The effect of substrate bias voltage on PbTe films deposited by magnetron sputtering

The PbTe films were deposited onto ITO glass substrate by radio frequency magnetron sputtering. Effect of external direct current electrical field applied between substrate and target on the quality of films was investigated. Stylus surface profile, X-ray diffraction (XRD), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the films. The film thickness was measured by a conventional stylus surface profile. The crystal structure and lattice parameters of films were determined by using XRD. The surface morphology of the films was measured by AFM. The absorption coefficients and optical band gaps of films were found from FTIR. The sheet resistance of the samples was measured with a four-point probe and the resistivity of the film was calculated. All the obtained films were highly textured with a strong (2 0 0) orientation. With increasing bias voltage to −30 V, the property of crystal structure, surface morphology and absorption coefficients and resistivity were improved. However, further increase of substrate bias leads to transformation of the property.     

Effect of asynchronous pulsing parameters on the structure and properties of CrAlN films deposited by pulsed closed field unbalanced magnetron sputtering (P-CFUBMS)

Controlled ion bombardment of growing thin films can be used to modify and improve the film structure and properties. Recently, higher energetic species (up to hundreds eV) were found in the plasma by pulsing the target(s) in magnetron sputtering. In this study, an electrostatic quadrupole plasma mass spectrometer (EQP) has been used in a pulsed closed unbalanced magnetron sputtering (P-CFUBMS) system to investigate the effect of different pulsing parameters (frequency and reverse time) on the ion energies and ion fluxes in the intrinsic plasma during Cr-Al-N film deposition. It is confirmed that pulsing both magnetrons in this P-CFUBMS configuration had a large effect on both the ion energies and ion fluxes generated within the plasma, which are shown to be strongly dependent on pulsing frequency and duty cycle.The effect of pulsing to provide a wide range of ion energies and ion fluxes on the film microstructure, mechanical and tribological properties was investigated using nanoindentation, microtribometry, X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM) and scanning transmission electron microscopy (TEM). In the current study, by taking −50 V substrate bias into consideration, it was found that total ion energies with controlled pulsing parameters to achieve moderate values (70-120 eV) can effectively increase the density and decrease the grain size of Cr-Al-N films. On the other hand, pulsing regimes that produce excessive total ion energy (∼ 200 eV) result in an increase in the residual strain, and point and lattice defects in the film, which will significantly decrease the toughness and tribological properties of the film. Under optimum pulsing conditions (100 kHz and 5.0 μs), Cr-Al-N films with a dense nanostructure (column grain size of 10-40 nm) of super hardness and good wear resistance (41 GPa, 0.099 H/E ratio, 0.46 COF, and a wear rate of 3.4 × 10^− 6 mm³N^− 1 m^− 1) have been deposited using a controlled maximum ion energy bombardment of 122 eV at high ion flux.     

Multi-component nitride coatings derived from Ti-Al-Cr-Si-V target in RF magnetron sputter

The nitride coatings comprised of various constituents Ti, Al, Cr, Si, V were deposited on mild steel by RF magnetron sputtering process. The Ti-Al-Cr-Si-V multi-component target introduced in this study was fabricated by conventional metallurgical method with atomic ratio of each selected element at 1:1:1:1:1. Different coatings were fabricated under various working pressure by adjusting nitrogen flux from 0 to 30 sccm during sputtering. Compositions of the target and the sputtered films were measured by FE-EPMA, and both of them were near equi-molar. According to XRD patterns, amorphous structures were revealed for the metallic and nitride 1 (N = 46.2 at.%) films. The face centered cubic phases were exhibited by nitride 2 and nitride 3 with nitrogen contents around 58 at.%. Two different surface morphologies were investigated by the AFM, and they were consistent with the nanostructure observed in the XRD pattern. In addition, microhardness of the nitride coatings was measured by nanoindentation, and hardness higher than 30 GPa was exhibited in both nitride 2 and nitride 3. The microhardness test provided evidence that the multi-component nitride could be a potential candidate coating for tool steel.     

Effect of bias voltage on microstructure and properties of Ti-doped graphite-like carbon films synthesized by magnetron sputtering

Ti-doped graphite-like carbon (GLC) films with different microstructures and compositions were fabricated using magnetron sputtering technique. The influence of bias voltages on microstructure, hardness, internal stress, adhesion strength and tribological properties of the as-deposited GLC films were systemically investigated. The results showed that with increasing bias voltage, the graphite-like structure component (sp² bond) in the GLC films increased, and the films gradually became much smoother and denser. The nanohardness and compressive internal stress increased significantly with the increase of bias voltage up to −300 V and were constant after −400 V. GLC films deposited with bias voltages in the range of -300--400 V exhibited optimum adhesion strength with the substrates. Both the friction coefficients and the wear rates of GLC films in ambient air and water decreased with increasing voltages in the lower bias range (0--300 V), however, they were constant for higher bias values (beyond −300 V) . In addition, the wear rate of GLC films under water-lubricated condition was significantly higher for voltages below −300 V but lower at high voltage than that under dry friction condition. The excellent tribological performance of Ti-doped GLC films prepared at higher bias voltages of −300--400 V are attributed to their high hardness, tribo-induced lubricating top-layers and planar (2D) graphite-like structure.     

Composition and mechanical properties of AlC, AlN and AlCN thin films obtained by r.f. magnetron sputtering

Aluminum carbide (Al-C), aluminum nitride (Al-N), and aluminum carbonitride (Al-C-N) thin films were grown onto Si [100] substrates by r.f. reactive magnetron sputtering at 400 °C. The Al-N coatings were obtained by sputtering of Al (99.9%) target in Ar/N₂ atmosphere and the Al-C and Al-C-N by co-sputtering of a binary (50% Al, 50% C) target in argon and in Ar/N₂ mixture, respectively. The d.c. bias voltage was varied between 0 and − 150 V. The films were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), Fourier transformed infrared spectroscopy (FTIR) and the mechanical properties by nanoindentation. The structure of the films has been determined by XRD, which shows that amorphous films are formed in all cases. The variation of polarization bias voltage produced chemical differences in the films. As the bias voltage is increased, the Al content is reduced in all three materials. The nitrogen content also varied between 10 and 14 at.% for Al-N coatings, remaining practically constant (21 at.%) for the Al-C-N films. The Berkovich hardness results were 7.0, 17.2 and 9.2 GPa for Al-C, Al-N, and Al-C-N films, respectively.     

X-ray reflectivity studies on DLC films deposited by microwave ECR CVD: Effect of substrate bias

Diamond like carbon (DLC) films were deposited at room temperature on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapor deposition (CVD) process using plasma of methane diluted with argon gas. During deposition, dc self bias (− 25 V to − 200 V) on substrate was varied by application of RF power to the substrate. The influence of substrate bias on density of the deposited films was studied by X-ray reflectivity (XRR). The results from these measurements are further correlated with the results from UV and visible Raman spectroscopy. DLC film is modeled as a structure having three different layers such as low density surface, bulk and interface with the substrate. This three-layer model is used to fit the measured XRR data to evaluate the surface, interface and interlayer roughness, thickness and density of these films. The surface roughness obtained from XRR is correlated with the results from Atomic Force Microscopy (AFM) measurements. The observed results are explained based on the subplantation model for DLC film growth.     

Hexagonal diamond formation on steel substrates by negative bias microwave plasma enhanced chemical vapor deposition

This paper reports for the first time the synthesis of hexagonal diamond thin films on high-speed steel substrates by multi-mode microwave plasma enhanced chemical vapor deposition. Before deposition of the films, the substrate surface was treated by scratching with diamond powder. The deposited films were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy. The XRD patterns of (100) and (101) planes and the Raman peaks at ~ 1317-1322 cm^− 1 were observed, confirming the formation of hexagonal diamond phase in the prepared films. The effects of voltage bias on the phase formation, microstructure and hardness of the films were also studied by setting the voltage to 0, − 70, − 150 and − 190 V. The highest hardness of 23.8 GPa was found in the film having clusters of size about 550 nm deposited under a bias voltage of − 150 V. These clusters were built up of grains of size about 14 nm.     

Investigation of metal distribution and carbide crystallite formation in metal-doped carbon films (a-C:Me, Me = Ti, V, Zr, W) with low metal content

Metal-doped amorphous carbon films (a-C:Me) were deposited at room temperature by magnetron sputtering using a metal (Me = Ti, V, Zr, W) and a graphite target. The metal distribution and the temperature-induced carbide crystallite formation were analyzed by X-ray diffraction (XRD), electron microscopy (TEM, STEM) and X-ray absorption spectroscopy (EXAFS, XANES), focusing on low metal concentrations between 6.5 and 9.5%. In as-deposited samples, the metal atoms are atomically distributed in the carbon matrix without significant formation of carbide particles. With annealing to 900 K the local atomic environment around the metal atoms becomes similar to the carbide. The carbide crystallites grow with annealing up to 1300 K, their size is dependent on the metal type: V > Ti > Zr≈W. W₂C and WC_1 − x crystallites were identified for W-doped films, whereas the monocarbides are formed for the other metals. It is demonstrated, that EXAFS and high resolution electron microscopy are required to get a correct picture of the structure of the analyzed a-C:W films.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

Structural and optical properties of diamond like thin films deposited by asymmetric bipolar pulsed-DC reactive magnetron sputtering

In contrast with PECVD technology, reactive sputtering of graphite allows an independent control of the substrate bias. This characteristic permits the modification of film properties without varying the plasma composition. In the present study, the characteristics of DLC films grown by pulsed-DC reactive sputtering were determined as a function of substrate bias. Asymmetric bipolar pulsed-DC in a gas mixture of Ar and 7.5% CH₄ with substrate bias in the range of − 300 V to 0 V, provided wear resistant a-C:H films with wear rate values in the range of 15 to 23 · 10^− 15 m³ m^− 1 N^− 1. DLC exhibit characteristics associated to hydrogenated DLC films (DLCH), namely: moderate sp³ content and mass density (up to 1.8 g/cm³), low hydrogen content (∼ 30%) and high transparency (> 90%) up to wavelengths of 700 nm with a Tauc gap energy up to 1.9 eV. Moreover, they also showed low stress values and moderate wear rates, as shown in previous studies.     

Mechanical and tribological properties of multi-element (AlCrTaTiZr)N coatings

Multi-element (AlCrTaTiZr)N coatings are deposited onto Si and cemented carbide substrates by reactive RF magnetron sputtering in an Ar + N₂ mixture. The influence of substrate bias voltage, ranging from 0 to − 200 V, on the microstructural, mechanical and tribological properties of these nitride coatings is studied. A reduction in concentration of N and Al is observed with increasing substrate biases. The (AlCrTaTiZr)N coatings show the face-centered-cubic crystal structure (B1-NaCl type). The use of substrate bias changes the microstructure of the (AlCrTaTiZr)N coating from the columns with microvoids in boundaries to the dense and less identified columns. The compressive macrostress increases from − 0.9 GPa to − 3.6 GPa with an increase of substrate bias. The hardness and adhesion increase to peak values of 36.9 GPa and 60.7 N at the bias voltage of − 150 V, respectively. The tribological properties of the (AlCrTaTiZr)N coatings against 100Cr6 steel balls are evaluated by a ball-on-disc tribometer with a 10 N applied load. With an increase of substrate bias, the wear rate reduces while the friction coefficient almost keeps constant at 0.75. The lowest wear rate of 3.65 × 10^− 6 mm³/Nm is obtained for the (AlCrTaTiZr)N coating deposited at the bias voltage of − 150 V.     

Influence of substrate bias, deposition temperature and post-deposition annealing on the structure and properties of multi-principal-component (AlCrMoSiTi)N coatings

Nitride films are deposited from a single equiatomic AlCrMoSiTi target by reactive DC magnetron sputtering. The influence of the substrate bias and deposition temperature on the coating structure and properties are investigated. The bias is varied from 0 to − 200 V while maintaining a substrate temperature of 573 K. And the temperature is changed from 300 to 773 K whilst maintaining a substrate bias of − 100 V. From X-ray diffraction analysis, it is found that all the as-deposited coatings are of a single phase with NaCl-type FCC structure. This is attributed to the high mixing entropy of AlN, CrN, MoN, SiN, and TiN, and the limited diffusion kinetics during coating growth. Specific aspects of the coating, namely the grain size, lattice constant and compressive stress, are seen to be influenced more by substrate bias than deposition temperature. In fact, it is possible to classify the deposited films as large grained (~ 15 nm) with a reduced lattice constant (~ 4.15 Å) and low compressive residual stresses for lower applied substrate biases, and as small grained (~ 4 nm) with an increased lattice constant (~ 4.25 Å) and high compressive residual stresses for applied biases of − 100 V or more. A good correlation between the residual stress and lattice constant under various deposition conditions is found. For the coatings deposited at − 100 V, and at temperatures above 573 K, the hardness could attain to the range of 32 to 35 GPa.Even after annealing in vacuum at 1173 K for 5 h, there is no notable change in the as-deposited phase, grain size or lattice constant of the coatings but an increase in hardness. The thermal stability of microstructure is considered to be a result of the high mixing entropy and sluggish diffusion of these multi-component coatings. For the anneal hardening it is proposed that the overall bonding between target elements and nitrogen is enhanced by thermal energy during annealing.     

Field emission enhancement of ZnO nanorod arrays with hafnium nitride coating

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved with hafnium nitride (HfN_x) coating under proper sputtering condition. HfN_x films with various composition have been coated on ZnO nanorod arrays using a reactive direct current (DC) magnetron sputtering system. Morphology and crystal configuration of the ZnO nanorod arrays were investigated by scanning electron microscopy and X-ray diffraction. The field emission properties of the coated and uncoated ZnO nanorod arrays were characterized. The as-grown ZnO nanorod arrays showed a turn-on electric field of 6.60 V μm^− 1 at a current density of 10 μA cm^− 2 and an emission current density of 1 mA cm^− 2 under the field of 9.32 V μm^− 1. While the turn-on electric field of the coated ZnO nanorod arrays sharply decreased to 2.42 V μm^− 1, an emission current density of 1 mA cm^− 2 under the field of only 4.30 V μm^− 1 can be obtained. A method to accurately measure the work function of the coated films was demonstrated.     

Exploring the potential of high power impulse magnetron sputtering for growth of diamond-like carbon films

Amorphous carbon films are deposited employing high power impulse magnetron sputtering (HiPIMS) at pulsing frequencies of 250 Hz and 1 kHz. Films are also deposited by direct current magnetron sputtering (dcMS), for reference. In both HiPIMS and dcMS cases, unipolar pulsed negative bias voltages up to 150 V are applied to the substrate to tune the energy of the positively charged ions that bombard the growing film. Plasma analysis reveals that HiPIMS leads to generation of a larger number of ions with larger average energies, as compared to dcMS. At the same time, the plasma composition is not affected, with Ar⁺ ions being the dominant ionized species at all deposition conditions. Analysis of the film properties shows that HiPIMS allows for growth of amorphous carbon films with sp³ bond fraction up to 45% and density up to 2.2 g cm^− 3. The corresponding values achieved by dcMS are 30% and 2.05 g cm^− 3, respectively. The larger fraction of sp³ bonds and mass density found in films grown by HiPIMS are explained in light of the more intense ion irradiation provided by the HiPIMS discharge as compared to the dcMS one.     

Magnetron reactively sputtered Ti-DLC coatings on HNBR rubber: The influence of substrate bias

In this study, Ti-containing diamond-like carbon (Ti-DLC) coatings have been deposited on HNBR (hydrogenated nitrile butadiene) rubber and also on Si wafer as reference via unbalanced magnetron reactive sputtering from a Ti target in C₂H₂/Ar plasma. The deposition rates of coatings on rubber and Si wafer were about the same. Columnar structures resulting from a rough interface were often observed in the coatings deposited on rubbers. Only at a high bias voltage of − 300 V the coating on HNBR rubber became column-free whereas a bias voltage of − 100 V could already restrain the columnar structure and thus produced dense and smooth coatings on Si wafer. A segmented morphology of the coatings on HNBR rubber is formed as a result of the large difference in thermal expansion between the coating and HNBR rubber. The crack network that separates the patches plays an important role in maintaining the coating flexibility. The size of the patches reduces with increasing bias voltage and thus the variation of deposition temperature. A high bias voltage enhances the hardness of Ti-coating and the rubber-coating adhesion, and guarantees a good tribological performance. When sliding against ø6 mm 100Cr6 steel ball counterpart, very low coefficients of friction were achieved (< 0.25 for the coated rubber versus > 1.3 for the uncoated). The Ti-DLC coating can be considered as a promising material for the enhancement of tribological performance of rubbers.     

Effect of bias voltage on microstructure and nanomechanical properties of Ti films

In order to investigate nanomechanical properties of nanostructured Ti metallic material, pure Ti films were prepared by magnetron sputtering at the bias voltage of 0-140 V. The microstructure of Ti films was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). It is interesting to find that the microstructure of pure Ti films was characterized by the composite structure of amorphous-like matrix embodied with nanocrystallines, and the crystallization was improved with the increase of bias voltage. The hardness of Ti films measured by nanoindentation tests shows a linear relationship with grain sizes in the scale of 6-15 nm. However, the pure Ti films exhibit a soft tendency characterized by a smaller slope of Hall-Petch relationship. In addition, the effect of bias voltage on the growth orientation of Ti films was discussed.     

Conductive and transparent Bi-doped ZnO thin films prepared by rf magnetron sputtering

Bi-doped ZnO thin films were grown on glass substrates by ratio frequency (rf) magnetron sputtering technique and followed by annealing at 400 °C for 4 h in vacuum (~ 10^− 1 Pa). The effect of argon pressure on the structural, optical, and electrical properties of the Bi-doped films were investigated. The XRD patterns show that the thin films were highly textured along the c-axis and perpendicular to the surface of the substrate. Some excellent properties, such as high transmittance (about 85%) in visible region, low resistivity value of 1.89 × 10^− 3 W cm and high carrier density of 3.45 × 10²⁰ cm^− 3 were obtained for the film deposited at the argon pressure of 2.0 Pa. The optical band gap of the films was found to increase from 3.08 to 3.29 eV as deposition pressure increased from 1 to 3 Pa. The effects of post-annealing treatments had been considered. In spite of its low conductivity comparing with other TCOs, Bi-doping didn't appreciably affect the optical transparency in the visible range of ZnO thin films.     

Nano-tribological characteristics of PZT thin film investigated by atomic force microscopy

In this work, the nano-scale tribological characteristics of PZT thin films (Pb(Zr_xTi_1 − x)O₃: PZT) with various Zr/Ti ratios were investigated using an Atomic Force Microscope (AFM). The PZT thin films deposited by the sol-gel method were characterized by using an AFM, X-Ray Diffraction (XRD), and a nano-indentation technique. From the experimental results, the friction coefficient of the PZT thin film was found to be about 0.1-0.2 under a 0.1-10 μN normal force. It was determined that the wear rate of the PZT thin film was in the order of 10^− 8 mm³/N·cycle. Also, it was observed that the crystalline structure of the PZT was amorphized due to mechanical stress.     

The effect of pulsed magnetron sputtering on the structure and mechanical properties of CrB2 coatings

CrB₂ thin films possess desirable combinations of properties (high hardness, wear resistance, chemical inertness, high thermal and electrical conductivity), which are attractive for a wide range of potential applications. Pulsed magnetron sputtering (PMS) of loosely-packed blended powder targets has allowed the deposition of stoichiometric chromium diboride coatings. The structure and properties of these coatings were found to be strongly dependent on the deposition process parameters; therefore investigation of the coating structures could explain certain differences between them and provide important information about the characteristics of the deposition process. In this study, characterization of the CrB₂ films was performed by scanning and transmission electron microscopy (SEM and TEM) techniques. The microstructures and properties of coatings deposited with different parameters are compared and changes that resulted from the variation of these parameters (particularly the pulsing duty cycle and the substrate biasing conditions) are discussed. The results show that besides the pulsing frequency, the target pulsing duty cycle is an important parameter of the PMS process, which is able to affect such coating properties as hardness, thickness and stress. Coating thickness measurement results suggest more intense bombardment of a growing film by energetic ions at lower values of duty cycle. Structural TEM analysis revealed two extremely different types of coating microstructures, obtained at quite similar substrate biasing conditions, i.e. floating (∼ − 15 V) and negatively biased (− 30 V). It appears that the structures of the coatings deposited at the negatively biased substrate are significantly affected by high-energy ion bombardment, which is a peculiarity of PMS that can modify film growth conditions. These conditions are not present when the substrate is allowed to float.     

Structural investigation of thin films of Ti1−xAlxN ternary nitrides using Ti K-edge X-ray absorption fine structure

Thin films of Ti_1−xAl_xN nitrides were prepared over a large range of composition (0 ≤ x < 1) on Si substrates using nitrogen reactive magnetron sputtering from composite metallic targets. Ti K-edge X-ray Absorption Spectroscopy experiments were carried for a better understanding of the local structure. The evolution of the intensity of Ti K-edge pre-edge peak gives evidence of the incorporation of Ti in hexagonal lattice of AlN for Al-rich films and in cubic lattice of TiN for Ti-rich films. An attempt to determine their atomic structure by combining X-ray diffraction and Ti K-edge Extended X-ray Absorption Fine Structure is presented. The evolution of the nearest neighbour and next-nearest neighbour distances depending on the composition is presented and discussed together the cubic and hexagonal lattice parameters. A possible contribution of amorphous nitrides is suggested.