Nitrogen pulsing to modify the properties of titanium nitride thin films sputter deposited

TiN _x thin films were grown on (100) Si and glass substrates by dc reactive magnetron sputtering. A titanium target was sputtered in Ar + N₂ atmosphere using a pulsing flow rate of the nitrogen gas. A constant pulsing period was used for every deposition whereas the nitrogen injection time was changed. The systematic variation of the nitrogen injection time led to a gradual decrease of the deposition rate and to a controlled modulation of the chemical composition of the TiN _x films (x between 0 and 1.05). Analysis of the crystallographic structure by X-ray diffraction showed that both Ti and TiN phases coexisted and a change of the preferential orientation from (200) to (111) occurred. The electrical conductivity and colour measurements in the CIE-L*a*b* system of colourimetry were also performed and correlated with the evolution of the N/Ti ratio.     

X-ray photoelectron spectroscopy analyses of titanium oxynitride films prepared by magnetron sputtering using air/Ar mixtures

X-ray photoelectron spectroscopy (XPS) has been employed to investigate titanium oxynitride (TiN_xO_y) films prepared by d.c. magnetron sputtering using air/Ar mixtures, which allows one to perform the deposition at a high base pressure (1.3 × 10^− 2 Pa) and can reduce substantially the processing time. XPS analyses revealed that all the prepared TiN_xO_y films comprised Ti-N, Ti-N-O, and Ti-O chemical states. When the air/Ar ratio was below 0.3, nitrogen-rich TiN_xO_y films were obtained. As the air/Ar ratio was above 0.4, oxygen-rich TiN_xO_y films were formed. XPS depth profile analyses were also performed in selected specimens. It has been found that at relatively low air/Ar ratios, such as 0.5, the oxygen content of the films increased toward the film/substrate interface and when the air/Ar ratio was higher, TiN_xO_y films with large oxygen content with uniform concentrations were then formed.     

Photoelectrochemical and optical properties of N-doped TiO2 thin films prepared by oxidation of sputtered TiNx films

Nitrogen-doped titanium dioxide thin films with visible light photoresponse were prepared by oxidation of sputtered TiN_x films, whose nitrogen contents can be easily changed by controlling the volume ratio of N₂/(Ar + N₂) during reactive direct current (DC) magnetron sputtering process. The reference TiO₂ sample was also deposited by the same method under Ar/O₂ gas mixture. The as-prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoemission spectroscopy, UV-vis spectrophotometry and photoelecrochemical measurements. The formation of anatase type TiO₂ is confirmed by XRD. SEM measurement indicates a rough surface morphology with sharp, protruding modules after annealing treatment. Optical properties reveal an extended tailing of the absorption edge toward the visible region due to nitrogen presence. The band gap of the N-doped sample is reduced from 3.36 eV to 3.12 eV compared with the undoped one. All the N-doped samples show red shift in photoresponse towards visible region and improved photocurrent density under visible irradiance is observed for the N-doped samples.     

TiNx coatings prepared by d.c. reactive magnetron sputtering

In this paper we describe an investigation of the correlation between the microstructure, morphology and microhardness of non-stoichiometric TiN_x films prepared by reactive d.c. magnetron sputtering in a narrow interval of partial pressure p_N2 of nitrogen. It was found that TiN_x films sputtered at p_N2 < p_N2crit have a quasi-amorphous microstructure and are extremely hard. The results of a detailed experimental study of the films' microstructure, morphology, microhardness and deposition rate are given. It is shown that reactive d.c. magnetron sputtering makes possible the production of TiN_x films with the high deposition rate of 0.5microm min⁻¹.     

Microstructure and tribological performance of CNx–TiNx composite films prepared by pulsed laser deposition

CN_x–TiN_x composite films were prepared on high-speed steel (HSS) substrate by pulsed KrF excimer laser co-deposition process with graphite/Ti combined targets and a substrate temperature of 200 °C. The composition, morphology and microstructure of the films were characterized by energy dispersive X-ray spectrum (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). The adhesion and tribological performance of the films were investigated using a conventional scratch tester and a ball-on-disk tribometer, respectively. In the graphite/Ti range of 0.5–2.0 of the target, TiN_x, a-CN_x and metallic Ti phase were found in the composite films. The TiN_x disappeared in the films at a high graphite/Ti ratio of the target. With increasing the graphite/Ti ratio of the target, the adhesion to substrate of the composite films deteriorated from 46 N to 26 N, and the friction coefficient decreased from 0.23 to 0.17. The composite film deposited at the graphite/Ti ratio of 1.0 showed a low friction coefficient, good adhesion and wear rate of 3.2 × 10⁻⁷ mm³/Nm in humid air.     

The effect of different methods to add nitrogen to titanium alloys on the properties of titanium nitride clad layers

In this investigation, titanium nitride (TiN) reinforcements are synthesized in situ on the surface of Ti–6Al–4V substrates with gas tungsten arc welding (GTAW) process by different methods to add nitrogen, nitrogen gas or TiN powder, to titanium alloys. The results showed that if nitrogen gas was added to titanium alloys, the TiN phase would be formed. But if TiN powder was added to titanium alloys, TiN + TiN_x dual phases would be presented. The results of the dry sliding wear test revealed that the wear performance of the Ti–6Al–4V alloy specimen coated with TiN or TiN + TiN_x clad layers were much better than that of the pure Ti–6Al–4V alloy specimen. Furthermore, the evolution of the microstructure during cooling was elucidated and the relationship among the wear behavior of the clad layer, microstructures, and microhardness was determined.     

Ti2Al(O,N) formation by solid-state reaction between substoichiometric TiN thin films and Al2O3 (0001) substrates

Titanium nitride TiN_x (0.1 ≤ x ≤ 1) thin films were deposited onto Al₂O₃(0001) substrates using reactive magnetron sputtering at substrate temperatures (T_s) ranging from 800 to 1000 °C and N₂ partial pressures (pN₂) between 13.3 and 133 mPa. It is found that Al and O from the substrates diffuse into the substoichiometric TiN_x films during deposition. Solid-state reactions between the film and substrate result in the formation of Ti₂O and Ti₃Al domains at low N₂ partial pressures, while for increasing pN₂, the Ti₂AlN MAX phase nucleates and grows together with TiN_x. Depositions at increasingly stoichiometric conditions result in a decreasing incorporation of substrate species into the growing film. Eventually, a stoichiometric deposition gives a stable TiN(111) || Al₂O₃(0001) structure without the incorporation of substrate species. Growth at T_s 1000 °C yields Ti₂AlN(0001), leading to a reduced incorporation of substrate species compared to films grown at 900 °C, which contain also Ti₂AlN(101?3) grains. Finally, the Ti₂AlN domains incorporate O, likely on the N site, such that a MAX phase oxynitride Ti₂Al(O,N) is formed. The results were obtained by a combination of structural methods, including X-ray diffraction and (scanning) transmission electron microscopy, together with spectroscopy methods, which comprise elastic recoil detection analysis, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy.     

Reactively sputtered N-doped titanium oxide films as visible-light photocatalyst

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared by reactive magnetron sputtering of a titanium metal target in gas mixtures of argon, oxygen and nitrogen. Two types of nitrogen species are formed in the films following the fraction of N₂ (F_N2) in the reactive atmosphere. One is substitutional nitrogen in anatase titania phase and the other is nitrogen in TiN phase. In a large range of F_N2 from 0 to 0.57, TiO_xN_y films in anatase structure with about 1.0–1.4 at.% substitutional nitrogen are produced and the films exhibit red shifts to ∼ 500 nm from the absorption edge of ∼ 380 nm of undoped TiO₂. The nitrogen is readily doped in the films by energetic nitrogen ions in the plasma and the films exhibited photocatalytic properties under visible light. When excess nitrogen is supplied as the F_N2 above 0.75, the resulting film contains 20.8 at.% of nitrogen with formation of TiN that makes the film opaque and destroys the photocatalytic activity largely.     

Low temperature preparation of transparent, antireflective TiO2 films deposited at different O2/Ar ratios by microwave electron cyclotron resonance magnetron sputtering

A serial of crystalline titanium oxide ceramic films were deposited at low temperature using microwave electron cyclotron resonance (MW-ECR) magnetron sputtering with different O₂/Ar ratios. The influences of O₂/Ar ratio on the deposition rate, morphology, crystalline nature, optical adsorption property of the obtained titanium oxide thin films were investigated by means of X-ray diffraction (XRD), atomic force microscopy (AFM) and UV-Vis spectra. Therefore, the optimum O₂/Ar ratio for deposition of anatase TiO₂ thin films on unheated glass substrate was realized in a MW-ECR magnetron sputtering process. The as-deposited anatase TiO₂ films were transparent and were antireflective in the visible region.     

Effect of the oxygen fraction on the structure and optical properties of HfOxNy thin films

The main purpose of this work was to prepare hafnium oxynitride (HfO_xN_y) thin films. HfO_xN_y thin films were deposited by radio frequency reactive magnetron sputtering from a pure Hf target onto Quartz and ZnS substrates at room temperature. The depositions were carried out under an oxygen-nitrogen-argon atmosphere by varying the flow rate of the reactive gases (oxygen/nitrogen ratio). The variation of the flow rate of the reactive gases changed the structure and properties of the films. Glancing incidence X-ray diffraction (GIXRD) was used to study the structural changes of as-deposited films; a new crystalline hafnium oxynitride phase was formed in a region of oxygen/nitrogen ratio. Cross-section of the films observed by SEM revealed that the films grew with a columnar-type structure, and surface observation with AFM showed values of surface roughness changed with the flow rate of the reactive gases, higher oxygen fraction had lower surface roughness than lower oxygen fraction. Visible spectra, infrared spectra, refractive index, absorption coefficient also changed with the variation of the oxygen fraction.     

Absorbing TiOx thin film enabling laser welding of polyurethane membranes and polyamide fibers

We report on the optical properties of thin titanium suboxide (TiO_x) films for applications in laser transmission welding of polymers. Non-absorbing fibers were coated with TiO_x coatings by reactive magnetron sputtering. Plasma process parameters influencing the chemical composition and morphology of the deposited thin films were investigated in order to optimize their absorption properties. Optical absorption spectroscopy showed that the oxygen content of the TiO_x coatings is the main parameter influencing the optical absorbance. Overtreatment (high power plasma input) of the fiber surface leads to high surface roughness and loss of mechanical stability of the fiber. The study shows that thin substoichiometric TiO_x films enable the welding of very thin polyurethane membranes and polyamide fibers with improved adhesion properties.     

Characterisation of SiOxCyHz thin films deposited by low-temperature PECVD

SiO_xC_yH_z thin films were deposited from hexamethyldisiloxane (HMDSO)/O₂ mixtures in a parallel plate, capacitively coupled, RF plasma reactor. Polyethylene terephthalate (PET), Si(1 0 0) wafers and KBr tablets were chosen as substrates. Effect of HMDSO/O₂ ratio, total treatment pressure and power input on the properties of the deposited films were investigated. The structure and bondings were studied by means of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Wettability characteristics of the deposited thin films were investigated by means of water droplet contact angle measurements. Surface morphology was investigated with atomic force microscopy. Barrier properties of the SiO_xC_yH_z thin films were investigated by measuring the water vapour transmission rate of the coated PET substrates. Correlations between the characteristics of the deposited film and their barrier properties were discussed.     

Magnetron sputtering of TiOxNy films

This article reports on the characterization and preparation of N-doped titanium dioxide (TiO₂) films by reactive magnetron sputtering from Ti(99.5) targets in a mixture of Ar/O₂/N₂ atmosphere on unheated glass substrates. A dual magnetron system supplied by a dc bipolar pulsed power source was used to sputter the TiO_xN_y films. The amount of N in the TiO_xN_y film ranges from 5 to 40 at%. Its structure was measured using X-ray diffraction (XRD), the optical band gap was calculated from Tauc plots and the decrease of the water contact angle α_ir after the film activation by UV irradiation was investigated as a function of at% of N in the TiO_xN_y film. The yellow-coloured TiO_xN_y films with high (≈8 at%) amount of N exhibited a strong decrease of the band gap E_g down to 2.7 eV. A significant decrease of the water contact angle α_ir after UV irradiation has been observed for 2 μm thick transparent nanocrystalline (anatase+rutile) N-doped TiO₂ films containing less than 6 at% of N.     

Properties of ZrNx films with x > 1 deposited by reactive radiofrequency magnetron sputtering

Thin ZrN_x films have been prepared by reactive radiofrequency magnetron sputtering varying the nitrogen partial pressure in the range 0-3.26 Pa. The films have been analyzed by X-ray photoelectron spectroscopy (XPS) and by optical characterization in the UV-Vis-IR range. The cross-section and surface morphology of the samples were examined by means of field emission gun-scanning electron microscopy. The effects of the nitrogen partial pressure on the ZrN_x films stoichiometry have been studied correlating the N 1s photoelectron peaks with different bounding states for the zirconium nitride. The XPS depth profile analysis has revealed the presence of metastable phases (ZrN₂, Zr₃N₄) that vanishes when lowering the nitrogen partial pressure. The optical analysis has permitted to distinguish two different behaviours of the deposited samples in the visible range: semi-transparent and absorbent. Drude-Lorentz model fitted the behaviour of absorbent films, while the O'Leary model was applied to the semi-transparent ones. The semi-transparent films had a band gap varying between 2.36 and 2.42 eV, typical values of N-rich zirconium nitride films. Morphological analysis showed a compact and dense columnar structure for all the samples. A simple growth model explains the presence of the different nitride phases considering implantation and re-sputtering effects.     

Perovskite oxynitride LaTiOxNy thin films: Dielectric characterization in low and high frequencies

Lanthanum titanium oxynitride (LaTiO_xN_y) thin films are studied with respect to their dielectric properties in low and high frequencies. Thin films are deposited by radio frequency magnetron sputtering on different substrates. Effects of nitrogen content and crystalline quality on dielectric properties are investigated. In low-frequency range, textured LaTiO_xN_y thin films deposited on conductive single crystal Nb-STO show a dielectric constant ε′ ≈ 140 with low losses tanδ = 0.012 at 100 kHz. For the LaTiO_xN_y polycrystalline films deposited on conductive silicon substrates with platinum (Pt/Ti/SiO₂/Si), the tunability reached up to 57% for a weak electric field of 50 kV/cm. In high-frequency range, epitaxial LaTiO_xN_y films deposited on MgO substrate present a high dielectric constant with low losses (ε′ ≈ 170, tanδ = 0.011, 12 GHz).     

Tribological and mechanical behaviors of TiN/CNx multilayer films deposited by magnetron sputtering

TiN/CN_x multilayer films with bilayer periods of 4.5-40.3 nm were deposited by direct-current magnetron sputtering. Layer morphology and structure of the multilayered films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The TiN/CN_x multilayers exhibited coherent epitaxial growth due to the mutual growth-promoting effect at small bilayer period and some crystalline regions going through the interface of TiN/CN_x. Nanoindentation tests showed that the hardness of the multilayers varied from 12.5 to 31 GPa, with the highest hardness being obtained with a bilayer period of 4.5 nm. The tribological properties of the films were investigated using a ball-on-disk tribometer in humid air, and the TiN/CN_x multilayer with a bilayer period of 4.5 nm also exhibited the lowest friction coefficient and the highest wear resistance.     

Properties of TiNxfilms reactively sputtered in an argon-nitrogen atmosphere

The dependence of the resistivity and temperature coefficient of resistivity (TCR) of TiN_x films on nitrogen pressure is described. The partial nitrogen pressure was varied from 10^?5 Torr to 2×10^?4 Torr. The maximum value of the resistivity (216 μΩ cm) and the lowest negative value of TCR (?33ppmK^?1) were obtained in the nitrogen pressure range (2?4)×10^?5 Torr. The minimum value of the resistivity (44 μΩ cm) and the highest positive value of the TCR (1160 ppm K^-1 were obtained in the nitrogen pressure range (4?10)×10^?5 Torr. The influence of aging temperature up to 573 K on the resistance changes are shown. X-ray diffraction analysis indicated the presence of oriented or non-oriented TiN in these films.     

Features of CoSi<Subscript>2</Subscript> phase formation by two-stage rapid thermal annealing of Ti/Co/Ti/Si(100) structures

A method of cobalt disilicide (CoSi₂) layer formation proceeding from a Ti(8 nm)/Co(10 nm)/Ti(5 nm)/Si(100) (substrate) structure prepared by magnetron sputtering is described. The initial structure was subjected to two-stage rapid thermal annealing (RTA) in nitrogen, and the samples after each stage were studied by the time-of-flight secondary-ion mass spectrometry, Auger electron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The RTA-1 stage (550°C, 45 s) resulted in the formation of a sacrificial surface layer of TiN _x O _y , which gettered residual impurities (O, C, N) from inner interfaces of the initial structure. After the chemical removal of this TiN _x O _y layer, the enrichment with cobalt at the RTA-2 stage (830°C, 25 s) led to the formation of a low-resistance CoSi₂ phase.     

Effects of TeOx films on temperature coefficients of delay of Love-type wave devices based on TeOx/36°YX-LiTaO3 structures

Tellurium oxide (TeO_x) thin films are prepared on 36°YX-LiTaO₃ substrates by RF magnetron sputtering technique under different deposition conditions. The structures and compositions of the TeO_x films are analyzed by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, which show that the TeO_x films are amorphous and with different ratios of Te to O prepared in different conditions. Then the Love-type wave devices based on TeO_x/36°YX-LiTaO₃ structures are fabricated, and the temperature coefficient of delay (TCD) of the Love-type wave devices are investigated. The results show that, when TeO_x films deposited at suitable deposition conditions, the TCD of the Love-type wave devices are less than that of the shear-horizontal (SH) wave devices fabricated on the bare 36°YX-LiTaO₃ substrates, which demonstrates that the TCD of the TeO_x films is negative. Moreover, the TCD of the devices are strongly dependent upon the preparation conditions and the thicknesses of the TeO_x films. Therefore, the TCD of the Love-type wave devices can be optimized by suitably selecting the preparation conditions and the thickness of TeO_x films.     

The influence of ambient conditions on properties of MgxZn1−xO films by sputtering

The Mg_xZn_1−xO films were prepared in different Ar-O₂ mixture ambience by magnetron sputtering. According to the X-ray diffraction (XRD) patterns and the energy dispersive X-ray spectroscopy (EDS) results, it was found that the Mg contents in the films varied with the different ratios of O₂/O₂+Ar, and the crystal quality of the films improved with the increasing of Mg contents. Meanwhile, the ultraviolet and visible (UV-vis) absorption spectroscopy indicated that the band gap of the films also increased. Moreover, it could be seen that the photoluminescence (PL) spectrum was different from that of undoped Zinc oxide (ZnO) films or the results in other reports on the Mg_xZn_1−xO films: there was no blueshift effect happening for the near-band-edge (NBE) emission in Mg_xZn_1−xO films with different Mg contents.