掺杂改性的氧化锡电子传输层在钙钛矿太阳能电池中研究进展

华鹏程; 李柯欣; 陈果; 曹进

掺杂改性的氧化锡电子传输层在钙钛矿太阳能电池中研究进展

上海大学　材料科学与工程学院上海 200072

基金项目: 国家重点研发计划项目(2022YFE0109000)

详细信息

通讯作者:
曹进，博士后，副研究员，硕士生导师，研究方向为有机发光二极管、钙钛矿太阳能电池等薄膜半导体器件　E-mail: cj2007@shu.edu.cn

中图分类号: TB332; TM914.4; TM23
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- HTML全文浏览量: 27
- 被引次数: 0
出版历程
- 收稿日期: 2024-04-15
- 修回日期: 2024-06-02
- 录用日期: 2024-06-17
- 网络出版日期: 2024-07-05

Research progress on doping modified tin oxide electron transport layer in perovskite solar cells

School of Materials Science and Engineering, ShangHai University, Shanghai, 200072, China

Funds: The State’s Key Project of Research and Development Plan (2022YFE0109000)

摘要

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。
- SnO₂ /
- 钙钛矿太阳能电池 /
- 掺杂工程 /
- 界面缺陷 /
- 能级排列
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.
- SnO₂ /
- Perovskite solar cells /
- Doping /
- Interfacial defects /
- Energy level alignment

HTML全文

图 1 金红石相氧化锡晶体结构^[40]

Figure 1. Crystal structure of rutile phase tin oxide^[40]

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图 2 (a) SnO₂中本征点缺陷形成能^[38]; (b) SnO₂中缺陷转变水平的示意图^[43](c) 60 nm膜厚的TiO₂与SnO₂膜与FTO衬底的透射光谱^[45]

Figure 2. (a) Eigenpoint defect formation energy in SnO₂ ^[38]; (b) Schematic diagram of defect transformation level in SnO₂^[43]; (c) Transmission spectra of 60 nm thick TiO₂ and SnO₂ films and FTO substrate^[45]

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图 3 氧化锡晶体中的常见缺陷^[43]

Figure 3. Common defects in tin oxide crystals ^[43]

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图 4 (a)能级悬崖结构; (b)能级尖峰结构^[54]

Figure 4. (a) Energy level cliff structure; (b) Energy level spike structure^[54]

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图 5 沉积在具有不同Nb含量的石英衬底上的SnO₂膜的(a)透射光谱，(b)紫外可见漫反射光谱，(c)迁移率，以及(d)的载流子浓度^[67]

Figure 5. (a) Transmission spectra, (b) UPS, (c) Mobility, and (d) Carrier concentrations of SnO₂ films deposited on quartz substrates with different Nb contents ^[67]

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图 6 (a)不同掺杂氧化锡的I-V特性; (b) 不同掺杂氧化锡的能级图^[77]

Figure 6. (a) I-V characteristics of different doped SnO₂; (b) Energy level diagrams of different doped SnO₂ ^[77]

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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SnO_2-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]

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图 8 (a) PL、PM和PC的PSCs结构和化学组成示意图; (b)本工作中SnO₂的原位钝化策略^[84]

Figure 8. (a) Schematic diagram of the structure and chemical composition of PSCs in PL, PM, and PC; (b) In situ passivation strategy of SnO₂ in this work^[84]

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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]

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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

ETL	CE/eV	Bulk mobility/cm²/(V·s)	ref
TiO₂	−4.1	0.15-4.1	[22]
ZnO	−4.2	80-150	[22]
WO₃	−4.2	10-20	[23]
SnO₂	−4.1	240	[22]
Cr₂O₃	−3.9	1	[24]
In₂O₃	−4.5	80-120	[25]
Nb₂O₅	−4	0.2	[16]
Notes: CE is the position of the inverted band energy level relative to the vacuum energy level.

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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	V_OC/V	J_SC/(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	[67]
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	[68]
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	[65]
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	[69]
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	[70]
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	[72]
AZO/SnO₂/Cs_x(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	[73]
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	[79]
ITO/SnO₂/(FA_0.98MA_0.02)_0.95Cs_0.05Pb(I_0.95Br_0.05)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/FA_0.95MA_0.05PbI₃/spiro-OMeTAD/Au	1.060	23.23	0.708	17.43	[82]
MES-doped	1.120	23.88	78.69	21.05	[82]
ITO/SnO₂/FA_0.95MA_0.05PbI₃/spiro-OMeTAD/Au	1.090	24.05	79.15	20.78	[83]
DMAPAI₂-doped	1.17	24.20	82.19	23.20	[83]
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	[84]
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	[85]
ITO/SnO₂/Cs_0.04FA_0.74MA_0.22/spiro-OMeTAD/Au	1.070	22.60	0.771	18.60	[87]
PEG-doped	1.110	22.70	0.818	20.80	[87]
ITO/SnO₂/FA_0.95MA_0.05PbI_2.95Br_0.05/spiro-OMeTAD/Au	1.103	23.16	0.792	20.22	[88]
PAM-doped	1.122	24.82	0.811	22.59	[88]
ITO/SnO₂/Cs_0.05(MA_0.17FA_0.83)_0.95Pb(I_0.83Br_0.17)₃/spiro-OMeTAD/Au	1.030	22.30	0.746	17.13	[91]
RCQ-doped	1.140	23.30	0.826	22.51	[91]
ITO/SnO₂/FA_0.95MA_0.05PbI₃/PCBM/Au	1.125	22.93	0.743	19.17	[36]
GYD-doped	1.137	23.32	0.796	21.11	[36]
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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