Titanium oxynitride thin films sputter deposited by the reactive gas pulsing process

International audienc

Tribological characterisation of magnetron sputtered Ti(C, O, N) thin films

Ti(C, O, N) thin films were prepared by magnetron sputtering and analysed in terms of their tribological properties. Surface and tribological parameters were analysed and discussed as a function of the films composition and structural features, as well as their thickness. The evolution of friction coefficient values was in concordance with the wear behaviour of the films. According to the atomic composition of the films, an increasing of the carbon percentage and a compound chemical formula closed to the stoichiometric TiC lead to a very good wear behaviour. This aspect is also directly correlated with the friction behaviour.Fundação para a Ciência e Tecnologia (FCT) SFRH/BPD/27114/2006 e PTDC/CTM/69362/200

Tribocorrosion behavior of Ti–C–O–N nanostructured thin films (black) for decorative applications

In the past few years, tribocorrosion has become a focus of research because of its relevance in terms of the future in-service degradation mechanisms of materials. In the particular case of decorative coatings, tribocorrosion is certainly one of the most important issues, and sweat corrosion and human contact wear are two other factors that may act as material selection tools. Thus, the current study aimed to investigate the tribocorrosion behavior of a new class of thin films, the Ti–C–O–N system, which is being developed to be used as a surface decorative material due to its relatively dark appearance. The films were prepared by reactive magnetron sputtering. The influence of the structural features on the tribocorrosion behavior is discussed.This research is supported by FEDER funds through COMPETE-Programa Operacional Factores de Competitividade and by national funds through the Fundacao para a Ciencia e a Tecnologia, project PTDC/CTM/69362/2006 and contract SFRH/BD/27569/2006

Development of dark Ti(C,O,N) coatings prepared by reactive sputtering

Accepted manuscriptDirect current reactive magnetron sputtering was implemented to successfully deposit dark Ti(C,O,N) thin films on silicon substrates. A titanium target was sputtered while a mixture of oxygen and nitrogen was injected into the deposition chamber, independently from an acetylene source. The deposition parameters were chosen as a function of pre-existing knowledge about sputtered Ti–O–N and Ti–C–O films. Tuning the oxygen/(nitrogen+carbon) ratio allowed obtaining a large spectrum of properties. In particular, the colour of the films was characterized by spectral reflectance spectroscopy, and expressed in the CIE 1976 L*a*b* colour space. An accurate control of the reactive gas mixture flow rate allowed obtaining intrinsic, stable and attractive dark colour for decorative applications. Surprisingly, the coatings with the lowest content of carbon and the highest content of oxygen presented the darkest tones. Composition analysis by electron probe microanalysis was done to quantify the titanium and metalloid concentrations in the films. X-ray diffraction experiments revealed the evolution of the film structure from a fcc structure for the lowest (O2+N2) flow rates to an amorphous one for the highest flow rates.Fundação para a Ciência e Tecnologia (FCT) - SFRH/BPD/27114/2006 and PTDC/CTM/69362/2006. CRUP (Acção Integrada Luso-francesa No. F-2307). GRICES/CNRS collaboration (Proc. 4.1.1 França

Properties changes of Ti(C, O, N) films prepared by PVD : the effect of reactive gases partial pressure

Dark Ti-C-O-N thin films were deposited by dc reactive magnetron sputtering. A titanium target was sputtered while three different gas flows were injected into the deposition chamber: argon (working gas), acetylene and a mixture of oxygen and nitrogen (reactive gases). The films were produced with variation of the gases flow rates, maintaining the remaining parameters constant. Varying the ratio between the reactive gases flow (gas mixture/acetylene) allowed obtaining films with different characteristics. The colour of the films was characterized by spectral reflectance spectroscopy, and expressed in the CIE 1976 L*a*b* colour space. An accurate control of the deposition conditions allowed obtaining intrinsic and stable dark colours for decorative applications. Composition analysis by electron probe microanalysis was done to quantify the elemental concentrations in the films. X-ray diffraction experiments revealed the evolution of the film structure which showed to be essentially amorphous, but with evidences of fcc structure.Fundação para a Ciência e Tecnologia (FCT) - SFRH/BPD/27114/2006 and PTDC/CTM/69362/2006

TiN-based decorative coatings : colour change by addition of C and O

As a result of technological progress in recent years, a new challenge was passed onto decorative hard coatings. While enhancing the appearance and lending attractive coloration to surfaces, the films are supposed to provide scratch resistance, protection against corrosion and durability. For this work, TiN(O) and TiN(C,O) thin films were prepared. Within the TiN(O) system, film colours varied from the glossy golden type for low oxygen contents to dark blue for higher oxygen contents. In order to reach darker colours (black), TiN(C,O) thin films were deposited, and results revealed the possibility to deposit very dark black films. All these results have been analysed and are presented as a function of both the deposition parameters and the particular composition and crystalline phases present in the films.(undefined

Structure and chemical bonds in reactively sputtered black Ti–C–N–O thin films

The evolution of the nanoscale structure and the chemical bonds formed in Ti–C–N–O films grown by reactive sputtering were studied as a function of the composition of the reactive atmosphere by increasing the partial pressure of an O2+N2 gas mixture from 0 up to 0.4 Pa, while that of acetylene (carbon source) was constant. The amorphisation of the films observed by transmission electron microscopy was confirmed by micro- Raman spectroscopy, but it was not the only effect associated to the increase of the O2+N2 partial pressure. The chemical environment of titanium and carbon, analysed by X-ray photoemission spectroscopy, also changes due to the higher affinity of Ti towards oxygen and nitrogen than to carbon. This gives rise to the appearance of amorphous carbon coexisting with poorly crystallized titanium oxynitride. The evolution of the films colour is explained on the basis of these structural changes.Fundação para a Ciência e a Tecnologia (FCT) - PTDC/CTM/69362/2006, SFRH/BPD/27114/2006CRUP (Acção Integrada Luso-francesa N° F-2307) and the GRICES/CNRS collaboration (Proc. 4.1.1 França

Influence of the chemical and electronic structure on the electrical behavior of zirconium oxynitride films

This work is devoted to the investigation of decorative zirconium oxynitride, ZrOxNy, films prepared by dc reactive magnetron sputtering, using a 17:3 nitrogen-to-oxygen-ratio gas mixture. The color of the films changed from metallic-like, very bright yellow pale, and golden yellow, for low gas mixture flows [from 0 to about 9 SCCM (SCCM denotes cubic centimeter per minute at STP)] to red brownish for intermediate gas flows (values up to 12 SCCM). Associated to this color change there is a significant decrease of brightness. With further increase of the reactive gas flow, the color of the samples changed from red brownish to dark blue (samples prepared with 13 and 14 SCCM). The films deposited with gas flows above 14 SCCM showed only apparent colorations due to interference effects. This change in optical behavior from opaque to transparent (characteristic of a transition from metallic to insulating-type materials), promoted by the change in gas flow values, revealed that significant changes were occurring in the film structure and electronic properties, thus opening new potential applications for the films, beyond those of purely decorative ones. Taking this into account, the electrical behavior of the films was investigated as a function of the reactive gas flow and correlated with the observed chemical, electronic, and structural features. The variations in composition disclosed the existence of four different zones, which were correlated to different crystalline structures. For the so-called zone I, x-ray diffraction revealed the development of films with a B1 NaCl face-centered cubic zirconium nitride-type phase, with some texture changes. Increasing the reactive gas flow, the structure of the films is that of a poorly crystallized over-stoichiometric nitride phase, which may be similar to that of Zr3N4, but with some probable oxygen inclusions within nitrogen positions. This region was characterized as zone II. Zone III was indexed as an oxynitride-type phase, similar to that of gamma-Zr2ON2 with some oxygen atoms occupying some of the nitrogen positions. Finally, occurring at the highest flow rates, zone IV was assigned to a ZrO2 monoclinic-type structure. The composition/structure variations were consistent with the chemical bonding analysis carried out by x-ray photoelectron spectroscopy, which showed oxygen doping in both Zr3N4- and ZrN-type grown films. The electronic properties of the films exhibited significant changes from zone to zone. Resistivity measurements revealed a very wide range of values, varying from relatively highly conductive materials (for zone I) with resistivity values around few hundreds of micro-ohm cm to highly insulating films within zones III and IV, which presented resistivity values in the order of 1015 micro-ohm cm. Regarding zone II, corresponding to oxygen doped Zr3N4-type compounds, the observed behavior revealed resistivity values increasing steeply from about 103 up to 1015 micro-ohm cm, indicating a systematic transition from metallic to insulating regimes.Fundação para a Ciência e Tecnologia (FCT) -PTDC/CTM/69362/2006, SFRH/BD/31907/2006 and SFRH/BBD/27114/2006