Effects of substrate bias voltage on adhesion of DC magnetron-sputtered copper films on E24 carbon steel: investigations by Auger electron spectroscopy

The adhesion strength of copper thin films on E24 carbon steel substrates was studied using the scratch test via the critical load. Coatings were deposited by a DC magnetron sputtering system. All substrates were mechanically polished; some of them were directly coated and others were ion-etched by argon ions prior to deposition process. The effects of substrate negative bias voltage during the film growth were investigated. Experimental results showed that the critical load depended on the bias voltage and that the higher bias voltage, the better adhesion. It was also observed that the deposition rate of deposited films gradually decreased with the increase of the substrate bias voltage. Furthermore, the working pressure during the substrate ion bombardment etching greatly affected the critical load. Scanning electron microscopy was used to observe the scratch tracks to accurately evaluate the critical load. Substrate surface profiles obtained by a mechanical profilometer showed that the critical load increased with the increase of the surface roughness. The analysis by Auger electron spectroscopy revealed that the interface, in case of an unbiased substrate, was relatively narrow and abrupt. However, in case of a bias voltage application, the interface was wider and more diffuse. These results suggest that the mechanisms involved in critical load enhancement are due firstly to the substrate surface roughness and the substrate temperature generated by the ion bombardment, secondly to the physical mixing in the interfacial domain and the densification of the deposited material created by the bias voltage.     

Investigation of substrate bias effects on the reactively sputtered ZrN diffusion barrier films

ZrN diffusion barrier films were prepared by DC reactive magnetron sputtering under different negative substrate bias. The composition, microstructure, resistivity and diffusion barrier properties of ZrN films, with respect to substrate bias, were studied by means of X-ray diffraction, electron probe microanalyzer, Auger electron spectroscopy, and four point probe method. Results showed that the deposition rate and impurity oxygen content of ZrN films were substantially influenced by the resputtering effects due to the ion bombardment on the film surface. The competition between surface energy and strain energy made the preferred orientation of ZrN films change from (1 1 1) to (2 0 0) and then back to highly (1 1 1) preferred orientation as a function of substrate bias. The application of negative substrate bias could effectively decrease the electrical resistivity due to the decrease of impurity oxygen content and the densification of films, resulting from the moderate-energy ion irradiation. The biased ZrN films could successfully be used as a diffusion barrier layer, between Cu and SiO₂, even up to the high temperature of 800 °C for 30 min.     

Growth of CeO2 Films on Sapphire and MgO by rf Magnetron Sputtering

pitaxial CeO₂ films on (1102) sapphire and (100) MgO were grown by rf magnetron sputtering. Substrate temperature, total pressure, and oxygen-to-argon mole ratio were varied to explore the optimal deposition condition. The X-ray diffraction spectra indicate that the degree of crystallinity of the deposited CeO₂ films depends on the oxygen- to-argon mole ratio and the substrate temperature. Atomic force microscopy images of the films on sapphire and MgO showed that substrate temperature and total pressure affect surface roughness. The best film surface is smooth with a 0.89 nm root-mean-square roughness. The quality of the films on MgO showed a strong dependence on substrate pretreatments. Epitaxial CeO₂ films could be grown on pre- annealed or pre-etched MgO if substrate temperatures reached higher than 790^deg;C. Additionally, the effect of ion bombardment at low total pressures on the crystallinity of the films was examined by growing the films outside the plasma region. Experimental results indicate that the ion bombardment does not prevent the films from preferred orientation.     

The role of ion-induced substrate damage in thin film adhesion strength

Variable-energy positrons are combined with Auger electron spectroscopy, scanning electron microscopy, and scratch test critical load measurements to study interfacial properties in thin film adhesion. This work complements an earlier investigation of the adhesion strength enhancement produced by ion bombardment of the substrate surface before deposition. In this study, we have investigated SiO₂ films deposited by radio-frequency (RF) sputtering onto stainless steel substrates. Extended ion bombardment etching leads to three related effects: the scratch test critical load is increased significantly, Auger electron spectroscopy shows a greater penetration of the film material into the substrate; and the interfacial positron annihilation signal is dominated by large, open-volume defects. These results are interpreted as confirmation that ion bombardment leads to the formation of microvoids in the interface layer and, consequently, to an increased adhesion strength by allowing mechanical interlocking between the coating and the substrate.     

Synthesis of nanocrystalline diamond films by DC plasma-assisted argon-rich hot filament chemical vapor deposition

Continuous nanocrystalline diamond (NCD) films were grown in an argon-rich gas atmosphere with relatively high growth rates by sustaining a low power (5 W) DC plasma in a hot filament chemical vapor deposition system (HFCVD). The parameter window for the synthesis of NCD films was studied as a function of argon, methane and hydrogen concentrations, as well as substrate temperature and DC bias. The results are consistent with reports indicating that the DC plasma induces re-nucleation by ion bombardment during the initial growth step and helps to maintain the atomic H and hydrocarbon species near the growing surface. It was found that DC plasma-assisted HFCVD enables high NCD growth rates and expands the parameter window, rendering it unnecessary to heat the filament above 2800 K.     

Surfaces of undoped and boron doped polycrystalline diamond films influenced by negative DC bias voltage

The hydrogen ion bombardment is performed by applying a negative bias voltage to the substrate during microwave plasma chemical vapor deposition process, using only hydrogen as reactant gas. The size of (001) faces increases after hydrogen ion etching while other grains are etched off. The surfaces of [001]-oriented films after doping boron are investigated by scanning electron microscopy (SEM) and cathodoluminescent (CL) spectra. The absence of the band-A emission in the CL spectra means a low density of dislocation in the films. It is the first time that the peak at 741.5 nm and the broad peak at approximately 575 and 625 nm in the CL spectra were reduced efficiently after boron doping in (001) polycrystalline diamond films and to propose that these phenomena should be explained in simple terms with penetration of the lattice nets of the [001]-oriented faces model.     

The effect of a buffer layer on the structure and the performance of cutting-tools for ZrWN films that are deposited using DCMS and HIPIMS

This paper determines the optimal settings for the deposition of ZrWN nitride films using reactive direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HIPIMS), with pure Zr and W metal targets and Ar plasma and N₂ reactive gases. The materials tested as buffer layers are metal tungsten (W) and tungsten nitride (WN) thin films. Using a Taguchi method, this study determines the effect of deposition parameters for the buffer layer (W DC power, substrate bias, N₂/(N₂+Ar) flow rate and substrate temperature) on the structural and mechanical properties, and the dry machining performance of cutting-tools for multilayer ZrWN/W and ZrWN/WN/substrates. In the confirmation runs using grey Taguchi analysis, there is an improvement of 32.31% and 13.38% in surface roughness and flank wear, respectively. The films are characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (FEI-TEM) and a nanoindenter. The TEM pattern for the ZrWN films shown corresponds to the (111), (200) and (220) planes of the face-center-cubic phase. Pretreatment of a tungsten carbide tool uses oxygen plasma etching to enhance the adhesion of the multilayer ZrWN/WN coating. Compared with coatings that are deposited using DCMS, the samples that are deposited using HIPIMS exhibit a higher film density and a smoother surface. In the HIPIMS mode, the XRD diffraction peaks of the films are sharper and more intense, which indicates an improvement in crystallinity.     

Surface roughness of AlN films deposited on negatively biased silicon and diamond substrates

Our previous studies on AlN microstructures have shown that smooth amorphous films (a-AlN) can be grown on negatively biased Si substrates by the versatile physical vapour deposition technique under reactive magnetron sputtering. These a-AlN films are produced by energetic Ar ion bombardment under negative bias whereas those grown without bias were columnar crystallized ones (c-AlN). Here, we show first that depositing an a-AlN layer on c-AlN/Si structures by switching a suitable bias to the Si substrate can efficiently reduce their surface roughness. We then extend this smoothening method to a c-AlN/Poly-crystallized diamond (PCD) structure to reduce its high surface roughness that hampers using such structures in SAW device design. In fact, the piezoelectric c-AlN surfaces grown on rough diamond surfaces are equally rough. Effectively, the a-AlN layer deposited on the c-AlN/PCD structure brings down the latter's RMS surface roughness to one tenth of its initial RMS roughness, as confirmed here by TEM and AFM observations. The insulating property of the diamond as biased substrate doesn't impede the growth of this a-AlN layer. This smoothening method is without process interruption, where simply a negative bias is switched on to the diamond substrate once the desired piezoelectric c-AlN film thickness as monitored here by in-situ reflectometry, is attained. This as-grown smoothening method can be therefore easily and rapidly implemented and can thus replace time-consuming and costly PCD ionic and/or mechanical polishing. Hopefully, the method can be advantageously applied to c-AlN/nano-crystallized diamond structures (NCD) where the NCD films are not prepared under rigorous conditions meant to minimize their surface roughness.     

Early Stages of Diamond-Film Formation on Cobalt-Cemented Tungsten Carbide

The surface composition of cemented tungsten carbide (WC-5.8 wt% Co) was studied by X-ray photoelectron spectroscopy (XPS), during the early stages of diamond-film deposition, by hot-filament chemical vapor deposition (HFCVD). The nucleated diamond films were analyzed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and automatic image analysis (AIA). The evolution of the surface composition of cemented tungsten carbide during the early stages of diamond-film deposition was strongly dependent on the substrate temperature. At relatively low temperature (750°C), cobalt-rich particles started to segregate at the substrate surface after a few minutes of diamond deposition. The conspicuous segregation of the binder partly inhibited the formation of stable diamond nuclei, through intense carbon dissolution or carbon segregation at the binder surface, but did not affect nucleic growth. At higher temperatures (940°C), no cobalt-rich particles formed at the substrate surface, even after 2 h of deposition. However, XPS results demonstrated the presence of cobalt in a surface layer, although in a lower amount than at 750°C. Nevertheless, the nucleation density of diamond at 940°C was much lower than at 750°C. Gaps between WC grains formed within 10 mins. Therefore, intergranular cobalt was removed at 940°C, a finding attributed to the etching performed by monohydrogen, rather than to binder evaporation. The time evolution of the substrate area fraction covered by diamond islands, S ( t ), was well described by Avrami kinetics for two-dimensional phase transformations, suggesting that diamond formation took place via a heterogeneous nucleation process. The S ( t ) functions exhibited a similar trend at 750° and 940°C, because the higher growth rate of diamond crystallites at higher temperature counteracted the slower nucleation rate at the higher temperature.     

Adhesion studies of radio-frequency sputtered SiO2 films on Ti,stainless steel,Ni and Inconel substrates. Effects of substrate surface ion bombardment etching

The scratch test was applied to determine the adhesion strength of radio-frequency (RF) sputtered SiO₂ films to Ti, stainless steel, Ni and Inconel substrates. The effect of substrate ion bombardment etching was investigated by using a mean critical load derived from a Weibull-like statistical analysis. It was found that the mean critical load values obtained on substrates etched by ion bombardment for a sufficiently long time were two to three times those obtained on mechanically polished substrates. Scratch tracks were observed by scanning electron microscopy and some X-ray spectra were measured after the electron beam of the scanning electron microscope was focused inside the scratch channel. Depth composition profiles were also recorded by Auger electron spectroscopy. No important presence of contamination was observed in the interfacial domain even after mechanical polishing, but the width of this interfacial domain was higher after ion bombardment than after mechanical polishing. This difference in width could result from the formation of microcavities and vacancies at the substrate surface during ion bombardment. In such a case, the significant adhesion improvement should principally occur from an enhanced interlocking of the coating to its substrate.     

Nanodiamond growth on diamond by energetic plasma bombardment

The present work studies the growth of nanodiamond under prolonged DC glow discharge plasma bombardment of 1 μm thick polycrystalline CVD diamond. Using Raman spectroscopy, near edge X-ray absorption fine structure (NEXAFS) and secondary ion mass spectroscopy (SIMS) it is shown that nanodiamond formation on diamond starts directly, skipping the nucleation stage required to form the precursor material with the appropriate density and hydrogen content. On the other hand, the amorphous carbon/nanodiamond composite structure is substantial to the nanodiamond nucleation under energetic plasma bombardment and cannot be eliminated by starting with a micro-crystalline diamond substrate. The results give additional insight to the phenomena of nanocrystalline nucleation and growth under energetic particle bombardment relevant to a variety of systems including bias enhanced nucleation of diamond and cBN deposition by ion assisted methods.     

Heteroepitaxial nucleation of diamond on Si(100) via double bias-assisted hot filament chemical vapor deposition

A new process has been developed to obtain high density epitaxial diamond nucleation via a double bias-assisted hot filament chemical vapor deposition (HFCVD). In the process, a negative bias voltage is applied to the Si substrate and a positive bias voltage is applied to a steel grid placed on top of the hot filaments. With this arrangement, a stable plasma can be generated between the grid and the hot filaments. Ions in the plasma are then drawn to the substrate by a negative substrate bias voltage. The impinging rate of these ions can be easily controlled by adjusting the grid current, and the ion energy can be independently controlled by adjusting the substrate bias voltage. Hence, the energy and dosage of ion bombardment onto the Si(100) substrate can be controlled easily and independently. With the controlled ion bombardment, high density and heteroepitaxial nucleation can be achieved routinely. After the nucleation process, highly textured diamond films were grown by either the HFCVD or the microwave plasma chemical vapor deposition process (MPCVD).     

Application of diamond-like carbon films to the integrated circuit fabrication process

On account of their attractive properties, amorphous diamond-like carbon (DLC) films have been developed as resist materials for lithography and as hard coatings. In this paper, we investigate the etching properties of DLC films and the electrical properties of a pn junction fabricated using DLC films.Using a parallel-plate radio frequency plasma glow discharge, methane gas was decomposed for the deposition of the DLC films on a silicon substrate. Then oxygen was used to etch the films. Properties, such as the etching rate and the cross-sectional profile, were evaluated by atomic force microscopy (AFM). In order to produce the diode, DLC films were applied to resist materials as a part of the fabrication process.The etching rate of DLC films increases with decreasing oxygen pressure. We suspect that the high etching rate at low pressure from the negative bias voltage originates from the sputtering of accelerated ionic species. The bias voltage also increases with decreasing oxygen pressure. In order to estimate the shape of the etched edge, AFM images and cross-sectional profiles of etched DLC films were investigated as a function of oxygen pressure. At high pressure, isotropic etching by neutral radicals occurred, as the shape of the etched edge was not vertical. The top and bottom edges coincided vertically at low pressure because of the high bias voltage. The yield of excellent pn junctions fabricated using DLC films as resist materials was investigated as a function of deposition and etching pressure. From the results of the characteristics of the pn junction and the yield, for the integrated circuit fabrication process the optimum condition for both deposition and etching is at low pressure.     

Deposition and Characterization of Highly Oriented Mg3(VO4)2 Thin Film Catalysts. 2. Controlled Variation of Oxygen Content

Thin films of magnesium vanadates oriented to expose a single crystalline face, could potentially serve as ideal models for high surface area magnesium vanadate catalysts for oxidative dehydrogenation. The growth of oriented films of one particular magnesium vanadate phase, the orthovanadate (Mg₃(VO₄)₂), has been achieved by rf sputter deposition of the orthovanadate onto Au(111) surfaces. X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy have been used to investigate the structure and composition of the films. The orthorhombic orthovanadate grows epitaxially with the (021) plane oriented parallel to the surface. By varying oxygen flow rates during deposition the stoichiometry of the films can be varied from fully oxidized to highly oxygen deficient. At very low oxygen flow rates or in the complete absence of oxygen, a reduced Mg₃V₂O₆ phase is formed. This reduced phase has a cubic structure and grows with the (100) plane parallel to the surface.     

Reactive sputter-deposition of oxygenated amorphous carbon thin films in Ar/O2

Oxygenated amorphous carbon thin films were deposited by DC magnetron sputtering using various argon and oxygen process gas mixtures. The X-ray diffraction data indicated that the predominantly amorphous films had more defined peaks with a higher partial pressure of oxygen. Results indicated that use of oxygen in the working gas enhanced the crystalline nature of the films. Scanning electron and atomic force microscopy revealed that the surface roughness and film topography differed with the oxygen process gas variations. X-ray photoelectron spectroscopy revealed increased surface oxygen content with higher oxygen concentration in the working gas. Raman spectroscopy results suggested that the increased oxygen in the films may have led to a higher percentage of sp³-bonded carbon atoms. The growth rate (deposition rate) of the films decreased as the amount of oxygen increased. This decreased deposition rate was associated with an oxygen etching of the film.     

Characterization of aluminium nitride thin films

Aluminium nitride (AlN) thin films have been synthesized by evaporation of aluminium and simultaneous irradiation with nitrogen ions, ion-vapour deposition method, at the substrate temperature of room temperature or 473K. The kinetic energy of the incident nitrogen ion beam has been kept at 0.5 keV and the deposition rate has been varied from 0.075 to 0.28 nm/s. The structure of the synthesized films has been examined by X-ray diffraction (XRD) and the surface morphology has been characterized by atomic force microscopy (AFM). In the XRD patterns of both films synthesized at room temperature and 473K, the diffraction lines due to the AlN(10.0), (00.2) and (10.1) planes have been discerned. AFM observations reveal that the surface of the films synthesized at 473K becomes rough as compared with the films synthesized at room temperature. This may be attributed to growth of AlN particles on the substrate kept at 473K. Furthermore, in the films synthesized at the 473K substrate, several aggregated protrusions can be observed on the relatively smooth surface at the deposition rate of 0.28 nm/s, while the surface of the films is uniform on nanometre scale at the deposition rate of less than 0.12 nm/s. The present results suggest that the synthesis of the AlN films with uniform surface is feasible by controlling the substrate temperature and the deposition rate.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: Effects of Substrate Pretreatments

The nucleation and growth of diamond films on Nicemented carbide is investigated. Substrates made of WC with 6 wt% of Ni were submitted to grinding, and then to different pretreatments (scratching, etching, and/or decarburization) before diamond deposition. Diamond synthesis was carried out by hot-filament chemical vapor deposition (HFCVD) using a mixture of CH₄ (1% v/v) and H₂. Depositions were performed for different lengths of time with the substrates at various temperatures. The specimens were analyzed before and after deposition by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffractometry (XRD). Raman spectra showed that the phase purity of the diamond films was not affected by the presence of nickel on the substrate surface. After wet etching pretreatments, the nucleation of diamond was enhanced, mainly at the WC grain boundaries. Continuous films were obtained on scratched and etched substrates. The decarburizing treatment led to the formation of metallic tungsten and of brittle nicke–tungsten carbide phases. These phases reacted in the early stages of diamond film formation with gaseous carbon species with a parallel process which competes with stable diamond nucleus formation. The diamond film formed after long-term deposition on these samples was not continuous.     

Boron carbide thin film deposition using supersonic plasma jet with substrate biasing

Hard, microcrystalline boron carbide thin films have been deposited from the thermal dissociation of hydrogen, methane and boron trichloride in a supersonic plasma jet. The influence of negative and positive substrate bias on the film properties and morphology has been investigated. A continuous ion bombardment has been found to increase the film crystallinity, however, it has led to poor adhesion to the substrate. Pulsed d.c. positive biasing has been developed as a means to elevate the electron temperature and control the gas phase chemistry, while limiting the total current flowing in the secondary discharge. In this case, it has been found that the deposition rates increase with bias voltage as a function of the third power, without affecting the film hardness and morphology. Also, the boron-to-carbon atomic ratio of the films increases with increasing positive bias voltage, from carbon-rich to stoichiometric boron carbide. Correlations between deposition rates and gas species line emission indicate that atomic boron is the primary growth species. The pulsed d.c. biasing enhancement presented in this paper constitutes a novel approach to controlling the film composition and deposition rate.     

An XPS study of argon ion beam and oxygen RIE modified BPDA-PDA polyimide as related to adhesion

Modification of polymer surfaces by changing the chemical structure, surface energy, and bonding characteristics has considerable technological importance in the area of adhesion. Reactive ion etching (RIE) and ion beam (IB) bombardment were employed to modify the surfaces of fully imidized 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride-p-diaminophenyl (BPDA-PDA)-based polyimide (PI) films. These modification techniques affect only a shallow surface region, approximately 10-20 nm, and the bulk properties of the polymer are unaffected. The angle-resolved X-ray photoelectron spectroscopy (XPS) technique was used to characterize the PI surfaces modified by argon IB bombardment or oxygen RIE treatment. On the argon ion-bombarded surfaces, the XPS spectra indicate that the carbonyl and imide groups are decreased. Oxygen RIE treatment resulted in an increase in the atomic concentration of oxygen. To understand the surface aging effect, the freshly modified PI surfaces were exposed to laboratory air for 1 and 2 days. The changes in composition as a function of the depth of the modified surface region right after treatment and after aging were determined by the angle-resolved XPS technique (ARXPS). Contact angle measurements were used to determine the polar and dispersion components, the sum of which is the surface free energy. The polar component of the surface free energy shows the greatest change, with an increase of 8.0-9.4 times for both the oxygen RIE and ion beam treatments as compared with the as-cured PI surface. Aging of these modified surfaces resulted in a decrease of surface free energy as compared with the just-modified surfaces. In the case of oxygen RIE treatment, the dispersion component of the surface free energy showed little or no change from the as-cured sample. Adhesion of chromium/copper/chromium (Cr/Cu/Cr) films on PI was determined by peel strength measurements. Significant increases in peel strength, by a factor of 10-80, were shown for the modified surfaces. A good correlation between the peel strength and the experimentally determined polar component of surface energy was shown.     

Study of the surface layer in cBN growth by PVD techniques

A sp² bonded boron nitride (sp² BN) surface layer is sometimes observed on top of cubic boron nitride (cBN) grains for BN films deposited using ion-assisted PVD techniques. Understanding the formation of such surface layer gives a clue to the cBN growth mechanisms. In the current study, the microstructure and phase composition near the top surface of several BN films were investigated in order to clarify the formation mechanism of such a surface layer. All the films investigated were synthesized using ion-assisted PVD techniques, but with different deposition parameters. It was found that such a surface layer is not necessarily present in some of the cBN growth, and its presence depends on the bombardment of ion energy during deposition. The cBN growth mechanisms are discussed based on these observations.