Over the past several decades, research has focused on utilizing ceramic materials in new technological applications. Their uses have been primarily in applications that involve high temperatures or corrosive environments. Unfortunately, ceramic materials have been limited especially since they can be brittle, failing in a sudden and catastrophic manner. A strong emphasis on understanding mechanical properties of ceramics and ways to improving their strength and toughness, has led to many new technologies.
The present work is part of a larger research initiative that is aimed at using RF magnetron sputter deposition of yttria-stabilized zirconia to improve the fracture toughness of brittle substrates (more specifically dental ceramics). Partially-stabilized zirconia (PSZ) has been studied extensively, due to its high temperature stability and stress-induced tetragonal to monoclinic (T⇒M) martensitic phase transformation. RF magnetron sputtering was chosen as the deposition method because of its versatility, especially the ability to deposit oxides at low temperatures.
Initial investigations focused on the development of process-structure-properties of YSZ sputtered deposited thin films. The YSZ thin films were deposited over a range of temperatures (22--300°C), pressures (5--25 mTorr), and gas compositions (Ar:O2 ratio). Initial studies characterized a select set of properties in relation to deposition parameters including: refractive index, structure, and film stress. X-ray Diffraction (XRD) showed that the films are comprised of mainly monoclinic and tetragonal crystal phases. The film refractive index determined by prism coupling, depends strongly on deposition conditions and ranged from 1.959 to 2.223. Wafer bow measurements indicate that the sputtered YSZ films can have initial stress ranging from 86 MPa tensile to 192 MPa compressive, depending on the deposition parameters. Exposure to ambient conditions (25°C, 75% relative humidity) led to large increase (∼ 100 MPa) in the compressive stress of the films. Environmental aging suggests the change in compressive stress was related to water vapor absorption. These effects were then evaluated for films formed under different deposition parameters with varying density (calculated packing density) and crystal structure (XRD).
Based on the above results, it was determined to evaluate stress as a function of substrate bias. It was shown that increasing substrate bias power disrupted columnar grain growth and reduced the percent change in compressive stress when exposed to ambient environments. TEM confirmed a reduction in inter-granular porosity for substrate bias depositions, but an increase in lateral defects. It was hypothesized that substrate bias would increase the film's density, but after inspection of SEM and TEM micrographs, it appeared that as bias was increased the density decreased.
This T⇒M phase transformation has been well documented for bulk PSZ, but limited data exists for PSZ thin films. Data is presented that supports a stress-induced T=>M transformation mechanism that occurs during sputter-deposition in the presence of a substrate bias. Substrate bias (0--50W) was originally applied to increase film density, modify microstructure, and vary film stress. The films were deposited using rf magnetron sputtering from a sintered yttria-stabilized zirconia (YSZ) target and subsequently characterized using scanning (SEM) and transmission electron microscopy (TEM), x-ray diffraction (XRD), and wafer bow measurement (for stress analysis). With no substrate bias the films exhibited a columnar grain structure consistent with sputter-deposited films, with a majority tetragonal phase as determined by XRD. Under higher substrate bias, wafer bow measurements indicated a steady increase in compressive stress as substrate bias increased (max. 310MPa at 50W bias), while XRD indicated a corresponding increase in the percentage of monoclinic phase. Both SEM and TEM analyses revealed a shift from a defect-free columnar structure to one consisting of lateral intra-columnar or trans-granular defects for films deposited under substrate bias conditions. It is believed that these defects form as a result of stress-relief in the growing film via the transformation from tetragonal to monoclinic phase due to bias-induced compressive stress. FEA modeling is used to confirm stress contours and defect generation within the films.
The structure developed under substrate bias deposition is hypothesized to provide beneficial strengthening mechanisms, similar to microcrack toughening, when deposited on brittle substrates. This manuscript concludes with an analysis of YSZ thin films deposited on an alternative substrate (soda-lime glass) that replicates a bio-inert material.