Role of Multiple Charge States of $\mathrm{Ce}$ in the Scintillation of $\mathit{AB}{\mathrm{O}}_3$ Perovskites

Journal Article · 20 August 2018 · Physical Review Applied

DOI: https://doi.org/10.1103/PhysRevApplied.10.024026 · OSTI ID:1473816

Pilania, Ghanshyam  ^[1]; Yadav, Satyesh K. ^[2]; Nikl, Martin ^[3]; Uberuaga, Blas P.  ^[1]; Stanek, Christopher Richard  ^[1]

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1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Indian Inst. of Technology (IIT), Madras (India). Metallurgical and Materials Engineering Dept.
3. Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic). Inst. of Physics

Ce-activated A²⁺B⁴⁺O₃ perovskites represent a class of compounds currently under active exploration for their potential as scintillators. Depending on the chemistry and synthesis conditions, perovskites can crystallize in multiple crystal structures, and a Ce substitutional dopant in an ABO₃ perovskite can adopt different charge states (i.e., Ce³⁺ or Ce⁴⁺) as well as different substitutional sites (namely, the 12-fold-coordinated A site or the octahedrally coordinated B site). We use first-principles density-functional-theory- and hybrid-functional-based computations to study relative trends in the structure, energetics, and electronic structure of bulk ABO₃ perovskites, where A = Ca, Sr, or Ba and B = Hf or Zr. Subsequently, we consider the relative energetics of preferential solution sites for Ce as a function of charge states, chemical potential, and defect configurations. Our results reveal that while Ce³⁺ or Ce⁴⁺ defects can be thermodynamically stable, depending on the choice of the substitutional site and synthesis conditions (i.e., prevailing chemical potential), only Ce³⁺ dopant at the A site leads to an electronic structure that can exhibit scintillation. Our comparative analysis shows that while the positions of the 5d¹ and 4$$\mathcal{f}$$ levels of Ce³⁺ as a dopant at the A site are favorably placed in the band structure, these levels are consistently higher for the Ce⁴⁺ charge state and are unlikely to manifest any luminescence. The findings of this study are also discussed in relation to previously reported results and display excellent agreement with past experimental observations. In general, it is demonstrated that control of the Ce charge state and local chemical environment can be used—in addition to band-gap and band-edge engineering—to manipulate the relative position of scintillating states with respect to the valence-band maximum and conduction-band minimum. While this study specifically focuses on perovskites, the results (in particular, the relative alignment of the positions of the 5d¹ and 4$$\mathcal{f}$$ levels of Ce dopant as a function of the activator’s charge state) are expected to be general and thus transferable to other chemistries.

• Research Organization: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
• Sponsoring Organization: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
• Grant/Contract Number: AC52-06NA25396
• OSTI ID: 1473816
• Alternate ID(s): OSTI ID: 1465250
• Report Number(s): LA-UR-18-21082; PRAHB2
• Journal Information: Physical Review Applied, Vol. 10, Issue 2; ISSN 2331-7019
• Publisher: American Physical Society (APS)Copyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
defects
density of states
electronic structure
luminescence
perovskite