Homologous substrate-temperature dependence of structure and properties of TiO2, ZrO2, and HfO2 thin films deposited by reactive sputtering

Abstract

Group 4 metal oxides TiO2, ZrO2, and HfO2 were deposited on glass substrates at substrate temperatures ranging from 100 to 800 °C by reactive direct current magnetron sputtering using an Ar and O2 mixture as discharge gas. On the basis of the obtained cross-sectional and surface morphologies, crystallographic structures, and film properties, the homologous substrate-temperature dependence of the film structure and properties for the sputter-deposited metal oxide thin films are discussed. The x-ray diffraction measurements show the diffraction patterns characteristic of the anatase (tetragonal) structure at substrate temperatures below 400 °C and those of the rutile (tetragonal) structure at substrate temperatures above 600 °C for TiO2 thin films and the patterns attributable to the monoclinic structure with 〈−111〉 orientation for ZrO2 and HfO2 thin films. Scanning electron microscopy (SEM) observations show voided columnar structures with rough surfaces for TiO2 thin films and fine columnar structures with smooth surfaces for ZrO2 and HfO2 thin films, which is supported by the results obtained from atomic force microscopy (AFM) analysis. The quantitative data on the lattice strain, crystallite size, surface roughness, and refractive index are plotted against the homologous substrate temperature, Tsub/Tm (Tsub: substrate temperature and Tm: melting point of thin film materials). The lattice strain reaches approximately zero at Tsub/Tm = 0.3–0.35, suggesting that the residual stress is relaxed at this point, and the crystallite size reaches a plateau at the same range of Tsub/Tm. The surface roughness increases sharply after passing Tsub/Tm = 0.25–0.30, and the refractive index shows a rise at Tsub/Tm = 0.30–0.35. The images obtained by SEM and AFM are categorized based on the property transition observed in the quantitative property changes. The data obtained in this work are utilized to systematically study the effectiveness and appropriateness of the homologous (normalized) substrate temperature to explain the changes in structure, morphology, and properties of oxide thin films. Furthermore, it is suggested that the structure zone model, which is normally applied to sputtered metal films, is also applicable to sputtered oxide thin films.