SiOxNy thin films with variable refraction index: Microstructural, chemical and mechanical properties

In this work amorphous silicon oxynitride films with similar composition (ca. Si_0.40N_0.45O_0.10) were deposited by reactive magnetron sputtering from a pure Si target under different N₂-Ar mixtures. Rutherford backscattering (RBS) studies revealed that the coatings presented similar composition but different density. The mechanical properties evaluated by nanoindentation show also a dependence on the deposition conditions that does not correlate with a change in composition. An increase in nitrogen content in the gas phase results in a decrease of hardness and Young's modulus.The microstructural study by high resolution scanning electron microscopy (SEM-FEG) on non-metalized samples allowed the detection of a close porosity in the form of nano-voids (3-15 nm in size), particularly in the coatings prepared under pure N₂ gas. It has been shown how the presence of the close porosity allows tuning the refraction index of the films in a wide range of values without modifying significantly the chemical, thermal and mechanical stability of the film.     

Silane effects on the surface morphology and abrasion resistance of transparent SiO2/UV-curable resin nano-composites

Transparent ultraviolet curable nano-composite coatings consisting of nano-sized SiO₂ and acrylate resin have been developed to improve the abrasion resistance of organic polymers. The nano-sized SiO₂ particles were surface-modified using various amounts of 3-methacryloxypropyltrimethoxysilane. The 3-methacryloxypropyltrimethoxysilane concentration effects on the surface morphology and abrasion resistance of the transparent SiO₂/ultraviolet-curable resin nano-composites were investigated using scanning electron microscopy, atomic force microscopy, and ultraviolet-visible spectrophotometer. The results showed that as the 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio increased from 0.2 to 0.6, the dispersion, compatibility and cross-linking density between the 3-methacryloxypropyltrimethoxysilane-modified SiO₂ particles and acrylate resin were improved, leading to an increase in abrasion resistance. However, as the 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio was increased to 1.5, the additional 3-methacryloxypropyltrimethoxysilane may exceed that needed to fill the pores with the probability of SiO₂ nano-particles existing on the coating surface was lower than that for samples with a 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio of 0.6. This produced a decrease in abrasion resistance.     

Optical emission spectroscopy investigation of sputtering discharge used for SiOxNy thin films deposition and correlation with the film composition

The r.f. discharge of sputtering silicon target using argon-oxygen-nitrogen plasma was investigated by optical emission spectroscopy. Electronic temperature (T_e) and emission line intensity were measured for different plasma parameters: pressure (from 0.3 to 0.7 Pa), power density (0.6-5.7 W cm⁻²) and gas composition. At high oxygen concentration in the plasma, both T_e and the target self-bias voltage (V_b) steeply decrease. Such behaviour traduces the target poisoning phenomenon. In order to control the deposition process, emission line intensity of different species present in the plasma were compared to the ArI (λ = 696.54 nm) line intensity and then correlated to the film composition analysed by Rutherford Backscattering Spectroscopy.     

Improvement in mechanical and optical properties of vapour chopped vacuum evaporated PANI/PMMA composite thin film

PANI/PMMA composite was synthesized by emulsion polymerization pathway and the composite thin film was obtained by vacuum evaporation. The effect of vapour chopping and varying PMMA concentration was also studied. The FTIR spectra showed that the PANI/PMMA composite thin film deposited as a short chain oligomers. Increase in transmittance and decrease in refractive index was obtained with increasing concentration of PMMA, which further increased the adhesion and decreased intrinsic stress. The vapour chopping improved its optical as well as mechanical properties and produced smoother surface morphology. Increase of PMMA made the film more amorphous and does not change its band gap.     

Influence of Y doping concentration on the properties of nanostructured MxZn1−xO (M=Y) thin film deposited by nebulizer spray pyrolysis technique

Yttrium doped Zinc Oxide (Y_xZn_1−xO) thin films deposited at a substrate temperature 400 °C. The effect of substrate temperature on the structural, surface morphology, compositional, optical and electrical properties of Y_xZn_1−xO thin films was studied. X-ray diffraction studies show that all films are polycrystalline in nature with hexagonal crystal structure having highly textured (002) plane parallel to the surface of the substrate. The structural parameters, such as lattice constants (a and c), crystallite size (D), dislocation density (δ), microstrain (σ) and texture coefficient were calculated for different yttrium doping concentrations (x). High resolution scanning electron microscopy measurements reveal that the surface morphology of the films change from platelet like grains to hexagonal structure with grain size increase due to the yttrium doping. Energy dispersive spectroscopy confirms the presence of Y, Zn and O elements in the films prepared. Optical studies showed that all samples have a strong optical transmittance higher than 70% in the visible range. A slight shift of the absorption edge towards the large wavelengths was observed as the Y doping concentration increased. This result shows that the band gap is slightly decreased from 3.10 to 2.05 eV with increase of the yttrium doping concentrations (up to 7.5%) and then slightly increased. Room temperature PL measurements were done and the band-to-band emission energies of films were determined and reported. The complex impedance of the 10%Y doped ZnO film shows two distinguished semicircles and the diameter of the arcs got decreased in diameter as the temperature increases from 70 to 175 °C.     

Influence of silicon on the microstructure and mechanical properties of Zr-Si-N composite films

A series of Zr-Si-N composite films with different Si contents were synthesized in an Ar and N₂ mixture atmosphere by the bi-target reactive magnetron sputtering method. These films’ composition, microstructure and mechanical properties were characterized by energy dispersive spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy and nanoindentation. Experimental results revealed that after the addition of silicon, Si₃N₄ interfacial phase formed on the surface of ZrN grains and prevented them from growing up. Zr-Si-N composite films were strengthened at low Si content with the hardness and elastic modulus reaching their maximum values of 29.8 and 352 GPa at 6.2 at% Si, respectively. With a further increase of Si content, the crystalline Zr-Si-N films gradually transformed into amorphous, accompanied with a remarkable fall of films’ mechanical properties. This limited enhancement of mechanical properties in the Zr-Si-N films may be due to the low wettability of Si₃N₄ on the surface of ZrN grains.     

Nanoindentation study of size effect and loading rate effect on mechanical properties of a thin film metallic glass Cu49.3Zr50.7

A binary metallic glass (MG) Cu_49.3Zr_50.7 in the form of thin film was successfully grown on a Si (1 0 0) substrate by magnetron sputtering. The mechanical properties, specifically, hardness and modulus at various peak loads and loading rates were characterized through instrumented nanoindentation. Unlike other metallic glasses showing an indentation size effect (ISE), the composition of this study does not have an ISE, which is phenomenologically the result of the negligible length scale according to the strain gradient plasticity model. The proportional specimen resistance model is applicable to the load-displacement behaviors and suggests that the frictional effect is too small to contribute to the ISE. The occurrence of plasticity depends on loading rates and can be delayed so that the displacement during the load holding segment increases logarithmically. In addition, the hardness and modulus are both dependent on the loading rates as well, i.e., they increase as the loading rate increases up to 0.1 mN/s and then hold constant, which is independent of creep time (≤100 s). These loading-rate-dependent behaviors are interpreted as the result of viscoelastic effect rather than free volume kinetics.     

The interface structure of nano-SiO2/PA66 composites and its influence on material's mechanical and thermal properties

The PA66-based nanocomposites containing surface-modified nano-SiO₂ were prepared by melt compounding. The interface structure formed in composite system was investigated by thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The influence of interface structure on material's mechanical and thermal properties was also studied. The results indicated that the PA66 chains were attached to the surface of modified-silica nanoparticles by chemical bonding and physical absorption mode, accompanying the formation of the composites network structure. With the addition of modified silica, the strength and stiffness of composites were all reinforced: the observed increase depended on the formation of the interface structure based on hydrogen bonding and covalent bonding. Furthermore, the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that the presence of modified silica could affect the crystallization behavior of the PA66 matrix and lead to glass transition temperature of composites a shift to higher temperature.     

Effect of spin polarization on the optical properties of Co-doped TiO2 thin films

A non-linear variation of bandgap energy with Co doping is observed in sputter deposited Co-doped TiO₂ thin films. This peculiar behavior is explained on the basis of mechanical stress in the films together with spin polarization due to s,p-d exchange interaction between the localized Co 3d electrons and delocalized electrons. Quantitative analyses of mechanical stress and grain boundary barrier potential due to spin polarization are performed from the below bandgap absorption tail. Furthermore, anomalous variations in both the refractive indices and extinction coefficients with Co doping are noted and are explained on the basis of ab-initio calculations based on density functional theory.     

Influence of substrate bias voltage on structure and properties of the CrAlN films deposited by unbalanced magnetron sputtering

The CrAlN films were deposited on silicon and stainless steel substrates by unbalanced magnetron sputtering system. The influence of substrate bias on deposition rate, composition, structure, morphology and properties of the CrAlN films was investigated. The results showed that, with the increase of the substrate bias voltage, the deposition rate decreased accompanied by a change of the preferred orientation of the CrAlN film from (2 2 0) to (2 0 0). The grain size and the average surface roughness of the CrAlN films declined as the bias voltage increases above −100 V. The morphology of the films changed from obviously columnar to dense glass-like structure with the increase of the bias voltage from −50 to −250 V. Meanwhile, the films deposited at moderate bias voltage had better mechanical and tribological properties, while the films deposited at higher bias voltage showed better corrosion resistance. It was found that the corrosion resistance improvement was not only attributed to the low pinhole density of the film, but also to chemical composition of films.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

First-principles study of the electronic and magnetic properties of a Nickel-Zinc ferrite: ZnxNi1−xFe2O4

Using first-principles density functional theory within the generalized gradient approximation method, the effect of Zn doping on electronic and magnetic properties of NiFe₂O₄ ferrite spinel has been studied. The crystal structure of the compounds is assigned to a pseudocubic structure and the lattice constant increases as the Zn concentration increases. Our spin-polarized calculations give a half-metallic state for NiFe₂O₄ and a normal metal state for Zn_xNi_1−xFe₂O₄ (0<x≤0.5). Based on the magnetic properties calculations, it is found that the saturation magnetic moment enhances linearly with increase in the Zn content in NiFe₂O₄. The Zn doping in NiFe₂O₄ also induces strong ferrimagnetism since it decreases the magnetic moment of A-sites.     

The effect of (00l) crystal plane orientation on the thermoelectric properties of Bi2Te3 thin film

Highly (00l)-oriented pure Bi₂Te₃ films with in-plane layered grown columnar nanostructure have been fabricated by a simple magnetron co-sputtering method. Compared with ordinary Bi₂Te₃ film and bulk materials, the electrical conductivity and Seebeck coefficient of such films have been greatly increased simultaneously due to raised carrier mobility and electron scattering parameter, while the thermal conductivity has been decreased due to phonon scattering by grain boundaries between columnar grains and interfaces between each layers. The power factor has reached as large as 33.7 μW cm⁻¹ K⁻², and the out-of-plane thermal conductivity is reduced to 0.86 W m⁻¹ K⁻¹. Our results confirm that tailoring nanoscale structures inside thermoelectric films effectively enhances their performances.     

Study on the electronic structure and optical properties of different Al constituent Ga1−xAlxAs

Using quantum mechanics GASTEP software package based on the first principle density function theory, the electronic structure and optical properties of Ga_1−xAl_xAs at different Al constituent are calculated. Result shows that with the increase of Al constituent, the band gap of Ga_1−xAl_xAs increases and varies from direct band gap to indirect band gap; the absorption band edge and the absorption peak move to high-energy side; the static reflectivity decreases. With the increasing of the incident photon energy, Ga_1−xAl_xAs shows metal reflective properties in certain energy range. With the increasing of Al constituent, static dielectric constant decreases and the intersection of dielectric function and the x-axis move towards high-energy side; the peak of energy loss function move to low-energy side and the peak value reduces.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

Influence of long-term aqueous exposure on surface properties of plasma sprayed oxides Al2O3, TiO2 and their mixture Al2O3-13TiO2

The surface properties of plasma sprayed Al₂O₃- and TiO₂-based coating materials were characterized in order to investigate the influence of surface strain and phase inhomogenity. The materials were water exposed up to 8 months. The bulk crystallographic structure, dissolution behaviour, effective charge (zeta potential, isoelectric point), surface compositions and oxidation states were determined. In addition, the properties of the aging solutions, such as conductivity, supernatant pH (point of zero charge), and redox potential, were monitored during aging.It was shown that the materials were stable under aging conditions, but that considerable surface rearrangements, such as dissolution-reprecipitation and surface site redistributions may occur. However, overall only minor changes in surface properties results from this restructuring process.     

Effect of Cr on the magnetic properties of evaporated CoxCr1−x/Si(1 0 0) and CoxCr1−x/glass thin films

Series of Co_xCr_1−x thin films have been evaporated under vacuum onto Si(1 0 0) and glass substrates. Thickness ranges from 17 to 220 nm, and x from 0.80 to 0.88. Alternating gradient field magnetometer (AGFM) measurements provided saturation magnetization values ranging from 220 to 1200 emu/cm³. Values of squareness exceeding 0.8 have been measured. Coercive field may reach values up to 700 Oe, depending on the percentage of chromium, as well as the substrate nature and the direction of the applied magnetic field. The saturation magnetization value decreases as the Cr content increases. In order to study their dynamical magnetic properties, Brillouin Light Scattering (BLS) measurements have been performed on these samples. Stiffness constant value and anisotropy magnetic field were adjusted to fit the experimental BLS spectra. These results are analyzed and correlated.     

强磁场对不同厚度Fe80Ni20薄膜的微观结构及磁性能的影响

有无6 T强磁场条件下利用分子束气相沉积方法制备了不同厚度的Fe₈₀Ni₂₀薄膜. 研究发现, 薄膜的面内矫顽力随厚度增加而降低且符合Neel理论; 矩形比随厚度的增加先快速增大后缓慢降低; 6 T磁场抑制了颗粒团聚及异常长大, 并降低了薄膜表面的粗糙度, 这使薄膜的矫顽力要小于无磁场作用的薄膜, 矩形比大于无磁场作用的薄膜; 而且薄膜在垂直于基片表面的6 T磁场作用下由0 T下的面内磁各向异性转变为磁各向同性. 关键词： 强磁场 气相沉积 微观结构 磁性能     

Studies on the structural and electrical properties of F-doped SnO2 film prepared by APCVD

Fluorine-doped tin oxide films (SnO₂:F, FTO) were deposited by atmosphere pressure chemical vapor deposition (APCVD) on Na-Ca-Si glass coated with a diffusion barrier layer of SiO_xC_y. The effects of post-heating time at 700 °C on the structural and electrical properties of SnO₂:F films were investigated. The results showed that SnO₂:F films were polycrystalline with tetragonal SnO₂ structure, SnO phase was present in SnO₂ film, and abnormal grain growth was observed. The element distribution in the film depth was measured with X-ray photoelectron spectroscopy (XPS) and revealed that when the heating time increased from 202 s to 262 s, the oxygen content in the surface increased from 78.63% to 83.38%. The resistivity increased from 3.13 × 10⁻⁴ for as-deposited films to 4.73 × 10⁻⁴ Ω cm when post-heated for 262 s. Hall mobility is limited by the ionized impurity scattering rather than the grain boundary scattering.     

The study of optimal oxidation time and different temperatures for high quality VO2 thin film based on the sputtering oxidation coupling method

The high quality Vanadium dioxide (VO₂) thin films have been fabricated successfully on sapphire by a simple novel sputtering oxidation coupling (SOC) method. All VO₂ thin film samples exhibit a good metal-insulator transition (MIT) at about 340 K. The optimal oxidation time at different temperatures has been experimentally investigated. We report on the relationship between optimal oxidation time and different temperatures of metal vanadium thin film samples of 101 nm thickness by oxidation in air. It is found that the optimal oxidation time ln(t) as a function of temperature 1/T shows a significant linear relationship among 703 K-783 K, in good agreement with the Wagner's high-temperature oxidation model.