The giant and negative dielectric tunability of Pb(Fe1/2Nb1/2)1-xTixO3 single crystals is reported. A low field of 120 V/cm can induce a great reduction of the capacitance, and the tunability is larger than 80% in low frequency range (<1 MHz) at room temperature. This giant tunability is ascribed to the interfacial polarization at the interface of electrode/sample. A negative dielectric tunability detected only in the tetragonal sample can be also attributed to the interfacial polarization. The origin of the giant and negative tunabilities is discussed with the multipolarization-mechanism model and equivalent circuit model, respectively.
We investigated the dielectric properties of Pb(Fe1/2Nb1/2)1-xTixO3 single crystals below room temperature. Two dielectric anomalies were detected in sample A while only one was detected in sample B in the temperature range 90~300 K. A Debye-like relaxation with strong frequency dispersion was detected in both samples. The pre-edge XAFS suggests that this dielectric anomaly is induced by the hopping conductivity between Fe2+ and Fe3+. The EXAFS results give us a clear picture of the local structure of iron ions. The weak frequency dependent dielectric anomaly only observed in sample A is supposed to be due to the dipole glass behavior.
Phase stabilities of Hf-Si-O and Zr-Si-O have been studied with first-principles and thermodynamic modeling. From the obtained thermodynamic descriptions, phase diagrams pertinent to thin film processing were calculated. We found that the relative stability of the metal silicates with respect to their binary oxides plays a critical role in silicide formation. It was observed that both the HfO$_2$/Si and ZrO$_2$/Si interfaces are stable in a wide temperature range and silicide may form at low temperatures, partially at the HfO$_2$/Si interface.
The Hf-O system has been modeled by combining existing experimental data and first-principles calculations results through the CALPHAD approach. Special quasirandom structures of $alpha$ and $beta$ hafnium were generated to calculate the mixing behavior of oxygen and vacancies. For the total energy of oxygen, vibrational, rotational and translational degrees of freedom were considered. The Hf-O system was combined with previously modeled Hf-Si and Si-O systems, and the ternary compound in the Hf-Si-O system, HfSiO$_4$ has been introduced to calculate the stability diagrams pertinent to the thin film processing.
Three different special quasirandom structures (SQS) of the substitutional hcp $A_{1-x}B_x$ binary random solutions ($x=0.25$, 0.5, and 0.75) are presented. These structures are able to mimic the most important pair and multi-site correlation functions corresponding to perfectly random hcp solutions at those compositions. Due to the relatively small size of the generated structures, they can be used to calculate the properties of random hcp alloys via first-principles methods. The structures are relaxed in order to find their lowest energy configurations at each composition. In some cases, it was found that full relaxation resulted in complete loss of their parental symmetry as hcp so geometry optimizations in which no local relaxations are allowed were also performed. In general, the first-principles results for the seven binary systems (Cd-Mg, Mg-Zr, Al-Mg, Mo-Ru, Hf-Ti, Hf-Zr, and Ti-Zr) show good agreement with both formation enthalpy and lattice parameters measurements from experiments. It is concluded that the SQSs presented in this work can be widely used to study the behavior of random hcp solutions.
