High-resolution spectroscopy of LaAlO3-Pr3+ pseudo-cubic perovskite single crystals: Crystal-field parameters, hyperfine and deformation splittings

Abstract

We report high-resolution measurements and analysis of the optical transmission and emission spectra of a concentration series of La(1-x)PrxAlO3 (x = 10−3, 9 ⋅ 10−3, and 2 ⋅ 10−2) single crystals in a wide frequency range ((2-27) ⋅ 103 cm−1) at temperatures 5–300 K, below the structural phase transition from the cubic Pm3‾m to the rhombohedral R3‾c phase. Pr3+ ions substitute for La3+ ions at sites with point symmetry D3. All recorded spectral lines are assigned to specific initial and final crystal-field (CF) energy levels, the scheme of CF levels is constructed and described by an appropriate set of CF parameters. The structural phase transition is accompanied by shear strains and the formation of ferroelastic twin domains of four types compressed along one of the four C3 axes in the parent cubic crystal lattice. Specific features of the measured spectra, namely, anomalous broadening of spectral lines and doublet structure of some lines corresponding to transitions between CF singlets and doublets, are considered as a result of interaction of 4f electrons with the field of random shear deformations competing at the boundaries of twin domains. Modeling of the observed line shapes was performed taking into account both hyperfine interactions and random lattice strains, as well as the effect of temperature. The width (6.6 ± 0.7)⋅10− 4 of the introduced two-dimensional distribution function of random strains was found from a comparison of simulated and measured profiles of the split spectral lines. The results of this work can be applied for quantitative assessment of crystal quality.