Structure and electronic properties of amorphous strontium titanate

Understanding the short-range structure of an amorphous material is the first step in predicting its macroscopic properties. Amorphous strontium titanate (a-STO) presents a unique challenge due to contradictory experimental findings regarding the local oxygen environment of titanium, concluded to be either tetrahedral or octahedral. To elucidate the discrepancy, 72 models of a-STO with density ranging from the crystalline value 5.12 to $3.07\phantom{\rule{4pt}{0ex}}\mathrm{g}/{\mathrm{cm}}^{3}$ were prepared using ab initio molecular dynamics liquid-quench simulations and characterized by extended x-ray absorption fine structure (EXAFS) for both Ti and Sr K edge. An excellent agreement between the calculated and two independent experimental EXAFS measurements demonstrates that the discrepancy in the Ti coordination stems from differences in the material's density. Next, density-dependent structural characteristics, including Ti-O and Sr-O coordination, distances, angles, polyhedral sharing, and vibrational density of states in a-STO are thoroughly analyzed and correlated with disorder-induced changes in the electronic properties that are calculated using a hybrid density functional. The obtained increase in the band gap and broadening of Ti-$d\phantom{\rule{4pt}{0ex}}{e}_{g}$-orbital contributions in the conduction band are in excellent agreement with our x-ray absorption spectroscopy for Ti L-edge spectra and optical absorption measurements for crystalline and amorphous STO grown by pulsed laser deposition. The derived microscopic understanding of the structure-property relationship in amorphous ``perovskite'' serves as a foundation for further investigations of a-STO and related materials.