Oxygen-vacancy centers in Y3Al5O12 garnet crystals: electron paramagnetic resonance and dielectric spectroscopy study.
F+ center, an electron trapped at oxygen vacancy (VO), was investigated in the oxygen deficient Y3Al5O12 (YAG) crystals by EPR. The measurements were performed at temperatures 5-450 K and frequencies 9.4-350 GHz with using both the continue wave and pulse EPR technique. The pulse electron-nuclear double resonance was applied to resolve the hyperfine interaction of the trapped electron with surrounding nuclei. The measurements show that at low temperatures, T < 50 K, EPR spectrum of the F+ center is anisotropic with g factors in the range 1.999-1.988 and originates from three magnetically inequivalent positions of the center in garnet lattice according to different directions of the Al(IV)-VO-Al(VI) chains, where Al(IV) and Al(VI) are the tetrahedral and octahedral Al sites, respectively. As the temperature increases, the EPR spectrum becomes isotropic suggesting a motional averaging of the anisotropy due to motion of electron between neighboring oxygen vacancies. With further increase of the temperature to T > 200 K, we observed delocalization of the electron into the conduction band with the activation energy about 0.4-0.5 eV that resulted in substantial narrowing of the EPR spectral line with simultaneous change of its shape from the Gaussian to Lorentzian due to diminish up to zero of the Fermi contact hyperfine field at 27Al and 89Y nuclei. Such temperature behavior of the F+-center electron in YAG is completely similar to behavior of a donor electron in a semiconductor. Our findings is further supported by measurements of the conductivity and dielectric properties. In particular, these data show that the conduction electrons are not homogeneously distributed in the crystal: there are high-conductive regions separated by poorly-conductive dielectric layers. This leads to the so-called Maxwell-Wagner dielectric relaxation with huge apparent dielectric constant at low frequencies.
Publisher URL: http://arxiv.org/abs/1812.11873