Growth of GaN films on CoGa(001): an EELS and AES study

The formation and properties of ultra-thin GaN films were investigated by means of high-resolution electron energy-loss spectroscopy (EELS) and Auger electron spectroscopy (AES). Using the intermetallic alloy CoGa as the substrate material, GaN can be prepared on the (001) surface upon adsorption of ammonia at 80 K and subsequent thermal decomposition. Ultra-thin GaN films were grown by repeated cycles of ammonia adsorption and heating to 650 K. The GaN films show an FK mode at 695 cm⁻¹, in agreement with calculated spectra based on IR parameters. The electronic energy gap is determined to be E_g ≈ 3.5 eV.     

Comparison of magnetoreflection from CoFe-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> multilayer and granular films in the infrared spectral region

The paper reports on a study of light reflection and of the magnetorefractive effect in CoFe-Al₂O₃ multilayer and granular films in the IR region at λ = 2.5–25 μm. These films exhibit a noticeable tunneling magnetoresistance of 5–8%. It has been found that the spectra of the magnetorefractive effect have features at λ ≈ 6.7 and ≈8.1 μm originating from phonon mode excitation in the dielectric matrix. It has been established that the magnitude of the magnetorefractive effect exceeds 2.5% for multilayer films, a value substantially larger than that for granular ones. Magnetoreflection has been analyzed for two film systems with roughly equal tunneling magnetoresistance. It has been shown that magnetoreflection for granular films can be described in a first approximation by the modified Hagen-Rubens relation, while the enhanced effect exhibited by multilayer films requires inclusion of interference of the magnetooptical response.     

Characterization of the crystallization behaviors in the PbTiO3 thin films on Si substrates by an infrared spectroscopy technique

PbTiO₃ thin films on silicon substrates derived from a modified sol–gel technique are characterized by IR reflectance spectroscopy for the first time. Seven infrared (IR) reflectance peaks modes have been observed in the crystallized perovskite PbTiO₃ thin films and are assigned to the corresponding phonon modes. Comparisons between the IR reflectance spectra of PbTiO₃ thin films obtained by different annealing processes, i.e., rapid thermal annealing (RTA) and conventional thermal annealing (CTA), have also been carried out. It is observed that the frequencies of most peaks in the RTA-derived PbTiO₃ films are lower than that in the CTA-derived films.     

Effect of magnetic field on the IR optical properties of dielectrics

Magnetic-field induced changes revealed in reflectance spectra R(λ) of nonmagnetic dielectrics Al₂O₃, LiF, and MgO in the IR range (λ = 2.5–25 μm) are reported. The reflectance spectra are shown to have specific features in the vicinity of the wavelengths corresponding to optical phonon mode excitation in these crystals, with the magnetic field giving rise to a noticeable change of reflectance ΔR/R(λ) at these wavelengths. The value of ΔR/R(λ) for p-(s-) polarized IR radiation in a magnetic field of ～13 kOe is ～0.6% (～0.4%) for Al₂O₃ at λ ≈ 9.6 μm, ～1.63% (～1.15) for LiF at λ ≈ 11.1 μm, and ～ 0.07 (～0.2%) for MgO at λ ≈ 11.7 μm, respectively. These changes can be increased substantially by irradiating the dielectric crystals by x-ray radiation. It is shown that the optical and magnetooptical properties of the above dielectrics in the IR spectral region can be described in terms of the polaron excitation theory.     

IR spectra of carbon-vacancy clusters in the topochemical transformation of silicon into silicon carbide

Using infrared (IR) spectroscopy and spectral ellipsometry, we experimentally confirmed the previously predicted mechanochemical effect of the stoichiometric composition disorder leading to the formation of carbon-vacancy structures in silicon carbide (SiC) films grown on silicon substrates by the atom substitution method. It was found that a band at 960 cm^–1 in the IR spectra of SiC films on silicon, corresponding to “carbon-vacancy clusters” is always present in SiC films grown under pure carbon monoxide (CO) or in a mixture of CO with silane (SiH₄) on Si substrates of different orientation and doping level and type. There is no absorption band in the region of 960 cm–1 in the IR spectra of SiC films synthesized at the optimum ratio of the CO and trichlorosilane (SiHCl₃) gas pressures. The previously predicted mechanism of the chemical reaction of substitution of Si atoms for carbon by the interaction of gases CO and SiHCl₃ on the surface of the silicon substrate, which leads to the formation of epitaxial layers of single-crystal SiC, is experimentally confirmed.     

New counter electrode prepared as vanadium oxide and V/Ce oxide films: preparation and characterization

Vanadium oxide and mixed V/Ce-oxide films at 78, 55, 38, 32 atomic % of V were prepared via the sol-gel route from an aqueous colloidal solution of inorganic precursors. The influence of the added cerium precursor on their electrochemical, optical and structural properties was investigated by cyclic voltammetry (CV), X-ray analysis, IR spectroscopy and UV-VIS techniques. The electrochemical stability of films was tested by CV measurements in 1 M LiClO₄ in propylene carbonate electrolyte. The addition of CeO₂ improved the poor stability of vanadium oxide films and enhanced their ion-charge capacity up to 30 mC/cm² for thicknesses about 300 nm. The intercalation of Li⁺ ions in vanadium oxide and V/Ce-oxide films was followed by FT-IR spectroscopy performed at near-grazing incidence angle (NGIA) conditions in combination with CV measurements at potentials of −1.5 V and +2.0 V (vs. Ag/AgCl). The observed shift of V–O_v vibrations in the IR spectra confirmed the intercalation of Li⁺ ions.     

Magnetorefractive effect in (Co<Subscript>50</Subscript>Fe<Subscript>50</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> granular films

The reflectivity spectra and the magnetorefractive effect (MRE) of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x metal-dielectric granular films (0.07<x<0.52) are analyzed in the IR spectral range λ=2.5–25 µm. It is revealed that the specific features observed in the spectra at λ≈8.5 and 20 µm are associated with the excitation of phonon modes in the dielectric matrix. The magnetorefractive effect in the films is observed below the percolation thresh-old only in p-polarized light and above the percolation threshold for both the p and s polarizations. It is demonstrated that the optical properties of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x films in the IR spectral range, to a first approximation, can be interpreted in the framework of the effective-medium theory and the magnetorefractive effect can be explained in terms of the modified Hagen-Rubens relation.     

Synthesis of Ge nanocrystals by atom beam sputtering and subsequent rapid thermal annealing

Ge nanocrystals embedded in an SiO₂ matrix were prepared by the atom beam co-sputtering (ABS) method from a composite target of Ge and SiO₂. The as-deposited films were rapid thermally annealed at the temperatures 700 and 800 °C in nitrogen ambience. The structure of the films was evaluated by using X-ray diffraction (XRD) and Raman spectroscopy. XRD results reveal that as-deposited films are amorphous in nature whereas annealed samples show crystalline nature. Raman scattering spectra showed a peak of Ge–Ge vibrational mode shifted downwards to 297 cm^?1, presumably caused by quantum confinement of phonons in the Ge nanocrystals. Rutherford backscattering spectrometry has been used to measure the thickness and Ge composition of the composite films. Size variation of Ge nanocrystals with annealing temperature has been discussed. The advantages of ABS over other methods are highlighted.     

SiCN thin film prepared at room temperature by r.f. reactive sputtering

Silicon–carbon nitride (SiCN) thin films were deposited on Si substrate at room temperature by r.f. reactive sputtering. Fourier transform infrared spectroscopy (FTIR), optical absorption spectra (α(λ)) and electrical conductivity (σ) were studied for the thin films. The effect of the annealing on IR and σ was investigated at different temperatures. IR analysis indicates that Si–H, C–N, Si–C, Si–N, C–N and CN bonds are present in a-SiCN:H films. A shift of the stretching mode for Si–H bond to the high-wavenumber side is observed with increasing the nitrogen flow ratio γ_N2(=N₂/(Ar+H₂+N₂+CH₄)). The shift is from 2000 to 2190 cm⁻¹ when γ_N2=13.7%. The study shows that the film structure and optical and electrical properties are obviously modified readily by controlling the process parameters of deposition. The improvement in the film properties, e.g., good thermal stability, is explained mainly in terms of the cross-linked structure between the Si, C and N atoms.     

Preparation and investigation of optical, structural, and morphological properties of nanostructured ZnO:Mn thin films

Nanostructured ZnO:Mn thin films have been prepared by sol–gel dip coating method. The content of Mn in the sol was varied from 0 to 12 wt%. The effect of Mn concentration on the optical, structural, and morphological properties of ZnO thin films were studied by using Fourier Transform Infrared (FTIR), UV–visible and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD results showed that the films have hexagonal wurtzite structure at lower content of Mn. The diffraction peaks corresponding to ZnO disappeared and two diffraction peaks of MnO₂ and Mn₃O₄ appeared at the highest value of doping concentration (viz., 12 wt%). SEM results revealed that the surface smoothness of the films improved at higher content of Mn. The optical band gap of the films decreased from 3.89 to 3.15 eV when the Mn concentration increased from 0 to 12 wt%. The PL spectra of the films showed the characteristic peaks linked to band-to-band, green and yellow emissions. Besides, the PL intensity of the samples decreased with increase in Mn concentration.     

Structural, magnetic and electronic structure studies of Mn doped TiO2 thin films

We report structural, magnetic and electronic structure study of Mn doped TiO₂ thin films grown using pulsed laser deposition method. The films were characterized using X-ray diffraction (XRD), dc magnetization, X-ray magnetic circular dichroism (XMCD) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. XRD results indicate that films exhibit single phase nature with rutile structure and exclude the secondary phase related to Mn metal cluster or any oxide phase of Mn. Magnetization studies reveal that both the films (3% and 5% Mn doped TiO₂) exhibit room temperature ferromagnetism and saturation magnetization increases with increase in concentration of Mn doping. The spectral features of XMCD at Mn L_3,2 edge show that Mn²⁺ ions contribute to the ferromagnetism. NEXAFS spectra measured at O K edge show a strong hybridization between Mn, Ti 3d and O 2p orbitals. NEXAFS spectra measured at Mn and Ti L_3,2 edge show that Mn exist in +2 valence state, whereas, Ti is in +4 state in Mn doped TiO₂ films.     

Formation of textured Ni(200) and Ni(111) films by magnetron sputtering

The effect of the working gas pressure (P ≈ 1.33–0.09 Pa) and the substrate temperature (T_s ≈ 77–550 K) on the texture and the microstructure of nickel films deposited by magnetron sputtering onto SiO₂/Si substrates is studied. Ni(200) films with a transition type of microstructure are shown to form at growth parameters P ≈ 0.13–0.09 Pa and T_s ≈ 300–550 K, which ensure a high migration ability of nickel adatoms on a substrate. This transition type is characterized by a change of the film structure from quasi-homogeneous to quasi-columnar when a film reaches a critical thickness. Ni(111) films with a columnar microstructure and high porosity form at a low migration ability, which takes place at P ≈ 1.33–0.3 Pa or upon cooling a substrate to T_s ≈ 77 K.     

Bioglass thin films for biomimetic implants

Pulsed laser deposition (PLD) method was used to obtain bioglass (BG) thin film coatings on titanium substrates. An UV excimer laser KrF* (λ = 248 nm, τ = 25 ns) was used for the multi-pulse irradiation of the BG targets with 57 or 61 wt.% SiO₂ content (and Na₂O-K₂O-CaO-MgO-P₂O₅ oxides). The depositions were performed in oxygen atmosphere at 13 Pa and for substrates temperature of 400 °C. The PLD films displayed typical BG of 2-5 μm particulates nucleated on the film surface or embedded in. The PLD films stoichiometry was found to be the same as the targets. XRD spectra have shown, the glass coatings obtained, had an amorphous structure. One set of samples, deposited in the same conditions, were dipped in simulated body fluids (SBFs) and subsequently extracted one by one after several time intervals 1, 3, 7, 14 and 21 days. After washing in deionized water and drying, the surface morphology of the samples and theirs composition were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy (FTIR) and energy dispersive X-ray analysis (EDX). After 3-7 days the Si content substantially decreases in the coatings and PO₄³⁻ maxima start to increase in FTIR spectra. The XRD spectra also confirm this evolution. After 14-21 days the XRD peaks show a crystallized fraction of the carbonated hydroxyapatite (HAP). The SEM micrographs show also significant changes of the films surface morphology. The coalescence of the BG droplets can be seen. The dissolution and growth processes could be assigned to the ionic exchange between BG and SBFs.     

Analysis of the optical properties of poly(3‐octylthiophene) partially dedoped

In this work, poly(3‐octylthiophene) (P3OT) films were synthesized electrochemically in non‐aqueous media through the oxidation of the monomer, (3‐octylthiophene), using a standard three‐electrode cell in acetonitrile with 0.05 mol L^?1 LiClO₄ or 0.05 mol L^?1 Et₄NBF₄. The polymeric films were deposited on fluorine tin oxide (FTO). The partial dedoping was obtained in NH₄OH solution, providing a good chemical stability of the formed material. The films obtained through this method have been characterized by Fourier‐transform infrared spectroscopy (FT‐IR), electron paramagnetic resonance (EPR), UV–Vis absorption, and photoluminescence (PL) spectroscopy. The FT‐IR and EPR spectra together gave the results that led to characterization of two structures (pristine and non‐pristine forms of thiophene rings) while forming the P3OT polymer chain. These results were associated with the stabilization of pristine chains and mixed chains (non‐pristine structures) in the polymeric film. Their bands in the PL spectra are wide and asymmetric and their adjustments by Gaussian functions was necessary; this was the main indication that there are two distinct contributions to the emission spectra. These two contributions are attributed to the emission by mixed chains (Gaussian centered at higher energy) and by pristine chains (Gaussian of lower energy) present in the formed polymeric material. Copyright © 2010 John Wiley & Sons, Ltd.     

Manifestation of an intermediate phase in a ferroelastic K3Na(CrO4)2:MnO 4 2− in raman and IR absorption spectra

In a broad temperature range of 4–300 K, we have performed a complex combined investigation of phase transitions in crystals of a ferroelastic K₃Na(CrO₄)₂:MnO ₄ ^2? using methods of Raman light scattering and IR light absorption. Considerable changes that we have observed in both Raman and IR spectra in the range of T ≈ 150 K testify to the occurrence of another phase transition that has not been observed before at this temperature. We have performed a group-theoretical analysis and compared its results with experimental spectra, which has allowed us to conclude that there are two phase transitions in this crystal, \(P\bar 3m1 \to C2/m \to C2/c\) , which occur at temperatures T _c1 ≈ 230 K and T _c2 ≈ 150 K, respectively.     

Preparation and photo-induced superhydrophilicity of composite TiO2-SiO2-In2O3 thin film

In this work, TiO₂-SiO₂-In₂O₃ composite thin films on glass substrates were prepared by the sol-gel dip coating process. X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF) and X-ray photoelectron spectroscopy (XPS) were used to evaluate the structural and chemical properties of the films. UV-vis spectrophotometer was used to measure the transmittance spectra of thin films. The water contact angle (WCA) of thin films during UV/vis irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicated that fabrication of composite film has a significant effect on transmittance and superhydrophilicity of TiO₂ films.     

Photocatalytic TiO2 films deposited by rf magnetron sputtering at different oxygen partial pressure

Titanium dioxide (TiO₂) films were deposited onto non-alkali glass substrates by r.f. magnetron sputtering at an [O₂/(Ar + O₂)] flow-rate of 0, 20, 40, 60 and 70%, respectively. The sputtering pressure was 10 mtorr, substrate temperature was around 450 °C after 3 h deposition. The crystalline structure, surface morphology and photocatalytic activity of the TiO₂ films were affected by various [O₂/(O₂ + Ar)] flow-rate ratios. The films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and UV–vis–NIR spectroscopy. X-ray diffraction spectra showed that all the films display anatase (1 0 1) preferred orientation. Photoinduced decomposition of methylene blue (MB) and photoinduced hydrophilicity were enhanced when the [O₂/(Ar + O₂)] flow-rate increased to 60%.     

Structural and optical properties of CuSe2 nanocrystals formed in thin solid Cu–Se film

This paper describes the structural and optical properties of Cu–Se thin films. The surface morphology of thin films was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Formation of Cu–Se thin films is concluded to proceed unevenly, in the form of islands which later grew into agglomerates. The structural characterization of Cu–Se thin film was investigated using X-ray diffraction pattern (XRD). The presence of two-phase system is observed. One is the solid solution of Cu in Se and the other is low-pressure modification of CuSe₂. The Raman spectroscopy was used to identify and quantify the individual phases present in the Cu–Se films. Red shift and asymmetry of Raman mode characteristic for CuSe₂ enable us to estimate nanocrystal dimension. In the analysis of the far-infrared reflection spectra, numerical model for calculating the reflectivity coefficient of layered system, which includes film with nanocrystalite inclusions (modeled by Maxwell-Garnett approximation) and substrate, has been applied.     

Probing the ferroelectric phase transition in sol–gel‐derived polycrystalline bismuth ferrite thin films

Polycrystalline BiFeO₃ (BFO) thin films were successfully grown on Pt/Ti/SiO₂/Si(100) and SrTiO₃ (STO) (100) substrates using the chemical solution deposition (CSD) technique. X‐ray diffraction (XRD) patterns indicate the polycrystalline nature of the films with rhombohedrally distorted perovskite crystal structure. Differential thermal analysis (DTA) was performed on the sol–gel‐derived powder to countercheck the crystal structure, ferroelectric (FE) to paraelectric (PE) phase transition, and melting point of bismuth ferrite. We observed a significant exothermic peak at 840 °C in DTA graphs, which corresponds to an FE–PE phase transition. Raman spectroscopy studies were carried out on BFO thin films prepared on both the substrates over a wide range of temperature. The room‐temperature unpolarized Raman spectra of BFO thin films indicate the presence of 13 Raman active modes, of which five strong modes were in the low‐wavenumber region and eight weak Raman active modes above 250 cm⁻¹. We observed slight shifts in the lower wavenumbers towards lower values with increase in temperature. The temperature‐dependent Raman spectra indicate a complete disappearance of all Raman active modes at 840 °C corresponding to the FE–PE phase transitions. There is no evidence of soft mode phonons. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of deposition time on structural and physical properties of Cu<Subscript>2</Subscript>CdSnS<Subscript>4</Subscript> thin films prepared by spray pyrolysis technique: experimental and ab initio study

Cu₂CdSnS₄ (CCdTS) thin films were synthesized using chemical spray pyrolysis deposition technique. The effect of various deposition times (20, 40, 60 min) on growth of these films was investigated. The as-synthesized Cu₂CdSnS₄ thin films were characterized by X-ray diffraction (XRD), ultraviolet–visible (UV–Vis) spectroscopy, Raman spectroscopy and Hall Effect measurements. The XRD pattern of Cu₂CdSnS₄ structured in stannite phase with preferential orientations along (112) planes. Raman spectrum revealed very strong peak at about 333 cm^?1. The films have the direct optical band gaps of 1.39–1.5 eV. The optimum hole mobility was found to be 3.212 × 10¹ cm² v^?1 s^?1 for the film deposited on 60 min. The electronic structure and optical properties of the stannite structure Cu₂CdSnS₄ were obtained by ab initio calculations using the Korringa–Kohn–Rostoker method combined with the Coherent Potential Approximation (CPA), as well as CPA confirms our results.