Ion bombardment-induced nanocrystallization of magnetron-sputtered chromium carbide thin films

Nearly stoichiometric chromium carbide thin films (Cr₃C₂) were deposited by unbalanced r.f. magnetron sputtering of a chromium carbide target in a pure argon discharge. Their microstructure and hardness are shown to be strongly influenced by the working pressure and substrate bias during deposition. Further correlation with the plasma parameters, i.e. the energy and flux of argon ions as well as the flux of film-forming particles, is illustrated, which indicates the momentum transferred by bombarding ions per film-forming particle P_dens which creates a densification and simultaneously does not cause a mobility enhancement to be dominant for the film structure. Below a threshold value of P_dens of about 0.91 u^0.5eV^0.5, the resulting films exhibited an amorphous structure with a relatively low hardness of 1200 HV0.02. A nanocrystalline structure emerged only for larger values of P_dens, and was responsible for a hardness enhancement to 3500 HV0.02.     

Investigation of the rf and dc hollow cathode plasma-jet sputtering systems for the deposition of silicon thin films

Both rf and dc hollow cathode plasma-jet sputtering systems have been investigated for thin film semiconductor deposition. These systems were studied as a modification of the well-known rf hollow cathode plasma jet system. The aim of this modification was to provide low temperature deposition of semiconductor silicon and silicon-based alloys as thin films with these plasma jet systems. As a first step, the deposition of an already well explored, hydrogenated amorphous silicon material, a-Si:H, was chosen for experimentation. Plasma erosion of single crystal silicon nozzles in an Ar and H₂ working gas mixture was utilized for this purpose. A comparison of both dc and rf hollow cathode plasma jets has been made and correlated to the a-Si:H thin film properties. As a preliminary result, large differences between the properties of a-Si:H thin films deposited using dc and rf plasmas have been found. Monohydride Si:H composition was found for a-Si:H films fabricated using the dc plasma jet system under certain experimental conditions. However, predominantly di-hydride and multi-hydride structures and strong oxidization were found for the a-Si:H films deposited using rf plasma excitation. The sputtering efficiencies of both the rf and dc jet sources for silicon films have been found to be similar.     

Nanoscale friction of partially oxidized silicon nitride thin films

The nanoscale friction of partially oxidized silicon nitride thin films deposited by reactive magnetron sputtering was investigated. Post deposition thermal annealing in O₂, trying to simulate the oxidation by atmospheric oxygen in working conditions, formed a partially oxidized layer at the surface with maximum thickness around 10 nm. Unidirectional sliding tests showed a decrease of the low-load friction coefficients of the sliding pair for the samples annealed in oxygen as compared to the non-annealed ones. The results are discussed on the lights of our extension of the crystal chemistry model, which establishes a relationship between ionic potential and friction coefficient.     

Surface modification of NiTi/PZT heterostructure thin films using various protective layers for potential MEMS applications

The present study explored the in-situ deposition of hard and adherent nanocrystalline protective coatings on NiTi/PZT/TiO_x thin film heterostructure prepared by dc/rf magnetron sputtering. Protective layers (AlN, CrN and TiCrN) of approximate thickness (~ 200 nm) were used to improve the surface, mechanical and corrosion properties of NiTi/PZT/TiO_x heterostructure without sacrificing the shape memory effect and ferroelectricity of the NiTi and PZT layers, respectively. The influence of the protective layer on structural, electrical and mechanical properties of NiTi/PZT/TiO_x heterostructure was systematically investigated and the results were compared. Nanoindentation studies were performed at room temperature to determine the hardness and reduced modulus. The surface modified NiTi/PZT/TiO_x heterostructures were found to exhibit high hardness, high elastic modulus and thereby better wear resistance as compared to pure NiTi/PZT/TiO_x films. From the results of potentiodynamic polarization test conducted in 1 M NaCl solution, the CrTiN coated NiTi/PZT/TiO_x heterostructure showed the best corrosion resistance with the lowest corrosion current density (1.52 × 10^? 8 A cm^? 2) and the highest protective efficiency (96.8%). The results presented here prove the potential of a surface modified NiTi/PZT/TiO_x heterostructure to be used in various microelectromechanical (MEMS) applications.     

Low temperature growth of thin film coatings for the surface modification of dental prostheses

In this work we present some results about the low temperature, plasma-assisted growth of silicon-oxygen amorphous thin film alloys (a-SiO_x) on different types of dental materials used for the fabrication of dental prostheses. The a-SiO_x films were grown at substrate temperatures lower than 70 °C by a PECVD deposition system using silane (SiH₄) and nitrous oxide (N₂O) as precursor gases. The chemical bonding structure of the films was investigated by Fourier transform infra-red spectroscopy (FTIR), while the morphological characteristics of the dental materials were analyzed before and after the coating deposition by means of high-resolution mechanical profilometry. The surface energy of dental materials was estimated before and after the coating process by contact angle measurements, revealing that the coating produced a considerable change of surface energy in all the tested samples, evidenced by a contact angle reduction from more than 90° to less than 10°. Some tests were also performed to estimate the effect of the coating on the bacterial adhesion properties, revealing that the a-SiO_x coatings show some effectiveness in reducing the bacterial adhesion on the dental materials surface.     

Preparation and characterization of silicon-substituted hydroxyapatite coating by a biomimetic process on titanium substrate

A biomimetic method has been used to prepare silicon-substituted hydroxyapatite coatings on titanium substrates. The surface structures of the coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and Fourier transformed infrared spectroscopy (FTIR). Si substituted hydroxyapatite (Si-HA) coatings with different Si contents were deposited successfully on the titanium substrate by immersing the pretreated titanium substrate into silicon containing supersaturated solutions (SSS) with different SiO₃²⁻ concentrations. The pretreatment of the Ti substrate in a mixed alkaline (NaOH + Ca(OH₂)) followed by a heat treatment produced a 3D porous surface structure with rutile and CaTiO₃ as main phases, which contributed mainly to the fast precipitation and deposition of Si-HA. FTIR results showed that Si in the Si-HA coating existed in the form of SiO₄⁴⁻ groups. The cross-section microstructure was observed by scanning electronic microscopy and the shear strength was tested. The coating was about 5-10 μm in thickness and no interval was observed at the interface between the coating and the substrate. Shear strength testing showed that Si-HA/Ti exhibited higher shear strength than HA/Ti due to the existence of the SiO₄⁴⁻ group in the coating.     

Surface characterization and properties of silicon nitride films prepared by ion-assisted deposition

Silicon nitride (SiN) films had been prepared at low substrate temperature (100 °C) using the ion-assisted deposition (IAD) process. The films had been analyzed by the measurement of X-ray diffraction, atomic force microscopy, Fourier transform infrared spectrometry, nano indenter, and ellipsometry. The effects of N-ion current density on the surface morphology, compositional, mechanical, and infrared optical properties of SiN thin films were investigated. The results showed that the stoichiometric Si₃N₄ thin film with desirable properties, such as continuous and smooth surface morphology, extremely low hydrogen content, mechanical strong, and low extinction coefficient, could be obtained by using the IAD technique.     

Physical properties and characterization of Ag doped CdS thin films

Thin films of cadmium sulfide with very well defined preferential orientation and relatively high absorption coefficient were fabricated by thermal evaporation technique. The research is focused to the fabrication and characterization of the compositional data of CdS thin films obtained by using X-ray diffraction, scanning electron microscope along with energy dispersive X-ray spectroscopy. The optical properties were studied by using a UV-VIS-NIR spectrophotometer. The effects of silver-doping by ion exchange process on the properties of as-deposited CdS thin films have been investigated.     

Pulsed laser modification of plasma-sprayed coatings: Experimental processing of hydroxyapatite and numerical simulation

A pulsed CO₂ laser was used to treat plasma-sprayed hydroxyapatite coatings. Pulses of 0.74 ms duration and powers equal to 41.6 and 45.3 W were focused onto a 300 μm spot of the coatings surface. The laser beam was scanned with speeds of 6.4 and 9.6 mm/s. The morphology of laser-treated deposits was observed by scanning electron microscopy (SEM) and the crystal phases identified using X-ray diffraction (XRD). This technique enabled also the determination of quantitative phase composition. The laser treatment process was modeled using the Fusion-2D, software and the temperature fields and depth of molten material were predicted. The latter were compared with the experimental ones found in metallographically prepared cross-sections. A reasonable convergence between the model and experiment was achieved after careful optimisation of initial material parameters as such coefficient of optical absorption and emissivity.     

Microstructures and electrical conductance of silver nanocrystalline thin films on flexible polymer substrates

Using sputtering technique, silver nanocrystalline thin films were deposited on two different polymer substrates, namely pretreated nylon and polyester fabrics, under identical conditions. It is found that the difference of the electrical conductance between the two samples is quite large. The highest conductivity obtained from the coated nylon fabric is 2.4 × 10⁷ Sm^− 1, indicating the feasibility to fabricate wearable electrodes using silver coated fabrics. However, the electrical conductance of the coated polyester fibre is found to be lower by six orders of magnitude. Transmission electron microscopy reveals that the silver grains coated on the polyester fibre are spatially separated while the silver grains coated on the nylon fibre are connective. The pre-deposition surface conditions of the fibres are suggested to be responsible to the remarkable differences in the electrical conductance and microstructures of the silver nanocrystalline films.     

Microstructure and electrical properties of Ti-Si-C-Ag nanocomposite thin films

Ti-Si-C-Ag nanocomposite coatings consisting of nanocrystalline TiC in an amorphous Si matrix with segregated Ag were deposited by dual magnetron sputtering from Ti₃SiC₂ and Ag targets. As evidenced by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, for Ag contents below 10 at.%, the Ag forms ∼ 10 nm large crystallites that are homogeneously distributed in the films. For higher Ag contents, coalescence during growth results in the formation of > ∼ 100 nm Ag islands on the film surface. The electrical resistivity of the coatings was measured in a four-point-probe setup, and ranged from 340 μΩcm (for Ti-Si-C coatings without Ag) to 40 μΩcm (for high Ag content).     

Printing of uniform PZT thin films for MEMS applications

A flexible manufacturing method for the deposition of lead zirconate titanate (PZT) thin films based on ink jet printing has been developed and used to fabricate a first functioning piezoelectric micromachined transducer by printing. The performance of the printed PZT based transducer was fit to established models to determine piezoelectric coupling and dielectric properties. The piezoelectric coefficient, d₃₁, for printed PZT was between −75 pC/N and −95 pC/N. The relative permittivity was 750–890 and the dielectric loss tangent was 2.4–2.8%. This process enables digital deposition of printed devices with the key properties within the range required for high performance piezoelectric MEMS.     

Structural and mechanical properties of amorphous silicon carbonitride films prepared by vapor-transport chemical vapor deposition

The deposition of amorphous silicon carbonitride (a-SiCN:H) films has been successfully achieved through an in-house developed vapor-transport chemical vapor deposition (VT-CVD) technique in a nitrogenated atmosphere. Polydimethylsilane (PDMS) was used as a single-source precursor for both silicon and carbon, while NH₃ was mixed with argon to ensure the in-situ nitrogenation of the films. The chemical bonding and the atomic composition of the a-SiCN:H films were systematically investigated, as a function of their N content, by means of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). AFM was used to obtain 2-D and 3-D views of the films. The mechanical properties [(hardness (H) and Young's modulus (E)] of the freshly prepared films were investigated by the nanoindentation technique. It is shown that by controlling the NH₃/Ar gas flow ratio in the reactor, a-SiCN:H films with various N contents [(0-27) at.% range] are achieved. On the microstructural level, the increase incorporation of N in the a-SiCN:H films is found not only to lead to C atom substitution by N atoms in the local Si-C-N environment but also to an enhanced incorporation of hydrogen bonded to both Si and N. Furthermore, the increase incorporation of N in the a-SiCN:H films resulted in an increase of the average R_rms surface roughness from 4 to 12 nm. Moreover, the films became porous with pore size and density increase as a result of increasing N at.%. Ultimately, both H and E of the a-SiCN:H films were found to be sensitive to their N content, as they decrease (from ~ 17 GPa and 160 GPa to ~ 13 GPa and 136 GPa, respectively) when the N content is increased from 0 to 27 at.%. The formation of Si-N, Si-H, and N-H bonds at the detriment of the more stiff Si-C bonds is thought to account for the observed lowering of the mechanical properties of the a-SiCN:H films as their N content increased.     

AgMgAl metallic glassy and intermetallic thin films for electric contact applications

The AgMgAl thin films, in an attempt in replacing the expensive pure Au contact films, are prepared by co-sputtering. The surface morphology, roughness, amorphous or crystalline atomic structure, grain size, and electric resistivity are systematically examined. Depending on the film compositions, the films can be fully amorphous or fully nanocrystalline, or a composite with the mixture of nanocrystalline phases dispersed in the amorphous matrix. Under the as-sputtered condition, the crystalline group has the lowest resistivity, ranging from 27 to 37 μΩ·cm, the composite group lies in the middle, 31–70 μΩ·cm, and the fully amorphous group possesses the highest resistivity, 87–122 μΩ·cm. Appropriate short thermal annealing for the amorphous films can drastically lower the resistivity down to as low as 9 μΩ·cm, already compatible to pure Au (3–7 μΩ·cm). This study demonstrates the feasibility of the AgMgAl films in replacing the pure Au.     

Surface characterization of plasma sprayed pure and reinforced hydroxyapatite coating on Ti6Al4V alloy

Hydroxyapatite coatings suffer from poor mechanical properties like fretting fatigue, toughness and abrasive wear resistance. These properties can be enhanced by incorporation of secondary ceramic and metallic reinforcements in HA. An attempt has been made to deposit HA and HA reinforced with 10 wt.% (80Al₂O₃-20TiO₂) by plasma spray process on Ti6Al4V substrate. These coatings have been characterized using SEM/EDAX, XRD and FTIR spectroscopy. Corrosion studies have been done in SBF solution. Bio compatibility study is not included in this work. Reinforcement has enhanced the tensile strength. There is marginal improvement in microhardness and surface roughness with reinforcement. Both pure and reinforced coatings show superior resistance against corrosion in simulated body fluid.     

The effect of film composition on the structure and mechanical properties of NiTi shape memory thin films

Shape memory NiTi-based thin films approximately 2 μm thick were deposited onto Si (100) substrates at room temperature by simultaneous DC magnetron sputter deposition from separate elemental Ni and Ti targets. The effect of composition on film structure, surface morphology, transformation temperature and mechanical behavior was studied using variable temperature X-ray diffraction, atomic force microscopy, electrical resistivity, and nanoindentation. The films showed the expected shape memory and superelasticity behavior corresponding to the different film compositions, comparable with bulk properties. The transformation from the low temperature martensitic phase to the high temperature parent phase takes place above room temperature in Ti-rich and near-equiatomic films, and below room temperature in Ni-rich films. Mechanical properties of films investigated at room temperature by a series of nanoindentations at mN loads (indentation depth < 200 nm) with a spherical indenter demonstrate superelasticity in Ni-rich material and martensitic deformation for Ti-rich and near-equiatomic compositions.     

Enhanced power factor of Indium co-doped ZnO:Al thin films deposited by RF sputtering for high temperature thermoelectrics

An improvement in the thermoelectric power factor of Al doped ZnO has been achieved by means of co-doping with indium using a dual magnetron sputtering system. The concentration of indium in the film was varied from 0 to 10 atomic % by varying the RF power of the In target, with the ZnO:Al target fixed at 100 W. It has been found that the films with In concentrations at or below 5 at.% have no significant change in microstructure, and yet a marked improvement in thermopower. At higher doping levels, the Seebeck coefficient continues to increase, however poly-crystallinity is induced in the ZnO matrix which results in a considerable decrease in electrical conductivity. This factor ultimately has a negative impact on the materials power factor. Taking into account the films studied, (ZnO)Al_.03In_.02 exhibited the best thermoelectric properties with an electrical conductivity of 5.88 × 10² S/cm and a Seebeck coefficient of −220 μV/K at 975 K, resulting in a power factor is 22.1 × 10⁻⁴ Wm⁻¹ K⁻², which is three times greater than for the film with no In doping. Film microstructure, composition, and thermal stability were investigated using X-ray diffraction, scanning electron microscopy, and Auger electron spectroscopy.     

Room temperature process for chemical vapor deposition of amorphous silicon carbide thin film using monomethylsilane gas

The silicon carbide thin film formation process, which was completely performed at room temperature, was developed by employing a reactive silicon surface preparation using argon plasma and a chemical vapor deposition using monomethylsilane gas. Time-of-flight secondary ion mass spectrometry showed that silicon-carbon bonds existed in the obtained film, the surface of which could remain specular after exposure to hydrogen chloride gas at 800 °C. The silicon dangling bonds formed at the silicon surface by the argon plasma are considered to easily accept the monomethylsilane molecules at room temperature to produce the amorphous silicon carbide film thicker than monolayer. Thus, the entire silicon carbide thin film formation process at room temperature is possible.     

Electrosynthesis and characterization of polymer films on silicon substrates for applications in micromanipulation

Aniline and p-phenylenediamine were electrochemically oxidized in aqueous solutions by potentiodynamic deposition using cyclic voltammetry (CV) technique. Resulting polymer films electrodeposited on Si substrates were identified by infrared spectroscopy as polyaniline and poly(p-phenylenediamine) films. Cyclic voltammograms demonstrated that poly(p-phenylenediamine) films are non conductive contrary to polyaniline films which are conductive and electropolymerized through an autocatalytic mechanism. The morphological features (thickness, roughness, morphology) of the electrodeposited polymer films were determined using profilometry, scanning electron microscopy (SEM) and atomic force microscopy (AFM). Adhesion force properties of polymer films were also studied by means of force–distance curves obtained by atomic force microscopy. The influence of some experimental parameters (potential scan rate, number of potential scans) was also studied. Thus, it was shown that the potential scan rate strongly influenced both morphological features and force adhesion, when the influence of the number of potential scans was less important. Under optimal conditions, it was possible to obtain low adhesive polymer films that could be useful to coat the fingers of the gripper and improve the Si objects manipulation tasks.