Bias effects on the tribological behavior of cathodic arc evaporated CrTiAlN coatings on AISI 304 stainless steel

In this study, CrTiAlN coatings were deposited on AISI 304 stainless steel by cathodic arc evaporation under a systematic variation of the substrate bias voltage. The coating morphology and properties including surface roughness, adhesion, hardness/elastic modulus (H/E) ratio, and friction behavior were analyzed to evaluate the impact of the substrate bias voltage on the coating microstructure and properties. The results suggest that for an optimized value of the substrate bias voltage, i.e. − 150 V, the CrTiAlN coatings showed increased Cr content and improved properties, such as higher adhesion strength, hardness, and elastic modulus in comparison to the coatings deposited by other substrate bias voltage. Moreover, the optimum coatings achieved a remarkable reduction in the steel friction coefficient from 0.65 to 0.45.     

Effects of substrate bias voltage and target sputtering power on the structural and tribological properties of carbon nitride coatings

Effects of substrate bias voltage and target sputtering power on the structural and tribological properties of carbon nitride (CN_x) coatings are investigated. CN_x coatings are fabricated by a hybrid coating process with the combination of radio frequency plasma enhanced chemical vapor deposition (RF PECVD) and DC magnetron sputtering at various substrate bias voltage and target sputtering power in the order of −400 V 200 W, −400 V 100 W, −800 V 200 W, and −800 V 100 W. The deposition rate, N/C atomic ratio, and hardness of CN_x coatings as well as friction coefficient of CN_x coating sliding against AISI 52100 pin in N₂ gas stream decrease, while the residual stress of CN_x coatings increases with the increase of substrate bias voltage and the decrease of target sputtering power. The highest hardness measured under single stiffness mode of 15.0 GPa and lowest residual stress of 3.7 GPa of CN_x coatings are obtained at −400 V 200 W, whereas the lowest friction coefficient of 0.12 of CN_x coatings is achieved at −800 V 100 W. Raman and XPS analysis suggest that sp³ carbon bonding decreases and sp² carbon bonding increases with the variations in substrate bias voltage and target sputtering power. Optical images and Raman characterization of worn surfaces confirm that the friction behavior of CN_x coatings is controlled by the directly sliding between CN_x coating and steel pin. Therefore, the reduction of friction coefficient is attributed to the decrease of sp³ carbon bonding in the CN_x coating. It is concluded that substrate bias voltage and target sputtering power are effective parameters for tailoring the structural and tribological properties of CN_x coatings.     

Modulation periods and ratios induced changes of microstructure and mechanical properties of AlN/ZrB2 multilayered coatings

AlN/ZrB₂ multilayered coatings were synthesized in a magnetron sputtering system. The extensive measurements were employed to investigate the influence of different nanoscale modulation periods and modulation ratios on microstructure and mechanical properties of the coatings. Analysis of X-ray diffraction, profiler and nanoindention indicated that multilayered coatings possessed much higher hardness and elastic modulus than monolithic AlN and ZrB₂ coatings. At the substrate negative bias of −80 V, maximum hardness (34.1 GPa) and elastic modulus (469.8 GPa) were obtained in the multilayer with Λ = 30 nm and t_AlN:t_ZrB2 = 1:3. This hardest multilayer showed a marked polycrystalline structure with the strong mixture of ZrB₂ (001), ZrB₂ (100), ZrB₂ (101), AlN (100) textures.     

Low temperature deposition of ITO on organic films by using negative ion assisted dual magnetron sputtering system

In a magnetron sputter type negative metal ion deposition, the influence of positive bias voltage (V_b) on the surface morphology, electrical resistivity, optical transmittance, and microhardness of ITO prepared on organic polycarbonate films has been investigated. In this study, the V_b increased from 0 to 250 V to attract secondary negative In and Sn metal ions, which were produced from ITO target by surface negative ionization with intense Cs ion bombardments. During deposition although reactive oxygen gas was not introduced into the chamber, by adjusting V_b at 100 V, ITO films on polycarbonate substrate with resistivity as low as 6.1×10⁻⁴ Ω cm and transmittance over 90% at 550 nm have been obtained without intentional substrate heating.AFM measurement also shows that surface roughness varied significantly with V_b. However, too intense ion bombardment originated by high V_b (>100 V) condition increased surface roughness and as a result deteriorated the electrical and optical property of ITO films.     

Structure, hardness and thermal stability of nanolayered TiN/CrN multilayer coatings

Nanolayered TiN/CrN multilayer coatings were deposited on silicon substrates using a reactive DC magnetron sputtering process at various modulation wavelengths (Λ), substrate biases (V_B) and substrate temperatures (T_S). X-ray diffraction (XRD), nanoindentation and atomic force microscopy (AFM) were used to characterize the coatings. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of the TiN/CrN multilayers was 3800 kg/mm² at Λ=80  Å, V_B=−150 V and T_S=400°C. Thermal stability of TiN, CrN and TiN/CrN multilayer coatings was studied by heating the coatings in air in the temperature range (T_A) of 400-800°C. The XRD data revealed that TiN/CrN multilayers retained superlattice structure even up to 700°C and oxides were detected only after T_A?750°C, whereas for single layer TiN and CrN coatings oxides were detected even at 550°C and 600°C, respectively. Nanoindentation measurements showed that TiN/CrN multilayers retained a hardness of 2800 kg/mm² upon annealing at 700°C, and this decrease in the hardness was attributed to interdiffusion at the interfaces.     

Effect of bias voltage on microstructure, mechanical and wear properties of Al-Si-N coatings deposited by cathodic arc evaporation

Al-Si-N coatings were deposited on tungsten carbide (WC-Co) and silicon wafer substrates using Cr and AlSi (12 at.% Si) alloy targets using a dual cathode source with short straight-duct filter in the cathode arc evaporation system. Al-Si-N coatings were synthesized under a constant flow of nitrogen, using various substrate bias voltages at a fixed AlSi cathode power. To enhance adhesive strength, the Cr/(Cr_xAl_ySi_z)N graduated layer between the top coating and the substrate was deposited as a buffer interlayer. The effects of bias voltage on the microstructure, mechanical and wear properties of the Al-Si-N films were investigated. Experimental results reveal that the Al-Si-N coatings exhibited a nanocomposite structure of nano-crystalline h-AlN, amorphous Si₃N₄ and a small amount of free Si and oxides. It was also observed that the deposition rate of as-deposited films gradually decreased from about 25.1 to 18.8 nm/min when the substrate bias was changed from − 30 to − 150 V. The XRD results revealed that h-AlN preferred orientation changed from (002) to (100) as the bias voltage increased. The maximum hardness of approximately 35 GPa was obtained at the bias voltage of −90 V. Moreover, the grain size was inversely proportional to the hardness of the film. Wear test results reveal that the Al-Si-N film had a lower coefficient of friction, between 0.5 and 0.7, than that 0.7 of the AlN film.     

Effects of applied substrate bias during reactive sputter deposition of nanocomposite tantalum carbide/amorphous hydrocarbon thin films

Nanocomposite tantalum carbide/amorphous hydrocarbon (TaC/a-C:H) thin film composition, structure, and mechanical properties depend on the direct current bias voltage (V_b) level applied to the substrate during reactive sputter deposition. A set of TaC/a-C:H films was deposited across the range V_b = 0 to − 300 V with all other deposition parameters held constant except substrate temperature, which was allowed to reach its steady state during the depositions. Effects of V_b on film composition and structure were explored, including TaC crystallite size and dispersion using X-ray diffraction and high resolution transmission electron microscopy. In addition, the dependency of stress and hardness on V_b was studied with an emphasis on relationships to a-C:H phase structure.     

Comparison of microstructure and mechanical properties of chromium nitride-based coatings deposited by high power impulse magnetron sputtering and by the combined steered cathodic arc/unbalanced magnetron technique

Sliding, abrasive, and impact wear tests were performed on chromium nitride (CrN)-based coatings deposited on mirror-polished M2 high speed steel substrates by the novel high power impulse magnetron sputtering (HIPIMS) utilising high peak cathode powers densities of 3000 W cm⁻². The coatings were compared to single layer CrN and multilayer superlattice CrN/NbN coatings deposited by the arc bond sputtering (ABS) technique designed to improve the coating substrate adhesion by a combined steered cathodic arc/unbalanced magnetron (UBM) sputtering process. The substrates were metal ion etched using non-reactive HIPIMS or steered cathodic arc at a substrate bias voltage of −1200 V. Subsequently a 2- to 3-μm thick CrN or CrN/NbN coating was deposited by reactive HIPIMS or UBM. No bias was used during the HIPIMS deposition, while the bias during UBM growth was in the range 75-100 V. The ion saturation current measured by a flat electrostatic probe reached values of 50 mA cm⁻² peak for HIPIMS and 1 mA cm⁻² continuous during UBM deposition. The microstructure of the HIPIMS coatings observed by transmission electron microscopy was fully dense in contrast to the voided columnar structure observed in conventional UBM sputtered CrN and CrN/NbN. The sliding wear coefficients of the HIPIMS CrN films of 2.3×10⁻¹⁶ m³ N⁻¹ m⁻¹ were lower by a factor of 4 and the roughness of the wear track was significantly reduced compared to the UBM-deposited CrN. The abrasive wear coefficient of the HIPIMS coating was 2.2×10⁻¹³ m³ N⁻¹ m⁻¹ representing an improvement by a factor of 3 over UBM deposited CrN and a wear resistance comparable to that of the superlattice CrN/NbN. The adhesion of the HIPIMS deposited CrN was comparable to state-of-the-art ABS technology.     

CrAlN coatings deposited by cathodic arc evaporation at different substrate bias

CrAlN is a good candidate as an alternative to conventional CrN coatings especially for high temperature oxidation-resistance applications. Different CrAlN coatings were deposited on hardened steel substrates by cathodic arc evaporation (CAE) from chromium-aluminum targets in a reactive nitrogen atmosphere at negative substrate bias between − 50 and − 400 V. The negative substrate bias has important effects on the deposition growth rate and crystalline structure. All our coatings presented hardness higher than conventional CrN coatings. The friction coefficient against alumina and tungsten carbide balls was around 0.6. The sliding wear coefficient of the CrAlN coatings was very low while an important wear was observed in the balls before a measurable wear were produced in the coatings. This effect was more pronounced as the negative substrate bias was increased.     

Effects of substrate bias on the structure and mechanical properties of (Al1.5CrNb0.5Si0.5Ti)Nx coatings

(Al_1.5CrNb_0.5Si_0.5Ti)N_x high-entropy nitride coatings were designed and investigated in this study. Nitride coatings are deposited under a sufficient amount of nitrogen at 415 °C on Si by direct current magnetron reactive sputtering from a non-equimolar Al_1.5CrNb_0.5Si_0.5Ti high-entropy alloy target. The effects of substrate bias (V_s) on film structure and mechanical properties are studied. All these coatings have a single NaCl-type face-centered cubic structure and nearly stoichiometric ratio of (Al_1.5CrNb_0.5Si_0.5Ti)₅₀ N₅₀. A distinct refinement of microstructure of the films is observed when V_s varies from 0 V to − 100 V. Typical columnar structure transits into a dense and featureless structure and grain size decreases from 70 nm to 5 nm. Similar refinement remains at larger bias(− 150 or − 200 V). At the same time, the residual compressive stress increases from near zero to − 3.9 GPa at − 150 V and then decreases to − 3.2 GPa at − 200 V. The hardness increases from 12 GPa at 0 V, peaks at 36 GPa at − 100 V, and then decreases to 26 GPa at − 200 V. The structural evolution strengthening mechanism are discussed and compared with equimolar high-entropy nitrides.     

Ion-bombardment characteristics during deposition of TiN films using a grid-assisted magnetron system with enhanced plasma potential

Energy-resolved mass spectroscopy was used to investigate differences in ion-bombardment characteristics during conventional reactive magnetron sputtering of TiN films and their deposition using a grid-assisted magnetron system with anode at a high potential (up to 350 V relative to grounded chamber walls). Narrow ion energy distributions with a maximum corresponding to the ion energy close to 100 eV were obtained for the conventional magnetron deposition on a biased substrate (V_b=−100 V) in an 80%Ar+20%N₂ gas mixture at a pressure of 0.5 Pa. On the contrary, the energy distributions of ions bombarding a grounded substrate in the grid-assisted modified magnetron system with the grid potential V_g=+100 V were broadened and extended to higher energies (up to 300 eV) under the same conditions. The change in the ion energy distributions is caused by increase in the plasma potential due to the high anode potential (approximately 320 V in this case). Simultaneously, the total ion flux to the substrate decreased 5.4 times compared with the conventional system. A combined effect of the enlarged kinetic energy of ions and their substantially reduced flux resulted in production of high-quality, densified TiN films with a smooth surface.     

Bias effects on microstructure, mechanical properties and corrosion resistance of arc-evaporated CrTiAlN nanocomposite films on AISI 304 stainless steel

CrTiAlN films were deposited on AISI 304 stainless steel by cathodic arc evaporation under a systematic variation of the substrate bias voltage. The effects of substrate bias on the coating morphology and mechanical properties, such as structure, composition, adhesion, hardness and Young's modulus, were studied in details using field emission scanning electron microscopy, X-ray diffraction, electron probe microanalysis and indenter. Polarization test and immersion test were also carried out to evaluate the corrosion behavior of the various films. CrTiAlN films are nanocrystalline that exhibit a CrN/TiAlN multi-layered morphology. At the optimal value of substrate bias voltage (i.e., − 150 V), the CrTiAlN film showed an increased Cr content and improved properties, such as higher adhesion, higher hardness (38 ± 2 GPa), and greater Young's modulus (319 ± 16 GPa) vs. the films deposited at other substrate bias voltages. Moreover, the optimum film has better corrosion resistance in 3.5 wt.% NaCl and 20 vol.% HCl solutions.     

Copper phthalocyanine thin-film field-effect transistor with SiO2/Ta2O5/SiO2 multilayer insulator

Top-contact Copper phthalocyanine (CuPc) thin-film field-effect transistor (TFT) with SiO₂/Ta₂O₅/SiO₂ (STS) multilayer as the dielectric was fabricated and investigated. With the multi-layer dielectric, drive voltage was remarkably reduced. A relatively large on-current of 1.1 × 10⁻⁷ A at a V_GS of −15 V was obtained due to the strong coupling capability provided by the STS multilayer gate insulator. The device shows a moderate performance: saturation mobility of μ_sat = 6.12 × 10⁻⁴ cm²/V s, on-current to off-current ratio of I_on/I_off = 1.1 × 10³, threshold voltage of V_TH = −3.2 V and sub-threshold swing SS = 1.6 V/dec. Atomic force microscope images show that the STS multilayer has a relative smooth surface. Experiment results indicate that STS multilayer is a promising insulator for the low drive voltage CuPc-based TFTs.     

The effects of pulse frequency and substrate bias to the mechanical properties of CrN coatings deposited by pulsed DC magnetron sputtering

The chromium nitride coatings have been prepared by the bipolar symmetric pulsed DC magnetron reactive sputtering process at 2 kHz and 20 kHz pulse frequencies, respectively. Different substrate bias was applied with a pulsed DC bias unit with 50 kHz pulse frequency. Oscilloscope traces of the I–V waveforms indicate high power and high current density outputs during the symmetric bipolar pulsed mode. It is concluded that the (200) orientation of CrN films is observed. The grain size decreases with increasing pulse frequency and substrate bias. The substrate bias has a strong influence on the mechanical properties of CrN films. The scratch tests of the CrN coatings show that almost only tiny chipping failure is occurred. Sufficient adhesion strength quality of the coating is also observed. The substrate bias for the deposition of CrN films with sufficient hardness and adhesion properties combination is − 290 V at 20 kHz and − 408 V at 2 kHz pulse frequency, respectively.     

Enhancement of mechanical and tribological properties in AISI D3 steel substrates by using a non-isostructural CrN/AlN multilayer coating

Enhancement of mechanical and tribological properties on AISI D3 steel surfaces coated with CrN/AlN multilayer systems deposited in various bilayer periods (Λ) via magnetron sputtering has been studied in this work exhaustively. The coatings were characterized in terms of structural, chemical, morphological, mechanical and tribological properties by X-ray diffraction (XRD), electron dispersive spectrograph, atomic force microscopy, scanning and transmission electron microscopy, nanoindentation, pin-on-disc and scratch tests. The failure mode mechanisms were observed via optical microscopy. Results from X-ray diffraction analysis revealed that the crystal structure of CrN/AlN multilayer coatings has a NaCl-type lattice structure and hexagonal structure (wurtzite-type) for CrN and AlN, respectively, i.e., made was non-isostructural multilayers. An enhancement of both hardness and elastic modulus up to 28 GPa and 280 GPa, respectively, was observed as the bilayer periods (Λ) in the coatings were decreased. The sample with a bilayer period (Λ) of 60 nm and bilayer number n  =  50 showed the lowest friction coefficient (∼0.18) and the highest critical load (43 N), corresponding to 2.2 and 1.6 times better than those values for the coating deposited with n = 1, respectively. The best behavior was obtained when the bilayer period (Λ) is 60 nm (n = 50), giving the highest hardness 28 GPa and elastic modulus of 280 GPa, the lowest friction coefficient (∼0.18) and the highest critical load of 43 N. These results indicate an enhancement of mechanical, tribological and adhesion properties, comparing to the CrN/AlN multilayer systems with 1 bilayer at 28%, 21%, 40%, and 30%, respectively. This enhancement in hardness and toughness for multilayer coatings could be attributed to the different mechanisms for layer formation with nanometric thickness such as the Hall–Petch effect and the number of interfaces that act as obstacles for the crack deflection and dissipation of crack energy.     

Mechanical properties of a-C:H thin films deposited by r.f. PECVD method

Internal stress, hardness and deposition rate were evaluated for hydrogenated amorphous carbon (a-C:H) films prepared by conventional r.f. plasma-enhanced chemical vapour deposition. The internal stress, hardness and deposition rate of 0.9, 18 and 58 nm/min, respectively, achieved at 40 Pa gas pressure for negative self-bias voltages (V_b) window (from −370 to −550 V). It was found that the negative self-bias voltage window was associated with the existence of two turning points, which shift to higher wavenumber of G band peak position of Raman spectroscopy (Raman) at different V_b in relation to the internal stress and hardness, and rapid decreasing of the relative total peak areas of Fourier Transform Infra-red absorption spectroscopy (FT-IR).The internal stress relaxed from approximately 35 eV ion energy when the energy is increased and rapidly decreased in comparison with the stress relaxation equation.     

Effect of substrate bias voltage on structural and mechanical properties of pulsed DC magnetron sputtered TiN-MoSx composite coatings

TiN-MoS_x composite coatings were deposited by pulsed DC closed-field unbalanced magnetron sputtering (CFUBMS) using separate Ti and MoS₂ targets in an Ar and N₂ gas environment. The effect of substrate bias voltage on the structure and mechanical properties of TiN-MoS_x composite coating has been studied. The structure and composition of the coating were evaluated using field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) by X-ray and grazing incidence X-ray diffraction (GIXRD). Scratch adhesion tests, Vickers microhardness tests and ball-on-disc tests with a cemented carbide (WC-6%Co) ball were carried out to investigate mechanical properties of the coating. Application of substrate bias was found to transform the structure of TiN-MoS_x composite coating from open columnar to a dense columnar structure. The changes in grain size and texture coefficient appear to be associated with variation in substrate bias voltage. The mechanical properties of the coating such as adhesion and composite microhardness were also observed to be related to the change in bias voltage. A maximum hardness of 22 GPa was obtained for a coating deposited at substrate bias voltage of −40 V. The improved structural and mechanical properties of the coating deposited at −40 V were also reflected in its excellent wear resistance property.     

Structural and mechanical properties of titanium and titanium diboride monolayers and Ti/TiB2 multilayers

Nano-multilayers represent a new class of engineering materials that are made up of alternating nanometer scale layers of two different components. In the present work a titanium (Ti) monolayer was combined with titanium diboride (TiB₂) to form a Ti/TiB₂ nano-multilayer. Designed experimental parameters enabled an evaluation of the effects of direct current bias voltage (U_b) and bilayer thickness (Λ) during multilayer deposition on the mechanical properties of reactively sputtered Ti/TiB₂ multilayer films. Their nanostructures and mechanical properties were characterized and analyzed using X-ray photoelectron spectroscopy (XPS), low-angle and high-angle X-ray diffraction (XRD), plan-view and cross-sectional high-resolution transmission electron microscopy (HRTEM), and microindentation measurements. Under the optimal bias voltage of U_b = − 60 V, it was found that Λ (varied from 1.1 to 9.8 nm) was the most important factor which dominated the nanostructure and hardness. The hardness values obtained varied from 12 GPa for Ti and 15 GPa for TiB₂ monolayers, up to 33 GPa for the hardest Ti/TiB₂ multilayer at Λ = 1.9 nm. The observed hardness enhancement correlated to the layer thickness, followed a relation similar to the Hall-Petch strengthening dependence, with a generalized power of ∼ 0.6. In addition, the structural barriers between two materials (hcp Ti/amorphous TiB₂) and stress relaxation at interfaces within multilayer films resulted in a reduction of crack propagation and high-hardness.     

Cr1−xAlxN coatings deposited by lateral rotating cathode arc for high speed machining applications

In this work, a series of Cr_1−xAl_xN (0 ≤ x ≤ 0.7) coatings were deposited on high speed steel substrates by a vacuum arc reactive deposition process from two lateral rotating elemental chromium and aluminum cathodes in a flowing pure nitrogen atmosphere. The composition, structural, mechanical, and tribological properties of the as-deposited coatings were systematically characterized by energy dispersive analysis of X-rays, X-ray diffraction, nanoindentation, and ball-on-disc tribometer experiments. All of the as-deposited CrAlN coatings exhibited a higher hardness than CrN, showing a maximum hardness of about 40 GPa (at around X = 0.63) which is twice higher than that of the CrN. The wear performance under ambient conditions of the CrAlN coatings was found much better, with both lower friction coefficient and wear rate, than TiAlN coatings deposited by the same technique. The wear rate of the CrAlN coatings against alumina counterpart was about 2-3 orders in magnitude lower than that of the TiAlN coatings. Selected CrAlN coatings with the highest hardness were also deposited on some WC-based end-mills. An evident better performance of the CrAlN-coated end-mills was observed than the TiAlN-coated ones for cutting a hardened tool steel material under high speed machining conditions.     

Effect of substrate temperature and bias voltage on the crystallite orientation in RF magnetron sputtered AlN thin films

The crystal orientation and residual stress of AlN thin films were investigated using X-ray diffraction and substrate curvature method. The AlN films were deposited on Si(100) by RF magnetron sputtering in a mixed plasma of argon and nitrogen under various substrate negative bias V_s (up to − 100 V) and deposition temperature T_s up to 800 °C. The results show that lower temperature and moderate bias favor the formation of (002) plane parallel to the substrate surface. On the contrary, strong biasing beyond − 75 V and deposition temperature higher than 400 °C lead to the growth of (100) plane. At the same time nanoindentation hardness and compressive stress measured by substrate curvature method showed significant enhancement with substrate bias and temperature. The biased samples develop compressive stress while unbiased samples exhibit tensile or compressive stress depending on plasma power and temperature. The relationships between deposition conditions and crystallographic orientation of the films are discussed in terms of surface energy minimization and ion bombardment effects.