-tritert-butoxycarbonylguanidine (TBG), and the perovskite precursor material is FA. 0.8 Cs 0.05 MA 0.15 Pb(I 0.75 Br 0.25 3. Perovskite; the molar amount of the multifunctional organic additive is 0.5% of the molar amount of Pb in the perovskite precursor material.
[0024] The method for preparing this wide-bandgap perovskite thin film includes the following steps: Under nitrogen atmosphere, a multifunctional organic additive is added to the perovskite precursor material, then dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirred to obtain a wide-bandgap perovskite film.
[0025] A perovskite / crystalline silicon tandem solar cell (e.g.) Figure 1 As shown), its preparation method includes the following steps: S1. An IZO intermediate interconnect layer is sputtered on a silicon substrate solar cell using radio frequency magnetic sputtering. S2. Nickel oxide is deposited on the intermediate connecting layer by spin coating and annealed to obtain a nickel oxide hole transport layer; spin coating at 3000-5000 rpm for 20-40 s and annealing at 80-150 ℃ for 5-20 min. S3. (4-(7H-dibenzo[c,g]carbazole-7-yl)butylphosphonic acid was deposited on the nickel oxide hole transport layer by spin coating, followed by annealing to obtain a 4PADCB hole transport layer; spin coating was performed at 2000-5000 rpm for 20-50 s, followed by annealing at 80-120 ℃ for 5-20 min. S4. Wide-bandgap perovskite thin films were prepared by spin-coating and annealing on the hole transport layer using the anti-solvent method to obtain a wide-bandgap perovskite absorber layer; spin-coating was performed at 3000-5000 rpm for 20-40 s, and annealing was performed at 80-120 ℃ for 5-20 min. S5. C is deposited on a wide-bandgap perovskite absorber layer using a thermal evaporation method. 60 Electron transport layer; S6. Using atomic layer deposition in C 60 A tin dioxide electron transport layer is deposited on the electron transport layer; S7. An IZO transparent conductive thin film layer is sputtered on the electron transport layer using radio frequency magnetic sputtering. S8. Silver metal grid electrodes and silver bottom electrodes are deposited on the transparent conductive thin film layer and the silicon bottom cell respectively by thermal evaporation to obtain perovskite / crystalline silicon tandem solar cell.
[0026] Example 3
[0027] A wide-bandgap perovskite thin film is prepared by a multifunctional organic additive and a perovskite precursor material; the multifunctional organic additive is 1,3-di-tert-butoxycarbonyl-2-(trifluoromethanesulfonyl)guanidine (DBTG), and the perovskite precursor material is FA. 0.8 Cs 0.05 MA 0.15 Pb(I 0.75 Br 0.25 3. Perovskite; the molar amount of the multifunctional organic additive is 0.5% of the molar amount of Pb in the perovskite precursor material.
[0028] The method for preparing this wide-bandgap perovskite thin film includes the following steps: Under nitrogen atmosphere, a multifunctional organic additive is added to the perovskite precursor material, then dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirred to obtain a wide-bandgap perovskite film.
[0029] A perovskite / crystalline silicon tandem solar cell (e.g.) Figure 1 As shown), its preparation method includes the following steps: S1. An IZO intermediate interconnect layer is sputtered on a silicon substrate solar cell using radio frequency magnetic sputtering. S2. Nickel oxide is deposited on the intermediate connecting layer by spin coating and annealed to obtain a nickel oxide hole transport layer; spin coating at 3000-5000 rpm for 20-40 s and annealing at 80-150 ℃ for 5-20 min. S3. (4-(7H-dibenzo[c,g]carbazole-7-yl)butylphosphonic acid was deposited on the nickel oxide hole transport layer by spin coating, followed by annealing to obtain a 4PADCB hole transport layer; spin coating was performed at 2000-5000 rpm for 20-50 s, followed by annealing at 80-120 ℃ for 5-20 min. S4. Wide-bandgap perovskite thin films were prepared by spin-coating and annealing on the hole transport layer using the anti-solvent method to obtain a wide-bandgap perovskite absorber layer; spin-coating was performed at 3000-5000 rpm for 20-40 s, and annealing was performed at 80-120 ℃ for 5-20 min. S5. C is deposited on a wide-bandgap perovskite absorber layer using a thermal evaporation method. 60 Electron transport layer; S6. Using atomic layer deposition in C 60 A tin dioxide electron transport layer is deposited on the electron transport layer; S7. An IZO transparent conductive thin film layer is sputtered on the electron transport layer using radio frequency magnetic sputtering. S8. Silver metal grid electrodes and silver bottom electrodes are deposited on the transparent conductive thin film layer and the silicon bottom cell respectively by thermal evaporation to obtain perovskite / crystalline silicon tandem solar cell.
[0030] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that no multifunctional organic additives were added.
[0031] Experimental Example Cross-sectional scanning electron microscope images of the solar cells in Example 3 and Comparative Example 1 were obtained, as shown below. Figure 2 and Figure 3 As shown; and the performance of the solar cells in Examples 1-3 and Comparative Example 1 was measured respectively, and the results are as follows. Figure 4 As shown.
[0032] Depend on Figure 2 and Figure 3 It can be seen that, with Figure 2 Compared to solar cells without multifunctional organic additives, the perovskite film with added 3-di-tert-butoxycarbonyl-2-(trifluoromethanesulfonyl)guanidine (DBTG) in Example 3 is thicker, has more uniform coverage on the crystalline silicon textured surface, and has better perovskite film quality.
[0033] Depend on Figure 4 It is known that using 3-di-tert-butoxycarbonyl-2-(trifluoromethanesulfonyl)guanidine (DBTG) doping can significantly reduce the losses caused by non-radiative recombination in the device, significantly improve the open-circuit voltage, short-circuit current and fill factor of the device, and ultimately improve the device efficiency.
[0034] 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, 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 wide-bandgap perovskite thin film, characterized in that, The film is made of multifunctional organic additives and perovskite precursor materials. The multifunctional organic additive is N,N'-di-Boc-guanidine, N,N′,N′′-tri-tert-butoxycarbonylguanidine, or 1,3-di-tert-butoxycarbonyl-2-(trifluoromethanesulfonyl)guanidine.
2. The wide-bandgap perovskite thin film as described in claim 1, characterized in that, The perovskite precursor material is FA. 0.8 Cs 0.05 MA 0.15 Pb(I 0.75 Br 0.25 3. Perovskite; the molar amount of the multifunctional organic additive is 0.1-2% of the molar amount of Pb in the perovskite precursor material.
3. The method for preparing the wide-bandgap perovskite thin film according to claim 1 or 2, characterized in that, Includes the following steps: Under nitrogen atmosphere, a multifunctional organic additive is added to the perovskite precursor material, then dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirred to obtain a wide-bandgap perovskite film.
4. The application of the wide-bandgap perovskite thin film according to claim 1 or 2 in the preparation of solar cells.
5. A perovskite / crystalline silicon tandem solar cell, characterized in that, The wide-bandgap perovskite film as described in claim 1 or 2 is used as the wide-bandgap perovskite absorber layer.
6. The method for preparing the perovskite / crystalline silicon tandem solar cell according to claim 5, characterized in that, Includes the following steps: S1. An IZO intermediate interconnect layer is sputtered on a silicon substrate solar cell using radio frequency magnetic sputtering. S2. Nickel oxide is deposited on the intermediate connecting layer by spin coating and then annealed to obtain a nickel oxide hole transport layer. S3. (4-(7H-dibenzo[c,g]carbazole-7-yl)butylphosphonic acid was deposited on the nickel oxide hole transport layer by spin coating, and then annealed to obtain a 4PADCB hole transport layer. S4. Wide-bandgap perovskite thin film was prepared by spin-coating and annealing on hole transport layer using anti-solvent method to obtain wide-bandgap perovskite absorber layer. S5. C is deposited on a wide-bandgap perovskite absorber layer using a thermal evaporation method. 60 Electron transport layer; S6. Using atomic layer deposition in C 60 A tin dioxide electron transport layer is deposited on the electron transport layer; S7. An IZO transparent conductive thin film layer is sputtered on the electron transport layer using radio frequency magnetic sputtering. S8. Silver metal grid electrodes and silver bottom electrodes are deposited on the transparent conductive thin film layer and the silicon bottom cell respectively by thermal evaporation to obtain perovskite / crystalline silicon tandem solar cell.
7. The method for preparing a perovskite / crystalline silicon tandem solar cell as described in claim 6, characterized in that, In step S2, spin coat at 3000-5000 rpm for 20-40 s, and anneal at 80-150 ℃ for 5-20 min.
8. The method for preparing a perovskite / crystalline silicon tandem solar cell as described in claim 6, characterized in that, In step S3, spin coat at 2000-5000 rpm for 20-50 s, and anneal at 80-120 ℃ for 5-20 min.
9. The method for preparing a perovskite / crystalline silicon tandem solar cell as described in claim 6, characterized in that, In step S4, spin coat at 3000-5000 rpm for 20-40 s, and anneal at 80-120 ℃ for 5-20 min.
10. The method for preparing a perovskite / crystalline silicon tandem solar cell as described in claim 6, characterized in that, The nickel oxide hole transport layer has a thickness of 5-20 nm, the 4PADCB hole transport layer has a thickness of 1-5 nm, the wide-bandgap perovskite absorber layer has a thickness of 300-600 nm, and the C... 60 The electron transport layer has a thickness of 15-30 nm, the tin dioxide electron transport layer has a thickness of 15-30 nm, the IZO transparent conductive film layer has a thickness of 30-100 nm, the silver metal gate electrode has a thickness of 100-500 nm, and the silver bottom electrode has a thickness of 50-200 nm.