SiNx Coatings Research Articles

SiNx Coating Deposition on CoCr by Plasma-Enhanced Chemical Vapor Deposition

AbstractCobalt chromium alloys (CoCr) are commonly used as total disc replacement components. However, there are concerns about its long-term biological effects. Coating the CoCr with a ceramic could improve the implant’s biocompatibility and wear resistance. Silicon nitride (SiNx) coatings have emerged as a recent alternative to this end. While many have evaluated physical vapour deposition (PVD) techniques to deposit these coatings, plasma-enhanced chemical vapour deposition (PECVD) may provide certain advantages. For example, it may allow for low-temperature depositions as well as more uniform coatings of complex structures. In this study, silicon nitride (SiNx) coatings with different nitrogen-to-silicon (N/Si ratio) compositions (0.65, 1.16 and 1.42) were deposited onto CoCr substrates by PECVD. It was found that the SiNx coating deposited at an NH3 flow rate of 30 sccm (i.e., N/Si ratio of 1.42), had the highest hardness and elastic modulus, 13.19 ± 1.29 GPa and 132.76 ± 9.32 GPa, respectively. While a coating roughness adequate for the application could be measured, further optimization of the coating adhesion is needed to adequately evaluate its wear properties. It was concluded that the PECVD SiNx coating deposited at an NH3 flow rate of 30 sccm showed the highest potential for the intended application.

Design and optimization of single, double and multilayer anti-reflection coatings on planar and textured surface of silicon solar cells

The present silicon solar cell industry's main concern is to increase efficiency by minimizing the surface reflection. As a result, lately, much attention has been paid to the composition and number of the layers used for anti-reflection coatings in order to reduce surface reflection. In the present work, single, double, triple, and quadruple anti-reflection coatings on silicon solar cells have been designed and optimized using FDTD and PC1D simulation methods. The different combinations of SiO2, SiON, Si3N4, and SiNx coatings on both planar and textured surfaces were simulated and their optical and electrical parameters were investigated. Compared to planar surfaces, the designed coatings on textured surfaces showed better optical and electrical results for almost all investigated parameters. On textured surfaces, SiO2/Si3N4/SiNx acquired the lowest weighted average reflection (0.121%), SiO2/SiNx, SiON/SiNx, SiO2/Si3N4/SiNx, and SiO2/SiON/Si3N4/SiNx the highest Jsc(38.5 mA/cm2) and finally SiO2/Si3N4/SiNx and SiO2/SiON/Si3N4/SiNx both the highest Voc(705.7 mV) and η(23%).

Estimated approach development and experimental validation of residual stress-induced warpage under the SiNx PECVD coating process

Depositing silicon nitride (SiNx) coating by utilizing the plasma-enhanced chemical vapor deposition (PECVD) procedure is currently an important approach in the semiconductor industry because SiNx coating has several excellent application functions, such as passivation layer and oxygen/vapor barrier. However, residual stress occurs in the thin film resulted from the coefficient of thermal expansion (CTE) mismatch, lattice mismatch, defects, and impurities during the PECVD process. The SiNx-coated wafer would induce harsh warpage generated by coating film's residual stress. Aforementioned issue might generate the defects in the products, thus resulting in disrupted process and reliability problems. Such warpage is also unfavorable to the high flatness requirement for subsequent fabrication with the continuous scaling of advanced-technology devices. Accordingly, this study presents a novel process-oriented simulation methodology integrated with fluid dynamics-mechanical coupling responses to estimate its induced warpage magnitude affected by the pressure and temperature distributions during PECVD process and the initial intrinsic stress of SiNx coating. Under the consideration of the abovementioned loadings, the resultant stress and warpage after force balance for depositing SiNx coatings are obtained through process-oriented layer-by-layer simulation. On the basis of the simulated results and the data of experimental measurements, an intrinsic stress surface for SiNx is established by the radio frequency power, ammonia, and silane gas flow rate. Accordingly, the warpage magnitude and intrinsic stress of PECVD SiNx thin coating prior to actual processing can be immediately and accurately judged by the simulation methodology and SiNx intrinsic stress surface presented in this investigation.

Do SiNx coatings bear the potential to reduce the risk of micromotion in modular taper junctions?

Fretting corrosion is one contributor to the clinical failure of modular joint arthroplasty. It is initiated by micromotion in metal junctions exposed to fluids. Omitting metal-on-metal contacts could help to reduce the corrosion risk. The coating of one metal taper partner with a ceramic-based silicon nitride (SiNx) coating might provide this separation. The aim of the study was to identify whether a SiNx coating of the male taper component influences the micromotion within a taper junction. Hip prosthesis heads made of CoCr29Mo6 (Aesculap) and Ti6Al4V (Peter Brehm) were assembled (2000 N) to SiNx-coated and uncoated stem tapers made of Ti6Al4V and CoCr29Mo6 (2×2×2 combinations, each n = 4). Consecutive sinusoidal loading representing three daily activities was applied. Contactless relative motion in six degrees of freedom was measured using six eddy-current sensors. Micromotion in the junction was determined by compensating for the elastic deformation derived from additional monoblock measurements. After pull-off, the taper surfaces were microscopically inspected. Micromotion magnitude reached up to 8.4 ± 0.8 µm during loading that represented stumbling. Ti6Al4V stems showed significantly higher micromotion than those made of CoCr29Mo6, while taper coating had no influence. Statistical differences in pull-off forces were found for none of the taper junctions. Microscopy revealed CoCr29Mo6 abrasion from the head taper surface if combined with coated stem tapers. Higher micromotion of Ti6Al4V tapers was probably caused by the lower Young's modulus. Even in the contact areas, the coating was not damaged during loading. The mechanics of coated tapers was similar to uncoated prostheses. Thus, the separation of the two metal surfaces with the objective to reduce in vivo corrosion appears to be achievable if the coating is able to withstand in vivo conditions. However, the hard ceramic-based stem coating lead to undesirable debris from the CoCr29Mo6 heads during loading.

The Effect of N, C, Cr, and Nb Content on Silicon Nitride Coatings for Joint Applications.

Ceramic coatings deposited on orthopedic implants are an alternative to achieve and maintain high wear resistance of the metallic device, and simultaneously allow for a reduction in metal ion release. Silicon nitride based (SiNx) coatings deposited by high power impulse magnetron sputtering (HiPIMS) have shown potential for use in joint replacements, as a result of an improved chemical stability in combination with a good adhesion. This study investigated the effect of N, C, Cr, and Nb content on the tribocorrosive performance of 3.7 to 8.8 µm thick SiNx coatings deposited by HiPIMS onto CoCrMo discs. The coating composition was assessed from X-ray photoelectron spectroscopy and the surface roughness by vertical scanning interferometry. Hardness and Young’s modulus were measured by nanoindentation and coating adhesion was investigated by scratch tests. Multidirectional wear tests against ultrahigh molecular weight polyethylene pins were performed for 2 million cycles in bovine serum solution (25%) at 37 °C, at an estimated contact pressure of 2.1 MPa. Coatings with a relatively low hardness tended to fail earlier in the wear test, due to chemical reactions and eventually dissolution, accelerated by the tribological contact. In fact, while no definite correlation could be observed between coating composition (N: 42.6–55.5 at %, C: 0–25.7 at %, Cr: 0 or 12.8 at %, and Nb: 0–24.5 at %) and wear performance, it was apparent that high-purity and/or -density coatings (i.e., low oxygen content and high nitrogen content) were desirable to prevent coating and/or counter surface wear or failure. Coatings deposited with a higher energy fulfilled the target profile in terms of low surface roughness (Ra < 20 nm), adequate adhesion (Lc2 > 30 N), chemical stability over time in the tribocorrosive environment, as well as low polymer wear, presenting potential for a future application in joint bearings.

The Effect of Coating Density on Functional Properties of SiNx Coated Implants.

Ceramic coatings may be applied onto metallic components of joint replacements for improved wear and corrosion resistance as well as enhanced biocompatibility, especially for metal-sensitive patients. Silicon nitride (SiNx) coatings have recently been developed for this purpose. To achieve a high coating density, necessary to secure a long-term performance, is however challenging, especially for sputter deposited SiNx coatings, since these coatings are insulating. This study investigates the time-dependent performance of sputter-deposited SiNx based coatings for joint applications. SiNx coatings with a thickness in the range of 4.3–6.0 µm were deposited by reactive high power impulse magnetron sputtering onto flat discs as well as hip heads made of CoCrMo. SiNx compositional analysis by X-ray photoelectron spectroscopy showed N/Si ratios between 0.8 and 1.0. Immersion of the flat disks in fetal bovine serum solution over time as well as short-term wear tests against ultra-high molecular weight polyethylene (UHMWPE) discs showed that a high coating density is required to inhibit tribocorrosion. Coatings that performed best in terms of chemical stability were deposited using a higher target power and process heating.

Towards Functional Silicon Nitride Coatings for Joint Replacements

Silicon nitride (SiNx) coatings are currently under investigation as bearing surfaces for joint implants, due to their low wear rate and the good biocompatibility of both coatings and their potential wear debris. The aim of this study was to move further towards functional SiNx coatings by evaluating coatings deposited onto CoCrMo surfaces with a CrN interlayer, using different bias voltages and substrate rotations. Reactive direct current magnetron sputtering was used to coat CoCrMo discs with a CrN interlayer, followed by a SiNx top layer, which was deposited by reactive high-power impulse magnetron sputtering. The interlayer was deposited using negative bias voltages ranging between 100 and 900 V, and 1-fold or 3-fold substrate rotation. Scanning electron microscopy showed a dependence of coating morphology on substrate rotation. The N/Si ratio ranged from 1.10 to 1.25, as evaluated by X-ray photoelectron spectroscopy. Vertical scanning interferometry revealed that the coated, unpolished samples had a low average surface roughness between 16 and 33 nm. Rockwell indentations showed improved coating adhesion when a low bias voltage of 100 V was used to deposit the CrN interlayer. Wear tests performed in a reciprocating manner against Si3N4 balls showed specific wear rates lower than, or similar to that of CoCrMo. The study suggests that low negative bias voltages may contribute to a better performance of SiNx coatings in terms of adhesion. The low wear rates found in the current study support further development of silicon nitride-based coatings towards clinical application.

Mixed mode interfacial crack energy estimation of glass interposer and SiNx coatings by using fracture mechanics based computer methods and experimental validations

Glass-based interposer is a promising candidate for novel 3D-IC integrations because of its characteristics, such as low cost, low coefficient of thermal expansion, smooth surface quality, and large size fabrication. However, an inherent behavior of brittle material such as glass is its low fracture toughness, which easily induces both interfacial delamination and fracture failure modes, particularly for bonds with neighboring passivation coating of silicon nitride (SiNx). Accordingly, this research proposes a simulated methodology based on the index of interfacial strain energy released rate (G-value) to estimate the glass/SiNx interface using a J-integral approach and modified virtual crack closure technique. Adhesion measurement of glass/SiNx was also implemented by means of four-point bending architecture to validate the predicted accuracy. The results show that a 17.95 J/m2 of G-value for aforementioned interface is obtained. A higher modulus of SiNx coating as determined by different deposited conditions utilized at the concerned glass/SiNx interface also had an effect on the critical fracture energy of the crack after it begins to advance.

SiNx coatings deposited by reactive high power impulse magnetron sputtering: Process parameters influencing the residual coating stress

The residual coating stress and its control is of key importance for the performance and reliability of silicon nitride (SiNx) coatings for biomedical applications. This study explores the most important deposition process parameters to tailor the residual coating stress and hence improve the adhesion of SiNx coatings deposited by reactive high power impulse magnetron sputtering (rHiPIMS). Reactive sputter deposition and plasma characterization were conducted in an industrial deposition chamber equipped with pure Si targets in N2/Ar ambient. Reactive HiPIMS processes using N2-to-Ar flow ratios of 0 and 0.28–0.3 were studied with time averaged positive ion mass spectrometry. The coatings were deposited to thicknesses of 2 μm on Si(001) and to 5 μm on polished CoCrMo disks. The residual stress of the X-ray amorphous coatings was determined from the curvature of the Si substrates as obtained by X-ray diffraction. The coatings were further characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and nanoindentation in order to study their elemental composition, morphology, and hardness, respectively. The adhesion of the 5 μm thick coatings deposited on CoCrMo disks was assessed using the Rockwell C test. The deposition of SiNx coatings by rHiPIMS using N2-to-Ar flow ratios of 0.28 yield dense and hard SiNx coatings with Si/N ratios &amp;lt;1. The compressive residual stress of up to 2.1 GPa can be reduced to 0.2 GPa using a comparatively high deposition pressure of 600 mPa, substrate temperatures below 200 °C, low pulse energies of &amp;lt;2.5 Ws, and moderate negative bias voltages of up to 100 V. These process parameters resulted in excellent coating adhesion (ISO 0, HF1) and a low surface roughness of 14 nm for coatings deposited on CoCrMo.

Influence of Substrate Heating and Nitrogen Flow on the Composition, Morphological and Mechanical Properties of SiNx Coatings Aimed for Joint Replacements.

Silicon nitride (SiNx) coatings are promising for joint replacement applications due to their high wear resistance and biocompatibility. For such coatings, a higher nitrogen content, obtained through an increased nitrogen gas supply, has been found to be beneficial in terms of a decreased dissolution rate of the coatings. The substrate temperature has also been found to affect the composition as well as the microstructure of similar coatings. The aim of this study was to investigate the effect of the substrate temperature and nitrogen flow on the coating composition, microstructure and mechanical properties. SiNx coatings were deposited onto CoCrMo discs using reactive high power impulse magnetron sputtering. During deposition, the substrate temperatures were set to 200 °C, 350 °C or 430 °C, with nitrogen-to-argon flow ratios of 0.06, 0.17 or 0.30. Scanning and transmission electron spectroscopy revealed that the coatings were homogenous and amorphous. The coatings displayed a nitrogen content of 23–48 at.% (X-ray photoelectron spectroscopy). The surface roughness was similar to uncoated CoCrMo (p = 0.25) (vertical scanning interferometry). The hardness and Young’s modulus, as determined from nanoindentation, scaled with the nitrogen content of the coatings, with the hardness ranging from 12 ± 1 GPa to 26 ± 2 GPa and the Young’s moduli ranging from 173 ± 8 GPa to 293 ± 18 GPa, when the nitrogen content increased from 23% to 48%. The low surface roughness and high nano-hardness are promising for applications exposed to wear, such as joint implants.

SiNx Coatings Deposited by Reactive High Power Impulse Magnetron Sputtering: Process Parameters Influencing the Nitrogen Content.

Reactive high power impulse magnetron sputtering (rHiPIMS) was used to deposit silicon nitride (SiNx) coatings for biomedical applications. The SiNx growth and plasma characterization were conducted in an industrial coater, using Si targets and N2 as reactive gas. The effects of different N2-to-Ar flow ratios between 0 and 0.3, pulse frequencies, target power settings, and substrate temperatures on the discharge and the N content of SiNx coatings were investigated. Plasma ion mass spectrometry shows high amounts of ionized isotopes during the initial part of the pulse for discharges with low N2-to-Ar flow ratios of <0.16, while signals from ionized molecules rise with the N2-to-Ar flow ratio at the pulse end and during pulse-off times. Langmuir probe measurements show electron temperatures of 2-3 eV for nonreactive discharges and 5.0-6.6 eV for discharges in transition mode. The SiNx coatings were characterized with respect to their composition, chemical bond structure, density, and mechanical properties by X-ray photoelectron spectroscopy, X-ray reflectivity, X-ray diffraction, and nanoindentation, respectively. The SiNx deposition processes and coating properties are mainly influenced by the N2-to-Ar flow ratio and thus by the N content in the SiNx films and to a lower extent by the HiPIMS frequencies and power settings as well as substrate temperatures. Increasing N2-to-Ar flow ratios lead to decreasing growth rates, while the N content, coating densities, residual stresses, and the hardness increase. These experimental findings were corroborated by density functional theory calculations of precursor species present during rHiPIMS.

Morphology and Dissolution Rate of Wear Debris from Silicon Nitride Coatings.

Silicon nitride (SiNx) coatings have recently been introduced as a potential material for joint implant bearing surfaces, but there is no data on wear debris morphology nor their dissolution rate, something that could play a central role to implant longevity. In this study, wear debris was generated in a ball-on-disc setup in simulated body fluid. After serum digestion the debris was analyzed with scanning electron microscopy and energy-dispersive X-ray spectroscopy. The particle dissolution rate was evaluated using inductively coupled plasma techniques, on model SiNx particles. The wear debris from SiNx coatings was found to be round, in the nm range and formed agglomerates in the submicrometer to micrometer range. Model particles dissolved in simulated body fluid at a rate of: c(t) = 39.45[1 - exp(-1.11 × 10-6t)], where [c(t)] = mg/L and [t] = s. This study can be used as a preliminary prediction of size, shape, and dissolution rate of wear debris from SiNx coatings.

Dissolution behaviour of silicon nitride coatings for joint replacements

In this study, the dissolution rate of SiNx coatings was investigated as a function of coating composition, in comparison to a cobalt chromium molybdenum alloy (CoCrMo) reference. SiNx coatings with N/Si ratios of 0.3, 0.8 and 1.1 were investigated. Electrochemical measurements were complemented with solution (inductively coupled plasma techniques) and surface analysis (vertical scanning interferometry and x-ray photoelectron spectroscopy). The dissolution rate of the SiNx coatings was evaluated to 0.2–1.4nm/day, with a trend of lower dissolution rate with higher N/Si atomic ratio in the coating. The dissolution rates of the coatings were similar to or lower than that of CoCrMo (0.7–1.2nm/day). The highest nitrogen containing coating showed mainly Si–N bonds in the bulk as well as at the surface and in the dissolution area. The lower nitrogen containing coatings showed Si–N and/or Si–Si bonds in the bulk and an increased formation of Si–O bonds at the surface as well as in the dissolution area. The SiNx coatings reduced the metal ion release from the substrate. The possibility to tune the dissolution rate and the ability to prevent release of metal ions encourage further studies on SiNx coatings for joint replacements.

Optical and Magneto-Optical Properties of Gd22Fe78 Thin Films in the Photon Energy Range From 1.5 to 5.5 eV.

Optical and magneto-optical properties of amorphous Gd22Fe78 (GdFe) thin films prepared by direct current (DC) sputtering on thermally oxidized substrates were characterized by the combination of spectroscopic ellipsometry and magneto-optical spectroscopy in the photon energy range from 1.5 to 5.5 eV. Thin SiNx and Ru coatings were used to prevent the GdFe surface oxidation and contamination. Using advanced theoretical models spectral dependence of the complete permittivity tensor and spectral dependence of the absorption coefficient were deduced from experimental data. No significant changes in the optical properties upon different coatings were observed, indicating reliability of used analysis.

Structure and composition of silicon nitride and silicon carbon nitride coatings for joint replacements

SiNx and SiCxNy coatings were fabricated with high power impulse magnetron sputtering (HiPIMS). The coatings microstructure, growth pattern, surface morphology, composition, and bonding structure were investigated by AFM, SEM, GIXRD, TEM, EDS as well as XPS, and related to the deposition parameters target powers and substrate temperature. Cross-sections of SiCxNy coatings showed either dense and laminar, or columnar structures. These coatings varied in roughness (Ra between 0.2 and 3.8nm) and contained up to 35at.% C. All coatings were substoichiometric (with an N/Si ratio from 0.27 to 0.65) and contained incorporated particles (so called droplets). The SiNx coatings, in particular those deposited at the lower power on the silicon target, demonstrated a dense microstructure and low surface roughness (Ra between 0.2 and 0.3nm). They were dominated by an (X-ray) amorphous structure and consisted mainly of Si–N bonds. The usefulness of these coatings is discussed for bearing surfaces for hip joint arthroplasty in order to prolong their life-time. The long-term aim is to obtain a coating that reduces wear and metal ion release, that is biocompatible, and with wear debris that can dissolve in vivo.

Microstructure and Corrosion Properties of Multilayered CrAlN / SiNx Coatings

The multilayers were deposited by radio-frequency reactive magnetron sputtering. In multilayers, the layer thickness varied from 0.3 to 1 nm, and the layer thickness ratios of CrAlN to were set to be 4:0.3, 13:1, and 4:1. The effects of the layer thickness on the crystalline behavior and microstructure of the multilayers were discussed by X-ray diffraction patterns, scanning electron microscopy, and high resolution transmission electron microscopy. In addition to transforming the structure from crystalline to amorphous with thickness increase from 0.3 to 1 nm, the films were changed from a columnar microstructure to a dense one. The corrosion resistance of the coatings in 3.5 wt % NaCl solution was investigated by Tafel measurement and electrochemical impedance spectroscopy. The multilayers refined the coarse columnar structure in single-layered CrAlN, leading to a denser microstructure, and revealed lower corrosion current density and higher corrosion impedance. Additionally, the multilayer with a thickness ratio of to was identified with a similar composition yet a denser microstructure compared to the one with an to thickness ratio of 4:0.3. The multilayer with the thickness ratio of to showed better corrosion resistance, suggesting that anticorrosion properties were dominated by microstructure rather than composition. Furthermore, the multilayer with the thickness ratio of to exhibited the densest microstructure and revealed the best corrosion resistance because the amorphous layers interrupted the columnar growth and then provided no direct diffusion paths.

Infrared study of the concentration of H introduced into Si by the postdeposition annealing of a SiNx coating

The postdeposition annealing of a SiNx antireflection coating is commonly used to introduce hydrogen into a multicrystalline Si solar cell to passivate defects in the Si bulk. A quantitative comparison has been made of the concentrations of H that are introduced into a Si model system from SiNx coatings with high and low density that have been characterized by infrared spectroscopy. Experiments have also been performed in which the processing of the SiNx/Si interface was modified to compare how the preparation of the interface and properties of the SiNx film itself affect the concentration of H that is introduced into the Si bulk.

Multi‐crystalline Si solar cells with very fast deposited (180 nm/min) passivating hot‐wire CVD silicon nitride as antireflection coating

AbstractHot‐wire chemical vapor deposition (HWCVD) is a promising technique for very fast deposition of high quality thin films. We developed processing conditions for device‐ quality silicon nitride (a‐SiNx:H) anti‐reflection coating (ARC) at high deposition rates of 3 nm/s. The HWCVD SiNx layers were deposited on multicrystalline silicon (mc‐Si) solar cells provided by IMEC and ECN Solar Energy. Reference cells were provided with optimized parallel plate PECVD SiNx and microwave PECVD SiNx respectively. The application of HWCVD SiNx on IMEC mc‐Si solar cells led to effective passivation, evidenced by a Voc of 606 mV and consistent IQE curves. For further optimization, series were made with HW SiNx (with different x) on mc‐Si solar cells from ECN Solar Energy. The best cell efficiencies were obtained for samples with a N/Si ratio of 1·2 and a high mass density of &gt;2·9 g/cm3. The best solar cells reached an efficiency of 15·7%, which is similar to the best reference cell, made from neighboring wafers, with microwave PECVD SiNx. The IQE measurements and high Voc values for these cells with HW SiNx demonstrate good bulk passivation. PC1D simulations confirm the excellent bulk‐ and surface‐passivation for HW SiNx coatings. Interesting is the significantly higher blue response for the cells with HWCVD SiNx when compared to the PECVD SiNx reference cells. This difference in blue response is caused by lower light absorption of the HWCVD layers (compared to microwave CVD; ECN) and better surface passivation (compared to parallel plate PECVD; IMEC). The application of HW SiNx as a passivating antireflection layer on mc‐Si solar cells leads to efficiencies comparable to those with optimized PECVD SiNx coatings, although HWCVD is performed at a much higher deposition rate. Copyright © 2007 John Wiley &amp; Sons, Ltd.

Electro-Fragmentation Analysis of Dielectric Thin Films on Flexible Polymer Substrates

AbstractA novel electro-fragmentation method was developed as a fast alternative to the time consuming fragmentation test carried out in situ in a microscope, to investigate the failure of dielectric coatings on polymer substrates using an ultrathin conductive layer. Focus was put on SiNx coatings on polyimide substrates. A careful selection of the conductive layer was carried out to avoid artifacts resulting for instance from a change of the residual stress state of the investigated coating. Au layers were found to be too ductile and Al-Ti layers altered the stress state of the nitride, which invalidated their use to probe the failure of the nitride coatings. In contrast, a 20 nm thick graphite layer was found to accurately reproduce the failure of the nitride, which was analyzed in terms of residual strain and cohesive properties of the graphite layer. An electro-fatigue device was built and preliminary results suggest that damage already develops in ultrathin coatings at relatively low strain levels under long-term fatigue loading.

TiSiN nanocomposite coatings by chemical vapor deposition in a fluidized bed reactor at atmospheric pressure (AP/FBR-CVD)

TiSiN nanocomposite coatings were deposited on stainless steel by chemical vapor deposition in a fluidized bed reactor at atmospheric pressure (AP/FBR-CVD) by reaction of TiCl4 and SiCl4 with NH3 at 850 °C. Coatings were characterized by means of GD-OES, XPS and XRD. TiSiN coatings with a Si content of 9 at.% showed a hardness of 28 GPa (the hardness of TiN and SiNx coatings was around 21 GPa) and a lower oxidation rate under dry air at 600 °C. Our results show for the first time that AP/FBR-CVD can be tuned for the deposition of nanocomposite ceramic coatings.