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Title: 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:
 [1];  [2];  [3];  [1];  [2];  [1];  [4]; ORCiD logo [5]; ORCiD logo [6];  [7];  [8];  [9]; ORCiD logo [10]; ORCiD logo [11]
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  1. Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering
  2. Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program
  3. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
  4. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
  5. 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
  6. East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices; East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics
  7. Florida State Univ., Tallahassee, FL (United States). High-Performance Materials Institute (HPMI)
  8. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
  9. 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)
  10. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  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). 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.
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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.
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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.
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@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}
}
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Journal Article:
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DOI:  10.1021/acs.chemmater.8b00129
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Cited by: 9 works
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Figures / Tables:

Figure 1 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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Works referencing / citing this record:

CCDC 1813002: Experimental Crystal Structure Determination: KEZGOO : bis(tetraphenylphosphonium) pentachloro-antimony
dataset, December 2017

Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission
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  • Gautier, Romain; Massuyeau, Florian; Galnon, Gabin
  • Advanced Materials, Vol. 31, Issue 14
  • DOI: 10.1002/adma.201807383

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
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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
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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
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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
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Locally collective hydrogen bonding isolates lead octahedra for white emission improvement
journal, November 2019

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
  • DOI: 10.1039/c9dt03469b

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
  • DOI: 10.1039/c9ta08268a

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
  • DOI: 10.1002/adma.201807383

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
  • DOI: 10.1002/ange.201806452

Locally collective hydrogen bonding isolates lead octahedra for white emission improvement
journal, November 2019

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
  • DOI: 10.1039/c9dt00575g

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
  • DOI: 10.1039/c9dt03469b

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
  • DOI: 10.1039/c9qi00684b

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
  • DOI: 10.1039/c9ta08268a

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
  • DOI: 10.1039/c9tc03067k

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
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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
  • DOI: 10.1002/anie.201806452

Lead‐Free Halide Rb 2 CuBr 3 as Sensitive X‐Ray Scintillator
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Colloidal Synthesis and Optical Properties of All‐Inorganic Low‐Dimensional Cesium Copper Halide Nanocrystals
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Hybrid Chloroantimonates(III): Thermally Induced Triple‐Mode Reversible Luminescent Switching and Laser‐Printable Rewritable Luminescent Paper
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Colloidal Synthesis and Optical Properties of All‐Inorganic Low‐Dimensional Cesium Copper Halide Nanocrystals
journal, November 2019

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  • Angewandte Chemie International Edition, Vol. 58, Issue 45
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A moisture-stable organosulfonate-based metal–organic framework with intrinsic self-trapped white-light emission
journal, January 2020

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  • Chemical Communications, Vol. 56, Issue 9
  • DOI: 10.1039/c9cc09486e

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Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li 2 B 12 H 12
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  • Du, Mao-Hua; Shi, Hongliang; Zhang, S. B.
  • Journal of Materials Chemistry C, Vol. 7, Issue 45
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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
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Optically pumped white light-emitting diodes based on metal halide perovskites and perovskite-related materials
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