碳纳米管和二甲基亚砜对钙钛矿太阳电池中PEDOT:PSS空穴传输层的协同影响

doi:10.15541/jim20170380

摘要/Abstract

摘要：

聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)是平面结构钙钛矿太阳电池中空穴传输层的典型材料, 为了改善其导电性能以及促进后续钙钛矿层的生长, 本文将碳纳米管(CNTs)和二甲基亚砜(DMSO)同时引入PEDOT:PSS进行共修饰。结果表明: CNTs和DMSO在CNT-DMSO-PEDOT:PSS共修饰膜中展现了优异的协同效应。均匀贯穿于基体且几近网格状的CNTs具有促进后续钙钛矿层生长及降低共修饰膜方块电阻的功能; DMSO扮演着加强共修饰膜的导电能力及控制CNTs流失的角色。因此, 与单修饰膜相比, 共修饰膜不仅能更有效地传输电荷, 而且其表面生长的钙钛矿层晶粒尺寸更大, 覆盖率更高。此外, 共修饰膜在可见光范围内仍然保持优异的透光率, 550 nm波长处的透光率为88.8%。组装成器件后, 共修饰膜的光电转换效率(PCE)为5.75%, 远高于CNTs和DMSO单修饰膜及纯PEDOT:PSS膜, 后三者的PCE分别为3.01%、2.03%和1.30%。

关键词: 碳纳米管, 二甲基亚砜, PEDOT:PSS, 空穴传输层, 钙钛矿太阳电池

Abstract:

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film is commonly used as hole transport layer in planar perovskite solar cells (PSCs). To further strengthen the charge transport within PEDOT:PSS film and boost the growth of the perovskite crystal on PEDOT:PSS film, carbon nanotubes (CNTs) and dimethyl sulfoxide (DMSO) were simultaneously used as additives to prepare the co-modified film of CNT-DMSO-PEDOT:PSS. Results demonstrate an advantageous cooperative effect of CNTs and DMSO on the co-modified film. The dispersed CNTs with a grid-like structure throughout PEDOT:PSS matrix plays dual roles: to promote the perovskite crystal growth on co-modified surface and to reduce the sheet resistance of the co-modified film, while DMSO improves the conductivity of the co-modified film and controls the loss of CNTs from the co-modified film. Due to the cooperative effect, co-modified film is significantly more capable to collect, transport charges and enhance the perovskite layer growth with larger grains on its surface than that with pristine PEDOT:PSS film or PEDOT:PSS films modified by a single additive of CNT or DMSO, CNT-PEDOT:PSS or DMSO-PEDOT:PSS. Meanwhile, the co-modified film maintains high transparency with a transmittance of 88.8% at 550 nm. As a result, the PSCs of co-modified film has a hig power conversion efficiency of 5.75% in contrast to the devices based on the CNT-PEDOT:PSS (3.01%), DMSO-PEDOT:PSS (2.03%) and pristine PEDOT:PSS (1.30%) films.

Key words: carbon nanotubes, dimethyl sulfoxide, PEDOT:PSS, hole transport layer, perovskite solar cells

中图分类号:

TM914

徐顺建, 肖宗湖, 罗晓瑞, 钟炜, 罗永平, 欧惠. 碳纳米管和二甲基亚砜对钙钛矿太阳电池中PEDOT:PSS空穴传输层的协同影响[J]. 无机材料学报, 2018, 33(6): 641-647.

XU Shun-Jian, XIAO Zong-Hu, LUO Xiao-Rui, ZHONG Wei, LOU Yong-Ping, OU Hui. Cooperative Effect of Carbon Nanotubes and Dimethyl Sulfoxide on PEDOT:PSS Hole Transport Layer in Planar Perovskite Solar cells[J]. Journal of Inorganic Materials, 2018, 33(6): 641-647.

图/表 9

图1 PEDOT:PSS修饰膜的SEM和AFM照片

Fig. 1 SEM and AFM images of different PEDOT:PSS films.(a, d) DMSO-PEDOT:PSS; (b, e) CNT-PEDOT:PSS; (c, f) CNT-DMSO-PEDOT:PSS

图2 PEDOT:PSS修饰膜在可见光范围内的UV-Vis光谱图

Fig. 2 UV-Vis spectra of different PEDOT:PSS films in the visible range

图3 PEDOT:PSS薄膜的方块电阻

Fig. 3 Sheet resistances of (a) pristine PEDOT:PSS, (b) DMSO-PEDOT:PSS, (c) CNT-PEDOT:PSS, and (d) CNT-DMSO- PEDOT:PSS films on ITO substrates

图4 共修饰膜和纯PEDOT:PSS膜的FT-IR谱图

Fig. 4 FT-IR spectra of CNT-DMSO-PEDOT:PSS co-modified film and pristine PEDOT:PSS film

图5 CH3NH3PbI3钙钛矿层的AFM照片和晶粒尺寸分布图

Fig. 5 AFM images and grain size distributions of CH3NH3PbI3 perovskite layers deposited on different PEDOT:PSS films(a) DMSO-PEDOT:PSS; (b) CNT-PEDOT:PSS; (c) CNT- DMSO-PEDOT:PSS

图6 PEDOT:PSS修饰膜组装的最优器件的J-V曲线

Fig. 6 J-V curves of best PSCs consisting of different PEDOT:PSS films as hole transport layers

图7 PEDOT:PSS修饰膜组装的器件的平均光电转换效率

Fig.7 Statistic PCE of PSCs employing the hole transport layers of (a) pristine PEDOT:PSS, (b) DMSO-PEDOT:PSS, (c) CNT-PEDOT:PSS and (d) CNT-DMSO-PEDOT:PSS

表1 PEDOT:PSS修饰膜组装的器件的最佳光电性能

Table 1 Best photovoltaic performances of PSCs employing various PEDOT:PSS films as hole transport layers

HTL	J_sc/(mA∙cm^-2)	V_oc/V	FF	PCE/%
Pristine PEDOT:PSS	6.67	0.60	0.32	1.30
DMSO-PEDOT:PSS	13.49	0.51	0.30	2.03
CNT-PEDOT:PSS	14.71	0.61	0.34	3.01
Co-modified film	15.63	0.77	0.48	5.75

图8 CNT-DMSO-PEDOT:PSS共修饰膜的UPS谱图

Fig. 8 UPS spectrum of CNT-DMSO-PEDOT:PSS co-modified film with insert showing energy band diagram of device employing PEDOT:PSS hole transport layer

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