二维钙钛矿单晶纳米片的漂浮法制备及其光电探测性能

doi:10.15541/jim20250426

无机材料学报 ›› 2026, Vol. 41 ›› Issue (6): 787-794.DOI: 10.15541/jim20250426

二维钙钛矿单晶纳米片的漂浮法制备及其光电探测性能

洪恩柳¹(), 涂欣晨¹, 李自清²(), 方晓生¹()

¹ 复旦大学智能材料与未来能源创新学院, 聚合物分子工程全国重点实验室, 上海 200433
² 复旦大学光电研究院, 未来信息创新学院, 光伏科学与技术全国重点实验室, 上海市智能光电与感知前沿科学研究基地, 上海 200433

收稿日期:2025-10-28 修回日期:2025-12-23 出版日期:2026-06-20 网络出版日期:2026-01-22
通讯作者: 李自清, 副教授. E-mail: lzq@fudan.edu.cn;
方晓生, 教授. E-mail: xshfang@fudan.edu.cn
作者简介:洪恩柳(2000-), 男, 博士研究生. E-mail: 21110300005@m.fudan.edu.cn
基金资助:
国家自然科学基金(524B2017);国家自然科学基金(62204047)

Two-dimensional Perovskite Single Crystal Nanosheets: Floating Growth and Optoelectronic Performance

HONG Enliu¹(), TU Xinchen¹, LI Ziqing²(), FANG Xiaosheng¹()

¹ State Key Laboratory of Molecular Engineering of Polymers, College of Smart Materials and Future Energy, Fudan University, Shanghai 200433, China
² Shanghai Frontiers Science Research Base of Intelligent Optoelectronics and Perception, State Key Laboratory of Photovoltaic Science and Technology, College of Future Information, Institute of Optoelectronics, Fudan University, Shanghai 200433, China

Received:2025-10-28 Revised:2025-12-23 Published:2026-06-20 Online:2026-01-22
Contact: LI Ziqing, associate professor. E-mail: lzq@fudan.edu.cn;
FANG Xiaosheng, professor. E-mail: xshfang@fudan.edu.cn
About author:HONG Enliu (2000-), male, PhD candidate. E-mail: 21110300005@m.fudan.edu.cn
Supported by:
National Natural Science Foundation of China(524B2017);National Natural Science Foundation of China(62204047)

摘要/Abstract

摘要：

Ruddlesden-Popper(RP)型二维层状钙钛矿因其本征量子阱结构、可调谐物理化学性质和良好光电性能, 在光电子领域展现出突出的应用潜力。然而, 如何快速且高质量地制备二维钙钛矿单晶薄片仍面临挑战。本工作开发了一种快速简便的液-气界面漂浮生长方法, 成功制备了一系列不同组分的高质量二维RP型钙钛矿单晶纳米片。该方法基于表面张力驱动晶体在液-气界面进行各向异性二维生长, 实现了对单晶纳米片的可控合成。通过调节前驱体溶液中长链铵盐、有机阳离子和卤素的种类与比例, 成功合成出12种组分不同、形状各异(条状、片状、板状等)的RP型钙钛矿单晶纳米片, 并验证了该策略的普适性。不同手段表征结果显示, 所制备的纳米片具有优异的结晶质量、原子级平整的表面和均匀的元素分布。这些结构和成分特性是获得稳定、一致光电性能的重要基础。进一步地, 基于(BA)₂PbBr₄单晶纳米片构筑的光电探测器展现出良好的紫外光探测性能, 其在370 nm紫外光照和3 V偏压下响应度达到19.7 mA/W, 探测率达到1.14×10¹¹ Jones, 充分显示出其成为紫外光电探测器有力候选材料的潜力。本研究为构建微型化钙钛矿光电子器件提供了良好的材料基础。

关键词: 二维钙钛矿, 单晶纳米片, 快速制备, 光电探测器

Abstract:

Ruddlesden-Popper (RP) two-dimensional layered perovskites have garnered extensive attention in the fields of optoelectronics due to their intrinsic natural quantum-well structures, tunable physicochemical properties, and remarkable optoelectronic performance. However, the rapid and high-quality preparation of two-dimensional single-crystalline perovskite flakes remains a significant challenge. In this work, a rapid and facile floating method was developed for growing a series of high-quality two-dimensional RP-type perovskite single-crystalline nanosheets with different compositions. The method involves the controlled growth of single-crystalline nanosheets at the liquid-air interface, where surface tension plays a critical role in driving the anisotropic two-dimensional growth of the crystals. By adjusting the types and proportions of long-chain ammonium salts, organic cations and halogens in the precursor solution, 12 kinds of RP-type perovskite single-crystalline nanosheets with different components and shapes (strip-shaped, flake-shaped, plate-shaped, etc.) are successfully prepared, demonstrating the universality of this strategy. The resultant nanosheets exhibit excellent crystalline quality, atomically flat surfaces, and uniform elemental distributions, as confirmed by different characterizations. These structural and compositional properties are essential for achieving consistent and stable optoelectronic performance. Moreover, the photodetectors fabricated based on (BA)₂PbBr₄ nanosheets exhibit ultraviolet detection capabilities. Under the conditions of 370 nm ultraviolet illumination and 3 V bias voltage, it achieves a responsivity of 19.7 mA/W and a specific detectivity of 1.14×10¹¹ Jones, demonstrating its strong potential as a promising candidate for ultraviolet photodetectors. This study provides a solid foundation for the miniaturization of perovskite optoelectronic devices.

Key words: two-dimensional perovskite, single-crystalline nanosheet, rapid preparation, photodetector

中图分类号:

TQ174

洪恩柳, 涂欣晨, 李自清, 方晓生. 二维钙钛矿单晶纳米片的漂浮法制备及其光电探测性能[J]. 无机材料学报, 2026, 41(6): 787-794.

HONG Enliu, TU Xinchen, LI Ziqing, FANG Xiaosheng. Two-dimensional Perovskite Single Crystal Nanosheets: Floating Growth and Optoelectronic Performance[J]. Journal of Inorganic Materials, 2026, 41(6): 787-794.

图/表 8

图1 采用液-气界面漂浮生长法制备单晶纳米片的实验过程示意图

Fig. 1 Experimental procedures of preparing single crystal nanosheets by liquid-air interface floating growth method

图2 利用微纳加工工艺和干法转移技术构筑MSM结构器件的全流程示意图

Fig. 2 Flowchart of constructing MSM-structure photodetectors using micro-nano processing technology and dry transfer technique

图3 液-气界面漂浮生长法制备的一系列组分可调的二维钙钛矿单晶纳米片的光学显微图像

Fig. 3 Optical microscopic images of various compositions of two-dimensional perovskite nanosheets grown by the liquid-air interfacial floating method Scale bar: 30 μm

图4 (BA)2PbBr4纳米片的物质组成与光学性质分析

Fig. 4 Analysis of the composition and optical properties of (BA)2PbBr4 nanosheets (a, b) Optical microscope magnification images in (a) bright field and (b) dark field (scale bar: 30 μm); (c) Thickness profile; (d) XRD pattern; (e) Photoluminescence spectrum; (f) UV-visible absorption spectrum

图5 (BA)2PbBr4纳米片的(a)晶体结构、(b) SEM照片(上)及对应的元素分布图(下)(比例尺: 30 μm)、(c)高分辨率TEM照片和(d)选区电子衍射图案

Fig. 5 (a) Crystal structure depiction, (b) SEM image (upper) and corresponding elemental distribution mappings (lower) (scale bar: 30 μm), (c) high-resolution TEM image and (d) selected area electron diffraction pattern of (BA)2PbBr4 nanosheets

图6 基于(BA)2PbBr4纳米片的光电探测性能分析

Fig. 6 Analysis of the optoelectronic properties of (BA)2PbBr4 nanosheets (a) Structural diagram of the device and the corresponding optical microscope image; (b) I-V curves of the device under light of different wavelengths; (c) I-t curves of the device at the optimal response wavelength with different bias voltages; (d) Responsivity curve of the device as a function of wavelength at 3 V bias voltage. Colorful figures are available on website

图S1 漂浮法多批次的工艺稳定性验证

Fig. S1 Verification of process reliability of multiple batches by floating method Taking the (BA)2PbBr4 component as an example; Scale bar: 100 μm

表S1 本工作器件与其他同类器件的性能对比

Table S1 Performance comparison of this working device with other similar devices

Material	Type	Testing condition	Responsivity/ (mA·W^-1)	Specific detectivity/ Jones	I_on/off	Ref.
MoS₂/CsPbBr₃	Film	10 V, 385 nm	0.4	3.5×10⁹	-	[S1]
(OA)₂FA_n_-1Pb_nBr₃_n₊₁	Film	3 V, 442 nm	3.2×10⁴	-	-	[S2]
(BA)₂Pb(Cl_0.1Br_0.9)₄	Single crystal	10 V, 340 nm	3.19	3.87×10¹¹	~10	[S3]
MAPbI₃/(BA)₂(MA)₃Pb₄I₁₃	Film	3 V, 405 nm	9.4	3.1×10⁸	8.91×10³	[S4]
(BA)₂(MA)₂Pb₃I₁₀	Film	30 V, -	12.78	-	1.6×10³	[S5]
MAPbI₃	Film	10 V, 650 nm	1×10²	1.02×10¹²	3×10²	[S6]
MoS₂/CsPbBr₃	Single crystal	10 V, 442 nm	4.4×10³	2.5×10¹⁰	1.67×10⁴	[S7]
(PEA)₂(MA)Pb₂I₇	Single crystal	9.5 V, 600 nm	3.87	2.92×10¹⁰	~10³	[S8]
(BA)₂(MA)₃Pb₄I₁₃	Single crystal	3 V, 532 nm	71.9	1.1×10¹²	~10⁵	[S9]
Si/CsPbBr₃	Film	−1 V, 532 nm	24.85	1.01×10¹¹	~9×10²	[S10]
(BA)₂PbBr₄	Single crystal	3 V, 370 nm	19.7	1.14×10¹¹	2.3×10²	This work

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二维钙钛矿单晶纳米片的漂浮法制备及其光电探测性能

Two-dimensional Perovskite Single Crystal Nanosheets: Floating Growth and Optoelectronic Performance

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