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有机-无机卤化钙钛矿材料因具有优异的光电性质而被广泛应用于太阳电池中, 然而材料及器件的稳定性及含铅问题却严重制约其生产发展. 与杂化钙钛矿相比, 无机非铅钙钛矿Cs3Bi2I9因具有更强的稳定性和环境友好性受到人们的广泛关注. Cs3Bi2I9具有单斜、三角和六方3种晶型, 目前, 对Cs3Bi2I9的理论和实验研究主要集中在六方相. 本文基于密度泛函理论的第一性原理对Cs3Bi2I9单斜、三角和六方相的电子性质、载流子有效质量(
$m^* $ )、稳定性和光学性质进行了理论研究. 结果表明, 3种晶相具有相近的稳定性, 三角相因具有较小的直接带隙(1.21 eV)性质成为最具研究潜力的对象. 3种晶相的$m^* $ 均具有沿a, b方向相同和沿c方向不同的特点, 三角相的电子有效质量最小、且沿a方向的电子有效质量小于c方向. 相比单斜和六方相, 三角相Cs3Bi2I9的光学性质均发生红移现象、具有更优异的光吸收性能. 此外, 3种晶相的光学性质也表现出沿a, b方向相同和沿c方向不同的性质, 且沿a方向的光吸收性能优于c方向. 因此, 对于Cs3Bi2I9钙钛矿, 期待三角晶相沿a方向在光电子器件方面有较好的贡献.Organic-inorganic halide perovskite materials are widely used in solar cells because of their excellent photoelectric properties. However, the stability and lead toxicity problems associated with materials and devices have restrict their production and development. Compared with the hybrid perovskite, the inorganic lead-free perovskite Cs3Bi2I9 has attracted wide attention because of its stronger stability and environmental friendliness. The Cs3Bi2I9 has three crystal types: monoclinic type, trigonal type, and hexagonal type. At present, the researches of Cs3Bi2I9 focus mainly on the hexagonal phase. In this paper, based on the first principles of density functional theory, the electronic properties, carrier effective mass values, stabilities, and optical properties of Cs3Bi2I9 monoclinic, trigonal, and hexagonal phases are studied theoretically. It is suggested that the stabilities of the three crystal phases are similar, and the direct band gap (1.21 eV) of the trigonal phase would be noticeable. For the three phases, their effective mass values show that their properties are the same along both the a direction and the b direction, but different along the c direction. The effective mass of electron of the trigonal phase is significantly smaller along the a-direction than along the c-direction. Corresponding to the red shift phenomenon of optical properties, the trigonal phase shows the better optical absorption performance than other phases. In addition, the optical properties also show that the properties are the same along the a direction and the b direction, but different along the c direction, and the optical absorption performance is better along the a-direction than along the c-direction.-
Keywords:
- perovskite /
- Cs3Bi2I9 /
- first-principles calculation
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图 1 Cs3Bi2I9的晶体结构 (a) 单斜; (b) 三角; (c) 六方. 其中蓝色、黑色和棕色小球分别为Cs原子、Bi原子和I原子
Fig. 1. Crystal structures of Cs3Bi2I9: (a) Mono; (b) Trig; (b) Hexa. The blue, black and brown balls are Cs, Bi and I atoms respectively.
图 2 Cs3Bi2I9的能带结构(考虑和未考虑SOC)和态密度(考虑SOC) (a) 单斜; (b) 三角; (c) 六方
Fig. 2. Band structures (with and without SOC) and density of states (with SOC) of Cs3Bi2I9: (a) Mono; (b) Trig; (c) Hexa.
图 3 Cs3Bi2I9的介电函数 (a) 实部; (b) 虚部
Fig. 3. Dielectric function of Cs3Bi2I9: (a) Real part; (b) imaginary part.
图 4 Cs3Bi2I9的光吸收系数 (a) 和能量损失函数 (b) (插图为可见光范围的局部放大)
Fig. 4. (a) Absorption coefficient α(ω) and (b) energy-loss function L(ω) of Cs3Bi2I9. (The illustration shows a partial enlargement of the visible light range)
表 2 Cs3Bi2I9沿不同方向的载流子有效质量(mo是电子质量)
Table 2. Carrier effective mass of Cs3Bi2I9 along different directions. (The mo is the electronic mass.)
Mono Trig Hexa ${m_{\rm{e} }^*}({\rm{a} })/m_{\rm{o}}$ 0.86 0.26 0.28 ${m_{\rm{e}}^*}({\rm{c} })/m_{\rm{o}}$ 1.48 0.48 1.45 ${m_{\rm{h}}^*} ({\rm{a} })/m_{\rm{o}}$ 0.80 1.02 1.15 ${m_{\rm{h} }^*}({\rm{c} })/m_{\rm{o} }$ 1.16 0.85 0.77 
下载: 导出CSV
表 3 介电函数实部ε1(0)和实部最大值ε1Max(ω)
Table 3. The real part of the dielectric function ε1(0) and the maximum value of the real part ε1Max(ω).
Mono Trig Hexa ε1(0) 6.12 7.10 6.14 ε1Max(ω) 8.91 9.43 8.93
下载: 导出CSV
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[1] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
Google Scholar
[2] Kim H S, Lee C R, Im J H, Lee K B, Moehl T, Marchioro A, Moon S J, Humphry-Baker R, Yum J H, Moser J E, Grätzel M, Park N G 2012 Sci. Rep. 2 591
Google Scholar
[3] 崔兴华, 许巧静, 石标, 侯福华, 赵颖, 张晓丹 2020 69 207401
Google Scholar
Cui X H, Xu Q J, Shi B, Hou F H, Zhao Y, Zhang X D 2020 Acta Phys. Sin. 69 207401
Google Scholar
[4] Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341
Google Scholar
[5] Dong Q, Fang Y, Shao Y, Mulligan P, Qiu J, Cao L, Hua J 2015 Science 347 967
Google Scholar
[6] Shi D, Adinolfi V, Comin R, Yuan M, Alarousu E, Buin A, Chen Y, Hoogland S, Rothenberger A, Katsiev K, Losovyj Y, Zhang X, Dowben P A, Mohammed O F, Sargent E H, Bakr O M 2015 Science 347 519
Google Scholar
[7] https://www.nrel.gov/pv/cell-efficiency.html [2020-11-9]
[8] Bella F, Griffini G, Correa-Baena J P, Saracco G, Grätzel M, Hagfeldt A, Turri S, Gerbaldi C 2016 Science 354 203
Google Scholar
[9] Lee J W, Kim D H, Kim H S, Seo S W, Cho S M, Park N G 2015 Adv. Energy Mater. 5 1501310
Google Scholar
[10] Saliba M, Matsui T, Seo J Y, Domanski K, Correa-Baena J P, Nazeeruddin M K, Zakeeruddin S M, Tress W, Abate A, Hagfeldt A, Grätzel M 2016 Energy Environ. Sci. 9 1989
Google Scholar
[11] Saliba M, Matsui T, Domanski K, Seo J Y, Ummadisingu A, Zakeeruddin S M, Correa-Baena J P, Tress W R, Abate A, Hagfeldt A, Grätzel M 2016 Science 354 206
Google Scholar
[12] Gratia P, Grancini G, Audinot J N, Jeanbourquin X, Mosconi E, Zimmermann I, Dowsett D, Lee Y, Grätzel M, De Angelis F, Sivula K, Wirtz T, Nazeeruddin M K 2016 J. Am. Chem. Soc. 138 15821
Google Scholar
[13] Philippe B, Saliba M, Correa-Baena J P, Cappel U B, Turren-Cruz S H, Grätzel M, Hagfeldt A, Rensmo H 2017 Chem. Mater. 29 3589
Google Scholar
[14] Akkerman Q A, Manna L 2020 ACS Energy Lett. 5 604
Google Scholar
[15] Luo J, Wang X, Li S, et al. 2018 Nature 563 541
Google Scholar
[16] Tsai H, Nie W, Blancon J C, et al. 2016 Nature 536 312
Google Scholar
[17] Saidaminov M I, Almutlaq J, Sarmah S, Dursun I, Zhumekenov A A, Begum R, Pan J, Cho N, Mohammed O F, Bakr O M 2016 ACS Energy Lett. 1 840
Google Scholar
[18] Yao D, Hoang M T, Wang H 2021 Small Methods 5 2001147
Google Scholar
[19] Li Y, Shi Z, Liang W, Ma J, Chen X, Wu D, Tian Y, Li X, Shan C, Fang X 2021 Mater. Horiz. 8 1367
Google Scholar
[20] Zhang Y X, Liu Y C, Xu Z, Ye H C, Yang Z, You J X, Liu M, He Y H, Kanatzidis M G, Liu S Z (Frank) 2020 Nat. Commun. 11 2304
Google Scholar
[21] Xu Q, Yang D, Lv J, Sun Y Y, Zhang L 2018 Small Methods 2 1700316
Google Scholar
[22] Li Y, Yang K 2019 Energy Environ. Sci. 12 2233
Google Scholar
[23] Gao Y, Pan Y, Zhou F, Niu G, Yan C 2021 J. Mater. Chem. A 9 11931
Google Scholar
[24] Miller N C, Bernechea M 2018 APL Mater. 6 084503
Google Scholar
[25] Attique S, Ali N, Ali S, Khatoon R, Li N, Khesro A, Rauf S, Yang S, Wu H 2020 Adv. Sci. 7 1903143
Google Scholar
[26] Park B W, Philippe B, Zhang X, Rensmo H, Boschloo G, Johansson E M J 2015 Adv. Mater. 27 6806
Google Scholar
[27] Ghosh B, Chakraborty S, Wei H, Guet C, Li S, Mhaisalkar S, Mathews N 2017 J. Phys. Chem. C 121 17062
Google Scholar
[28] Hong K H, Kim J, Debbichi L, Kim H, Im S H 2017 J. Phys. Chem. C 121 969
Google Scholar
[29] Zhang H J, Xu Y D, Sun Q H, Dong J P, Lu Y F, Zhang B B, Jie W Q 2018 CrystEngComm 20 4935
Google Scholar
[30] Yu B B, Liao M, Yang J, Chen W, Zhu Y, Zhang X, Duan T, Yao W, Wei S H, He Z 2019 J. Mater. Chem. A 7 8818
Google Scholar
[31] Arakcheeva A V, Chapuis G, Meyer M 2001 Zeitschrift für Kristallographie - Crystalline Materials 216 199
Google Scholar
[32] Ivanov Y N, Sukhovskii A A, Lisin V V, Aleksandrova I P 2001 Inorg. Mater. 37 623
Google Scholar
[33] Yu B B, Liao M, Yang J X, Chen W, Zhu Y D, Zhang X S, Duan T, Yao W T, Wei S H, He Z B 2019 Journal of Materials Chemistry A 7 8818
[34] Johansson M B, Zhu H, Johansson E M J 2016 J. Phys. Chem. Lett. 7 3467
Google Scholar
[35] Zhang L, Liu C, Wang L, Liu C, Wang K, Zou B 2018 Angew. Chem. Int. Ed. 57 11213
Google Scholar
[36] Tewari N, Shivarudraiah S B, Halpert, J E 2021 Nano Lett. 21 5578
Google Scholar
[37] Kresse G, Furthmüller J 1996 Comput. Mater. Sci. 6 15
Google Scholar
[38] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
Google Scholar
[39] Perdew J P, Ruzsinszky A, Csonka G I, Vydrov O A, Scuseria G E, Constantin L A, Zhou X, Burke K 2008 Phys. Rev. Lett. 100 136406
Google Scholar
[40] 汪志刚, 曾祥明, 张杨, 黄娆, 文玉华 2015 物理化学学报 31 1677
Google Scholar
Wang Z G, Zeng X M, Zhang Y, Huang R, Wen Y H 2015 Acta Phys. -Chim. Sin. 31 1677
Google Scholar
[41] Sun Y J, Wang D, Shuai Z G 2016 J. Phys. Chem. C 120 21866
Google Scholar
[42] Even J, Pedesseau L, Jancu J M, Katan C 2013 J. Phys. Chem. Lett. 4 2999
Google Scholar
[43] Rai D P, Sandeep, Shankar A, Sakhya A P, Sinha T P, Merabet B, H-E M M S, Khenata R, Boochani A, Solaymani S, Thapa R K 2017 Mater. Chem. Phys. 186 620
Google Scholar
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