Recent Advances in Halide Perovskite Semiconductor Single Crystals for Radiation Detection Applications

doi:10.16553/j.cnki.issn1000-985x.2025.0107

Abstract

Abstract: Halide perovskite crystals have emerged as promising candidates for nuclear radiation detection due to their high average atomic numbers， large carrier mobility lifetime products （μτ）， scalable large-area fabrication， and diverse material system. This review systematically examines the growth methods of perovskite semiconductor single crystals， as alongside recent advancements in radiation detector research. Controllable growth of large-size， high-quality single crystals is crucial for developing high-performance detectors. Through innovative crystal growth techniques combined with strategies such as cation-donor， anion-acceptor co-doping， and additive-assisted engineering， significant improvements in crystal dimensions and electrical performance acquired. Perovskite semiconductor single crystals offer unparalleled advantages in photon-counting X-ray imaging and γ-ray energy spectrum resolution that perovskite thin films cannot match. However， key challenges persist， including further improving the intrinsic quality of the crystals， addressing device stability issues caused by ion migration， and optimizing the bonding process between the crystals and pixel chips. Future research should focus on exploring the relationship between crystal structure and performance， optimizing growth process parameters， and innovating detector architectures to accelerate the industrialization of halide perovskite crystals in nuclear radiation detection applications.

Key words: halide perovskite; semiconductor single crystal; X-ray detection; γ-ray detection; crystal growth; radiation detector

CLC Number:

O782

MA Wenjun, ZHANG Guodong, SUN Xue, LIU Hongjie, LIU Jiaxin, TAO Xutang. Recent Advances in Halide Perovskite Semiconductor Single Crystals for Radiation Detection Applications[J]. Journal of Synthetic Crystals, 2025, 54(7): 1091-1099.

Figures/Tables 8

Fig.1 Solubility curves and principle diagrams of crystal growth by solution method［1-3］

Fig.2 Perovskite crystals grown by solution methods. （a）~（d） Perovskite crystals grown by solution temperature-lowering method［4-6］；（e）~（j） perovskite crystals grown by inverse temperature crystallization［1，13-15］

Fig.3 Large perovskite single crystals growth by improved technologies［16，18-20］. （a） Space confinement crystallization for single crystals with adjustable thickness；（b） temperature and speed controlled antisolvent diffusion crystallization for MAPbBr3 single crystal；（c） steady self-supply solution crystallization for MAPbI3 single crystal；（d） close-to-equilibrium crystallization for FAPbBr3 single crystal

Fig.4 Progress in the growth of CsPbBr3 single crystals by melt method［25-31］

Fig.5 Inorganic perovskite crystals grown by vertical Bridgman method［32，28，36］. （a） Mixed-halide CsPbBr3-n I nperovskite crystals；（b） mixed-halide Cs3Bi2I9-n Br n perovskite crystals；（c） mixed cation Cs1-m Rb m PbBr3 single crystals

Fig.6 Methods of restraining ion migration［37-40］. （a） Detecting novel low dimensional perovskite materials；（b） surface passivation；（c） applying reverse bias；（d） constructing the Schottky junction to form a barrier

Table 1 Energy resolution of perovskite single crystals in γ-ray detection

材料	生长方法	电极材料与结构	载流子迁移率寿命积/（cm²·V^-1）	能量分辨率
MAPbBr_2.94Cl_0.06	溶液法	Ga-Au结构，保护环电极	1.8×10^-2	6.5%@¹³⁷Cs
MAPbI₃	溶液法	Ga/Pb-Au不对称结构	0.8×10^-3	6.8%@⁵⁷Co
FACsPbBr₃	溶液法	—	2.2×10^-3	2.9%@¹³⁷Cs
FAPbI₃	溶液法	—	1.2×10^-1	35%@²⁴¹Am
MAPbBr_2.85Cl_0.15	溶液法	Cr-Cr平面对称结构	—	25%@¹³⁷Cs
CsPbCl₃	熔体法	Ga-Au不对称结构	3.2×10^-4	16%@⁵⁷Co
CsPbBr₃	熔体法	Ga-Au不对称结构	1.34×10^-3	3.8%@¹³⁷Cs
CsPbBr₃	熔体法	Au-Au平面结构	8×10^-3	1.4%@¹³⁷Cs
CsPbBr₃	熔体法	Au-Au准半球形	8×10^-3	1.6%@¹³⁷Cs
CsPbBr₃	熔体法	Au-Au像素电极	—	1.8%@¹³⁷Cs
CsPbBr₃	熔体法	Au-In不对称结构	1.7×10^-2	2%@¹³⁷Cs
CsPbBr₃	熔体法	EGaIn-In保护环电极	—	4.8%@⁵⁷Co

Fig.7 Device design of γ-ray detection［40，48-49，52］. （a） Metal contacts；（b） electron and hole transport layers；（c） device geometry

References 53

[1]	LIU Y C， ZHANG Y X， YANG Z， et al. Low-temperature-gradient crystallization for multi-inch high-quality perovskite single crystals for record performance photodetectors［J］. Materials Today， 2019， 22： 67-75.
[2]	SAIDAMINOV M I， ABDELHADY A L， MURALI B， et al. High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization［J］. Nature Communications， 2015， 6： 7586.
[3]	SHI D， ADINOLFI V， COMIN R， et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals［J］. Science， 2015， 347（6221）： 519-522.
[4]	DANG Y Y， LIU Y， SUN Y X， et al. Bulk crystal growth of hybrid perovskite material CH₃NH₃PbI₃ ［J］. CrystEngComm， 2015， 17（3）： 665-670.
[5]	DANG Y Y， ZHOU Y A， LIU X L， et al. Formation of hybrid perovskite tin iodide single crystals by top-seeded solution growth［J］. Angewandte Chemie International Edition， 2016， 55（10）： 3447-3450.
[6]	周怡安. 甲胺基铅卤钙钛矿晶体的生长与性能研究［D］. 济南：山东大学， 2018.
	ZHOU Y A. Study on the growth and properties of methylammonium lead halide perovskite single crystal materials［D］. Jinan： Shandong University， 2018 （in Chinese）.
[7]	PENG J L， XIA C Q， XU Y L， et al. Crystallization of CsPbBr₃ single crystals in water for X-ray detection［J］. Nature Communications， 2021， 12（1）： 1531.
[8]	FAN Q S， XU H J， ZHU Z K， et al. 3D lead-free double perovskite via anchoring A-site cation for ultralow dose and stable X-ray detection［J］. Advanced Functional Materials， 2025： 2505546.
[9]	ZENG X， LIU Y， CHEN Y Y， et al. Achieving effective self-driven X-ray detection sensitivity via pyroelectric-photovoltaic coupling in a layered perovskite pyroelectric［J］. ACS Energy Letters， 2024， 9（2）： 381-387.
[10]	JIANG W， DI H P， SUN H， et al. Role of DMSO concentration in the crystallization process of MAPbBr₃ perovskite single crystal films［J］. Journal of Crystal Growth， 2020， 550： 125880.
[11]	MACULAN G， SHEIKH A D， ABDELHADY A L， et al. CH₃NH₃PbCl₃ single crystals： inverse temperature crystallization and visible-blind UV-photodetector［J］. The Journal of Physical Chemistry Letters， 2015， 6（19）： 3781-3786.
[12]	ZHUMEKENOV A A， SAIDAMINOV M， HAQUE A， et al. Formamidinium lead halide perovskite crystals with unprecedented long carrier dynamics and diffusion length［J］. ACS Energy Letters， 2016， 1（1）： 32-37.
[13]	LIU Y C， YANG Z， CUI D， et al. Two-inch-sized perovskite CH₃NH₃PbX₃ （X=Cl， Br， I） crystals： growth and characterization［J］. Advanced Materials， 2015， 27（35）： 5176-5183.
[14]	LIU Y C， SUN J K， YANG Z， et al. 20-mm-large single-crystalline formamidinium-perovskite wafer for mass production of integrated photodetectors［J］. Advanced Optical Materials， 2016， 4（11）： 1829-1837.
[15]	LIU Y C， ZHANG Y X， ZHU X J， et al. Inch-sized high-quality perovskite single crystals by suppressing phase segregation for light-powered integrated circuits［J］. Science Advances， 2021， 7（7）： eabc8844.
[16]	CHEN Y X， GE Q Q， SHI Y， et al. General space-confined on-substrate fabrication of thickness-adjustable hybrid perovskite single-crystalline thin films［J］. Journal of the American Chemical Society， 2016， 138（50）： 16196-16199.
[17]	ZHANG L L， LIU Y， YE X， et al. Exploring anisotropy on oriented wafers of MAPbBr₃ crystals grown by controlled antisolvent diffusion［J］. Crystal Growth & Design， 2018， 18（11）： 6652-6660.
[18]	ZHANG L L， CUI S Y， GUO Q， et al. Anisotropic performance of high-quality MAPbBr₃ single-crystal wafers［J］. ACS Applied Materials & Interfaces， 2020， 12（46）： 51616-51627.
[19]	WANG W Z， MENG H， QI H Z， et al. Electronic-grade high-quality perovskite single crystals by a steady self-supply solution growth for high-performance X-ray detectors［J］. Advanced Materials， 2020， 32（33）： 2001540.
[20]	YIN H， LIAO M Q， SHI Y P， et al. Close-to-equilibrium crystallization for large-scale and high-quality perovskite single crystals［J］. Advanced Materials， 2025， 37（10）： 2415957.
[21]	JAO M H， LU C F， TAI P Y， et al. Precise facet engineering of perovskite single crystals by ligand-mediated strategy［J］. Crystal Growth & Design， 2017， 17（11）： 5945-5952.
[22]	WANG W J， CAI M L， WU G， et al. Facet control of the lead-free methylammonium bismuth iodide perovskite single crystals via ligand-mediated strategy［J］. Crystal Growth & Design， 2021， 21（10）： 5840-5847.
[23]	FENG Y X， PAN L， WEI H T， et al. Low defects density CsPbBr₃ single crystals grown by an additive assisted method for gamma-ray detection［J］. Journal of Materials Chemistry C， 2020， 8（33）： 11360-11368.
[24]	MA L， YAN Z G， ZHOU X Y， et al. A polymer controlled nucleation route towards the generalized growth of organic-inorganic perovskite single crystals［J］. Nature Communications， 2021， 12（1）： 2023.
[25]	STOUMPOS C C， MALLIAKAS C D， PETERS J A， et al. Crystal growth of the perovskite semiconductor CsPbBr₃： a new material for high-energy radiation detection［J］. Crystal Growth & Design， 2013， 13（7）： 2722-2727.
[26]	ZHANG P， ZHANG G D， LIU L， et al. Anisotropic optoelectronic properties of melt-grown bulk CsPbBr₃ single crystal［J］. The Journal of Physical Chemistry Letters， 2018， 9（17）： 5040-5046.
[27]	ZHANG P， SUN Q H， XU Y D， et al. Enhancing carrier transport properties of melt-grown CsPbBr₃ single crystals by eliminating inclusions［J］. Crystal Growth & Design， 2020， 20（4）： 2424-2431.
[28]	ZHANG P， HUA Y Q， XU Y D， et al. Ultrasensitive and robust 120 keV hard X-Ray imaging detector based on mixed-halide perovskite CsPbBr_3- _n I _n single crystals［J］. Advanced Materials， 2022， 34（12）： 2106562.
[29]	CHUNG D Y， LIN W W， UNAL M， et al. Growth of high-purity CsPbBr₃ crystals for enhanced gamma-Ray detection［J］. Crystal Growth and Design， 2024， 24（22）： 9590-9600.
[30]	TOUFANIAN R， SWAIN S， BECLA P， et al. Cesium lead bromide semiconductor radiation detectors： crystal growth， detector performance and polarization［J］. Journal of Materials Chemistry C， 2022， 10（35）： 12708-12714.
[31]	HUA Y Q， ZHANG G D， SUN X， et al. Suppressed ion migration for high-performance X-ray detectors based on atmosphere-controlled EFG-grown perovskite CsPbBr₃ single crystals［J］. Nature Photonics， 2024， 18（8）： 870-877.
[32]	LI X， ZHANG G D， HUA Y Q， et al. Dimensional and optoelectronic tuning of lead-free perovskite Cs₃Bi₂I_9- _n Br _n single crystals for enhanced hard X-ray detection［J］. Angewandte Chemie International Edition， 2023， 62（50）： e202315817.
[33]	ZHAO L， ZHOU Y， SHI Z F， et al. High-yield growth of FACsPbBr₃ single crystals with low defect density from mixed solvents for gamma-ray spectroscopy［J］. Nature Photonics， 2023， 17（4）： 315-323.
[34]	WANG Z W， ZENG L W， ZHU T， et al. Suppressed phase segregation for triple-junction perovskite solar cells［J］. Nature， 2023， 618（7963）： 74-79.
[35]	LIU Y C， ZHANG Y X， ZHU X J， et al. Triple-cation and mixed-halide perovskite single crystal for high-performance X-ray imaging［J］. Advanced Materials， 2021， 33（8）： 2006010.
[36]	ZHANG P， HUANG L， LI L L， et al. High-flux hard X-ray Cs_1- _m Rb _m PbBr₃ single-crystal detector with suppressed ion migration［J］. ACS Materials Letters， 2024， 6（10）： 4810-4818.
[37]	XIA M L， YUAN J H， NIU G D， et al. Unveiling the structural descriptor of A₃B₂X₉ perovskite derivatives toward X-Ray detectors with low detection limit and high stability［J］. Advanced Functional Materials， 2020， 30（24）： 1910648.
[38]	YANG B， PAN W C， WU H D， et al. Heteroepitaxial passivation of Cs₂AgBiBr₆ wafers with suppressed ionic migration for X-ray imaging［J］. Nature Communications， 2019， 10（1）： 1989.
[39]	ZHANG B-B， WANG F B， LIU X， et al. Ion migration controlled stability in α-particle response of CsPbBr_2.4Cl_0.6 detectors［J］. The Journal of Physical Chemistry C， 2021， 125（7）： 4235-4242.
[40]	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.
[41]	LIU H J， SUN X， LIU J X， et al. Lead-free perovskite Cs₂AgBiBr₆/Cs₃Bi₂Br₉ single-crystalline heterojunction X-ray detector with enhanced sensitivity and ultra-low detection limit［J］. Science China Materials， 2025， 68（2）： 561-570.
[42]	KIM Y C， KIM K H， SON D Y， et al. Printable organometallic perovskite enables large-area， low-dose X-ray imaging［J］. Nature， 2017， 550（7674）： 87-91.
[43]	XIA M L， SONG Z H， WU H D， et al. Compact and large-area perovskite films achieved via soft-pressing and multi-functional polymerizable binder for flat-panel X-ray imager［J］. Advanced Functional Materials， 2022， 32（16）： 2110729.
[44]	DONG S Y， FAN Z H， WEI W， et al. Bottom-up construction of low-dimensional perovskite thick films for high-performance X-ray detection and imaging［J］. Light， Science & Applications， 2024， 13（1）： 174.
[45]	LIU Y L， GAO C S， LI D， et al. Dynamic X-ray imaging with screen-printed perovskite CMOS array［J］. Nature Communications， 2024， 15（1）： 1588.
[46]	XU Q， WANG X， ZHANG H， et al. CsPbBr₃ single crystal X-ray detector with Schottky barrier for X-ray imaging application［J］. ACS Applied Electronic Materials， 2020， 2（4）： 879-884.
[47]	PANG J C， WU H D， LI H， et al. Reconfigurable perovskite X-ray detector for intelligent imaging［J］. Nature Communications， 2024， 15（1）： 1769.
[48]	HE Y H， PETRYK M， LIU Z F， et al. CsPbBr₃ perovskite detectors with 1.4% energy resolution for high-energy γ-rays［J］. Nature Photonics， 2020， 15（1）： 36-42.
[49]	SHEN N N， GAO T T， OUYANG X， et al. Enhancing gamma-ray spectral resolution in perovskite CsPbBr₃ detectors through dark current reduction with guard ring electrodes［J］. ACS Photonics， 2024， 11（9）： 3662-3671.
[50]	WEI H T， DESANTIS D， WEI W， et al. Dopant compensation in alloyed CH₃NH₃PbBr_3- _x Cl _x perovskite single crystals for gamma-ray spectroscopy［J］. Nature Materials， 2017， 16（8）： 826-833.
[51]	HE Y H， KE W J， ALEXANDER G C B， et al. Resolving the energy of γ-ray photons with MAPbI₃ single crystals［J］. ACS Photonics， 2018， 5（10）： 4132-4138.
[52]	GRUNDMANIS N， SARAKOVSKIS A， LUPILOV A， et al. The X- and gamma-ray detection properties of CsPbBr₃ perovskite crystals grown by the Bridgman-Stockbarger method［J］. Nuclear Instruments and Methods in Physics Research Section A： Accelerators， Spectrometers， Detectors and Associated Equipment， 2025， 1073： 170305.
[53]	LIU F Z， WU R， ZENG Y C， et al. Halide perovskites and perovskite related materials for particle radiation detection［J］. Nanoscale， 2022， 14（18）： 6743-6760.