Citation: Prosolov, K.A.;
Lastovka,V.V.; Khimich, M.A.;
Chebodaeva, V.V.; Khlusov, I.A.;
Sharkeev, Y.P. RF Magnetron
Sputtering of Substituted
Hydroxyapatite for Deposition of
Biocoatings. Materials 2022, 15, 6828.
https://doi.org/10.3390/ma15196828
Academic Editor: Csaba Balázsi
Received: 31 August 2022
Accepted: 28 September 2022
Published: 1 October 2022
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materials
Article
RF Magnetron Sputtering of Substituted Hydroxyapatite for
Deposition of Biocoatings
Konstantin A. Prosolov
1,
* , Vladimir V. Lastovka
1
, Margarita A. Khimich
1
, Valentina V. Chebodaeva
1,2
,
Igor A. Khlusov
2
and Yurii P. Sharkeev
1,3,
*
1
Laboratory of Physics of Nanostructured Biocomposites, Institute of Strength Physics and Materials Science,
Siberian Branch of Russian Academy of Sciences, 634055 Tomsk, Russia
2
Laboratory of Cellular and Microfluidic Technologies, Siberian State Medical University, 634050 Tomsk, Russia
3
Research School of High-Energy Physics, National Research Tomsk Polytechnic University, Lenin Avenue 30,
634050 Tomsk, Russia
* Correspondence: konstprosolov@gmail.com (K.A.P.); sharkeev@ispms.ru (Y.P.S.);
Tel.: +7-961-888-58-33 (K.A.P.)
Abstract: Functionalization of titanium (Ti)-based alloy implant surfaces by deposition of calcium
phosphates (CaP) has been widely recognized. Substituted hydroxyapatites (HA) allow the coating
properties to be tailored based on the use of different Ca substitutes. The formation of antibacterial
CaP coatings with the incorporation of Zn or Cu by an RF magnetron sputtering is proposed. The
influence of RF magnetron targets elemental composition and structure in the case of Zn-HA and
Cu-HA, and the influence of substrate’s grain size, the substrate’s temperature during the deposition,
and post-deposition heat treatment (HT) on the resulting coatings are represented. Sintering the
targets at 1150
◦
C resulted in a noticeable structural change with an increase in cell volume and
lattice parameters for substituted HA. The deposition rate of Cu-HA and Zn-HA was notably higher
compared to stochiometric HA (10.5 and 10) nm/min vs. 9 ± 0.5 nm/min, respectively. At the
substrate temperature below 100
◦
C, all deposited coatings were found to be amorphous with an
atomic short-range order corresponding to the {300} plane of crystalline HA. All deposited coatings
were found to be hyper-stochiometric with Ca/P ratios varying from 1.9 to 2.5. An increase in
the substrate temperature to 200
◦
C resulted in the formation of equiaxed grain structure on both
coarse-grained (CG) and nanostructured (NS) Ti. The use of NS Ti notably increased the scratch
resistance of the deposited coatings from18 ± 1 N to 22 ± 2 N. Influence of HT in air or Ar atmosphere
is also discussed. Thus, the deposition of Zn- or Cu-containing CaP is a complex process that could
be fine-tuned using the obtained research results.
Keywords: antibacterial effect; biocompatibility; calcium phosphate; ion substitution; physical vapor
deposition; thin films
1. Introduction
New materials for regenerative medicine are in high demand due to the aging of the
ever-increasing population [1]. The most important parameter among others for newly
developed materials ready to be introduced into clinical practice is their biocompatibil-
ity [2]. Biocompatible materials can be divided into three groups: biotolerant, bioinert, and
bioactive [3]. Bioinert alloys, a striking representative of which are titanium (Ti)-based
alloys, are characterized by osteoconductive property, which means that these materials
are not included into the metabolic process, are not dissolved in the body, but their surface
can provide a physical and mechanical connection to body tissues, and their oxide film
promotes the adhesion of various proteins that trigger the osseointegration process [4]. On
the other hand, it is known that the wear of the metal surface of implants occurs during
their service life, e.g., the cobalt-chrome-molybdenum alloy wears at an average rate of
0.02–0.06 mm over 10 years. The metal chips or particles that appear during wear are
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