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

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

复旦大学 1.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; 2.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
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, 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. State Key Laboratory of Photovoltaic Science and Technology, Shanghai Frontiers Science Research Base of Intelligent Optoelectronics and Perception, College of Future Information, Institute of Optoelectronics, Fudan University, Shanghai 200433, China

Received:2025-10-28 Revised:2025-12-23
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, 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-气界面处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,验证出该策略的普适性。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, we developed a rapid and facile floating method for growing a serious 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 perovskites, single-crystalline nanosheets, rapid preparation, photodetectors

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, DOI: 10.15541/jim20250426.

HONG Enliu, TU Xinchen, LI Ziqing, FANG Xiaosheng. Two-dimensional Perovskite Single Crystal Nanosheets: Floating Growth and Optoelectronic Performance[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250426.

参考文献

[1] LI L, YAO J, ZHU J,et al. Colloid driven low supersaturation crystallization for atomically thin Bismuth halide perovskite. Nature Communications, 2023, 14: 3764.
[2] LIN K B, YAN C Z, SABATINI R P,et al. Dual-phase regulation for high-efficiency perovskite light-emitting diodes. Advanced Functional Materials, 2022, 32(24): 2200350.
[3] HONG E L, LI Z Q, ZHANG X Y,et al. Deterministic fabrication and quantum-well modulation of phase-pure 2D perovskite heterostructures for encrypted light communication. Advanced Materials, 2024, 36(29): 202400365.
[4] LIANG C, SALIM K M M, LI P W,et al. Controlling the film structure by regulating 2D Ruddlesden-Popper perovskite formation enthalpy for efficient and stable tri-cation perovskite solar cells. Journal of Materials Chemistry A, 2020, 8(12): 5874.
[5] LI J W, YU Q, HE Y H,et al. Cs₂PbI₂Cl₂, all-inorganic two-dimensional Ruddlesden-Popper mixed halide perovskite with optoelectronic response. Journal of the American Chemical Society, 2018, 140(35): 11085.
[6] CAI K, JIN Z W.Photodetector based on two-dimensional perovskite(PEA)₂PbI₄.Journal of Inorganic Materials, 2023, 38(9): 1069.
[7] HU Y, LI Z Q, FANG X S.Solution-prepared AgBi₂I₇ thin films and their photodetecting properties.Journal of Inorganic Materials, 2023, 38(9): 1055.
[8] TIAN X X, ZHANG Y Z, ZHENG R K,et al. Two-dimensional organic-inorganic hybrid Ruddlesden-Popper perovskite materials: preparation, enhanced stability, and applications in photodetection. Sustainable Energy & Fuels, 2020, 4(5): 2087.
[9] LIANG J, ZHANG Z, XUE Q,et al. A finely regulated quantum well structure in quasi-2D Ruddlesden-Popper perovskite solar cells with efficiency exceeding 20%. Energy & Environmental Science, 2022, 15(1): 296.
[10] YAN L, MA J, LI P,et al. Charge-carrier transport in quasi-2D Ruddlesden-Popper perovskite solar cells. Advanced Materials, 2022, 34(7): 2106822.
[11] CHEN K, ZHANG Q P, LIANG Y,et al. Quasi-two dimensional Ruddlesden-Popper halide perovskites for laser applications. Frontiers of Physics, 2024, 19(2): 23502.
[12] GAO X, ZHANG X, YIN W,et al. Ruddlesden-Popper perovskites: synthesis and optical properties for optoelectronic applications. Advanced Science, 2019, 6(22): 1900941.
[13] WU L F, CAO Q W, LI H Y,et al. A 2D perovskite photodetector for NIR range and weak-Light imaging applications via thermal regulation. Advanced Functional Materials, 2025, 35(48): 2505180.
[14] LI Z J, GU H, LIU X L,et al. Uniform phase permutation of efficient Ruddlesden-Popper perovskite solar cells via binary spacers and single srystal coordination. Advanced Materials, 2024, 36(48): 2410408.
[15] TEALE S, DEGANI M, CHEN B,et al. Molecular cation and low-dimensional perovskite surface passivation in perovskite solar cells. Nature Energy, 2024, 9(10): 779.
[16] LI S H, WU Y, ZHONG J,et al. Toward efficient and stable Ruddlesden-Popper perovskite: unraveling the selection rule of binary spacer cations. Advanced Functional Materials, 2025, 35(19): 2420854.
[17] WAN J X, YUAN H, XIAO Z X,et al. 2D Ruddlesden-Popper polycrystalline perovskite pyro-phototronic photodetectors. Small, 2023, 19(38): 202207185.
[18] WANG R, DONG X Y, LING Q,et al. Nucleation and crystallization in 2D-Ruddlesden-Popper perovskites using formamidinium-based organic semiconductor spacers for efficient solar cells. Angewandte Chemie-International Edition, 2023, 62(50): 202314690.
[19] LI J, HUANG J, MA F,et al. Unveiling microscopic carrier loss mechanisms in 12% efficient Cu₂ZnSnSe₄ solar cells. Nature Energy, 2022, 7(8): 754.
[20] WEI L J, LIU Y, MA Y,et al. Centimeter-level double perovskite single crystals with strong interlaminar hydrogen bonds for high-performance X-ray detection. Journal of Materials Chemistry C, 2025, 13(4): 1675.
[21] CAO F, LIU Y, ZHANG X L,et al. Lead-free single crystal metal halide perovskite detectors. Materials Science & Engineering R-Reports, 2025, 164(10): 100991.
[22] DI J Y, CHANG J J, LIU S Z.Recent progress of two-dimensional lead halide perovskite single crystals: crystal growth, physical properties, and device applications.Ecological Materials, 2020, 2(3): 12036.
[23] ZHANG Y R, HAN E Q, ZHANG B W,et al. 2D and quasi-2D hybrid halide perovskite single crystals: from fundamentals to functionalized photodetectors. Nano Energy, 2024, 132(17): 110368.
[24] LEE Y H, PARK J Y, NIU P R,et al. One-step solution patterning for two-dimensional perovskite nanoplate arrays. ACS Nano, 2023, 17(14): 13840.
[25] YAN J K, LI H J, ALDAMASY M H,et al. Advances in the synthesis of halide perovskite single crystals for optoelectronic applications. Chemistry of Materials, 2023, 35(7): 2683.
[26] GAO W, WEI Q, WANG T,et al. Two-photon lasing from two-dimensional homologous Ruddlesden-Popper perovskite with giant nonlinear absorption and natural microcavities. American Chemical Society Nano, 2022, 16(8): 13082.
[27] LUO J, LIU B, YANG J L,et al. Regulation of luminescence properties of the ultrathin two-dimensional halide perovskite Cs₂PbI_xCl₄-_x(x=0,1,2,3,4)with Ruddlesden-Popper structure. Physical Review Applied, 2023, 20(2): 024047.
[28] DING Y F, ZHAO Q Q, YU Z L,et al. Strong thickness-dependent quantum confinement in all-inorganic perovskite Cs₂PbI₄ with a Ruddlesden-Popper structure. Journal of Materials Chemistry C, 2019, 7(24): 7433.
[29] WANG Z, LIU X D, REN H,et al. Insight into the enhanced charge transport in quasi-2D perovskite via fluorination of ammonium cations for photovoltaic applications. ACS Applied Materials & Interfaces, 2022, 14(6): 7917.
[30] CAO J G, DUAN C H, LI Z H,et al. Theoretical selection of 2D perovskite for constructing efficient heterojunction solar cells. ACS Materials Letters, 2023, 5(4): 970.
[31] DU J Y, ZHANG M Q, TIAN J J.Controlled crystal orientation of two-dimensional Ruddlesden-Popper halide perovskite films for solar cells.International Journal of Minerals Metallurgy and Materials, 2022, 29(1): 49.
[32] YANG B, GUO P, HAO D D,et al. Self-powered photodetectors based on CsPbBr quantum dots/organic semiconductors/SnO heterojunction for weak light detection. Science China-Materials, 2023, 66(2): 716.
[33] GUAN X Y, CHEN Y, MA Y H,et al. New paradigms of 2D layered material self-driven photodetectors. Nanoscale, 2024, 16(45): 20811.
[34] HAN S G, LIU X T, LIU Y,et al. High-temperature antiferroelectric of lead iodide hybrid perovskites. Journal of the American Chemical Society, 2019, 141(32): 12470.
[35] LIU X T, WANG S S, LONG P Q,et al. Polarization-driven self-powered photodetection in a single-phase biaxial hybrid perovskite ferroelectric. Angewandte Chemie-International Edition, 2019, 58(41): 14504.