上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响

doi:10.15541/jim20230424

无机材料学报 ›› 2024, Vol. 39 ›› Issue (4): 359-366.DOI: 10.15541/jim20230424 CSTR: 32189.14.10.15541/jim20230424

所属专题：【能源环境】钙钛矿(202409)；【能源环境】太阳能电池(202409)

上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响

于嫚¹(), 高荣耀², 秦玉军², 艾希成²()

1.西安航空学院材料工程学院, 西安 710077
2.中国人民大学化学系, 北京 100872

收稿日期:2023-09-18 修回日期:2023-11-29 出版日期:2024-04-20 网络出版日期:2023-12-19
通讯作者: 艾希成, 教授. E-mail: xcai@ruc.edu.cn
作者简介:于嫚(1989−), 女, 博士. E-mail: yuman@xaau.edu.cn
基金资助:
国家自然科学基金(21903062);国家自然科学基金(21973112);陕西省科学技术协会青年人才托举计划项目(20220462);国家级大学生创新创业训练计划项目(202311736016)

Influence of Upconversion Luminescent Nanoparticles on Hysteresis Effect and Ion Migration Kinetics in Perovskite Solar Cells

YU Man¹(), GAO Rongyao², QIN Yujun², AI Xicheng²()

1. School of Materials Engineering, Xi'an Aeronautical Institute, Xi’an 710077, China
2. Department of Chemistry, Renmin University of China, Beijing 100872, China

Received:2023-09-18 Revised:2023-11-29 Published:2024-04-20 Online:2023-12-19
Contact: AI Xicheng, professor. E-mail: xcai@ruc.edu.cn
About author:YU Man (1989-), female, PhD. E-mail: yuman@xaau.edu.cn
Supported by:
National Natural Science Foundation of China(21903062);National Natural Science Foundation of China(21973112);Young Talent Fund of Association for Science and Technology in Shaanxi, China(20220462);National College Students' Innovation and Entrepreneurship Training Program(202311736016)

摘要/Abstract

摘要：

迟滞效应是影响钙钛矿太阳能电池性能和稳定性的重要问题, 离子迁移和由此产生的界面离子积累是引起迟滞效应最重要的原因之一。本研究采用上转换发光纳米材料(Upconversion Luminescent Nanoparticles, UCNP)修饰电子传输层/钙钛矿活性层的界面及本征钙钛矿活性层, 系统探究了UCNP对钙钛矿的形貌、结构、光谱/光电性能和离子迁移动力学的影响。结果表明: 钙钛矿活性层经过UCNP修饰后器件的光电转换效率(Power Conversion Efficiency, PCE)最佳(16.27%), 而且迟滞因子(Hysteresis Factor, HF)得到显著改善(0.05)。进一步采用回路切换瞬态光电技术系统探究了钙钛矿太阳能电池不受光生载流子干扰的离子迁移动力学过程, 证明UCNP在光电转换过程中起到抑制离子累积和迁移的双重作用: 一方面UCNP可以形成阻隔层, 阻碍离子累积; 另一方面, UCNP可以在退火过程中进入到钙钛矿体相晶界处, 阻碍离子迁移, 使恢复电压从0.43 V降低到0.28 V。极化诱导缺陷态模型解释了离子-载流子相互作用机制, 阐释了UCNP抑制钙钛矿光伏器件迟滞效应的机理。本研究可以为调控钙钛矿太阳能电池迟滞提供一种有效的解决方案。

关键词: 上转换发光纳米材料, 钙钛矿太阳能电池, 迟滞效应, 离子迁移

Abstract:

Hysteresis effect greatly impacted performance and stability of perovskite solar cells. Ion migration and the resulting accumulation of interface ions were widely recognized as the most important origins. In this study, upconversion luminescent nanoparticles (UCNP) were used to modify the interface of the electron transport layer/perovskite active layer and the intrinsic perovskite active layer, and the effects of UCNP on the morphology, structure, spectral/optoelectronic properties, and ion migration kinetics of perovskite were systematically explored. The results indicated that the device with UCNP modified perovskite active layer has the best photoelectric conversion efficiency (PCE, 16.27%) and significantly improves the hysteresis factor (HF, 0.05). Furthermore, circuit switching transient optoelectronic technology was employed to investigate the ion migration kinetics without interference from photo-generated carriers, revealing the dual role of UCNP in suppressing ion migration and accumulation during the optoelectronic conversion process of perovskite solar cells. On the one hand, UCNP formed barrier layers that hinder ion accumulation. On the other hand, UCNP infiltrated into grain boundaries of perovskite phase during annealing, hindering ion migration and reducing the recovery voltage from 0.43 V to 0.28 V. The mechanism of carriers and ions interaction was explained based on the polarization-induced trap state model to declare the process of UCNP suppressing the hysteresis of perovskite photovoltaic devices. This work provides effective solution for regulating the hysteresis of perovskite solar cells.

Key words: upconversion luminescent nanoparticles, perovskite solar cell, hysteresis effect, ion migration

中图分类号:

O649

于嫚, 高荣耀, 秦玉军, 艾希成. 上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响[J]. 无机材料学报, 2024, 39(4): 359-366.

YU Man, GAO Rongyao, QIN Yujun, AI Xicheng. Influence of Upconversion Luminescent Nanoparticles on Hysteresis Effect and Ion Migration Kinetics in Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2024, 39(4): 359-366.

图/表 14

图1 (a)钙钛矿太阳能电池的和(b) UCNP的结构示意图

Fig. 1 Schematic diagrams of structures of (a) perovskite solar cells and (b) UCNP

图2 (a) Compact/PVK、(b) UCNP+Compact/PVK、(c) Compact/ PVK+UCNP和(d) UCNP+Compact/PVK+UCNP的SEM照片

Fig. 2 SEM images of (a) Compact/PVK, (b) UCNP+ Compact/PVK, (c) Compact/PVK+UCNP, and (d) UCNP+ Compact/PVK+UCNP

图3 Compact/PVK、UCNP+Compact/PVK、Compact/PVK+ UCNP和UCNP+Compact/PVK+UCNP的XRD图谱

Fig. 3 XRD patterns of Compact/PVK, UCNP+Compact/PVK, Compact/PVK+UCNP, and UCNP+Compact/PVK+UCNP samples

图4 (a)基于石英基底的本征钙钛矿薄膜的紫外-可见吸收光谱和稳态荧光光谱图, 以及(b)四种钙钛矿薄膜样品的时间分辨荧光光谱图

Fig. 4 (a) UV-Vis absorption and steady-state fluorescence spectra of perovskite films deposited on quartz substrates, and (b) time resolved fluorescence spectra of four perovskite thin films

图5 (a) Compact/PVK、(b) UCNP+Compact/PVK、(c) Compact/PVK+UCNP和(d)UCNP+Compact/PVK+UCNP钙钛矿太阳能电池在正扫和反扫条件下的最佳J-V曲线

Fig. 5 J-V curves under forward and reverse scanning conditions for perovskite solar cells with champion performances of (a) Compact/PVK, (b) UCNP+Compact/PVK, (c) Compact/PVK+UCNP, and (d) UCNP+Compact/PVK+UCNP

表1 四种钙钛矿器件正反扫条件下的光伏参数及HF

Table 1 Photovoltaic parameters and hysteresis factors (HF) of four perovskite devices upon forward and reverse scanning conditions

Sample	Scan direction	Open-circuit voltage/ mV	Short-circuit current/ (mA·cm^-2)	FF/%	PCE/%	HF
Compact/PVK	Reverse	996	19.56	63.45	12.36	0.42
Compact/PVK	Forward	912	17.89	44.13	7.20	0.42
UCNP+Compact/PVK	Reverse	1038	20.37	0.74	15.65	0.07
UCNP+Compact/PVK	Forward	1045	19.84	0.70	14.52	0.07
Compact/PVK+UCNP	Reverse	1034	20.96	0.75	16.27	0.05
Compact/PVK+UCNP	Forward	1032	20.39	0.73	15.37	0.05
UCNP+Compact/PVK+UCNP	Reverse	1016	18.31	0.66	12.28	0.15
UCNP+Compact/PVK+UCNP	Forward	976	17.76	0.60	10.40	0.15

图6 不同钙钛矿太阳能电池的(a)开路光电压上升曲线和(b) cs-TPT动力学曲线

Fig. 6 (a) Open-circuit photovoltage buildup curves and (b) cs-TPT kinetics curves of different perovskite solar cells

图7 UCNP抑制离子迁移机制

Fig. 7 Mechanism of UCNP inhibiting ion migration (a) Control group and (b) UCNP regulated perovskite solar cells

图S1 (a) cs-TPT装置示意图[1](ND filter: neutral density filter, DUT: device under test, Sync.: synchronizing, Trig.: trigger, Sig. = signal); (b)典型cs-TPT设置(Trigger, Laser, VG, and RS)的时间序列

Fig. S1 (a) Schematic illustration of the cs-TPT setup ](ND filter: neutral density filter, DUT: device under test, Sync.: synchronizing, Trig.: trigger, Sig.= signal); (b) Time sequences of typical cs-TPT settings (Trigger, Laser, VG, and RS)

图S2 NaLuF4:20%Yb3+, 2%Er3+的(a)TEM照片和(b)XRD图谱

Fig. S2 (a) TEM image and (b) XRD pattern of NaLuF4:20%Yb3+, 2%Er3+

图S3 980 nm 激光照射(a) UCNP+Compact和(b) PVK+ UCNP的混合溶液

Fig. S3 Mixed solutions of (a) UCNP+Compact and (b) PVK+ UCNP irradiated with 980 nm laser

图S4 980 nm激光照射(a) UCNP+Compact/PVK、(b) Compact/PVK+UCNP和(c) UCNP+Compact/PVK+UCNP的照片

Fig. S4 Pictures of (a) UCNP+Compact/PVK, (b) Compact/PVK+UCNP and (c) UCNP+Compact/PVK+UCNP irradiated with 980 nm laser

图S5 不同器件的正反扫PCE及HF统计数据

Fig. S5 PCE and HF statistical data of different devices under forward and reverse scanning

表S1 四种电池的HF和正反扫条件下的PCE的方差

Table S1 HF and variance of PCE under forward and reverse scanning conditions of cells

Sample	S²(PCE_reverse)	S²(PCE_forward)	S²(HF)
Compact/PVK	0.55956	0.58046	0.01156
UCNP+Compact/PVK	0.41318	0.40968	0.01130
Compact/PVK+UCNP	0.25838	0.33691	0.00810
UCNP+Compact/PVK+UCNP	0.19304	0.96262	0.01451

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上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响

Influence of Upconversion Luminescent Nanoparticles on Hysteresis Effect and Ion Migration Kinetics in Perovskite Solar Cells

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