Effect of substrate bias voltage on the texture and microstructure of Cu thin films deposited by ion beam deposition

Cu thin films deposited by non-mass separated ion beam deposition under various substrate bias voltages were investigated. The film textures and microstructure were analyzed by X-ray diffraction and field emission scanning electron microscopy, and the resistivity of the film was measured with the Van der Pauw method. It was found that the optimum negative substrate bias voltage for Cu films was −50 V. The Cu films deposited without substrate bias voltage showed a columnar grain structure with small grains and random orientation. However, when a substrate bias voltage of −50 V was applied, the Cu films had a non-columnar structure with a strong (111) texture and large grains. The electrical resistivity of the Cu films decreased remarkably with increasing negative substrate bias voltage, and reaching a minimum value of 1.8±0.13 μΩ cm at the substrate bias voltage of −50V.     

Dielectric properties of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films deposited onto Ti and TiO<Subscript>2</Subscript> layer

The present study describes the dielectric properties of RF sputtered Ta₂O₅ thin films as a function of the buffer layer and annealing condition. The buffer layers were Ti or TiO₂. And the thin film was annealed in various conditions. The X-ray pattern results showed that the phase of the RF sputtered Ta₂O₅ thin films was amorphous and this state was kept stable to RTA (rapid thermal annealing) even at 700°C. Measurements of the electrical and dielectric properties of the reactive sputtered Ta₂O₅ fabricated in two simple metal insulator semiconductor (MIS) structures, (Cu/Ta₂O₅/Ti/Si/Cu and Cu/Ta₂O₅/TiO₂/Si/Cu) indicated that the amorphous Ta₂O₅ grown on Ti possesses a high dielectric constant (30–70) and high leakage current (10⁻¹–10⁻⁴ A/cm²), whereas a relatively low dielectric constant (−10) and low leakage current (−10⁻¹⁰ A/cm²) were observed in the amorphous Ta₂O₅ deposited on the TiO₂ buffer layer. In addition, the leakage current mechanisms of the two amorphous Ta₂O₅ thin films were investigated by plotting the relation of current density (J) vs. applied electric field (E). The Ta₂O₅/Ti film exhibited three dominant conduction mechanism regimes contributed by the Ohmic emission at low electrical field, by the Schottky emission at intermediate field and by the Poole-Frenkel emission at high field. In the case of Ta₂O₅/TiO₂ film, the two conduction mechanisms, the Ohmic and Schottky emissions, governed the leakage current density behavior. The conduction mechanisms at various electric fields applied were related to the diffusion of Ta, Ti and O, followed by the creation of vacancies, in the rapid thermal treated capacitors.     

Effects of dopant content on optical and electrical properties of In<Subscript>2</Subscript>O<Subscript>3</Subscript>: W transparent conductive films

The In2O3:W (IWO) films with different W content were deposited on glass substrate using direct current sputtering method. The structure, surface morphology, and optical and electrical properties were investigated. Results showed that both the carrier concentration and carrier mobility were increased with the doping of W. The IWO film with the lowest resistivity of 1. 0× 10-3 Ω· cm, highest carrier mobility of 43. 7 cm2. W-1. s-1 and carrier concentration of 1. 4× 1020 cm-3 was obtained at the content of 2. 8 wt. ％. The average optical transmittance from 300 nm to 900 nm reached 87. 6％.     

Precise analysis of H, C, N, and O as dominant impurities in Cu films: complementary use of SIMS and GDMS

Secondary ion mass spectrometry (SIMS) and glow discharge mass spectrometry (GDMS) were used to determine the impurity concentrations of hydrogen, carbon, nitrogen, and oxygen elements in Cu films, and the results of SIMS and GDMS were carefully interpreted. The Cu films were deposited on Si (100) substrates at substrate bias voltages ranging from 0 V to −150 V using a non-mass separated ion beam deposition method. From the results of SIMS using a Cs⁻ ion beam, as a whole, many high intensity peaks were observed in the Cu films deposited without substrate bias voltage. From the quantitative GDMS results, these peaks were determined to be signals detected as a cluster state such as C_xH_x, O_xH_x, C_xO_xH_x. Therefore, using a combination of these dominant impurities, all the unknown peaks observed in the SIMS results could be interpreted. Moreover, it was found that the dominant impurities having a great influence on the film purity were hydrogen, carbon, nitrogen, and oxygen.     

Cathodic arc plasma deposition of nano-multilayered Zr-O/Al-O thin films

Thin films of Zr-O/Al-O were deposited on SKD 11 tool steel substrate using Zr and Al cathodes in a cathodic arc plasma deposition system. The substrates were mounted on a rotating holder which alternatively exposed them to plasma from the two cathodes. The influence of the Zr and Al cathode arc currents and the substrate bias on the mechanical and the structural properties of the films were investigated. Films with a nano-layered structure of alternating Al-rich and Zr-rich layers were obtained. The Zr layers contained nano-crystallites of (101) oriented t-ZrO structure. Crystallites with α-Al₂O₃ structure were observed only when the substrate was negatively biased in the 100-150 V range. The hardness of the film decreased with the increase of Zr cathode current from 60 to 80 A, increased when the Al cathode current increased from 25 to 30 A, and decreased when the Al cathode current increased from 30 to 35 A. The hardness of the film increased with the increase of bias voltage up to − 150 V and then decreased with further increase of the negative bias. The film structure was elucidated by HRTEM microscopy. Good correlation between the residual stress and the hardness enhancement of the films was observed.     

Oxidation Behavior of TiAl<Subscript>3</Subscript>/Al Composite Coating on Orthorhombic-Ti<Subscript>2</Subscript>AlNb Based Alloy at Different Temperatures

This paper reports the oxidation behavior of TiAl₃/Al composite coating deposited by cold spray. The substrate alloy was orthorhombic-Ti-22Al-26Nb (at.%). The oxidation kinetics of the coating was tested at 650, 800, and 950 °C, respectively. The parabolic rate constant for the coating oxidized at 650 °C was k _p = 7.2 × 10⁻² mg·cm⁻²·h^−1/2 for the tested 1200 h. For the coating oxidized at 800 °C, the oxidation kinetics could be separated into two stages with k _p value of 39.8 × 10⁻² mg·cm⁻²·h^−1/2 for the initial 910 h and 17.7 × 10⁻² mg·cm⁻²·h^−1/2 for the stage thereafter. For the coating oxidized at 950 °C, the oxidation kinetics can be separated into three stages with k _p of 136.9 × 10⁻² mg·cm⁻²·h^−1/2 in the first 100 h, followed by 26.9 × 10⁻² mg·cm⁻²·h^−1/2 from 100 to 310 h, and 11.8 × 10⁻² mg·cm⁻²·h^−1/2 from 310 to 1098 h. XRD, SEM, and EPMA were used to study the microstructure of the coating. The results indicated that the oxidation took place throughout the entire coating instead of only at the surface. The aluminum phase in the composite coating was soon oxidized to Al₂O₃ in all tested cases. The aluminum in TiAl₃ phase was depleted gradually and oxidized to Al₂O₃ along with the degradation of TiAl₃ to TiAl₂ and TiAl as the temperature increased and time proceeded. AlTi₂N was also a typical oxidation product at temperature higher than 800 °C. The experimental results also indicated that the protection of the coating was attributed greatly to the interlayer formed between the coating and the substrate.     

Comparative study on mechanical properties of MoSiN multilayer films deposited on Si(100) and Ti-covered Si(100) substrates

We deposited MoSiN multilayer films using a MoSi₂ target via pulsed-DC and radio-frequency (RF) magnetron sputtering methods. For the fabrication of the Ti-covered Si(100) substrate, we also grew Ti layers via the RF magnetron sputtering method. To improve the mechanical properties of the as-grown MoSiN thin films, argon and nitrogen plasmas ignited by RF and pulse DC under vacuum conditions were also used with a total pressure of 0.7 Pa, a substrate bias of −100 V, and a substrate ion current density of 1.5 mA/cm². The as-grown MoSiN films were investigated for hardness (Gpa) and macro-stress(s) properties, and the relationship between film composition and micro-structures was analyzed using x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). The maximum hardness and stress values of the MoSiN films were 32 GPa and −2.5 GPa, respectively, depending on variations of substrates and reactive gas.     

Obtaining ZrO<Subscript>2</Subscript> + CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> + TiO<Subscript>2</Subscript>/Ti compositions by plasma-electrolytic oxidation of titanium and investigating their properties

Regularities of the effect produced by Ce₂(SO₄)₃ salt introduced in an aqueous electrolyte containing Zr(SO₄)₂ on the plasma-electrolytic formation of oxide coatings on titanium, their composition, and structure are studied. ZrO₂ + CeO _x + TiO₂ three-phase oxide coatings with a thickness about 10 μm are obtained. The coatings involve ZrO₂ cubic phase. The ZrO₂-to-TiO₂ phase ratio in the coatings can be controlled. The zirconium content in the coatings reaches 20 at %, while that of cerium is 3–5 at %. The surface layer (∼3-nm thick) contains Ce³⁺ (∼30%) and Ce⁴⁺ (∼70%). Pores in the surface part of coatings have diameters around or smaller than 1 μm and are regularly arranged. The obtained systems have a certain catalytic activity with respect to the oxidation of CO to CO₂ at temperatures above 400–450°C. The coatings are corrosion-resistant in chloride-containing environments. The thickness h of coatings depending on the charge Q supplied to the cell is described by the equation h = h ₀(Q/Q ₀) ⁿ , where n = 0.35 and h ₀ is the thickness of the coating formed at Q ₀ = 1 C/cm².     

Oxidation of Ti−B−C−N film deposited on steel

Ti−B−C−N films were deposited on tool steel substrates by a DC magnetron sputtering system, and their oxidation characteristics were investigated at the temperature range of 200°C to 800°C for up to 5 h in air. Ti−B−C−N films were oxidized to TiO₂, which further reacted with FeO to become FeTiO₃. The films did not display good oxidation resistance, owing to the evaporation of B, C and N into the air, film breakage, and poor film adherence owing to the mismatch of the thermal expansion coefficients between film and substrate.     

Properties of Zr-ZrC-ZrC/DLC gradient films on TiNi alloy by the PIIID technique combined with PECVD

The Zr-ZrC-ZrC/DLC gradient composite films were prepared on TiNi alloy by the techniques combined plasma immersion ion implantation and deposition (PIIID) and plasma enhanced chemical vapor deposition (PECVD). With this method, the Zr-ZrC intermixed layers can be obtained by the ion implantation and deposition before the deposition of the ZrC/DLC composite film. In our study, an optimal gradient composite film has been deposited on the NiTi alloys by optimizing the process parameters for implantation and deposition. The surface topography was observed through AFM and the influence of the deposition voltage on the surface topography of the film was investigated. XPS results indicate that on the outmost layer, the Zr ions are mixed with the DLC film and form ZrC phase, the binding energy of C 1s and the composition concentration of ZrC depend heavily on the bias voltage. With the increase of bias voltage, the content of ZrC and the ratio of sp³/sp² firstly increases, reaching a maximum value at 200 V, and then decreases. The nano-indentation and friction experiments indicate that the gradient composite film at 200 V has a higher hardness and lower friction coefficient compared with that of the bare NiTi alloy. The microscratch curve tests indicate that gradient composite films have an excellent bonding property comparing to undoped DLC film. Based on the electrochemical measurement and ion releasing tests, we have found that the gradient composite films exhibit better corrosion resistance property and higher depression ability for the Ni ion releasing from the NiTi substrate in the Hank's solution at 37°C.     

Characteristics of IZSO films deposited by a co-sputtering system

In−Zn−Sn−O films were deposited on a polycarbonate (PC) substrate by a magnetron co-sputtering system using two cathodes (DC, RF) without substrate heating. Two types of ITO targets (target A: doped with 5 wt.% SnO₂, target B: doped with 10 wt.% SnO₂) were used as an In−Sn−O source. The ITO and ZnO targets were sputtered by DC and RF discharges, respectively, and the composition of the In−Zn−Sn−O films was controlled via the power ratio of each cathode. In the case of ITO target A, the lowest resistivity (4.3×10⁻⁴ Ωcm) was obtained for the film deposited at the RF power (ZnO) of 55W. In the case of ITO target B, the lowest resistivity (2.9×10⁻⁴ Ωcm) of the film was obtained at the RF power (ZnO) of 30W, which was attributed to the increase in carrier density. Hall mobility decreased with increasing carrier density, which could be explained by the increase in ionized impurity scattering.     

Kinetics of formation and growth of epitaxial SrTiO<Subscript>3</Subscript> films of single-crystal (001) SrTiO<Subscript>3</Subscript> supports

The aim of this study was to quantitatively estimate the kinetics of the formation and growth of oxide SrTiO₃ (STO) films using the method of the in situ reflection high-energy electron diffraction (RHEED) and compare the obtained results with the known growth models and theoretical estimates. The kinetics of the relaxation and crystallization of particles is studied under pulsed laser deposition (PLD) from oxide targets onto (001) STO supports or onto the surface of STO film growth at 650–800°C. Deposition frequencies of 0.1–10 Hz typical of PLD were used. The surface morphology and film structure was studied ex situ using the methods of AFM and X-ray-structural analysis. It was found that the time of relaxation of deposited particles is within the range of 2–20 s, which greatly exceeds or is comparable to the relative pulse duration. It was experimentally shown that structural distortions in epitaxial films for temperatures of ≤900°C are mainly due to the high rate of deposition and limited surface mobility of particles. The effect of structural relaxation in films is observed after the end of deposition; the time constant of bulk structural relaxation is ∼10 − ∼10² s or more. The obtained kinetic parameters of the formation of an oxide structure may be useful for the development of crystallization theory, as well as to optimize the conditions of epitaxial oxide film growth.     

Physical processes of the formation of structure and properties of films of transition-metal diborides

Physical processes are described that occur during the formation of the structure of film coatings of transition-metal diborides produced by the method of magnetron sputtering (in the DC and HF modes). The factors that affect the formation of the structure of the film coatings (energy of condensing atoms and substrate temperature) have been determined. The role of each factor in the formation of the film structure is shown. The optimum energy conditions for the formation of the transition-metal diboride films with the highest physicomechanical characteristics have been determined, i.e., the bias voltage equal to −50 V (DC regime) and ±50 V (HF regime); the substrate temperature ∼500°C. Under these conditions, there are formed hyperstoichiometric MB_2.4 films with a grain size of ∼20 nm and greater. If the energy supplied to the growing film is insufficient in order to stimulate its crystallization and the formation of a (00.1) growth texture, hypostoichiometric nanostructured or amorphous (clusterized) films are formed. A physical model of the formation of critical nuclei leading to growth of a columnar structure in the films of transition-metal diborides is suggested.     

Electrochemical properties of carbon-coated LiFePO<Subscript>4</Subscript> and LiFe<Subscript>0.98</Subscript>Mn<Subscript>0.02</Subscript>PO<Subscript>4</Subscript> cathode materials synthesized by solid-state reaction

Olivine structured LiFePO4/C (lithium iron phosphate) and Mn2+-doped LiFe0. 98Mn0. 024/C powders were synthesized by the solid-state reaction. The effects of manganese partial substitution and different carbon content coating on the surface of LiFePO4 were considered. The structures and electrochemical properties of the samples were measured by X-ray diffraction (XRD), cyclic voltammetry (CV), charge/discharge tests at different current densities, and electrochemical impedance spectroscopy (EIS). The electrochemical properties of LiFePO4 cathodes with x wt. ％ carbon coating (x=3, 7, 11, 15) at γ=0. 2C, 2C (1C=170 mAh·g-1) between 2. 5 and 4. 3 V were investigated. The measured results mean that the LiFePO4 with 7 wt. ％ carbon coating shows the best rate performance. The discharge capacity of LiFe0. 98Mn0. 02PO4/C composite is found to be 165 mAh·g 1 at a discharge rate, γ=0. 2C, and 105 mAh·g-1 at γ=2C, respectively. After 10cycles, the discharge capacity has rarely fallen, while that of the pristine LiFePO4/C cathode is 150 mAh·g-1 and 98 mAh·g-1 at γ=0. 2 and 2C, respectively. Compared to the discharge capacities of both electrodes above, the evident improvement of the electrochemical performance is observed, which is ascribed to the enhancement of the electronic conductivity and diffusion kinetics by carbon coating and Mn2+-substitution.     

Cathodic arc plasma deposition of nano-multilayered ZrN/AlSiN thin films

Thin films of ZrN/AlSiN were deposited on SKD 11 tool steel substrate using Zr and AlSi cathodes in an Ar/N₂ gas mixture in a cathodic arc plasma deposition system. The influence of the AlSi cathode arc current and the substrate bias voltage on the mechanical and structural properties of the films was investigated. X-ray diffraction, electron probe micro-analysis, high resolution transmission electron microscopy, nanoindentation and profilometry were used to characterize the films. The ZrN/AlSiN thin films had a multilayered structure by rotating the substrate in which nano-crystalline ZrN layers alternated with amorphous AlSiN layers. The hardness of the films increased as the AlSi cathode arc current was raised from 35 to 40 A, and then decreased with a further increase of the current. The hardness of the films increased with the increase of the bias voltage from − 50 to − 100 V. Further increase in the bias voltage decreased the hardness. The films exhibited a maximum hardness of 38 GPa. With the increase of bias voltage, the residual stress of the films correlated well with the hardness.     

Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties

In this work, the influence of substrate bias voltage on the microhardness, adhesive strength, friction coefficient, and wear rate of AIP Cr₂O₃ films deposited on AISI 304 stainless steel substrates was investigated systematically. In the meantime, the wear failure mechanism of AIP Cr₂O₃ films in dry sliding contact was also analyzed and discussed. The results showed that the mechanical properties, adhesive behaviors, and tribological performance of AIP Cr₂O₃ films were greatly altered by applying a negative bias voltage. With increasing the bias voltage, the hardness, critical load, and tribological performance of AIP Cr₂O₃ films first were improved gradually, and then were impaired slightly again. When the bias voltage is − 100 V, the Cr₂O₃ film possessed the highest hardness, the strongest adhesion, and the best wear resistance. The essence of above phenomena was attributed to the variations of microstructure and defect density in the films induced by the substrate bias voltage increase. The main wear failure mechanism of AIP Cr₂O₃ films is crack initiation and propagation under the high contact stresses, inducing the local film with small area to flake off gradually, and eventually leading to the formation of a wear scar.     

Oxidation Behavior of Nickel-Base Single-Crystal Superalloy with Rhenium-Base Diffusion Barrier Coating System at 1,423 K in Air

The oxidation behavior of the nickel-base single-crystal superalloy TMS-82+ coated with a duplex Re(W)–Cr–Ni/Ni(Cr)–Al layer was investigated in air at 1,150 °C for up to 100 h. The coating layer was formed by electroplating Re(Ni) and Ni(W) films on the alloy, followed by Cr-pack cementation at 1,300 °C, and as a result, forming a continuous Re(W)–Cr–Ni diffusion-barrier layer. A Ni film containing fine Zr particles was then electroplated on the duplex layer, followed by Al pack cementation at 1,000 °C for 1 and 5 h to form an Al reservoir layer with a duplex Ni₂Al₃/γ-Ni layer, which changed quickly to γ-Ni phase containing (10∼13)at.% Al for the 1 h Al-pack coat and a mixture of γ′-Ni₃Al and β-NiAl phases for the 5 h Al-pack coat during high-temperature oxidation. A protective α-Al₂O₃ scale formed during oxidation at 1,150 °C in air, and parabolic rate constants of 7.4 × 10⁻¹¹ and 6.6 × 10⁻¹⁰ kg² m⁻⁴ s⁻¹ were obtained for the 1 h- and 5 h-Al pack-coatings, respectively. There was little change in the structures of the superalloy substrate after oxidation at 1,150 °C in air for up to 100 h. It was found that the Re(W)–Cr–Ni layer remained stable, acting as a diffusion barrier between the alloy substrate and Al reservoir layers.     

Study on nanocrystalline Cr2O3 films deposited by arc ion plating: I. composition, morphology, and microstructure analysis

Nanocrystalline Cr₂O₃ thin films were deposited on silicon wafers with (100) orientation by arc ion plating (AIP) technique at various negative bias voltages. By virtue of X-ray diffraction analysis, scanning electron microscope, and high-resolution transmission electron microscope, the influence of substrate bias voltage on the film growth process, microstructure, and characteristics was investigated systematically, including the phase constituents, grain size, lattice constant, chemical compositions, as well as surface and cross-section morphologies. With increasing the bias voltage, the grain size and lattice constant of AIP Cr₂O₃ films first decreased slightly, and then increased gradually again. Both reached the minimum (35 nm and 13.57 Å) when the bias voltage was − 100 V. However, the bias voltage had little effect on the phase constituents and chemical compositions of AIP Cr₂O₃ films. During the film growth process, the surfaces of Cr₂O₃ films were getting smoother with the negative bias voltage increase, in the meantime, their microstructures evolved from coarse columnar grains to fine columnar grains, short columnar recrystallized grains, and fine columnar grains again.     

Multiferroic BiFeO<Subscript>3</Subscript> thick film fabrication by aerosol deposition

BiFeO₃ (BFO) multiferroic materials in the crystalline phase require very delicate processing conditions. In order to fabricate a high quality BFO thick film, aerosol deposition (AD) was employed and the phase evolution and multiferroic properties of the film were investigated for different annealing temperatures. A BFO thick film annealed at 500 °C had a dielectric constant of 80 at 1 kHz and possessed ferroelectric characteristics. At an applied electric field of ∼900 kV/cm, the remaining polarization and coercive field (E_c) were approximately 7.5 μC/cm² and 370 kV/cm, respectively. In addition, the BFO thick film fabricated via AD and annealed at 500 °C showed weak ferromagnetic behavior between −1250 Oe and +1250 Oe and was saturated at the higher magnetic field strength, showing ferromagnetic behavior.     

Removal of hydrocarbon films from the surface of metal materials in air glow discharge

Selective oxidation of amorphous hydrocarbon (a-C:H) films deposited on tungsten, molybdenum, and stainless steel by chemically active oxygen (with a source of glow discharge in air) has been studied. Film oxidation was carried out both directly in the discharge and in the area of afterglow. It has been shown that plasmolysis products of a-C:H films in air are CO, CO₂, H₂O, and H₂. The rate of film oxidation depended on the position in relation to plasma and decreased in the hollow cathode-positive column-afterglow series. The coefficients of carbon erosion in afterglow increased from 10⁻³ to 10⁻² at. C/at. O at a temperature increase from room temperature to 130°C.