无机材料学报 ›› 2023, Vol. 38 ›› Issue (9): 1089-1096.DOI: 10.15541/jim20220710
所属专题: 【能源环境】钙钛矿(202310); 【能源环境】太阳能电池(202310)
代晓栋1,2(), 张露伟2, 钱奕成2, 任智鑫2, 曹焕奇2(
), 印寿根2
收稿日期:
2022-11-28
修回日期:
2023-01-27
出版日期:
2023-09-20
网络出版日期:
2023-04-15
通讯作者:
曹焕奇, 教授. E-mail: caoh@tjut.edu.cn作者简介:
代晓栋(1996-), 男, 硕士研究生. E-mail: 1021385583@qq.com
基金资助:
DAI Xiaodong1,2(), ZHANG Luwei2, QIAN Yicheng2, REN Zhixin2, CAO Huanqi2(
), YIN Shougen2
Received:
2022-11-28
Revised:
2023-01-27
Published:
2023-09-20
Online:
2023-04-15
Contact:
CAO Huanqi, professor. E-mail: caoh@tjut.edu.cnAbout author:
DAI Xiaodong (1996-), male, Master candidate. E-mail: 1021385583@qq.com
Supported by:
摘要:
带隙1.1~1.4 eV的锡铅混合卤化物钙钛矿是单结太阳能电池光电转换效率(PCE)接近Shockley-Queisser (S-Q)理论效率极限值的理想材料。钙钛矿薄膜垂直方向上的化学组分梯度会通过影响能带结构影响载流子的传输和分离, 因此对锡铅混合钙钛矿薄膜的结晶过程进行控制十分重要。本研究发现使用不同剂量的反溶剂制备锡铅混合钙钛矿会形成不同的垂直组分梯度, 并且随反溶剂用量增大薄膜表面铅含量增加。调整溶剂组分可以控制锡铅混合钙钛矿的垂直组分梯度, 增大溶剂中V(DMSO):V(DMF)可以形成底部富铅而表面富锡的垂直组分梯度。当铅基前驱液溶剂中V(DMSO):V(DMF)最优化为1 : 2时, 相比于1 : 4的对照组, 器件在标准光照条件下的开路电压从0.725 V提高到0.769 V, 短路电流密度从30.95 mA·cm-2提高到31.65 mA·cm-2, PCE从16.22%提升到接近18%。利用SCAPS软件数值模拟进一步证明了垂直组分梯度的必要性, 当钙钛矿薄膜底部富铅、顶部富锡时, 载流子在空穴传输层界面区域的复合有所减少, 因而电池性能得到提升。
中图分类号:
代晓栋, 张露伟, 钱奕成, 任智鑫, 曹焕奇, 印寿根. 锡铅混合钙钛矿太阳能电池垂直组分梯度的溶剂工程调控[J]. 无机材料学报, 2023, 38(9): 1089-1096.
DAI Xiaodong, ZHANG Luwei, QIAN Yicheng, REN Zhixin, CAO Huanqi, YIN Shougen. Controlling Vertical Composition Gradients in Sn-Pb Mixed Perovskite Solar Cells via Solvent Engineering[J]. Journal of Inorganic Materials, 2023, 38(9): 1089-1096.
图1 不同反溶剂乙酸乙酯用量制备钙钛矿薄膜的晶体结构
Fig. 1 Crystal structures of perovskite films prepared with different amounts of antisolvent (a) XRD patterns of perovskite films prepared with different amounts of antisolvent; (b) Magnified XRD patterns of (100) lattice plane diffraction peaks; (c) Half-peak width of (100) lattice plane diffraction peaks of thin films at different antisolvent dosages; (d-f) Top-down SEM images of films prepared by 100, 300 and 500 μL antisolvents and statistics of grain sizes
图2 (a) PF-DMSO0.25正面和背面的PL谱图; (b) PF-DMSO0.25对应的PSCs的横截面SEM照片及EDS面扫分析区域; (c) PF-DMSO0.25或PF-DMSO0.50的SEM截面照片中不同深度区域的铅锡元素比
Fig. 2 (a) PL spectra from the front and back sides of PF-DMSO0.25; (b) Cross-sectional SEM images of PSCs of PF-DMSO0.25 and EDS scanning areas; (c) Lead/tin elemental ratios in different depth regions of the cross-sectional SEM images of PF-DMSO0.25 or PF-DMSO0.50; Colorful figures are available on website
图3 PF-DMSOx的物相结构和光电性能
Fig. 3 Phase structure and photoelectric properties of perovskites films PF-DMSOx (a) XRD patterns of films and (b) PCE statistics of devices; (c) Time-resolved photoluminescence spectra; (d) Tauc plots of ultraviolet-visible absorption spectra and (e) ultraviolet photoelectron spectra of PF-DMSO0.50 and PF-DMSO0.25; (f) Energy level relationship, (g) J-V curves, (h) external quantum efficiency and integrated current density, (i) Urbach band edge absorption obtained from EQE spectra and fitted electroluminescence spectra of devices fabricated with PF-DMSO0.50 and PF-DMSO0.25; Colorful figures are available on website
Ingredient | Thickness/μm | Eg/eV | χ/eV | εr | Nc/cm-3 | Nv/cm-3 | μn/(cm2∙ V-1∙s-1) | μp/(cm2∙ V-1∙s-1) | Nd/cm-3 | Na/cm-3 | Nt/cm-3 | Ref. |
---|---|---|---|---|---|---|---|---|---|---|---|---|
PEDOT: PSS | 0.03 | 2.2 | 3 | 3 | 2.2×1015 | 1.8×1018 | 0.02 | 0.0002 | - | 3.17×1014 | 1×1015 | [ |
Perovskite | 0.6 | 1.25-1.23 | 4.15-4.2 | 100 | 1.0×1018 | 1.0×1018 | 2 | 2 | - | 1.0×1018 | 2.5×1016 | [ |
PCBM | 0.05 | 2.0 | 3.9 | 3.9 | 2.5×1021 | 2.5×1020 | 0.2 | 0.2 | 2.93×1017 | - | 1×1015 | [ |
BCP | 0.01 | 3.5 | 3.7 | 10 | 1.8×1018 | 2.2×1018 | 0.02 | 0.002 | 1×1021 | 1×1010 | 1×10 | [ |
表1 钙钛矿太阳能电池各层结构主要模拟参数
Table 1 Main simulation parameters of perovskite solar cell structures
Ingredient | Thickness/μm | Eg/eV | χ/eV | εr | Nc/cm-3 | Nv/cm-3 | μn/(cm2∙ V-1∙s-1) | μp/(cm2∙ V-1∙s-1) | Nd/cm-3 | Na/cm-3 | Nt/cm-3 | Ref. |
---|---|---|---|---|---|---|---|---|---|---|---|---|
PEDOT: PSS | 0.03 | 2.2 | 3 | 3 | 2.2×1015 | 1.8×1018 | 0.02 | 0.0002 | - | 3.17×1014 | 1×1015 | [ |
Perovskite | 0.6 | 1.25-1.23 | 4.15-4.2 | 100 | 1.0×1018 | 1.0×1018 | 2 | 2 | - | 1.0×1018 | 2.5×1016 | [ |
PCBM | 0.05 | 2.0 | 3.9 | 3.9 | 2.5×1021 | 2.5×1020 | 0.2 | 0.2 | 2.93×1017 | - | 1×1015 | [ |
BCP | 0.01 | 3.5 | 3.7 | 10 | 1.8×1018 | 2.2×1018 | 0.02 | 0.002 | 1×1021 | 1×1010 | 1×10 | [ |
图4 数值模拟顺梯度(NG)、无梯度(WO)和逆梯度(IG)异质结结构器件性能
Fig. 4 Numerical simulation of devices with NG, WO, IG heterojunctions (a) Schematic diagram of the solar cell structures with different vertical composition gradients; (b) Positions of the conduction band, valence band, electron and hole quasi-Fermi levels, (c) electron and hole carrier concentrations, (d) J-V curves and (e) EQE curves; (f) Hole deep-level defect trapping probabilities of normal or inverted gradient devices; Colorful figures are available on website
图S2 (a~d) PF-DMSO0.50薄膜中, 区域1~4的EDS能谱图; (e~h) PF-DMSO0.25薄膜中, 区域1~4的EDS能谱图
Fig. S2 (a-d) EDS spectra of regions 1-4 of PF-DMSO0.50 film and (e-h) EDS spectra of regions 1-4 of PF-DMSO0.25 film
图S3 PF-DMSOx (x=0.20,0.25,0.33,0.50,1.00)对应器件的(a)开路电压, (b)填充因子和(c)短路电流密度统计图
Fig. S3 Statistical charts of (a) open-circuit voltage, (b) fill factor and (c) short-circuit current density for devices of PF-DMSOx (x=0.20,0.25,0.33,0.50,1.00)
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