大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究※

doi:10.6023/A21120613

化学学报 ›› 2022, Vol. 80 ›› Issue (3): 237-243.DOI: 10.6023/A21120613 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究通讯

大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究^※

张芬^a^,^b, 李霄琪^b, 韩世国^b, 邬发发^b, 刘希涛^a^,^b^,^*(), 孙志华^a^,^b, 罗军华^a^,^b

a 福建师范大学化学与材料学院福州 350007
b 中国科学院福建物质结构研究所福州 350002

投稿日期:2021-12-31 发布日期:2022-02-11
通讯作者: 刘希涛
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(21833010); 国家自然科学基金(21921001); 国家自然科学基金(22075285); 国家自然科学基金(22125110); 中国科学院前沿科学重点研究项目(ZDBS-LY-SLH024); 福建省自然科学基金(2020J01112); 中国科学院战略性先导研究项目(XDB20010200); 中国科学院青年创新促进会(2020307); 博士后创新研究计划(BX2021315)

Bulk Single Crystal Growth of a Two-Dimensional Halide Perovskite Ferroelectric for Highly Polarized-Sensitive Photodetection^※

Fen Zhang^a^,^b, Xiaoqi Li^b, Shiguo Han^b, Fafa Wu^b, Xitao Liu^a^,^b(), Zhihua Sun^a^,^b, Junhua Luo^a^,^b

a Fujian Normal University, College of Chemistry and Materials Science, Fuzhou 350007
b Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

Received:2021-12-31 Published:2022-02-11
Contact: Xitao Liu
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(21833010); National Natural Science Foundation of China(21921001); National Natural Science Foundation of China(22075285); National Natural Science Foundation of China(22125110); Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024); Natural Science Foundation of Fujian Province(2020J01112); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20010200); Youth Innovation Promotion of Chinese Academy of Sciences(2020307); National Postdoctoral Program for Innovative Talents(BX2021315)

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1. Supporting Information-A21120613.pdf(409KB)

摘要/Abstract

低维半导体材料, 尤其是近些年快速发展的二维卤化物钙钛矿材料, 因其固有的结构各向异性、独特的量子限域效应和优异的半导体特性, 在偏振光电探测等领域展现出巨大的应用潜力. 其中, 铁电极化所产生的体光伏效应为实现高灵敏的偏振光电探测提供了一种简单有效的途径. 然而二维卤化物钙钛矿铁电体的大尺寸晶体生长仍然是其在光电器件应用中所面临的一个科学难题. 本工作中, 利用溶液降温法生长出了厘米级尺寸的高质量二维卤化物钙钛矿(iPA)₂EA₂Pb₃I₁₀ (iPA为异戊胺, EA为乙胺)铁电单晶, 其最大晶体尺寸达15 mm×15 mm×3 mm. 实验结果表明二维钙钛矿结构赋予(iPA)₂EA₂Pb₃I₁₀晶体强的光学各向异性、窄的光学带隙(1.80 eV)和极其优异的光电特性(光电响应开关比达到10³). 更重要的是, 基于(iPA)₂EA₂Pb₃I₁₀铁电单晶组装的光电探测器在弱偏振光的照射下表现出极其优异的光电特性, 包括大二色比(2.3)、高响应度(193 mA•W^–1)和探测率(7.0×10¹¹ Jones), 超过大多数基于材料本征光学各向异性的光电探测器件. 这项工作不仅为高度各向异性卤化物钙钛矿铁电体的晶体生长指明了方向, 而且推动了铁电材料在高性能偏振光电探测器等方面的应用.

关键词: 铁电体, 晶体生长, 杂化钙钛矿, 二维结构, 偏振光电探测

Low-dimensional semiconductors, especially recent emerging two-dimensional halide perovskites, have shown great potential in extensive optoelectronic applications due to their large structural anisotropy, unique quantum well effect and excellent semiconductor properties. Meanwhile, the bulk photovoltaic effect with a highly sensitive angle-resolved photoresponse arising from ferroelectric materials presents a promising approach for highly polarized-sensitive photodetection. Despite the blooming development of two-dimensional halide perovskite ferroelectric materials, it is a great challenge to grow bulk single crystals of two-dimensional halide perovskite ferroelectric, which restricts their further applications in polarized-sensitive optoelectronic devices. This work mainly focuses on the developing of low-dimensional halide perovskite ferroelectric crystals with excellent photoelectric response. Two-dimensional (2D) halide perovskite ferroelectric (iPA)₂EA₂Pb₃I₁₀ (iPA=isopentammonium, EA=ethylammonium) was synthesized by a solution method through the reaction of stoichiometric lead acetate, isoamine and ethylamine in concentrated aqueous hydroiodic acid. Meanwhile, high quality centimeter-size single crystals of ferroelectric (iPA)₂EA₂Pb₃I₁₀ with the max dimensions up to 15 mm×15 mm×3 mm have been grown via temperature cooling method. On the basis of grown bulk single crystals, further investigations on the crystal structure, optical properties measurements and electrical properties characterization were carried out. The photoelectric response performance and polarization photodetection performance of photoelectric detectors based on the compound ferroelectric single crystal assembly. The result indicated that the unique two-dimensional perovskite structure endows (iPA)₂EA₂Pb₃I₁₀ with strong optical anistropy, narrow bandgap (1.80 eV) and fascinating photoelectric features (on/off ratio=10³). Strikingly, the fabricated photodetectors based on ferroelectric crystal (iPA)₂EA₂Pb₃I₁₀ manifest excellent photoelectric features, including large dichroism ratio (2.3), high responsibility (193 mA•W^–1) and photodetectivity (7.0×10¹¹ Jones), better than most photodetector based on intrinsic optical anisotropy of 2D materials. This work will be of great significance to lay a foundation for the exploring of multifunctional halide perovskites and points out the direction for bulk grown of highly anisotropic halide perovskite ferroelectric crystals and promotes their further applications in highly polarized-sensitive photodetection.

Key words: ferroelectric, crystal growth, hybrid perovskites, two-dimensional structure, polarized-sensitive photodetection

引用此文

张芬, 李霄琪, 韩世国, 邬发发, 刘希涛, 孙志华, 罗军华. 大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究^※[J]. 化学学报, 2022, 80(3): 237-243.

Fen Zhang, Xiaoqi Li, Shiguo Han, Fafa Wu, Xitao Liu, Zhihua Sun, Junhua Luo. Bulk Single Crystal Growth of a Two-Dimensional Halide Perovskite Ferroelectric for Highly Polarized-Sensitive Photodetection^※[J]. Acta Chimica Sinica, 2022, 80(3): 237-243.

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图/表 6

图1. (a) (iPA)2EA2Pb3I10晶体照片. (b) (iPA)2EA2Pb3I10模拟晶体形貌. (c) (iPA)2EA2Pb3I10的晶体结构(蓝色箭头为铁电极化方向)

Figure 1. (a) Photograph of crystals (iPA)2EA2Pb3I10. (b) Simulated crystal morphology of (iPA)2EA2Pb3I10. (c) The crystal structure of (iPA)2EA2Pb3I10 (the blue arrow shows the direction of ferroelectric polarization)

图2. (iPA)2EA2Pb3I10晶体的P-E电滞回线

Figure 2. P-E hysteresis loop of (iPA)2EA2Pb3I10晶体

图3. (iPA)2EA2Pb3I10的紫外可见吸收光谱和荧光光谱(插图为漫反射光谱)

Figure 3. The ultraviolet-visible absorption optical spectra and fluorescence spectra of (iPA)2EA2Pb3I10 (insert shows the diffuse reflection spectrum)

图4. (a) (iPA)2EA2Pb3I10在不同光功率的637 nm激光照射下的I-V曲线. (b)光伏效应

Figure 4. (a) I-V curves of (iPA)2EA2Pb3I10 under 637 nm laser irradiation with different optical power. (b) Photovoltaic effect of (iPA)2EA2Pb3I10

图5. (a)基于(iPA)2EA2Pb3I10晶体的偏振光电探测器示意图; 不同波长偏振光下光电流-角度极坐标曲线: (b) 405 nm; (c) 520 nm; (d) 637 nm(零偏压)

Figure 5. (a) Polarizaiton-sensitive photodetector based on (iPA)2EA2Pb3I10 crystals; photocurrent-angle curve under polarized light with different wavelength: (b) 405 nm; (c) 520 nm; (d) 637 nm (under zero bias)

图6. (a) 基于(iPA)2EA2Pb3I10晶体的光电探测器的响应时间, 上升和下降响应时间分别为210和429 µs; (b)光响应的重复切换循环. 不同功率弱偏振光下的响应度R (c)和探测率D* (d)

Figure 6. (a) Temporal photoresponse with the rise/decay times of 210 and 429 µs, respectively. (b) Repetitive switching cycles of photoresponse. Responsibility (c) and photodetectivity (d) of polarizaiton-sensitive photodetector based on (iPA)2EA2Pb3I10 crystals under weak polarized light with different power intensity

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大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究^※

Bulk Single Crystal Growth of a Two-Dimensional Halide Perovskite Ferroelectric for Highly Polarized-Sensitive Photodetection^※

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大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究※

Bulk Single Crystal Growth of a Two-Dimensional Halide Perovskite Ferroelectric for Highly Polarized-Sensitive Photodetection※

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大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究^※

Bulk Single Crystal Growth of a Two-Dimensional Halide Perovskite Ferroelectric for Highly Polarized-Sensitive Photodetection^※