Preferential Eu Site Occupation and Its Consequences in the Ternary Luminescent HalidesAB2I5:Eu2+(A=Li–Cs;B=Sr, Ba)

Fang, C.  M.; Biswas, Koushik

doi:10.1103/PhysRevApplied.4.014012

Title: Preferential Eu Site Occupation and Its Consequences in the Ternary Luminescent Halides ${AB}_{2} I_{5} : {Eu}^{2 +}$ ( $A = Li - Cs$ ; $B = Sr$ , Ba)

Journal Article · Wed Jul 22 00:00:00 EDT 2015 · Physical Review Applied

DOI:https://doi.org/10.1103/PhysRevApplied.4.014012· OSTI ID:1201007

Fang, C. M. ^[1]; Biswas, Koushik ^[1]

Arkansas State Univ., Jonesboro, AR (United States)

Several rare-earth-doped, heavy-metal halides have recently been identified as potential next-generation luminescent materials with high efficiency at low cost. AB₂I₅:Eu²⁺ (A=Li–Cs; B=Sr, Ba) is one such family of halides. Its members, such as CsBa₂I₅:Eu²⁺ and KSr₂I₅:Eu²⁺, are currently being investigated as high-performance scintillators with improved sensitivity, light yield, and energy resolution less than 3% at 662 keV. Within the AB₂I₅ family, our first-principles-based calculations reveal two remarkably different trends in Eu site occupation. The substitutional Eu ions occupy both eightfold-coordinated B1(VIII) and the sevenfold-coordinated B2(VII) sites in the Sr-containing compounds. However, in the Ba-containing crystals, Eu ions strongly prefer the B2(VII)sites. This random versus preferential distribution of Eu affects their electronic properties. The calculations also suggest that in the Ba-containing compounds one can expect the formation of Eu-rich domains. These results provide atomistic insight into recent experimental observations about the concentration and temperature effects in Eu-doped CsBa₂I₅. We discuss the implications of our results with respect to luminescent properties and applications. We also hypothesize Sr, Ba-mixed quaternary iodides ABa^VIIISr^VIII₅:Eu as scintillators having enhanced homogeneity and electronic properties.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: ECCS-1348341; AC52-06NA25946

OSTI ID:: 1201007

Journal Information:: Physical Review Applied, Journal Name: Physical Review Applied Vol. 4 Journal Issue: 1; ISSN 2331-7019

Publisher:: American Physical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 16 works

Citation information provided by
Web of Science

References (42)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
High-energy-resolution scintillator: Ce³⁺ activated LaBr₃ van Loef, E. V. D.; Dorenbos, P.; van Eijk, C. W. E. Applied Physics Letters, Vol. 79, Issue 10, p. 1573-1575 https://doi.org/10.1063/1.1385342	journal	September 2001
Suppression of nonradiative recombination in ionic insulators by defects: Role of fast electron trapping in Tl-doped CsI Bang, Junhyeok; Wang, Z.; Gao, F. Physical Review B, Vol. 87, Issue 20 https://doi.org/10.1103/PhysRevB.87.205206	journal	May 2013
Inorganic Luminescent Materials: 100 Years of Research and Application Feldmann, C.; Jüstel, T.; Ronda, C. R. Advanced Functional Materials, Vol. 13, Issue 7 https://doi.org/10.1002/adfm.200301005	journal	July 2003
Formation, stability, and mobility of self-trapped excitations in NaI and NaI $_{1 - x}$ Tl $_{x}$ from first principles Prange, M. P.; Van Ginhoven, R. M.; Govind, N. Physical Review B, Vol. 87, Issue 11 https://doi.org/10.1103/PhysRevB.87.115101	journal	March 2013
DX-like centers in NaI:Tl upon aliovalent codoping Adhikari, Rajendra; Li, Qi; Williams, Richard T. Journal of Applied Physics, Vol. 116, Issue 22 https://doi.org/10.1063/1.4903766	journal	December 2014
Thermal quenching of Eu ²⁺ 5d–4f luminescence in inorganic compounds Dorenbos, P. Journal of Physics: Condensed Matter, Vol. 17, Issue 50 https://doi.org/10.1088/0953-8984/17/50/027	journal	December 2005
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
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
Energy of the first 4f7→4f65d transition of Eu2+ in inorganic compounds Dorenbos, P. Journal of Luminescence, Vol. 104, Issue 4 https://doi.org/10.1016/S0022-2313(03)00078-4	journal	August 2003
Challenges for Density Functional Theory Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao Chemical Reviews, Vol. 112, Issue 1 https://doi.org/10.1021/cr200107z	journal	December 2011
Chemical trends of electronic and optical properties of ns ² ions in halides Du, M. H. J. Mater. Chem. C, Vol. 2, Issue 24 https://doi.org/10.1039/c4tc00485j	journal	January 2014
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Promising Alkaline Earth Halide Scintillators for Gamma-Ray Spectroscopy Shirwadkar, U.; Hawrami, R.; Glodo, J. IEEE Transactions on Nuclear Science, Vol. 60, Issue 2 https://doi.org/10.1109/TNS.2013.2240696	journal	April 2013
A Study on AB2X5 Compounds (A: K, In, Tl; B: Sr, Sn, Pb; X: Cl, Br, I) Beck, H. P.; Clicqu�, G.; Nau, H. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 536, Issue 5 https://doi.org/10.1002/zaac.19865360505	journal	May 1986
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Strontium and barium iodide high light yield scintillators Cherepy, Nerine J.; Hull, Giulia; Drobshoff, Alexander D. Applied Physics Letters, Vol. 92, Issue 8, Article No. 083508 https://doi.org/10.1063/1.2885728	journal	February 2008
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Quasiparticle spectra, absorption spectra, and excitonic properties of NaI and ${SrI}_{2}$ from many-body perturbation theory Erhart, Paul; Schleife, André; Sadigh, Babak Physical Review B, Vol. 89, Issue 7 https://doi.org/10.1103/PhysRevB.89.075132	journal	February 2014
Near optical isotropy in noncubic SrI2: Density functional calculations Singh, D. J. Applied Physics Letters, Vol. 92, Issue 20 https://doi.org/10.1063/1.2936079	journal	May 2008
Growth and characterization of potassium strontium iodide: A new high light yield scintillator with 2.4% energy resolution Stand, L.; Zhuravleva, M.; Lindsey, A. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 780 https://doi.org/10.1016/j.nima.2015.01.052	journal	April 2015
Density-Functional Theory of the Electronic Structure of Molecules Parr, Robert G.; Yang, Weitao Annual Review of Physical Chemistry, Vol. 46, Issue 1 https://doi.org/10.1146/annurev.pc.46.100195.003413	journal	October 1995
Structure and optical properties of high light output halide scintillators Singh, David J. Physical Review B, Vol. 82, Issue 15 https://doi.org/10.1103/PhysRevB.82.155145	journal	October 2010
Role of ${Ce}^{4 +}$ in the Scintillation Mechanism of Codoped ${Gd}_{3} {Ga}_{3} {Al}_{2} O_{12} ∶ Ce$ Wu, Yuntao; Meng, Fang; Li, Qi Physical Review Applied, Vol. 2, Issue 4 https://doi.org/10.1103/PhysRevApplied.2.044009	journal	October 2014
Electronic structure of LaBr $_{3}$ from quasiparticle self-consistent $G W$ calculations Åberg, Daniel; Sadigh, Babak; Erhart, Paul Physical Review B, Vol. 85, Issue 12 https://doi.org/10.1103/PhysRevB.85.125134	journal	March 2012
Structure and scintillation of Eu2+-activated solid solutions in the BaBr2–BaI2 system Gundiah, Gautam; Bizarri, Gregory; Hanrahan, Stephen M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 652, Issue 1 https://doi.org/10.1016/j.nima.2010.10.058	journal	October 2011
Scintillation and Optical Properties of ${\rm BaBrI}\!:\!{\rm Eu}^{2+}$ and ${\rm CsBa}_{2}{\rm I}_{5}\!:\!{\rm Eu}^{2+}$ Bizarri, Gregory; Bourret-Courchesne, Edith D.; Yan, Zewu IEEE Transactions on Nuclear Science, Vol. 58, Issue 6 https://doi.org/10.1109/TNS.2011.2166999	journal	December 2011
Search for improved-performance scintillator candidates among the electronic structures of mixed halides Li, Qi; Williams, Richard T.; Burger, Arnold SPIE Optical Engineering + Applications, SPIE Proceedings https://doi.org/10.1117/12.2063583	conference	September 2014
Developments in Luminescence and Display Materials Over the Last 100 Years as Reflected in Electrochemical Society Publications Chen, Reuven; Lockwood, David J. Journal of The Electrochemical Society, Vol. 149, Issue 9 https://doi.org/10.1149/1.1502258	journal	January 2002
Electron correlations in narrow energy bands Hubbard, J. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 276, Issue 1365, p. 238-257 https://doi.org/10.1098/rspa.1963.0204	journal	November 1963
First-principles study of luminescence in Eu $^{2 +}$ -doped inorganic scintillators Chaudhry, A.; Boutchko, R.; Chourou, S. Physical Review B, Vol. 89, Issue 15 https://doi.org/10.1103/PhysRevB.89.155105	journal	April 2014
Scintillation properties of CsBa2I5 activated with monovalent ions Tl+, Na+ and In+ Gascón, M.; Samulon, E. C.; Gundiah, G. Journal of Luminescence, Vol. 156 https://doi.org/10.1016/j.jlumin.2014.07.017	journal	December 2014
HEPHAISTOSITE, TlPb2Cl5, A NEW THALLIUM MINERAL SPECIES FROM LA FOSSA CRATER, VULCANO, AEOLIAN ISLANDS, ITALY Campostrini, I.; Demartin, F.; Gramaccioli, C. M. The Canadian Mineralogist, Vol. 46, Issue 3 https://doi.org/10.3749/canmin.46.3.701	journal	June 2008
High energy resolution scintillators for nuclear nonproliferation applications Zhuravleva, M.; Melcher, C. L.; Stand, L. SPIE Optical Engineering + Applications, SPIE Proceedings https://doi.org/10.1117/12.2064191	conference	September 2014
Eu²⁺-doped Ba₂CsI₅, a new high-performance scintillator Bourret-Courchesne, E. D.; Bizarri, G.; Borade, R. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 612, Issue 1, p. 138-142 https://doi.org/10.1016/j.nima.2009.10.146	journal	December 2009
Optical and scintillation properties of CsBa2I5:Eu2+ Alekhin, Mikhail S.; Biner, Daniel A.; Krämer, Karl W. Journal of Luminescence, Vol. 145 https://doi.org/10.1016/j.jlumin.2013.08.058	journal	January 2014
Optical and scintillation properties of SrI2:Yb2+ Alekhin, Mikhail S.; Biner, Daniel A.; Krämer, Karl W. Optical Materials, Vol. 37 https://doi.org/10.1016/j.optmat.2014.06.030	journal	November 2014
Tern�re Bromide und Iodide zweiwertiger Lanthanide und ihre Erdalkali-Analoga vom Typ AMX3 und AM2X5 Schilling, Gaby; Meyer, Gerd Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 5 https://doi.org/10.1002/zaac.19966220502	journal	May 1996
Radiation detector materials: An overview Milbrath, B. D.; Peurrung, A. J.; Bliss, M. Journal of Materials Research, Vol. 23, Issue 10 https://doi.org/10.1557/JMR.2008.0319	journal	October 2008

Similar Records

Improved Lithium Iodide neutron scintillator with Eu

^{2 +}

activation II: Activator zoning and concentration effects in Bridgman-grown crystals

Journal Article · Sat Sep 01 00:00:00 EDT 2018 · Nuclear Instruments and Methods in Physics Research. Section A, Accelerators, Spectrometers, Detectors and Associated Equipment · OSTI ID:1201007

Boatner, Lynn A.; Comer, Eleanor P.; Wright, Gomez W.; +4 more

Observation of

e^{+} e^{-} \to π^{+} π^{-} π^{0} χ_{b J}

and Search for

X_{b} \to ω Y (1 S)

\sqrt{s} = 10.867 GeV

Journal Article · Tue Sep 30 00:00:00 EDT 2014 · Physical Review Letters · OSTI ID:1201007

He, X. H.; Shen, C. P.; Yuan, C. Z.; +162 more

Role of Multiple Charge States of

Ce

in the Scintillation of

AB O_{3}

Perovskites

Journal Article · Mon Aug 20 00:00:00 EDT 2018 · Physical Review Applied · OSTI ID:1201007

Pilania, Ghanshyam; Yadav, Satyesh K.; Nikl, Martin; +2 more

Title: Preferential Eu Site Occupation and Its Consequences in the Ternary Luminescent Halides AB 2 I 5 : Eu 2 + ( A = Li – Cs ; B = Sr , Ba)

Citation Formats

References (42)

Similar Records

Related Subjects

Title: Preferential Eu Site Occupation and Its Consequences in the Ternary Luminescent Halides ${AB}_{2} I_{5} : {Eu}^{2 +}$ ( $A = Li - Cs$ ; $B = Sr$ , Ba)