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Band-gap and band-edge engineering of multicomponent garnet scintillators from first principles

Journal Article · · Physical Review Applied
 [1];  [1];  [2];  [3];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Academy of Sciences of the Czech Republic, Prague (Czech Republic)
  3. Thermo-Calc Software Inc., Pittsburgh, PA (United States)
+ Show Author Affiliations
Complex doping schemes in R3Al5O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-band maximum (VBM). We consider two sets of compositions based on Lu3B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5O12, where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. Furthermore, this approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1248741
Alternate ID(s):
OSTI ID: 1227086
Report Number(s):
LA-UR--15-23403
Journal Information:
Physical Review Applied, Journal Name: Physical Review Applied Journal Issue: 5 Vol. 4; ISSN 2331-7019; ISSN PRAHB2
Publisher:
American Physical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Nanoengineered Gd 3 Al 2 Ga 3 O 12 Scintillation Materials with Disordered Garnet Structure for Novel Detectors of Ionizing Radiation journal March 2019
Excitation Transfer Engineering in Ce-Doped Oxide Crystalline Scintillators by Codoping with Alkali-Earth Ions journal February 2018
Evidence of Optically Stimulated Luminescence in Lu 3 Al 5 O 12 :Ce journal April 2019
Influence of Disorder in Scintillating Solid Solutions on Thermalization and Recombination of Electronic Excitations journal December 2019
Physics-informed machine learning for inorganic scintillator discovery journal June 2018
Hole Self-Trapping in Y 3 Al 5 O 12 and Lu 3 Al 5 O 12 Garnet Crystals journal September 2018
Role of Y Admixture in ( Lu 1 − x Y x ) 3 Al 5 O 12 ∶ Pr Ceramic Scintillators Free of Host Luminescence journal December 2016
Ultrafast Zn(Cd,Mg)O:Ga nanoscintillators with luminescence tunable by band gap modulation journal January 2018

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