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甲脒铅碘钙钛矿(FAPbI3)因其优异的光电性能而成为新兴太阳电池最具潜力的候选材料, 但是稳定性较差成为制约其发展的主要瓶颈. 通过离子掺杂可以有效地改善FAPbI3的稳定性, 如通过共掺杂Cs+和Br–形成FA1–xCsxPbI3–yBry钙钛矿材料, 其耐热及耐水稳定性得到显著改善. 本文利用第一性原理计算了FA1–xCsxPbI3–yBry (x = 0.125, y = 0—0.6)体系的几何结构、电子结构和光学性质. 通过分析发现Cs+和Br–的掺入使得体系能量降低, FA0.875Cs0.125PbI2.96 Br0.04最稳定. 利用等效光学导纳法模拟计算了平面结构钙钛矿太阳电池的吸收率、载流子收集效率、外量子效率、短路电流密度、开路电压和伏安特性. 对于FA1–xCsxPbI3–yBry钙钛矿太阳电池, 当x = 0.125, y = 0.04, 厚度为0.5—1.0 μm时, 电池的短路电流密度均为24.7 mA·cm–2, 开路电压为1.06 V. 结果表明Cs+和Br–的共掺杂在没有降低电池短路电流的同时提高了体系的稳定性, 可为实验上制备高效稳定的钙钛矿太阳电池提供理论参考.Formamdinium lead triiodide (FAPbI3) perovskite has developed as a promising candidate in solar cells for its excellent optoelectronic property. However, the poor environmental stability is still a critical hurdle for its further commercial application. Element doping is an effective method of improving the stability of FAPbI3 materials. It has been reported that the FA1–xCsxPbI3–yBry stability for heat and water resistance were greatly improved by Cs cations and Br anions co-doping. In this study, we perform first-principles calculations to systematically investigate the crystal structures, electronic structures, and optical properties of FA1–xCsxPbI3–yBry. We obtain several stable crystal structures of FA1–xCsxPbI3–yBry (x = 0.125, y = 0—0.6) in the cubic phase for different ratios of Cs cations to Br anions. By analyzing the structures of these mixed ion perovskites, it is revealed that the lattice parameters decrease linearly with the increase of concentration of Cs cations and Br anions, which is consistent with previous experimental result. In this work, the formation energy difference (∆E) is calculated and our results show that the mixing of Cs cations and Br anions could increase the thermodynamic stability compared with pure FAPbI3. The FA0.875Cs0.125PbI2.96Br0.04 is found to be the most stable in all composites investigated. Furthermore, the band gap, hole and electron effective mass increase with increasing proportion of Br anions, indicating an effective strategy for extending the absorption range of FAPbI3 perovskites into the ultraviolet of the solar spectrum, thereby affecting the carrier transport mechanism in this material. Density of states (DOS) analysis indicates that the DOS of valence band edge increases with increasing proportion of Br anions and enhancing transitions between the valence and conduction bands. Finally, the absorption rate, carrier collection efficiency, external quantum efficiency, short-circuit current density, open circuit voltage and volt-ampere characteristics for the planar structure perovskite solar cell are analyzed by the equivalent optical admittance method. For the FA1–xCsxPbI3–yBry (x = 0.125, y = 0.04, thickness = 0.5—1.0 μm) solar cell, the short-circuit current density and the open circuit voltage are estimated at about 24.7 mA·cm–2 and 1.06 V. It is demonstrated that the co-doping Cs cations and Br anions can improve the stability of the system without reducing short-circuit current density, which may provide some theoretical guidance in preparing the perovskite solar cells with high efficiency and excellent stability.
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Keywords:
- first-principle calculations /
- electronic structure theory /
- optical properties /
- perovskite solar cell
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图 1 (a) α-FAPbI3的赝立方2 × 2 × 2超胞; (b) 正交晶格的第一布里渊区中各对称点和对称轴的记号示意图; (c) 利用图(b)中k空间路径得到α-FAPbI3的2 × 2 × 2超胞的能带图和态密度; (d) 钙钛矿太阳电池结构示意图
Fig. 1. (a) Pseudocubic crystal structures of α-FAPbI3 with 2 × 2 × 2 supercell; (b) the first Brillouin zone for the orthorhombic lattice of α-FAPbI3 and the k-path (red line) used to plot the band structure in the present paper; (c) band structure and DOS of α-FAPbI3 calculated using 2 × 2 × 2 supercell; (d) schematic diagram of perovskite solar cell structure.
图 2 Cs+和Br–不同掺杂比例前后能量的变化∆E和2 × 2 × 2超胞体积.
Fig. 2. Calculated total energy change ∆E and 2 × 2 × 2 supercell volume for different doping ratio of Cs and Br.
图 3 禁带宽度、电子和空穴有效质量
Fig. 3. Band gap and effective masses of electron and hole versus different Bromine content.
图 4 FA1–xCsxPbI3–yBry的能带结构、总态密度和分态密度 (a), (d) FA0.875Cs0.125PbI3; (b), (e) FAPbI2.96Br0.04; (c), (f) FA0.875Cs0.125PbI2.96Br0.04
Fig. 4. Band structure, total and partial density of states of α perovskite phase: (a), (d) FA0.875Cs0.125PbI3; (b), (e) FAPbI2.96Br0.04; (c), (f) FA0.875Cs0.125PbI2.96Br0.04.
图 6 FAPbI3钙钛矿太阳电池的光电性能参数 (a) 吸收系数和AM1.5 G光谱; (b) 不同厚度的FAPbI3的吸收率; (c) 由FAPbI3的吸收系数α(ω)计算不同载流子收集长度(ΔZ)下载流子的收集效率H(λ); (d) 外量子效率; (e) 积分电流密度; (f) J-V特性
Fig. 6. Photovoltaic performance parameters of FAPbI3 perovskite solar cell: (a) Absorption coefficient and AM1.5 G illumination; (b) absorptance spectra of the FAPbI3 layer; (c) carrier collection efficiency H(λ) calculated from the α(ω) of the FAPbI3 using different values of carrier collection length (ΔZ); (d) external quantum efficiency spectrum; (e) integrated current density; (f) J-V curves
图 7 短路电流密度随FA1–xCsxPbI3–yBry厚度的变化
Fig. 7. Variation of the short circuit current density with the perovskite film thickness.
表 1 FA1–xCsxPbI3–yBry太阳电池的电学参数
Table 1. Photovoltaic parameters of the pure FA and the dopes Cs and Br perovskite solar cells.
Composition Jsc/(mA·cm–2) Voc/V FF/% η/% FAPbI3 (experiment) 24.7 1.06 77.5 20.3 FAPbI3 25.2 1.06 81.2 21.7 FA0.875Cs0.125PbI3 23.6 1.06 82.2 20.6 FAPbI2.96Br0.04 25.3 1.06 78.8 21.1 FA0.875Cs0.125PbI2.96Br0.04 24.7 1.06 82.4 21.6 
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[1] Burschka J, Pellet N, Moon S J, Humphry B R, Gao P, Nazeeruddin M K, Gratzel M 2013 Nature 499 316
Google Scholar
[2] Dong Q F, Fang Y J, Shao Y C, Mulligan P, Qiu J, Cao L, Huang J S 2015 Science 347 967
Google Scholar
[3] Wang C H, Zhang C J, Tong S C, Shen J Q, Wang C, Li Y Z, Xiao S, He J, Zhang J, Gao Y L, Yang J L 2017 J. Phys. Chem. C 121 6575
Google Scholar
[4] Zhang W H, Xiong J, Jiang L, Wang J Y, Mei T, Wang X B, Gu H S, Daoud W A, Li J H 2017 Appl. Mater. Interfaces 9 38467
Google Scholar
[5] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
Google Scholar
[6] Park N G, Zhu K 2020 Nat. Rev. Mater. 5 333
Google Scholar
[7] Green M A, Dunlop E D, Levi D H, Hohl-Ebinger J, Yoshita M, Ho-Baillie A W Y 2019 Prog. Photovolt. Res. Appl. 27 565
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Google Scholar
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Google Scholar
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Google Scholar
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