English

Structural, Thermodynamical and Electronic Properties of All-Inorganic Lead Halide Perovskites

• Li Yawen ^1, ,
• Na Guangren ^1, ,
• Luo Shulin ^1, ,
• He Xin ^{1,2, ,} ,
• Zhang Lijun ^{1, ,}

• 1.

  State Key Laboratory of Integrated Optoelectronics, Key Laboratory of Automobile Materials of MOE, College of Materials Science and Engineering, Jilin University, Changchun 130012, China

• 2.

  College of Physics, Jilin University, Changchun 130012, China

Corresponding author: He Xin, xin_he@jlu.edu.cn Zhang Lijun, lijun_zhang@jlu.edu.cn

• Received Date: 06 July 2020
  Accepted Date: 11 August 2020
  Revised Date: 10 August 2020
  Available Online: 15 April 2021
• Fund Project:

  The project was supported by the Postdoctoral Innovative Talents Supporting Program, China (BX20190143) and the Jilin Province Science and Technology Development Program, China (20190201016JC)

Abstract: Organic-inorganic hybrid lead halide perovskites have emerged as the most promising materials in the field of optoelectronics due to their unique electronic and optical properties. However, the poor long-term material and device stabilities of these materials have limited their practical application. Compared to organic-inorganic hybrid perovskites, all-inorganic halide perovskites like CsPbX₃ (X = Cl, Br, I) show enhanced thermal stability and the potential to resolve the issue of instability. Nevertheless, the structural and physical properties of all-inorganic CsPbX₃ halide perovskites with multiple structural polymorphs are still under debate. A recent research article on CsPbI₃ reported the wrongly indexed the XRD pattern of γ-CsPbI₃ as α-CsPbI₃. Consequently, the band gap of γ-CsPbI₃ (1.73 eV) was erroneously designated for α-CsPbI₃. Therefore, there is a need for systematic research on the relationship between the structural features and electronic properties of CsPbX₃. Here, we present a comprehensive theoretical study of the structural, thermodynamical and electronic properties of three polymorphic phases, α-, β-, and γ-CsPbX₃. The space group of α-, β-, and γ-CsPbX₃ are Pm3m, P4/mbm, and Pnma, respectively. First-principles calculations indicate that the phase transition from the high-temperature α-phase to the low-temperature β-phase and then to the γ phase is accompanied by an increase in the degree of PbX₆ octahedral distortion. The zero-temperature energetic calculations reveal that the γ-phase is the most stable. This is consistent with the fact that experimentally, the γ-phase is stabilized at a relatively low temperature. Analysis of the electronic properties indicates that all the CsPbX₃ perovskites exhibit a direct-gap nature and the band gap values increase from α to β, and then to the γ phase. From the analysis of the orbital hybridization near the band gap edges, the increase can be explained by the downshift of the valence band edges caused by the gradual weakening of the Pb-X chemical bond. Among all the phases, the strongest Pb-X interaction in the α-phase leads to the most dispersive band-edge states and thus the smallest carrier effective masses, which are beneficial for carrier transport. Additionally, the band gaps decreased by changing the halogen type from Cl to Br and I under the same phase. this is a consequence of the increased X np orbital energies from Cl 3p to Br 4p and then to I 3p that leads to a high valence band edge for CsPbI₃ and results in the smallest band gap. Our results provide deep understanding on the relationship between the physical properties and structural features of all-inorganic lead halide perovskites.

Key words:
• Inorganic halide perovskite
•  /  Optoelectronic property
•  /  First-principles calculation
•  /  Electronic structure

• 1. [1]

     Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. doi: 10.1021/ja809598r

  2. [2]

     Powalla, M.; Paetel, S.; Ahlswede, E.; Wuerz, R.; Wessendorf, C. D.; Friedlmeier, T. M. Appl. Phys. Rev. 2018, 5, 041602. doi: 10.1063/1.5061809

  3. [3]

     Jost, M.; Bertram, T.; Koushik, D.; Marquez, J. A.; Verheijen, M. A.; Heinemann, M. D.; Köhnen, E.; Al-Ashouri, A.; Braunger, S.; Lang, F.; et al. ACS Energy Lett. 2019, 4, 583. doi: 10.1021/acsenergylett.9b00135

  4. [4]

     Yang, W. S.; Park B. W.; Jung, E. H.; Jeon, N. J.; Kim, Y. C.; Lee, D. U.; Shin, S. S.; Seo, J.; Kim, E. K.; Noh, J. H.; Seok, S. Science 2017, 356, 1376. doi: 10.1126/science.aan2301

  5. [5]

     Huang, P.; Chen, Q.; Zhang, K.; Yuan, L.; Zhou, Y.; Song, B.; Li, Y. J. Mater. Chem. A 2019, 7, 6213. doi: 10.1039/C8TA11841H

  6. [6]

     Yang, B.; Mahjouri-Samani, M.; Rouleau, C. M.; Geohegan, D. B.; Xiao, K. Phys. Chem. Chem. Phys. 2016, 18, 27067. doi: 10.1039/C6CP02896A

  7. [7]

     Chen, X.; Tang, L. J.; Yang, S.; Hou, Y.; Yang, H. G. J. Mater. Chem. A 2016, 4, 6521. doi: 10.1039/C6TA00893C

  8. [8]

     Schulze, P. S. C.; Bett, A. J.; Winkler, K.; Hinsch, A.; Lee, S.; Mastroianni, S.; Mundt, L. E.; Mundus, M.; Würfel, U.; Glunz, S. W.; Hermle, M.; Goldschmidt, J. C. Interfaces 2017, 9, 30567. doi: 10.1021/acsami.7b05718

  9. [9]

     Azmi, R.; Hwang, S.; Yin, W.; Kim, T. W.; Ahn, T. K.; Jang, S. Y. ACS Energy Lett. 2018, 3, 1241. doi: 10.1021/acsenergylett.8b00493

  10. [10]

      Tan, H.; Jain, A.; Voznyy, O.; Lan, X.; García de Arquer, F. P.; Fan, J. Z.; Quintero-Bermudez, R.; Yuan, M.; Zhang, B.; Zhao, Y. Science 2017, 355, 722. doi: 10.1126/science.aai9081

  11. [11]

      赵电龙, 李天姝, 徐巧玲, 王雪婷, 张立军.中国光学, 2019, 12, 964. doi: 10.3788/CO.20191205.0964Zhao, D.; Li, T.; Xu, Q.; Wang, X.; Zhang, L. Chinese Optics 2019, 12, 964. doi: 10.3788/CO.20191205.0964

  12. [12]

      Meng, L.; You, J.; Guo, T. F.; Yang, Y. Acc. Chem. Res. 2016, 49, 155. doi: 10.1021/acs.accounts.5b00404

  13. [13]

      https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20200406.pdf (accessed Apr 4, 2020).

  14. [14]

      Wang, P.; Zhang P.; Zhou, Y.; Jiang, Q.; Ye Q.; Chu, Z.; Li X.; Yang, X.; Yin, Z.; You, J. Nat. Commun. 2018, 9, 1. doi: 10.1038/s41467-018-04636-4

  15. [15]

      王雪婷, 付钰豪, 那广仁, 李红东, 张立军.物理学报, 2019, 68, 27. doi: 10.7498/aps.68.20190596Wang, X.; Fu, Y.; Na, G.; Li, H.; Zhang, L. Acta Phys. Sin. 2019, 68, 27. doi: 10.7498/aps.68.20190596

  16. [16]

      Yang, Y.; You, J. Nature 2017, 544, 155. doi: 10.1038/544155a.

  17. [17]

      Liu, Z.; Na, G.; Tian, F.; Yu, L.; Li, J.; Zhang, L. InfoMat. 2020, 27, 1. doi: 10.1002/inf2.12099

  18. [18]

      Wang, X.; Li, Y.; Pang, Y. X.; Sun, Y.; Zhao, X. G.; Wang, J. R.; Zhang, L. Sci. China Phys. Mech. Astron. 2018, 61, 107311. doi: 10.1007/s11433-018-9207-9

  19. [19]

      Wang, Z.; Zhao, D.; Yu, S.; Nie, Z.; Li, Y.; Zhang, L. Prog. Nat. Sci-Mater. 2019, 29, 316. doi: 10.1016/j.pnsc.2019.03.015

  20. [20]

      丁绪坤, 李效民, 高相东, 张树德, 黄宇迪, 李浩然.物理化学学报, 2015, 31, 576. doi: 10.3866/PKU.WHXB201501201Ding, X.; Li, X.; Gao, X.; Zhang, S.; Huang, Y.; Li, H. Acta Phys. -Chim. Sin. 2015, 31, 576. doi: 10.3866/PKU.WHXB201501201

  21. [21]

      高素雯, 兰章, 吴晚霞, 阙兰芳, 吴季怀, 林建明, 黄妙良.物理化学学报, 2014, 30, 446. doi: 10.3866/PKU.WHXB201401022Gao, S.; Lan, Z.; Wu, X.; Kan, L.; Wu, J.; Lin, J.; Huang, M. Acta Phys. -Chim. Sin. 2014, 30, 446. doi: 10.3866/PKU.WHXB201401022

  22. [22]

      卫会云, 王国帅, 吴会觉, 罗艳红, 李冬梅, 孟庆波.物理化学学报, 2016, 32, 201. doi: 10.3866/PKU.WHXB201512031Wei, H.; Wang, S.; Wu, H.; Hong, Y.; Li, D.; Meng, Q. Acta Phys. -Chim. Sin. 2016, 32, 201. doi: 10.3866/PKU.WHXB201512031

  23. [23]

      Xu, Q.; Stroppa, A.; Lv, J.; Zhao, X.; Yang, D.; Biswas, K.; Zhang, L. Phys. Rev. Mater. 2019, 3, 125401. doi: 10.1103/PhysRevMaterials.3.125401

  24. [24]

      Wang, Y.; Dar, M. I.; Ono, L. K.; Zhang, T.; Kan, M.; Li, Y.; Zhang, L.; Wang, X.; Yang, Y.; Gao, X.; et al. Science 2019, 365, 591. doi: 10.1126/science.aav8680

  25. [25]

      Wang, H.; Bian, H.; Jin, Z.; Zhang, H.; Liang, L.; Wen, J.; Wang, Q.; Ding, L.; Liu, S. F. Chem. Mater. 2019, 31, 6231. doi: 10.1021/acs.chemmater.9b02248

  26. [26]

      Jia, X.; Zuo, C.; Tao, S.; Sun, K.; Zhao, Y.; Yang, S.; Cheng, M.; Wang, M.; Yuan, Y.; Yang, J.; et al. Sci. Bull. 2019, 64, 1532. doi: 10.1016/j.scib.2019.08.017

  27. [27]

      Zhang, T.; Wang, Y.; Wang, X.; Wu, M.; Liu, W.; Zhao, Y. Sci. Bull. 2019, 64, 1773. doi: 10.1016/j.scib.2019.09.022

  28. [28]

      Shi, J.; Wang, Y.; Zhao, Y. Energy Environ. Mater. 2019, 2, 73. doi: 10.1002/eem2.12039

  29. [29]

      Eperon, G. E.; Paternò, G. M.; Sutton, R. J.; Zampetti, A.; Haghighirad, A. A.; Cacialli, F.; Snaith, H. J. J. Mater. Chem. A 2015, 3, 19688. doi: 10.1039/C5TA06398A

  30. [30]

      Kulbak, M.; Cahen, D.; Hodes, G. J. Phys. Chem. Lett. 2015, 6, 2452. doi: 10.1021/acs.jpclett.5b00968

  31. [31]

      Wang, Y.; Zhang, T.; Kan, M.; Zhao, Y. J. Am. Chem. Soc. 2018, 140, 12345. doi: 10.1021/jacs.8b07927

  32. [32]

      Wang, D.; Wright, M.; Elumalai, N. K.; Uddin, A. Sol. Energy Mater. Sol. Cells 2016, 147, 255. doi: 10.1016/j.solmat.2015.12.025

  33. [33]

      Lim, A. R.; Jeong, S. Y. Phys. B: Condensed Matter 1998, 245, 277. doi: 10.1016/S0921-4526(97)00883-1

  34. [34]

      Haeger, T.; Ketterer, M.; Bahr, J.; Pourdavoud, N.; Runkel, M.; Heiderhoff, R.; Riedl, T. J. Phys. Mater. 2020, 3, 024004. doi: 10.1088/2515-7639/ab749d

  35. [35]

      Hirotsu, S.; Harada, J.; Iizumi, M.; Gesi, K. J. Phys. Soc. Jpn. 1974, 37, 1393. doi: 10.1143/JPSJ.37.1393

  36. [36]

      Stoumpos, C. C.; Malliakas, C. D.; Peters, J. A.; Liu, Z.; Sebastian, M.; Im, J.; Chasapis, T. C.; Wibowo, A. C.; Chung, D. Y.; Freeman, A. J. Cryst. Growth & Des. 2013, 13, 2722. doi: 10.1021/cg400645t

  37. [37]

      Marronnier, A.; Roma, G.; Boyer-Richard, S.; Pedesseau, L.; Jancu, J. M.; Bonnassieux, Y.; Katan, C.; Stoumpos, C. C.; Kanatzidis, M. G.; Even, J. ACS Nano 2018, 12, 3477. doi: 10.1021/acsnano.8b00267

  38. [38]

      Zhang, L., Wang, L., Wang, K., Zou, B. J. Phys. Chem. C 2018, 122, 15220. doi: 10.1021/acs.jpcc.8b05397

  39. [39]

      Wang, Y., Zhang, Y., Zhang, P., Zhang, W. Phys. Chem. Chem. Phys. 2015, 17, 11516. doi: 10.1039/c5cp00448a

  40. [40]

      Liu, Z.; Peters, J. A.; Stoumpos, C. C.; Sebastian, M.; Wessels, B. W.; Im, J.; Freeman, A. J.; Kanatzidis, M. G. Heavy Metal Ternary Halides for Room-Temperature X-ray and Gamma-ray Detection. Proceedings SPIE 8852, Hard X-Ray, Gamma-Ray, and Neutron Detector Physics XV, California, United States, September 26, 2013. SPIE press: Unite states, 2013.

  41. [41]

      Sutton, R. J.; Filip, M. R.; Haghighirad, A. A.; Sakai, N.; Wenger, B.; Giustino, F.; Snaith, H. J. ACS Energy Lett. 2018, 3, 1787. doi: 10.1021/acsenergylett.8b00672

  42. [42]

      Zhang, T.; Dar, M. I.; Li, G.; Xu, F.; Guo, N.; Grätzel, M.; Zhao, Y. Sci. Adv. 2017, 3, e1700841. doi: 10.1126/sciadv.1700841

  43. [43]

      Kresse, G.; Furthmüller, J. Comp. Mater. Sci. 1996, 6, 15. doi: 10.1016/0927-0256(96)00008-0

  44. [44]

      Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758

  45. [45]

      Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865

  46. [46]

      Perdew, J. P.; Zunger, A. Phys. Rev. B 1981, 23, 50g. doi: 10.1103/PhysRevB.23.5048

  47. [47]

      Hrirotsu, S. J. Phys. Soc. Jpn. 1971, 31, 552. doi: 10.1143/JPSJ.31.552

  48. [48]

      Møller, C. K. Nature 1958, 182, 1436. doi: 10.1038/1821436a0.

  49. [49]

      Sharma, S.; Weiden, N.; Weiss, A. Z. Phys. Chem. 1992, 175, 63. doi: 10.1524/zpch.1992.175.Part_1.063

  50. [50]

      Paul, T.; Chatterjee, B. K.; Maiti, S.; Sarkar, S.; Besra, N.; Das, B. K.; Panigrahi, K. J.; Thakur, S.; Ghorai, U. K.; Chattopadhyay, K. K. J. Mater. Chem. C 2018, 6, 3322. doi: 10.1039/C7TC05703B

  51. [51]

      Cottingham, P.; Brutchey, R. L. Chem. Mater. 2018, 30, 6711. doi: 10.1023/A:1022836800820

  52. [52]

      Gesi, K.; Ozawa, K.; Hirotsu, S. J. Phys. Soc. Jpn. 1975, 38, 463. doi: 10.1143/JPSJ.38.463

  53. [53]

      Pandey, N.; Kumar, A.; Chakrabarti, S. RSC Adv. 2019, 9, 29556. doi: 10.1039/C9RA05685H

  54. [54]

      Zhang, L.; Hu, T.; Li, J.; Zhang, L.; Li, H.; Lu, Z.; Wang, G. Front. Mater. 2020, 6. 1. doi: 10.3389/fmats.2019.00330

  55. [55]

      Saidi, W. A.; Choi, J. J. J. Chem. Phys. 2016, 145, 144702. doi: 10.1063/1.4964094

  56. [56]

      Yin, W.; Yang, J.; Kang, J.; Yan, Y.; Wei, S. J. Mater. Chem. A, 2015, 3, 8926. doi: 0.1039/C4TA05033A

  57. [57]

      Long, M. Q.; Tang, L.; Wang, D.; Wang, L.; Shuai, Z. J. Am. Chem. Soc. 2009, 131, 17728. doi: 10.1021/ja907528a

  58. [58]

      Xie, J.; Zhang, Z. Y.; Yang, D. Z.; Xue, D. S.; Si, M. S. J. Phys. Chem. Lett. 2014, 5, 4073. doi: 10.1021/jz502006z

  59. [59]

      Fang, Z.; Shang, M.; Hou, X.; Zheng, Y.; Du, Z.; Yang, Z.; Chou, K. C.; Yang, W.; Wang, Z. L.; Yang, Y. ano Energy 2019, 61, 389. doi: 10.1016/j.nanoen.2019.04.084

  60. [60]

      Giorgi, G.; Fujisawa, J. I.; Segawa, H.; Yamashita, K. J. Phys. Chem. Lett. 2013, 4, 4213. doi: 10.1021/jz4023865

•