快速球磨法制备钙钛矿颗粒的光电性质和X射线探测性能研究

doi:10.16553/j.cnki.issn1000-985x.2025.0079

摘要/Abstract

摘要： 本文研究了球磨时长对钙钛矿粉末和钙钛矿厚膜物相、载流子动力学的影响。研究发现，随着球磨时间的延长，会引入更多的缺陷，导致钙钛矿粉末和钙钛矿厚膜的荧光强度降低，载流子寿命减少。同时发现，厚膜制备过程中的溶剂混合和热处理会进一步提高钙钛矿粉末的结晶性能与载流子寿命。因此在可以获得纯相钙钛矿厚膜的前提下，球磨时间越短越好。最终，采用球磨15 min制备的样品制备的钙钛矿厚膜获得了最长的载流子寿命（820.0 ns）和最高的X射线灵敏度（728.85 μC·Gy_air^-1·cm^-2）。该研究为大规模快速制备基于钙钛矿厚膜的X射线探测器件提供了参考。

关键词: 球磨法; 钙钛矿; 载流子动力学; 缺陷浓度; X射线灵敏度; 荧光强度

Abstract: The effects of ball milling duration on the phase and carrier dynamics of perovskite powders and thick films were investigated in the study. It is found that as the ball milling time increases， more defects are introduced in the obtained perovskie powder， leading to a decrease in the photoluminescence intensities and carrier lifetimes of both perovskite powders and final thick films. Additionally， solvent mixing and thermal treatment during the thick film preparation process are found to further enhance the crystallinity and carrier lifetime. Therefore， under the premise of obtaining pure perovskite thick films， the shorter is the ball milling time， the better is the thick films. Ultimately， a sample prepared with 15 min of ball milling achieves the longest carrier lifetime of 820.0 ns and the highest X-ray sensitivity of 728.85 μC·Gy_air^-1·cm^-2. This study provides a useful guide for the rapid preparation of X-ray detectors based on perovskite thick films.

Key words: ball milling method; perovskite; carrier dynamics; trap density; X-ray sensitivity; PL intensity

中图分类号:

O474

程嘉甜, 范鑫雨, 杨周. 快速球磨法制备钙钛矿颗粒的光电性质和X射线探测性能研究[J]. 人工晶体学报, 2025, 54(7): 1297-1303.

CHENG Jiatian, FAN Xinyu, YANG Zhou. Photoelectric Properties and X-Ray Detection Performance of Perovskite Particles Prepared by Rapid Ball Milling Method[J]. Journal of Synthetic Crystals, 2025, 54(7): 1297-1303.

图/表 7

图1 球磨法制备Cs0.1FA0.9Pb（I0.9Br0.1）3粉末及其厚膜的实验流程

Fig.1 Experimental process of Cs0.1FA0.9Pb（I0.9Br0.1）3 powder and its thick film prepared by ball milling method

图2 Cs0.1FA0.9Pb（I0.9Br0.1）3粉末（a）与的厚膜（b）的XRD图谱

Fig.2 XRD patterns of Cs0.1FA0.9Pb（I0.9Br0.1）3 powders （a） and thick films （b）

图3 球磨法制备Cs0.1FA0.9Pb（I0.9Br0.1）3粉末的微观形貌

Fig.3 Microstructure of Cs0.1FA0.9Pb（I0.9Br0.1）3 powers prepared by ball milling method

图4 Cs0.1FA0.9Pb（I0.9Br0.1）3厚膜的微观形貌。表面微观形貌：（a）15-CsFA；（b）30-CsFA；（c）60-CsFA；（d）90-CsFA；截面微观形貌：（e）和（i）15-CsFA；（f）和（j）30-CsFA；（g）和（k）60-CsFA；（h）和（l）90-CsFA

Fig.4 Microstructure of Cs0.1FA0.9Pb（I0.9Br0.1）3 thick film. Surface microstructure：（a） 15-CsFA；（b） 30-CsFA；（c） 60-CsFA；（d） 90-CsFA. Microstructure of cross-section：（e） and （i） 15-CsFA；（f） and （j） 30-CsFA；（g） and （k） 60-CsFA；（h） and （l） 90-CsFA

图5 球磨时间对钙钛矿粉末与厚膜荧光强度和载流子寿命的影响。（a）球磨钙钛矿粉末荧光光谱；（b）球磨钙钛矿粉末瞬态荧光光谱；（c）钙钛矿厚膜荧光光谱；（d）钙钛矿厚膜瞬态荧光光谱

Fig.5 Effects of ball milling duration on the PL intensity and carrier lifetime. （a） PL spectra of ball milled powders；（b） TRPL spectra of ball milled powders；（c） PL spectra of perovskite thick films；（d） TRPL spectra of perovskite thick films

表1 球磨时间对钙钛矿粉末和厚膜载流子寿命的影响

Table 1 Effects of ball milling time on the carrier lifetime of perovskite powders and thick films

Sample	τ_ave/ns	τ₁/ns	A₁/%	τ₂/ns	A₂/%
bm 15	39.84	77.66	45.00	8.88	55.00
bm 30	7.12	13.22	44.89	2.14	55.11
bm 60	5.95	15.04	28.65	2.30	71.35
bm 90	2.93	8.05	21.56	1.53	78.44
15-CsFA	820.0	833.4	98.29	37.5	1.71
30-CsFA	506.7	528.7	95.56	34.4	4.44
60-CsFA	340.4	371.0	91.08	28.0	8.92
90-CsFA	312.1	347.3	89.16	23.3	10.84

图6 （a）Cs0.1FA0.9Pb（I0.9Br0.1）3厚膜样品在剂量率范围在251.0 μGyair·s-1至15.1 μGyair·s-1和-1 V偏压下的X射线响应；（b）Cs0.1FA0.9Pb（I0.9Br0.1）3厚膜在-1 V偏压下的响应电流密度-剂量率曲线

Fig.6 （a） X-ray responses of the Cs0.1FA0.9Pb（I0.9Br0.1）3 thick film samples at dose rates ranging from 251.0 μGyair·s-1 to15.1 μGyair·s-1 and -1 V bias；（b） response current-dose rate curves of Cs0.1FA0.9Pb（I0.9Br0.1）3 thick films under -1 V bias

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