Influence of ultrasonic combined supercritical-CO2 electrodeposition process on copper film fabrication: Electrochemical evaluation

Introducing ultrasound irradiation to the electrodeposition process can significantly improve the physical and chemical properties of deposited films. Meanwhile, the beneficial effects from supercritical-CO_2, such as high diffusivity, high permeability, low surface tension, etc., would improve the electrodeposition process with better surface quality. In the shed of the light, the present work deals with the preparation of copper (Cu) films using the integrated techniques, i.e., ultrasonic-assisted supercritical-CO₂ (US-SC-CO₂) electrodeposition approach. For comparison, Cu films were also prepared by normal supercritical-CO₂ (SC-CO₂) and conventional electrodeposition methods. To investigate the characteristics of Cu films, surface morphology analysis, roughness analysis, X-ray diffraction studies (XRD), Linear polarization, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were performed. In this work, EIS analysis was utilized for interfacial charge transfer resistance analysis with 5 mM [Fe(CN)₆]^−3/−4 redox system and corrosion analysis with 3.5 wt% NaCl solution. The observed results revealed that the film prepared with the US-SC-CO₂ method have superior properties than those produced by normal SC-CO₂ and conventional methods. Due to the combination of US-SC-CO₂, the cavitation implosion occurs rapidly that enriches the deposited film quality, such as sufficient grain size, smoother surface, enhanced corrosion resistance, and charge carrier dynamics. On the other hand, the ultrasound effect with SC-CO₂ helped to remove the weakly adhered metal ions on the electrode’s surface.     

Ultrasonic-assisted supercritical-CO2 electrodeposition of Zn-Co film for high-performance corrosion inhibition: A greener approach

The ultrasonic-assisted electrodeposition process significantly improves the mechanical and electrochemical properties. Meanwhile, supercritical fluid technology also enhances the electrodeposition process with increased benefits, such as low surface tension, permeability, high diffusivity, and density, which improves the surface quality through grain refinement. In this study, Zn-Co films were prepared using the ultrasonic-assisted supercritical-CO₂ (US-SC-CO₂) electrodeposition approach, and its pressure effect on the film was evaluated. The films were also prepared by the conventional and typical supercritical-CO₂ (SC-CO₂) methods for a comparison study. All the prepared films were characterized by morphological studies, elemental composition, crystal structure orientation, and microhardness tests. Later, the fabricated films were examined by potentiodynamic polarization technique and electrochemical impedance technique (EIS) with 3.5 wt.% NaCl solution for corrosion evaluation. Based on results, Zn-Co film prepared through the US-SC-CO₂ process shows a spherical nodule like structure with reduced grain size and significantly enhanced hardness property. In XRD studies, the shift in diffracted peak’s position reveals the increased proportion of Co ions. Further, EDX results also confirm the same with the characteristic peaks. Finally, compared to the other methods, the corrosion resistance was more efficient in the US-SC-CO₂ process by 73.75%.     

Considering agitation in ultrasonic electroplating through observation of cavitation

Ultrasonic electroplating produces various effects, including refinement of the plating film structure, by generating localized agitation through cavitation bubbles. However, details of the agitation mechanism have not been clarified because ultrasonic cavitation is very small in scale and occurs rapidly, and its reproducibility is low. Therefore, using laser-induced cavitation, which can generate cavitation similar to ultrasonic waves with high reproducibility, the author attempted to elucidate the conditions and frequency of cavitation generation that affect the agitation phenomenon in ultrasonic electroplating. By controlling the laser irradiation position, three different cavitation conditions were established, and the microstructures of the plated films produced were compared. Microstructural refinement was the most advanced under the condition of microjet generation. The frequency of cavitation generation at any position in the ultrasonic electroplating was estimated to be < 1 Hz.     

Hydrophobic properties of carbon fabric with Teflon AF 2400 fluoropolymer coating deposited from solutions in supercritical carbon dioxide

A method for uniform deposition of a hydrophobizing polymer from a solution in supercritical carbon dioxide (SC-CO₂) onto the surface of carbon fabric used for manufacturing gas diffusion layers of fuel cells is developed. This approach, based on using Teflon AF 2400, a SC-CO₂-soluble copolymer, is compared to the traditional method for hydrophobization of the gas diffusion layer of a fuel cell, based on the use of an aqueous dispersion of Teflon 30N. Hydrophobizing polymers were deposited on the surface of a highly rough carbon fabric (Saati), an electrically conductive gas diffusion layer material with good mechanical and resource characteristics. In one of the versions of the method of deposition from SC-CO₂, the hydrophobic film was subjected to additional annealing at a temperature above the glass transition temperature of Teflon AF 2400 amorphous copolymer. It is shown that this approach makes it possible to form a uniform thin fluoropolymer film on carbon fibers, which imparts the most stable superhydrophobic properties to the surface of the gas diffusion layer at very low amounts of deposited polymer. In this case, the contact angle reaches a value much greater than that previously reported in the literature for similar methods. Prolonged immersion in water (for 1000 h) or wash in the presence of detergent does not impair the superhydrophobicity of the gas diffusion layer. The developed gas-diffusion layer was used to prepare an electrode for phosphoric fuel cell, the current-voltage characteristic of which indicates a satisfactory performance. The results obtained show that adopted approach is promising for developing gas diffusion layers for fuel cell electrodes.     

Structural and magnetic characterization of LaSrMnO3 thin films deposited by laser ablation on MgO substrates

La_2/3Sr_1/3MnO_3?δ thin films were deposited by laser ablation on MgO substrates under low oxygen pressure cool down. Their structural and magnetic properties are presented. The magnetic and electrical resistivity measurements indicate a reduction of the Curie and the metal–insulator transition temperatures due to the formation of magnetic inhomogeneneous films, where clusters of a metallic phase are mixed in a magnetically disordered insulating matrix. By a low-angle X-ray reflectivity study we show that the thin films are chemically inhomogeneous with an oxygen deficiency in bulk of the film when compared with the film/air interfacial region.     

Deposition of MgF2 thin films for antireflection coating by using thermionic vacuum arc (TVA)

In this study, optical and surface properties of MgF₂ thin films produced by thermionic vacuum arc (TVA) technique have been investigated. By means of this technique the MgF₂ thin film produced by condensing the plasma of anode material generated by using TVA under high vacuum conditions on the glass. The optical properties have been investigated by using Filmetrics F20 and UV/VIS spectrometer. For surface properties of produced thin films EDS, SEM and AFM have been used. Our analysis shows that MgF₂ thin films produced by using TVA are proper single and multi layer anti-reflective (AR) coating and TVA technique brings very important advantages for ophthalmic glass coating and industrial applications' optical purposes.     

The influence of the number of pulses on the morphological and photoluminescence properties of SrAl2O4:Eu,Dy thin films prepared by pulsed laser deposition

The current work reports on the influence of the number of laser pulses on the morphological and photoluminescence properties of SrAl₂O₄:Eu²⁺,Dy³⁺ thin films prepared by the pulsed laser deposition (PLD) technique. Atomic force microscopy (AFM) was used to study the surface topography and morphology of the films. The AFM data showed that the film deposited using a higher number of laser pulses was packed with a uniform layer of coarse grains. In addition, the surface of this film was shown to be relatively rougher than the films deposited at a lower number of pulses. Photoluminescence (PL) data were collected using the Cary Eclipse fluorescence spectrophotometer equipped with a monochromatic xenon lamp. An intense green photoluminescence was observed at 517 nm from the films prepared using a higher number of laser pulses. Consistent with the PL data, the decay time of the film deposited using a higher number of pulses was characteristically longer than those of the other films. The effects of laser pulses on morphology, topography and photoluminescence intensity of the SrAl₂O₄:Eu²⁺,Dy³⁺ thin films are discussed.     

Direct current magnetron sputtering deposition of InN thin films

In this paper, InN thin films were deposited on Si (1 0 0) and K9 glass by reactive direct current magnetron sputtering. The target was In metal with the purity of 99.999% and the gases were Ar (99.999%) and N₂ (99.999%). The properties of InN thin films were studied. Scanning electron microscopy (SEM) shows that the film surface is very rough and energy dispersive X-ray spectroscopy (EDX) shows that the film contains In, N and very little O. X-ray diffraction (XRD) and Raman scattering reveal that the film mainly contains hexagonal InN. The four-probe measurement shows that InN film is conductive. The transmission measurement demonstrates that the transmission of InN deposited on K9 glass is as low as 0.5% from 400 nm to 800 nm.     

Spectroscopic ellipsometry modeling of ZnO thin films with various O2 partial pressures

ZnO films were deposited on thermally oxidized SiO₂/p-type Si (100) substrates and glass substrates by DC magnetron sputtering using a metal Zn target. Three types of samples were prepared with various O₂/(Ar + O₂) ratios (O₂ partial pressure) of 20%, 50%, and 80%. The properties of these ZnO thin films were investigated using X-ray diffraction (XRD), optical transmittance, atomic force microscopy (AFM), and spectroscopic ellipsometry in the spectral region of 1.7–3.1 eV. The structural and optical properties of ZnO thin films were affected by O₂ partial pressure. Relationships between crystallinity, the ZnO surface roughness layer, and the refractive index (n) were investigated with varying O₂ partial pressure. It was shown that the spectroscopic ellipsometry extracted parameters well represented the ZnO thin film characteristics for different O₂ partial pressures.     

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 process parameters on surface morphology and characterization of PE-ALD SnO2 thin films for gas sensing

Tin dioxide (SnO₂) thin films were deposited by plasma enhanced-atomic layer deposition (PE-ALD) on Si(1 0 0) substrate using dibutyl tin diacetate (DBTA) ((CH₃CO₂)₂Sn[(CH₂)₃-CH₃]₂) as precursor. The process parameters were optimized as a function of substrate temperature, source temperature and purging time. It is observed that the surface phenomenon of the thin films was changed with film thickness. Atomic force microscopy (AFM) images and X-ray diffraction (XRD) pattern were used to observe the texture and crystallanity of the films. The films deposited for 100, 200 and 400 cycles were characterized by XPS to determine the chemical bonding properties. XPS results reveal that the surface dominant oxygen species for 100, 200 and 400 cycles deposited films are O₂⁻, O⁻ and O²⁻, respectively. The 200 cycles film has exhibited highest concentration of oxygen (O⁻) species before and after annealing. Conductivity studies revel that this film has best adsorption strength to the oxygen ions forming on the surface. The sensor with 200 cycles SnO₂ thin film has shown highest sensitivity to CO gas than other films. A correlation between the characteristics of Sn3d_5/2 and O1s XPS spectra before and after annealing and the electrical behavior of the SnO₂ thin films is established.     

A novel way of modifying nano grain size by solution concentration in the growth of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

A novel route to the growth of thin films of ZnAl₂O₄ in nano-scale order was developed and nano-thin films of ZnAl₂O₄ are grown. The variation of grain size with solution concentration is reported. The thin film was deposited by modified liquid-phase deposition (LPD) technique using a novel acid based chemical reaction for the first time to ternary system. This modified LPD is based on a novel reaction that favours the formation of nanostructures during the treatment of a precursor (here ZnO) and a metal foil (Al) in diluted HF acid. The acid serves both as a solvent and catalyst. Usually, in wet process synthesis of binary systems, the metal foil will act as F⁻ ion scavenger. In this method, formation of a ternary compound as well as growth of thin film nanostructures of that compound was achieved by the same chemical reaction at room temperature. The role of acid concentration in the nanostructure formation is discussed. The relationship between HF concentration and grain size were also graphically enumerated. Structural, compositional and surface morphological properties of thin films were studied using Philips, Xpert-MPD: X-ray diffractometer and Philips, ESEM-TMP + EDAX, Nanoscope-III: AFM. The technique is a novel, simple and low cost route for the growth of nano-thin films of ternary oxide material.     

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.     

氧化法结合快速热处理制备VOx薄膜及其性质研究

采用磁控溅射法在单晶Si〈100〉基底上沉积金属钒(V)薄膜,在高纯氧环境下快速热处理制备具有相变特性的氧化钒(VOx)薄膜.利用X射线衍射仪、X射线光电子能谱和扫描电子显微镜对薄膜结晶结构、薄膜中V的价态与组分及表面微观形貌进行分析,应用四探针测试方法和太赫兹时域频谱技术对样品的电学和光学特性进行测试.结果表明:在一定范围的快速热处理保温温度和保温时间下,都可以制备出具有热致相变特性的氧化钒薄膜,相变前后薄膜的方块电阻变化超过两个数量级,薄膜成分主要由V2O5和VO2混合组成,薄膜中V整体价态不因热处理条件改变而不同.在快速热处理条件范围内,500℃ 25 s左右条件下(中温区)制备出的氧化钒薄膜相变特性最佳,并且对THz波有一定的调制作用.     

Electric and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> bilayer thin films prepared by pulsed-laser deposition

CoFe₂O₄ (CFO) thin film with highly (111)-preferential orientation was first deposited on the silicon substrate by a pulsed-laser deposition, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) layers were deposited with different oxygen pressures to form the bilayer CFO/PZT nanocomposite thin films. X-ray diffraction showed that the PZT preferential orientation was strongly dependant on the oxygen pressure. The smooth film surface was obtained after depositing the CFO and PZT layers. The bilayer thin films exhibit good ferromagnetic and ferroelectric properties, and a low leakage current density of 0.004 μA/cm² at 50 kV/cm. The leakage current density curves show loops for the electric polarized field when the electric field reverses. PACS 77.84.Lf; 75.80+q; 81.05.Zx; 81.15.Fg     

Optical properties of molybdenum oxide thin films deposited by?chemical vapor transport of MoO3(OH)2

MoO₃ thin films are useful for optical devices due to their electrochromic properties. In this study, deposition of MoO₂ thin films was successfully accomplished by chemical vapor transport (CVT) of volatile MoO₃(OH)₂. Subsequently, a MoO₃ thin film was obtained by annealing of the deposited MoO₂ at 400°C in an O₂ atmosphere. As annealing commenced, the optical transmittance of the films increased and their absorbance peaks were broadened and red-shifted due to reduced oxygen vacancy. Thus, the molybdenum oxide thin films can successfully be deposited using the CVT technique.     

EFFECTS OF THE QUALITY OF SUBSTRATE ON THE STRUCTURE AND SUPERCONDUCTING PROPERTIES OF Yba2Cu3O7-x THIN FILM

We have systematically investigated the structures, morphologies, microwave surface resistance, DC performances and the substrate qualities of three YBa₂Cu₃O_7-x(YBCO) thin films 30mm in diameter. The three samples deposited by the same process have been proved of different properties. It has been shown that the structure and superconducting properties of the thin film depend strongly on the quality of substrate.     

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO₂ thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO₂ thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO₂ thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances.     

Preparation of Bi:TiO2 thin films by an hybrid deposition configuration: pulsed laser deposition and thermal evaporation

The aim of this work was to report the application of an hybrid deposition configuration to deposit Titanium dioxide (TiO₂) thin films modified with different amounts of bismuth (Bi:TiO₂). The samples were synthesized combining a TiO₂ laser ablation plasma with a flux of vapor of bismuth produced by thermal evaporation. By varying the deposition rate of Bi it was possible to control the amount of Bi incorporated in the film and consequently the film properties. A detailed compositional, structural, and optical characterization by XPS, RBS, Raman spectroscopy, and UV–Vis spectrometry techniques is discussed. Photocatalytic response of the deposited thin films was studied through the degradation of a malachite green solution.     

Structural and magnetic properties of bulk and thin films of Mg0.95Mn0.05Fe2O4

We present here a comparative study on structural and magnetic properties of bulk and thin films of Mg_0.95Mn_0.05Fe₂O₄ ferrite deposited on two different substrates using X-ray diffraction (XRD) and dc magnetization measurements. XRD pattern indicates that the bulk sample and their thin films exhibit a polycrystalline single phase cubic spinel structure. It is found that the film deposited on indium tin oxide coated glass (ITO) substrate has smaller grain size than the film deposited on platinum coated silicon (Pt–Si) substrate. Study of magnetization hysteresis loop measurements infer that the bulk sample of Mg_0.95Mn_0.05Fe₂O₄ and its thin film deposited on Pt–Si substrate shows a well-defined hysteresis loop at room temperature, which reflects its ferrimagnetic behavior. However, the film deposited on ITO does not show any hysteresis, which reflects its superparamagnetic behavior at room temperature.