高稳定性(EDA)(FA)2[Pb3I10]层状钙钛矿薄膜的制备与表征

doi:10.15541/jim20160156

摘要/Abstract

摘要：

为了提高钙钛矿太阳能电池在潮湿环境中的稳定性, 采用一步法, 通过在DMF中混合(EDA)I₂、(FA)I和PbI₂, 将乙二胺离子引入钙钛矿晶格, 成功制备了一种具有较高稳定性的二维片层状的钙钛矿结构薄膜。通过原位掠入射X射线衍射(GIXRD)、X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见吸收光谱(UV-Vis)和原子力显微镜(AFM)等方法检测分析(EDA)(FA)₂[Pb₃I₁₀]在低湿度及高湿度环境下的结构、形貌以及光学性能变化。结果表明: 制备的 (EDA)(FA)₂[Pb₃I₁₀]薄膜在相同湿度环境下比当前广泛应用于钙钛矿太阳能电池的甲胺铅碘薄膜(CH₃NH₃PbI₃)稳定性更高; 薄膜的光学带隙约为1.67 eV, 与太阳能电池最佳带隙比较接近。另外, (EDA)(FA)₂[Pb₃I₁₀]薄膜在可见光范围吸光性能较好; 薄膜的粗糙度很小, 适合制备太阳能电池, 而且, 成本较硅基太阳能电池低廉, 在分子水平较CH₃NH₃PbI₃的可调谐性更大, 使钙钛矿太阳能电池在未来大面积应用成为可能。

关键词: 一步法, 钙钛矿, 掠入射X射线衍射, 乙二胺甲脒铅碘

Abstract:

A new two-dimensional layered hybrid perovskite solar-cell absorber was synthesized by one-step method, using (EDA)I₂, (FA)I, and PbI₂with a 1:2:3 stoichiometric ratio in a solvent mixture of N, N-dimethylformamide(DMF). Ethylenediamine(EDA) cation was introduced into the perovskite lattice to synthesize a layered structure with improved resistance to the degradation by humidity in air. The effects of humidity and time on crystal structure, composition, morphology, and absorption spectra of (EDA)(FA)₂[Pb₃I₁₀] and CH₃NH₃PbI₃were analyzed by in situ grazing incidence X-ray diffraction(GIXRD), X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope(AFM), and UV-Vis spectroscope. The results reveal that the prepared (EDA)(FA)₂[Pb₃I₁₀] film is more moisture resistant than the CH₃NH₃PbI₃ film which is widely used in the perovskite solar cell. SEM analysis reveals that the (EDA)(FA)₂[Pb₃I₁₀] film has a layered structure, which can reduce the degradation caused by moisture. What’s more, UV-Vis light absorption spectroscopy and atomic force microscopy(AFM) results show that the layered structure film is also a suitable absorber for perovskite solar cells. Photoluminescence spectrum(PL) reveals that bandgap of the (EDA)(FA)₂[Pb₃I₁₀] film is 1.67 eV, which is close to the optimum value for solar photoelectric conversion. As compared to CH₃NH₃PbI₃ film, the low-cost perovskite structure offers greater tunability on a molecular level for further material optimization and possibility for widely used in the future.

Key words: one-step method, perovskite, GIXRD, (EDA)(FA)₂[Pb₃I₁₀]

中图分类号:

TM914

高延敏, 姜文龙, 杨铁莹, 左银泽. 高稳定性(EDA)(FA)₂[Pb₃I₁₀]层状钙钛矿薄膜的制备与表征[J]. 无机材料学报, 2016, 31(10): 1129-1134.

GAO Yan-Min, JIANG Wen-Long, YANG Tie-Ying, ZUO Yin-Ze. Fabrication and Characterization of High Stability (EDA)(FA)₂[Pb₃I₁₀] Layered Perovskite Film[J]. Journal of Inorganic Materials, 2016, 31(10): 1129-1134.

图/表 7

图1 (a) (EDA)(FA)2[Pb3I10]和(b)CH3NH3PbI3薄膜的SEM照片

Fig. 1 SEM images of (a) (EDA)(FA)2[Pb3I10] and (b) CH3NH3PbI3 films

图2 (a)湿度控制及检测装置示意图和(b)掠入射X射线衍射示意图

Fig. 2 (a) Schematic of the humidity control apparatus and (b) and the GIXRD experimental setup for perovskite films on glass

图3 在(80±1)% 的相对湿度下, (EDA)(FA)2[Pb3I10]薄膜放置(a) 0 min, (b) 120 min; 甲胺铅碘(CH3NH3PbI3)薄膜放置(c) 0 min, (d) 15 min之后的掠入射X射线衍射图

Fig. 3 2D GIXRD patterns of EDA(FA)2[Pb3I10] film on glass after (a) 0 min, (b) 120 min; and CH3NH3PbI3 film on glass after (c) 0 min, (d) 15 min exposure to (80±1)% RH

图4 <100>方向的单层钙钛矿结构示意图

Fig. 4 Schematic representation of single-layer <100>-oriented perovskites (a) monoammonium (PEA=C6H5(CH2)2NH3+) or (b) diammonium (EDA=+ H3N(CH2)2NH3+) organic cations

图5 水滴与(a) CH3NH3PbI3和(b) (EDA)(FA)2[Pb3I10]薄膜形成的接触角

Fig. 5 Photograph of contact angles of a water drop on (a) CH3NH3PbI3 and (b) (EDA)(FA)2[Pb3I10] film surfaces

图6 35%相对湿度下的(a) (EDA)(FA)2[Pb3I10]和(b) CH3NH3PbI3的紫外-可见吸收光谱图

Fig. 6 UV-Vis absorption spectra for (a) (EDA)(FA)2[Pb3I10] and (b) CH3NH3PbI3 films in a 35% RH environment after different storage times

图7 (a)(EDA)(FA)2[Pb3I10]和(b)CH3NH3PbI3的AFM图片

Fig. 7 AFM images of (a) (EDA)(FA)2[Pb3I10] and (b) CH3NH3PbI3 films

参考文献 17

[1]	MICHAEL G.The light and shade of perovskite soar cells.Nature Materials, 2014, 13: 838-842.
[2]	HENRY J S.Perovskites: the emergence of a new era for low-cost, high-efficiency solar cells.The Journal of Physical Chemistry Letters, 2013, 4(21): 3623-3630.
[3]	AKIHIRO K, KENJIRO T, YASUO S, et al.Organometal halide perovskites as visible-light sensitizers for photovoltaic cells.Journal of the American Chemical Society, 2009, 131(17): 6050-6051.
[4]	Bi D Q, TRESS W G, DAR M I, et al.Efficient luminescent solar cells based on tailored mixed-cation perovskites.Science Advances, 2016, 2(1): 1150-1170.
[5]	JENO N J, LEE H G, KIM Y C, et al.o-Methoxy substituents in spiro-OMeTAD for efficient inorganic-organic hybrid perovskite solar cells. Journal of the American Chemical Society, 2014, 136(22): 7837-7840.
[6]	KO H S, LEE J W, PARK N G.15.76% efficiency perovskite solar cells prepared under high relative humidity: importance of PbI2 morphology in two-step deposition of CH3NH3PbI3.Journal of Materials Chemistry A, 2015, 3(16): 8808-8815.
[7]	RYU S, NOH J H, JEON N J, et al.Voltage output of efficient perovskite solar cells with high open-circuit voltage and fill factor.Energy & Environmental Science, 2014, 7: 2614-2618.
[8]	WANG Q, SHAO Y, DONG Q, et al.Large fill-factor bilayer iodine perovskite solar cells fabricated by a low-temperature solution- process.Energy & Environmental Science, 2014, 7: 2359-2365.
[9]	WOJCIECHOWSKI K, SALIBA M, LEIJTENS T, ABATE A, et al.Sub-150 C processed meso-superstructured perovskite solar cells with enhanced efficiency. Energy & Environmental Science, 2014, 7: 1142-1147.
[10]	XIAO Z G, BI C, SHAO Y C, et al.Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers.Energy & Environmental Science, 2014, 7: 2619-2623.
[11]	GREEN M A, EMERY K, HISHIKAWA Y, et al.Solar cell efficiency tables (version 47).Progress in Photovoltaics, 2016, 24: 3-11.
[12]	HODES G, CAHEN D.Photovoltaics: perovskite cells roll forward.Nature Photonics, 2014, 8(2): 87-88.
[13]	CALABRESE J, JONES N L, HARLOW R L, et al.Preparation and characterization of layered lead halide compounds.Journal of the American Chemical Society, 1991, 113(6): 2328-2330.
[14]	GANOSE A M, SAVORY C N, SCANLON D O.(CH3NH3)2Pb (SCN)2I2: A more stable structural motif for hybrid halide photovoltaics?The Journal of Physical Chemistry Letters, 2015, 6(22): 4594-4598.
[15]	SMITH I C, HOKE E T, SOLIS-IBARRA D, et al.A Layered hybrid perovskite solar-cell absorber with enhanced moisture stability.Angewandte Chemie, 2014, 126: 11414-11417.
[16]	PANG S P, HU H, ZHANG J L, et al.NH2CH=NH2PbI3: an alternative organolead iodide perovskite sensitizer for mesoscopic solar cells.Chemistry of Materials, 2014, 26(3): 1485-1491.
[17]	YANG J L, SIEMPELKAMP B D, LIU D Y, et al.Investigation of CH3NH3PbI3 degradation rates and mechanisms in controlled humidity environments using in situ techniques.ACS Nano, 2015, 9(2): 1955-1963.

高稳定性(EDA)(FA)₂[Pb₃I₁₀]层状钙钛矿薄膜的制备与表征

Fabrication and Characterization of High Stability (EDA)(FA)₂[Pb₃I₁₀] Layered Perovskite Film

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 17

相关文章 15

编辑推荐

Metrics

本文评价

[1]	贺丹琪, 魏明旭, 刘蕤之, 汤志鑫, 翟鹏程, 赵文俞. 一步法制备重费米子YbAl₃热电材料及其性能提升[J]. 无机材料学报, 2023, 38(5): 577-582.
[2]	张万文, 罗建强, 刘淑娟, 马建国, 张小平, 杨松旺. 氧化锆间隔层的低温喷涂制备及其三层结构钙钛矿太阳能电池应用性能[J]. 无机材料学报, 2023, 38(2): 213-218.
[3]	柳琪, 朱璨, 谢贵震, 王俊, 张东明, 邵刚勤. Ce掺杂SrMgF₄超结构多晶体的吸收/光致发光光谱[J]. 无机材料学报, 2022, 37(8): 897-902.
[4]	林啊鸣, 孙宜阳. Cs₂SnI₆低指数晶面稳定性的第一性原理计算研究[J]. 无机材料学报, 2022, 37(6): 691-696.
[5]	黄郅航, 滕官宏伟, 铁鹏, 范德松. 钙钛矿陶瓷薄膜的电致变色特性[J]. 无机材料学报, 2022, 37(6): 611-616.
[6]	焦博新, 刘兴翀, 全子威, 彭永姗, 周若男, 李海敏. L-精氨酸掺杂钙钛矿太阳电池性能研究[J]. 无机材料学报, 2022, 37(6): 669-675.
[7]	张国庆, 秦鹏, 黄富强. 空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用[J]. 无机材料学报, 2022, 37(4): 445-451.
[8]	张枫娟, 韩博宁, 曾海波. 钙钛矿量子点光伏与荧光聚光电池: 现状与挑战[J]. 无机材料学报, 2022, 37(2): 117-128.
[9]	明月, 胡玥, 梅安意, 荣耀光, 韩宏伟. 醋酸铅添加剂在印刷钙钛矿太阳能电池中的应用[J]. 无机材料学报, 2022, 37(2): 197-203.
[10]	王万海, 周杰, 唐卫华. 钙钛矿薄膜缺陷调控策略在太阳能电池中的应用[J]. 无机材料学报, 2022, 37(2): 129-139.
[11]	焦志翔, 贾帆豪, 王永晨, 陈建国, 任伟, 程晋荣. 基于机器学习的BiFeO₃-PbTiO₃-BaTiO₃固溶体居里温度预测[J]. 无机材料学报, 2022, 37(12): 1321-1328.
[12]	徐婷婷, 李云云, 王谦, 王京康, 任国浩, 孙大志, 吴云涛. 低成本溶液法制备厘米级Cs₃Cu₂I₅单晶及其闪烁发光性能[J]. 无机材料学报, 2022, 37(10): 1129-1134.
[13]	杨新月, 董庆顺, 赵伟冬, 史彦涛. 基于对氯苄胺的2D/3D钙钛矿太阳能电池[J]. 无机材料学报, 2022, 37(1): 72-78.
[14]	刘雯雯, 胡志蕾, 王立, 曹梦莎, 张晶, 张婧, 张帅, 袁宁一, 丁建宁. L-3-(4-吡啶基)-丙氨酸钝化钙钛矿太阳电池界面缺陷[J]. 无机材料学报, 2021, 36(6): 629-636.
[15]	张晓燕, 刘馨玥, 闫金华, 谷耀行, 齐西伟. 钙钛矿型(La_0.2Li_0.2Ba_0.2Sr_0.2Ca_0.2)TiO₃高熵氧化物陶瓷的制备及性能研究[J]. 无机材料学报, 2021, 36(4): 379-385.