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甲胺铅碘(CH3NH3PbI3 MAPbI3)和甲脒铅碘(CH(NH2)2PbI3 FAPbI3)是目前最常用于太阳电池研究的有机铅碘钙钛矿材料. 对于层状结构的钙钛矿太阳电池来说, 每层薄膜的光学性质和厚度都影响着电池的光电转换效率. 本文利用光学导纳法和严格耦合波分析法计算了金属氧化物透明导电薄膜掺锡氧化铟(In2O3:Sn)、掺氟氧化锡(SnO2:F), TiO2, MAPbI3和FAPbI3的吸收率和透射率, 分析了各层厚度以及器件结构对电池短路电流密度的影响. 结果表明: 对于FTO(ITO)/TiO2/MAPbI3结构, FTO薄膜的厚度在50—450 nm, ITO厚度在10—150 nm时对入射光波长在360—800 nm的平均透射率为85%, 对于FTO(ITO)/TiO2/FAPbI3结构, FTO和ITO薄膜的厚度分别在50—250 nm和10—150 nm时对入射光波长在360—840 nm的平均透射率分别为81.6%和78%. 在FTO和TiO2最优厚度下, MAPbI3和FAPbI3的厚度从300—1000 nm变化时, 对应太阳电池短路电流密度分别在21.9—23.7 mA·cm–2和23.0—24.4 mA·cm–2范围. 本文的研究对于设计和制备高转换效率的钙钛矿太阳电池具有指导意义.Methylamine lead iodide (CH3NH3PbI3 MAPbI3) and formamidine lead iodide (CH(NH2)2PbI3 FAPbI3) are the most commonly used organic lead iodine perovskite materials for solar cell research. For the perovskite solar cell with a layered structure, the optical properties and thickness of each layer affect the photoelectric conversion efficiency of the cell. In this paper, the optical admittance method and rigorous coupled wave analysis method are used to calculate the absorptivities and transmittances of metal oxide transparent conductive films for tin-doped indium oxide (In2O3:Sn), fluorine-doped tin oxide (SnO2:F), TiO2, MAPbI3 and FAPbI3. The influence of each layer thickness and device structure on the short-circuit current density of the cell are analyzed. It is shown that for the FTO(ITO)/TiO2/MAPbI3 structure, when the thickness of the FTO film is 50–450 nm and the thickness of the ITO film is 10–150 nm, the average transmittance for the 360–800 nm wavelength light is 85%. For the FTO(ITO)/TiO2/FAPbI3 structure, when the thickness of the FTO film and ITO film are 50–250 nm and 10–150 nm, respectively, the average values of the transmittance for the 360-840 nm wavelength light are 81.6% and 78%, respectively. Under the optimal thickness of FTO and TiO2, and the thickness of MAPbI3 and FAPbI3 are 300–1000 nm, the corresponding short-circuit current densities are in a range of 21.9–23.7 and 23.0–24.4 mA·cm–2, respectively. The band gap of MAPbI3 and FAPbI3 are 1.56 and 1.48 eV, for which the corresponding absorption cut-off wavelengths are 796 and 840 nm, respectively, indicating that FAPbI3 has a wider absorption spectrum than MAPbI3. In order to maximize the Jsc value of the organic lead iodine perovskite solar cell, the thickness range of each layer for MAPbI3 perovskite solar cell (FTO thickness is (80 ± 50) nm, ITO thickness is less than 120 nm, MAPbI3 thicknessis 300–600 nm) and for FAPbI3 perovskite solar cell (FTO thickness is (120 ± 50) nm, ITO thickness is less than 180 nm, FAPbI3 thickness is 300–600 nm) are given. The research results of this article have guiding significance in designing and preparing the perovskite solar cells with high conversion efficiency.
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Keywords:
- perovskite solar cell /
- photoelectric properties /
- optical-admittance method /
- rigorous coupled-wave analysis method
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图 4 (a) 文献[21, 29]中报道的由Gass/FTO/TiO2/MAPbI3(FAPbI3)/piro-OMeTAD/Au组成的MAPbI3和FAPbI3太阳电池的光学模型; (b) 光学导纳法和严格耦合波分析法计算MAPbI3 = 400 nm的吸收率; (c) MAPbI3太阳电池各层吸收率和外量子效率; (d) FAPbI3和MAPbI3 = 590 nm的吸收率; (e) 外量子效率和对应的积分电流密度; (f) J-V曲线
Fig. 4. (a) Optical model constructed for a MAPbI3 and FAPbI3 solar cell consisting of Gass/FTO/TiO2/MAPbI3(FAPbI3)/piro-OMeTAD/Au reported in Ref.[21, 29]; (b) calculation absorption coefficient of the optical admittance method and rigorous coupled-wave analysis method; (c) calculated A spectra of the component layers and EQE spectrum for theMAPbI3 solar cell; (d) absorption coefficient of FAPbI3 and MAPbI3 = 590 nm; (e) the integrated photocurrents calculated from the overlap integral of the EQE spectra with the AM1.5 G solar emission are also shown; (f) J-V curves.
图 5 (a) FTO和(b) ITO的透射率随厚度变化图; 电池的短路电流密度随(c) FTO和MAPbI3以及(d) ITO和MAPbI3厚度变化图; (e) 钙钛矿太阳电池的吸收光谱; (f) 积分电流密度随MAPbI3厚度变化
Fig. 5. Transmittance spectra of (a)FTO and (b)ITO; variations of short circuit current density with (c) FTO and MAPbI3, and (d) ITO and MAPbI3 thickness; (e) absorptance spectrum of the MAPbI3 solar cell; (f) changes in the relationship of the integrated Jsc with MAPbI3 thickness.
图 6 (a) FTO和(b) ITO的透射率随厚度变化图; 电池的短路电流密度随(c) FTO和FAPbI3以及(d) ITO和FAPbI3厚度的变化图; (e) 钙钛矿太阳电池的吸收光谱; (f) 积分电流密度随FAPbI3厚度变化
Fig. 6. Transmittance spectra of (a) FTO and (b) ITO; variations of short circuit current density with (c) FTO and FAPbI3 and (d) ITO and FAPbI3 thickness; (e) absorptance spectrum of the FAPbI3 solar cell; (f) changes in the relationship of the integrated Jsc with FAPbI3 thickness
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[1] Liu W, Liu N J, Ji S L, Hua H F, Ma Y H, Hu R Y, Zhang J, Chu L, Li X A, Huang W 2020 Nano-Micro Lett. 12 119
Google Scholar
[2] Chen H Y, Zhan Y, Xu C Y, Chen W J, Wang S H, Zhang M Y, Li Y W, Li Y F 2020 Adv. Funct. Mater. 30 2001788
Google Scholar
[3] Li N X, Luo Y Q, Chen Z H, Niu X X, Zhang X, Lu J Z, Kumar R S, Jiang J K, Liu H F, Guo X, Lai B, Brocks G, Chen Q, Tao S X, Fenning D P, Zhou H P 2020 Joule 4 1
Google Scholar
[4] Yi C Y, Luo J S, Meloni S, Boziki A, Astani N A, Gratzel C, Zakeeruddin S M, Rothlisberger U, Gratzel M 2016 Energy Environ. Sci. 9 656
Google Scholar
[5] Huang Y, Li L, Liu Z H, Jiao H Y, He Y Q, Wang X G, Zhu R, Wang D, Sun J L, Chen Q, Zhou H P 2017 J. Mater. Chem. A 5 8537
Google Scholar
[6] Li N X, Tao S X, Chen Y H, Niu X X, Onwudinanti C K, Hu C, Qiu Z W, Xu Z Q, Zheng G H J, Wang L G, Zhang Y, Li L, Liu H F, Lun Y Z, Hong J W, Wang X Y, Liu Y Q, Xie H P, Gao Y L, Bai Y, Yang S H, Brocks G, Chen Q, Zhou H P 2019 Nat. Energy 4 408
Google Scholar
[7] Lu H Z, Liu Y H, Ahlawat P, Mishra A, Tress W R, Eickemeyer F T, Yang Y G, Fu F, Wang Z W, Avalos C E, Carlsen B I, Agarwalla A, Zhang X, Li X G, Zhan Y Q, Zakeeruddin S M, Emsley L, Rothlisberger U, Zheng L R, Hagfeldt A, Gratzel M 2020 Science 370 1
[8] Yee K S 1966 IEEE Trans. Antennas Propag. 17 585
[9] Sarkar S, Gupta V, Kumar M, Schubert J, Probst P T, Joseph J, Konig T A F 2019 ACS Appl. Mater. Interfaces 11 13752
Google Scholar
[10] Berning J A, Berning P H 1960 J. Opt. Soc. Am. 50 813
Google Scholar
[11] Darkwi A Y, Loke W K, Ibrahim K S 2000 Energy Mater. Sol. Cells 60 1
Google Scholar
[12] Nakane A, Tampo H, Tamakoshi M, Fujimoto S, Kim K M, Kim S, Shibata H, Niki S, Fujiwara H 2016 J. Appl. Phys. 120 064505
Google Scholar
[13] Young M, Traverse C J, Pandey R, Barr M C, Lunt R R 2013 Appl. Phys. Lett. 103 133304
Google Scholar
[14] Ball J M, Stranks S D, Horantner M T, SHuttner S, Zhang W, Crossland E J W, Ramirez I, Riede M, Johnston M B, Friend R H, Snaith J H 2015 Energy Environ. Sci. 8 602
Google Scholar
[15] Bush K A, Palmstrom A F, Yu Z S J, Boccard M, Cheacharoen R, Mailoa J P, McMeekin D P, Hoye R L Z, Bailie C D, Leijtens T, Peters I M, Minichetti M C, Rollston N, Prasanna R, Sofia S, Harwood D, Ma W, Moghadam F, Snaith H J, Buonassisi T, Holman Z C, Bent S F, McGehee M D 2017 Nat. Energy 2 17009
Google Scholar
[16] Hsue Y C, Freeman A, Gu B Y 2005 Phys. Rev. B 72 195118
Google Scholar
[17] Moharam M G, Grann E B, Pommet D A, Gaylord T K 1995 J. Opt. Soc. Am. A 12 1068
Google Scholar
[18] Li L F 1996 J. Opt. Soc. Am. A 13 1870
Google Scholar
[19] Lyndin N M, Parriaux O, Tishchenko A V 2007 J. Opt. Soc. Am. A 24 3781
Google Scholar
[20] Dewan R, Vasilev I, Jovanov V, Knipp D 2011 J. Appl. Phys. 110 013101
Google Scholar
[21] Yang W S, Noh J H, Jeon N J, Kim Y C, Ryu S, Seo J, Seok S I 2015 Science 348 1234
Google Scholar
[22] Pham N D, Zhang C M, Tiong V T, Zhang S L, Will G, Bou A, Bisquert J, Shaw P E, Du A J, Wilson G J, Wang H X 2019 Adv. Funct. Mater. 29 1806479
Google Scholar
[23] 张晨, 张海玉, 郝会颖, 董敬敬, 邢杰, 刘昊, 石磊, 仲婷婷, 唐坤鹏, 徐翔 2020 物理学报 69 178101
Google Scholar
Zhang C, Zhang H Y, Hao H Y, Dong J J, Xing J, Liu H, Shi L, Zhong T T, Tang K P, Xu X 2020 Acta Phys. Sin. 69 178101
Google Scholar
[24] Tavakoli M M, Yadav P, Tavakoli R, Kong J 2018 Adv. Energy Mater. 8 1800794
Google Scholar
[25] Lin R X, Xiao K, Qin Z Y, Han Q L, Zhang C F, Wei M Y, Saidaminov M I, Gao Y, Xu J, Xiao M, Li A D, Zhu J, Sargent E H, Tan H R 2019 Nat. Energy 4 864
Google Scholar
[26] Jeong M Y, Choi I W, Go E M, Cho Y J, Kim M J, Lee B K, Jeong S H, Jo Y Y, Choi H W, Lee J Y, Bae J H, Kwak S K, Kim D S, Yang C D 2020 Science 369 1615
Google Scholar
[27] 毕富珍, 郑晓, 任志勇 2019 物理化学学报 35 69
Google Scholar
Bi F Z, Zheng X, Reng Z Y 2019 Acta Phys.-Chim. Sin. 35 69
Google Scholar
[28] Barraud L, Holman Z C, Badel N, Reiss P, Descoeudres A, Battaglia C, Wolf S D, Ballif C 2013 Sol. Energy Mater. Sol. Cells 115 151
Google Scholar
[29] Shirayama M, Kadowaki H, Miyadera M, Sugita T, Tamakoshi M, Kato M, Fujiseki T, Murata D, Hara S, Murakami T N, Fujimoto S, Chikamatsu M, Fujiwara H 2016 Phys. Rev. Appl. 5 014012
Google Scholar
[30] Rodríguez-de Marcos L V, Larruquert J I, Méndez J A, Aznárez J A 2017 Opt. Mater. Express 7 989
Google Scholar
[31] Sarkar S, Gupta V, Kumar M, Schubert J, Probst P T, Joseph J, König T A F 2019 ACS Applied Material Interfaces 11 13752
[32] Ball J M, Stranks S D, Horantner M T, SHuttner S, Zhang W, Crossland E J W, Ramirez I, Riede M, Johnston M B, Friend R H, Snaith J H 2015 Energy and Environ. Sci. 8 602
[33] 卢辉东, 韩红静, 刘杰 2021 物理学报 70 036301
Google Scholar
Lu H D, Han H J, Liu J 2021 Acta Phys. Sin. 70 036301
Google Scholar
[34] Rosenblatt G, Simkhovich B, Bartal G, Orenstein M 2020 Phys. Rev. X 10 011071
[35] Baikie T, Fang Y, Kadro J M, Schreyer M, Wei F, Mhaisalkar S G, Gratzel M and White T J 2013 J. Mater. Chem. A 1 5628
Google Scholar
[36] Eperon G E, Stranks S D, Menelaou C, Johnston M B, Herz L M, Snaith H J 2014 Energy Environ 7 982
Google Scholar
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