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Inorg Chem. 2016 Sep 19;55(18):9436-44. doi: 10.1021/acs.inorgchem.6b01693. Epub 2016 Sep 8.

Raman Study of the Structural Distortion in the Ni1-xCoxTiO3 Solid Solution.

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Finnish Research and Engineering , Jaalaranta 9 B 42, 00180 Helsinki, Finland.
Center for Nanophase Materials Science, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
Lujan Neutron Scattering Center, Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.


Raman spectra were collected on Ni1-xCoxTiO3 (0 ≤ x ≤ 1) ilmenite samples as a function of the temperature between 4 and 1200 K. An evident symmetry lowering from the prototype R3̅ symmetry is observed. The distortion was largest for the x = 0.40 and 0.50 samples and significantly diminished for small and large values of x. The distortion was preserved in the whole temperature range and, except for the x = 0.50 sample, did not show significant changes. Notably, between 25 and 69 K, distortion of the x = 0.40 sample is accompanied by ferromagnetic order. The direct cation-cation and O-mediated indirect interactions are discussed as mechanisms behind the distortion and magnetic order. A reversible order-disorder phase transformation, assigned to occur between the ilmenite and corundum phases, took place at 973 K in the x = 0.50 sample. Completion of the transformation took over 1 h. The role of the overlap of Co/Ni and Ti 3d orbitals through O octahedral faces for charge transfer is discussed.

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