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:
-
[5];
[6];
[10];
[11]
- 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 Laboratory (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. https://doi.org/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. https://doi.org/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 = {Mon Mar 12 00:00:00 EDT 2018},
month = {Mon Mar 12 00:00:00 EDT 2018}
}
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Figures / Tables:
Figure 1: a) View of the structure of (Ph4P)2SbCl5 (red spheres: antimony atoms; blue spheres: chloride atoms; orange spheres: nitrogen atoms; gray spheres: carbon atoms; red polyhedra: SbCl52-; hydrogen atoms are hidden for clarity). b) View of an individual SbCl52- anion and nearest neighbor Ph4P+ cations.
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