Thin Solid Films 453 454 (2004) 208214

High-energy ion beam implantation of hydroxyapatite thin films grown on TiN and ZrO2 inter-layers by pulsed laser deposition
V. Neleaa,*, H. Pelletiera, P. Millea, D. Mullerb
a

Laboratoire dIngenierie des Surfaces, Institut National des Sciences Appliquees, 24, Bld. de la Victoire, 67084 Strasbourg, France b Laboratoire PHASE, CNRS, 23 rue de Loess, BP 20CR, 67037 Strasbourg, France

Abstract Current drawbacks in the hydroxyapatite (HA) thin film production for applications in bone surgery are their poor mechanical strength and limited adherence. This paper presents the ion beam implantation technique as an efficient method to improve the mechanical characteristics of HA films. Crystalline films of HA were grown by pulsed laser deposition, using a KrF* excimer laser (ls248 nm, t020 ns). The depositions were performed from pure HA targets on Ti5Al2.5Fe alloys coated with TiN or ZrO2 buffer layers. Samples were then implanted with Arq ions of high-energy (1.5 MeV) at a dose of 1016 cmy2. The asdeposited and implanted films were characterized by light microscopy and energy dispersive X-ray spectrometry. The mechanical properties of films were studied by nanoindentation and nano-scratch techniques using a Berkovich indenter tip. Films become harder and exhibit a higher Young modulus after implantation. The best values (5 GPa hardness and 130 GPa Young modulus, respectively) were obtained for the implanted films grown on TiN. An influence of the buffer layer nature on the mechanical behavior of films was observed. Films grown on ZrO2 are brittle and crack at moderate load (;12 mN) during scratch while these ones deposited on TiN successfully withstand loading. Residual stresses occur into the HAyZrO2 structure during processing and ion bombardment. 2003 Elsevier B.V. All rights reserved.
Keywords: Hydroxyapatite thin films; Pulsed laser deposition; Ion beam implantation; Nanoindentation

1. Introduction Hydroxyapatite (HA, Ca5(PO4)3OH) ceramics are widely used as substitute of bone w1x. As coated on metallic prostheses, HA offers the biocompatibility necessary for bone cell apposition. Current drawbacks in the HA thin film production are their poor mechanical strength and limited adherence. A feasible and modern technique for thin film production is the pulsed laser deposition (PLD) w2x. Different growth procedures of HA thin films using PLD were reported w36x. Since depositions were performed in oxidizing environment on heated Ti-based substrates, precautions against substrate surface deterioration by oxidation during equilibration of deposition conditions and film growing should be taken. The quality of the filmsubstrate interface influences the film properties
*Corresponding author. Tel.: q33-3-88-14-47-00; fax: q33-3-8814-47-39. E-mail addresses: nelea@mail.insa-strasbourg.fr (V. Nelea), vnelea@yahoo.fr (V. Nelea). 0040-6090/04/$ - see front matter doi:10.1016/j.tsf.2003.11.119

and its subsequent functionality. Ti oxidation induces structural modifications of HA layers in the region near the substrate w6x and considerably reduces its adherence w7 x . As previously reported w6x, high quality HA films were growing by PLD inserting different buffer layers (TiN, ZrO2 or Al2O3) at the filmsubstrate interface. Since HA starts to decompose at temperatures up to 900 8C w8x, the densification of HA films during growing or by subsequent annealing was limited. An efficient way to increase the density and adherence of a coating at low temperature is the ion beam implantation technique w9x. Ions accelerated at convenient energies (MeV range) are passed through the film and come to stop in the substrate. The film density and adherence enhances by multiple in depth collisions and mixing of atoms at the interface. Lopatin et al. w10x reported densification of HA coatings by high-energy ion beam implantation. The films were created on Si substrates by solgel routes and implanted therefore with Siqq ions. Recently we

2003 Elsevier B.V. All rights reserved.

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have extended the ion implantation technique to HA films grown on metallic substrates covered with TiN inter-layers using Arq ions w11x. The hardness and mechanical resistance of films increase after implantation while the crystalline structure of HA was preserved. This paper presents comparative results of the ion beam implantation method applied to HA thin films grown on TiN and ZrO2 buffer layers by PLD in order to improve the mechanical properties and adherence of HA films. 2. Experimental details The HA films were deposited by a KrF* excimer laser (ls248 nm, tFWHM020 ns). The laser beam was focused at 458 on a hot-pressing pellet obtained from a high-purity (99.98%) polycrystalline HA powder. Polished disks cut from Ti5Al2.5Fe (TiAlFe) alloy bars were used as collectors. Before deposition the substrates were coated with a TiN or ZrO2 buffer layer. Buffer layers were also grown by PLD from stoichiometric TiN and ZrO2 targets in low-pressure of nitrogen and oxygen, respectively, on substrates heated at 650 8C w12,13x. HA films were grown in vacuum (;10y4 Pa residual pressure) at room temperature of substrates and subsequently annealed in ambient air at 5508 C for 1 h. HA films have a thickness of ;1 mm, while the TiN and ZrO2 buffer layers are approximately 500 nm thick. After deposition the samples were implanted with Arq ions using a Van de Graaff-type implanter. The ion beam was 1.5 MeV energy and 1016 cmy2 dose. The current density was held at 1 mA cmy2. In order to choose the proper implantation energy, simulations of ions distributions as implanted in the films depth were performed using the TRIM code w14x. Calculations were run for multi-layer systems of HAy TiNyTiAlFe and HAyZrO2 yTiAlFe using different values of thickness and density of layers. According to the LindhardScharffSchiott (LSS) model w15x, the theoretical projection can be described by the mean projected range (Rp), its standard deviation (DRP) and the maximal concentration (Cmax) of the implanted atoms. The as-deposited and implanted films were characterized by light microscopy and energy dispersive X-ray spectrometry (EDS). EDS microanalyses were carried out in order to determine the CayP atomic ratio in the films. We used a Kevex EDX analyser operated on a Philips XL 30 environmental scanning electron microscope. To study the distribution of Ca, P and O elements on the film surface, cartography analyses (elemental distribution maps) were performed. The mechanical properties of films were studied by nanoindentation and nano-scratch techniques. The hardness (H) and Young modulus (E) were determined using an ultra-low load indentation system, the Nano Indenter XP (MTS, Corp.), equipped with a Berkovich

Table 1 Mean projected range (Rp) and its standard deviation (DRP) of Arq ions implanted at 1.5-MeV energy and 1016 cmy2 dose, as calculated by the TRIM code Multi-layer system HAyTiNyTiAlFe Density of buffer Density of HA Rp DRp layers (g cmy3) films (g cmy3) (mm) (nm) 2.8 4 2.5 2.5 2.5 2.5 1.33 1.18 1.24 1.07 207 153 169 162

HAyZrO2 yTiAlFe 3.5 4.5

indenter tip. This highly accurate microprobe of mechanical properties analysis has the capability of sensing continuously the load (F) and displacement (h) as indents are being made in the sample. Multiple indentations were made with load ranging from 0.5 to 15 mN. E and H were calculated starting from the load displacement curves using the OliverPharr model w16x. Friction behavior was studied on the same apparatus equipped with a nano-scratch attachment. A well-defined trigonal diamond Berkovich indenter (tip radius less than 40 nm) is drawing over the film surface with a constant translating speed of 10 mm sy1. The normal applied load was linearly ramped between two imposed values, F1s5 mN and F2s25 mN, respectively. The length of the sliding track was approximately 500 mm. The normal load (F), indentation depth (h), friction force (Ff) and friction coefficient (m) are simultaneously monitored. In order to show possible conformational differences between the implanted and non-implanted regions of films, tests at a constant normal load of 25 mN were also performed. 3. Results 3.1. TRIM simulations Table 1 presents the values of Rp and DRP characteristic to a HA (1 mm)ybuffer layer (500 nm)yTiAlFe multi-layer system obtained by implantation simulations with Arq ions of 1.5-MeV energy and 1016 cmy2 dose. Two values of the buffer layer density were used for each system, 2.8 and 4 g cmy3 as estimated for TiN and 3.5 and 4.5 g cmy3 as supposed for ZrO2, respectively. The density of HA films was assumed to be 2.5 g cmy3, i.e. 79% of theoretical density of HA bulk. Calculated Rp values are within the (11.5 mm) range with values of DRP down to 210 nm. These results show that Arq ions were generally centered at the middle of the buffer layer. This avoids gaseous argon bubbles to appear into the HA coating, often observed for ionimplanted films. 3.2. Surface morphology Fig. 1 presents light micrographs showing the surface morphology of an as-deposited (a) and implanted HAy

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significantly reduced and films exhibited practically particles-free surfaces. It was supposed that passing through the film, the ion beam destroys droplets and other defects. However, the interaction between Arq ions and droplets and their mechanism of destruction is not very clear. As shown in Fig. 1c, the implanted surface of HAyZrO2 film has a particular morphology, in contrast to the implanted one of HAyTiN (Fig. 1b). Large formations of grains delimited by well-defined frontiers were formed after implantation. The occurrence of frontiers proves residual stress developing in the film structure by ion bombardment. 3.3. Chemical microanalysis As measured by EDS, the CayP atomic ratio of films varies within the 1.82 range, independently of the buffer layer nature and ion treatment. A depletion in P of the as-deposited films with respect to the HA target stoichiometry (CayPs1.7) was evidenced. As lighter than Ca, P can be lost during film deposition or reevaporate from the substrate under bombardment with energetic species of plasma. The film stoichiometry was not modified by ion bombardment. Elemental distribution maps show that Ca and P are uniformly distributed on the film surface. Oxygen was found as homogenous located on the entire surface. Its signal should been coming from both HA structure and molecular oxygen trapped in the film surface from air. No particular features between the implanted and nonimplanted regions were observed. Signals of Ti, Al and Fe, characteristic to the Ti alloy substrate, were also recorded. 3.4. Nanoindentation and nano-scratch tests Fig. 2 presents the evolution of the maximum depth with the applied load obtained by nanoindentation for the as-deposited and implanted films grown on TiN (a) and ZrO2 (b) buffer layers. The curves give qualitative information on the films resistance at the indenter penetration, i.e. films toughness. Curves show that both implanted films (grown on TiN and ZrO2) were tougher. Comparing the penetration depth, it concludes that films grown on TiN became more resistant after implantation than those ones grown on zirconia. Results demonstrate that a more compact structure of HA was formed by implantation. Table 2 presents the measured and mean values of the hardness and Young modulus of as-deposited and ion-implanted HA films as measured by nanoindentation. Implanted films were harder and have a higher Young modulus. The highest values (5 GPa hardness and 130 GPa Young modulus, respectively) were obtained for films grown on TiN.

Fig. 1. Light micrographs showing the surface morphology of an asdeposited (a) and implanted HAyTiN (b) and HAyZrO2 (c) films.

TiN (b) and HAyZrO2 (c) films. An irregular granular morphology suggesting an important surface roughness of non-implanted films was observed. The surface is constituted by agglomerations of grain-shape particles (droplets) that are typical for pulsed laser deposited films w2x. An important modification of the surface aspect after implantation was observed. The number of droplets was

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Fig. 2. Evolution of the maximum depth with the applied load obtained by nanoindentation for as-deposited and implanted films grown on TiN (a) and ZrO2 (b) buffer layers. Table 2 Hardness (H) and Young modulus (E) of as-deposited and implanted HA films as measured by nanoindentation Films HAyTiNyTiAlFe H (GPa) Hm (GPa) E (GPa) Em (GPa) NI 2.53 I 45.5 2.8 5 0.6 3.5 60130 110 100150 130 3045 6070 35 65

HAyZrO2 yTiAlFe NI 0.40.8 I 34

I, implanted; NI, non-implanted; m, mean value.

Table 3 collects films behaviors under nanoindentation in term of toughness increasing and test reproducibility performed on the as-deposited and implanted structures. Again, the best results were obtained for the implanted films grown on TiN. Worse results of as-deposited films are due to the presence of pores and droplets into the film depth w2x. Accidents occur under loading and poor loaddisplacement curves are recorded. The extent of pores, droplets and other defects are reduced after ionimplantation by network structural relaxation and grains rearrangement. Indeed, films became denser and load displacement curves became smoother and more reproducible under loading. Fig. 3a displays the profiles under load as measured in the implanted regions during a scratch test. The normal load was linearly increased from 5 to 25 mN. Films grown on TiN successfully withstand loading,
Table 3 Films behavior under nanoindentation Films HAyTiNyTiAlFe HAyZrO2 yTiAlFe Non-implanted

while films grown on ZrO2 crack and damage at loads up to 12 mN. Curves show that until cracking the penetration depth are lower for films grown on TiN, confirming better resistance of HAyTiN films, observed in static nanoindentation. In Fig. 3b the friction force (Ff) between indenter and film material as a function of the applied normal load (F) was drawn. As evidenced by the data fluctuations, film grown on ZrO2 suddenly cracks when the load reaches a critical load of approximately 12 mN value. In order to study features of non-implanted and implanted zones of HAyZrO2 films, scratch tests at a constant load of 25 mN were performed. The indenter was translated on the same typical 500-mm length distance, starting from a non-implanted zone to an implanted one. Fig. 4 presents the friction coefficient (m) as varying with the scratch length (a) and a light micrograph (b) showing the scratching track at the frontier of nonimplantedimplanted zones. It means that, after a relatively constant 0.6 value of m measured in the non-implanted region, great instabilities of the friction coefficient immediately when the indenter reaches the implanted zone was recorded. The implanted zone cracks and failures at the level of TiAlFe substrate by delamination (Fig. 4b). As recently reported, similar tests performed on HAy TiN samples showed that films withstand loading wear

Implanted (1) The best results (2) No accidents on the loaddisplacement curves (1) Very good results (2) No accidents on the loaddisplacement curves

(1) Good results (2) Rare accidents on the loaddisplacement curves (1) Satisfactory results (2) Sometimes accidents occur on the curves

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Fig. 3. (a) Profiles under loading as drawn in the films implanted regions during a scratch test. The normal load was linearly increased from 5 to 25 mN. (b) Friction force in function of the applied load recorded during the same test. Films grown on TiN successfully withstand loads, while those grown on ZrO2 crack and damage at 12 mN load.

w11x. Moreover, the width of the scratch trace diminishes when the indenter arrives in the implanted region, demonstrating film toughness increasing. Results show that, despite the density increasing (as evidenced by the better mechanical characteristics obtained by indentation), the films grown on zirconia buffer became brittle after implantation. This characteristic, less convenient for the subsequent biomedical application, comes from residual stress developed in the film structure during deposition and ion beam treatment. 4. Discussion HA coatings with application in bone implantology should have high crystallinity, proper stoichiometry, good control of densityyporosity and excellent adherence to the metallic support. They should have also sufficient toughness and acceptable mechanical properties necessary for load-bearing devices. As known, under optimal conditions, crystalline, stoichiometric, dense and adherent HA thin films can be produced by PLD w25x. PLD offers decisive advantages with respect to other deposition techniques, for example plasma spraying that is commercially used to cover bone prosthesis with HA. In plasma spraying, HA powder injected into the plasma is heated to several 1000 8C and propelled at high speed to a substrate w17x. The obtained coatings contain anhydrous calcium phosphate phases decomposed from HA at high temperature and an important level of amorphous material due to rapid cooling of particles reaching the substrate. In PLD, material is transferred to the substrate following laser beamHA target interaction. Due to short laser pulse duration, large optical absorption and poor thermal conductivity of HA, heating is confined to a thin surface layer during laser irradiation. The target

Fig. 4. Friction coefficient as varying with the scratching length (a) and the corresponding scratching trace (b) obtained during a test performed at a constant load of 25 mN starting from the non-implanted to the implanted regions of HAyZrO2 films. The implanted zone cracks and failure by delamination.

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surface is melted and rapid thermal expansion inducing a massive explosion of the material occurs. The expulsed material forms a plasma plume containing ions, atoms, molecules, clusters and hot particles. In contrast to plasma spraying that is essentially a thermal processing technique, in PLD other physical phenomena, like absorption of energy by inverse bremsstrahlung are of high importance yielding particles with energies far higher than those of thermal regime w18x. Ion beam implantation is a non-conventional technique used for surface modification and thin films densification. The ion beam passes through and looses its energy by deceleration into the film depth. During ion bombardment electronic and nuclear collisions occur. Ions collide with the atoms of film and of the substrate, physically moving them so that the interface becomes integrated and blurred. Some authors reported densification of thin films using ion beam implantation technique. Harder and more difficult to scratch HA thin films were obtained by implantation with Ar, N and O ions of 100-keV energy w19x. Levine et al. performed densification of zirconia solgel thin films by implantation with 280-keV-energy Xeq ions w20x. Our results showed that HA films grown on TiN and ZrO2 inter-layers became denser after implantation with Arq ions of 1.5-MeV energy. The densification is proven by the improved mechanical properties of films as measured by nanoindentation. By passing through the film, Arq ions diminish the number of pores, particles and defects, inducing structural relaxation and redistribution of grains into the film network. It is also very probably that grains frontiers suffer conformational modification that induces material compactness. However, the interaction between Arq ions and droplets and their mechanism of destruction is not exhaustively clear. We believe that film densification is due to combined effects of electronic and nuclear loss modes of bombarding ions. Densification is most likely achieved by condensationycross-linking reactions and structural relaxation. These phenomena are favored by increased network mobility due to some bond-breaking and network rupture following the ionmatter interaction. This densification way fundamentally differs from that of conventional sintering at high temperature characterized by condensation, structural relaxation and viscous flow w20x. The scratch tests showed different behavior after implantation between films grown on TiN and ZrO2 inter-layers. Films grown on ZrO2 delaminate under scratch, while films grown on TiN withstand tests. As both inter-layer and HA film were proceeded on heated substrate (650 and 550 8C, respectively) residual stress into the multi-layers are expected to appear during PLD processing due to difference between the thermal expansion coefficients of the involved materials. Moreover, the stress level may increase after ion bombardment. The theoretical thermal expansion coefficients of Ti-

based substrate w8x, ZrO2 w21x, TiN w22x and HA w8x are (10, 78, 9.3 and 11)=10y6 Ky1, respectively. It means that residual stress is expected to be greater for the HAy ZrO2 yTiAlFe structure. Stress should be localized in both ZrO2 inter-layer and HA film. Its existence was proved by the surface morphology of film (Fig. 1c), where well-defined grain frontiers have been observed. Moreover, film delamination occurs at the level of second interface, ZrO2 yTiAlFe substrate, proving stress existence at this interface. As TiN is a related compound of the substrate (forming by insertion of N atoms within the Ti lattice), it was expected that a high-quality TiNy TiAlFe interface with greater bond strength with respect to the ZrO2 yTiAlFe interface develops. 5. Conclusion The ion beam implantation technique revealed to be a convenient tool for mechanical properties improvement of HA films. After implantation, films were harder, more resistant and have a higher Young modulus. The best results were obtained for the implanted films grown on TiN buffer layer. Ca, P and O are uniformly distributed on the film surface for both as-deposited and implanted films. Despite a density increasing, the films grown on zirconia buffer layers accumulate residual stress and became brittle after implantation. The HAyTiN films withstand the loading and no cracks or film damage occurred. References
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