Citation: 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[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(7): 1371-1379. doi: 10.11862/CJIC.20240401 shu

First-principles study of the electronic structure and optical properties of Au and I doped-inorganic lead-free double perovskite Cs₂NaBiCl₆

Science of College, Chongqing University of Technology, Chongqing 400052, China

Corresponding author: Jianwei WEI, redskywei@cqut.edu.cn
Received Date: 8 November 2024
Revised Date: 30 April 2025

Figures(10)

The electronic structure and optical properties of Au and I monodoped and co-doped double perovskite Cs₂NaBiCl₆ were studied using the first-principles method based on density functional theory. The results showed that when Au was mono-doped with Cs₂NaBiCl₆ by replacing Na at a ratio of 0.25, the band gap of the doped struc-ture decreased significantly, reaching a minimum of 1.86 eV. The band gap of the single-doped structure decreased with increased doping concentration. Compared to the pre-doping state, the absorption spectra of various concentra- tions of Au and I monodoped structures exhibited a redshift. The co-doping of Au and I resulted in a reduced band gap. Among them, when Au and I were uniformly adjacent to each other in the Cs₂NaBiCl₆ crystal, the band gap of the co-doped structure was the smallest, the light absorption capacity in the visible light region of 400-700 nm was the strongest, and the utilization rate of visible light was the highest.
- double perovskite,
- Cs₂NaBiCl₆,
- first principle,
- doping,
- optical property
1. [1]
  FAN Q Q, BIESOLD-MCGEE G V, MA J Z, XU Q N, PAN S, PENG J, LIN Z Q. Lead-free halide perovskite nanocrystals: Crystal structures, synthesis, stabilities, and optical properties[J]. . Angew. Chem.?Int. Edit, 2020,59(3):1030-1046. doi: 10.1002/anie.201904862
2. [2]
  YUAN, QUAN, COMIN, WALTERS, SABATINI, VOZNYY, HOOGLAND, ZHAO, M. BEAUREGARD E, KANJANABOOS P, LU Z H, KIM D, H. SARGENT E. Perovskite energy funnels for efficient light-emitting diodes[J]. . Nat. Nanotechnol., 2016,11(10):872-877. doi: 10.1038/nnano.2016.110
3. [3]
  WANG Y Y, ZHANG Y Z, WEI J W, ZENG H, ZHAO M, YANG C, FENG W L, MA Z W. First principles calculation on photoelectric properties of Cs₂TiBr₆ by substitution doping with Cl and Pd[J]. . Chinese J. Inorg. Chem., 2022,38(5):884-890.
4. [4]
  CORREA-BAENA J P, SALIBA M, BUONASSISI T, GRÄTZEL M, ABATE A, TRESS W, HAGFELDT A. Promises and challenges of perovskite solar cells[J]. Science, 2017,358(6364):739-744. doi: 10.1126/science.aam6323
5. [5]
  STRANKS, EPERON, GRANCINI, MENELAOU, ALCOCER, LEIJTENS, M. HERZ L, PETROZZA A, J.SNAITH H. Electron-hole diffusion lengths exceeding 1 micron in an organometal trihalide perovskite absorber[J]. . Science, 2013,342(6156):341-344. doi: 10.1126/science.1243982
6. [6]
  KOJIMA A, TESHIMA K, SHIRAI Y, MIYASAKA T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells[J]. . J. Am. Chem. Soc., 2009,131(17):6050-6051. doi: 10.1021/ja809598r
7. [7]
  ZHOU J J, TAN L G, LIU Y, LI H, LIU X P, LI M H, WANG S Y, ZHANG Y, JIANG C F, HUA R M, TRESS W, MELONI S, YI C Y. Highly efficient and stable perovskite solar cells via a multifunctional hole transporting material[J]. . Joule, 2024,8(6):1691-1706. doi: 10.1016/j.joule.2024.02.019
8. [8]
  BABAYIGIT A, ETHIRAJAN A, MULLER M, CONINGS B. Toxicity of organometal halide perovskite solar cells[J]. . Nat. Mater., 2016,15(3):247-251. doi: 10.1038/nmat4572
9. [9]
  JELLICOE T C, RICHTER J M, GLASS H F J, TABACHNYK M, BRADY R, DUTTON S E, RAO A, FRIEND R H, CREDGINGTON D, GREENHAM N C, BOHM M L. Synthesis and optical properties of lead-free cesium tin halide perovskite nanocrystals[J]. . J. Am. Chem. Soc., 2016,138(9):2941-2944. doi: 10.1021/jacs.5b13470
10. [10]
  WANG A F, YAN X X, ZHANG M, SUN S B, YANG M, SHEN W, PAN X Q, WANG P, DENG Z T. Controlled synthesis of lead-free and stable perovskite derivative Cs₂SnI₆ nanocrystals via facile hotinjection process[J]. . Chem. Mater., 2016,28(22):8132-8140. doi: 10.1021/acs.chemmater.6b01329
11. [11]
  PENG C, WEI J W, WU J H, MA Z W, QIAO C K, ZENG H. Modulation mechanism of electronic and optical properties of Cs₂SnX₆ (X=Cl, Br and I) under hydrostatic or uniaxial pressure[J]. . Funct. Mater.Lett., 2024,17(3)2451012. doi: 10.1142/S1793604724510123
12. [12]
  LI B H, LONG R Y, XIA Y, MI Q X. All-inorganic perovskite CsSnBr₃ as a thermally stable, free-carrier semiconductor[J]. . Angew. Chem.?Int. Edit, 2018,57(40):13154-13158. doi: 10.1002/anie.201807674
13. [13]
  KHAN I, HAQ I U, ALI A, ALI Z, AHMAD I. Elastic and optoelectronic properties of Cs₂NaMCl₆ (M=In, Tl, Sb, Bi)[J]. . J. Electron. Mater., 2021,50(2):456-466. doi: 10.1007/s11664-020-08603-y
14. [14]
  LOCARDI F, CIRIGNANO M, BARANOV D, DANG Z Y, PRATO M, DRAGO F, FERRETTI M, PINCHETTI V, FANCIULLI M, BROVELLI S, TRIZIO L D, MANNA L. Colloidal synthesis of double perovskite Cs₂AgInCl₆ and Mn - doped Cs₂AgInCl₆ nanocrystals[J]. . J. Am. Chem. Soc., 2018,140(40):12989-12995. doi: 10.1021/jacs.8b07983
15. [15]
  PENG C, WEI J W, CHEN Y T, HU N, ZENG H. First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi2X₉ (X=Cl, Br, I)[J]. . Chinese J. Inorg. Chem., 2024,40(3):555-560.
16. [16]
  JIANG J T, NIU G M, SUI L Z, WANG X W, ZHANG Y T, CHE L, WU G R, YUAN K Y, YANG X M. Transformation between the dark and bright self - trapped excitons in lead - free double - perovskite Cs₂NaBiCl₆ under pressure[J]. . J. Phys. Chem. Lett., 2021,12(30):7285-7292. doi: 10.1021/acs.jpclett.1c02072
17. [17]
  WU C C, ZHANG Q H, LIU Y, LUO W, GUO X, HUANG Z R, TING H, SUN W H, ZHONG X R, WEI S Y, WANG S F, CHEN Z J, XIAO L X. The dawn of lead-free perovskite solar cell: Highly stable double perovskite Cs₂AgBiBr₆ film[J]. . Adv. Sci., 2018,5(3)1700759. doi: 10.1002/advs.201700759
18. [18]
  SUN Y M, FERNáNDEZ-CARRIóN A J, LIU Y H, YIN C L, MING X, LIU B M, WANG J, FU H, KUANG X J, XING X R. Bismuth-based halide double perovskite Cs₂LiBiCl₆: Crystal structure, luminescence, and stability[J]. . Chem. Mater., 2021,33(15):5905-5916. doi: 10.1021/acs.chemmater.1c00854
19. [19]
  ZHOU J, RONG X M, ZHANG P, MOLOKEEV M S, WEI P J, LIU Q L, ZHANG X W, XIA Z G. Manipulation of Bi³⁺/In³⁺ transmutation and Mn²⁺-doping effect on the structure and optical properties of double perovskite Cs₂NaBi_1-xIn_xCl₆[J]. . Adv. Opt. Mater., 2019,7(8)1801435. doi: 10.1002/adom.201801435
20. [20]
  SHI H L, DU M H. Discrete electronic bands in semiconductors and insulators: Potential high-light-yield scintillators[J]. . Phys. Rev. Appl., 2015,3(5)054005. doi: 10.1103/PhysRevApplied.3.054005
21. [21]
  WANG C, LIU Y, GUO Y R, MA L L, LIU Y L, ZHOU C Y, YU X, ZHAO G J. Lead - free sodium bismuth halide Cs₂NaBiX₆ double perovskite nanocrystals with highly efficient photoluminesence[J]. . Chem. Eng. J., 2020,397125367. doi: 10.1016/j.cej.2020.125367
22. [22]
  YAO M M, WANG L, YAO J S, WANG K H, CHEN C, ZHU B S, YANG J N, WANG J J, XU W P, ZHANG Q, YAO H B. Improving lead-free double perovskite Cs₂NaBiCl₆ nanocrystal optical properties via ion doping[J]. . Adv. Opt. Mater., 2020,8(8)1901919. doi: 10.1002/adom.201901919
23. [23]
  WU S F, LI W B, HU J J, GAO P. Antimony doped lead-free double perovskites (Cs₂NaBi_1-xSb_xCl₆) with enhanced light absorption and tunable emission[J][J]. . J. Mater. Chem. C, 2020,8(39):13603-13611. doi: 10.1039/D0TC03003A
24. [24]
  LEE W, CHOI D, KIM S. Colloidal synthesis of shape - controlled Cs₂NaBiX₆ (X=Cl, Br) double perovskite nanocrystals: Discrete optical transition by non-bonding characters and energy transfer to Mn dopants[J]. . Chem. Mater., 2020,32(16):6864-6874. doi: 10.1021/acs.chemmater.0c01315
25. [25]
  SHAH S Z A, NIAZ S, NASIR T, SIFUNA J. Eco-friendly bismuth based double perovskites X₂NaBiCl₆(X=Cs, Rb, K) for optoelectronic and thermoelectric applications: A first-principles study[J]. . Results Chem., 2023,5100828. doi: 10.1016/j.rechem.2023.100828
26. [26]
  OUHAMMOU A, FAZOUAN N, ES-SMAIRI A, KHUILI M, ATMANI E H. DFT analysis of Cs₂NaBiCl₆, Cs₂NaBiBr₆, and Cs₂NaBiI₆ perovskites for optoelectronic and thermoelectric applications[J]. . Comput. Theor. Chem., 2024,1238114673. doi: 10.1016/j.comptc.2024.114673
27. [27]
  MORSS L R, SIEGAL M, STENGER L, EDELSTEIN N. Preparation of cubic chloro complex compounds of trivalent metals: Cs₂NaMCl₆[J]. . Inorg. chem., 1970,9(7):1771-1775. doi: 10.1021/ic50089a034
28. [28]
  LIAO P Z, ZHAO X J, LI G L, SHEN Y, WANG M K. A new method for fitting current-voltage curves of planar heterojunction perovskite solar cells[J]. . Nano?Micro Lett., 2018,1(1):1-8.
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
5. [5]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
6. [6]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
7. [7]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
8. [8]
  Shu'e Song , Xiaokui Wang , Yongmei Liu , Wanchun Zhu , Hong Yuan , Fuping Tian , Yunshan Bai , Yunchao Li , Li Wang , Zhongyun Wu , Yuan Chun , Jianrong Zhang , Shuyong Zhang . Suggestions on Operating Specifications of Physical Chemistry Experiment: Measurement of Viscosity, Density and Optical Properties. University Chemistry, 2025, 40(5): 148-156. doi: 10.12461/PKU.DXHX202503026
9. [9]
  Pingping LU , Shuguang ZHANG , Peipei ZHANG , Aiyun NI . Preparation of zinc sulfate open frameworks based probe materials and detection of Pb²⁺ and Fe³⁺ ions. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 959-968. doi: 10.11862/CJIC.20240411
10. [10]
  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
11. [11]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
12. [12]
  Zhihao HE , Jiafu DING , Yunjie WANG , Xin SU . First-principles study on the structure-property relationship of AlX and InX (X=N, P, As, Sb). Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1007-1019. doi: 10.11862/CJIC.20240390
13. [13]
  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
14. [14]
  Haiyu Zhu , Zhuoqun Wen , Wen Xiong , Xingzhan Wei , Zhi Wang . Accurate and efficient prediction of Schottky barrier heights in 2D semimetal/silicon heterojunctions. Acta Physico-Chimica Sinica, 2025, 41(7): 100078-0. doi: 10.1016/j.actphy.2025.100078
15. [15]
  Li Jiang , Changzheng Chen , Yang Su , Hao Song , Yanmao Dong , Yan Yuan , Li Li . Electrochemical Synthesis of Polyaniline and Its Anticorrosive Application: Improvement and Innovative Design of the “Chemical Synthesis of Polyaniline” Experiment. University Chemistry, 2024, 39(3): 336-344. doi: 10.3866/PKU.DXHX202309002
16. [16]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-. doi: 10.3866/PKU.WHXB202404023
17. [17]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
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]
  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
20. [20]
  Xiting Zhou , Zhipeng Han , Xinlei Zhang , Shixuan Zhu , Cheng Che , Liang Xu , Zhenyu Sun , Leiduan Hao , Zhiyu Yang . Dual Modulation via Ag-Doped CuO Catalyst and Iodide-Containing Electrolyte for Enhanced Electrocatalytic CO₂ Reduction to Multi-Carbon Products: A Comprehensive Chemistry Experiment. University Chemistry, 2025, 40(7): 336-344. doi: 10.12461/PKU.DXHX202412070

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3)
HTML views(1)

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

First-principles study of the electronic structure and optical properties of Au and I doped-inorganic lead-free double perovskite Cs2NaBiCl6

Metrics

通讯作者: 陈斌, bchen63@163.com

First-principles study of the electronic structure and optical properties of Au and I doped-inorganic lead-free double perovskite Cs₂NaBiCl₆