Improving phase transition temperature of VO2 via Ge doping: a combined experimental and theoretical study

Abstract

Enhancing the semiconductor–metal phase transition temperature (TSMT) of VO2 is of great consequence for further exploring the potential applications of VO2 at elevated temperatures. In this study, Ge4+-doped VO2 (GexV1−xO2) samples were prepared by the hydrothermal and annealing approach. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), differential scanning calorimetry (DSC) and resistivity–temperature (R-T) analyses were used to investigate the influence of Ge doping on the lattice structures and phase transition properties of GexV1–xO2 samples. We found that the lattice parameter of GexV1−xO2 decreased with the Ge concentration increasing from 2 at% to 18 at%, which was further supported by density functional theory (DFT)-based first-principle simulations. TSMT firstly increased from 64.5 to 73.0 °C at 8 at% Ge and then decreased to 71.5 °C at higher Ge concentration. Furthermore, DFT analysis revealed that the impact of lattice distortion induced by Ge doping rather than the changes in electronic structure is more pronounced on modulating TSMT of GexV1−xO2. The present work has pointed out the direction that the TSMT could be enhanced and illustrated the physical reason behind the regulation of TSMT in ions-doped VO2 systems. The d (logρ)/dT vs T curves are plotted for GexV1−xO2 (0≤x≤0.18) samples (a) un-doped VO2 ; (b) 2%; (c) 8%; (d) 18%, the transition temperatures upon heating, Th, and cooling, Tc. The difference between Th and Tc gives the hysteresis width, ΔTt, while the FWHM determines the sharpness of the semiconductor-to-metal transition