Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency
Abstract
Here, we report the synthesis and characterization of (Ph4P)2SbCl5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph4P+) and antimony (Sb3+) chloride salts, (Ph4P)2SbCl5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl52– with strong excited-state structural distortion. Interestingly, (Ph4P)2SbCl5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.
- Authors:
-
- Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering
- Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
- East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices; East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices; East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics
- Florida State Univ., Tallahassee, FL (United States). High-Performance Materials Institute (HPMI)
- Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
- Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering; Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering; Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program; Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1435249
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 7; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b00129.
Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, & Ma, Biwu. Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency. United States. doi:10.1021/acs.chemmater.8b00129.
Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Mon .
"Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency". United States. doi:10.1021/acs.chemmater.8b00129. https://www.osti.gov/servlets/purl/1435249.
@article{osti_1435249,
title = {Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency},
author = {Zhou, Chenkun and Worku, Michael and Neu, Jennifer and Lin, Haoran and Tian, Yu and Lee, Sujin and Zhou, Yan and Han, Dan and Chen, Shiyou and Hao, Ayou and Djurovich, Peter I. and Siegrist, Theo and Du, Mao-Hua and Ma, Biwu},
abstractNote = {Here, we report the synthesis and characterization of (Ph4P)2SbCl5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph4P+) and antimony (Sb3+) chloride salts, (Ph4P)2SbCl5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl52– with strong excited-state structural distortion. Interestingly, (Ph4P)2SbCl5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.},
doi = {10.1021/acs.chemmater.8b00129},
journal = {Chemistry of Materials},
number = 7,
volume = 30,
place = {United States},
year = {2018},
month = {3}
}
Web of Science
Figures / Tables:

Works referencing / citing this record:
CCDC 1813002: Experimental Crystal Structure Determination: KEZGOO : bis(tetraphenylphosphonium) pentachloro-antimony
dataset, December 2017
- Zhou, Chenkun; Worku, Michael; Neu, Jennifer
- Cambridge Structural Database (CSD)
Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission
journal, February 2019
- Gautier, Romain; Massuyeau, Florian; Galnon, Gabin
- Advanced Materials, Vol. 31, Issue 14
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides
journal, July 2018
- Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia
- Angewandte Chemie International Edition, Vol. 57, Issue 35
Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019
- Dehnhardt, Natalie; Böth, André; Heine, Johanna
- Dalton Transactions, Vol. 48, Issue 16
Organic cation directed hybrid lead halides of zero-dimensional to two-dimensional structures with tunable photoluminescence properties
journal, January 2019
- Yue, Cheng-Yang; Sun, Hai-Xiao; Liu, Quan-Xiu
- Inorganic Chemistry Frontiers, Vol. 6, Issue 10
Enhancing the phosphorescence of hybrid metal halides through molecular sensitization
journal, January 2019
- Gong, Liao-Kuo; Li, Jian-Rong; Wu, Zhao-Feng
- Journal of Materials Chemistry C, Vol. 7, Issue 32
Locally collective hydrogen bonding isolates lead octahedra for white emission improvement
journal, November 2019
- Cui, Bin-Bin; Han, Ying; Huang, Bolong
- Nature Communications, Vol. 10, Issue 1
Broadband white-light emission from supramolecular piperazinium-based lead halide perovskites linked by hydrogen bonds
journal, January 2019
- Jung, Mi-Hee; Ko, Kyoung Chul; Lee, Woo Ram
- Dalton Transactions, Vol. 48, Issue 40
Direct emission from quartet excited states triggered by upconversion phenomena in solid-phase synthesized fluorescent lead-free organic–inorganic hybrid compounds
journal, January 2019
- Jana, Atanu; Zhumagali, Shynggys; Ba, Qiankai
- Journal of Materials Chemistry A, Vol. 7, Issue 46
Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission
journal, February 2019
- Gautier, Romain; Massuyeau, Florian; Galnon, Gabin
- Advanced Materials, Vol. 31, Issue 14
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides
journal, July 2018
- Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia
- Angewandte Chemie, Vol. 130, Issue 35
Locally collective hydrogen bonding isolates lead octahedra for white emission improvement
journal, November 2019
- Cui, Bin-Bin; Han, Ying; Huang, Bolong
- Nature Communications, Vol. 10, Issue 1
Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019
- Dehnhardt, Natalie; Böth, André; Heine, Johanna
- Dalton Transactions, Vol. 48, Issue 16
Broadband white-light emission from supramolecular piperazinium-based lead halide perovskites linked by hydrogen bonds
journal, January 2019
- Jung, Mi-Hee; Ko, Kyoung Chul; Lee, Woo Ram
- Dalton Transactions, Vol. 48, Issue 40
Organic cation directed hybrid lead halides of zero-dimensional to two-dimensional structures with tunable photoluminescence properties
journal, January 2019
- Yue, Cheng-Yang; Sun, Hai-Xiao; Liu, Quan-Xiu
- Inorganic Chemistry Frontiers, Vol. 6, Issue 10
Direct emission from quartet excited states triggered by upconversion phenomena in solid-phase synthesized fluorescent lead-free organic–inorganic hybrid compounds
journal, January 2019
- Jana, Atanu; Zhumagali, Shynggys; Ba, Qiankai
- Journal of Materials Chemistry A, Vol. 7, Issue 46
Enhancing the phosphorescence of hybrid metal halides through molecular sensitization
journal, January 2019
- Gong, Liao-Kuo; Li, Jian-Rong; Wu, Zhao-Feng
- Journal of Materials Chemistry C, Vol. 7, Issue 32
Crystal structure and luminescence properties of lead-free metal halides (C 6 H 5 CH 2 NH 3 ) 3 MBr 6 (M = Bi and Sb)
journal, January 2020
- Chen, Da; Dai, Fulong; Hao, Shiqiang
- Journal of Materials Chemistry C
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides
journal, July 2018
- Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia
- Angewandte Chemie International Edition, Vol. 57, Issue 35
Lead‐Free Halide Rb 2 CuBr 3 as Sensitive X‐Ray Scintillator
journal, September 2019
- Yang, Bo; Yin, Lixiao; Niu, Guangda
- Advanced Materials, Vol. 31, Issue 44
Hybrid Chloroantimonates(III): Thermally Induced Triple‐Mode Reversible Luminescent Switching and Laser‐Printable Rewritable Luminescent Paper
journal, June 2019
- Wang, Zeping; Zhang, Zhizhuan; Tao, Luqi
- Angewandte Chemie, Vol. 131, Issue 29
Colloidal Synthesis and Optical Properties of All‐Inorganic Low‐Dimensional Cesium Copper Halide Nanocrystals
journal, September 2019
- Cheng, Pengfei; Sun, Lei; Feng, Lu
- Angewandte Chemie, Vol. 131, Issue 45
Hybrid Chloroantimonates(III): Thermally Induced Triple‐Mode Reversible Luminescent Switching and Laser‐Printable Rewritable Luminescent Paper
journal, July 2019
- Wang, Zeping; Zhang, Zhizhuan; Tao, Luqi
- Angewandte Chemie International Edition, Vol. 58, Issue 29
Colloidal Synthesis and Optical Properties of All‐Inorganic Low‐Dimensional Cesium Copper Halide Nanocrystals
journal, November 2019
- Cheng, Pengfei; Sun, Lei; Feng, Lu
- Angewandte Chemie International Edition, Vol. 58, Issue 45
A moisture-stable organosulfonate-based metal–organic framework with intrinsic self-trapped white-light emission
journal, January 2020
- Zhang, Guiyang; Yin, Jinlin; Song, Xueling
- Chemical Communications, Vol. 56, Issue 9
Zero-dimensional metal oxide Li 4 TiO 4
journal, January 2019
- Du, Mao-Hua
- Journal of Materials Chemistry C, Vol. 7, Issue 19
Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li 2 B 12 H 12
journal, January 2019
- Du, Mao-Hua; Shi, Hongliang; Zhang, S. B.
- Journal of Materials Chemistry C, Vol. 7, Issue 45
Microscopic origin of multiple exciton emission in low-dimensional lead halide perovskites
journal, November 2019
- Du, Mao-Hua
- The Journal of Chemical Physics, Vol. 151, Issue 18
Optically pumped white light-emitting diodes based on metal halide perovskites and perovskite-related materials
journal, January 2020
- Worku, Michael; Xu, Liang-Jin; Chaaban, Maya
- APL Materials, Vol. 8, Issue 1
Figures / Tables found in this record: