Citation: Zhao Zigang, Niu Yongqiang, Zhao Yang, Song Qinghua, Xin Ling, Lu Xiaoqing. First-Principles Theory Investigation on Structural and Photoelectronic Properties of Formamidinium Lead Halide Perovskites[J]. Acta Chimica Sinica, ;2016, 74(8): 689-693. doi: 10.6023/A16050245 shu

First-Principles Theory Investigation on Structural and Photoelectronic Properties of Formamidinium Lead Halide Perovskites

1.
College of Science, China University of Petroleum, Qingdao 266580, China

Corresponding author: Lu Xiaoqing, luxq@upc.edu.cn
Received Date: 17 May 2016

Fund Project: Postgraduate's Innovation Project YCXJ2016084Student's Platform for Innovation and Entrepreneurship Training Program 20151342the National Natural Science Foundation of China 21303266

Figures(5)

Formamidinium lead halide perovskites have attracted wide attention as photoelectronic conversion materials due to the high photoelectronic conversion efficiency (PCE), low cost and simple synthetic process. The structural, electronic and optical properties of mixed formamidinium lead halide perovskites FAPbI_xCl_3-x (FA=NH₂CH=NH₂⁺, x=0～3) have been investigated by the first-principles theory. Our results show that FA cations lie along [001] direction in the trigonal FAPbX₃ (X=Cl, Br, I). However, the direction is slightly shifted owing to the distortion of PbX₆ (X=Cl, I) octahedrons in the mixed FAPbI_xCl_3-x. The Pb-I bond distances (0.315～0.334 nm) are larger than Pb-Cl bond distances (0.282～0.302 nm). With the increase of I/Cl ratio, the lattice parameters and volumes of FAPbI_xCl_3-x increase. The FA cations play a crucial role in balancing the crystal structure, but they do not participate into the process of frontier orbital transition directly. They just play the role of charge donors to contribute ca. 0.76 e to PbI₃ framework. FAPbI_xCl_3-x are direct band-gap semiconductors, with the direct bandgap nature at Z (0, 0, 0.5) symmetry point. The valence band maximum (VBM) is composed of antibonding orbitals of I 5p (Cl 3p) and a few Pb 6s orbitals, and the conduction band minimum (CBM) is composed of Pb 6p orbital. There exists a combined covalent and ionic bonding mechanism between Pb and I (Cl) ions. As the I/Cl ratio increases, the band gaps decrease and the absorption spectra are red shifted. FAPbI₃ has an ideal band gap of 1.53 eV. It exhibits the superior absorption spectrum especially in the range of 300 nm to 500 nm, which elucidates that FAPbI₃ has great potential as the photoelectronic conversion material. Our results could provide theoretical guidance for the experimental design and synthesis of perovskite solar cells.
- perovskite,
- first-principles theory,
- photoelectronic property,
- band structure,
- absorption spectrum
1. [1]
  Snaith, H. J. J. Phys. Chem. Lett. 2013, 4, 3623. doi: 10.1021/jz4020162
2. [2]
  Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. doi: 10.1021/ja809598r
3. [3]
  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.; Gratzel, M.; Park, N. G. Sci. Rep. 2012, 2, 591.
4. [4]
  Burschka, J.; Pellet, N.; Moon, S. J.; Humphry-Baker, R.; Gao, P.; Nazeeruddin, M. K.; Gratzel, M. Nature 2013, 499, 316. doi: 10.1038/nature12340
5. [5]
  Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith, H. J. Science 2012, 338, 643. doi: 10.1126/science.1228604
6. [6]
  You, J.; Hong, Z.; Yang, Y.; Chen, Q.; Cai, M.; Song, T. B.; Chen, C. C.; Lu, S.; Liu, Y.; Zhou, H.; Yang, Y. ACS Nano 2014, 8, 1674. doi: 10.1021/nn406020d
7. [7]
  Wehrenfennig, C.; Eperon, G. E.; Johnston, M. B.; Snaith, H. J.; Herz, L. M. Adv. Mater. 2014, 26, 1584. doi: 10.1002/adma.201305172
8. [8]
  Gao, P.; Gratzel, M.; Nazeeruddin, M. K. Energy Environ. Sci. 2014, 7, 2448. doi: 10.1039/C4EE00942H
9. [9]
  Boix, P. P.; Nonomura, K.; Mathews, N.; Mhaisalkar, S. G. Mater. Today 2014, 17, 16. doi: 10.1016/j.mattod.2013.12.002
10. [10]
  Noh, J. H.; Im, S. H.; Heo, J. H.; Mandal, T. N.; Seok, S. I. Nano Lett. 2013, 13, 1764. doi: 10.1021/nl400349b
11. [11]
  Im, J. H.; Chung, J.; Kim, S. J.; Park, N. G. Nanoscale Res. Lett. 2012, 7, 1. doi: 10.1186/1556-276X-7-1
12. [12]
  Koh, T. M.; Fu, K.; Fang, Y.; Chen, S.; Sum, T. C.; Mathews, N.; Mhaisalkar, S. G.; Boix, P. P.; Baikie, T. J. Phys. Chem. C 2014, 118, 16458. doi: 10.1021/jp411112k
13. [13]
  Lv, S.; Pang, S.; Zhou, Y.; Padture, N. P.; Hu, H.; Wang, L.; Zhou, X.; Zhu, H.; Zhang, L.; Huang, C.; Cui, G. Phys. Chem. Chem. Phys. 2014, 16, 19206. doi: 10.1039/C4CP02113D
14. [14]
  Yang, W. S.; Noh, J. H.; Jeon, N. J.; Kim, Y. C.; Ryu, S.; Seo, J.; Seok, S. I. Science 2015, 348, 1234. doi: 10.1126/science.aaa9272
15. [15]
  Kresse, G.; Furthmüller, J. Comp. Mater. Sci. 1996, 6, 15. doi: 10.1016/0927-0256(96)00008-0
16. [16]
  Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188. doi: 10.1103/PhysRevB.13.5188
17. [17]
  Even, J.; Pedesseau, L.; Jancu, J. M.; Katan, C. J. Phys. Chem. Lett. 2013, 4, 2999. doi: 10.1021/jz401532q
18. [18]
  Mosconi, E.; Amat, A.; Nazeeruddin, M. K.; Grätzel, M.; De Angelis, F. J. Phys. Chem. C 2013, 117, 13902. doi: 10.1021/jp4048659
19. [19]
  Goldschmidt, V. M. Naturwissenschaften 1926, 14, 477. doi: 10.1007/BF01507527
20. [20]
  Guo, X.; Niu, G.; Wang, L. Acta Chim. Sinica 2014, 73, 211.
21. [21]
  Yao, X.; Ding, Y.; Zhang, X.; Zhao, Y. Acta Phys. Sin. 2015, 64, 38805.
22. [22]
  McKinnon, N. K.; Reeves, D. C.; Akabas, M. H. J. Gen. Physiol. 2011, 138, 453. doi: 10.1085/jgp.201110686
23. [23]
  Green, M. A.; Ho-Baillie, A.; Snaith, H. J. Nat. Photon. 2014, 8, 506. doi: 10.1038/nphoton.2014.134
24. [24]
  Eperon, G. E.; Stranks, S. D.; Menelaou, C.; Johnston, M. B.; Herz, L.; Snaith, H. Energy Environ. Sci. 2014, 7, 982. doi: 10.1039/c3ee43822h
25. [25]
  Pang, S.; Hu, H.; Zhang, J.; Lv, S.; Yu, Y.; Wei, F.; Qin, T.; Xu, H.; Liu, Z.; Cui, G. Chem. Mater. 2014, 26, 1485. doi: 10.1021/cm404006p
26. [26]
  Lee, J. W.; Seol, D. J.; Cho, A. N.; Park, N. G. Adv. Mater. 2014, 26, 4991. doi: 10.1002/adma.201401137
27. [27]
  Yuan, J.; Gao, B.; Wang, W.; Wang, J. Acta Phys.-Chim. Sin. 2015, 31, 1302.
1. [1]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
2. [2]
  Xin XIONG , Qian CHEN , Quan XIE . First principles study of the photoelectric properties and magnetism of La and Yb doped AlN. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1519-1527. doi: 10.11862/CJIC.20240064
3. [3]
  Ximeng CHI , Jianwei WEI , Yunyun WANG , Wenxin DENG , Jiayi DAI , Xu ZHOU . First-principles study of the electronic structure and optical properties of Au and I doped-inorganic lead-free double perovskite Cs₂NaBiCl₆. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1371-1379. doi: 10.11862/CJIC.20240401
4. [4]
  Yao Ma , Xin Zhao , Hongxu Chen , Wei Wei , Liang Shen . Progress and Perspective of Perovskite Thin Single Crystal Photodetectors. Acta Physico-Chimica Sinica, 2025, 41(4): 2309045-0. doi: 10.3866/PKU.WHXB202309045
5. [5]
  Lixing ZHANG , Yaowen WANG , Xu HAN , Junhong ZHOU , Jinghui WANG , Liping LI , Guangshe LI . Research progress in the synthesis of fluorine-containing perovskites and their derivatives. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1689-1701. doi: 10.11862/CJIC.20250007
6. [6]
  Yixuan Gao , Lingxing Zan , Wenlin Zhang , Qingbo Wei . Comprehensive Innovation Experiment: Preparation and Characterization of Carbon-based Perovskite Solar Cells. University Chemistry, 2024, 39(4): 178-183. doi: 10.3866/PKU.DXHX202311091
7. [7]
  Lin Song , Dourong Wang , Biao Zhang . Innovative Experimental Design and Research on Preparing Flexible Perovskite Fluorescent Gels Using 3D Printing. University Chemistry, 2024, 39(7): 337-344. doi: 10.3866/PKU.DXHX202310107
8. [8]
  Jia Zhou , Huaying Zhong . Experimental Design of Computational Materials Science Combined with Machine Learning. University Chemistry, 2025, 40(3): 171-177. doi: 10.12461/PKU.DXHX202406004
9. [9]
  Haiyu Zhu , Zhuoqun Wen , Wen Xiong , Xingzhan Wei , Zhi Wang . 二维半金属/硅异质结中肖特基势垒高度的准确高效预测. Acta Physico-Chimica Sinica, 2025, 41(7): 100078-0. doi: 10.1016/j.actphy.2025.100078
10. [10]
  Shiqian WEI , Xinyu TIAN , Hong LIU , Maoxia CHEN , Fan TANG , Qiang FAN , Weifeng FAN , Yu HU . Oxygen reduction reaction/oxygen evolution reaction catalytic performances of different active sites on nitrogen-doped graphene loaded with iron single atoms. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1776-1788. doi: 10.11862/CJIC.20250102
11. [11]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . Accelerated Interfacial Electron Transfer in Perovskite Solar Cell by Ammonium Hexachlorostannate Modification and fs-TAS Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-0. doi: 10.3866/PKU.WHXB202402006
12. [12]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
13. [13]
  Xinyuan Shi , Chenyangjiang , Changyu Zhai , Xuemei Lu , Jia Li , Zhu Mao . Preparation and Photoelectric Performance Characterization of Perovskite CsPbBr₃ Thin Films. University Chemistry, 2024, 39(6): 383-389. doi: 10.3866/PKU.DXHX202312019
14. [14]
  Jian Li , Yu Zhang , Rongrong Yan , Kaiyuan Sun , Xiaoqing Liu , Zishang Liang , Yinan Jiao , Hui Bu , Xin Chen , Jinjin Zhao , Jianlin Shi . Highly Efficient, Targeted, and Traceable Perovskite Nanocrystals for Photoelectrocatalytic Oncotherapy. Acta Physico-Chimica Sinica, 2025, 41(5): 100042-0. doi: 10.1016/j.actphy.2024.100042
15. [15]
  Qilin YU , Yifei XU , Pengjun ZHANG , Shuwei HAO , Chongqiang ZHU , Chunhui YANG . Effect of regulating K⁺/Na⁺ ratio on the structure and optical properties of double perovskite Cs₂NaBiCl₆: Mn²⁺. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1058-1067. doi: 10.11862/CJIC.20240418
16. [16]
  Ying Liang , Yuheng Deng , Shilv Yu , Jiahao Cheng , Jiawei Song , Jun Yao , Yichen Yang , Wanlei Zhang , Wenjing Zhou , Xin Zhang , Wenjian Shen , Guijie Liang , Bin Li , Yong Peng , Run Hu , Wangnan Li . Machine learning-guided antireflection coatings architectures and interface modification for synergistically optimizing efficient and stable perovskite solar cells. Acta Physico-Chimica Sinica, 2025, 41(9): 100098-0. doi: 10.1016/j.actphy.2025.100098
17. [17]
  Jin CHANG . Supercapacitor performance and first-principles calculation study of Co-doping Ni(OH)₂. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1697-1707. doi: 10.11862/CJIC.20240108
18. [18]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
19. [19]
  Fengying Zhang , Yanglin Mei , Yuman Jiang , Shenshen Zheng , Kaibo Zheng , Ying Zhou . Research progress of transient absorption spectroscopy in solar energy conversion and utilization. Acta Physico-Chimica Sinica, 2025, 41(9): 100118-0. doi: 10.1016/j.actphy.2025.100118
20. [20]
  Mengyao Shi , Kangle Su , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Potassium Content in Tobacco Stem Ash by Flame Atomic Absorption Spectroscopy. University Chemistry, 2024, 39(10): 255-260. doi: 10.12461/PKU.DXHX202404105

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3416)
HTML views(890)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142