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碳基无空穴传输层钙钛矿太阳能电池(C-PSCs)因其替换了昂贵的贵金属电极, 以及去掉了稳定性差的空穴传输材料而受到广泛关注. 但是C-PSCs内部载流子分离和传输性能差阻碍了效率的提高, 而内建电场的增强可以改善载流子传输性能从而提升电池光电性能. 本文将铁电材料钛酸钡(BaTiO3)粉末作为添加剂引入钙钛矿前驱液中制备C-PSCs, 改善钙钛矿薄膜形态, 降低薄膜缺陷密度及提高C-PSCs载流子传输性能. 结果表明, 当BaTiO3质量分数为1.0%时, 钙钛矿薄膜均匀致密, 电池的光电转换效率最高. 对薄膜施加正向电压极化处理后, 铁电材料BaTiO3剩余极化电场增大了内建电场, 为载流子输运和萃取提供充足的动力, 从而抑制非辐射复合的发生; 同时耗尽层宽度增大, 反向饱和电流减小, 电池性能显著提升, 优化后最佳器件效率为9.02%. 本文为钙钛矿吸收层掺杂实现内建电场调控提供了一种有效策略.The preparation of hybrid perovskite solar cells is expensive and environmentally demanding. Carbon-based HTL-free perovskite solar cells (C-PSCs) have attracted much attention because they replace the expensive precious metal electrode and remove the poor stability of the hole transport material. However, the improvement of efficiency is hampered by poor carrier separation and transport performance within C-PSCs, while the enhancement of the built-in electric field can improve the carrier transport performance, thus enhancing photoelectric performance. The built-in electric field can be regulated by doping. The anomalous photovoltaic effect and the built-in electric field of ferroelectric material play an important role in the field of optoelectronics. In this work, a simple and effective method is developed to improve the performance of perovskite solar cells via the combination of internal doping of ferroelectric polymer and external control of electric field. Ferroelectric material barium titanate (BaTiO3) powder is added into perovskite precursor solution as an additive to prepare C-PSCs, which can improve the perovskite film morphology, reduce the film defect density, and enhance the carrier transport performance of C-PSCs. The results show that when the addition of BaTiO3 is 1.0% (mass fraction), the perovskite film is uniform and dense, and the photoelectric conversion efficiency of the cell is the highest. After the forward voltage polarization treatment, the residual polarized electric field of ferroelectric material BaTiO3 increases the built-in electric field, which provides sufficient power for realizing carrier transport and extraction, thus inhibiting the occurrence of non-radiative recombination. At the same time, the depletion layer width is increased, and the reverse saturation current is reduced, so the cell performance is significantly improved. The optimal device efficiency is 9.02%. This work provides an efficient strategy for regulating the built-in electric field by doping perovskite absorption layer.
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Keywords:
- perovskite solar cells /
- built-in electric field /
- ferroelectric materials /
- carrier transport
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图 1 (a) BaTiO3浓度不同时所制备的MAPbI3薄膜的XRD衍射图谱; (b)—(d)对应BaTiO3:MAPbI3复合薄膜(110)衍射峰归一化处理(b), 强度变化(c), 半峰宽(FWHM)变化(d)
Fig. 1. (a) XRD patterns of MAPbI3 films prepared with different BaTiO3 concentrations. (b)–(d) Corresponding to the (110) diffraction peak of BaTiO3:MAPbI3 composite film: (b) (110) crystal plane normalization treatment; (c) strength variation; (d) full-width at half-maximum (FWHM) variation.
图 2 不同质量分数BaTiO3掺杂MAPbI3薄膜的FE-SEM图 (a) 0; (b) 0.5%; (c) 1.0%; (d) 2.0%
Fig. 2. FE-SEM images of MAPbI3 films prepared with different BaTiO3 concentrations: (a) 0; (b) 0.5%; (c) 1.0%; (d) 2.0%.
图 3 (a) FTO/TiO2/MAPbI3和(b) FTO/TiO2/BaTiO3:MAPbI3薄膜的截面图
Fig. 3. Film cross-section of (a) FTO/TiO2/MAPbI3 and (b) FTO/TiO2/BaTiO3:MAPbI3.
图 4 BaTiO3浓度不同时所制备的MAPbI3 C-PSCs的J -V特性曲线
Fig. 4. J -V curves of MAPbI3 C-PSCs prepared with different BaTiO3 concentrations.
图 5 基于MAPbI3和BaTiO3:MAPbI3单电子器件的空间电荷限制电流(SCLC)测试曲线
Fig. 5. Space charge limited current measurement curves for MAPbI3 and BaTiO3:MAPbI3 single-electron device.
图 6 MAPbI3和BaTiO3:MAPbI3基C-PSCs的(a)暗电流曲线, (b) EQE曲线, (c)稳态输出电流曲线, (d)电化学阻抗谱(暗态, 偏压0.6 V, 插图为等效电路图)
Fig. 6. MAPbI3 and BaTiO3:MAPbI3 C-PSCs: (a) Dark current curves; (b) EQE curves; (c) steady-state output current curves; (d) electrochemical impedance spectroscopy (dark state, 0.6 V bias, illustrated as equivalent circuit diagram).
图 7 不同极化电压处理的BaTiO3:MAPbI3基C-PSCs的J -V特性曲线
Fig. 7. J -V curves of BaTiO3:MAPbI3 C-PSCs treated with different polarization voltages.
图 8 极化处理前后BaTiO3:MAPbI3基C-PSCs的(a) Mott-Schottky曲线和(b)稳态PL光谱
Fig. 8. BaTiO3:MAPbI3 C-PSCs before and after polarization treatment: (a) Mott-Schottky curves; (b) steady-state PL spectrum.
图 9 极化处理前后BaTiO3:MAPbI3基C-PSCs的(a) –dV/dJ与(JSC – J )–1关系曲线; (b) d(J/JSC)/dV与V – Voc关系曲线; (c) 电化学阻抗谱; (d)不同偏压的Rrec
Fig. 9. BaTiO3:MAPbI3 C-PSCs before and after polarization treatment: (a) Relationship between –dV/dJ and (JSC – J )–1; (b) relationship between d(J/JSC)/dV and V – Voc; (c) electrochemical impedance spectroscopy; (d) Rrec with different bias.
图 10 极化处理前后BaTiO3:MAPbI3基C-PSCs的(a)暗电流曲线和(b)电压衰减曲线
Fig. 10. BaTiO3:MAPbI3 C-PSCs before and after polarization treatment: (a) Dark current curves; (b) voltage decay curves.
图 11 BaTiO3:MAPbI3基C-PSCs的(a)极化原理图和(b)性能提升原理图
Fig. 11. BaTiO3:MAPbI3 C-PSCs: (a) Polarization schematic diagram; (b) performance improvement schematic diagram.
表 1 不同浓度BaTiO3所制备的MAPbI3 C-PSCs的光伏性能参数
Table 1. Photovoltaic parameters of MAPbI3 C-PSCs prepared with different BaTiO3 concentrations.
Voc/V JSC/(mA·cm–2) FF/% PCE/% Pristine 0.868 10.39 48.26 4.35 0.5% 0.885 12.41 46.92 5.15 1.0% 0.904 12.72 50.99 5.87 2.0% 0.921 11.92 43.70 4.80 
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表 2 不同极化电压处理的BaTiO3:MAPbI3基C-PSCs的光伏性能参数
Table 2. Photovoltaic parameters of BaTiO3:MAPbI3 C-PSCs treated with different polarization voltages.
Voc/V JSC/(mA·cm–2) FF/% PCE/% Pristine 0.888 13.47 47.10 5.64 0.5 V/μm 0.989 15.72 55.66 8.65 1.0 V/μm 1.005 15.59 56.40 8.83 2.0 V/μm 0.940 14.92 50.57 7.09
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表 3 极化处理前后BaTiO3:MAPbI3基C-PSCs的NA, Vbi, W值
Table 3. NA, Vbi, W values of BaTiO3:MAPbI3 C-PSCs before and after polarization treatment.
NA/cm–3 W/nm Vbi/V With BaTiO3 5.82×1015 75.23 0.926 After Poling 3.91×1015 86.30 1.002
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[1] Qiu L B, Ono L K, Qi Y B 2018 Mater. Today Energy 7 169
Google Scholar
[2] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
Google Scholar
[3] NREL, Best Research-Cell Efficiencies: Emerging Photovoltaics https://www.nrel.gov/pv/cell-efficiency.html [2023-5-28
[4] Cai Y, Liang L S, Gao P 2018 Chin. Phys. B 27 018805
Google Scholar
[5] Jeon N J, Na H, Jung E H, Yang T Y, Lee Y G, Kim G, Shin H W, Seok S I, Lee J, Seo J 2018 Nat. Energy 3 682
Google Scholar
[6] Su H, Xiao J Y, Li Q H, Peng C, Zhang X X, Mao C, Yao Q, Lu Y J, Ku Z L, Zhong J 2020 Mater. Sci. Semicond. Proc. 107 104809
Google Scholar
[7] Etgar L, Gao P, Xue Z S, Peng Q, Chandiran A K, Liu B, Nazeeruddin M K, Gratzel M 2012 J. Am. Chem. Soc. 134 17396
Google Scholar
[8] 李家森 2021 硕士学位论文 (北京: 北京交通大学)
Li J S 2021 M. S. Thesis (Beijing: Beijing Jiaotong University
[9] Zhang L Z, Liu C, Zhang J, Li X N, Cheng C, Tian Y Q, Jen A K Y, Xu B M 2018 Adv. Mater. 30 1804028
Google Scholar
[10] Ye T, Hou Y C, Nozariasbmarz A, Yang D, Yoon J, Zheng L Y, Wang K, Wang K, Ramakrishna S, Priya S 2021 ACS Energy Lett. 6 3044
Google Scholar
[11] Wang K, Zheng L Y, Hou Y C, Nozariasbmarz A, Poudel B, Yoon J, Ye T, Yang D, Pogrebnyakov A V, Gopalan V, Priya S 2022 Joule 6 756
Google Scholar
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Google Scholar
Zhang S N, Zhang X, Yang S, Yu W J, Ren B W, Wu C C, Xiao L X 2023 Chin. Sci. Bull. 68 39
Google Scholar
[13] 王明梓 2022 博士学位论文 (西安: 西北大学)
Wang M Z 2022 Ph. D. Dissertation (Xi’an: Northwest University
[14] Feng K Y, Liu X Y, Si D H, Tang X, Xing A, Osada M, Xiao P 2017 J. Power Sources 350 35
Google Scholar
[15] Chen W J, Liu S, Li Q Q, Cheng Q R, He B S, Hu Z J, Shen Y X, Chen H Y, Xu G Y, Ou X M, Yang H Y, Xi J C, Li Y W, Li Y F 2022 Adv. Mater. 34 2110482
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
[29] 朱丽杰 2018 博士学位论文 (北京: 北京交通大学)
Zhu L J 2018 Ph. D. Dissertation (Beijing: Beijing Jiaotong University
[30] Niu T Q, Lu J, Tang M C, Barrit D, Smilgies D M, Yang Z, Li J B, Fan Y Y, Luo T, McCulloch I, Amassian A, Liu S Z, Zhao K 2018 Energy Environ. Sci. 11 3358
Google Scholar
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