表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能※

doi:10.6023/A21120622

化学学报 ›› 2022, Vol. 80 ›› Issue (5): 581-589.DOI: 10.6023/A21120622 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能^※

何新蕊^a^,^b, 蔡丽娜^a^,^b, 陈汉生^b, 尹攀^b, 尹志刚^b^,^c^,^*(), 郑庆东^b^,^*()

a 福州大学化学学院福州 350108
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002
c 中国福建光电信息科学与技术创新实验室福州 350108

投稿日期:2021-12-31 发布日期:2022-05-31
通讯作者: 尹志刚, 郑庆东
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
福建省杰出青年科学基金(2019J06023); 国家自然科学基金(52130306); 国家自然科学基金(52173241); 中国福建光电信息科学与技术创新实验室(闽都创新实验室)主任基金(2021ZR116)

A Dual Post-Treatment Method for Improving the Performance of Ternary NiMgO Semiconductor Interfacial Layers and Their Organic Solar Cells^※

Xinrui He^a^,^b, Lina Cai^a^,^b, Hansheng Chen^b, Pan Yin^b, Zhigang Yin^b^,^c(), Qingdong Zheng^b()

a College of Chemistry, Fuzhou University, Fuzhou 350108
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002
c Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108

Received:2021-12-31 Published:2022-05-31
Contact: Zhigang Yin, Qingdong Zheng
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
Natural Science Foundation of Fujian Province for Distinguished Young Scholars(2019J06023); National Natural Science Foundation of China(52130306); National Natural Science Foundation of China(52173241); Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR116)

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1. Supporting Information-A21120622.pdf.pdf(644KB)

摘要/Abstract

采用溶胶-凝胶法制备了Mg掺杂氧化镍(NiO)的三元氧化物半导体NiMgO薄膜, 研究了不同表面后处理方法对薄膜结构、性质和能级的影响. 利用NiMgO薄膜作为新型空穴传输界面层构建了非富勒烯有机太阳能电池, 研究了器件性能变化及其物理机制. 结果表明, 以未表面处理NiMgO为界面层时, 器件的能量转化效率(PCE)为5.90%; 使用紫外-臭氧(UVO)表面后处理的NiMgO界面层, 器件PCE大幅提升至12.67%. 而NiMgO在UVO处理前进行润洗, 可以去除表面残留物, 薄膜变平整且透光率增加. 因此, 采用润洗与UVO结合的表面双重后处理新策略后, 器件的开路电压不变, 但短路电流密度和填充因子分别提高到23.48 mA•cm^–2和64.29%, 最终PCE达到13.17%. 该研究为半导体氧化物薄膜及器件的优化提供了一条有效途径.

关键词: 有机光伏, 三元氧化物, 空穴传输层, 表面处理, 界面工程

Organic solar cells (OSCs) are among the most promising photovoltaic technologies to solve energy and environmental problems. To achieve highly efficient OSCs, controlling over electrode interfacial layers is greatly important for improving charge transportation and collection. Here, ternary metal oxide semiconductor films of Mg-doped NiO (NiMgO) have been prepared via a sol-gel method, and further optimized by several post-treatment strategies. The structures, properties and energy levels of different NiMgO films have been investigated to explore the influence of various post-treatment strategies. Incorporating the ternary NiMgO films as a novel type of hole transport layers (HTLs), non-fullerene OSCs have been fabricated based on a promising bulk-heterojunction of PM6:M36. Their photovoltaic performances and mechanisms of device physics are also investigated. When the sol-gel derived NiMgO film without post-treatment is used as an HTL, the OSCs show a relatively low power conversion efficiency (PCE) of 5.90%. By contrast, after simple ultraviolet-ozone (UVO) post-treatment on the NiMgO HTL, the resulted OSCs exhibit greatly enhanced photovoltaic performances, with an increased open-circuit voltage (V_OC) of 0.87 V and an improved PCE of 12.67%. More importantly, a new dual post-treatment combining surface rinse with UVO treatment has been demonstrated to further optimize NiMgO HTLs and improve device performances. The rinse process can remove excess impurities and flatten the surface of NiMgO films as well as increase the transmittance, while the UVO treatment process is beneficial for reducing surface defects of the ternary oxide films. Benefit-ing from such an efficient dual post-treatment on NiMgO HTLs, the OSCs afford a high PCE of 13.17% with a retained V_OC of 0.87 V, an increased short-circuit current density of 23.48 mA•cm^–2, and an improved fill factor of 64.29%. These results provide an effective way for surface post-treatment and property optimization of semiconducting metal oxide films, and contribute to the development of high-performance optoelectronic devices.

Key words: organic photovoltaic, ternary oxide, hole transport layer, surface treatment, interface engineering

引用此文

何新蕊, 蔡丽娜, 陈汉生, 尹攀, 尹志刚, 郑庆东. 表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能^※[J]. 化学学报, 2022, 80(5): 581-589.

Xinrui He, Lina Cai, Hansheng Chen, Pan Yin, Zhigang Yin, Qingdong Zheng. A Dual Post-Treatment Method for Improving the Performance of Ternary NiMgO Semiconductor Interfacial Layers and Their Organic Solar Cells^※[J]. Acta Chimica Sinica, 2022, 80(5): 581-589.

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图/表 10

图1. 不同后处理NiMgO薄膜的X射线光电子能谱(XPS)图谱

Figure 1. X-Ray photoelectron spectroscopy (XPS) spectra of NiMgO films derived from different post-treatment methods

图2. 不同后处理NiMgO薄膜的(a~d)高度图和(e~h)粘度图

Figure 2. (a~d) Height images and (e~h) viscosity images of NiMgO films derived from different post-treatment methods

图3. (a)不处理、(b)只润洗、(c)只UVO处理和(d)双重后处理NiMgO薄膜(N1至N4)与水的接触角

Figure 3. Contact angles of water and NiMgO films derived from different conditions including (a) without post-treatment, (b) only rinse, (c) only UVO treatment, and (d) dual post-treatment

图4. 不同后处理NiMgO薄膜的(a)透过光谱和(b)吸收光谱

Figure 4. (a) Transmission and (b) absorption spectra of NiMgO films derived from different post-treatment methods

NiMgO film	E_onset/eV	E_cutoff/eV	VBM/eV	CBM/eV	E_g^a/eV
N1	0.20	16.92	–4.50	–0.32	4.18
N2	0.13	17.15	–4.20	–0.04	4.16
N3	1.59	17.24	–5.57	–1.54	4.03
N4	1.49	17.42	–5.29	–1.20	4.09

表1. 不同NiMgO薄膜的能级水平参数及光学带隙

Table 1. Energy level parameters and optical bandgap values of different NiMgO films

图5. 不同NiMgO薄膜的(a)UPS图谱及其(b)低结合能端和(c)高结合能端的放大图谱

Figure 5. (a) UPS spectra of different NiMgO films and their enlarged views on (b) the low binding energy side and (c) the high binding energy side

图6. (a)有机太阳能电池结构示意图和PM6与M36的分子结构式以及(b)器件组成材料的能带图

Figure 6. (a) Schematic structure of OSCs and molecular structures of PM6 and M36 as well as (b) energy band diagram of materials used in the device

图7. 基于不同NiMgO空穴传输层有机太阳能电池的(a) J-V曲线和(b) EQE图谱及其积分电流密度曲线

Figure 7. (a) J-V curves as well as (b) EQE spectra and integral current density curves of OSCs based on different NiMgO HTLs

NiMgO HTLs	V_OC/V	J_SC/(mA•cm^–2)	FF/%	PCE/%		R_Sh/(kΩ•cm²)	R_S/(Ω•cm²)
NiMgO HTLs	V_OC/V	J_SC/(mA•cm^–2)	FF/%	Best	Avg.	R_Sh/(kΩ•cm²)	R_S/(Ω•cm²)
N1	0.63	21.77	43.20	5.90	5.18	0.25	15.40
N2	0.55	21.19	46.30	5.40	5.05	0.29	11.45
N3	0.87	22.64	63.82	12.67	12.03	0.94	6.92
N4	0.87	23.48	64.29	13.17	12.61	0.93	6.02

表2. 基于不同NiMgO薄膜作为空穴传输层的有机太阳能电池器件性能参数

Table 2. Device parameters of OSCs based on different NiMgO films as HTLs

图8. 不同NiMgO空穴传输层有机太阳能电池的(a) Jph-Veff曲线以及(b) JSC与(c) VOC对光强的依赖关系曲线

Figure 8. (a) Jph-Veff curves, and light intensity dependent curves of JSC (b) and VOC (c) of OSCs based on different NiMgO HTLs

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表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能^※

A Dual Post-Treatment Method for Improving the Performance of Ternary NiMgO Semiconductor Interfacial Layers and Their Organic Solar Cells^※

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表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能※

A Dual Post-Treatment Method for Improving the Performance of Ternary NiMgO Semiconductor Interfacial Layers and Their Organic Solar Cells※

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表面双重后处理方法提升三元NiMgO半导体界面层及其有机太阳能电池的性能^※

A Dual Post-Treatment Method for Improving the Performance of Ternary NiMgO Semiconductor Interfacial Layers and Their Organic Solar Cells^※