A complete characterization of Ca5(PO4)3OH sputter-deposited films by ion beam analysis: RBS and ERD

RF magnetron sputter deposition was used to deposit thin calcium phosphate (hydroxyapatite) layers on titanium alloy substrate material. We determined the precise amount of calcium, phosphorus, oxygen, and hydrogen in these films by combining two ion-beam analysis techniques: Rutherford backscattering spectrometry (RBS) and elastic recoil detection (ERD). Variables were power level, partial oxygen pressure, or additional water vapor. Also examined was the influence of additional bias power to the substrates during deposition and the effect of annealing on the final composition of the deposited layers. Measurements showed that the Ca/P ratio decreased with increasing oxygen pressure or decreasing sputtering power. In addition, the Ca/P ratio increased when a bias was applied to the substrates. The O/P ratio of the films decreased with additional oxygen pressure but increased when additional water vapor was applied during deposition. All as-deposited films showed a higher hydrogen content than stoichiometric HA. The hydrogen content in the films deposited with water vapor was more than 7 times higher than in the films deposited under pure argon conditions. After annealing, the hydrogen content decreased to about 3.5 at % whereas in stoichiometric HA the hydrogen content amounts to 4.5 at %. After annealing, the oxygen concentration in the film also decreased. We assume that hydrogen disappears out of the film as H₂O during annealing. For the targets used in these experiments, sputter deposition at 400 W, with additional water vapor and annealing at 500^oC, produced films with a stoichiometry closest to that of hydroxyapatite.