Microstructural characterizations and hardness evaluation of d.c. reactive magnetron sputtered CrN thin films on stainless steel substrate

Chromium nitride (CrN) thin films were deposited on stainless steel (grade: SA304) substrate by using d.c. reactive magnetron sputtering and the influence of process parameters such as substrate temperature, pressure, and power on their microstructural characteristics were investigated in the present work. The CrN films were characterized with X-ray diffraction (XRD) to reveal the formation of different phases and its texture. The films showed the (111) preferred orientation but its intensity decreased, while intensity of peak (200) increased with increase in working pressure. The mixture of CrN and Cr₂N phases were identified at low working pressure and temperature. The preferred orientations of CrN thin films are strongly influenced by sputtering conditions, thickness, and the induced residual stress in the films as observed in the present work. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology and surface topography of thin films, respectively. The study shows that the hardness of films strongly depends on the grain size and the film density, which are influenced by combined effect of the working pressure, temperature, and power of the sputtering process.     

Femtosecond laser deposited zinc oxide film and its optical properties

Zinc oxide (ZnO) thin films have been grown on Si (100) substrates using a femto-second pulsed laser deposition (fsPLD) technique. The effects of substrate temperature and laser energy on the structural, surface morphological and optical properties of the films are discussed. The X-ray diffraction results show that the films are highly c-axis oriented when grown at 80 °C and (103)-oriented at 500 °C. In the laser energy range of 1.0 mJ-2.0 mJ, the c-axis orientation increases and the mean grain size decreases for the films deposited at 80 °C. The field emission scanning electron microscopy indicates that the films have a typical hexagonal structure. The optical transmissivity results show that the transmittance increases with the increasing substrate temperature. In addition, the photoluminescence spectra excited with 325 nm light at room temperature are studied. The structural properties of ZnO films grown using nanosecond (KrF) laser are also discussed.     

Characteristics of highly orientated BiFeO3 thin films on a LaNiO3-coated Si substrate by RF sputtering

BiFeO₃ (BFO) films were grown on LaNiO₃-coated Si substrate by a RF magnetron sputtering system at temperatures in the range of 300-700 °C. X-ray reflectivity and high-resolution diffraction measurements were employed to characterize the microstructure of these films. For a substrate temperature below 300 °C and at 700 °C only partially crystalline films and completely randomly polycrystalline films were grown, whereas highly (001)-orientated BFO film was obtained for a substrate temperature in the range of 400-600 °C. The crystalline quality of BFO thin films increase as the deposition temperature increase except for the film deposited at 700 °C. The fitted result from X-ray reflectivity curves show that the densities of the BFO films are slightly less than their bulk values. For the BFO films deposited at 300-600 °C, the higher the deposition temperature, the larger the remnant polarization and surface roughness of the films present.     

Effect of heat treatment on characteristics of nanocrystalline ZnO films by electron beam evaporation

Zinc oxide thin films have been grown on glass substrate at room temperature by electron beam evaporation and then were annealed in annealing pressure 600 mbar at different temperatures ranging from 250 to 550 °C for 30 min. Electrical, optical and structural properties of thin films such as electrical resistivity, optical transmittance, band gap and grain size have been obtained as a function of annealing temperature. X-ray diffraction has shown that the maximum intensity peak corresponds to the (002) predominant orientation for ZnO films annealed at various temperatures. The full width at half maximum, decreases after annealing treatment which proves the crystal quality improvement. Scanning electron microscopy images show that the grain size becomes larger by increasing annealing temperature and this result agrees with the X-ray diffraction analysis.     

Growth of SrTiO3 thin epitaxial films by aerosol MOCVD

SrTiO₃ thin films were prepared by aerosol metal-organic chemical vapour deposition on (001) MgO, R-plane Al₂O₃ and (001) Si single-crystal substrates. Strontium tetramethyl heptadionate and titanium n-butoxide dissolved in diethyleneglycol dimethyl ether were used as precursors. The structure of the films was investigated by X-ray diffraction and transmission electron microscopy. Epitaxial films with [001] and [111] orientation perpendicular to the substrate surface were obtained on MgO and Al₂O₃, respectively. The epitaxial films on the MgO substrate were found to be in a relaxed state with lattice parameters corresponding to the bulk values. SrTiO₃ films on the Si substrate were grown as highly textured in the [011]direction and randomly oriented in the plane parrallel to the substrate surface.     

Effect of layer thickness on thermal properties of multilayer thin films produced by PVD

Cr/CrN/CrAlN, CrN/CrAlN and Cr/CrN thin layers were deposited by PVD (Physical Vapor Deposition). The multilayers were obtained from the combined deposition of different layers Cr, CrN and CrAlN thick films on on AISI4140 steel and silicon substrates at 200 °C, and evaluated with respect to fundamental properties such as structure and thermal properties. Cr, CrN and CrAlN single layers were also prepared for comparison purposes. The structural and morphological properties of PVD layers were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with EDS + WDS microanalyses, stresses were determined by the Newton’s rings methods using the Stoney’s equation and surface hardening and hardness profiles were evaluated by micro hardness measurements. The XRD data and HRTEM showed that both the Cr/CrN, CrN/CrAlN and Cr/CrN/CrAlN multilayer coatings exhibited B1NaCl structure with a prominent reflection along (200) plane, and CrAlN sub-layer microstructures composed of nanocrystallites uniformly embedded in an amorphous matrix. The innovation of this work was to use the thickness of three different coating types to determine the thermal properties. Furthermore, an empirical equation was developed for the thermal properties variations with temperature of AISI4140 steel coated with different multilayer coatings. The thermal conductivity of CrAlN single layered was lower than the multilayer and the bulk material AISI4140. Moreover, the influences of structure and composition of the multilayer coatings on the thermal properties are discussed.The thermal conductivity of nanoscale thin film is remarkably lower than that of bulk materials because of its various size effects.     

Influence of sputtering parameters and nitrogen on the microstructure of chromium nitride thin films deposited on steel substrate by direct-current reactive magnetron sputtering

Chromium nitride thin films were deposited on SA-304 stainless steel substrates by using direct-current reactive magnetron sputtering. The influence of process conditions such as nitrogen content in the fed gas, substrate temperature, and different sputtering gases on microstructural characteristics of the films was investigated. The films showed (200) preferred orientation at low nitrogen content (< 30%) in the fed gas. The formation of Cr₂N and CrN phases was observed when 30% and 40% N₂ were used, with a balance of Ar, respectively. Field emission scanning electron microscopy and atomic force microscopy were used to characterize the morphology and surface topography of the thin films, respectively. Microhardness tests showed a maximum hardness of 16.95 GPa for the 30% nitrogen content.     

Effects of substrate parameters on structure and optical properties of ZnO thin films fabricated by pulsed laser deposition

Highly oriented zinc oxide thin films have been grown on quartz, Si (1 1 1) and sapphire substrates by pulsed laser deposition (PLD). The effect of temperature and substrate parameter on structural and optical properties of ZnO thin films has been characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectra and PL spectra. The experimental results show that the best crystalline thin films grown on different substrate with hexagonal wurtzite structure were achieved at growth temperature 400–500 °C. The growth temperature of ZnO thin film deposited on Si (1 1 1) substrate is lower than that of sapphire and quartz. The band gaps are increasing from 3.2 to 3.31 eV for ZnO thin film fabricated on quartz substrate at growth temperature from 100 to 600 °C. The crystalline quality and UV emission of ZnO thin film grown on sapphire substrate are significantly higher than those of other ZnO thin films grown on different substrates.     

Room temperature ferromagnetism and hopping transport in amorphous CrN thin films

Magnetic and electronic properties of stoichiometric amorphous CrN thin films grown on MgO (001) substrates by radio-frequency nitrogen-plasma-assisted molecular beam epitaxy have been investigated. The magnetic property of the amorphous CrN thin films shows a ferromagnetic behavior even at room temperature, and can be interpreted by the percolation theory of magnetic polaron where we consider Cr³⁺ defects as magnetic impurities which lead to the formation of bound magnetic polarons. The obtained results of electrical conductivity are explained by the variable-range-hopping theory of the Mott and Davis model.     

Epitaxial (Pb,La)(Zr,Ti)O3 thin films on buffered Si(100) by on-axis radio frequency magnetron sputtering

In this study, we discuss the case for integration of epitaxial (Pb,La)(Zr,Ti)O₃ (PLZT) thin films with silicon for electro-optic device applications. PLZT films, approximately 500 nm thick, were grown by on-axis radio frequency magnetron sputtering on CeO₂/YSZ-buffered Si(100) substrate with a SrRuO₃ electrode layer embedded between CeO₂ and PLZT. The structural properties and surface topography of the different oxide layers were examined with X-ray diffraction analysis and atomic force microscopy. The perovskite thin films were predominantly (001)-oriented, with a (002) rocking curve halfwidth of approximately 0.3° and a surface roughness compatible with requirements for application in optical devices. The PLZT cation stoichiometry was assessed from quantitative X-ray photoelectron spectroscopy. These measurements uncovered a substantial depletion of lead in the film surface for layers deposited at substrate temperatures above ~ 600 °C, whereas the surface concentration of La, Zr and Ti remained virtually unaffected over a wide range of growth temperatures.     

Temperature dependent biaxial texture evolution in Ge films under oblique angle vapor deposition

The morphology and texture of Ge films grown under oblique angle vapor deposition on native oxide covered Si(001) substrates at temperatures ranging from 230 °C to 400 °C were studied using scanning electron microscopy, X-ray diffraction and X-ray pole figure techniques. A transition from polycrystalline to {001}<110> biaxial texture was observed within this temperature range. The Ge films grown at substrate temperatures < 375 °C were polycrystalline. At substrate temperatures of 375 °C and 400 °C, a mixture of polycrystalline and biaxial texture was observed. The 230 °C sample consisted of isolated nanorods, while all other films were continuous. The observed biaxial texture is proposed to be a result of the loss of the interface oxide layer, resulting in epitaxial deposition of Ge on the Si and a texture following that of the Si(001) substrates used. The rate of oxide loss was found to increase under oblique angle vapor deposition.     

Analysis on microstructure and characteristics of TiAlN/CrN nano-multilayer films deposited by cathodic arc deposition

In this study, TiAlN/CrN multilayer thin films were deposited on SUS 403 stainless steel by cathodic arc deposition. The effects of substrate orientation (substrate surface parallel/perpendicular to target surface) and rotation speed were investigated in detail. Microstructure of the coatings was analyzed by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Meanwhile, tribological and corrosion tests were performed. The experimental results showed that the as-deposited films exhibit a nano-scale multilayer structure consisting of TiAlN and CrN phases. The TiAlN/CrN multilayer films prepared by a parallel orientation and a rotation speed of 4 rpm not only possesses the best coating hardness and hardness/elastic modulus ratio, but also reveals superior abrasion resistance and corrosion resistance.     

Crystal Structure and Superconductivity of MgB2 Thin Films Grown on Various Oxide Substrates

The crystal structure and superconductivity of MgB₂ thin films grown on various oxide substrates were investigated by X-ray diffraction and resistance measurement. The films were prepared by a two-step method, in which precursors B films were annealed in Mg vapor at 900C. The X-ray diffraction shows that the MgB₂ films grown on C–AL₂O₃, R–AL₂O₃, and MgO (001) are c-axis oriented while the films grown on SrTiO₃ (001), LaAlO₃ (001), and ZrO₂ (001) are aligned with the (101) direction normal to the substrate planes. All the grown films show superconductivity and their transition temperature varies with the substrates in the range of 34–39 K. We think that the transition temperature variation is probably due to the lattice matching between the film and the substrate, as well as the interdiffusion at the film/substrate interface. The experimental results suggest that if there is no severe interdiffusion at the film/substrate interface in the high temperature annealing process, more substrates could be used for the growth of MgB₂ films using the two-step method.     

Crystal Structure and Superconductivity of MgB2 Thin Films Grown on Various Oxide Substrates

The crystal structure and superconductivity of MgB₂ thin films grown on various oxide substrates were investigated by X-ray diffraction and resistance measurement. The films were prepared by a two-step method, in which precursors B films were annealed in Mg vapor at 900^○C. The X-ray diffraction shows that the MgB₂ films grown on C–AL₂O₃, R–AL₂O₃, and MgO (001) are c-axis oriented while the films grown on SrTiO₃ (001), LaAlO₃ (001), and ZrO₂ (001) are aligned with the (101) direction normal to the substrate planes. All the grown films show superconductivity and their transition temperature varies with the substrates in the range of 34–39 K. We think that the transition temperature variation is probably due to the lattice matching between the film and the substrate, as well as the interdiffusion at the film/substrate interface. The experimental results suggest that if there is no severe interdiffusion at the film/substrate interface in the high temperature annealing process, more substrates could be used for the growth of MgB₂ films using the two-step method.     

Development of low temperature approaches to device quality CdS: A modified geometry for solution growth of thin films and their characterisation

Cadmium sulphide thin films have been grown using a modified chemical bath deposition method with four innovative features: i) ethylenediamine was used as the complexing agent, enabling the use of low cadmium concentrations, ii) a rectangular bath geometry with heated glass plate walls was employed, iii) a low deposition temperature (30 °C) was used and iv) nitrogen gas was flowed over the substrate surface during growth. The latter two features eliminate the formation and adherence of gas bubbles on the substrate during growth, hence reducing pinhole formation. On inspection, films were found to be specularly reflective and homogeneous with no visible pinholes. Characterisation was performed by atomic force microscopy, grazing incidence X-ray diffraction, optical transmittance and photoluminescence spectroscopy. It was shown that films possessed a low surface roughness value of 5.2 nm, were highly crystalline, textured, had a grain size of 15 nm and a bandgap of 2.42 eV. Preliminary results from CdTe/CdS thin film photovoltaic devices demonstrate a notable efficiency of 9.8%.     

Structure, hardness and thermal stability of TiAlN and nanolayered TiAlN/CrN multilayer films

TiAlN films were deposited on silicon (1 1 1) substrates from a TiAl target using a reactive DC magnetron sputtering process in Ar+N₂ plasma. Films were prepared at various nitrogen flow rates and TiAl target compositions. Similarly, CrN films were prepared from the reactive sputtering of Cr target. Subsequently, nanolayered TiAlN/CrN multilayer films were deposited at various modulation wavelengths (Λ). X-ray diffraction (XRD), energy dispersive X-ray analysis, nanoindentation and atomic force microscopy were used to characterize the films. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of TiAlN/CrN multilayers was 3900 kg/mm², whereas TiAlN and CrN films exhibited maximum hardnesses of 3850 and 1000 kg/mm², respectively. Thermal stability of TiAlN and TiAlN/CrN multilayer films was studied by heating the films in air in the temperature range (T_A) of 500-900 °C for 30 min. The XRD spectra revealed that TiAlN/CrN multilayers were stable up to 800 °C and got oxidized substantially at 900 °C. On the other hand, the TiAlN films were stable up to 700 °C and got completely oxidized at 800 °C. Nanoindentation measurements performed on the films after heat treatment showed that TiAlN retained a hardness of 2200 kg/mm² at T_A=700 °C and TiAlN/CrN multilayers retained hardness as high as 2600 kg/mm² upon annealing at 800° C.     

Pulsed-laser deposition of textured cerium oxide thin films on glass substrates at room temperature

Cerium oxide thin films are deposited on glass by pulsed laser deposition at room temperature and characterized by X-ray diffraction and atomic force microscopy. The effects of ambient gas, rate of deposition and fluence on growth of films have been studied. The films grown in forming gas and with a high rate of deposition are polycrystalline and show preferential orientation along <011> direction with a roughness of ∼ 2 nm. Films prepared in oxygen have low crystallinity.     

ZnO thin films deposited by a CVT technique in closed ampoules

ZnO thin films were prepared on quartz glass, Si (100), and sapphire (001) substrates by a chemical vapour transport (CVT) technique. During the growing processes, the source and substrate temperatures were maintained at 1000 °C and 600 °C, respectively. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements showed that the crystalline qualities of ZnO thin films were sensitively dependent on substrates. ZnO thin film deposited on sapphire substrate exhibited the best morphology with the largest crystallite size of more than 20 μm. Meanwhile, the XRD patterns showed that ZnO thin film deposited on sapphire substrate was strongly c-axis preferred-oriented with high crystalline quality. The optical properties of ZnO thin films were investigated by photoluminescence (PL) spectroscopy at room temperature (RT). The results suggested that the optical properties of ZnO thin films were highly influenced by their crystalline qualities and surface morphologies.     

The effects of substrates on the thin-film structures of BaTiO3

Barium titanate (BaTiO₃) thin films prepared on magnesia, silicon and strontium titanate substrates by r.f. sputtering has been investigated. As a function of substrate and annealing temperatures, the crystal structure and shape were examined by X-ray diffraction and scanning electron microscopy. Thin films were grown on both MgO and silicon substrates; they were amorphous when deposited on MgO if the substrate temperature was less than 450 °C, while for those grown on silicon the temperature had to be less than 500 °C. Above these elevated temperatures, the films were crystalline, with cubic symmetry. After annealing the thin films on magnesia, the crystal structure changed from cubic to tetragonal phase above 1100 °C; thebe c-axis or annealing thus caused the grain growth of the BaTiO₃. The thin films on SrTiO₃ were found toc-axis oriented tetragonal films for a substrate temperature above 500 °C.     

Structural studies on some doped CdS thin films deposited by thermal evaporation

The influence of the Mn, Se and Sb impurities on the structure and morphology of CdS thin films grown on p⁺ Si wafers was studied. The starting powders were mixed in the same molar ratios (0.3%) and deposited in the same conditions by vacuum thermal evaporation. X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reflectance studies made on thermal treated thin films (573 K, 2 h in air) evidenced that thin films have a hexagonal oriented structure, and that dopants enter into the CdS lattice merely by substitution. The dopant nature influences the thin film thickness and chemical composition. The doped CdS thin films have roughness in nanometer region and a reflectivity lower than 40%. Silicon substrate acts as a template and favors the retention of Mn and scatters the Sb dopants. The CdS:Se thin film is thicker than CdS:Mn and CdS:Sb ones and is a mixture of doped and undoped nanocrystals.