Abstract:[Objective] Perovskite solar cells have drawn considerable attention in recent years. The addition of additives to perovskite precursor solutions is an important method to improve the quality of perovskite films for enhancing the performance of perovskite solar cells. In the past, alkali metal ions were extensively used as additives. Rubidium ions (Rb+) were generally added into perovskite films alongside other kinds of cations, following which the photovoltaic performance of the solar cells was clearly improved. However, few researchers studied the effects of only adding various proportions of Rb+ on perovskite films. In this study, rubidium chloride (RbCl) was used as an additive in perovskite precursor solutions and the morphology and structure of perovskite films were analyzed. Perovskite films were fabricated using a two-step method. RbCl was used as an additive into lead (II) iodide (PbI2) precursor solutions with the RbCl proportions 2 %, 4 %, 6 %, 8 %, 10 %, and 12 % versus PbI2, and a PbI2 precursor solution with no RbCl added was used as the control. Scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD) analysis were employed to analyze the difference in surface morphology and structure of the perovskite films. Steady-state photoluminescence (SSPL) and time-resolved photoluminescence (TRPL) spectra were recorded using devices of fluorine-doped tin oxide (FTO)/SnO2/perovskite films to study the carrier-transporting properties. The photovoltaic performances of the perovskite solar cells were studied through a solar simulator and external quantum efficiency testing. UV-visible (UV-vis) absorption spectra were recorded to explore the change in light absorption. The crystalline grain size is clearly enhanced upon adding 4 % RbCl. The grain size is 1.61 μm in the control and 2.14 μm upon adding 4 % RbCl. However, a high addition proportion (>8 %) damages and distorts the crystal structure, decreasing the film quality. Adding RbCl at a low proportion is beneficial for guiding the growth of perovskite grains, increasing grain size, and forming a dense film with fewer holes. The XRD patterns reveal that the peak at 12.6° corresponding to PbI2 is suppressed upon adding RbCl, whereas a new peak appears at 11.3°. The suppression of the PbI2 peak and the appearance of the new peak can be attributed to the formation of the RbCl complex and excessive PbI2, and the complex can be observed in the SEM images, which is confirmed by EDS results. The TRPL results reveal that adding RbCl at a low proportion enhances the transport and extraction of charge carriers, which is consistent with the SSPL results. Furthermore, the photovoltaic performance results reveal that with RbCl as an additive, the photoelectric conversion efficiency of the perovskite solar cells increases from 18.88 % to 20.06 %, and photoelectric properties such as open-circuit voltage, short-circuit current density, and filling factor are considerably improved. However, the UV-vis absorption spectra show that the absorption is not improved upon adding RbCl and even decreases with a high addition proportion, which is due to the increasing roughness of the perovskite films with increasing RbCl proportion. The enhancement of the photoelectric properties is due to the increase in transport and extraction of charge carriers caused by the improvement in film quality. This research demonstrates that adding RbCl at low proportions can enhance the grain size and transport of the carriers, improving the photovoltaic performance. The optimal RbCl addition proportion is ~4 %. This study has considerable potential for improving the performance of perovskite solar cells.
[1] IEA. Projected costs of generating electricity 2020[R/OL]. (2020-12-31)[2023-06-06]. https://www.iea.org/reports/projected-costs-of-generating-electricity-2020. [2] GAO Y, YANG X X, TAN Z C, et al. Effects of beam splitting on photovoltaic properties of monocrystalline silicon, multicrystalline silicon, GaAs, and perovskite solar cells for hybrid utilization[J]. International Journal of Green Energy, 2023, 20(8):835-843. [3] ZHU P C, GU S, LUO X, et al. Simultaneous contact and grain-boundary passivation in planar perovskite solar cells using SnO2-KCl composite electron transport layer[J]. Advanced Energy Materials, 2020, 10(3):1903083. [4] 汪志鹏, 李瑞, 张梅, 等. SnO2基钙钛矿太阳能电池界面调控与性能优化[J]. 工程科学学报, 2023, 45(2):263-277. WANG Z P, LI R, ZHANG M, et al. Interface modification and performance optimization of SnO2 based perovskite solar cells[J]. Chinese Journal of Engineering, 2023, 45(2):263-277. (in Chinese) [5] WANG Z W, ZENG L W, ZHU T, et al. Suppressed phase segregation for triple-junction perovskite solar cells[J]. Nature, 2023, 618(7963):74-79. [6] NREL. Best research-cell efficiencies chart[R/OL]. (2023- 09-05)[2023-09-26].https://www.nrel.gov/pv/cell-efficiency.html. [7] JIANG Q, ZHAO Y, ZHANG X W, et al. Surface passivation of perovskite film for efficient solar cells[J]. Nature Photonics, 2019, 13(7):460-466. [8] 柳宇, 徐凌波, 崔灿. 基于有机胺盐表面修饰的CsPbI3全无机钙钛矿太阳能电池性能的提升[J/OL]. 浙江理工大学学报(自然科学版), 2023:1-8.[2023-10-09]. http://kns.cnki.net/kcms/detail/33.1338.ts.20230724.1105.020.html. LIU Y, XU L B, CUI C. Enhancement of the performance of CsPbI3 all-inorganic perovskite solar cells based on organic ammonium salt surface modification[J/OL]. Journal of Zhejiang Sci-Tech University (Natural Sciences Edition), 2023:1-8.[2023-10-09]. http://kns.cnki.net/kcms/detail/33.1338.ts.20230724.1105.020.html. (in Chinese) [9] 储乐平, 赵晓磊, 杨利营, 等. 添加剂对钙钛矿太阳能电池性能的影响[J]. 天津工业大学学报, 2019, 38(2):27-31. CHU L P, ZHAO X L, YANG L Y, et al. Effect of additive on performance of perovskite solar cells[J]. Journal of Tianjin Polytechnic University, 2019, 38(2):27-31. (in Chinese) [10] 王海军, 徐凌波, 崔灿. 咪唑添加剂对钙钛矿太阳能电池性能的影响[J/OL]. 浙江理工大学学报(自然科学版), 2023:1-10.[2023-10-09]. http://kns.cnki.net/kcms/detail/33.1338.TS.20230724.1104.018.html. WANG H J, XU L B, CUI C. Effects of imidazole additive on the performance of perovskite solar cells[J/OL]. Journal of Zhejiang Sci-Tech University (Natural Sciences Edition), 2023:1-10.[2023-10-09]. http://kns.cnki.net/kcms/detail/33.1338.TS.20230724.1104.018.html. (in Chinese) [11] 陈翔, 鲍付杰, 刘乙力, 等. 氨甲环酸对于CsPbI2Br钙钛矿太阳能电池性能优化[J]. 青岛科技大学学报(自然科学版), 2023, 44(2):31-36. CHEN X, BAO F J, LIU Y L, et al. Improving of the performance of CsPbI2Br perovskite solar cells by tranexamic acid[J]. Journal of Qingdao University of Science and Technology (Natural Science Edition), 2023, 44(2):31-36. (in Chinese) [12] GAO Y, ZHOU H, ZHANG Y G, et al. Effects of RbI doping on perovskite film and photovoltaic performance[C]//Conference on Infrared, Millimeter, Terahertz Waves and Applications (IMT2022). Shanghai, 2022. [13] ZHAO P J, YIN W P, KIM M, et al. Improved carriers injection capacity in perovskite solar cells by introducing A-site interstitial defects[J]. Journal of Materials Chemistry A, 2017, 5(17):7905-7911. [14] YAO Y J, ZOU X P, CHENG J, et al. Impact of K+ doping on modulating majority charge carrier type and quality of perovskite thin films by two-step solution method for solar cells[J]. Coatings, 2019, 9(10):647. [15] ZHOU Z X, ZOU X P, ZHU J L, et al. K+ doping effect on grain boundary passivation and photoelectronics properties of NiOx/perovskite films[J]. Chemical Physics Letters, 2020, 757:137882. [16] ENOMOTO A, SUZUKI A, OKU T, et al. Effects of Cu, K and guanidinium addition to CH3NH3PbI3 perovskite solar cells[J]. Journal of Electronic Materials, 2022, 51(8):4317-4328. [17] MACHIBA H, OKU T, KISHIMOTO T, et al. Fabrication and evaluation of K-doped MA0.8FA0.1K0.1PbI3(Cl) perovskite solar cells[J]. Chemical Physics Letters, 2019, 730:117-123. [18] 罗烈升, 李文辉, 韩修训. 钾离子掺杂对CsPbIBr2钙钛矿薄膜光伏性能的影响[J]. 西北师范大学学报(自然科学版), 2020, 56(6):40-43, 74. LUO L S, LI W H, HAN X X. Effects of K+ doping on photovoltaic performances of CsPbIBr2[J]. Journal of Northwest Normal University (Natural Science), 2020, 56(6):40-43, 74. (in Chinese) [19] ZHANG M, YUN J S, MA Q S, et al. High-efficiency rubidium-incorporated perovskite solar cells by gas quenching[J]. ACS Energy Letters, 2017, 2(2):438-444. [20] 曹冰冰. 钙钛矿太阳能电池中的碱金属离子掺杂和界面工程[D]. 厦门:厦门大学, 2019. CAO B B. Alkali metal cations doping and interface engineering in perovskite solar cells[D]. Xiamen:Xiamen University, 2019. (in Chinese) [21] ZHAO Y, MA F, QU Z H, et al. Inactive (PbI2)2RbCl stabilizes perovskite films for efficient solar cells[J]. Science, 2022, 377(6605):531-534. [22] NAMVAR M J, ABBASPOUR-FARD M H, ROKNABADI M R, et al. Enhancement of perovskite solar cells characteristics by incorporating mixed sodium/cesium cations[J]. Optik, 2019, 185:1019-1023. [23] UEOKA N, OKU T, SUZUKI A. Additive effects of alkali metals on Cu-modified CH3NH3PbI3-δClδ photovoltaic devices[J]. RSC Advances, 2019, 9(42):24231-24240. [24] UEOKA N, OKU T, SUZUKI A. Effects of doping with Na, K, Rb, and formamidinium cations on (CH3NH3)0.99 Rb0.01Pb0.99Cu0.01I3-x(Cl, Br)x perovskite photovoltaic cells[J]. AIP Advances, 2020, 10(12):125023. [25] 李玉娇. 碱金属掺杂对MAPbI3多晶薄膜光电物理性能的影响[D]. 曲阜:曲阜师范大学, 2022. LI Y J. Influence of alkali metal doping on photoelectric physical properties of MAPbI3 polycrystalline thin films[D]. Qufu:Qufu Nomal University, 2022. (in Chinese) [26] GIESBRECHT N, SCHLIPF J, GRILL I, et al. Single-crystal-like optoelectronic-properties of MAPbI3 perovskite polycrystalline thin films[J]. Journal of Materials Chemistry A, 2018, 6(11):4822-4828. [27] ZHAO W G, YAO Z, YU F Y, et al. Alkali metal doping for improved CH3NH3PbI3 perovskite solar cells[J]. Advanced Science, 2018, 5(2):1700131. [28] XIONG Z H, LAN L K, WANG Y Y, et al. Multifunctional polymer framework modified SnO2 enabling a photostable α-FAPbI3 perovskite solar cell with efficiency exceeding 23%[J]. ACS Energy Letters, 2021, 6(11):3824-3830. [29] 韩亮, 崔灿. (NH4)2S修饰SnO2/钙钛矿界面对钙钛矿太阳能电池性能的影响. 浙江理工大学学报(自然科学版), 2023:1-9.. http://kns.cnki.net/kcms/detail/33.1338.TS.20230724.1045.006.html.HAN L, CUI C. Effects of (NH4)2S modified SnO2/perovskite interface on the performance of perovskite solar cells. Journal of Zhejiang Sci-Tech University (Natural Sciences Edition), 2023:1-9.. http://kns.cnki.net/kcms/detail/33.1338.TS.20230724.1045.006.html. (in Chinese) [30] 邵梦婷, 林萍, 崔灿. 锡酸钡/钙钛矿的界面修饰对钙钛矿太阳能电池性能的影响[J]. 浙江理工大学学报(自然科学版), 2023, 49(1):50-58. SHAO M T, LIN P, CUI C. Influence of BaSnO3/perovskite interface modification on the performance of perovskite solar cells[J]. Journal of Zhejiang Sci-Tech University (Natural Sciences Edition), 2023, 49(1):50-58. (in Chinese) [31] 张思健, 胡建, 吕梅, 等. 聚合物钝化钙钛矿量子点的红光放大自发辐射性能[J]. 液晶与显示, 2022, 37(7):787-796.ZHANG S J, HU J, LV M, et al. Red amplified spontaneous emission of polymer passivated perovskite quantum dots[J]. Chinese Journal of Liquid Crystals and Displays, 2022, 37(7):787-796. (in Chinese)