Thermally-activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations

Abstract

Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I (4) over bar 2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 degrees C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I (4) over bar space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4. ; This study was supported by the Spanish government MEC under grants MAT2010-21270-C04-01/03/04 and MAT2010-19837-C06-06, by MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by the Vicerrectorado de Investigacion y Desarrollo of the Universitat Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). EP-G, AM, and PR-H acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. Finally, the authors would also like to acknowledge M C Moron for stimulating discussions and revision of the present manuscript. ; Vilaplana Cerda, RI.; Gomis Hilario, O.; Pérez-González, E.; Ortiz, HM.; Manjón Herrera, FJ.; Rodríguez-Hernández, P.; Muñoz, A. (2013). Thermally-activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations. Journal of Physics: Condensed ...