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 3.07g/cm3 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-𝑑𝑒𝑔-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.
Structure and electronic properties of amorphous strontium titanate
Motti F.;Torelli P.;Guarino A.;Di Gennaro E.;
2022
Abstract
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 3.07g/cm3 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-𝑑𝑒𝑔-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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
