Growth， Electrical and Optical Properties of All Inorganic Tin Perovskite CsSnBr3 Crystals

doi:10.16553/j.cnki.issn1000-985x.2025.0049

Abstract

Abstract: ?12 mm×35 mm CsSnBr₃ crystals doped with 1% Sn（Ⅳ） and undoped crystals were successfully prepared by Bridgman method， and the solution grown CsSnBr₃ crystal was used as the control. The phase， electrical and optical properties of all crystal samples were studied. CsSnBr₃ crystals belong to the cubic system with space group Pm3m. The band gap of undoped CsSnBr₃ is 1.79 eV. The carrier concentration and mobility of CsSnBr₃ crystals can be significantly improved by doping 1%Sn（Ⅳ）， with the carrier concentration increasing from 6.1×10¹⁶ cm^-3 to 1.0×10¹⁸ cm^-3， and the mobility from 5.7 cm2·V^-1·s^-1 to 36 cm2·V^-1·s^-1. The mobility reaches the equivalent level of the solution method crystal. CsSnBr₃ has a photoluminescence （PL） emission peak at about 680 nm. Sn（Ⅳ） can also inhibit the non-radiative recombination process of carriers， reducing the non-radiative recombination probability and improving the PL intensity， while the PL lifetime remains unaffected. Calculation results indicate that the minority carrier diffusion length of the CsSnBr₃ crystal with 1% Sn（Ⅳ） is nearly three times as long as that of the undoped crystal. CsSnBr₃ crystals exhibit tolerance to stoichiometric ratio deviations. Within the deviation range of ±1%， the crystal performance is not significantly affected， and the excess components are separated from the crystal surface in specific forms. It is concluded that a small amount of Sn（Ⅳ） can actually increase the conductivity of tin perovskite materials and may protect grain boundaries， weakening the scattering and the non-radiative recombination of carriers at grain boundaries. The discovery of stoichiometric tolerance provides flexibility in raw material ratio for the preparation of tin perovskite materials， deepens the understanding of the growth mechanism of CsSnBr₃ crystal， and reduces the technical difficulty.

Key words: CsSnBr₃; tin perovskite; optoelectronic material; semiconductor crystal; Bridgman method; carrier concentration; mobility

CLC Number:

XIAO Daizhen, GAO Rong, CHEN Yi, MI Qixi. Growth， Electrical and Optical Properties of All Inorganic Tin Perovskite CsSnBr₃ Crystals[J]. Journal of Synthetic Crystals, 2025, 54(7): 1245-1255.

Figures/Tables 16

Fig.1 Photos of the CsSnBr3 crystal

Fig.2 PXRD patterns of CsSnBr3 prepared by different methods

Fig.3 Hall effect curves of CsSnBr3 samples

Fig.4 Statistical data on electrical properties of a large number of CsSnBr3 samples

Fig.5 Schematic diagram of Sn （Ⅳ） protection

Fig.6 Schematic diagram of Sn（Ⅳ） from different directions

Fig.7 UV-Vis-NIR diffuse reflection spectrum and analysis of CsSnBr3

Fig.8 PL spectra of CsSnBr3 prepared at different conditions

Table 1 Electrical transport properties of different CsSnBr3 samples

Sample	Mobility/（cm²·V^-1·s^-1）	Life time/ns	Diffusion length/nm
EG-CSB	40	1.12	346
VB-CSB∶Sn（Ⅳ）	36	0.65	252
VB-CSB	5.7	0.57	91

Fig.9 Morphology characterization and component analysis of impurity crystals

Table 2 Element composition and content of impurity crystals

Element	Atomic ratio	Approximation
Br	66.89	6
Cs	22.26	2
Sn	10.84	1

Fig.10 Structural analysis of impurity crystals

Table 3 Accuracy test of gravimetric analysis of Cs+

Number	1	2	3	4	5	6	Average
Relative error/%	0.53	0.05	0.07	0.21	0.24	0.18	0.21

Table 4 Molar percentage of Cs+ in all positive ions in CsSnBr3 sample obtained by gravimetric method

Number	VB-CSB/%	EG-CSB/%
1	50.11	50.48
2	50.48	50.36
3	50.40	50.55
4	50.33	50.27
5	50.13	50.41
6	50.56	50.45
Average	50.29	50.41
Standard deviation	0.19	0.10

Fig.11 Electrical properties of of crystals obtained at different Cs-Sn ratios

Fig.12 XRD patterns of surface precipitates of CsBr and SnBr2 under excessive conditions

References 24

[1]	DOU L T， YANG Y M， YOU J B， et al. Solution-processed hybrid perovskite photodetectors with high detectivity［J］. Nature Communications， 2014， 5： 5404.
[2]	ZHU H M， FU Y P， MENG F， et al. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors［J］. Nature Materials， 2015， 14（6）： 636-642.
[3]	CORREA-BAENA J P， SALIBA M， BUONASSISI T， et al. Promises and challenges of perovskite solar cells［J］. Science， 2017， 358（6364）： 739-744.
[4]	RONG Y G， HU Y， MEI A Y， et al. Challenges for commercializing perovskite solar cells［J］. Science， 2018， 361（6408）： eaat8235.
[5]	LIN K B， XING J， QUAN L N， et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 percent［J］. Nature， 2018， 562（7726）： 245-248.
[6]	QUAN L N， RAND B P， FRIEND R H， et al. Perovskites for next-generation optical sources［J］. Chemical Reviews， 2019， 119（12）： 7444-7477.
[7]	FENG A B， JIANG X M， ZHANG X Y， et al. Shape control of metal halide perovskite single crystals： from bulk to nanoscale［J］. Chemistry of Materials， 2020， 32（18）： 7602-7617.
[8]	CAO J P， TAI Q D， YOU P， et al. Enhanced performance of tin-based perovskite solar cells induced by an ammonium hypophosphite additive［J］. Journal of Materials Chemistry A， 2019， 7（46）： 26580-26585.
[9]	KONSTANTAKOU M， STERGIOPOULOS T. A critical review on tin halide perovskite solar cells［J］. Journal of Materials Chemistry A， 2017， 5（23）： 11518-11549.
[10]	ABDELMAGEED G， JEWELL L， HELLIER K， et al. Mechanisms for light induced degradation in MAPbI₃ perovskite thin films and solar cells［J］. Applied Physics Letters， 2016， 109（23）： 233905.
[11]	DEEPTHI JAYAN K， SEBASTIAN V. Comprehensive device modelling and performance analysis of MASnI₃ based perovskite solar cells with diverse ETM， HTM and back metal contacts［J］. Solar Energy， 2021， 217： 40-48.
[12]	WU Y， ZHOU H W， YIN J， et al. Growth， structural， optical and electronic transport properties of tetragonal CH₃NH₃SnBr₃ perovskite single crystals［J］. Dalton Transactions， 2022， 51（12）： 4623-4626.
[13]	SUN L， LI W， ZHU W， et al. Single-crystal perovskite detectors： development and perspectives［J］. Journal of Materials Chemistry C， 2020， 8（34）： 11664-11674.
[14]	YAO H H， ZHOU F G， LI Z Z， et al. Strategies for improving the stability of tin-based perovskite （ASnX₃） solar cells［J］. Advanced Science， 2020， 7（10）： 1903540.
[15]	LI B H， LONG R Y， XIA Y， et al. All-inorganic perovskite CsSnBr₃ as a thermally stable， free-carrier semiconductor［J］. Angewandte Chemie International Edition， 2018， 57（40）： 13154-13158.
[16]	HEO J M， CHO H C， LEE S C， et al. Bright lead-free inorganic CsSnBr₃ perovskite light-emitting diodes［J］. ACS Energy Letters， 2022， 7（8）： 2807-2815.
[17]	ZHANG Y Y， YAO Q S， QIAN J C， et al. Thermoelectric properties of all-inorganic perovskite CsSnBr₃： a combined experimental and theoretical study［J］. Chemical Physics Letters， 2020， 754： 137637.
[18]	WU Z， ZHUANG J， LIN Y， et al. One- and two-photon excited photoluminescence and suppression of thermal quenching of CsSnBr₃ microsquare and micropyramid［J］. ACS Nano， 2021， 15（12）： 19613-19620.
[19]	ZOU Y Q， ZHOU Y X， XI Y Y， et al. Surface field effect probed by THz emission in lead-free perovskite CsSnBr₃ films and CsSnBr₃/SiO₂/Si heterojunction［J］. Surfaces and Interfaces， 2024， 46： 104046.
[20]	LIU Z H， JUNG， H B， SOTOME M， et al. Substrate temperature dependence of vapor phase deposition of all-inorganic lead-free CsSnBr₃ perovskite thin films［J］. Japanese Journal of Applied Physics， 2024， 63： 02SP23.
[21]	介万奇. 晶体生长原理与技术［M］. 2版. 北京：科学出版社， 2019： 333.
	JIE W Q. Principles and techniques of crystal growth［M］. 2nd Edition. Beijing： Science Press， 2019： 333 （in Chinese）.
[22]	CHUNG I， SONG J H， IM J， et al. CsSnI₃： semiconductor or metal？ High electrical conductivity and strong near-infrared photoluminescence from a single material. high hole mobility and phase-transitions［J］. Journal of the American Chemical Society， 2012， 134（20）： 8579-8587.
[23]	HE Y H， MATEI L， JUNG H J， et al. High spectral resolution of gamma-rays at room temperature by perovskite CsPbBr₃ single crystals［J］. Nature Communications， 2018， 9（1）： 1609.
[24]	PIERRE V. Springer Materials： Br-Cs-Sn vertical section of ternary phase diagram［DB/OL］. ［2025-03-12］. .

Growth， Electrical and Optical Properties of All Inorganic Tin Perovskite CsSnBr₃ Crystals

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