Microstructure and residual stress of TiN films deposited at low temperature by arc ion plating

The TiN films were deposited on 316 L stainless steel substrates at low temperature by arc ion plating. The influences of substrate bias voltage and temperature on microstructure, residual stress and mechanical properties of the films were investigated by EDS, SEM, XRD and nanoindenter tester, respectively. The results showed that the TiN films were highly oriented in（111） orientation with a face-centered cubic structure. With the increase of substrate bias voltage and temperature, the diffraction peak intensity increased sharply with simultaneous peak narrowing, and the small grain sizes increased from 6.2 to 13.8 nm. As the substrate temperature increased from 10 to 300℃, the residual compressive stress decreased sharply from 10.2 to 7.7 GPa, which caused the hardness to decrease from 33.1 to 30.6 GPa, while the adhesion strength increased sharply from 9.6 to 21 N.

Uniformity of TiN Films Fabricated by Hollow Cathode Discharge

Titanium nitride （TIN） films were deposited on AISI 304 stainless steel substrates using hollow cathode plasma physical vapor deposition （HC-PVD）. Titanium was introduced by eroding the Ti cathode nozzle and TiN was formed in the presence of a nitrogen plasma excited by radio frequency （RF）. The substrate bias voltage was varied from 0 to -300 V and the uniformity in film thickness, surface roughness, crystal size, microhardness and wear resistance for the film with a diameter of 20 mm was evaluated. Although the central zone of the plasma had the highest ion density, the film thickness did not vary appreciably across the sample. The results from atomic force microscopy （AFM） revealed a low surface roughness dominated by an island-like morphology with a similar crystal size on the entire surface. Higher microhardness was measured at the central zone of the sample. The sample treated at -200 V had excellent tribological properties and uniformity.

Effect of deposition parameters on mechanical properties of TiN films coated on 2A12 aluminum alloys by arc ion plating (AIP)

TiN films were deposited on 2A12 aluminum alloy by arc ion plating (AIP). The Vickers hardness of the films deposited at different bias voltages and different nitrogen gas pressures, and that of the substrate were measured. The surface roughness of the TiN films diposited at –30 V and –80 V respectively and at different nitrogen gas pressure was measured also. The mass loss of TiN films deposited at 0 V, –30 V and –80 V respectively were analyzed in dry sand rubber wheel abrasive wear tests and wet ones in comparison with uncoated Al alloy and austenitic stainless steel (AISI 316L). It is revealed that the highest hardness of the TiN film is obtained at a bias voltage of –30 V and a N2 gas pressure of 0.5 Pa. The surface roughness of the film is larger at –80 V than that at –30 V and reduces as the increase of the N2 gas pressure. The mass loss of TiN-film coated 2A12 aluminum alloy is remarkably less than that of uncoated Al alloy and also that of AISI 316L, which indicates that the abrasive wear rate is greatly reduced by the application of TiN coating. TiN coating deposited by arc ion plating (AIP) technique on aluminum alloy can be a potential coating for machine parts requiring preciseness and lightness.

Effect of Sample Configuration on Droplet-Particles of TiN Films Deposited by Pulse Biased Arc Ion Plating

Orthogonal experiments are used to design the pulsed bias related parameters, including bias magnitude, duty cycle and pulse frequency, during arc ion deposition of TiN films on stainless steel substrates in the case of samples placing normal to the plasma flux. The effect of these parameters on the amount and the size distribution of droplet-particles are investigated, and the results have provided sufficient evidence for the physical model, in which particles reduction is due to the case that the particles are negatively charged and repulsed from negative pulse electric field. The effect of sample configuration on amount and size distribution of the particles are analyzed. The results of the amount and size distribution of the particles are compared to those in the case of samples placing parallel to the plasma flux.

Cu Diffusion in Co/Cu/TiN Films for Cu Metallization

Some information on how to use in-situ determined diffusion coefficient of Cu to make barrier layer of Cu metallization in ultra large scale integrations （ULSIs） was provided. Diffusion coefficients of Cu in Co at low temperature were determined to analyze Cu migration to Co surface layer. The diffusion depths were analyzed using X-ray photoelectron spectroscopy （XPS） depth profile to investigate the diffusion effect of Cu in Co at different temperatures. The possible pretreatment temperature and time of barrier layer can be predicted according to the diffusion coefficients of Cu in Co.

Problems in the Determination of Internal Stresses in Plasma Assisted CVD TiN Films

The measurement of internal stresses in a PACVD TiN film proved experimentally to be difficult by a conventional X-ray diffraction technique.The linear relationship between 2θ and sin^2(?) could hardly be reached in some cases.Nevertheless.a good confirmation between the variation of FWHM-sin^2(?) and 20-sin^2(?) was revealed for every nonlinear forms.It followed that the effect of nondistributed micro-strains might exist in plasma assisted vapor deposited films,which usually have a strong crystal orientation,and the method of effectively separating macro-stress and micro-strain must be applied for the precise determination of internal stresses in PACVD films.

PREPARATION OF TiN FILMS BY N_2 ASSISTED Xe^+ ION BEAM ENHANCED DEPOSITION AND THEIR MECHANICAL PROPERTIES

A new method for preparation of hard TiN films has been developed by using electron beam evaporation-deposition of Ti and bombardment with 40 keV Xe^+ ion beam in a N_2 gas environment.The synthesized TiN films were superior to PVD and CVD ones in respects of improved adhesion to substrate and low preparing temperature.They exhibited good wear resistance and high hardness up to 2200 kg/mm^2.Some industrial applications have been reported.

Effect of Axial Magnetic Field on the Microstructure, Hardness and Wear Resistance of TiN Films Deposited by Arc Ion Plating

TiN films were deposited on stainless steel substrates by arc ion plating. The influence of an axial magnetic field was examined with regard to the microstructure, chemical elemental composition, mechanical properties and wear resistance of the films. The results showed that the magnetic field puts much effect on the preferred orientation, chemical composition, hardness and wear resistance of TiN films. The preferred orientation of the TiN films changed from（111） to（220） and finally to the coexistence of（111） and（220） texture with the increase in the applied magnetic field intensity. The concentration of N atoms in the TiN films increases with the magnetic field intensity, and the concentration of Ti atoms shows an opposite trend. At first, the hardness and elastic modulus of the TiN films increase and reach a maximum value at 5 m T and then decrease with the further increase in the magnetic field intensity. The high hardness was related to the N/Ti atomic ratio and to a well-pronounced preferred orientation of the（111） planes in the crystallites of the film parallel to the substrate surface. The wear resistance of the Ti N films was significantly improved with the application of the magnetic field, and the lowest wear rate was obtained at magnetic field intensity of 5 m T. Moreover, the wear resistance of the films was related to the hardness H and the H3/E＊2 ratio in the manner that a higher H3/E＊2 ratio was conducive to the enhancement of the wear resistance.

Influence of bias voltage on structure,mechanical and corrosion properties of reactively sputtered nanocrystalline TiN films

Nanocrystalline TiN films were prepared by DC reactive magnetron sputtering.The influence of substrate biases on structure,mechanical and corrosion properties of the deposited films was studied using X-ray diffraction,field emission scanning electron microscopy,nanoindentation and electrochemical techniques.The deposited films have a columnar structure,and their preferential orientation strongly depends on bias voltage.The preferential orientations change from（200）plane at low bias to（111）plane at moderate bias and then to（220）plane at relatively high bias.Nanohardness H,elastic modulus E,H/E＊and H3/E＊2 ratios,and corrosion resistance of the deposited films increase first and then decrease with the increase in bias voltage.All the best values appear at bias of-120 V,attributing to the film with a fine,compact and less defective structure.This demonstrates that there is a close relation among microstructure,mechanical and corrosion properties of the TiN films,and the film with the best mechanical property can also provide the most effective corrosion protection.

Preparation,Characterization and Electronic Properties of Fluorine-doped Tin Oxide Films

Tin oxide（SnO2） and fluorine doped tin oxide（FTO） films were prepared on glass substrates by sol-gel spin-coating using SnCl4 and NH4F precursors.Fluorine doping concentration was fixed at 4 at%and 20 at%by controlling precursor sol composition.Films exhibited the tetragonal rutile-type crystal structure regardless of fluorine concentration.Uniform and highly transparent FTO films,with more than 85%of optical transmittance,were obtained by annealing at 600℃.Florine doping of films was verified by analyzing the valence band region obtained by XPS.It was found that the fluorine doping affects the shape of valence band of SnO2 films.In addition,it was observed that the band gap of SnO2 is reduced as well as the Fermi level is upward shifted by the effect of fluorine doping.

Preparation and Characterization of Transparent Conductive Zinc Doped Tin Oxide Thin Films Prepared by Radio-frequency Magnetron Sputtering

High transparent and conductive thin films of zinc doped tin oxide （ZTO） were deposited on quartz substrates by the radio-frequency （RF） magnetron sputtering using a 12 wt% ZnO doped with 88 wt% SnO2 ceramic target.The effect of substrate temperature on the structural,electrical and optical performances of ZTO films has been studied.X-ray diffraction （XRD） results show that ZTO films possess tetragonal rutile structure with the preferred orientation of （101）.The surface morphology and roughness of the films was investigated by the atomic force microscope （AFM）.The electrical characteristic （including carrier concentration,Hall mobility and resistivity） and optical transmittance were studied by the Hall tester and UV- VIS,respectively.The highest carrier concentration of -1.144×1020 cm-3 and the Hall mobility of 7.018 cm2（V ·sec）-1 for the film with an average transmittance of about 80.0% in the visible region and the lowest resistivity of 1.116×10-2 Ω·cm were obtained when the ZTO films deposited at 250 oC.

Enhancement and Optimization of ATO Nano-crystalline Films Properties by the Addition of Acetylacetone as Modifier in the Sol-gel Process

Sb-doped Sn O2(ATO) thin films have been prepared using the spin coating method by selecting the proper amount of acetylacetone as solution modifier. All ATO powders and films exhibited the cassiterite rutile-like structure in a crystal size below 10 nm under all the experimental conditions and a nonpreviously reported crystal structure was observed at high acetylacetone loads. The acetylacetone molar ratio influenced notably the optical and electrical properties of ATO films. When prepared at an acetylacetone molar ratio of 4, ATO films exhibited optical transparencies above 90% in the visible region and above 40% in the UV region for thicknesses of 100 and 300 nm. Films in a thickness of 100 nm and at an annealing temperature of 650 ℃ accounted for a high transparency of 97% in the visible wavelength. Films prepared at an acetylacetone molar ratio of 4 exhibited an electric resistivity of 1.33×10-3 Ω·cm at an annealing temperature of 650 ℃. The optimal Sb content for ATO films was found to be 8 at%. The relationships among the properties of starting solutions, the experimental parameters, and properties of ATO films are discussed.

Fretting wear behavior of Ti/TiN multilayer film on uranium surface under various displacement amplitudes

Ti/TiN multilayer film was deposited on uranium surface by arc ion plating technique to improve fretting wear behavior. The morphology, structure and element distribution of the film were measured by scanning electric microscopy（SEM）, X-ray diffractometry（XRD） and Auger electron spectroscopy（AES）. Fretting wear tests of uranium and Ti/TiN multilayer film were carried out using pin-on-disc configuration. The fretting tests of uranium and Ti/TiN multilayer film were carried out under normal load of 20 N and various displacement amplitudes ranging from 5 to 100 μm. With the increase of the displacement amplitude, the fretting changed from partial slip regime（PSR） to slip regime（SR）. The coefficient of friction（COF） increased with the increase of displacement amplitude. The results indicated that the displacement amplitude had a strong effect on fretting wear behavior of the film. The damage of the film was very slight when the displacement amplitude was below 20 μm. The observations indicated that the delamination was the main wear mechanism of Ti/TiN multilayer film in PSR. The main wear mechanism of Ti/TiN multilayer film in SR was delamination and abrasive wear.

Effect of surfactants on the structure and photoelectric properties of ITO films by sol-gel method

The Indium tin oxide（ITO） thin film possesses excellent photoelectric properties that enable it to act as an ideal transparent conductor.To obtain high-quality ITO films through sol-gel method, the ionic surfactant monoethanolamine and the non-ionic surfactant polyethylene glycol（PEG） were added to the ITO precursor slurry.The influences of surfactants on the structural and photoelectric properties of ITO film samples were investigated.XRD patterns indicated that surfactant monoethanolamine contributed to film predominant grain orientation along the（400） plane.The high transmittance（over 95%） was attributed to the preferred orientation and the grain size expansion of ITO films.SEM showed that the surface particle size and the morphology of ITO films were strongly dependent on the kind of surfactants used.Moving to the shortwave region, the absorption edge of the films exhibited the Burstein-Moss shift.

Electrical and optical properties of indium tin oxide/epoxy composite film

The electrical and optical properties of the indium tin oxide （ITO）/epoxy composite exhibit dramatic variations as functions of the ITO composition and ITO particle size. Sharp increases in the conductivity in the vicinity of a critical volume fraction have been found within the framework of percolation theory. A conductive and insulating transition model is extracted by the ITO particle network in the SEM image, and verified by the resistivity dependence on the temperature. The dependence of the optical transmittance on the particle size was studied. Further decreasing the ITO particle size could further improve the percolation threshold and light transparency of the composite film.

TENSILE AND ADHESIVE STRENGTHS OF FINE TiN FILM ON Ti SUBSTRATE

The cantilever bending test,particularly monitored by an acoustic emission technique, was adopted to measure the tensile and interfacial adhesive strengths of the HCD ion plated fine TiN film on pure Ti substrate.The behaviors of film damaging were found to be characterized by:an internal tensile stress which exceeded its tensile strength for TiN facing upward,and a shearing stress along film substrate interface which exceeded its adhesive strength for TiN facing downward.The measured tensile and adhcsive strengths are 603 and 242 MPa respectively.

Interfacial Bonding Strength of TiN Film Coated on Si_3N_4 Ceramic Substrate

The fraction of TiN/Si3N4 in the cross section was observed with scanning electric microscope （SEM）, and residual stresses of TiN coated on the surface of Si3N4 ceramic were measured with X-ray diffraction （XRD）.The hardness of TiN film was measured, and bonding strength of TiN film coated on Si3N4 substrate was measured by scratching method. The formed mechanism of residual stress and the failure mechanism of the bonding interface in the film were analyzed, and the adhesion mechanism of TiN film was investigated preliminarily. The results show that residual stresses of TiN film are all behaved as compressive stress, and TiN film is represented smoothly with brittle fracture, which is closely bonded with Si3N4 substrate. TiN film has high hardness and bonding strength of about 500 MPa, which could satisfy usage requests of the surface of cutting Si3N4 ceramic.

X-RAY STUDY ON TITANIUM NITRIDE FILMS DEPOSITED BY VCAD METHOD

TiN films deposited by the VCAD method at the substrate of stainless steel and superhigh speed tool steels are uniform and dense.Their colour,orientation and lattice parameter depend on deposited condition The lattice structure of deposited film,the change of the lattice parameter and its preferred orientation were studied by the XRD method,different behaviours of TiNx film were analysed.The lattice parameter of TiNx films is increased with the nitrogen content and The colour of TiNx film is strongly related to the content of Nitrogen also.The change of preferred orientation depends mainly on the Bias.

Infrared laser-induced fast photovoltaic effect observed in orthorhombic tin oxide film

The SnO_2/SnO with an orthorhombic structure is a material known to be stable at high pressures and temperatures and expected to have new optical and electrical properties. The authors report a new finding of the infrared laser induced a fast photovoltaic effect arising from orthorhombic tin oxide film with an indirect band gap（~2.4 e V） which is deposited by pulsed laser deposition. The rising time of the photovoltaic signal is about 3 ns with a peak value of 4.48 mV under the pulsed laser beam with energy density 0.015 m J/mm^2. The relation between the photovoltages and laser positions along the line between two electrodes of the film is also exhibited. A possible mechanism is put forward to explain this phenomenon.All data and analyses demonstrate that the orthorhombic tin oxide with an indirect band gap could be used as a candidate for an infrared photodetector which can be operated at high pressures and temperatures.

SYNTHESIS OF TiN FILM WITH ION BEAM ENHANCED DEPOSITION AND ITS PROPERTIES

The TiN films were synthesized with an alternate process of depositing titanium from a E-gun evaporation source and 40 keV N^+ bombarding onto the target.It is shown from the composi- tion analysis and structure investigations using RBS,AES,TEM,XPS and X-ray diffraction spectrum that the formed fihns are mainly composed of TiN phase with grain size of 30—40 nm and without preferred orientation,the nitrogen content in the film is much less than that in case without N^+ bombarding,and an intermixed region about 40 nm thick exists between the film and the substrate.The films exhibt high microhardness and low friction. ZHOU Jiankun,Ion Beam Laboratory,Shanghai Institute of Metallurgy,Academia Sinica, Shanghai 200050,China