Crystal structure and luminescence properties of lead-free metal halides (C6H5CH2NH3)3MBr6 (M = Bi and Sb)

Chen, Da; Dai, Fulong; Hao, Shiqiang; Zhou, Guojun; Liu, Quanlin; Wolverton, Christopher; Zhao, Jing; Xia, Zhiguo

doi:10.1039/d0tc00562b

Crystal structure and luminescence properties of lead-free metal halides (C₆H₅CH₂NH₃)₃MBr₆ (M = Bi and Sb)

Journal Article · Thu Mar 19 00:00:00 EDT 2020 · Journal of Materials Chemistry C

DOI:https://doi.org/10.1039/d0tc00562b· OSTI ID:1777408

Chen, Da ^[1]; Dai, Fulong ^[2]; Hao, Shiqiang ^[3]; Zhou, Guojun ^[2]; ^[2]; Wolverton, Christopher ^[3]; ^[2]; Xia, Zhiguo ^[4]

Univ. of Science and Technology Beijing (China); Northwestern University
Univ. of Science and Technology Beijing (China)
Northwestern Univ., Evanston, IL (United States)
Univ. of Science and Technology Beijing (China); South China Univ. of Technology, Guangzhou (China)

Organic–inorganic hybrid metal halides have received extensive attention owing to their versatile structures and optoelectronic properties. Herein, we report two lead-free metal halides, (PMA)₃BiBr₆ and (PMA)₃SbBr₆ [PMA⁺: (C₆H₅CH₂NH₃)⁺, as the abbreviation of phenylmethylammonium], which possess iso-structural zero-dimensional structures and crystallize in the monoclinic space group P2₁/c. (PMA)₃BiBr₆ and (PMA)₃SbBr₆ exhibit optical band gaps of ~3.50 and 3.40 eV, respectively, and density functional theory calculations reveal their indirect bandgap behaviors. Upon 350 and 425 nm excitation, (PMA)₃BiBr₆ and (PMA)₃SbBr₆ exhibit broadband emission peaking at 510 nm and 625 nm with wide full-widths at half-maximum of ~153 and 175 nm, respectively. The emission mechanism of the metal halides is attributed to self-trapped exciton emission. The relationship between the crystal structure and luminescence intensity is also discussed. Lastly, both metal halides have high decomposition temperatures and are stable for long-term storage under ambient conditions, demonstrating their potential for optoelectronic applications.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014520

OSTI ID:: 1777408

Alternate ID(s):: OSTI ID: 1632768

Journal Information:: Journal of Materials Chemistry C, Journal Name: Journal of Materials Chemistry C Journal Issue: 22 Vol. 8; ISSN 2050-7526

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

All-Inorganic Bismuth-Based Perovskite Quantum Dots with Bright Blue Photoluminescence and Excellent Stability Leng, Meiying; Yang, Ying; Zeng, Kai Advanced Functional Materials, Vol. 28, Issue 1 https://doi.org/10.1002/adfm.201704446	journal	November 2017
Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission Gautier, Romain; Massuyeau, Florian; Galnon, Gabin Advanced Materials, Vol. 31, Issue 14 https://doi.org/10.1002/adma.201807383	journal	February 2019
Lead-Free, Blue Emitting Bismuth Halide Perovskite Quantum Dots Leng, Meiying; Chen, Zhengwu; Yang, Ying Angewandte Chemie, Vol. 128, Issue 48 https://doi.org/10.1002/ange.201608160	journal	October 2016
Lead-Free, Blue Emitting Bismuth Halide Perovskite Quantum Dots Leng, Meiying; Chen, Zhengwu; Yang, Ying Angewandte Chemie International Edition, Vol. 55, Issue 48 https://doi.org/10.1002/anie.201608160	journal	October 2016
Air-Stable, Lead-Free Zero-Dimensional Mixed Bismuth-Antimony Perovskite Single Crystals with Ultra-broadband Emission Zhang, Ruiling; Mao, Xin; Yang, Yang Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201812865	journal	February 2019
Novel bismuth nanotube arrays synthesized by solvothermal method Liu, Xin-yuan; Zeng, Jing-hui; Zhang, Shu-yuan Chemical Physics Letters, Vol. 374, Issue 3-4 https://doi.org/10.1016/S0009-2614(03)00730-9	journal	June 2003
Structural characterization, vibrational studies and optical properties of a new luminescent organic-inorganic material [C 6 H 20 N 3 ]BiI 6 ·H 2 O Elfaleh, N.; Kamoun, S. Journal of Organometallic Chemistry, Vol. 819 https://doi.org/10.1016/j.jorganchem.2016.06.029	journal	September 2016
Rational Design of Halide Double Perovskites for Optoelectronic Applications Zhao, Xin-Gang; Yang, Dongwen; Ren, Ji-Chang Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.06.017	journal	September 2018
Methylammonium Chloride Induces Intermediate Phase Stabilization for Efficient Perovskite Solar Cells Kim, Minjin; Kim, Gi-Hwan; Lee, Tae Kyung Joule, Vol. 3, Issue 9 https://doi.org/10.1016/j.joule.2019.06.014	journal	September 2019
Optical properties and ab initio study on the hybrid organic–inorganic material [(CH3)2NH2]3[BiI6] Samet, A.; Ahmed, A. Ben; Mlayah, A. Journal of Molecular Structure, Vol. 977, Issue 1-3 https://doi.org/10.1016/j.molstruc.2010.05.016	journal	August 2010
Crystal structure, vibrational and optical properties of N-(3-ammoniumpropyl)-1,3 diammoniumpropane hexabromobismuthate monohydrate: [C6H20N3]BiBr6 H2O Elfaleh, N.; Kamoun, S. Journal of Molecular Structure, Vol. 1075 https://doi.org/10.1016/j.molstruc.2014.07.018	journal	October 2014
Synthesis, crystal structure, and spectroscopic studies of organic–inorganic hybrid material: [C7H10NO]2BiBr5 Aloui, Z.; Ferretti, V.; Abid, S. Journal of Molecular Structure, Vol. 1118 https://doi.org/10.1016/j.molstruc.2016.04.036	journal	August 2016
Crystal structure, ionic conductivity and dielectric relaxation studies in the (C5H10N)2BiBr5 compound Masmoudi, W.; Kamoun, S.; Ayedi, H. F. Physica B: Condensed Matter, Vol. 407, Issue 13 https://doi.org/10.1016/j.physb.2012.02.037	journal	July 2012
Synthesis, crystal structure, vibrational spectroscopy, optical properties and theoretical studies of a new organic–inorganic hybrid material: [((CH3)2NH2)+]6·[(BiBr6)3−]2 Ben Ahmed, A.; Feki, H.; Abid, Y. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 133 https://doi.org/10.1016/j.saa.2014.05.073	journal	December 2014
Crystal structure, vibrational spectra and non-linear optical properties of diethylenetriammonium hexabromobismuthate: C4H16N3BiBr6 Dammak, Hajer; Feki, Habib; Boughzala, Habib Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 137 https://doi.org/10.1016/j.saa.2014.08.150	journal	February 2015
White-Light Emission from Layered Halide Perovskites Smith, Matthew D.; Karunadasa, Hemamala I. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00433	journal	February 2018
Rb as an Alternative Cation for Templating Inorganic Lead-Free Perovskites for Solution Processed Photovoltaics Harikesh, P. C.; Mulmudi, Hemant Kumar; Ghosh, Biplab Chemistry of Materials, Vol. 28, Issue 20 https://doi.org/10.1021/acs.chemmater.6b03310	journal	October 2016
Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency Zhou, Chenkun; Worku, Michael; Neu, Jennifer Chemistry of Materials, Vol. 30, Issue 7 https://doi.org/10.1021/acs.chemmater.8b00129	journal	March 2018
From 0D Cs ₃ Bi ₂ I ₉ to 2D Cs ₃ Bi ₂ I ₆ Cl ₃ : Dimensional Expansion Induces a Direct Band Gap but Enhances Electron–Phonon Coupling McCall, Kyle M.; Stoumpos, Constantinos C.; Kontsevoi, Oleg Y. Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00636	journal	March 2019
Hybrid Charge-Transfer Semiconductors: (C ₇ H ₇ )SbI ₄ , (C ₇ H ₇ )BiI ₄ , and Their Halide Congeners Oswald, Iain W. H.; Mozur, Eve M.; Moseley, Ian P. Inorganic Chemistry, Vol. 58, Issue 9 https://doi.org/10.1021/acs.inorgchem.9b00170	journal	March 2019
Two Heteromorphic Crystals of Antimony-Based Hybrids Showing Tunable Optical Band Gaps and Distinct Photoelectric Responses Li, Yaobin; Xu, Zhiyun; Liu, Xitao Inorganic Chemistry, Vol. 58, Issue 9 https://doi.org/10.1021/acs.inorgchem.9b00718	journal	April 2019
Lead-Free Broadband Orange-Emitting Zero-Dimensional Hybrid (PMA) ₃ InBr ₆ with Direct Band Gap Chen, Da; Hao, Shiqiang; Zhou, Guojun Inorganic Chemistry, Vol. 58, Issue 22 https://doi.org/10.1021/acs.inorgchem.9b02669	journal	October 2019
Sb ³⁺ Doping-Induced Triplet Self-Trapped Excitons Emission in Lead-Free Cs ₂ SnCl ₆ Nanocrystals Jing, Yuyu; Liu, Ying; Zhao, Jing The Journal of Physical Chemistry Letters, Vol. 10, Issue 23 https://doi.org/10.1021/acs.jpclett.9b03035	journal	November 2019
Optoelectronic Properties of (CH ₃ NH ₃ ) ₃ Sb ₂ I ₉ Thin Films for Photovoltaic Applications Hebig, Jan-Christoph; Kühn, Irina; Flohre, Jan ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00170	journal	June 2016
Broadband Emission in a New Two-Dimensional Cd-Based Hybrid Perovskite Yangui, Aymen; Pillet, Sebastien; Bendeif, El-Eulmi ACS Photonics, Vol. 5, Issue 4 https://doi.org/10.1021/acsphotonics.8b00052	journal	January 2018
Temperature Quenching of Yellow Ce ³⁺ Luminescence in YAG:Ce Bachmann, Volker; Ronda, Cees; Meijerink, Andries Chemistry of Materials, Vol. 21, Issue 10 https://doi.org/10.1021/cm8030768	journal	May 2009
Identification, Isolation, and Characterization of Cysteinate and Thiolactate Complexes of Bismuth Briand, Glen G.; Burford, Neil; Eelman, Melanie D. Inorganic Chemistry, Vol. 43, Issue 20 https://doi.org/10.1021/ic049594n	journal	October 2004
Ultraviolet photoelectron spectroscopy of thiaboranes Fehlner, T. P.; Wu, M.; Meneghelli, B. J. Inorganic Chemistry, Vol. 19, Issue 1 https://doi.org/10.1021/ic50203a011	journal	January 1980
Intrinsic White-Light Emission from Layered Hybrid Perovskites Dohner, Emma R.; Jaffe, Adam; Bradshaw, Liam R. Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja507086b	journal	September 2014
Hybrid Germanium Iodide Perovskite Semiconductors: Active Lone Pairs, Structural Distortions, Direct and Indirect Energy Gaps, and Strong Nonlinear Optical Properties Stoumpos, Constantinos C.; Frazer, Laszlo; Clark, Daniel J. Journal of the American Chemical Society, Vol. 137, Issue 21 https://doi.org/10.1021/jacs.5b01025	journal	May 2015
2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications Cao, Duyen H.; Stoumpos, Constantinos C.; Farha, Omar K. Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03796	journal	June 2015
Structural Diversity in White-Light-Emitting Hybrid Lead Bromide Perovskites Mao, Lingling; Guo, Peijun; Kepenekian, Mikaël Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b08691	journal	September 2018
Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation Morad, Viktoriia; Shynkarenko, Yevhen; Yakunin, Sergii Journal of the American Chemical Society, Vol. 141, Issue 25 https://doi.org/10.1021/jacs.9b02365	journal	June 2019
Luminescence and Energy Transfer in Lu ₃ Al ₅ O ₁₂ Scintillators Co-Doped with Ce ³⁺ and Tb ³⁺ Ogiegło, Joanna M.; Zych, Aleksander; Ivanovskikh, Konstantin V. The Journal of Physical Chemistry A, Vol. 116, Issue 33 https://doi.org/10.1021/jp301337f	journal	August 2012
Room-Temperature Near-Infrared High-Q Perovskite Whispering-Gallery Planar Nanolasers Zhang, Qing; Ha, Son Tung; Liu, Xinfeng Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl503057g	journal	September 2014
Solution-processed hybrid perovskite photodetectors with high detectivity Dou, Letian; Yang, Yang (Micheal); You, Jingbi Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6404	journal	November 2014
Lead-free solid-state organic–inorganic halide perovskite solar cells Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh Nature Photonics, Vol. 8, Issue 6 https://doi.org/10.1038/nphoton.2014.82	journal	May 2014
Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells Wang, Nana; Cheng, Lu; Ge, Rui Nature Photonics, Vol. 10, Issue 11 https://doi.org/10.1038/nphoton.2016.185	journal	September 2016
Locally collective hydrogen bonding isolates lead octahedra for white emission improvement Cui, Bin-Bin; Han, Ying; Huang, Bolong Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13264-5	journal	November 2019
Efficient and stable emission of warm-white light from lead-free halide double perovskites Luo, Jiajun; Wang, Xiaoming; Li, Shunran Nature, Vol. 563, Issue 7732 https://doi.org/10.1038/s41586-018-0691-0	journal	November 2018
Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency Zhou, Chenkun; Lin, Haoran; Tian, Yu Chemical Science, Vol. 9, Issue 3 https://doi.org/10.1039/C7SC04539E	journal	January 2018
Luminescent perovskites: recent advances in theory and experiments Song, Zhen; Zhao, Jing; Liu, Quanlin Inorganic Chemistry Frontiers, Vol. 6, Issue 11 https://doi.org/10.1039/C9QI00777F	journal	January 2019
Properties and structural phase transitions of (CH ₃ NH ₃ ) ₃ Sb ₂ I ₉ Zaleski, J.; Jakubas, R.; Sobczyk, L. Ferroelectrics, Vol. 103, Issue 1 https://doi.org/10.1080/00150199008211375	journal	June 1990
The Structures of s ² Metal Complexes in the Ground and sp Excited States Vogler, Arnd; Nikol, Hans Comments on Inorganic Chemistry, Vol. 14, Issue 4 https://doi.org/10.1080/02603599308048663	journal	January 1993
Luminescence linewidths of excitons in GaAs quantum wells below 150 K Lee, Johnson; Koteles, Emil S.; Vassell, M. O. Physical Review B, Vol. 33, Issue 8 https://doi.org/10.1103/PhysRevB.33.5512	journal	April 1986
Time-resolved luminescence study of self-trapped-exciton relaxation in quasi-one-dimensional halogen-bridged mixed-valence metal complexes Wada, Y.; Lemmer, U.; Göbel, E. O. Physical Review B, Vol. 52, Issue 11 https://doi.org/10.1103/PhysRevB.52.8276	journal	September 1995
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Femtosecond Dynamics of the Exciton Self-Trapping Process in a Quasi-One-Dimensional Halogen-Bridged Platinum Complex Tomimoto, S.; Nansei, H.; Saito, S. Physical Review Letters, Vol. 81, Issue 2 https://doi.org/10.1103/PhysRevLett.81.417	journal	July 1998
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra Robinson, K.; Gibbs, G. V.; Ribbe, P. H. Science, Vol. 172, Issue 3983 https://doi.org/10.1126/science.172.3983.567	journal	May 1971
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals Shi, D.; Adinolfi, V.; Comin, R. Science, Vol. 347, Issue 6221 https://doi.org/10.1126/science.aaa2725	journal	January 2015
Photoluminescence Spectra of $\bf Eu^{2+}$ Centers in Ca(S, Se):Eu and Sr(S, Se):Eu Yamashita, Nobuhiko; Harada, Osamu; Nakamura, Kaizo Japanese Journal of Applied Physics, Vol. 34, Issue Part 1, No. 10 https://doi.org/10.1143/JJAP.34.5539	journal	October 1995
Rb as an Alternative Cation for Templating Inorganic Lead-Free Perovskites for Solution Processed Photovoltaics Harikesh, P. C.; Mulmudi, Hemant; Ghosh, Biplab Open Science Framework https://doi.org/10.17605/osf.io/894g2	text	January 2019
Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells Wang, Nana; Cheng, L.; Ge, R. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.9307	text	January 2016
Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation Viktoriia, Morad,; Yevhen, Shynkarenko,; Sergii, Yakunin, ETH Zurich https://doi.org/10.3929/ethz-b-000353692	text	January 2019
The Structures of s² Metal Complexes in the Ground and sp Excited States Vogler, Arnd; Nikol, H. Universität Regensburg https://doi.org/10.5283/epub.13582	text	January 1993

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Crystal structure and luminescence properties of lead-free metal halides (C₆H₅CH₂NH₃)₃MBr₆ (M = Bi and Sb)