Inorganic Chemistry, Vol.53, No.23, 12378-12383, 2014
Thermochromism in Yttrium Iron Garnet Compounds
Polycrystalline yttrium iron garnet (Y3Fe5O12, hereafter labeled YIG) has been synthesized by solid-state reaction, characterized by X-ray diffraction, Mossbauer spectroscopy, and UV-vis-NIR diffuse reflectance spectroscopy, and its optical properties from room temperature (RT) to 300 similar to C are discussed. Namely, its greenish color at RT is assigned to an O2- ? Fe3+ ligand-to-metal charge transfer at 2.57 eV coupled with d-d transitions peaking at 1.35 and 2.04 eV. When the temperature is raised, YIG displays a marked thermochromic effect; i.e., the color changes continuously from greenish to brownish, which offers opportunities for potential application as a temperature indicator for everyday uses. The origin of the observed thermochromism is assigned to a gradual red shift of the ligand-to-metal charge transfer with temperature while the positioning in energy of the d-d transitions is almost unaltered. Attempts to achieve more saturated colors via doping (e.g., Al3+, Ga3+, Mn3+ ...) remained unsuccessful except for chromium. Indeed, Y3Fe5O12:Cr samples exhibit at RT the same color than the undoped garnet at 200 similar to C. The introduction of Cr3+ ions strongly impacts the color of the Y3Fe5O12 parent either by an inductive effect or, more probably, by a direct effect on the electronic structure of the undoped material with formation of a midgap state.