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Organic-inorganic metal halide perovskites are a new type of photovoltaic material, they have attracted wide attention and made excellent progress in recent years. The power conversion efficiency of a single-junction perovskite solar cell has been increased to 25.2% just within a decade. Meanwhile, crystalline silicon solar cells account for nearly 90% of industrialized solar cells and have a maximum efficiency of 26.7%, approaching to their theoretical limit. It is more difficult to further improve the efficiency of single junction solar cells. It has been shown that multi-junction tandem solar cells prepared by stacking absorption layers with different bandgaps can better use sunlight, which is one of the most promising strategies to break the efficiency limitation of single-junction solar cells. Due to the bandgap tunability and low-temperature solution processability, perovskites stand out among many other materials for manufacturing multi-junction tandem solar cells. Wide bandgap perovskites with a bandgap of 1.63 eV or above have been combined with narrow band gap inorganic absorption layers such as silicon, copper indium gallium selenide, cadmium telluride or narrow bandgap perovskite to produce high efficiency tandem solar cells. In addition to the promoting of the efficiency improvement of solar cells, the wide bandgap perovskites have broad applications in photovoltaic building integration and photocatalytic fields. Therefore, it is very important to explore and develop high quality wide bandgap perovskite materials and solar cells. Unfortunately, the wide bandgap perovskites have several intrinsic weaknesses, including being more vulnerable to the migration of halogen ions under being illuminated, more defects, and greater possibility of energy level mismatching with the charge transport layers than the narrow bandgap counterparts, which limits the further development of the wide bandgap perovskite solar cells. In this review, the development status of wide bandgap perovskite solar cells is summarized and corresponding strategies for improving their performance are put forward. Furthermore, some personal views on the future development of wide bandgap perovskite solar cells are also presented here in this paper.
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图 1 宽带隙钙钛矿太阳电池性能统计图(Eg ≥ 1.63 eV, PCE > 15%) (a) VOC与Eg之间的关系, 红色阴影部分表示的是qVOC与Eg的比值小于0.75, 其中q表示单位电荷量; (b) PCE和Eg之间的关系
Figure 1. Performance statistics of WBG-PSCs (Eg ≥ 1.63 eV, PCE > 15%): (a) Relationship between VOC and Eg. The red shaded part indicates that the ratio between qVOC and Eg is less than 0.75, where q represents the unit charge; (b) relationship between PCE and Eg.
图 3 (a) MAPb(BrxI1–x)3的紫外可见吸收光谱、不同颜色钙钛矿薄膜照片以及带隙随Br含量变化的函数图[70]; (b) FAPb(Br1–yIy)3的紫外可见吸收光谱和光致发光(PL)光谱[71]; (c) CsPb(BrzI1–z)3的钙钛矿溶液和对应的光致发光(PL)谱[79]
Figure 3. (a) UV-visible absorption spectra, photos of perovskite films with different colors, as well as functional graph between bandgap and bromine content of MAPb(BrxI1–x)3[70]; (b) UV-visible absorption spectra and photoluminescence (PL) spectra of FAPb(Br1–yIy)3[71]; (c) photos of CsPb(BrzI1–z)3 solutions and corresponding PL spectra[79].
图 4 (a)卤素离子在光照下发生迁移和团簇示意图[90]; (b) MAPb(Br0.4I0.6)3在光照下的光致发光(PL)光谱, 插图表示初始PL增长率的温度依赖性[85]; (c)在约50 mW /cm2的条件下, MAPb(Br0.4I0.6)3膜在白光浸泡5 min前(黑色线)、后(红色线)的XRD图谱, 将MAPb(Br0.2I0.8)3膜(绿色虚线)和MAPb(Br0.7I0.3)3膜(棕色虚线)的XRD图谱进行比较[85]
Figure 4. (a) Schematic illustration of halogen ion migration and clusters under light[90]; (b) photoluminescence (PL) spectra of MAPb(Br0.4I0.6)3 under light. The illustration shows the temperature dependence of the initial PL growth rate[85]; (c) the XRD pattern of MAPb(Br0.4I0.6)3 film before (black) and after (red) white-light soaking for 5 min at about 50 mW/cm2. XRD patterns of the MAPb(Br0.2I0.8)3 film (dashed green) and the MAPb(Br0.7I0.3)3 film (dashed brown) are included for comparison[85].
图 5 (a) APbI3钙钛矿的容差因子[56]; (b) FACs基钙钛矿光稳定性明显提高[57]; (c) CsxFA1–xPb(BryI1–y)3材料中的带隙和VOC 变化[37]; (d) K+钝化作用示意图[52]
Figure 5. (a) Tolerance factor of APbI3[56]; (b) FACs-based perovskite light stability was improved obviously[57]; (c) changes of Eg and VOC in the CsxFA1–xPb(BryI1–y)3 compositions[37]; (d) schematic of K+ passivation[52].
图 6 (a) 3种阳离子的分子构型以及MA+空间旋转的示意图[55]; (b) CsFA和CSMAFA钙钛矿太阳电池最佳J-V曲线和EQE曲线[55]; (c) Cs+和GA+混合到钙钛矿晶格以及对带隙的调控曲线[102]; (d) DMA+对钙钛矿带隙的调整[43]
Figure 6. (a) The molecular configurations of the three cations and the rotation of MA+ in space[55]; (b) J-V and EQE curves of the best-performing CsFA and CsMAFA PSCs[55]; (c) Cs+ and GA+ are mixed into the perovskite lattice and the tuning curves of the Eg[102]; (d) DMA+ adjusts the Eg of perovskite[43].
图 8 三卤化物钙钛矿的光稳定性 (a), (b)对照组钙钛矿薄膜(Cs25Br20)经过10倍和100倍太阳光照20 min后的PL光谱, 箭头表示PL峰位随时间变化的方向; (c)对照组薄膜的光谱中心随时间的移动, 在更强光照下, 红移变得更加明显; (d), (e)三卤钙钛矿薄膜(Cs25Br20+Cl3)分别经过10倍和100倍太阳光照20 min后的PL光谱; (f)三卤钙钛矿薄膜的光谱中心随时间的移动, 在更强光照下, 蓝移变得更加明显[44]
Figure 8. Light stability of triple-halide perovskite: (a), (b) PL spectra of control perovskite films (Cs25Br20) under 10-sun and 100-sun illumination for 20 min, respectively. Arrows indicate the direction of the PL shift over time; (c) the shift of the spectral centroids of control films over time. The red shift becomes more obvious under higher injection; (d), (e) PL spectra of triple-halide perovskites (Cs22Br15+Cl3) under 10-sun and 100-sun illumination for 20 min, respectively; (f) the shift of the spectral centroids of triple-halide perovskites over time. The blue shift becomes more obvious under higher injection[44].
图 10 (a)非加快反溶剂萃取(左)和加快反溶剂萃取(右)制备的钙钛矿薄膜SEM图像[119]; (b)无尿素添加剂(左)和尿素添加剂(右)的700 nm厚钙钛矿薄膜SEM图像[119]; (c)甲酰胺诱导直接形成钙钛矿相, 抑制非钙钛矿相的形成[53]; (d)甲酰胺添加剂提高钙钛矿薄膜结晶质量(右)[53]
Figure 10. (a) SEM images of perovskite films prepared using no-boosted solvent extraction (BSE) (left) and BSE (right) methods [119]; (b) SEM images of thick perovskite films without urea additives (left) and with urea additives (right) [119]; (c) formamide induces direct formation of perovskite phase and inhibits the formation of non-perovskite phase[53]; (d) improvement of perovskite film crystallization quality by formamide additives (right)[53].
图 11 (a) BA分子与钙钛矿薄膜表面作用示意图[49]; (b)用BABr的异丙醇溶液处理钙钛矿薄膜表面形成二维钙钛矿薄层[59]; (c)经过BABr溶液处理的钙钛矿太阳电池J-V曲线59; (d) BABr溶液处理的钙钛矿太阳电池稳定功率输出曲线(SPCE)59; (e)在连续照明(AM 1.5 G)下测量的最优电池的稳态开路电压(VOC)59; (f), (g)两种电池的开路电压和效率统计[59]
Figure 11. (a) Schematic of the impact of BA modification on the perovskite film[49]; (b) the perovskite film surface was treated with BABr solution to form a 2D perovskite thin layer[59]; (c) J-V and (d) SPCE curve of PSC with and without BABr treatment[59]; (e) steady-state VOC of the best-performing PSC measured under continuous illumination (AM 1.5 G)[59]; (f), (g) VOC and PCE statistics of two kinds of PSCs[59].
图 13 (a) 2T叠层太阳电池的理论效率图[81]; (b), (c) N-I-P型和P-I-N型2T钙钛矿/硅TSCs结构示意图(TCO: 透明导电氧化物, AR coating: 抗反射膜)
Figure 13. (a) Theoretical efficiency limit for 2T tandem solar cells; (b), (c) schematics of device structures for N-I-P and P-I-N 2T perovskite/silicon TSCs (TCO: Transparent Conductive Oxide. AR coating: Antireflective coating).
表 1 宽带隙钙钛矿太阳电池性能统计(Eg ≥ 1.63 eV, PCE > 15%)
Table 1. WBG-PSCs performance statistics (Eg ≥ 1.63 eV and PCE > 15%).
Type Perovskite Eg/eV VOC/V qVOC/Eg JSC/mA·cm–2 FF/% PCE/% Ref. p-i-n MAPbI2.5Br0.5 1.72 1.060 0.61 18.30 78.2 16.60 [35] p-i-n (FA0.83MA0.17)0.95Cs0.05Pb(I0.6Br0.4)3 1.71 1.210 0.71 19.70 77.5 18.50 [36] p-i-n FA0.6Cs0.4Pb(I0.7Br0.3)3 1.75 1.170 0.67 17.50 80.0 16.30 [37] p-i-n FA0.83MA0.17Pb(I0.6Br0.4)3 1.72 1.150 0.67 19.40 77.0 17.20 [38] p-i-n FA0.8Cs0.2Pb(I0.7Br0.3)3 1.75 1.240 0.71 17.92 81.9 18.19 [39] p-i-n (FA0.65MA0.20Cs0.15)Pb(I0.8Br0.2)3 1.68 1.170 0.70 21.20 79.8 19.50 [27] p-i-n Cs0.15(FA0.83MA0.17)0.85Pb(I0.8Br0.2)3 1.64 1.190 0.73 19.50 80.2 18.60 [40] p-i-n CsPbI3 1.73 1.160 0.67 17.70 78.6 16.10 [41] p-i-n CsPbI2Br 1.80 1.230 0.67 15.26 78.0 15.19 [42] p-i-n FA0.6Cs0.3DMA0.1PbI2.4Br0.6 1.70 1.200 0.70 19.60 82.0 19.40 [43] p-i-n FA0.75Cs0.25Pb(I0.8Br0.2)3 1.68 1.217 0.72 20.18 83.6 20.42 [44] p-i-n (FA0.65MA0.2Cs0.15)Pb(I0.8Br0.2)3 1.67 1.200 0.72 NA NA 20.70 [45] p-i-n (FA0.64MA0.20Cs0.15)Pb0.99(I0.79Br0.2)3 1.68 1.196 0.71 21.65 81.5 21.00 [46] n-i-p Rb0.05(FA0.75MA0.15Cs0.1)0.95PbI2Br 1.73 1.120 0.71 19.40 73.0 15.90 [47] n-i-p FA0.83Cs0.17Pb(I0.6Br0.4)3 1.75 1.160 0.66 18.27 78.5 16.28 [48] n-i-p FA0.85Cs0.15Pb(I0.73Br0.27)3 1.72 1.240 0.72 19.83 73.7 18.13 [49] n-i-p FA0.8Cs0.2Pb(I0.7Br0.3)3 1.75 1.250 0.71 18.53 79.0 18.27 [50] n-i-p MAPb(Br0.2I0.8)3 1.72 1.120 0.65 17.30 82.3 15.90 [51] n-i-p K0.1(Cs0.06FA0.79MA0.15)0.9Pb(I0.4Br0.6)3 1.78 1.230 0.69 17.90 79.0 17.50 [52] n-i-p FA0.83Cs0.17Pb(I0.6Br0.4)3 1.75 1.230 0.70 18.34 79.0 17.80 [53] n-i-p Cs0.17FA0.83PbI2.2Br0.8 1.72 1.270 0.74 19.30 77.4 18.60 [54] n-i-p Cs0.12MA0.05FA0.83Pb(I0.6Br0.4)3 1.74 1.250 0.72 19.00 81.5 19.10 [55] n-i-p Rb5(Cs5MAFA)95Pb(I0.83Br0.17)3 1.63 1.240 0.76 22.80 81.0 21.60 [56] n-i-p FA0.83Cs0.17Pb(I0.6Br0.4)3 1.74 1.200 0.70 19.40 75.1 17.00 [57] n-i-p FA0.17Cs0.83PbI2.2Br0.8 1.72 1.244 0.72 19.80 75.0 18.60 [51] n-i-p Cs0.2FA0.8Pb(I0.75Br0.25)3 1.65 1.220 0.74 21.20 80.5 20.70 [55] n-i-p BA0.09(FA0.83 Cs0.17)0.91Pb(I0.6Br0.4)3 1.72 1.180 0.69 19.80 73.0 17.30 [38] n-i-p FA0.15Cs0.85Pb(I0.73Br0.27)3 1.72 1.240 0.72 19.83 73.7 18.10 [58] n-i-p FA0.83Cs0.17Pb(I0.6Br0.4)3 1.72 1.310 0.76 19.30 78.0 19.50 [59] n-i-p Rb0.05Cs0.095 MA0.1425 FA0.7125PbI2Br 1.72 1.205 0.70 18.00 78.9 17.10 [54] n-i-p CsPbI3 1.73 1.080 0.62 18.41 79.32 15.71 [60] n-i-p CsPbI2Br 1.80 1.230 0.68 16.79 77.81 16.07 [61] n-i-p β-CsPbI3 1.68 1.110 0.66 20.23 82.0 18.40 [62] n-i-p CsPbI3-xBrx 1.77 1.234 0.69 18.30 82.5 18.64 [63] n-i-p CsPbI2Br 1.80 1.270 0.71 15.40 79.0 15.50 [64] 注: NA表示文献中没有给出具体数值; FF表示填充因子. 序号 钙钛矿中常用离子 有效半径R/pm 1 胍离子(GA+) 278 2 二甲胺离子(DMA+) 272 3 甲脒离子(FA+) 253 4 甲胺离子(MA+) 217 5 铯离子(Cs+) 167 6 铷离子(Rb+) 152 7 钾离子(K+) 138 8 钠离子(Na+) 102 9 铅离子(Pb2+) 119 10 锡离子(Sn2+) 112 11 碘离子(I–) 220 12 溴离子(Br–) 196 13 氯离子(Cl–) 181 表 3 近年来典型的2T钙钛矿/硅TSCs的详细性能参数总结
Table 3. Summary of detailed performance of typical 2T perovskite/silicon TSCs in recent years.
Type Perovskite Eg/eV VOC/V Jsc/mA·cm–2 FF/% PCE/% Year Area/cm2 Ref. N-I-P MAPbI3 1.61 1.580 11.50 75.00 13.70 2015 1.00 [15] FA0.83MA0.17Pb(I0.84Br0.16)3 1.63 1.785 14.00 79.50 19.90 2016 0.16 [133] MAPbI3 1.60 1.692 15.80 79.90 21.40 2016 0.17 [134] MAPbI3 1.60 1.701 16.10 70.10 19.20 2016 1.22 [134] Cs0.19MA0.81PbI3 1.59 1.751 18.80 77.10 22.70 2018 0.25 [135] Cs0.19MA0.81PbI3 1.59 1.779 16.50 74.10 21.70 2018 1.43 [135] Cs0.19FA0.81Pb(I0.78Br0.22)3 1.63 1.769 16.50 65.40 19.10 2018 12.96 [135] MA0.37FA0.48Cs0.15PbI2.01Br0.99 1.69 1.703 15.26 79.20 20.57 2017 0.03 [136] FA0.5MA0.38Cs0.12PbI2.04Br0.96 1.69 1.655 16.50 81.10 22.22 2018 0.06 [137] FA0.75MA0.25 Pb(I0.76B0.24)3 1.65 1.710 15.49 71.00 18.81 2018 0.13 [138] Cs0.08FA0.74MA0.18Pb(I0.88Br0.12)3 1.65 1.780 17.82 75.00 23.73 2018 0.13 [139] Cs0.1(FA0.75MA0.25)0.9Pb(I0.78Br0.22)3 1.67 1.830 16.74 70.00 21.31 2019 0.13 [133] Cs 0.08FA0.69MA0.23Pb(I0.78Br22)3 1.67 1.750 16.89 74.18 21.93 2019 0.13 [140] CsRbFAMAPbI3-xBrx 1.62 1.763 17.80 78.10 24.50 2018 1.00 [132] P-I-N Cs0.17FA0.83Pb(Br0.17I0.83)3 1.63 1.650 18.10 79.00 23.60 2017 1.00 [141] FA 0.75Cs0.25Pb(I0.8Br0.2)3 1.68 1.770 18.40 77.00 25.00 2018 1.00 [142] Cs0.05(MA0.17FA0.83)Pb1.1(I0.83Br0.17)3 1.60 1.760 18.50 78.50 25.50 2018 0.81 [143] CsxFA1-xPb(I, Br)3 1.60 1.788 19.50 73.10 25.20 2018 1.42 [144] CsxFA1-x Pb(I, Br)3 1.60 1.741 19.50 74.70 25.40 2018 1.42 [145] Cs0.15(FA0.83MA0.17)0.85Pb(I0.8Br0.2)3 1.64 1.800 17.80 79.40 25.40 2018 0.49 [40] Cs0.05(FA0.83MA0.17)0.95Pb(I0.82Br0.18)3 1.63 1.792 19.02 74.60 25.43 2019 1.00 [146] Cs0.1MA0.9Pb(I0.9Br0.1)3 1.60 1.820 19.20 75.30 26.20 2020 NA [147] Cs 0.25FA0.75Pb(I0.85Br0.15Cl0.05)3 1.67 1.890 19.10 75.30 27.04 2020 1.00 [44] Cs0.05MA0.15FA0.8Pb(I0.75Br0.25)3 1.68 1.700 19.80 77.00 25.70 2020 0.83 [46] (FA0.65MA0.2Cs0.15)Pb(I0.8Br0.2)3 1.68 1.818 18.90 76.40 26.20 2020 1.00 [45] 注: NA表示文献中没有给出具体数值. -
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