Material exploration via designing spatial arrangement of octahedral units: a case study of lead halide perovskites

Abstract

Halide perovskites have attracted tremendous attention as semiconducting materials for various optoelectronic applications. The functional metal-halide octahedral units and their spatial arrangements play a key role in the optoelectronic properties of these materials. At present, most of the efforts for material exploration focus on substituting the constituent elements of functional octahedral units, whereas designing the spatial arrangement of the functional units has received relatively little consideration. In this work, via a global structure search based on density functional theory (DFT), we discovered a metastable three-dimensional honeycomb-like perovskite structure with the functional octahedral units arranged through mixed edge- and corner-sharing. We experimentally confirmed that the honeycomb-like perovskite structure can be stabilized by divalent molecular cations with suitable size and shape, such as 2,2′-bisimidazole (BIM). DFT calculations and experimental characterizations revealed that the honeycomb-like perovskite with the formula of BIMPb₂I₆, synthesized through a solution process, exhibits high electronic dimensionality, a direct allowed bandgap of 2.1 eV, small effective masses for both electrons and holes, and high optical absorption coefficients, which indicates a significant potential for optoelectronic applications. The employed combination of DFT and experimental study provides an exemplary approach to explore prospective optoelectronic semiconductors via spatially arranging functional units.

Graphical abstract

Keywords

lead halide perovskite / electronic dimensionality / functional octahedral units / optoelectronic properties / photodetector

References

[1] Kim J Y, Lee J W, Jung H S, Shin H, Park N G. High-efficiency perovskite solar cells. Chemical Reviews, 2020, 120(15): 7867–7918

[2] Jena A K, Kulkarni A, Miyasaka T. Halide perovskite photovoltaics: background, status, and future prospects. Chemical Reviews, 2019, 119(5): 3036–3103

[3] Yu X, Tsao H N, Zhang Z, Gao P. Miscellaneous and perspicacious: hybrid halide perovskite materials based photodetectors and sensors. Advanced Optical Materials, 2020, 8(21): 2001095

[4] Fang Y, Dong Q, Shao Y, Yuan Y, Huang J. Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination. Nature Photonics, 2015, 9(10): 679–686

[5] Wang H P, Li S, Liu X, Shi Z, Fang X, He J H. Low-dimensional metal halide perovskite photodetectors. Advanced Materials, 2021, 33(7): e2003309

[6] Tan Z K, Moghaddam R S, Lai M L, Docampo P, Higler R, Deschler F, Price M, Sadhanala A, Pazos L M, Credgington D, Hanusch F, Bein T, Snaith H J, Friend R H. Bright light-emitting diodes based on organometal halide perovskite. Nature Nanotechnology, 2014, 9(9): 687–692

[7] Xu W, Hu Q, Bai S, Bao C, Miao Y, Yuan Z, Borzda T, Barker A J, Tyukalova E, Hu Z, Kawecki M, Wang H, Yan Z, Liu X, Shi X, Uvdal K, Fahlman M, Zhang W, Duchamp M, Liu J M, Petrozza A, Wang J, Liu L M, Huang W, Gao F. Rational molecular passivation for high-performance perovskite light-emitting diodes. Nature Photonics, 2019, 13(6): 418–424

[8] Luo J, Wang X, Li S, Liu J, Guo Y, Niu G, Yao L, Fu Y, Gao L, Dong Q, Zhao C, Leng M, Ma F, Liang W, Wang L, Jin S, Han J, Zhang L, Etheridge J, Wang J, Yan Y, Sargent E H, Tang J. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature, 2018, 563(7732): 541–545

[9] Yan C, Lin K, Lu J, Wei Z. Composition engineering to obtain efficient hybrid perovskite light-emitting diodes. Frontiers of Optoelectronics, 2020, 13(3): 282–290

[10] Huang J, Yuan Y, Shao Y, Yan Y. Understanding the physical properties of hybrid perovskites for photovoltaic applications. Nature Reviews. Materials, 2017, 2(7): 17042

[11] Xiao Z, Yan Y. Progress in theoretical study of metal halide perovskite solar cell materials. Energy Materials, 2017, 7(22): 1701136

[12] Yin W J, Shi T, Yan Y. Unique properties of halide perovskites as possible origins of the superior solar cell performance. Advanced Materials, 2014, 26(27): 4653–4658

[13] Meng W, Wang X, Xiao Z, Wang J, Mitzi D B, Yan Y. Parity-forbidden transitions and their impact on the optical absorption properties of lead-free metal halide perovskites and double perovskites. Journal of Physical Chemistry Letters, 2017, 8(13): 2999–3007

[14] Umari P, Mosconi E, De Angelis F. Relativistic GW calculations on CH₃NH₃PbI₃ and CH₃NH₃SnI₃ perovskites for solar cell applications. Scientific Reports, 2014, 4(1): 4467

[15] Green M A, Jiang Y, Soufiani A M, Ho-Baillie A. Optical properties of photovoltaic organic-inorganic lead halide perovskites. Journal of Physical Chemistry Letters, 2015, 6(23): 4774–4785

[16] Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L M, Petrozza A, Snaith H J. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science, 2013, 342(6156): 341–344

[17] Yin W J, Shi T, Yan Y. Unusual defect physics in CH₃NH₃PbI₃ perovskite solar cell absorber. Applied Physics Letters, 2014, 104(6): 063903

[18] Kang J, Wang L W. High defect tolerance in lead halide perovskite CsPbBr₃. Journal of Physical Chemistry Letters, 2017, 8(2): 489–493

[19] Huang H, Bodnarchuk M I, Kershaw S V, Kovalenko M V, Rogach A L. Lead halide perovskite nanocrystals in the research spotlight: stability and defect tolerance. ACS Energy Letters, 2017, 2(9): 2071–2083

[20] Meggiolaro D, Motti S G, Mosconi E, Barker A J, Ball J, Andrea Riccardo Perini C, Deschler F, Petrozza A, De Angelis F. Iodine chemistry determines the defect tolerance of lead-halide perovskites. Energy & Environmental Science, 2018, 11(3): 702–713

[21] Chen K, Li L. Ordered structures with functional units as a paradigm of material design. Advanced Materials, 2019, 31(32): e1901115

[22] Xiao Z, Meng W, Wang J, Mitzi D B, Yan Y. Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality. Materials Horizons, 2017, 4(2): 206–216

[23] Stoumpos C C, Malliakas C D, Kanatzidis M G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorganic Chemistry, 2013, 52(15): 9019–9038

[24] Brgoch J, Lehner A J, Chabinyc M L, Seshadri R. Ab initio calculations of band gaps and absolute band positions of polymorphs of RbPbI₃ and CsPbI₃: implications for main-group halide perovskite photovoltaics. Journal of Physical Chemistry C, 2014, 118(48): 27721–27727

[25] Saparov B, Mitzi D B. Organic-inorganic perovskites: structural versatility for functional materials design. Chemical Reviews, 2016, 116(7): 4558–4596

[26] Kahwagi R F, Thornton S T, Smith B, Koleilat G I. Dimensionality engineering of metal halide perovskites. Frontiers of Optoelectronics, 2020, 13(3): 196–224

[27] Raptopoulou C P, Terzis A, Mousdis G A, Papavassiliou G C. Preparation, structure and optical properties of [CH₃SC(NH₂)₂]₃SnI₅, [CH₃SC(NH₂)₂][HSC(NH₂)₂]SnBr₄, (CH₃C₅H₄NCH₃)PbBr₃, and [C₆H₅CH₂SC(NH₂)₂]₄Pb₃I₁₀. Zeitschrift für Naturforschung. Teil B. Anorganische Chemie, Organische Chemie, Biochemie, Biophysik, Biologie, 2002, 57(6): 645–650

[28] Saidaminov M I, Almutlaq J, Sarmah S, Dursun I, Zhumekenov A A, Begum R, Pan J, Cho N, Mohammed O F, Bakr O M. Pure Cs₄PbBr₆: highly luminescent zero-dimensional perovskite solids. ACS Energy Letters, 2016, 1(4): 840–845

[29] Zhang Y, Saidaminov M I, Dursun I, Yang H, Murali B, Alarousu E, Yengel E, Alshankiti B A, Bakr O M, Mohammed O F. Zero-dimensional Cs₄PbBr₆ perovskite nanocrystals. Journal of Physical Chemistry Letters, 2017, 8(5): 961–965

[30] Lin H, Zhou C, Tian Y, Siegrist T, Ma B. Low-dimensional organometal halide perovskites. ACS Energy Letters, 2018, 3(1): 54–62

[31] Smith M D, Connor B A, Karunadasa H I. Tuning the luminescence of layered halide perovskites. Chemical Reviews, 2019, 119(5): 3104–3139

[32] Tan Z, Li J, Zhang C, Li Z, Hu Q, Xiao Z, Kamiya T, Hosono H, Niu G, Lifshitz E, Cheng Y, Tang J. Highly efficient blue-emitting Bi-doped Cs₂SnCl₆ perovskite variant: photoluminescence induced by impurity doping. Advanced Functional Materials, 2018, 28(29): 1801131

[33] Li J, Tan Z, Hu M, Chen C, Luo J, Li S, Gao L, Xiao Z, Niu G, Tang J. Antimony doped Cs₂SnCl₆ with bright and stable emission. Frontiers of Optoelectronics, 2019, 12(4): 352–364

[34] Tan Z, Chu Y, Chen J, Li J, Ji G, Niu G, Gao L, Xiao Z, Tang J. Lead-free perovskite variant solid solutions Cs₂Sn_1−xTe_xCl₆: bright luminescence and high anti-water stability. Advanced Materials, 2020, 32(32): e2002443

[35] Xiao Z, Song Z, Yan Y. From lead halide perovskites to lead-free metal halide perovskites and perovskite derivatives. Advanced Materials, 2019, 31(47): e1803792

[36] Zhao X G G, Yang D, Ren J C C, Sun Y, Xiao Z, Zhang L. Rational design of halide double perovskites for optoelectronic applications. Joule, 2018, 2(9): 1662–1673

[37] Swarnkar A, Marshall A R, Sanehira E M, Chernomordik B D, Moore D T, Christians J A, Chakrabarti T, Luther J M. Quantum dot-induced phase stabilization of α-CsPbI₃ perovskite for high-efficiency photovoltaics. Science, 2016, 354(6308): 92–95

[38] Jiang Y, Yuan J, Ni Y, Yang J, Wang Y, Jiu T, Yuan M, Chen J. Reduced-dimensional α-CsPbX₃ perovskites for efficient and stable photovoltaics. Joule, 2018, 2(7): 1356–1368

[39] Han B, Cai B, Shan Q, Song J, Li J, Zhang F, Chen J, Fang T, Ji Q, Xu X, Zeng H. Stable, efficient red perovskite light-emitting diodes by (α,δ)-CsPbI₃ phase engineering. Advanced Functional Materials, 2018, 28(47): 1804285

[40] Chen K, Zhong Q, Chen W, Sang B, Wang Y, Yang T, Liu Y, Zhang Y, Zhang H. Short-chain ligand-passivated stable α-CsPbI₃ quantum dot for all-inorganic perovskite solar cells. Advanced Functional Materials, 2019, 29(24): 1900991

[41] Hu Y, Bai F, Liu X, Ji Q, Miao X, Qiu T, Zhang S. Bismuth incorporation stabilized α-CsPbI₃ for fully inorganic perovskite solar cells. ACS Energy Letters, 2017, 2(10): 2219–2227

[42] Woodward P M. Octahedral tilting in perovskites. I. Geometrical considerations. Acta Crystallographica. Section B, Structural Science, 1997, 53(1): 32–43

[43] Umeyama D, Leppert L, Connor B A, Manumpil M A, Neaton J B, Karunadasa H I. Expanded analogs of three-dimensional lead-halide hybrid perovskites. Angewandte Chemie International Edition, 2020, 59(43): 19087–19094

[44] Tang Z, Guan J, Guloy A M. Synthesis and crystal structure of new organic-based layered perovskites with 2,2′-biimidazolium cations. Journal of Materials Chemistry, 2001, 11(2): 479–482

[45] Quarti C, Grancini G, Mosconi E, Bruno P, Ball J M, Lee M M, Snaith H J, Petrozza A, Angelis F D. The Raman spectrum of the CH₃NH₃PbI₃ hybrid perovskite: interplay of theory and experiment. Journal of Physical Chemistry Letters, 2014, 5(2): 279–284

[46] Cortecchia D, Neutzner S, Srimath Kandada A R, Mosconi E, Meggiolaro D, De Angelis F, Soci C, Petrozza A. Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. Journal of the American Chemical Society, 2017, 139(1): 39–42

[47] Yaffe O, Guo Y, Tan L Z, Egger D A, Hull T, Stoumpos C C, Zheng F, Heinz T F, Kronik L, Kanatzidis M G, Owen J S, Rappe A M, Pimenta M A, Brus L E. Local polar fluctuations in lead halide perovskite crystals. Physical Review Letters, 2017, 118(13): 136001

[48] Xiao Z, Meng W, Saparov B, Duan H S, Wang C, Feng C, Liao W, Ke W, Zhao D, Wang J, Mitzi D B, Yan Y. Photovoltaic properties of two-dimensional (CH₃NH₃)₂Pb(SCN)₂I₂ perovskite: a combined experimental and density functional theory study. Journal of Physical Chemistry Letters, 2016, 7(7): 1213–1218

[49] Saba M, Cadelano M, Marongiu D, Chen F, Sarritzu V, Sestu N, Figus C, Aresti M, Piras R, Lehmann A G, Cannas C, Musinu A, Quochi F, Mura A, Bongiovanni G. Correlated electron-hole plasma in organometal perovskites. Nature Communications, 2014, 5(1): 5049

[50] Shi J, Zhang H, Li Y, Jasieniak J J, Li Y, Wu H, Luo Y, Li D, Meng Q. Identification of high-temperature exciton states and their phase-dependent trapping behaviour in lead halide perovskites. Energy & Environmental Science, 2018, 11(6): 1460–1469

[51] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996, 54(16): 11169–11186

[52] Wang Y, Lv J, Zhu L, Ma Y. Crystal structure prediction via particle-swarm optimization. Physical Review B: Condensed Matter and Materials Physics, 2010, 82(9): 094116

[53] Wang Y, Lv J, Zhu L, Ma Y. CALYPSO: a method for crystal structure prediction. Computer Physics Communications, 2012, 183(10): 2063–2070

[54] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[55] Togo A, Tanaka I. First principles phonon calculations in materials science. Scripta Materialia, 2015, 108: 1–5

[56] Zheng Q. VASP_TDM, https://github.com/QijingZheng/VASP_TDM, 2016

[57] Heyd J, Scuseria G E, Ernzerhof M. Hybrid functionals based on a screened Coulomb potential. Journal of Chemical Physics, 2003, 118(18): 8207–8215

[58] Heyd J, Scuseria G E, Ernzerhof M. Erratum: “Hybrid functionals based on a screened Coulomb potential”. Journal of Chemical Physics, 2006, 124(21): 219906

[59] Fonari A, Stauffer S. VASP_RAMAN.PY, https://github.com/raman-sc/VASP, 2013

[60] Matsumoto S, Watanabe M, Akazome M. Incrementing Stokes shifts through the formation of 2,2′-biimidazoldiium salts. Organic Letters, 2018, 20(12): 3613–3617

[61] Momma K, Izumi F. VESTA : a three-dimensional visualization system for electronic and structural analysis. Journal of Applied Crystallography, 2008, 41(3): 653–658

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (NSFC) (Grant No. 51972130), Startup Fund of Huazhong University of Science and Technology, and Director Fund of Wuhan National Laboratory for Optoelectronics. The authors thank Prof. Kezhao Du in Fujian Normal University, China for the UV–Vis measurement, Yunpeng Yao in Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, China for providing experimental assistance toward photoresponse measurement, and Prof. Zhijun Ning in ShanghaiTech University, China for supporting the early-stage exploration.

Open Access

ƒThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.ƒTo view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

RIGHTS & PERMISSIONS

2021 The Author(s) 2021. This article is published with open access at link.springer.com and journal.hep.com.cn