n-i-p结构钙钛矿太阳能电池界面钝化的研究进展

李晓果; 张欣; 施则骄; 张海娟; 朱成军; 詹义强

doi:10.7498/aps.68.20190468

摘要

近年来有机-无机杂化钙钛矿材料因其吸收系数高、成本低廉、制备工艺简单等优点吸引了大批科研人员进行研究, 目前在实验室制备的电池能量转换效率已经超过23%. 钙钛矿太阳能电池一般采用溶液法逐层制备, 在此过程中由于退火温度、结晶速率等因素的影响, 钙钛矿内部以及界面会产生大量的缺陷, 这些缺陷会增加载流子复合概率, 降低载流子寿命, 严重影响钙钛矿太阳能电池的性能. 因此研究和理解钙钛矿的缺陷对制备高效钙钛矿太阳能电池至关重要. 本文讨论了在正式结构中, 钙钛矿太阳能电池缺陷的产生以及缺陷对钙钛矿太阳能电池的影响, 分析了不同材料钝化电子传输层/钙钛矿层界面以及钙钛矿层/空穴传输层界面缺陷的机理, 对比了不同钝化材料对钙钛矿太阳能电池光伏性能的影响, 总结了界面钝化材料在钙钛矿太阳能电池中的作用. 最后指出了钙钛矿太阳能电池钝化缺陷的研究趋势和发展方向.

关键词:

Abstract

In recent years, organic-inorganic hybrid perovskite solar cells have aroused the interest of a large number of researchers due to the advantages of large optical absorption coefficient, tunable bandgap and easy fabrication. Recently, the power conversion efficiency of organic-inorganic hybrid perovskite solar cells has been enhanced to more than 23% in laboratory. In solution processed perovskite solar cells, perovskite and charge transport layer are stacked together, due to the different crystallization rates leading to lattice mismatch near the surface region of perovskite film, resulting in a lot of interface defects, especially at the interface between perovskite and charge transport layer. What is more, the photo-induced free carriers must transfer across the interfaces to be collected. But the defects near the interface can trap photogeneration electrons, thus reducing the carrier lifetime and causing the charges to be recombined, which greatly influence the performance and stability of perovskite solar cells. Therefore, reducing and passivating these defects is critical for obtaining the high performance perovskite solar cells. Now, there have been made tremendous efforts devoting to advancing passivation techniques, such as doping and surface modification, for high efficiency perovskite solar cell with improved stability and reduced hysteresis. These approaches also contribute to improving the energy band alignment between carrier transport layers and perovskite absorber improving device performance, or resistance moisture to enhance device stability. In this review we mainly introduce the formation and the effect of defects on perovskite solar cells, analyze the mechanism for passivating the interfacial defects between charge transport layer and perovskite photo absorption layer for different materials, compare the effects of different passivation materials on the photovoltaic performance of perovskite solar cells, and summarize the role of these materials in passivating the defects. Finally we discuss the research trend and development direction of passivation defects in perovskite solar cells.

Keywords:

作者及机构信息

1.
内蒙古大学物理科学与技术学院, 内蒙古自治区半导体光伏技术重点实验室, 呼和浩特　010021

2.
复旦大学工程与应用技术研究院, 上海　200433

3.
复旦大学信息科学与工程学院, 上海　200433

通信作者: 朱成军, cjzhu@imu.edu.cn ; 詹义强, yqzhan@fudan.edu.cn

基金项目: 国家自然科学基金(批准号: 11564027)资助的课题.

Authors and contacts

1.
Key Laboratory of Semiconductor Photovoltaic Technology of Inner Mongolia Autonomous Region, School of Physical Science and Technology, Inner Mongolia University, Hohhot 010021, China

2.
Academy for Engineering and Technology, Fudan University, Shanghai 200433, China

3.
School of Information Science and Technology, Fudan University, Shanghai 200433, China

Corresponding author: Zhu Cheng-Jun, cjzhu@imu.edu.cn ; Zhan Yi-Qiang, yqzhan@fudan.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11564027).

文章全文 : translate this paragraph

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施引文献

图 1 钙钛矿晶体结构示意图

Fig. 1. Structure diagram of perovskite crystal.

下载: 全尺寸图片幻灯片

图 2 晶体缺陷类型^[16]　(a)完美晶体结构; (b)空位缺陷; (c)间隙缺陷; (d)反位替代缺陷; (e)替位杂质缺陷; (f)间隙杂质缺陷

Fig. 2. Types of crystal defects^[16]: (a) perfect lattice; (b) vacancy defects; (c) interstitial defects; (d) antisite substitution defects; (e) substitutional impurity; (f) interstitial impurity.

下载: 全尺寸图片幻灯片

图 3 (a) KCl钝化缺陷原理图^[42]; (b)磺酸钾钝化缺陷示意图^[45]; (c) APTES钝化缺陷原理图^[46]; (d) DA钝化缺陷原理图^[48]; (e) HS的结构式^[49]; (f) HOCO-R-NH₃⁺在界面处的结构^[50]

Fig. 3. (a) Schematic diagram of KCl passivation defects^[42]; (b) schematic diagram of potassium xanthate passivation defects^[45]; (c) schematic diagram of APTES passivation PSCs interface defects^[46]; (d) schematic diagram of DA passivation PSCs interface defects^[48]; (e) diagram structure of HS^[49]; (f) structure of HOCO-R-NH₃⁺ at interface^[50].

下载: 全尺寸图片幻灯片

图 4 (a)钙钛矿表面电子陷阱的产生^[54]; (b)吡啶缺陷钝化原理图^[54]; (c)碘五氟苯与卤素阴离子之间卤素键作用的示意图^[47]; (d) TPA掺杂钙钛矿器件的I-V曲线, 插图为TPA钝化原理图以及钙钛矿薄膜的SEM图^[66]

Fig. 4. (a) Formation of perovskite surface traps^[54]; (b) schematic diagram of pyridine passivation defects^[54]; (c) schematic of the halogen bond interaction between the IPFB and halogen anion^[47]; (d) I-V curves of TAP-doped perovskite devices, illustrated diagrams is TAP passivation schematic and SEM of perovskite films^[66].

下载: 全尺寸图片幻灯片

图 5 所有钝化方法以及钝化的机理的总结

Fig. 5. Summary of all passivation methods and passivation mechanism.

下载: 全尺寸图片幻灯片

表 1 钝化和不钝化ETL/Perovskite界面钙钛矿太阳能电池的性能

Table 1. Performance of perovskite solar cells with and without passivation on ETL/Perovskite interface.

Interface to be modified	Modifier		V_oc/V	J_sc/mA·cm^–2	FF	PCE/%	文献
SnO₂/MAPbI_xCl_3–x	LiF	W	1.15	21.62	0.73	18.33	[27]
SnO₂/MAPbI_xCl_3–x	LiF	W/O	1.08	20.40	0.71	15.60	[27]
SnO₂/MAPbI_xCl_3–x	KCl	W	1.12	21.82	0.79	19.44	[42]
SnO₂/MAPbI_xCl_3–x	KCl	W/O	1.08	21.59	0.76	18.12	[42]
TiO₂/MAPbI_xCl_3–x	CsBr	W	1.06	20.70	0.75	16.30	[44]
TiO₂/MAPbI_xCl_3–x	CsBr	W/O	0.99	18.70	0.69	13.10	[44]
SnO₂/MAPbI₃	Xanthate	W	1.06	22.61	0.70	18.41	[45]
SnO₂/MAPbI₃	Xanthate	W/O	1.03	21.74	0.73	16.56	[45]
SnO₂/MAPbI₃	APTES SAM	W	1.06	20.84	0.66	14.69	[46]
SnO₂/MAPbI₃	APTES SAM	W/O	1.16	21.23	0.69	17.03	[46]
SnO₂/MAPbI₃	DA SAM	W	1.05	21.80	0.73	16.87	[48]
SnO₂/MAPbI₃	DA SAM	W/O	1.04	19.96	0.67	14.05	[48]
TiO₂/MAPbI₃	Li-TiO₂	W	1.03	23.91	0.74	18.25	[52]
TiO₂/MAPbI₃	Li-TiO₂	W/O	1.01	22.46	0.69	15.64	[52]
TiO₂/MAPbI₃	HS	W	1.11	23.34	0.77	20.10	[49]
TiO₂/MAPbI₃	HS	W/O	1.09	21.29	0.74	17.20	[49]
TiO2/MAPbI₃	GABAH⁺I^–	W	1.00	19.20	0.62	12.00	[50]
TiO2/MAPbI₃	GABAH⁺I^–	W/O	—	—	—	8.00	[50]
TiO2/MAPbI₃	LA	W	0.99	22.40	0.64	14.22	[51]
TiO2/MAPbI₃	LA	W/O	0.95	17.08	0.66	10.76	[51]
TiO2/MAPbI₃	GnPs	W	1.00	23.67	0.69	15.14	[41]
TiO2/MAPbI₃	GnPs	W/O	0.97	22.33	0.80	19.23	[41]

下载: 导出CSV

表 2 钝化和不钝化Perovskite/HTL钙钛矿太阳能电池的性能

Table 2. Performance of perovskite solar cells with and without passivation on Perovskite/HTL interface.

Interface to be modified	Modifier		V_oc/V	J_sc/mA·cm^–2	FF	PCE/%	文献
MAPbI_xCl_3–x/Spiro-OMeTAD	IPFB	W	1.06	23.38	0.67	15.70	[47]
MAPbI_xCl_3–x/Spiro-OMeTAD	IPFB	W/O	1.02	23.80	0.57	13.00	[47]
MAPbI₃/Spiro-OMeTAD	GO	W	1.03	20.00	0.72	14.50	[59]
MAPbI₃/Spiro-OMeTAD	GO	W/O	0.93	18.50	0.64	10.00	[59]
MAPbI_xCl_3–x/Spiro-OMeTAD	Thiophene	W	0.95	20.70	0.68	13.10	[54]
MAPbI_xCl_3–x/Spiro-OMeTAD	Thiophene	W/O	1.02	21.30	0.68	15.30	[54]
MAPbI_xCl_3–x/Spiro-OMeTAD	Pyridine	W	0.95	20.70	0.68	13.10	[54]
MAPbI_xCl_3–x/Spiro-OMeTAD	Pyridine	W/O	1.05	24.10	0.72	16.50	[54]
MAPbI₃/Spiro-OMeTAD	V-pyridine	W	1.15	22.00	0.73	9.50	[55]
MAPbI₃/Spiro-OMeTAD	V-pyridine	W/O	0.80	19.20	0.63	18.50	[55]
MAPbI₃/Spiro-OMeTAD	F4TCNQ	W	1.04	19.40	0.70	15.30	[56]
MAPbI₃/Spiro-OMeTAD	F4TCNQ	W/O	1.06	20.30	0.75	18.10	[56]
MAPbI₃/Spiro-OMeTAD	ZnPc	W	1.09	23.23	0.77	19.56	[65]
MAPbI₃/Spiro-OMeTAD	ZnPc	W/O	1.08	22.93	0.76	18.83	[65]
MAPbI₃/Spiro-OMeTAD	TAP	W	1.05	23.49	0.75	18.51	[66]
MAPbI₃/Spiro-OMeTAD	TAP	W/O	0.99	22.09	0.71	15.53	[66]

下载: 导出CSV

map

[1]	Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050 Google Scholar
[2]	NREL https://www.nrel.gov/pv/assets/pdfs/best-reserch-cell-efficiencies.pdf [2019-03-31]
[3]	Christians J A, Schulz P, Tinkham J S, Schloemer T H, Harvey S P, Tremolet de Villers B J, Sellinger A, Berry J J, Luther J M 2018 Nat. Energy 3 68 Google Scholar
[4]	Wu Y, Xie F, Chen H, Yang X, Su H, Cai M, Zhou Z, Noda T, Han L 2017 Adv. Mater. 29 1701073 Google Scholar
[5]	Lin Y, Bai Y, Fang Y, Chen Z, Yang S, Zheng X, Tang S, Liu Y, Zhao J, Huang J 2018 J. Phys. Chem. Lett. 9 654 Google Scholar
[6]	Ball J M, Petrozza A 2016 Nat. Energy 1 16149 Google Scholar
[7]	Meggiolaro D, Mosconi E, De Angelis F 2017 ACS Energy Lett. 2 2794 Google Scholar
[8]	Kieslich G, Sun S, Cheetham A K 2014 Chem. Sci. 5 4712 Google Scholar
[9]	Travis W, Glover E N K, Bronstein H, Scanlon D O, Palgrave R G 2016 Chem. Sci. 7 4548 Google Scholar
[10]	Cai B, Xing Y, Yang Z, Zhang W H, Qiu J 2013 Energy Environ. Sci. 6 1480 Google Scholar
[11]	Xing G, Mathews N, Lim S S, Yantara N, Liu X, Sabba D, Grätzel M, Mhaisalkar S, Sum T C 2014 Nat. Mater. 13 476 Google Scholar
[12]	Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341 Google Scholar
[13]	Chen B, Bai Y, Yu Z, Li T, Zheng X, Dong Q, Shen L, Boccard M, Gruverman A, Holman Z, Huang J 2016 Adv. Energy Mater. 6 1601128 Google Scholar
[14]	Sahli F, Werner J, Kamino B A, et al. 2018 Nat. Mater. 17 820 Google Scholar
[15]	Bush K A, Palmstrom A F, Yu Z J, et al. 2017 Nat. Energy 2 17009 Google Scholar
[16]	Li B, Ferguson V, Silva S R P, Zhang W 2018 Adv. Mater. Interfaces 5 1800326 Google Scholar
[17]	Liu N, Yam C 2018 Phys. Chem. Chem. Phys. 20 6800 Google Scholar
[18]	Yin W J, Shi T, Yan Y 2014 Appl. Phys. Lett. 104 063903 Google Scholar
[19]	Li W, Liu J, Bai F Q, Zhang H X, Prezhdo O V 2017 ACS Energy Lett. 2 1270 Google Scholar
[20]	Xiao Z, Yuan Y, Wang Q, Shao Y, Bai Y, Deng Y, Dong Q, Hu M, Bi C, Huang J 2016 Materials Science and Engineering R 101 1 Google Scholar
[21]	Sherkar T S, Momblona C, Gil-Escrig L, Ávila J, Sessolo M, Bolink H J, Koster L J A 2017 ACS Energy Lett. 2 1214 Google Scholar
[22]	Queisser H J, Haller E E 1998 Science 281 945 Google Scholar
[23]	Shao Y, Xiao Z, Bi C, Yuan Y, Huang J 2014 Nat. Commun. 5 5784 Google Scholar
[24]	Collins J 2015 ECS J. Solid State Sci. Technol. 5 R3170
[25]	Ran C, Xu J, Gao W, Huang C, Dou S 2018 Chem. Soc. Rev. 47 4581 Google Scholar
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