Electrochemical deposition of Bi2Te3-based thin films

The electrochemical reduction processes on stainless-steel substrates from an aqueous electrolyte composed of nitric acid, Bi³⁺, HTeO₂⁺, SbO⁺ and H₂SeO₃ systems were investigated using cyclic voltammetry. The thin films with a stoichiometry of Bi₂Te₃, Bi_0.5Sb_1.5Te₃ and Bi₂Te_2.7Se_0.3 have been prepared by electrochemical deposition at selected potentials. The structure, composition, and morphology of the films were studied by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and electron microprobe analysis (EMPA). The results showed that the films were single phase with the rhombohedral Bi₂Te₃ structure. The morphology and growth orientation of the films were dependent on the deposition potentials.     

Electrochemical behaviour of nano-sized spinel LiMn2O4 and LiAlxMn2−xO4 (x=Al: 0.00-0.40) synthesized via fumaric acid-assisted sol-gel synthesis for use in lithium rechargeable batteries

Pristine spinel LiMn₂O₄ and LiAl_xMn_2−xO₄ (x=Al: 0.00-0.40) with sub-micron sized particles have been synthesized using fumaric acid as chelating agent by sol-gel method. The synthesized samples were subjected to thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and cyclic voltammetry (CV) and galvanostatic cycling studies. The TGA curve of the gel shows several weight-loss regions stepwise amounting to 55% till 800 °C attributed to the decomposition of the precursors. Calcination to higher temperatures (800 °C) yields pure-phase spinel (LiAl_xMn_2−xO₄), as it is evident from the high-intensity XRD reflections matching to the standard pattern. SEM and TEM studies confirm that the synthesized grains are of uniform regular surface morphology. FT-IR studies show stretching and bending vibration bands of Li-O, Li-Al-Mn-O. LiAl_0.1Mn_1.90O₄ spinel was found to deliver discharge capacity of 139 mA h/g during the first cycle with columbic efficiency of 97%. LiAl_0.1Mn_1.90O₄ spinel exhibits the high cathodic peak current indicating better electrochemical performance. Low doping (x=0.1) of Al is found to be beneficial in stabilizing the spinel structure.     

Thermodynamic and kinetic properties of Ho1−xTixCo2-hydrogen system

The hydrogen absorption behavior of Laves phase Ho_1−xTi_xCo₂ (x=0.1-0.6) alloys has been investigated by pressure-concentration (PC) isotherms and cyclic-, temperature- and pressure-dependent absorption kinetics. The PC isotherms and kinetics of hydrogen absorption have been studied in the pressure range 0.01-1 bar and temperature range 50-200 °C using Sievert's-type apparatus. The drastic changes in the induction period and particle size during the activation process have been discussed based on the kinetics of repeated hydrogenation cycles and scanning electron microscopy (SEM) images of the hydrides at different hydriding cycles, respectively. The experimental results of kinetic curves are interpreted using the Johnson-Mehl-Avrami (JMA) model, and the reaction order and reaction rate have been determined. The α-, (α+β)- and β-phase regions in Ho_1−xTi_xCo₂-H have been identified from the different slope regions of the first-order-type kinetic plots. The dependence of the reaction rate parameter on hydriding pressure and temperature in the (α+β)-phase region has been discussed.     

Preparation and characterization of electrodeposited Sb2Se3 thin films from non-aqueous media

Semiconducting Sb₂Se₃ thin films have been prepared onto the stainless steel and fluorine doped tin oxide coated glass substrates from non-aqueous media using an electrodeposition technique. The electrodeposition potentials for different bath compositions and concentrations of solution have been estimated from the polarization curves. SbCl₃ and SeO₂ in the volumetric proportion as 1:1 with their equimolar solution concentration of 0.05 M form good quality films. The films are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and optical absorption techniques. The SEM studies show that the film covers the total substrate surface with uneven surface morphology. The XRD patterns of the films obtained by varying compositions and concentrations show that the as-deposited films are polycrystalline with relatively higher grain size for 1:1 composition and 0.05 M concentration. The optical band gap energy for indirect transition in Sb₂Se₃ thin films is found to be 1.195 eV.     

Optical and electronic properties of nano-Cd1−xMnxTe alloy

Cd_1−xMn_xTe thin films were fabricated by thermal interdiffusion of multilayers of sputtered compound semiconductors as well as thermally evaporated elements. Electron microscopy revealed their nanostructures. The alloys have been investigated for evaluation of optical and electronic parameters. Spectrophotometry helped to find out the bandgap and composition; photoluminescence was used for observing relative transition probabilities at room temperature. Photoresponse showed the light dependence of the resistance of the alloy films. Hall measurements and four-probe tests indicated the influence of manganese on the room-temperature electronic properties of the alloy.     

Preparation and characterization of Cd2Nb2O7 thin films on Si substrates

Thin Cd₂Nb₂O₇ films were grown on single-crystal p-type SiO₂/Si substrates by the metallo-organic decomposition (MOD) technique. The films were investigated by X-ray diffraction, X-ray energy-dispersive spectroscopy, and field emission scanning electron microscopy, and showed a single phase (cubic pyrochlore), a crack-free spherical grain structure, and nanoparticles with a mean size of about 68 nm. A Cauchy model was also used in order to obtain the thickness and index of refraction of the stack layers (transparent layer/SiO₂/Si) by spectroscopic ellipsometry (SE). The dielectric constant (K) of the films was calculated to be about 25 from the capacitance-voltage (C-V) measurements.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

Photoelectrochemical properties of electrochemically deposited CdIn2S4 thin films

Thin films of CdIn₂S₄ have been deposited on to stainless steel and fluorine-doped tin oxide (FTO)-coated glass substrates from aqueous acidic bath using an electrodeposition technique. Ethylene diamine tetra-acetic acid (EDTA) disodium salt is used as complexing agent to obtain good-quality deposits by controlling the rate of the reaction. The different preparative parameters like concentration of bath, deposition time, bath temperature, pH of the bath have been optimized by the photoelectrochemical (PEC) technique in order to get good-quality photosensitive material. Different techniques have been used to characterize CdIn₂S₄ thin films. Optical absorption shows the presence of direct transition with band gap energy 2.17 eV. The X-ray diffraction (XRD) analysis of the as-deposited and annealed films showed the presence of polycrystalline nature. Energy-dispersive analysis by X-ray (EDAX) study for the sample deposited at optimized preparative parameters shows that the In-to-Cd ratio is almost 2 and S-to-Cd ratio is almost 4. Scanning electron microscopy (SEM) for samples deposited at optimized preparative parameters reveals that spherical grains are uniformly distributed over the surface of the substrate indicates the well-defined growth of polycrystalline CdIn₂S₄ thin film. PEC characterization of the films is carried out by studying photoresponse, spectral response and photovoltaic output characteristics. The fill factor (ff) and power conversion efficiency (η) of the cell are 69 and 2.94%, respectively.     

Growth and structure of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 thin films prepared by pulsed laser deposition technique

Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ (BNKLT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition (PLD) technique. The films prepared were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effects of the processing parameters, such as oxygen pressure, substrate temperature and laser power, on the crystal structure, surface morphology, roughness and deposition rates of the thin films were investigated. It was found that the substrate temperature of 600 °C and oxygen pressure of 30 Pa are the optimized technical parameters for the growth of textured film, and all the thin films prepared have granular structure, homogeneous grain size and smooth surfaces.     

Composition and morphology of partially selenized CuIn1−XGaXSe2 thin films prepared using diethylselenide (DESe) as selenium source

CuIn_1−xGa_xSe₂ (CIGS) thin films are being prepared by selenization of Cu-In-Ga precursors using diethylselenide, (C₂H₅)₂Se, (DESe) as selenium source in place of H₂Se gas because of lower toxicity and ease of handling. Rough estimates indicate that selenization process using DESe would cost approximately same or slightly less compared to that using H₂Se. Price of DESe per mole is approximately five times that of H₂Se. However, partial pressure of DESe, which reflects source material consumption, is approximately three to four times less than that of H₂Se, due to higher decomposition rate of DESe compared to that of H₂Se. The actual DESe consumption would be four to ten times less compared to that of H₂Se. A selenization set-up using DESe as selenium source has been designed, fabricated and installed at FSEC Photovoltaic Materials Lab. Initial characterization of CIGS thin films have been carried out using electron probe microanalysis (EPMA), X-ray diffraction (XRD), scanning electron microscopy, secondary ion mass spectroscopy and Auger electron spectroscopy. EPMA showed elemental ratios of film to be near stoichiometric composition CuInSe₂ with very low gallium content mainly because of tendency of gallium to diffuse towards back contact. XRD data shows formation of high crystalline CuInSe₂ phase consistent with the EPMA data.     

A facile and environmentally friendly chemical route for the synthesis of metastable VO2 nanobelts

Metastable VO₂ nanobelts, designated as VO₂ (B), were successfully fabricated by a facile hydrothermal route in the presence of V₂O₅ and glucose. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), transmission electron microscopy (TEM), selected area electronic diffraction (SAED), high-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) techniques. The main synthesis parameters such as temperature, reaction time and molar ratio of the starting materials have been also discussed. The results showed that pure B phase VO₂ nanobelts with high crystallinity can be prepared easily at 180 °C in 24 h at the molar ratio of V₂O₅:glucose=1:1. Typically, the belt-like products were 0.6-1.2 μm long, 80-150 nm wide and 20-30 nm thick. It is noted that the whole process is free of any harmful reducing reagents and surfactants, and valuable gluconic acid can be formed as the main by-product. From an economic and environmental point of view, the present approach is particularly fit for the synthesis of VO₂ (B) nanobelts on a large scale.     

Compositional dependence of the optical properties of amorphous semiconducting glass Ge10AsxSe(90−x) thin films

Optical properties of ternary chalcognide amorphous Ge₁₀As_xSe_(90−x) (with 10?x?25 at%) thin films prepared by thermal evaporation have been measured in visible and near-infrared spectral region. The straightforward analysis proposed by Swanepoel has been successfully employed, and it has allowed us to determine the average thickness , and the refractive index, n, of the films, with high accuracy. The refractive index, n and the average thickness has been determined from the upper and lower envelopes of the transmission spectra measured at normal incidence, in the spectral range 400-2500 nm. The absorption coefficient α, and therefore extinction coefficient k, have been determined from the transmission spectra in the strong-absorption region. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple-DiDomenico model, and the optical absorption edge is described using the ‘nondirect transition’ model proposed by Tauc. Likewise, the optical energy gap is derived from Tauc's extrapolation. The relationship between the optical gap and chemical composition in Ge₁₀As_xSe_(90−x) amorphous system is discussed in terms of the average heat of atomization H_s and average coordination number N_c. Finally, the chemical bond approach has been also applied successfully to interpret the decrease of the glass optical gap with increasing As content.     

Chemical spray pyrolysis deposition and characterization of p-type CuCr1−xMgxO2 transparent oxide semiconductor thin films

A chemical spray pyrolysis technique for deposition of p-type Mg-doped CuCrO₂ transparent oxide semiconductor thin films using metaloorganic precursors is described. As-deposited films contain mixed spinel CuCr₂O₄ and delafossite CuCrO₂ structural phases. Reduction in spinel CuCr₂O₄ fraction and formation of highly crystalline films with single phase delafossite CuCrO₂ structure is realized by annealing at temperatures ?700 °C in argon. A mechanism of synthesis of CuCrO₂ films involving precursor decomposition, oxidation and reaction between constituent oxides in the spray deposition process is presented. Post-annealed CuCr_0.93Mg_0.07O₂ thin films show high (?80%) visible transmittance and sharp absorption at band gap energy with direct and indirect optical band gaps 3.11 and 2.58 eV, respectively. Lower (∼450 °C) substrate temperature formed films are amorphous and yield lower direct (2.96 eV) and indirect (2.23 eV) band gaps after crystallization. Electrical conductivity of CuCr_0.93 Mg_0.07O₂ thin films ranged 0.6-1 S cm⁻¹ and hole concentration ∼2×10¹⁹ cm⁻³ determined from Seebeck analysis. Temperature dependence of conductivity exhibit activation energies ∼0.11 eV in 300-470 K and ∼0.23 eV in ?470 K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Heterojunction diodes of the structure Au/n-(ZnO)/p-(CuCr_0.93Mg_0.07O₂)/SnO₂ (TCO) were fabricated which show potential for transparent wide band gap junction device.     

Composition-dependent structural and electrical properties of PbSe1−xTex thin films

Polycrystalline PbSe_1−xTe_x ingots were prepared by solid-state microwave synthesis. Thin films of PbSe_1−xTe_x were then deposited onto clean glass substrates using vacuum evaporation technique. Their nanostructure morphologies and stoichiometric ratio were examined using scanning electron microscopy (SEM) and energy dispersive X-ray spectra (EDX). X-ray diffraction (XRD) patterns indicated that the lattice constants of PbSe_1−xTe_x powders and thin films increased with the increasing amount of Te. From the electrical property measurements, the thin films were characterized by n-type behavior.     

Ferromagnetism of epitaxially grown CaRu1−xMxO3 (M=Ti, Mn) films

Epitaxial thin films of CaRu_1−xM_xO₃ (M=Ti, Mn) were fabricated on a (0 0 1)-SrTiO₃ substrate by spin-coat method using organometallic solutions (metal alkoxides). Results of X-ray diffraction and transmission electron microscopy indicate that the epitaxial films were grown pseudomorphically so as to align the [0 0 l] axis of the CaRu_1−xM_xO₃ films perpendicular to the (0 0 1) plane of the SrTiO₃ substrate. Ferromagnetism and metal-insulator transition are induced by the substitution of transition metal ions. The occurrence of ferromagnetism was explained qualitatively assuming a TiRu₆ cluster model for CaRu_1−xTi_xO₃ film and a mixed valence model for CaRu_1−xMn_xO₃ film. Ferromagnetism was also observed for layered CaRuO₃/CaMnO₃ film and CaRuO₃/CaMnO₃/CaRuO₃/CaMnO₃ multilayer film and the magnetism was explained by an interfacial exchange interaction model with magnetic Mn³⁺, Mn⁴⁺, and Ru⁵⁺ ions.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Synthesis and materials properties of transparent conducting In2O3 films prepared by sol-gel-spin coating technique

Transparent conducting indium oxide (In₂O₃) thin films have been prepared on glass substrates by the simple sol-gel-spin coating technique. These films have been characterized by X-ray diffraction, resistivity and Hall effect measurements, optical transmission, scanning electron microscopy and atomic force microscopy for their structural, electrical, optical and morphological properties. The influence of spin parameters, number of coating, process temperature on the quality of In₂O₃ films are studied. In the operating range of deposition, 400-475 °C, all the films showed predominant (2 2 2) orientation. Films deposited at optimum process conditions exhibited a resistivity of 2×10⁻² Ω cm along with the average transmittance of about 80% in the visible spectral range (400-700 nm).     

Low temperature synthesis of Mn0.4Zn0.6In0.5Fe1.5O4 nanoferrite for high-frequency applications

In the present study, nanoferrite of composition Mn_0.4Zn_0.6In_0.5Fe_1.5O₄ has been synthesized by co-precipitation method. Decomposition of residue at a temperature as low as 200 °C gives the ferrite powder. The ferrite has been, finally, sintered at 500 °C. The structural studies have been made by using X-ray diffraction (XRD) technique and scanning electron microscopy (SEM), which confirm the formation of single spinel phase and nanostructure. The dc resistivity is studied as a function of temperature and values found are more than twice those for the samples prepared by the other chemical methods. It is found that the resistivity decreases with increase in temperature. The initial permeability value is found to be higher as compared to the other chemical routes. The initial permeability value is found to increase with increase in temperature. At a certain temperature called Curie temperature, it attains a maximum value, after which the initial permeability decreases sharply. Even at nanolevel, appreciable value of initial permeability is obtained and low magnetic losses make these ferrites especially suitable for high-frequency applications. The particle size is calculated using Scherrer's equation for Lorentzian peak, which comes out between 35 and 49 nm. Possible mechanisms contributing to these processes have been discussed.     

Preparation and characterization of NiFe2O4/NiO composite film via a single-source precursor route

NiFe₂O₄/NiO nanocomposite thin films have been successfully prepared through a facile route using nickel iron layered double hydroxide (NiFe-LDH) as a single-source precursor. This synthetic approach mainly involves the formation of NiFe-LDH film by casting the slurry of NiFe-LDH precursor on the α-Al₂O₃ substrate, followed by high-temperature calcination. The composition, microstructure and properties of the films were characterized in detail by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and vibrating sample magnetometer (VSM). The results indicate that NiFe₂O₄/NiO composite film was composed of granules with diameter less than 100 nm, and the thickness of the film was in the range 1-2 μm. The magnetization of the film can be tuned by alternating the Ni/Fe molar ratio of LDH precursor. In addition, the method developed should be easily extended to fabricate other MFe₂O₄/MO composite film systems with specific applications just by an appropriate combination of divalent/trivalent composition in the precursor of LDHs.