Research progress on doping modified tin oxide electron transport layer in perovskite solar cells
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摘要: 自从制备出第一件钙钛矿太阳能电池器件以来,钙钛矿太阳能电池的光电转换效率已从3.8%飞跃至26.1%,是下一代商用太阳能电池的有力竞争者。近10年来,SnO2因其适宜的能带结构、较好的电子传输性能、简单的制备工艺以及良好的化学稳定性成为n-i-p型钙钛矿太阳能电池电子传输层材料的首选。虽然SnO2电子传输层优点众多,但还存在电子传输性能较差、传输层与钙钛矿层之间能级偏移、界面缺陷造成光生载流子大量损失以及成膜性能较差容易出现针孔等问题。鉴于此,本文总结了上述问题形成的主要原因,并通过金属离子掺杂、卤素离子掺杂、有机分子掺杂、纳米颗粒掺杂等不同溶液掺杂工艺研究结果的分析,阐明了不同掺杂工艺在解决溶液法SnO2薄膜缺陷以及在钙钛矿电池器件中应用的优点与缺点,并针对钙钛矿器件掺杂SnO2传输层性能优化做出展望。Abstract: Since the preparation of the first perovskite solar cell device, the photoelectric conversion efficiency of perovskite solar cells has jumped from 3.8% to 26.1%, making them a favorable competitor for the next generation of commercial solar cells. In the past decade, tin oxide has become the preferred electron transport layer material for n-i-p perovskite solar cells due to its suitable band structure, good electron transfer performance, simple preparation process, and good chemical stability. Although tin oxide electron transport layer has many advantages, there are still issues that need to be improved in terms of electron transport performance, such as energy level shift between the transport layer and the perovskite layer, interface defects causing significant loss of photo generated carriers, and poor film-forming performance that is prone to pinholes. In view of this, this article summarizes the main reasons for the formation of the above problems, and analyzes the research results of different solution doping processes such as metal ion doping, halogen ion doping, organic molecule doping, and nanoparticle doping. It elucidates the advantages and disadvantages of different doping processes in solving the defects of solution based tin oxide thin films and their applications in perovskite battery devices, and makes prospects for optimizing the performance of doped tin oxide transport layers in perovskite devices.
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Key words:
- SnO2 /
- Perovskite solar cells /
- Doping /
- Interfacial defects /
- Energy level alignment
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图 7 (a) SnO2和(b) SnO2-Cl膜的SEM图像; (c) SnO2和(d) SnO2-Cl膜的AFM图像; (e) SnO2和SnO2-Cl薄膜的透射光谱 (f) SnO2和SnO2-Cl薄膜的吸收光谱; (g)单载流子器件的J-V特性曲线; (h)器件光电流的演变,偏置电压为0.8 V[79]
Figure 7. (a) SEM images of SnO2 and (b) SnO2-Cl films; (c) AFM images of SnO2 and (d) SnO2-Cl films; (e) Transmission spectra of SnO2 and SnO2-Cl films; (f) Absorption spectra of SnO2 and SnO2-Cl films; (g) J-V characteristic curve of single carrier devices; (h) Evolution of device photocurrent with bias voltage of 0.8 V [79]
图 9 (a)PAM改性SnO2的原理示意图。(b) SnO2、SnO2:PAM和PAM薄膜的XPS光谱。(c) 薄膜中锡元素的高分辨率XPS光谱。(d) SnO2和SnO2:PAM溶液的电势。[88]
Figure 9. Illustration of perovskite films on pristine SnO2 and PAM-modified SnO2. (b) XPS spectra for the SnO2, SnO2:PAM, and PAM films. (c) High-resolution XPS spectra for Sn in the films. (d) Potential of SnO2 and the SnO2:PAM solution.[88]
表 1 钙钛矿太阳能电池中常见金属氧化物电子传输层(ETL)的导带能级与体相迁移率
Table 1. The conduction band energy levels and bulk phase mobility of common metal oxide electron transport layers (ETL) in perovskite solar cells
表 2 SnO2电子传输层基钙钛矿太阳能电池中常见的添加剂及其对太阳能电池性能的贡献
Table 2. Dopants and their contribution to the improvement of PSCs based on SnO2 ETL.
Device Structure VOC/V JSC/(mA·cm−2) FF PCE/% ref FTO/SnO2/FAPbI3/spiro-OMeTAD/Au 1.144 21.43 0.752 19.69 [67] Nb-doped 1.157 22.77 0.747 20.47 ITO/SnO2/FAPbI3/spiro-OMeTAD/Au 1.158 21.65 0.777 19.48 [68] Ta-doped 1.161 22.79 0.786 2.80 FTO/SnO2/MAPbI3/spiro-OMeTAD/Au 1.000 16.80 0.530 9.02 [65] Al-doped 1.030 19.40 0.580 12.10 ITO/SnO2/(FAPbI3)0.95(MAPbBr3)0.05/spiro-OMeTAD/Au 1.060 24.80 0.66 17.30 [69] Zr-doped 1.080 25.30 0.72 19.54 FTO/SnO2/MAPbI3/spiro-OMeTAD/Au 1.030 18.60 0.610 11.69 [70] Y-doped 1.070 21.80 0.670 15.60 FTO/SnO2/CsFAMA/spiro-OMeTAD/Ag 1.078 23.20 0.771 19.43 [72] Cu-doped 1.108 24.20 0.790 21.35 AZO/SnO2/Csx(FAMA)100-x/spiro-OMeTAD/Au 0.997 22.10 0.570 12.50 [73] Ga-doped 1.070 22.80 0.786 22.80 FTO/SnO2/(FAPbI3)0.85(MAPbBr3)0.15/spiro-OMeTAD/Au 1.020 21.00 0.590 15.07 [79] Cl-doped 1.110 23.00 0.690 18.10 ITO/SnO2/(FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.05)3/spiro-MeOTAD/Au 1.060 24.46 0.759 19.72 [77] K-doped 1.080 24.47 0.769 20.40 Rb-doped 1.100 24.51 0.776 20.84 Cs-doped 1.060 24.37 0.802 20.64 ITO/SnO2/FA0.95MA0.05PbI3/spiro-OMeTAD/Au 1.060 23.23 0.708 17.43 [82] MES-doped 1.120 23.88 78.69 21.05 ITO/SnO2/FA0.95MA0.05PbI3/spiro-OMeTAD/Au 1.090 24.05 79.15 20.78 [83] DMAPAI2-doped 1.17 24.20 82.19 23.20 FTO/SnO2/(FAPbI3)0.96(MAPbBr3)0.04/spiro-OMeTAD/Au 1.136 24.89 0.811 22.92 [84] PC-doped 1.188 24.98 0.821 24.36 ITO/SnO2/CsFAMA/spiro-OMeTAD/Ag 1.070 21.80 0.740 18.74 [85] PEIE-doped 1.140 23.80 0.760 20.61 ITO/SnO2/Cs0.04FA0.74MA0.22/spiro-OMeTAD/Au 1.070 22.60 0.771 18.60 [87] PEG-doped 1.110 22.70 0.818 20.80 ITO/SnO2/FA0.95MA0.05PbI2.95Br0.05/spiro-OMeTAD/Au 1.103 23.16 0.792 20.22 [88] PAM-doped 1.122 24.82 0.811 22.59 ITO/SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/spiro-OMeTAD/Au 1.030 22.30 0.746 17.13 [91] RCQ-doped 1.140 23.30 0.826 22.51 ITO/SnO2/FA0.95MA0.05PbI3/PCBM/Au 1.125 22.93 0.743 19.17 [36] GYD-doped 1.137 23.32 0.796 21.11 Notes: Voc is the open circuit voltage; Jsc is the short-circuit current; PCE is the photoelectric conversion efficiency; FF is the fill factor; MES is the 4-morpholine ethane sulfonic acid sodium salt; DMAPAI2 is the N, N-dimethyl-1,3-propanediamine dihydroiodide; PC is the potassium citrate; PEIE is the polyethylenimine-ethoxylated; PEG is the polyethylene glycol; PAM is the polyacrylamide; RCQ is the red-carbon quantum dots; GYD is the graphdiyne. -
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