氧化镍在倒置平面钙钛矿太阳能电池中的应用进展

王佩佩; 张晨曦; 胡李纳; 李仕奇; 任炜桦; 郝玉英

doi:10.7498/aps.70.20201896

摘要

近年来有机-无机杂化钙钛矿太阳能电池(perovskite solar cells, PSCs)因具有光电转换效率高、制备工艺简单等优点而受到广泛关注. 空穴传输层(hole transport layer, HTL)的选择及其优化对器件的性能至关重要. 氧化镍(NiO_x) HTL具有化学稳定性好、空穴迁移率高、制备方法简单等特点, 在PSCs中得到了广泛应用. 本综述从NiO_x HTL在平面PSCs中的应用入手, 系统介绍了通过掺杂和表面修饰法实现对NiO_x HTL薄膜的结构和光电性能的改性, 并从能级匹配、空穴迁移率及结晶性等多个角度详细评述了NiO_x改性对PSCs光电转换效率、填充因子、开路电压、短路电流和稳定性的影响规律, 最后对于NiO_x平面PSCs的未来进行了展望.

关键词:

Abstract

In recent years, organic-inorganic hybrid perovskite solar cells (PSCs) have attracted wide attention due to their high photoelectric conversion efficiency and simple preparation process. Hole transport layer (HTL) is one of the most critical components in PSCs. As a kind of inorganic HTL material, nickel oxide (NiO_x) has been widely used in perovskite solar cells because of its excellent advantages, such as outstanding chemical stability, high carrier mobility, simple methods for its preparation, etc. In this paper, the applications of NiO_x HTL in planar PSCs are systematically summarized from the aspects of the improvment of its structure and photoelectric properties by doping and interface modification. The reasons for affecting the device performances, i.e. fill factor, open-circuit voltage, short-circuit current, photoelectric conversion efficiency, and stability are emphatically analyzed from several aspects, such as energy level matching, hole mobility and crystallinity. In addition, the future development directions of the planar PSCs are prospected.

Keywords:

作者及机构信息

太原理工大学物理与光电工程学院, 新型传感与智能控制教育部重点实验室, 太原　030024

通信作者: 张晨曦, zhangchenxi@tyut.edu.cn ; 郝玉英, haoyuying@tyut.edu.cn

基金项目: 国家自然科学基金(批准号: 62074108)、国家自然科学基金委员会-山西省煤基低炭联合基金(批准号: U1710115)、山西省科学技术重大专项(批准号: 20201101012)、山西省科技创新培育团队建设项目(批准号: 201805D131012-3)和山西省自然科学基金(批准号: 201901D211114)资助的课题

Authors and contacts

College of Physics and Optoelectronics, Key Lab of Advanced Transducers and Intelligent Control System, Taiyuan University of Technology, Taiyuan 030024, China

Corresponding author: Zhang Chen-Xi, zhangchenxi@tyut.edu.cn ; Hao Yu-Ying, haoyuying@tyut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 62074108), the Joint Foundation of National Natural Science Foundation of China and Shanxi Coal-Based Low-Carbon Nurturing Project (Grant No. U1710115), the Major Special Projects of Shanxi Province in Science and Technology, China (Grant No. 20201101012), the Platform and Base Special Project of Shanxi, China (Grant No. 201805D131012-3), and the Natural Science Foundation of Shanxi Province, China (Grant No. 201901D211114)

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施引文献

图 1 钙钛矿太阳电池结构示意图

Fig. 1. Schematic diagram of PSCs.

下载: 全尺寸图片幻灯片

图 2 NiO的立方晶体结构

Fig. 2. NiO cubic crystal structure

下载: 全尺寸图片幻灯片

图 3 (a) NiO_x和Cu:NiO_x薄膜的紫外光电子能谱^[33]; (b) 基于NiO_x或Cs: NiO_x单空穴器件的J-V曲线, 器件结构为FTO/ NiO_x 或 Cs:NiO_x/MoO₃/Ag^[37]; (c) 不同HTLs的PSCs能级图; (d) 倒置平面PSCs的结构^[38]; (e) F6TCNNQ掺杂分子的化学结构及其与NiO_x的能级排列^[41]; (f) NiO_x与TCNQ, F2TCNQ, F4TCNQ和F2HCNQ的电荷转移和能级分布示意图^[17]

Fig. 3. (a) Ultraviolet photoelectron spectra of NiO_x and Cu:NiO_x films^[33]; (b) J-V curves of hole only devices with NiO_x or Cs:NiO_x hole extraction layers, the device structure is FTO/ NiO_x or Cs:NiO_x/MoO₃/Ag^[37]; (c) energy-level diagram of the various layers in the PSCs exhibiting the transfer of photoinduced holes; (d) structural illustration of the inverted planar PSCs^[38]; (e) band alignment of NiO_x and molecular dopants of F6TCNNQ and the chemical structure^[41]; (f) schematic of charge transfer and energy level distribution of NiO_x, TCNQ, F2TCNQ, F4TCNQ, and F2HCNQ^[17].

下载: 全尺寸图片幻灯片

图 4 (a) 钙钛矿前驱体在NiO_x薄膜以及甘油处理后NiO_x膜上的接触角^[46]; (b) 三种氨基酸的三维分子模型^[47]; (c) NiO_x和NiO_x/FDA 薄膜上钙钛矿层的SEM图像; (d) NiO_x和NiO_x/FDA 薄膜上钙钛矿层的X射线衍射图^[48]; (e) 基于TPV实验计算的具有不同HTLs器件的载流子复合寿命与光强度关系图^[49]; (f) 在10 kHz下KCl修饰前后NiO_x基PSCs的Mott-Schottky图, 以及基于TPV实验计算的KCl修饰前后NiO_x基PSCs的陷阱态密度谱^[51]

Fig. 4. (a) Contact angles of the solvents of perovskite precursor solution on NiO_x: pristine film and with glycerol treatment^[46]; (b) molecular 3D models and formula of three amino acids^[47]; (c) SEM images of the perovskite layer on NiO_x and NiO_x/FDA films; (d) XRD patterns of the perovskite layer on NiO_x and NiO_x/FDA films^[48]; (e) recombination lifetime versus light intensity plots of complete cells having various HTLs, calculated by TPV experiments^[49]; (f) Mott–Schottky plots for the CsFAMA perovskite PSCs with pristine and KCl-modified NiO_x HTLs at 10 kHz and trap density of states (DOS) spectra for CsFAMA perovskite PSCs with pristine and KCl-modified NiO_x HTLs^[51]

下载: 全尺寸图片幻灯片

表 1 基于掺杂NiO_x薄膜的PSCs的性能

Table 1. Performances of the PSCs based on doped NiO_x films.

器件结构	电压 V_oc/V	电流 J_sc/(mA·cm^–2)	填充因子FF	光电转换效率PCE/%	掺杂/方法	文献
ITO/F2HCNQ:NiO_x/PMMA/CsMAFA/PCBM/BCP/Ag	1.14	23.44	0.83	22.13	F2HCNQ:NiO_x spin-coating	[17]
ITO/F6TCNNQ:NiO_x/CsFAMA/ PCBM/ZrAcac/Ag	1.12	23.18	0.80	20.86	F6TCNNQ/Spin coating	[41]
ITO/Cu:NiO_x/CH₃NH₃PbI₃/C₆₀/BCP/Ag	1.12	22.28	0.81	20.26	Cu:NiO_x NPs/Spin coating	[42]
ITO/Li:Co NiO_x/MA_1yFA_yPbI_3xCl_x/ PCBM/BCP/Ag	1.09	23.80	0.78	20.10	Li:Co/Spin-coating	[40]
ITO/Sr:NiO_x/CH₃NH₃PbI₃/C₆₀/BCP/Ag	1.14	22.66	0.76	19.49	Sr:NiO/Spin-coating	[38]
ITO/NiO_x:AGQDs/CsFAMA/PCBM/BCP/Ag	1.05	22.30	0.83	19.40	NiO_x:AGQDs/Spin-coating	[43]
FTO/Cs:NiO_x/MAPbI₃/PCBM/ZrAcac/Ag	1.12	21.77	0.79	19.35	Cs/Spin coating sol	[37]
ITO/NiMgO/CH₃NH₃PbI₃/PCBM/ZnMgO/Al	1.08	21.30	0.80	18.50	Mg/Sputtering	[44]
FTO/NIR-Co:NiO_x/MAPbI₃/PC₆₁BM/PEI/Ag	1.09	20.46	0.80	17.77	Co/Spin-coating	[35]
FTO/NiMgLiO/MAPbI₃/PCBM/Ti(Nb)O_x/Ag	1.07	20.21	0.75	16.20	Li-Mg/Spray pyrolysis	[45]

下载: 导出CSV

表 2 基于改性NiO_x薄膜的PSCs的性能

Table 2. Performances of the PSCs based on modified NiO_x films

器件结构	电压 V_oc/V	电流 J_sc/(mA·cm^–2)	填充因子FF	光电转换效率PCE/%	改性/方法	文献
ITO/NiO_x/KCl/CsFAMA/PCBM/ZrAcac/Ag	1.15	22.89	0.80	20.96	KCl or NaCl/ Spin-coating	[51]
ITO/NiO_x/PFN-P2/CsFAMA/C₆₀/BCP/Ag	1.13	23.33	0.78	20.50	PFN-P2	[53]
FTO/NiO_x/SDBS/CH₃NH₃PbI₃/ PCBM/BCP/Ag	1.12	22.94	0.78	20.15	SDBS/Spin-coating	[54]
ITO/NiO_x/NH₄F/CH₃NH₃PbI₃/C₆₀/BCP/Ag	1.09	22.45	0.77	18.94	NH₄F/Spin-coating	[50]
ITO/NiO_x/TPI-6MEO/MAPbI₃/ PCBM/BCP/Ag	0.98	23.31	0.81	18.42	TPI-6MEO/ Spin-coating	[49]
ITO/NiO_x/SAM/Perovskite/ PCBM/Bis-C₆₀/Ag	1.11	21.70	0.76	18.40	Benzoic acid modification	[55]
ITO/NiO_x/FDA/CH₃NH₃PbI₃/PCBM/AgAl	1.04	22.55	0.76	17.87	FDA modification	[48]
FTO/NiO_x/PTAA/FA_1–xMA_xPb (I_3–yBr_y)/PCBM/Au	1.06	21.54	0.75	17.10	PTAA/Sol–gel	[56]

下载: 导出CSV

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