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Hafnium oxide (HfO₂) thin film has remarkable physical and chemical properties, which makes it useful for a variety of applications. In this work, HfO₂ films were prepared on silicon through plasma enhanced atomic layer deposition (PEALD) at various substrate temperatures. The growth per cycle, structural, morphology and crystalline properties of HfO₂ films were measured by spectroscopic ellipsometer, grazing-incidence X-ray diffraction (GIXRD), X-ray reflectivity (XRR), field-emission scanning electron microscopy, atomic force microscopy and x-ray photoelectron spectroscopy. The substrate temperature dependent electrical properties of PEALD–HfO₂ films were obtained by capacitance–voltage and current–voltage measurements. GIXRD patterns and XRR investigations show that increasing the substrate temperature improved the crystallinity and density of HfO₂ films. The crystallinity of HfO₂ films has a major effect on electrical properties of the films. HfO₂ thin film deposited at 300 °C possesses the highest dielectric constant and breakdown electric field.