银纳米相吸收增强型钙钛矿太阳电池薄膜的制备及性能研究

doi:10.15541/jim20160041

摘要/Abstract

摘要：

分别将银纳米相溶胶(银纳米颗粒、Ag@SiO₂核壳结构、银纳米线)掺入氧化铝异丙醇溶液中制成具有蜂窝结构的介孔层材料, 然后在介孔层表面制备CH₃NH₃PbI₃钙钛矿吸收层得到Al₂O₃/CH₃NH₃PbI₃复合薄膜, 并对复合膜的微观结构、光吸收特性及太阳电池器件性能进行了测试和分析。研究表明, Al₂O₃/CH₃NH₃PbI₃复合膜与CH₃NH₃PbI₃在可见光区域吸收光谱基本相同, 含量极少的Al₂O₃对CH₃NH₃PbI₃吸光性能影响较小。而掺入银纳米相可明显改善CH₃NH₃PbI₃钙钛矿薄膜的吸收性能。当银纳米颗粒、Ag@SiO₂核壳结构和银纳米线相对浓度比分别为0.15、0.3及0.15时, CH₃NH₃PbI₃吸光性能分别达到最佳; 银纳米相浓度继续增大时, 薄膜的光吸收性能逐渐减弱。此外, 掺入Ag@SiO₂核壳结构可使钙钛矿薄膜太阳电池光电转换效率由6.28%增大到7.09%, 而银纳米颗粒和银纳米线由于会增大太阳电池内部载流子传输路径, 提高电子空穴对复合效率, 最终反而降低了太阳电池短路电流密度和光电转换效率。

关键词: 银纳米相, 钙钛矿, 太阳电池, 吸收性能

Abstract:

Silver nanostructures (Ag nanoparticles, Ag@SiO₂ core-shell nanoparticles & Ag nanowires) were firstly added into aluminum oxide isopropanol solution to form cellular Al₂O₃mesoporous layers for perovskite solar cell applications, respectively. Then CH₃NH₃PbI₃organic-inorganic hybrid perovskites were fabricated and attached to this matrix. Absorption spectra of Al₂O₃/CH₃NH₃PbI₃ composite and CH₃NH₃PbI₃were found to be basically the same in the visible region, indicating that Al₂O₃ had less impact on the absorption performance of CH₃NH₃PbI₃. However, the incorporation of silver nanostructures could significantly improve the absorption properties of the perovskites, and the best performance could be achieved with the concentration ratios of Ag nanoparticles, Ag@SiO₂ core-shell nanoparticles and Ag nanowires of 0.15, 0.3 and 0.15, respectively. Further increasing the concentration of silver incorporation would probably cause halogenation and reduce the absorption properties of CH₃NH₃PbI₃. In addition, the efficiency of perovskite solar cell could be improved from original 6.28% to 7.09% after addition of Ag@SiO₂ core-shell nanoparticles. In contrast, the incorporation of Ag nanoparticles & nanowires tended to reduce the short circuit current density and conversion efficiency of the fabricated solar cells, because they could prolong the internal carrier transport path and hence increase the recombination probability of the electron-hole pairs.

Key words: silver nanostructures, perovskite, solar cell, absorption property

中图分类号:

TB303

檀满林, 马东超, 符冬菊, 马清, 李冬霜, 王晓伟, 张维丽, 陈建军, 张化宇. 银纳米相吸收增强型钙钛矿太阳电池薄膜的制备及性能研究[J]. 无机材料学报, 2016, 31(9): 908-914.

TAN Man-Lin, MA Dong-Cao, FU Dong-Ju, MA Qing, LI Dong-Shuang, WANG Xiao-Wei, ZHANG Wei-Li, CHEN Jian-Jun, ZHANG Hua-Yu. Properties of Silver Nanostructures Incorporated Perovskite Based Thin Films for Solar Cell Applications[J]. Journal of Inorganic Materials, 2016, 31(9): 908-914.

图/表 11

图1 银纳米相的SEM和TEM照片

Fig. 1 SEM & TEM image of silver nanostructures(a) Ag nanoparticles; (b) Ag@SiO2 core-shell structure; (c) Ag nanowires

图2 Al2O3/CH3NH3PbI3薄膜的(a)表面和(b)截面的SEM照片

Fig. 2 Surface (a) and cross-section (b) SEM images of Al2O3/CH3NH3PbI3 film

图3 Al2O3/CH3NH3PbI3复合薄膜XRD图谱

Fig. 3 XRD patterns of Al2O3/CH3NH3PbI3 composite

图4 Al2O3/CH3NH3PbI3复合薄膜和CH3NH3PbI3薄膜的吸收光谱和光学带隙

Fig. 4 Ultraviolet-visible absorption spectra and optical band gap of Al2O3/CH3NH3PbI3 composite film and CH3NH3PbI3 film

图5 掺入不同浓度银纳米颗粒的Al2O3/CH3NH3PbI3钙钛矿复合薄膜紫外可见光吸收光谱

Fig. 5 Ultraviolet-visible absorption spectra of Al2O3/ CH3NH3PbI3 doped with different contents of Ag nanoparticles(a) 0; (b) 0.05; (c) 0.10; (d) 0.15; (e) 0.20; (f) 0.25; (g) 0.30

图6 Ag@SiO2核壳结构的XRD图谱

Fig. 6 XRD patterns of Ag@SiO2 core-shell structure

图7 掺入不同浓度Ag@SiO2核壳结构的Al2O3/CH3NH3PbI3钙钛矿复合薄膜紫外可见光吸收光谱

Fig. 7 Ultraviolet-visible absorption spectra of Al2O3/CH3NH3PbI3 doped with different contents of Ag@SiO2 core-shell structure(a) 0; (b) 0.05; (c) 0.10; (d) 0.15; (e) 0.20; (f) 0.25; (g) 0.30

图8 掺入不同浓度银纳米线的Al2O3/CH3NH3PbI3钙钛矿复合薄膜紫外可见光吸收光谱

Fig. 8 Ultraviolet-visible absorption spectra of Al2O3/CH3NH3PbI3 doped with different contents of Ag nanowires(a) 0; (b) 0.05; (c) 0.10; (d) 0.15; (e) 0.20; (f) 0.25; (g) 0.30

图9 掺入不同银纳米相的CH3NH3PbI3钙钛矿太阳电池的J-V曲线

Fig. 9 J-V curves of CH3NH3PbI3 Perovskite solar cell with the incorporation of silver nanostructures(a) No doping; (b) Ag@SiO2; (c) Ag nanoparticles; (d) Ag nanowires

表1 CH3NH3PbI3钙钛矿太阳电池样品性能参数

Table 1 Parameters of CH3NH3PbI3 Perovskite solar cells

Sample	V_oc/V	J_sc/ (mA·cm^-2)	FF	η/%
No doping	0.91	11.31	0.61	6.28
Ag@SiO₂	0.89	13.64	0.58	7.09
Ag nanoparticles	0.92	10.86	0.61	6.07
Ag nanowires	0.86	10.57	0.62	5.95

图10 银纳米相型CH3NH3PbI3钙钛矿薄膜光致发光谱

Fig. 10 Photoluminescence spectra of silver nanostructures incorporated CH3NH3PbI3 thin film

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