Influence of oblique angle deposition on Cu-substituted hydroxyapatite nano-roughness and morphology

In this work, we study the effect of RF magnetron oblique angle deposition (OAD) on morphology, structure, and elemental composition of as-deposited and heat-treated Cu containing calcium phosphates. The control over the surface morphology and nano roughness provided by OAD is of great interest as both Mesenchymal Stem Cells and various types of bacteria respond strongly to nanoscale topography. A Cu substituted hydroxyapatite target was used to deposit coatings on the surface of titanium (Ti) and silicon (Si) substrates. The samples were placed at an oblique angle of 80° relative to the surface of the sample holder and in a normal configuration with respect to the flux direction and, therefore, parallel to the target. The dense homogeneous coatings with globular surface features deposited at normal flux incidence (NFI) configuration changed to elliptical, highly oriented structures with the direction dictated by the atomic shadowing effect when the substrate was deposited at an oblique angle. As-deposited thin films were subjected to post-deposition-heat-treatment at 700 °C in an Ar atmosphere. This led to a drastic change in the surface morphology and, namely, lost the directionality of the nanostructures. According to the X-ray diffraction data, the samples deposited obliquely showed preferential growth in the (002) plane and lower internal stress, than samples coated at NFI for both the Si and Ti substrates. The RMS roughness of the films deposited obliquely on Si was twice that of the films deposited at NFI (860 ± 80 pm and 408 ± 60 pm, respectively). However, it was not the case for the Ti substrate, the RMS roughness decreased from 42 ± 4 nm for coatings deposited at normal flux geometry to 33 ± 2 nm for coatings deposited obliquely. The heat-treatment of the samples deposited at 80° resulted in a significant increase in the surface roughness: 8 ± 0.7 nm for Si and 71 ± 4 nm for Ti substrates. The obtained results demonstrate that the oblique angle deposition can be used to fabricate nano-rough surface morphologies.