低温生长高质量MAPbI3钙钛矿单晶及其光电探测性能

doi:10.16553/j.cnki.issn1000-985x.2025.0215

摘要/Abstract

摘要： 钙钛矿单晶凭借低缺陷密度、优异光伏性能、高湿稳定性及强抗离子迁移能力，在光电子器件领域彰显出巨大应用潜力。然而，钙钛矿单晶在光伏、发光二极管等核心应用场景中的效率仍落后于多晶薄膜，其发展进程受材料特性、生长工艺等多重因素制约。针对这一瓶颈，本文开发了一种以2-甲氧基乙醇（2ME）为溶剂的低温晶体生长策略。该策略能有效缓解钙钛矿单晶生长过程中的温度波动问题，显著减少缺陷态形成，同时，2ME较高的饱和蒸汽压可降低溶剂在单晶表面的残留，进一步优化晶体质量。与传统GBL溶剂相比，基于2ME溶剂制备的MAPbI₃单晶性能实现全面提升：光致发光（PL）强度提高2.7倍，载流子寿命延长1.5倍，缺陷态密度降低16%，离子迁移活化能提升19%。将2ME溶剂制备的MAPbI₃单晶应用于自驱动光电探测器，在0 V偏压下，器件响应度R达到0.55 A·W^-1，比探测率D^*高达0.80×10¹³ Jones，分别为GBL溶剂制备器件的1.72倍和1.59倍，且响应时间提升49%以上。本研究提出的低温晶体生长策略为钙钛矿单晶的性能优化提供了新思路，有望加速其在高端成像、光通信、量子探测等先进光电子器件领域的产业化应用。

关键词: 钙钛矿单晶; 低温生长; 溶剂残留; 离子迁移; 自驱动; 光电探测器

Abstract: Perovskite single crystals are regarded as highly promising materials for optoelectronic devices， owing to their low defect density， outstanding photovoltaic characteristics， high resistance to moisture， and effective suppression of ion migration. However， the efficiency of perovskite single crystals-based devices in applications such as photovoltaics and light-emitting diodes has remained inferior to that of polycrystalline thin-film counterparts， primarily due to limitations in material processing and crystal growth quality. To address these challenges， a low-temperature crystal growth strategy was developed using 2-methoxyethanol （2ME） as the solvent. This approach was designed to minimize thermal fluctuations during the crystallization process， thereby suppressing the formation of defect states. In addition， owing to the low boiling point of 2ME， solvent retention on the perovskite surface was significantly reduced. When compared with MAPbI₃ single crystals prepared using conventional gamma-butyrolactone （GBL） solvent， the 2ME-grown crystals exhibited a 2.7-fold enhancement in photoluminescence （PL） intensity and a 1.5-fold extension of carrier lifetime. A reduction in defect state density by 16% was achieved， along with a 19% increase in the activation energy for ion migration. Furthermore， a self-powered photodetector fabricated from 2ME-derived MAPbI₃ single crystals demonstrated a responsivity of 0.55 A·W^-1 and a specific detectivity of 0.80×10¹³ Jones at 0 V bias. These values exceed those of devices based on GBL-grown crystals by factors of 1.72 and 1.59， respectively. The response speed was also markedly improved， with rise and fall times of 2.1 ms and 3.2 ms—representing a 54% and 49% enhancement over the GBL-based device （~4.6 ms rise， ~6.3 ms fall）. This study establishes a reliable low-temperature pathway for the production of high-quality， low-defect MAPbI₃ single crystals via 2ME. The findings indicate that this method effectively enhances the optoelectronic performance and stability of perovskite single crystals， facilitating their application in advanced devices such as high-sensitivity imaging systems， optical communication modules， and quantum detection platforms.

Key words: perovskite single crystal; low-temperature growth; solvent residue; ion migration; self-powered; photodetector

中图分类号:

O782

刘东, 李玉鑫, 李大林, 路斌, 郭政, 陈谦, 张晓静, 王雅雪, 陈丹平, 郭可欣, 何涛. 低温生长高质量MAPbI₃钙钛矿单晶及其光电探测性能[J]. 人工晶体学报, 2026, 55(3): 349-358.

LIU Dong, LI Yuxin, LI Dalin, LU Bin, GUO Zheng, CHEN Qian, ZHANG Xiaojing, WANG Yaxue, CHEN Danping, GUO Kexin, HE Tao. Low-Temperature Grown High-Quality MAPbI₃ Perovskite Single Crystals and Its Photodetection Performance[J]. Journal of Synthetic Crystals, 2026, 55(3): 349-358.

图/表 6

图1 MAPbI3钙钛矿单晶的可控生长。（a）GBL与2ME溶剂生长MAPbI3钙钛矿单晶的示意图。（b）GBL和2ME在ITO生长的MAPbI3钙钛矿单晶的光学图片；GBL和2ME生长的MAPbI3钙钛矿单晶的XRD图谱（c）和紫外吸收光谱（d）；（e）MAPbI3钙钛矿单晶的UPS表征；（f）两种溶剂生长的MAPbI3钙钛矿单晶的AFM照片

Fig.1 Controllable growth of MAPbI3 perovskite single crystals. （a） Schematic illustration of MAPbI3 perovskite single crystal growth using GBL and 2ME solvents；（b） optical microscopy image of MAPbI3 perovskite single crystals grown on ITO substrates from GBL and 2ME； XRD patterns （c） and ultraviolet-visible absorption （d） of MAPbI3 perovskite single crystals grown from GBL and 2ME， respectively；（e） UPS characterization of MAPbI3 perovskite single crystals；（f） AFM image of MAPbI3 perovskite single crystals grown from the two solvents

图2 MAPbI3钙钛矿单晶的结构表征。（a） GBL与2ME溶剂的分子结构与饱和蒸汽压（20 ℃）；GBL（b）和2ME（c）溶剂生长的MAPbI3钙钛矿单晶的EDS mapping图；GBL生长的MAPbI3钙钛矿单晶XPS（d）和局部放大图（e）；（f）2ME生长的MAPbI3钙钛矿单晶XPS

Fig.2 Structural characterization of MAPbI3 perovskite single crystals. （a） Structures and saturated vapor pressure （20 ℃） of GBL and 2ME solvents； EDS mapping images of MAPbI3 perovskite single crystals grown from GBL （b） and 2ME （c） solvents， respectively； XPS （d） and corresponding magnified view （e） of MAPbI3 perovskite single crystals grown from GBL；（f） XPS of MAPbI3 perovskite single crystals grown from 2ME

图3 基于GBL和2ME生长的MAPbI3钙钛矿单晶的晶体质量表征。GBL和2ME溶剂生长的MAPbI3钙钛矿单晶的PL（a）和TRPL（b）图谱；（c）两种溶剂生长的MAPbI3钙钛矿单晶的SCLC测试；（d）GBL和2ME溶剂生长的MAPbI3钙钛矿单晶在暗态下的电流-电压特性； GBL（e）和2ME（f）溶剂生长的MAPbI3钙钛矿单晶的XRD摇摆曲线

Fig.3 Characterization of crystal quality of MAPbI3 perovskite single crystals grown from GBL and 2ME. PL （a） and TRPL （b） spectra of MAPbI3 perovskite single crystals grown from GBL and 2ME solvents， respectively；（c） SCLC measurements for evaluating the trap density of MAPbI3 perovskite single crystals grown from the two solvents；（d） temperature-dependent conductivity measurements of MAPbI3 perovskite single crystals grown from GBL and 2ME； XRD rocking curves of MAPbI3 perovskite single crystals grown from GBL （e） and 2ME （f） solvents

图4 基于GBL和2ME生长的MAPbI3钙钛矿单晶的光电性能。（a）ITO/MAPbI3/Au自驱动光电探测器的能带结构示意图；（b）ITO/MAPbI3/Au光电探测器在暗态与445 nm激光照射下的I-V曲线；（c）在445 nm激光（0.01 mW·cm-2）照射下，GBL与2ME生长的MAPbI3单晶的光电流响应对比；（d）2ME生长的MAPbI3单晶在445 nm激光、不同光强下的I-t曲线；（e）两种溶剂生长的MAPbI3单晶光电流随光功率密度的变化关系；（f）两种溶剂所制备MAPbI3单晶光电探测器的响应度（R）与比探测率（D*）

Fig.4 Optoelectronic properties of MAPbI3 perovskite single crystals grown from GBL and 2ME. （a） Energy band diagram of the self-powered ITO/MAPbI3/Au photodetector；（b） dark and photoinduced （445 nm） I-V curves of the self-powered ITO/MAPbI3/Au photodetectors；（c） I-t photoresponse of GBL- and 2ME-grown crystals at 445 nm （0.01 mW·cm-2）；（d） I-t curves of the 2ME-grown crystal under 445 nm light at varying intensities；（e） relationship between photocurrent and optical power density of MAPbI3 single crystals grown in two solvents；（f） responsivity （R） and detectivity （D*） of the photodetectors based on MAPbI3 single crystals prepared using the two solvents

表1 与已报道的MAPI3钙钛矿光电探测器的参数对比

Table 1 Comparison of parameters with reported MAPI3 perovskite photodetectors

Device structure	Bias/V	R/（A·W^-1）	D^*/Jones	Reference
Au/MoO₃/MAPbI₃/ZnO/FTO	-6	10.8	3.5 × 10¹¹	［32］
MAPbI₃∶PC61BM/Au/ZnO	7	7	2.6 × 10¹²	［33］
ITO/PEDOT∶PSS/MAPbI₃（with ODT）/PC70BM/Al	-0.1	0.366	1.45 × 10¹²	［34］
ITO/NiO _x /MAPbI₃（with urea）/PCBM/BCP/Ag	-0.1	1.06	7.3 × 10¹²	［35］
ITO/PEDOT∶PSS/MAPbI₃/QD@APDEMS/PC70BM/Ag	-0.1	0.47	1.77 × 10¹²	［36］
ITO/NiO _x /MAPbI₃（TFTPN）/C60/BCP/Cu	0	0.503	9.44 × 10¹²	［36］
ITO/NiO _x /MAPbI₃（with PBFDO）/PCBM/BCP/Ag	0	0.49	8.1 × 10¹²	［36］
ITO/NiO _x /PMMA/MAPbI₃/PMMA/PCBM/ZnO/BCP/Al	0	0.415	1.30 × 10¹²	［37］
ITO/MAPbI₃/Au	0	0.55	0.80 ×10¹³	This work

图5 光电探测器的稳定性测试。持续开关1 000次后，GBL（a）和2ME（b）生长的MAPbI3单晶自驱动光电探测器I-t曲线；（c）保存一个月后，2ME生长的MAPbI3单晶自驱动光电探测器I-t曲线；GBL（d）和2ME（e）生长的MAPbI3单晶自驱动光电探测器的响应时间对比

Fig.5 Stability characterization of the photodetectors. After 1 000 on/off switching cycles， the I-t curves of the self-powered photodetectors based on GBL-grown （a） and 2ME-grown （b） MAPbI3 single crystals， respectively；（c） I-t curves of the self-powered photodetectors based on 2ME-grown MAPbI3 single crystals after one month aging； response time of the photodetectors fabricated with GBL-grown （d） and 2ME-grown （e） MAPbI3 single crystals， respectively

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低温生长高质量MAPbI₃钙钛矿单晶及其光电探测性能

Low-Temperature Grown High-Quality MAPbI₃ Perovskite Single Crystals and Its Photodetection Performance

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