Optical and magnetic characterisation of Co3+ and Ni3+ in LaAlO3: interplay between the spin state and Jahn-Teller effect

The coordination, the electronic structures and the spin of the ground state of Ni3+ (3d7) and Co3+ (3d6) introduced as impurities in LaAlO3 are investigated through optical spectroscopy and magnetic measurements. The unusual trivalent valence state in both transition-metal ions was stabilised via a sol-gel process followed by high oxygen pressure treatments. We show that the crystal-field strength at the nearly Oh transition-metal site in LaAlO3 locates Ni3+ and Co3+ near the spin state crossover, yielding a low-spin ground state in both cases. We analyse how the interplay between the Jahn-Teller (JT) effect and the spin state affects the magnetic moment of the ion and its temperature dependence. The optical spectra reveal a JT effect associated with a low-spin ground state in Ni3+ and with a thermally populated high-spin low-lying first excited state in Co3+. The corresponding JT distortions are derived from structural correlations. We conclude that the JT effect is unable to stabilise the intermediate spin state in Co3+. A low-spin ground state in thermal equilibrium with a high-spin low-lying first excited state is detected in diluted Co3+-doped LaAlO3. These results are compared with those obtained in the parent pure compounds LaNiO3 and LaCoO3. (paper)