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

Title: Using DFT Methods to Study Activators in Optical Materials

Abstract

Density functional theory (DFT) calculations of various activators (ranging from transition metal ions, rare-earth ions, ns 2 ions, to self-trapped and dopant-bound excitons) in phosphors and scintillators are reviewed. As a single-particle ground-state theory, DFT calculations cannot reproduce the experimentally observed optical spectra, which involve transitions between multi-electronic states. However, DFT calculations can generally provide sufficiently accurate structural relaxation and distinguish different hybridization strengths between an activator and its ligands in different host compounds. This is important because the activator-ligand interaction often governs the trends in luminescence properties in phosphors and scintillators, and can be used to search for new materials. DFT calculations of the electronic structure of the host compound and the positions of the activator levels relative to the host band edges in scintillators are also important for finding optimal host-activator combinations for high light yields and fast scintillation response. Mn 4+ activated red phosphors, scintillators activated by Ce 3+, Eu 2+, Tl +, and excitons are shown as examples of using DFT calculations in phosphor and scintillator research.

Authors:
 [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1210163
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ECS Journal of Solid State Science and Technology
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2162-8769
Publisher:
Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; luminescence

Citation Formats

Du, Mao-Hua. Using DFT Methods to Study Activators in Optical Materials. United States: N. p., 2015. Web. doi:10.1149/2.0011601jss.
Du, Mao-Hua. Using DFT Methods to Study Activators in Optical Materials. United States. doi:10.1149/2.0011601jss.
Du, Mao-Hua. Mon . "Using DFT Methods to Study Activators in Optical Materials". United States. doi:10.1149/2.0011601jss. https://www.osti.gov/servlets/purl/1210163.
@article{osti_1210163,
title = {Using DFT Methods to Study Activators in Optical Materials},
author = {Du, Mao-Hua},
abstractNote = {Density functional theory (DFT) calculations of various activators (ranging from transition metal ions, rare-earth ions, ns2 ions, to self-trapped and dopant-bound excitons) in phosphors and scintillators are reviewed. As a single-particle ground-state theory, DFT calculations cannot reproduce the experimentally observed optical spectra, which involve transitions between multi-electronic states. However, DFT calculations can generally provide sufficiently accurate structural relaxation and distinguish different hybridization strengths between an activator and its ligands in different host compounds. This is important because the activator-ligand interaction often governs the trends in luminescence properties in phosphors and scintillators, and can be used to search for new materials. DFT calculations of the electronic structure of the host compound and the positions of the activator levels relative to the host band edges in scintillators are also important for finding optimal host-activator combinations for high light yields and fast scintillation response. Mn4+ activated red phosphors, scintillators activated by Ce3+, Eu2+, Tl+, and excitons are shown as examples of using DFT calculations in phosphor and scintillator research.},
doi = {10.1149/2.0011601jss},
journal = {ECS Journal of Solid State Science and Technology},
number = 1,
volume = 5,
place = {United States},
year = {2015},
month = {8}
}

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

Save / Share:

Works referenced in this record:

Electronic structure engineering of elpasolites: Case of Cs2AgYCl6
journal, November 2013


Blue Light-Emitting Diode Phosphors Based upon Oxide, Oxyhalide, and Halide Hosts
journal, November 2012

  • Setlur, A. A.; Lyons, R. J.; Murphy, J. E.
  • ECS Journal of Solid State Science and Technology, Vol. 2, Issue 2
  • DOI: 10.1149/2.009302jss

Novel γ- and X-ray scintillator research: on the emission wavelength, light yield and time response of Ce3+ doped halide scintillators
journal, January 2009

  • Birowosuto, M. D.; Dorenbos, P.
  • physica status solidi (a), Vol. 206, Issue 1, p. 9-20
  • DOI: 10.1002/pssa.200723669

Energy of the first 4f7→4f65d transition of Eu2+ in inorganic compounds
journal, August 2003


Scintillators With Potential to Supersede Lanthanum Bromide
journal, June 2009

  • Cherepy, Nerine J.; Payne, Steve A.; Asztalos, Stephen J.
  • IEEE Transactions on Nuclear Science, Vol. 56, Issue 3, p. 873-880
  • DOI: 10.1109/TNS.2009.2020165

Current trends in scintillator detectors and materials
journal, July 2002

  • Moses, William W.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 487, Issue 1-2
  • DOI: 10.1016/S0168-9002(02)00955-5

Influence of Covalency on the Mn 4+ 2 E g4 A 2g Emission Energy in Crystals
journal, December 2014

  • Brik, M. G.; Camardello, S. J.; Srivastava, A. M.
  • ECS Journal of Solid State Science and Technology, Vol. 4, Issue 3
  • DOI: 10.1149/2.0031503jss

On the optical properties of the Mn4+ ion in solids
journal, January 2013


Phosphor Selection Considerations for Near-UV LED Solid State Lighting
journal, November 2012

  • McKittrick, J.; Hannah, M. E.; Piquette, A.
  • ECS Journal of Solid State Science and Technology, Vol. 2, Issue 2
  • DOI: 10.1149/2.017302jss

Systematic analysis of the spectroscopic characteristics of 3d ions in a free state and some cubic crystals
journal, August 2013


Sharp-Line Fluorescence, Electron Paramagnetic Resonance, and Thermoluminescence of Mn 4 + in α - Al 2 O 3
journal, June 1962


Spectroscopic characterization of photoinduced Mn 5 + ions in YAlO 3
journal, January 2000


Alkali halide crystals containing impurity ions with the ns2 ground-state electronic configuration†
journal, January 1991


The optical properties of thallium-like impurities in alkali-halide crystals
journal, January 1983


Photoluminescent Materials for Solid-State Lighting: State of the Art and Future Challenges
journal, January 2015


Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes
journal, July 2014

  • Zhu, Haomiao; Lin, Chun Che; Luo, Wenqin
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5312

Narrow-band red-emitting Sr[LiAl3N4]:Eu2+ as a next-generation LED-phosphor material
journal, June 2014

  • Pust, Philipp; Weiler, Volker; Hecht, Cora
  • Nature Materials, Vol. 13, Issue 9
  • DOI: 10.1038/nmat4012

Recent R&D Trends in Inorganic Single-Crystal Scintillator Materials for Radiation Detection
journal, February 2015


First-principles study of luminescence in Ce-doped inorganic scintillators
journal, March 2011


First-principles study of luminescence in Eu 2 + -doped inorganic scintillators
journal, April 2014


The a b i n i t i o model potential representation of the crystalline environment. Theoretical study of the local distortion on NaCl:Cu +
journal, November 1988

  • Barandiarán, Zoila; Seijo, Luis
  • The Journal of Chemical Physics, Vol. 89, Issue 9
  • DOI: 10.1063/1.455549

The ab initio model potential method: Lanthanide and actinide elements
journal, January 2001

  • Seijo, Luis; Barandiarán, Zoila; Harguindey, Eduardo
  • The Journal of Chemical Physics, Vol. 114, Issue 1
  • DOI: 10.1063/1.1330209

Ab initio embedded cluster study of the excitation spectrum and Stokes shifts of Bi3+-doped Y2O3
journal, September 2007

  • Réal, Florent; Vallet, Valérie; Flament, Jean-Pierre
  • The Journal of Chemical Physics, Vol. 127, Issue 10
  • DOI: 10.1063/1.2768532

Ab initio Theoretical Study on the 4f 2 and 4f5d Electronic Manifolds of Cubic Defects in CaF 2 :Pr 3+
journal, December 2013

  • Krośnicki, Marek; Kędziorski, Andrzej; Seijo, Luis
  • The Journal of Physical Chemistry A, Vol. 118, Issue 2
  • DOI: 10.1021/jp410740u

Electronic spectra of Yb2+-doped SrCl2
journal, September 2010

  • Sánchez-Sanz, Goar; Seijo, Luis; Barandiarán, Zoila
  • The Journal of Chemical Physics, Vol. 133, Issue 11
  • DOI: 10.1063/1.3490088

Yb2+-doped SrCl2: Electronic structure of impurity states and impurity-trapped excitons
journal, September 2010

  • Sánchez-Sanz, Goar; Seijo, Luis; Barandiarán, Zoila
  • The Journal of Chemical Physics, Vol. 133, Issue 11
  • DOI: 10.1063/1.3475562

First-Principles Study on Electronic Properties and Optical Spectra of Ce-Doped La 2 CaB 10 O 19 Crystal
journal, July 2013

  • Ning, Lixin; Wang, Zongcui; Wang, Yongfeng
  • The Journal of Physical Chemistry C, Vol. 117, Issue 29
  • DOI: 10.1021/jp402706x

Ab initio theoretical study of the <mml:math altimg="si0291.gif" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd" xmlns:sa="http://www.elsevier.com/xml/common/struct-aff/dtd"><mml:mn>4</mml:mn><mml:msup><mml:mrow><mml:mi mathvariant="normal">f</mml:mi></mml:mrow><mml:mrow><mml:mn>8</mml:mn></mml:mrow></mml:msup></mml:math> and 4f75d manifolds of Tb3+-doped BaF2 cubic sites
journal, January 2014


Mn4+ emission in pyrochlore oxides
journal, January 2015


Inhomogeneous Electron Gas
journal, November 1964


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients
journal, October 1992


The density functional formalism, its applications and prospects
journal, July 1989


A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

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

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Screened hybrid density functionals applied to solids
journal, April 2006

  • Paier, J.; Marsman, M.; Hummer, K.
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2187006

Theoretical Prediction of Intrinsic Self-Trapping of Electrons and Holes in Monoclinic HfO 2
journal, October 2007


Spectroscopic properties of oxygen vacancies in monoclinic Hf O 2 calculated with periodic and embedded cluster density functional theory
journal, May 2007


Defect Energy Levels in Density Functional Calculations: Alignment and Band Gap Problem
journal, July 2008


Band Offsets at Semiconductor-Oxide Interfaces from Hybrid Density-Functional Calculations
journal, September 2008


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


Hybrid functional studies of the oxygen vacancy in TiO 2
journal, February 2010


AX centers in II-VI semiconductors: Hybrid functional calculations
journal, May 2011

  • Biswas, Koushik; Du, Mao-Hua
  • Applied Physics Letters, Vol. 98, Issue 18
  • DOI: 10.1063/1.3583661

Alignment of defect levels and band edges through hybrid functionals: Effect of screening in the exchange term
journal, May 2010


Chemical trends of electronic and optical properties of ns 2 ions in halides
journal, January 2014


DX-like centers in NaI:Tl upon aliovalent codoping
journal, December 2014

  • Adhikari, Rajendra; Li, Qi; Williams, Richard T.
  • Journal of Applied Physics, Vol. 116, Issue 22
  • DOI: 10.1063/1.4903766

Scintillation mechanisms in Ce3+ doped halide scintillators
journal, January 2005


Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators
journal, May 2015


Modeling charge self-trapping in wide-gap dielectrics: Localization problem in local density functionals
journal, January 2003


First-principles and semiempirical calculations for bound-hole polarons in KNbO 3
journal, July 1999

  • Kotomin, E. A.; Eglitis, R. I.; Postnikov, A. V.
  • Physical Review B, Vol. 60, Issue 1
  • DOI: 10.1103/PhysRevB.60.1

Energy-Efficient, High-Color-Rendering LED Lamps Using Oxyfluoride and Fluoride Phosphors
journal, July 2010

  • Setlur, Anant A.; Radkov, Emil V.; Henderson, Claire S.
  • Chemistry of Materials, Vol. 22, Issue 13
  • DOI: 10.1021/cm100960g

Manganese-doped yttrium orthoaluminate: A potential material for holographic recording and data storage
journal, February 1998


Photoluminescence studies of Mn 4+ ions in YAlO 3 crystals at ambient and high pressure
journal, November 2006

  • Zhydachevskii, Ya; Galanciak, D.; Kobyakov, S.
  • Journal of Physics: Condensed Matter, Vol. 18, Issue 49
  • DOI: 10.1088/0953-8984/18/49/028

Mn-doped YAlO3 crystal: a new potential TLD phosphor
journal, January 2005

  • Zhydachevskii, Ya.; Durygin, A.; Suchocki, A.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 227, Issue 4
  • DOI: 10.1016/j.nimb.2004.09.013

Luminescence spectra of SrTiO3:Mn4+
journal, May 2000


Spectroscopy of Mn 4 + -doped Ca-substituted gadolinium gallium garnet
journal, August 1992


Electronic Energy Levels of the Mn 4+ Ion in the Perovskite, CaZrO 3
journal, January 2013

  • Brik, Mikhail G.; Srivastava, Alok M.
  • ECS Journal of Solid State Science and Technology, Vol. 2, Issue 7
  • DOI: 10.1149/2.020307jss

Multiphoton excitation of Mn4+ and Cr3+ luminescence in MgO
journal, January 1990


Mn[sup 4+]-Activated Red Photoluminescence in K[sub 2]SiF[sub 6] Phosphor
journal, January 2008

  • Takahashi, Toru; Adachi, Sadao
  • Journal of The Electrochemical Society, Vol. 155, Issue 12
  • DOI: 10.1149/1.2993159

Dynamics of Magnetostatically Coupled Vortices Observed by Time-Resolved Photoemission Electron Microscopy
journal, May 2011

  • Arai, Kuniaki; Okuda, Taichi; Fukumoto, Keiki
  • Japanese Journal of Applied Physics, Vol. 50, Issue 5R
  • DOI: 10.7567/JJAP.50.053001

Properties of Na2SiF6:Mn4+ and Na2GeF6:Mn4+ red phosphors synthesized by wet chemical etching
journal, January 2009

  • Xu, Yan Kai; Adachi, Sadao
  • Journal of Applied Physics, Vol. 105, Issue 1
  • DOI: 10.1063/1.3056375

Optical properties of Mn4+-activated Na2SnF6 and Cs2SnF6 red phosphors
journal, December 2011


On the Absorption Spectra of Complex Ions II
journal, September 1954

  • Tanabe, Yukito; Sugano, Satoru
  • Journal of the Physical Society of Japan, Vol. 9, Issue 5
  • DOI: 10.1143/JPSJ.9.766

On the Absorption Spectra of Complex Ions, III The Calculation of the Crystalline Field Strength
journal, August 1956

  • Tanabe, Yukito; Sugano, Satoru
  • Journal of the Physical Society of Japan, Vol. 11, Issue 8
  • DOI: 10.1143/JPSJ.11.864

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Structural and crystal chemical properties of rare-earth titanate pyrochlores
journal, August 2014


The synthesis and structures of complex rare-earth halides
journal, January 1982


Scintillation Process in CsI(Tl). II. Emission Spectra and the Possible Role of Self-Trapped Holes
journal, July 1963


The nature of the X-ray-induced luminescence and the hole centres in CsI:Tl studied by optically detected electron paramagnetic resonance
journal, May 1994


Interpretation of the Properties of Alkali Halide‐Thallium Phosphors
journal, March 1938

  • Seitz, Frederick
  • The Journal of Chemical Physics, Vol. 6, Issue 3
  • DOI: 10.1063/1.1750216

An Absolute Theory of Solid‐State Luminescence
journal, April 1951

  • Williams, Ferd E.
  • The Journal of Chemical Physics, Vol. 19, Issue 4
  • DOI: 10.1063/1.1748247

Solid State Luminescence Theory and Oscillator Strengths in KCl: Tl
journal, December 1956


Molecular‐Orbital Model for Alkali Halide Phosphors Activated by Heavy Metals
journal, January 1962

  • Sugano, Satoru
  • The Journal of Chemical Physics, Vol. 36, Issue 1
  • DOI: 10.1063/1.1732280

Molecular-Orbital Model for KCl: Tl
journal, June 1971


Absorption Spectra of F 2 , Cl 2 , Br 2 , and I 2 in the Alkali Halides
journal, February 1961


Enhanced Born charge and proximity to ferroelectricity in thallium halides
journal, April 2010


Enhanced Born charges in III-VII, IV-VII 2 , and V-VII 3 compounds
journal, July 2010


VUV and UV Spectroscopy of Pb2+ and Bi3+ Centres in Alkaline-Earth Fluorides
journal, August 1989

  • Oboth, K. P.; Lohmeier, F. J.; Fischer, F.
  • physica status solidi (b), Vol. 154, Issue 2
  • DOI: 10.1002/pssb.2221540238

Luminescence and decay kinetics of Pb2+ center in LiCaAlF6 single crystal host
journal, September 2009


The luminescence of Pb2+ in alkaline earth sulfates
journal, November 1995


Growth and spectroscopic characterization of Pb2+:CaF2 crystals
journal, August 2012


Optical studies of Pb 2+ ions in a LiBaF 3 crystal
journal, May 2006

  • Aminov, L. K.; Nikitin, S. I.; Silkin, N. I.
  • Journal of Physics: Condensed Matter, Vol. 18, Issue 20
  • DOI: 10.1088/0953-8984/18/20/021

Luminescence Studies on γ-Irradiated BaF2:Pb Single Crystals
journal, May 1996


Electronic structure, small polaron, and F center in LiCaAlF 6
journal, December 2012

  • Du, Mao-Hua; Singh, David J.
  • Journal of Applied Physics, Vol. 112, Issue 12
  • DOI: 10.1063/1.4770469

Luminescence and scintillation properties of the small band gap compound LaI3:Ce3+
journal, January 2005

  • Bessiere, A.; Dorenbos, P.; van Eijk, C. W. E.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 537, Issue 1-2, p. 22-26
  • DOI: 10.1016/j.nima.2004.07.224

Crystal Growth and Scintillation Properties of Strontium Iodide Scintillators
journal, June 2009

  • van Loef, Edgar V.; Wilson, Cody M.; Cherepy, Nerine J.
  • IEEE Transactions on Nuclear Science, Vol. 56, Issue 3
  • DOI: 10.1109/TNS.2009.2013947

Quasiparticle spectra, absorption spectra, and excitonic properties of NaI and SrI 2 from many-body perturbation theory
journal, February 2014


Optical and scintillation properties of pure and Ce3+-doped Cs2LiYCl6 and Li3YCl6:Ce3+ crystals
journal, October 1999


Spectroscopy and anomalous emission of Ce doped elpasolite Cs 2 LiY Cl 6
journal, March 2004

  • Bessière, A.; Dorenbos, P.; Eijk, C. W. E. van
  • Journal of Physics: Condensed Matter, Vol. 16, Issue 10
  • DOI: 10.1088/0953-8984/16/10/019

Crystal Scintillators
journal, January 1984


Phonon scattering and energy relaxation in two-, one-, and zero-dimensional electron gases
journal, November 1990


Intrinsic mechanism for the poor luminescence properties of quantum-box systems
journal, November 1991


Radiative and non-radiative inter-subband transition in self assembled quantum dots
journal, July 1998