skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Zero-dimensional Cs 4EuX 6 (X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy

Abstract

Organic–inorganic and all-inorganic halide perovskites have become leading candidates toward high-performance optoelectronic devices and radiation detectors. In this work, we report novel zero-dimensional Cs 4EuX 6 (X = Br, I) perovskite single crystals as self-activated scintillators with superior performance for gamma-ray spectroscopy. Both Cs 4EuBr 6 and Cs 4EuI 6 single crystals grown by the Bridgman method were determined to have the trigonal crystal structure with the R$$\bar{3}$$c space group, and have a melting point of approximately 540°C. Cs 4EuBr 6 and Cs4EuI 6 exhibit blue emission under UV excitation and high light yields of 78,000 ± 4000 photons/MeV and 53,000 ± 3000 photons/MeV under 137Cs gamma-ray irradiation, respectively. In particular, the former represents the best result achieved for self-activated scintillators thus far. Thermally stimulated luminescence studies and density functional theory calculations elucidate the correlation between halogen vacancies and long-lived emission (afterglow) at room temperature in Cs4EuX 6 (X=Br, I) single crystals. In conclusion, our findings not only demonstrate the high gamma-ray detection efficiency in Cs 4EuX 6 (X=Br, I), but will further promote the development of 0D metal halide-based novel luminescent and radiation detection materials.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6];  [1];  [1];  [1];  [7];  [8];  [9]
  1. Univ. of Tennessee, Knoxville, TN (United States). Scintillation Materials Research Center; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
  2. East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices (Ministry of Education); East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  4. Beihang Univ., Beijing (China). Key Lab. of Micro-Nano Measurement-Manipulation and Physics (Ministry of Education), Dept. of Physics
  5. East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices (Ministry of Education)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  7. Univ. of Tennessee, Knoxville, TN (United States). Scintillation Materials Research Center; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education
  8. Univ. of Tennessee, Knoxville, TN (United States). Scintillation Materials Research Center
  9. Univ. of Tennessee, Knoxville, TN (United States). Scintillation Materials Research Center; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Nuclear Engineering
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)
OSTI Identifier:
1459274
Alternate Identifier(s):
OSTI ID: 1455088
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 6; Journal Issue: 25; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Perovskites; zero-dimensional; radiation detection; scintillators

Citation Formats

Wu, Yuntao, Han, Dan, Chakoumakos, Bryan C., Shi, Hongliang, Chen, Shiyou, Du, Mao-Hua, Greeley, Ian, Loyd, Matthew, Rutstrom, Daniel J., Stand, Luis, Koschan, Merry, and Melcher, Charles L. Zero-dimensional Cs4EuX6 (X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy. United States: N. p., 2018. Web. doi:10.1039/C8TC01458B.
Wu, Yuntao, Han, Dan, Chakoumakos, Bryan C., Shi, Hongliang, Chen, Shiyou, Du, Mao-Hua, Greeley, Ian, Loyd, Matthew, Rutstrom, Daniel J., Stand, Luis, Koschan, Merry, & Melcher, Charles L. Zero-dimensional Cs4EuX6 (X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy. United States. https://doi.org/10.1039/C8TC01458B
Wu, Yuntao, Han, Dan, Chakoumakos, Bryan C., Shi, Hongliang, Chen, Shiyou, Du, Mao-Hua, Greeley, Ian, Loyd, Matthew, Rutstrom, Daniel J., Stand, Luis, Koschan, Merry, and Melcher, Charles L. Fri . "Zero-dimensional Cs4EuX6 (X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy". United States. https://doi.org/10.1039/C8TC01458B. https://www.osti.gov/servlets/purl/1459274.
@article{osti_1459274,
title = {Zero-dimensional Cs4EuX6 (X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy},
author = {Wu, Yuntao and Han, Dan and Chakoumakos, Bryan C. and Shi, Hongliang and Chen, Shiyou and Du, Mao-Hua and Greeley, Ian and Loyd, Matthew and Rutstrom, Daniel J. and Stand, Luis and Koschan, Merry and Melcher, Charles L.},
abstractNote = {Organic–inorganic and all-inorganic halide perovskites have become leading candidates toward high-performance optoelectronic devices and radiation detectors. In this work, we report novel zero-dimensional Cs4EuX6 (X = Br, I) perovskite single crystals as self-activated scintillators with superior performance for gamma-ray spectroscopy. Both Cs4EuBr6 and Cs4EuI6 single crystals grown by the Bridgman method were determined to have the trigonal crystal structure with the R$\bar{3}$c space group, and have a melting point of approximately 540°C. Cs4EuBr6 and Cs4EuI6 exhibit blue emission under UV excitation and high light yields of 78,000 ± 4000 photons/MeV and 53,000 ± 3000 photons/MeV under 137Cs gamma-ray irradiation, respectively. In particular, the former represents the best result achieved for self-activated scintillators thus far. Thermally stimulated luminescence studies and density functional theory calculations elucidate the correlation between halogen vacancies and long-lived emission (afterglow) at room temperature in Cs4EuX6 (X=Br, I) single crystals. In conclusion, our findings not only demonstrate the high gamma-ray detection efficiency in Cs4EuX6 (X=Br, I), but will further promote the development of 0D metal halide-based novel luminescent and radiation detection materials.},
doi = {10.1039/C8TC01458B},
url = {https://www.osti.gov/biblio/1459274}, journal = {Journal of Materials Chemistry C},
issn = {2050-7526},
number = 25,
volume = 6,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) A 12-mm diameter as-grown Cs 4EuBr 6 single crystal. (b) A 7-mm diameter as-grown Cs 4EuI 6 single crystal and (c) a 1-mm thick Cs 4EuI 6 slab. (d) Optical transmission spectra of 1 mm thick Cs 4EuBr 6 and Cs 4EuI 6 crystal slabs. (e) Differentialmore » scanning calorimeter curves of Cs 4EuBr 6 and Cs 4EuI 6 single crystals. (f) DVS curves of Cs 4EuBr 6 and Cs 4EuI 6 single crystals. The DVS curve of a NaI standard sample is also shown for comparison.« less

Save / Share:

Works referenced in this record:

WinGX and ORTEP for Windows : an update
journal, July 2012


Detection of X-ray photons by solution-processed lead halide perovskites
journal, May 2015


Interface engineering of highly efficient perovskite solar cells
journal, July 2014


Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Ramifications of codoping SrI 2 :Eu with isovalent and aliovalent impurities
journal, December 2016


Defect Engineering by Codoping in KCaI 3 : Eu 2 + Single-Crystalline Scintillators
journal, September 2017


Impurity-bound small polarons in ZnO: Hybrid density functional calculations
journal, September 2009


Using DFT Methods to Study Activators in Optical Materials
journal, August 2015


Printable organometallic perovskite enables large-area, low-dose X-ray imaging
journal, October 2017


Crystal growth and scintillation properties of Cs3EuI5 crystals
journal, March 2011


Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency
journal, January 2018


CeBr/sub 3/ scintillators for gamma-ray spectroscopy
journal, December 2005


Electro-optics of perovskite solar cells
journal, December 2014


Crystal Growth of the Perovskite Semiconductor CsPbBr 3 : A New Material for High-Energy Radiation Detection
journal, June 2013


A Self-Powered and Stable All-Perovskite Photodetector-Solar Cell Nanosystem
journal, January 2016


Crystal growth and characterization of CsSr1-xEux I3 high light yield scintillators
journal, December 2010


Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals
journal, March 2016


Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016


Crystal structure, electronic structure, temperature-dependent optical and scintillation properties of CsCe 2 Br 7
journal, January 2015


Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination
journal, August 2015


A short history of SHELX
journal, December 2007


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Dopant compensation in alloyed CH3NH3PbBr3−xClx perovskite single crystals for gamma-ray spectroscopy
journal, July 2017


Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX 3 )
journal, October 2015


Origin of resolution enhancement by co-doping of scintillators: Insight from electronic structure calculations
journal, May 2014


Role of self-trapping in luminescence and p -type conductivity of wide-band-gap oxides
journal, February 2012


VESTA : a three-dimensional visualization system for electronic and structural analysis
journal, May 2008


Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite
journal, June 2015


Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells
journal, December 2015


Inorganic Halide Perovskites for Efficient Light-Emitting Diodes
journal, October 2015


A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission
journal, December 2017


Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013


Measurement of the Time Dependence of Scintillation Intensity by a Delayed‐Coincidence Method
journal, September 1961


First-principles study of codoping in lanthanum bromide
journal, April 2015


Under the spotlight: The organic–inorganic hybrid halide perovskite for optoelectronic applications
journal, June 2015


Compositional engineering of perovskite materials for high-performance solar cells
journal, January 2015


Rationale for mixing exact exchange with density functional approximations
journal, December 1996


Host structure dependence of light yield and proportionality in scintillators in terms of hot and thermalized carrier transport
journal, July 2012


Crystal Growth and Scintillation Properties of Eu2+ doped Cs4CaI6 and Cs4SrI6
journal, March 2018


First principles calculations and experiment predictions for iodine vacancy centers in SrI 2
journal, January 2013


A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission
journal, December 2017


    Works referencing / citing this record:

    CSD 1832863: Experimental Crystal Structure Determination: Non-CSD Structure
    dataset, March 2018


    CSD 1832864: Experimental Crystal Structure Determination: Non-CSD Structure
    dataset, March 2018


    A Self-Powered and Stable All-Perovskite Photodetector-Solar Cell Nanosystem
    journal, January 2016


    Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX 3 )
    journal, October 2015


    Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite
    journal, June 2015


    A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission
    journal, December 2017


    First principles calculations and experiment predictions for iodine vacancy centers in SrI 2
    journal, January 2013


    Crystal growth and characterization of CsSr1-xEux I3 high light yield scintillators
    journal, December 2010


    Host structure dependence of light yield and proportionality in scintillators in terms of hot and thermalized carrier transport
    journal, July 2012


    Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
    journal, July 1996


    Crystal growth and scintillation properties of Cs3EuI5 crystals
    journal, March 2011


    Crystal Growth and Scintillation Properties of Eu2+ doped Cs4CaI6 and Cs4SrI6
    journal, March 2018


    Under the spotlight: The organic–inorganic hybrid halide perovskite for optoelectronic applications
    journal, June 2015


    Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
    journal, March 2016


    Inorganic Halide Perovskites for Efficient Light-Emitting Diodes
    journal, October 2015


    Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells
    journal, December 2015


    Crystal Growth of the Perovskite Semiconductor CsPbBr 3 : A New Material for High-Energy Radiation Detection
    journal, June 2013


    Efficient planar heterojunction perovskite solar cells by vapour deposition
    journal, September 2013


    Compositional engineering of perovskite materials for high-performance solar cells
    journal, January 2015


    High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
    journal, July 2016


    Printable organometallic perovskite enables large-area, low-dose X-ray imaging
    journal, October 2017


    Dopant compensation in alloyed CH3NH3PbBr3−xClx perovskite single crystals for gamma-ray spectroscopy
    journal, July 2017


    Electro-optics of perovskite solar cells
    journal, December 2014


    Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination
    journal, August 2015


    Detection of X-ray photons by solution-processed lead halide perovskites
    journal, May 2015


    Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals
    journal, March 2016


    Crystal structure, electronic structure, temperature-dependent optical and scintillation properties of CsCe 2 Br 7
    journal, January 2015


    Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency
    journal, January 2018


    Measurement of the Time Dependence of Scintillation Intensity by a Delayed‐Coincidence Method
    journal, September 1961


    Rationale for mixing exact exchange with density functional approximations
    journal, December 1996


    Origin of resolution enhancement by co-doping of scintillators: Insight from electronic structure calculations
    journal, May 2014


    Ramifications of codoping SrI 2 :Eu with isovalent and aliovalent impurities
    journal, December 2016


    Defect Engineering by Codoping in KCaI 3 : Eu 2 + Single-Crystalline Scintillators
    journal, September 2017


    From ultrasoft pseudopotentials to the projector augmented-wave method
    journal, January 1999


    Impurity-bound small polarons in ZnO: Hybrid density functional calculations
    journal, September 2009


    Role of self-trapping in luminescence and p -type conductivity of wide-band-gap oxides
    journal, February 2012


    First-principles study of codoping in lanthanum bromide
    journal, April 2015


    VESTA : a three-dimensional visualization system for electronic and structural analysis
    journal, May 2008


    WinGX and ORTEP for Windows : an update
    journal, July 2012


    A short history of SHELX
    journal, December 2007


    CeBr/sub 3/ scintillators for gamma-ray spectroscopy
    journal, December 2005


    Interface engineering of highly efficient perovskite solar cells
    journal, July 2014


    Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
    journal, January 2015


    Using DFT Methods to Study Activators in Optical Materials
    journal, August 2015


    Zero-dimensional metal oxide Li 4 TiO 4
    journal, January 2019


    Eu 2+ : A suitable substituent for Pb 2+ in CsPbX 3 perovskite nanocrystals?
    journal, December 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.