Investigation on Phase-Induced Surface Energy Change of HfO2 Thin Films Prepared By Plasma Enhanced Atomic Layer Deposition

Abstract

Wettability of nanomaterials has been researched for the scientific physics based on solid/liquid interfaces. In particular, wettability of ceramic materials which is directly relevant to the surface free energy has been researched for its nature continuously in terms of thin film coatings.1 The development of such materials with finely tunable surface free energy and adequate stability under harsh conditions has been attracted enormous interests involving various applications.2,3 Among them, Hafnium oxide (HfO2), one of the representative transition metal oxides, has been recently studied for robust coating materials with investigation of its surface free energy. However, due to the complexity derived from environmental factors in a stack and differences between variety of deposition parameters, the surface free energy of HfO2 films has not been fully understood. Apart from the fact that the previously reported water contact angle (WCA) of HfO2 thin or bulk films highly vary between literatures, the interpretation of surface free energy of HfO2 and its intrinsic wettability still lacks of systematic approaches. In this study, we comprehensively investigated the surface free energy variation in HfO2 films prepared by plasma enhanced atomic layer deposition (PE-ALD). Upon precise control of film thickness with the aid of PE-ALD technique, we analyzed the surface free energy changes depending on the various properties of HfO2 films including film thickness, chemical composition, surface roughness, film crystallinity. We focused on a dependency of surface free energy of HfO2 films on film crystallinity as a determining factor for wettability changes. For in-depth studies, we performed thermal annealing treatment on PE-ALD HfO2 films and observed apparent correlation between wettability and film crystallinity. Based on the control of film crystallinity, PE-ALD HfO2 thin films show versatile wetting behaviors as to exposure of liquids with different surface energies. The experimental results from our work will contribute to the fundamental understanding of surface free energy of thin film HfO2 and its scientific backgrounds, and can also lead to feasible applications including liquid separation and purifications using HfO2 as robust coating film.