Substrate dependent structural variations of biomimetic carbonated hydroxyapatite deposited on glass, Ti and sputtered ZnO thin films

Abstract

The formation of hydroxyapatite films on glass, titanium (Ti), and sputtered ZnO is attempted to understand the crystal growth and its manipulation by substrates of a different kind. The substrates used are commercially available glass and polished Ti (99.9% purity), as-deposited, and annealed nanostructured ZnO thin films developed by pulsed DC magnetron sputtering, which are immersed in the calcifying solution for the nucleation and growth of the hydroxyapatite. The calcifying solution is obtained by mixing equal volumes of aqueous calcium (5 mM) and carbonate-containing phosphate (3 mM) solutions prepared at 37 °C and with a pH of ~7.4. X-ray diffraction, Raman spectroscopy, and Field Emission Scanning & Transmission Electron Microscopy (FESEM & FETEM) analyses reveal that the structure and morphology of the hydroxyapatite films are dependent on the growth duration, substrate type, and even on the post-deposition annealing of the sputtered ZnO substrates. The Ti substrate induces greater crystallinity in hydroxyapatite, whereas sputtered ZnO thin films cause a significantly reduced crystallinity. Moreover, the thicknesses of HAp are exacerbated by increasing deposition time irrespective of the substrate. FETEM analyses reveal the formation of needle-shaped hydroxyapatite nanocrystals grown on Ti and ZnO thin films. Thicker needle-shaped hydroxyapatite nanocrystals are observed when grown on Ti (~6–12 nm) than ZnO thin films (~4–6 nm). Further, the amorphous calcium phosphate phase coexists with nanocrystalline hydroxyapatite when ZnO thin films deposited at 50 and 70 W sputtering powers are used as the substrates. Both charged surfaces and the supersaturation of the calcifying solution impact the nucleation of hydroxyapatite onto substrates.