Improvement of corrosion resistance of NiTi sputtered thin films by anodization

Anodization of sputtered NiTi thin films has been studied in 1 M acetic acid at 23 °C for different voltages from 2 to 10 V. The morphology and cross-sectional structures of the untreated and anodized surfaces were investigated by field emission scanning electron microscopy (FE-SEM). The results show that increasing anodization voltage leads to film surface roughening and unevenness. It can be seen that the thickness of the anodized layer formed on the NiTi surface is in the nanometer range. The corrosion resistance of anodized thin films was studied by potentiodynamic scan (PDS) and impedance spectroscopy (EIS) techniques in Hank's solution at 310 K (37 °C). It was shown that the corrosion resistance of the anodized film surface improved with increasing voltage to 6 V. Anodization of austenitic sputtered NiTi thin films has also been studied, in the same anodizing conditions, at 4 V. Comparison of anodized sputtered NiTi thin films with anodized austenitic shape memory films illustrate that the former are more corrosion resistant than the latter after 1 h immersion in Hank's solution, which is attributed to the higher grain boundary density to quickly form a stable and protective passive ?lm.     

Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films

The Cu₂ZnSnS₄ (CZTS) thin films have been electrochemically deposited on Mo-coated glass substrate from weak acidic medium (pH 4.5-5) at room temperature. The effect of complexing agent (tri-sodium citrate) on the structural, morphological and compositional properties of CZTS thin films has been investigated. The as-deposited and annealed thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM),EDAX and X-ray photoelectron spectroscopy (XPS) techniques for their structural, morphological, compositional and chemical properties, respectively. XRD studies reveal that the amorphous nature of as-deposited thin film changes into polycrystalline with kesterite crystal structure after annealing in Ar atmosphere. The film prepared without complexing agent showed well-covered surface morphology on the substrate with some cracks on the surface of the film whereas those prepared using complexing agent, exhibited uneven and slightly porous and some overgrown particles on the surface of the films. After annealing, morphology changes into the flat grains, uniformly distributed over the entire surface of the substrate. The EDAX and XPS study reveals that the films deposited using 0.2 M tri-sodium citrate are nearly stoichiometric.     

Effect of N2 ambient annealing on the field emission properties of HfNxOy thin films

HfN_xO_y thin films were deposited on Si substrates by direct-current sputtering. The influence of N₂ ambient annealing on the morphology, structure and field emission properties of the HfN_xO_y thin films was studied systematically. Scanning electron microscopy indicates that both the as-deposited and the annealed films are composed of nanoparticles, and the particle sizes of these films do not change much before and after annealing. Atomic force microscopy shows that the surface of the as-deposited films is smooth while that of the annealed films becomes rough, with many protrusions. X-ray diffraction patterns demonstrate that the as-deposited films are amorphous while the samples annealed at over 500 °C are polycrystalline. It is found that the field electron emission properties of the annealed films are better than those of the as-deposited films. The film annealed at 800 °C shows the best field emission properties. The mechanism for the improvement of the field electron emission property of the annealed thin films is also discussed. PACS 73.61.-r; 79.70.+q; 81.05.-t     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Synthesis and electrochemical characteristics of Ta-N thin films fabricated by cathodic arc deposition

Ta-N thin films were deposited on AISI 317L stainless steel (SS) substrates by cathodic arc deposition (CAD) at substrate biases of −50 and −200 V. The as-deposited films were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX). The results show that stoichiometric TaN with hexagonal lattice (3 0 0) preferred orientation was achieved at the bias of −200 V. On the other hand, Ta-rich Ta-N thin film deposited at −50 V shows amorphous nature. According to the XPS result, Ta element in the films surface exist in bonded state, including the Ta-N bonds characterized by the doublet (Ta 4f_7/2 = 23.7 eV and Ta 4f_5/2 = 25.7 eV). Electrochemical properties of the Ta-N coated stainless steel systems were investigated using potentiodynamic polarization and electrochemical impedance spectroscope (EIS) in Hank's solution at 37 °C. For the Ta-N coated samples, the corrosion current (i_corr) is two or three orders of magnitude lower than that of the uncoated ones, indicating a significantly improved corrosion resistance. Growth defects in the Ta-N thin films produced by CAD, however, play a key role in the corrosion process, especially the localised corrosion. Using the polarization fitting and the EIS modelling, we compared the polarization resistance (R_p) and the porosity (P) of the Ta-N coatings deposited at different biases. It seems that Ta-N film with comparatively lower bias (−50 V) shows better corrosion behavior in artifical physiological solution. That may be attributed to the effect of ion bombarding, which can be modulated by the substrate bias.     

Studies on Structural,Morphological and Optical Properties of Chemically Deposited CdS<Subscript>1-x</Subscript>Se<Subscript>x</Subscript> Thin Films

The thin films of CdS_1-xSe_x were successfully deposited over glass substrates by chemical bath deposition technique. Cadmium acetate, thiourea and sodium selenosulfate were used as source materials for Cd²⁺, S^2? and Se^2? ions, while 2-mercaptoethanol was used as capping agent. The various deposition conditions such as precursor concentration, deposition temperature, pH and deposition time were optimized for the deposition of CdS_1-xSe_x thin films of good quality and the films were annealed at 200° and 300 °C. The structural, morphological, chemical and optical properties were examined by various characterization techniques and discussed in detail. The optical band gap of CdS_1-xSe_x thin film samples were estimated and found in the range from 2.11 to 1.79 eV for as-deposited and annealed thin films.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

不同衬底和CdCl2退火对磁控溅射CdS薄膜性能的影响

在科宁7059玻璃, FTO, ITO, AZO四种衬底上磁控溅射CdS薄膜, 并在CdCl₂+干燥空气380 ℃退火, 分别研究了不同衬底和退火工艺对CdS薄膜形貌、结构和光学性能的影响. 扫描电子显微镜形貌表明: 不同衬底原位溅射CdS薄膜的形貌不同, 退火后相应CdS薄膜的晶粒度和表面粗糙度明显增大. XRD衍射图谱表明: 不同衬底原位溅射和退火CdS薄膜均为六角相和立方相的混相结构, 退火前后科宁7059玻璃, FTO, AZO衬底上CdS薄膜有 H(002)/C(111) 最强衍射峰, ITO衬底原位溅射CdS薄膜没有明显的最强衍射峰, 退火后出现 H(002)/(111) 最强衍射峰. 紫外-可见分光光度计分析表明: AZO, FTO, ITO, 科宁7059玻璃衬底CdS薄膜的可见光平均透过率依次减小, 退火后相应衬底CdS薄膜的可见光平均透过率增大, 光学吸收系数降低; 退火显著增大了不同衬底CdS薄膜的光学带隙. 分析得出: 上述结果是由于不同衬底类型和退火工艺对CdS多晶薄膜的形貌、结构和带尾态掺杂浓度改变的结果. 关键词： CdS薄膜 磁控溅射 退火再结晶 带尾态     

Formation of CdO films from chemically deposited Cd(OH)2 films as a precursor

Formation of cadmium hydroxide at room temperature onto glass substrates from an aqueous alkaline cadmium nitrate solution using a simple soft chemical method and its conversion to cadmium oxide (CdO) by thermal annealing treatment has been studied in this paper. The as-deposited film was given thermal annealing treatment in oxygen atmosphere at 450 °C for 2 h for conversion into cadmium oxide. The structural, surface morphological and optical studies were performed for as-deposited and the annealed films. The structural analyses revealed that as-deposited films consists of mixture of Cd(OH)₂ and CdO, while annealed films exhibited crystalline CdO. From surface morphological studies, conversion of clusters to grains after annealing was observed. The band gap energy was changed from 3.21 to 2.58 eV after annealing treatment. The determination of elementals on surface composition of the core-shell nanoparticles of annealed films was carried out using X-ray photoelectron spectroscopy (XPS).     

Annealing effect on microstructure and mechanical properties of amorphous Al-C-N films

Al-C-N thin films with different Al contents were deposited on Si (1 0 0) substrates by closed-field unbalanced reactive magnetron sputtering in the mixture of argon and nitrogen gases. These films were subsequently vacuum-annealed at 700 °C and 1000 °C, respectively. The microstructures of as-deposited and annealed films were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM); while the hardness and elastic modulus values were measured by nano-indention method. The results indicated that the microstructure of both as-deposited and annealed Al-C-N films strongly depended on Al content. For thin films at low Al content, film delamination rather than crystallization occurred after the sample was annealed at 1000 °C. For thin films at high Al content, annealing led to the formation of AlN nanocrystallites, which produced nanocomposites of AlN embedded into amorphous matrices. Both the density and size of AlN nanocrystallites were found to decrease with increasing depth from the film surface. With increasing of annealing temperature, both hardness and elastic modulus values were decreased; this trend was decreased at high Al content. Annealing did not change elastic recovery property of Al-C-N thin films.     

Fabrication and characterization of freestanding ultrathin diamond-like carbon targets for high-intensity laser applications

Here, we report the fabrication of diamond-like carbon (DLC) thin films using pulsed laser deposition (PLD). PLD is a well-established technique for deposition of high-quality DLC thin films. Carbon tape target was ablated using a KrF (248 nm, 25 ns, 20 Hz) excimer laser to deposit DLC films on soap-coated substrates. A laser fluence between 8.5 and 14 J/cm² and a target to substrate distance of 10 cm was used. These films were then released from substrates to obtain freestanding DLC thin foils. Foil thicknesses from 20 to 200 nm were deposited using this technique to obtain freestanding targets of up to 1-inch square area. Typically, 100-nm-thick freestanding DLC films were characterized using different techniques such as AFM, XPS, and nano-indentation. AFM was used to obtain the film surface roughness of 9 nm rms of the released film. XPS was utilized to obtain 74 % sp², 23 % sp³, and 3 % C–O bond components. Nano-indentation was used to characterize the film hardness of 10 GPa and Young’s modulus of 110 GPa. Damage threshold properties of the DLC foils were studied (1,064 nm, 6 ns) and found to be 7 × 10¹⁰ W/cm² peak intensity for our best ultrathin DLC foils.     

Surface and bulk properties of CuGaSe2 thin films

Using complementary techniques, namely X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS), we present a comparative study of the bulk and surface composition in device grade CuGaSe₂ (CGSe) thin films. The films were deposited in two stages by an open-tube chemical vapor deposition (CVD) process. The first stage leads to a nearly stoichiometric polycrystalline CGSe film of approximately 1.5 μm thickness. During the second stage the film is annealed in a Ga- and Se-rich atmosphere. While the XRF-data show a nearly stoichiometric integrated film composition, the surface composition, as determined by XPS analysis, is Cu-poor, pointing towards a highly non-stoichiometric surface layer. In addition, sodium was found at the film surfaces. The data are discussed in the framework of an ordered defect compound formation and the formation of a (Cu,Na)–Ga–Se compound at the surface of the CuGaSe₂ films. Complementary ultraviolet photoelectron- and inverse photoelectron spectroscopy investigations of the film surface derive a widening of the surface energy band gap up to 2.2 eV in comparison with a bulk energy band gap around 1.65 eV (obtained by optical transmission analysis). The observed data are consistent with our model of a two layer film structure containing a defect-rich near-surface region and a defect-poor bulk.     

Effect of Al doping on structural,optical and electrical properties of SnO2 thin films synthesized by pulsed laser deposition

Aluminium-doped (Al = 0–5?wt.%) SnO₂ thin films with low-electrical resistivity and high optical transparency have been successfully synthesized by pulsed laser deposition technique at 500 °C. Structural, optical and electrical properties of the as-deposited and post-annealed thin films were investigated. X-ray diffraction patterns suggest that the films transform from crystalline to amorphous state with increasing aluminium content. The root mean square (R_q) surface roughness parameter, determined by atomic force microscopy decreases upon annealing of the as-deposited film. While resistivity of the film is the lowest (9.49 × 10^?4 Ω-cm) at a critical doping level of 1?wt.% Al, optical transparency is the highest (nearly 90%) in the as-deposited condition. Temperature dependence of the electrical resistivity suggests that the Mott’s variable range hopping process is the dominant carrier transport mechanism in the lower temperature range (40–135 K) for all the films whereas, thermally activated band conduction mechanism seems to account for conduction in the higher temperature region (200–300 K).     

Atomic force microscopy study of thermal stability of silver selenide thin films grown on silicon

Silver selenide thin films were grown on silicon substrates by the solid-state reaction of sequentially deposited Se and Ag films of suitable thickness. Transmission electron microscopy and particle-induced X-ray emission studies of the as-deposited films showed the formation of single phase polycrystalline silver selenide from the reaction of Ag and Se films. Atomic force microscopy images of the as-deposited and films annealed at different temperatures in argon showed the film morphology to evolve into an agglomerated state with annealing temperature. The results indicate that when annealed above 473 K, silver selenide films on silicon become unstable and agglomerate through holes generated at grain boundaries.     

Semiconducting In2S3 quantum dots in thin film form: sonochemical versus conventional chemical synthesis and investigation of their structural and optical properties

Indium(III) sulfide quantum dots were deposited in thin film form using both a conventional chemical bath deposition method and a sonochemical route. The developed routes allow deposition of cubic α-In₂S₃ nanocrystals in thin film form. The as-deposited films produced by the conventional and sonochemical approaches are highly nanocrystalline, with average crystal sizes of 2.5 and 2.0 nm correspondingly (as determined from the Scherrer formula), which increase to 4.1 nm upon annealing treatment, due to coalescence and crystal-growth processes. Refinement of the lattice-constant value in the case of as-deposited and annealed films was performed using linear regression analysis. Blue-shifted band-gap energy values of as-deposited films with respect to those corresponding to bulk specimen, accompanied with the red shift of absorption onset upon annealing, strongly indicate the quantum-dot behavior of the synthesized nanocrystals. The detected three-dimensional quantum-confinement effects in the synthesized nanocrystals were discussed in terms of the Brus model. On the basis of optical spectroscopic data, we estimated the Bohr's excitonic radius value in this semiconductor. Presented at the X-th Symposium on Suface Physics, Prague, Czech Republic, July 11–15, 2005.     

Structural and microwave properties of (Ba,Sr)TiO3 films grown by pulsed laser deposition

The relationship between the structure and the microwave dielectric properties of epitaxial Ba_0.5Sr_0.5TiO₃ (BST) films has been investigated. Single-phase BST films (40-160 nm) have been deposited onto (100) MgO substrates by pulsed laser deposition. As-deposited films show a significant tetragonal distortion. The in-plane lattice parameters (a) are always larger than the surface normal lattice parameters (c). The tetragonal distortion depends on the thickness of the films and the post-deposition annealing conditions. Films annealed at 900 °C show less tetragonal distortion than the as-deposited film and the films annealed at higher temperatures. The distortion in the film is due to stress caused by the lattice mismatch and thermal expansion coefficient differences between the film and the substrate. The dielectric constant and its change with dc bias voltage of BST films on MgO at microwave frequencies increase with increasing annealing temperature from 900 °C to 1200 °C, which corresponds to an increase in the tetragonal distortion.     

Vibrational spectroscopic studies on Ba0.8Sr0.2TiO3 thin films prepared by RF sputtering technique

Thin films of Ba_0.8Sr_0.2TiO₃ have been deposited on p-type Si substrate by radio frequency magnetron sputtering. Polycrystalline bulk Ba_0.8Sr_0.2TiO₃ sample has also been studied for comparison. X-ray diffraction patterns reveal that both the bulk sample and thin films are polycrystalline without any preferential orientation and belong to paraelectric cubic phase. We have compared the room temperature Raman and IR spectra of powder and thin films (both annealed and as-deposited) of Ba_0.8Sr_0.2TiO₃. The extra feature in the Raman spectrum for the annealed film has been explained as due to the presence of intergrain stresses from the submicron size grains in it.     

Effect of aluminum on the corrosion behavior of NiTiAl thin films

An electrochemical study for the evaluation of corrosion behavior using potentiodynamic and Tafel techniques was conducted in 0.9% NaCl solution on Ni-Ti and Ni-Ti-Al shape memory thin films. Atomic force microscopy (AFM) and electron probe microanalyzer (EPMA) were applied to observe morphology of the surface film and elemental distribution, respectively, prior to and after immersion in 0.9% NaCl solution. The concentration of dissolved Ni from Ni-Ti-Al thin films in the electrolyte, measured with inductively coupled plasma atomic emission spectrometer (ICP-AES), was significantly lower after immersion for 7 days, as compared to Ni-Ti thin film. This demonstrated that a better corrosion resistance and lower corrosion current density were revealed for Ni-Ti-Al thin films than that for Ni-Ti thin film. The improved corrosion performance of Ni-Ti-Al thin films would be potentially beneficial for related biological applications. This was attributed to the introduction of aluminum after exposure to an aqueous environment.     

Effect of thermal annealing on the structure and microstructure of TiO2 thin films

Nanostructured TiO₂ thin films have been prepared through chemical route using sol-gel and spin coating techniques. The deposited films were annealed in the temperature range 400–1000°C for 1 h. The structure and microstructure of the annealed films were characterized by GAXRD, micro-Raman spectroscopy and AFM. The as-deposited TiO₂ thin films are found to be amorphous. Micro-Raman and GAXRD results confirm the presence of the anatase phase and absence of the rutile phase for films annealed up to 700°C. The diffraction pattern of the film annealed at 800 to 1000°C contains peaks of both anatase and rutile reflections. The intensity of all peaks in micro-Raman and GAXRD patterns increased and their width (FWHM) decreased with increasing annealing temperature, demonstrating the improvement in the crystallinity of the annealed films. Phase transformation at higher annealing temperature involves a competition among three events such as: grain growth of anatase phase, conversion of anatase to rutile and grain growth of rutile phase. AFM image of the asdeposited films and annealed films indicated exponential grain growth at higher temperature.      

Structural, compositional, thermal resistant and hydro-oleophobic properties of fluorine based block-co-polymer films on quartz substrates by wet chemical process

Crack free and smooth surfaces of poly [4,5-difluoro 2,2-bis (trifluoromethyl)-(1,3 dioxole)-co-tetrafluoroethylene] (TFE-co-TFD) thin films have been deposited by wet chemical dip coating technique on polished quartz and glass slide substrates. The deposited films have been subjected to annealing at different temperatures ranging from 100 to 500 °C for 1 h in argon atmosphere. The elemental composition of the as-deposited (xerogel) thin film as well as film annealed at 400 °C was measured by X-ray photoelectron spectroscopy and observed that there was no change in the composition of the film. X-ray diffraction pattern revealed the amorphous behaviour of both as-deposited and film annealed at 400 °C. Surface morphology and elemental composition of the films have been examined by employing scanning electron microscopy attached with energy dispersive X-ray analyser, respectively. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures have been grown, which in turn has shown increase in the water contact angle from 122^o to 148^o and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.