Remote vapor-phase dual alkali halide salts assisted quasi-van der Waals epitaxy of m-phase ZrO2 thin films with high dielectric constant and stable flexible properties

Abstract

High-κ dielectric constant and wideband gap of ZrO2 material render it as an excellent candidate for transistor gate dielectric layers. However, current reported synthesis techniques suffer the problems of high precursor volatilization rate, ultrasmall grains with low dielectric constant, and high leakage current, which largely impede its application in electronic devices. Here, the quasi-van der Waals epitaxy growth of compact m-phase ZrO2 thin films has been developed, in which the stable supply of Zr source is realized by the tuned sublimation of ZrC powder with remote vapor-phase dual halide salts assistant. The formation of m-phase ZrO2 is due to the lower Gibbs free energy, in which the crystal nucleates at the etched hole edges of mica substrate, thus forming hexagonal shape polycrystal grains and merging as the continuous thin films. The microstructures and Raman spectrum characterization reveal the two dominated growth orientations and good crystal qualities, which indicate the uniform dielectric constant. The excellent growth reproducibility could be easily adapted to thin metal substrates, such as tungsten, molybdenum, and stainless steel, where the adhesion strength is strong because of the higher density of interfacial chemical bonding. Meanwhile, the metal–insulator–metal flexible capacitors show the high dielectric constant of 23–26 and low leakage current density of 10−4 A/cm2 at large voltage and only exhibit the decreased capacitance density of 7% after several hundred bending cycles. Our work paves a way to achieve the high-quality dielectric thin films on various substrates by the unique chemical vapor deposition design strategy.