Structure and spectroscopic properties of (AA′)(BB′)O3 mixed-perovskite crystals

Dorota A. Pawlak

Institute of Electronic Materials Technology, 01-919 Warszawa, Poland

Masahiko Ito

Physical Chemistry of Luminescent Materials, Claude Bernard/Lyon University, CNRS UMR 5620, Villeurbanne, Cedex 69622, France

Lukasz Dobrzycki and Krzysztof Wozniak

Warsaw University, Chemistry Department, 02-093 Warszawa, Poland

Masaoki Oku

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Kiyoshi Shimamura

Advanced Materials Laboratory National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan

Tsuguo Fukuda

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan

Five different mixed-perovskite (AA′)(BB′)O3 single crystals were grown, where A = La, Nd; A′ = Sr; B = Al, Ga; and B′ = Ta, Nb. The as-grown crystals were yellowish/brownish. After annealing in air, the coloration was more intense. Annealing in a reducing atmosphere decreased coloration. The crystals were investigated by transmission spectroscopy, electron spectroscopy for chemical analysis (ESCA), and single-crystal x-ray diffraction. Additional broad absorption bands in the transmission spectra were observed for the as-grown samples. They are in line with the changes of the shape of O(1s) ESCA peaks. Redundant interstitial oxygen ions were recognized as the reason for the crystal coloration. All structures were solved and refined in different space groups of their regular systems. Some of the unit cells have a doubled lattice constant: (i) LSGN, Pm3 m, 3.9323(5) Å, at 100K, 3.9270(5) Å; (ii) NSAT, Pm3 m, 3.8353(4) Å; (iii) LSAT, Pn3 m, 7.720(1) Å, annealed in reducing atmosphere, 7.708(1) Å; (iv) NSAN, Fm3 m, 7.744(4) Å.