Improving electrical conductivity and wear resistance of hafnium nitride films via tantalum incorporation

Transition metal nitrides are being widely applied, as durable sensors, semiconductor and superconductor devices, their electrical conductivity and wear resistance having a significant influence on these applications. However, there are few reports about how to improve above properties. In this paper, tantalum was incorporated into hafnium nitride films through Hf_1-xTa_xN_y [x=Ta/(Hf+Ta), y=N/(Hf+Ta)] solid solution. The electrical conductivity and wear resistance of the films were significantly improved, due to the increase of the electron concentration (tantalum has one more valence electron than hafnium) and the increase in H/E and H³/E² ratios caused by the effect of solid solution hardening, respectively. The highest electrical conductivity of Hf_1-xTa_xN_y films is 8.3×10⁵ S m⁻¹, which is 1.7 times and 5.2 times of that of hafnium nitride and tantalum nitride films, respectively. In addition, the lowest wear rate of films is 1.2×10⁻⁶ mm³/N m, which is only 10% and 48% of that of hafnium nitride and tantalum nitride films, respectively. These results indicate that alloying with another transition metal is an effective method to improve electrical conductivity and wear resistance of transition metal nitrides.     

Preparation,characterization and properties of Cr-incorporated DLC films on magnesium alloy

Cr-incorporated diamond-like carbon (Cr-DLC) films were deposited on AZ31 magnesium alloy as protective coatings by a hybrid beams deposition system, which consists of a DC magnetron sputtering of Cr target (99.99%) and a linear ion source (LIS) supplied with CH₄ precursor gas. The Cr concentration (from 2.34 to 31.5 at.%) in the films was controlled by varying the flow ratio of Ar/CH₄. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to investigate the microstructure and composition of Cr-DLC films systematically. An electrochemical system and a ball-on-disk tribotester were applied to test the corrosion and tribological properties of the film on the AZ31 substrate, respectively. At low Cr doping (2.34 at.%), the film mainly exhibited the feature of amorphous carbon, while at high doping (31.5 at.%), chromium carbide crystalline phase occurred in the amorphous carbon matrix of the film. In this study, all the prepared Cr-DLC films showed higher adhesion to AZ31 than the DLC film. Especially for the film with low Cr doping (2.34 at.%), it owned the lowest internal stress and the highest adhesion to substrate among all the films. Furthermore, this film could also improve the wear resistance of magnesium alloy effectively. But, none of the films could improve the corrosion resistance of the magnesium alloy in 3.5 wt.% NaCl solution due to the existence of through-thickness defects in the films.     

Tribological study of boron nitride films

Boron nitride (BN) films with different cubic and hexagonal phase compositions were deposited on silicon substrates via diamond interlayers by magnetron sputtering and electron cyclotron resonance microwave plasma chemical vapor deposition. The tribological behaviors of the BN films were investigated systematically using a ball-on-disc tribometer with silicon nitride as the counterpart. Comparison studies were also performed on sintered cubic and hexagonal BN compacts. The influence of phase compositions and surface roughness of BN coatings on their tribological characteristics was studied. The cubic BN (cBN) films showed excellent wear resistance against silicon nitride. The wear rate of the cBN films was estimated to be about 1.0 × 10^?7 mm³/N m by measuring the cross-sectional area of the wear track after the sliding test over a distance of 12 km.     

Duplex DLC coatings fabricated on the inner surface of a tube using plasma immersion ion implantation and deposition

A duplex plasma immersion ion implantation and deposition (PIIID) process, involving carbon ion implantation and diamond-like carbon (DLC) deposition, is proposed to modify the inner surface of a tube. In the research, samples of GCr15 bearing steel were placed inside a tube in the vacuum chamber. After the vacuum chamber was evacuated to a base pressure of 6 × 10^− 3 Pa, C₂H₂ gas was introduced into the chamber, and the tube was biased by a negative pulsed bias. Since a pulsed glow discharge (PGD) plasma can be formed by the bias, carbon ion implantation and DLC film deposition process can be obtained by biasing the tube with a high and low bias, respectively. To synthesize different DLC films, single PIIID processes employing a low voltage (several kV) PGD method and duplex PIIID processes combining the high (several tens kV) and low voltage PGD techniques were carried out. The as-synthesized films were characterized by Raman spectrum, nano-indentation, scratch, tribological and electrochemical tests. Raman results show that duplex DLC films were synthesized by this duplex PIIID process. In addition, compared with the single DLC film synthesized by the low voltage PGD process, the duplex DLC films can obtain a high wear and corrosion resistances. Furthermore, using this duplex PIIID method, batch treatment of outer-rings of the bearing was realized.     

Electron field emission from filtered arc deposited diamond-like carbon films using Au and Ti layers

In this work, tetrahedral diamond-like carbon (DLC) films are deposited on Si, Ti/Si and Au/Si substrates by a new plasma deposition technique — filtered arc deposition (FAD). Their electron field emission characteristics and fluorescent displays of the films are tested using a diode structure. It is shown that the substrate can markedly influence the emission behavior of DLC films. An emission current of 0.1 μA is detected at electric field E_DLC/Si=5.6 V/μm, E_DLC/Au/Si=14.3 V/μm, and E_DLC/Ti/Si=5.2 V/μm, respectively. At 14.3 V/μm, an emission current density J_DLC/Si=15.2 μA/cm², J_DLC/Au/Si=0.4 μA/cm², and J_DLC/Ti/Si=175 μA/cm² is achieved, respectively. It is believed that a thin TiC transition layer exists in the interface between the DLC film and Ti/Si substrate.     

Growth and properties of hydrogen-free DLC films deposited by surface-wave-sustained plasma

Hydrogen-free diamond-like carbon (DLC) films were deposited by a new surface-wave-sustained plasma physical vapor deposition (SWP-PVD) system in various conditions. Electron density was measured by a Langmuir probe; the film thickness and hardness were characterized using a surface profilometer and a nanoindenter, respectively. Surface morphology was investigated using an atomic force microscope (AFM). It is found that the electron density and deposition rate increase following the increase in microwave power, target voltage, or gas pressure. The typical electron density and deposition rate are about 1.87 × 10¹¹–2.04 × 10¹² cm^− 3 and 1.61–14.32 nm/min respectively. AFM images indicate that the grain sizes of the films change as the experimental parameters vary. The optical constants, refractive index n and extinction coefficient k, were obtained using an optical ellipsometry. With the increase in microwave power from 150 to 270 W, the extinction coefficient of DLC films increases from 0.05 to 0.27 while the refractive index decreases from 2.31 to 2.11.     

A superhard diamond-like carbon film

A superhard hydrogen-free amorphous diamond-like carbon (DLC) film was deposited by pulsed arc discharge using a carbon source accelerator in a vacuum of 2×10⁻⁴ Pa. The growth rate was about 15 nm/min and the optimum ion-plasma energy was about 70 eV. The impact of doping elements (Cu, Zr, Ti, Al, F(Cl), N) on the characteristics of DLC films deposited on metal and silicon substrates was studied aiming at the choice of the optimum coating for low friction couples. The microhardness of thick (≥20 μm) DLC films was studied by Knoop and Vickers indentations, medium thick DLC films (1–3 μm) were investigated using a ‘Fischerscope’, and Young's module of thin films (20–70 nm) was studied by laser induced surface acoustic waves. The bonds in DLC films were investigated by electron energy loss spectroscopy (EELS), X-ray excited Auger electron spectroscopy (XAES), and X-ray photoelectron spectroscopy (XPS). The adhesion of DLC films was defined by the scratch test and Rockwell indentation. The coefficient of friction of the Patinor DLC film was measured by a rubbing cylinders test and by a pin-on-disk test in laboratory air at about 20% humidity and room temperature. The microhardness of the Patinor DLC film was up to 100 GPa and the density of the film was 3.43–3.65 g/cm³. The specific wear rate of the Patinor DLC film is comparable to that of other carbon films.     

Nano-texture for a wear-resistant and near-frictionless diamond-like carbon

The effect of nano-scale surface texture on wear resistance of diamond-like carbon (DLC) films was studied using a reciprocating ball-on-flat tribometer in dry, humid, and liquid water environments. The nano-scale surface texture was produced by depositing ∼1 μm thick DLC films onto silicon substrates pre-textured with pyramidal wells and polystyrene spheres. The surface roughness of the textured DLC films was about 50 nm in both cases. The friction and wear behavior of the flat and nano-textured DLC films were tested with AISI 440C-grade stainless steel balls at a contact load creating about 360 nm deep Hertzian deformation which is significantly larger than the surface roughness. At this condition, nano-texturing did not affect the friction coefficient, but it significantly reduced the wear of DLC films in dry and humid nitrogen compared to flat DLC. In dry nitrogen, the nano-textured DLC films showed the ultra-low friction without substantial wear of DLC and deposition of thick transfer films onto the counter-surface. The wear reduction appeared to be related to the stress relief in the nano-textured DLC film. In liquid water, surface features on the nano-textured DLC films were diminished due to tribochemical oxidation and material removal at the sliding interface.     

Influence of countersurface materials on dry sliding performance of CuO/Y-TZP composite at 600 °C

Dry sliding wear tests on 5 wt.% copper oxide doped yttria stabilized zirconia polycrystals (CuO–TZP) composite have been performed against alumina, zirconia and silicon nitride countersurfaces at 600 °C. The influences of load and countersurface materials on the tribological performance of this composite have been studied. The friction and wear test results indicate a low coefficient of friction and specific wear rate for alumina and zirconia countersurfaces at F = 1 N load (maximum Hertzian pressure ～0.5 GPa). Examination of the worn surfaces using scanning electron microscope/energy dispersive spectroscopy confirmed the presence of copper rich layer at the edge of wear scar on the alumina and zirconia countersurfaces. However, Si₃N₄ countersurface sliding against CuO–TZP shows a relatively higher coefficient of friction and higher wear at 1 N load condition. These results suggest that the countersurface material significantly affect the behavior of the third body and self-lubricating ability of the composite.     

Mechanical and tribological properties of boron,nitrogen-coincorporated diamond-like carbon films prepared by reactive radio-frequency magnetron sputtering

We have deposited boron- and/or nitrogen-incorporated DLC films by radio-frequency magnetron sputtering, and systematically investigated the structure and the mechanical and tribological properties. The N content in DLC films increased with increasing N₂ flow ratio [N₂/(Ar + N₂)], and it tended to be saturated at higher N₂ flow ratios. The N content further increased with an increase in the B content of the targets. The B/C ratios of the films were almost the same as those of the B-containing targets regardless of the N content. Scratch tests revealed that the adhesion strength of N-incorporated DLC films decreased with increasing N₂ flow ratio and the critical loads of B-incorporated films were lower than that of an unincorporated film. It was found that for B, N-coincorporated films there was an optimum N₂ flow ratio at which the critical load became a maximum value, which was higher than that of the unincorporated film. The optimum N₂ flow ratio increased with an increase in the B composition of the targets. The N-incorporated films peeled off during ball-on-plate friction tests. On the other hand, the B, N-coincorporated films showed good wear-resistant properties that the specific wear rates were lower than those of the unincorporated and B-incorporated films.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Preparation of diamond like carbon thin films above room temperature and their properties

Diamond like carbon (DLC) thin films were deposited on p-type silicon (p-Si), quartz and ITO substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at different substrate temperatures (RT ∼ 300 °C). Argon (Ar: 200 sccm) was used as carrier gas while acetylene (C₂H₂: 20 sccm) and nitrogen (N: 5 sccm) were used as plasma source. Analytical methods such as X-ray photoelectron spectroscopy (XPS), FT-IR and UV–visible spectroscopy were employed to investigate the structural and optical properties of the DLC thin films respectively. FT-IR spectra show the structural modification of the DLC thin films with substrate temperatures showing the distinct peak around 3350 cm^− 1 wave number; which may corresponds to the sp² C–H bond. Tauc optical gap and film thickness both decreased with increasing substrate temperature. The peaks of XPS core level C 1 s spectra of the DLC thin films shifted towards lower binding energy with substrate temperature. We also got the small photoconductivity action of the film deposited at 300 °C on ITO substrate.     

The influence of ion beam assisted deposition parameters on the properties of boron nitride thin films

We studied ion beam assisted deposition of cubic boron nitride thin films on silicon (100) and high speed steel. The boron nitride films were grown by the electron beam evaporation of pure boron (99.4%) and the simultaneous ion bombardment of a mixture of nitrogen and argon ions from a Kaufman ion source. At a constant boron evaporation rate, the ion energy, ion current density, substrate temperature and process gas mixture was varied. The thickness of the films was kept between 200 and 300 nm. Boron nitride films with >80% of the cubic phase (determined by Fourier transform infrared spectroscopy) were obtained with nitrogen/argon mixtures of 50/50 at ion energies of 450 eV and substrate temperatures of 400°C. The current density amounted to 0.45 mA cm⁻² at a nominal boron rate of 200 pm s⁻¹. Cubic boron nitride films were deposited on high speed steel by introducing a titanium interlayer for adhesion improvement.     

An atomistic study of the abrasive wear and failure of graphene sheets when used as a solid lubricant and a comparison to diamond-like-carbon coatings

The failure mechanisms of graphene under nanoscale sliding conditions are examined using atomistic simulations to evaluate its use as a solid lubricant and to simultaneously answer principal questions regarding wear of lamellar films comprised of atomically-thin sheets. To determine the failure behavior of graphene and the impact of adhesion on wear and failure, an asperity is slid over a substrate-supported graphene film with various adhesion strengths. For a purely-repulsive asperity, the graphene never delaminates and lower substrate-membrane adhesion appears to reduce the overall damage to the graphene layer and permits the recovery of more of the load-bearing capability of the graphene post-tearing. When tri-layer graphene is benchmarked with a 2 nm repulsive asperity against an 86% sp³ content diamond-like-carbon (DLC) coating of the same thickness (1.0 nm), the graphene supports up to 8.5 times the normal load of DLC during indentation, and up to twice the normal load of DLC during sliding even after failure of one or more layers. The preliminary results indicate that graphene has promise as a solid lubricant with thickness on the order of nanometers due to its atomically-thin configuration and high load carrying capacity.     

Chemical synthesis of TiO2 nanoparticles and their inclusion in Ni–P electroless coatings

The work addresses the preparation of Ni3P3TiO₂ nanocomposite coatings on mild steel substrate by the electroless technique. Nanosized TiO₂ particles were first synthesized by the precipitation method and then were codeposited (4 g/l) into the Ni3P matrix using alkaline hypophosphite reduced EL bath. The surface morphology, particle size, elemental composition and phase analysis of as-synthesized TiO₂ nanoparticles and the coatings were characterized by field emission scanning electron microscopy (FESEM), energy-dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD). Coatings with 20 µm thickness were heat treated at 400 °C for 1 h in argon atmosphere. The morphology, microhardness, wear resistance and friction coefficient characteristics (ball on disc) of electroless Ni3P3TiO₂ nanocomposite coatings were determined and compared with Ni3P coatings. The results show that as-synthesized TiO₂ nanoparticles are spherical in shape with a size of about12 nm. After heat treatment, the microhardness and wear resistance of the coatings are improved significantly. Superior microhardness and wear resistance are observed for Ni3P3TiO₂ nanocomposite coatings over Ni3P coatings.     

Effect of oxygen plasma treatment on non-thrombogenicity of diamond-like carbon films

The non-thrombogenicity of oxygen-plasma-treated DLC films was investigated as surface coatings for medical devices. DLC films were deposited on polycarbonate substrates by a radio frequency plasma enhanced chemical vapor deposition method using acetylene gas. The deposited DLC films were then treated with plasma of oxygen gas at powers of 15 W, 50 W, and 200 W. Wettability was evaluated by water contact angle measurements and the changes in surface chemistry and roughness were examined by X-ray photoelectron spectroscopy and atomic force microscope analysis, respectively. Each oxygen-plasma-treated DLC film exhibited a hydrophilic nature with water contact angles of 11.1°, 17.7° and 36.8°. The non-thrombogenicity of the samples was evaluated through the incubation with platelet-rich plasma isolated from human whole blood. Non-thrombogenic properties dramatically improved for both 15 W- and 50 W-oxygen-plasma-treated DLC films. These results demonstrate that the oxygen plasma treatment at lower powers promotes the non-thrombogenicity of DLC films with highly hydrophilic surfaces.     

Molecular structure of SiOx-incorporated diamond-like carbon films; evidence for phase segregation

Silicon-oxide incorporated amorphous hydrogenated diamond-like carbon films (SiO_x–DLC, 1 ≤ x ≤ 1.5) containing up to 24 at.% of Si (H is excluded from the atomic percentage calculations reported here) were prepared using pulsed direct current plasma-enhanced chemical vapour deposition (DC-PECVD). Molecular structure, optical properties and mechanical properties of these films were assessed as a function of Si concentration. The spectroscopic results indicated two structural regimes. First, for Si contents up to ~ 13 at.%, SiO_x–DLC is formed as a single phase with siloxane, O–Si–C₂, bonding networks. Second, for films with Si concentrations greater than 13 at.%, SiO_x–DLC with siloxane bonding and SiO_x deposit simultaneously as segregated phases. The variations in mechanical properties and optical properties as a function of Si content are consistent with the above changes in the film composition.     

Anti-adhesion performance of various nitride and DLC films against high strength steel in metal forming operation

High strength steel (HSS) is widely used for automobile reinforcement parts and the quantity required is rapidly grown. However, the strength and hardness of the steel are relatively high, its formability is very low and adhesion to tool material can be easily found under forming operation. This paper aimed to evaluate the anti-adhesion performance of commercial nitride and DLC films coated on cold work tool steel against HSS in forming operation. The friction coefficient and wear rate of the non-coated ball (SKD11; hardness 60 ± 2 HRC), balls coated with TiN-PVD, TiCN-PVD, AlTiN-PVD, Nitride + CrN and DLC have been evaluated in sliding contact against SPFH 590 (JIS) disk. The scratch and nano-indentation tests were done on each type of coated tools to characterize the adhesive strength between the film and the substrate, and the hardness and the elastic modulus, respectively. The anti-adhesion performance of various films coated tool in metal stamping process was also investigated by performing U-bending experiment. The cold roll carbon steel; SPCC (JIS) was also used to compare a material transfer problem to the case of using HSS (JIS: SPFH590). As the results, for HSS sheet, the adhesion of workpiece material on a non-coated die surface was detected after 49 strokes whereas adhesion could not be found in case of stamping SPCC sheet up to 500 strokes. The TiCN, AlTiN, and Nitride + CrN films showed good anti-adhesion performance when forming HSS, while the TiN and DLC films did not provide the satisfied results.     

Wear damage of Si3N4-graphene nanocomposites at room and elevated temperatures

Mechanical and tribological properties of nanocomposites with silicon nitride matrix with addition of 1 and 3 wt.% of multilayered graphene (MLG) platelets were studied and compared to monolithic Si₃N₄. The wear behavior was observed by means of the ball-on-disk technique with a silicon nitride ball used as the tribological counterpart at temperatures 25 °C, 300 °C, 500 °C, and 700 °C in dry sliding. Addition of such amounts of MLG did not lower the coefficient of friction. Graphene platelets were integrated into the matrix very strongly and they did not participate in lubricating processes. The best performance at room temperature offers material with 3 wt.% graphene, which has the highest wear resistance. At medium temperatures (300 °C and 500 °C) coefficient of friction of monolithic Si₃N₄ and composite with 1%MLG reduced due to oxidation. Wear resistance at high temperatures significantly decreased, at 700 °C differences between the experimental materials disappeared and severe wear regime dominated in all cases.     

Photoconductivity of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited by a new pulsed DC discharge plasma chemical vapour deposition (CVD) using hydrogen and methane gas mixture. When methane concentration (Cm) i.e. CH₄/(H₂ + CH₄) was increased from 3 to 40%, the graphitization of the carbon film increases as evident from Raman study. When Cm was increased to 30%, DLC film shows photoconducting property. The white light photoconductivity (S = I_l/I_d, where I_l is light current and I_d is dark current) measured with solar simulator under AM 1.5 condition was approximately 20 at room temperature. The photoconductivity was not clear when Cm was lower than 20%. ESR measurements also show that the electron spin density was slightly decreased with decreasing concentration of methane. Thus we can conclude here that at higher concentrations of methane at 30%, Sp² content of the film increases and the DLC film becomes photoconducting.