Effect of C doping on the structural and optical properties of sol–gel TiO2 thin films

Undoped and C-doped TiO₂ thin films have been prepared by sol–gel process. Their structure and optical properties have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–vis spectroscopy. It has been observed that C dopants retard the transformation from anatase-to-rutile phase. Namely, C doping effect is attributed to the anatase phase stabilization. The optical analyses show that the optical band gap of anatase C-doped TiO₂ decreases with increasing amount of C. Also, it is founded that C dopants have been shown to make TiO₂ have a visible light photoresponse.     

Epitaxial growth of highly transparent and conducting Sc-doped ZnO films on c-plane sapphire by sol–gel process without buffer

Highly transparent and conductive scandium doped zinc oxide (ZnO:Sc) films were deposited on c-plane sapphire substrates by sol–gel technique using zinc acetate dihydrate [Zn(CH₃COO)₂·2H₂O] as precursor, 2-methoxyethanol as solvent and monoethanolamine as a stabilizer. The doping with scandium is achieved by adding 0.5 wt% of scandium nitrate hexahydrate [(ScNO₃·6H₂O)] in the solution. The influence of annealing temperature (300–550 °C) on the structural, optical and electrical properties was investigated. X-ray Diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.16° are obtained at an annealing temperature of 400 °C. The surface morphology of the films was judged by SEM and AFM images which indicated formation of grains. The average transmittance was found to be above 92% in the visible region. ZnO:Sc film, annealed at 400 °C exhibited minimum resistivity of 1.91 × 10⁻⁴ Ω cm. Room-temperature photoluminescence measurements of the ZnO:Sc films annealed at 400 °C showed ultraviolet peak at 3.31eV with a FWHM of 11.2 meV, which are comparable to those found in high-quality ZnO films. Reflection high-energy electron diffraction pattern confirmed the epitaxial nature of the films even without introducing any buffer layer.     

Densification of sol–gel silica thin films induced by hard X‐rays generated by synchrotron radiation

In this article the effects induced by exposure of sol–gel thin films to hard X‐rays have been studied. Thin films of silica and hybrid organic–inorganic silica have been prepared via dip‐coating and the materials were exposed immediately after preparation to an intense source of light of several keV generated by a synchrotron source. The samples were exposed to increasing doses and the effects of the radiation have been evaluated by Fourier transform infrared spectroscopy, spectroscopic ellipsometry and atomic force microscopy. The X‐ray beam induces a significant densification on the silica films without producing any degradation such as cracks, flaws or delamination at the interface. The densification is accompanied by a decrease in thickness and an increase in refractive index both in the pure silica and in the hybrid films. The effect on the hybrid material is to induce densification through reaction of silanol groups but also removal of the organic groups, which are covalently bonded to silicon via Si—C bonds. At the highest exposure dose the removal of the organic groups is complete and the film becomes pure silica. Hard X‐rays can be used as an efficient and direct writing tool to pattern coating layers of different types of compositions.     

Raman spectroscopy of sol–gel derived titanium oxide thin films

Raman spectra of TiO₂ films prepared via the sol–gel process were studied by UV and visible Raman spectroscopy. The evolution of the phases of TiO₂ films during annealing was investigated, and the relative intensities of the Raman bands excited with 325 nm were found to be distinct from those of the bands excited with 514 nm. The transmittance and FTIR spectra of the films annealed at different temperatures were characterized. The crystallization process of the powders and thin films treated by different annealing methods were also studied with Raman spectroscopy. The results show that the change in the relative intensities is caused by the resonance Raman effect. The anatase to rutile transition of the powder occurs at 700 °C, while that of the thin film occurs at 800 °C. The analysis of Raman band shape (peak position and full width at half‐maximum) after conventional furnace annealing and rapid thermal annealing indicates the influence of the non‐stoichiometry and phonon confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and high-frequency magnetic properties of sol–gel derived Ni–Zn ferrite–forsterite composites

Ni_0.5Zn_0.5Fe₂O₄–forsterite composites were synthesized by a sol–gel method. X-ray diffraction and SEM were used to characterize the crystallization behavior of the composite samples which were heat treated at temperatures varying from 800 to 1100°C. The results showed that Ni_0.5Zn_0.5Fe₂O₄ and forsterite (Mg₂SiO₄) can co-crystallize and the crystallites grow even more larger with increasing heat-treatment temperature. High-frequency (10 MHz–1 GHz) magnetic and dielectric properties of the composite samples were presented. Permeability increased with heat-treatment temperature. Quality factor was found to be two orders higher than that of equivalent pure, bulk ferrite.     

Preparation of LiMn2O4 thin films by a sol–gel method

LiMn₂O₄ thin films were prepared by a sol–gel method using spin-coating and annealing processes. Anhydrous Mn(CH₃COCHCOCH₃)₃ (manganese acetylacetonate) and LiCH₃COCHCO–CH₃ (lithium acetylacetonate) were chosen as source materials. The film electrochemical properties depended on the drying temperature even when subjected to the same annealing conditions. The discharge capacity of annealed film increased as the drying temperature was increased. However, the rate of capacity fading during cycling increased as the drying temperature was increased.     

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.     

Synthesis and optical characterization of c-axis oriented GaN thin films on amorphous quartz glass via sol–gel process

c-Axis oriented GaN nanocrystalline thin films were fabricated by nitridation of three different thin films of -GaO(OH), -Ga₂O₃ or β-Ga₂O₃ obtained by sol–gel technique on amorphous quartz glass substrates. All these GaN thin films showed near band edge emission at 390 nm and yellow luminescence at 570 nm. The crystalline nature and c-axis orientation as well as luminescence properties of the GaN thin films increased by several times by using a buffer layer of GaN on the substrate.     

Synthesis of self-assembly BaTiO3 nanowire by sol–gel and microwave method

Self-assembly ferroelectric BaTiO₃ nanowires were fabricated using sol–gel and microwave method. The X-ray diffraction patterns show that BaTiO₃ nanowires belong to the tetragonal perovskite structure. An increase in the intensity of (1 1 0) peak was observed as the annealing time increased. The shape of BaTiO₃ nanowires microwave-annealed for different minutes was investigated using atomic force microscopy. It is found that nanowires of BaTiO₃ annealed for 2.5 min are very clear-cut, orderly and almost uninterrupted. The height of nanowire is near to the film thickness. However, nanowires of BaTiO₃ annealed for 5 min are lesser, shorter and lower, and the distances among these nanowires are wider and well-proportioned. The origin of the distinct differences due to the remotion of atoms obtained enough energy was discussed.     

Structural characterization of the sol–gel oxide powders from the ZnO–TiO2–SiO2 system

This work is a study that deals with the synthesis by the sol–gel method and the structural characterization of the oxide powders belonging to the ternary system ZnO–TiO₂–SiO₂ (ZTS). The sol–gel synthesis starts from inorganic precursors, which have been processed under the variation of different technological parameters. We have investigated the dependence of the gelling time on pH and on the temperature of synthesis as well as on water and ammonia amounts. In the case of ZTS samples, the shortest gelling duration appears for low pH values when ZnO content is increased and at small ammonia concentrations when the ZnO content is decreased, respectively. On the contrary, ZTS samples containing high amounts of TiO₂ provide evidence of a short gelling time for high pH and large ammonia amounts. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy provided structural information on these ternary oxide powders. These analyses revealed that relative high amounts of ZnO yields in a change from octahedral [ ZnO₆] units to tetrahedral [ ZnO₄] units in the powder structure. Optical phonons specific for SiO₂ and TiO₂ in both octahedral and tetrahedral groups are shown. High thermal and chemical stability was put in evidence by differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) in the 20–1000 C temperature range.     

Enhanced thermal stability of optical nonlinearity for anilino–silane derived inorganic–organic hybrid thin films

A series of chromophore-bonded inorganic–organic hybrid films were successfully prepared via a sol–gel process using the alkoxysilane dye (ICTES-DR1), anilinomethyltriethoxysilane (AMTES) and tetraethoxysilane (TEOS) as precursors. Second-order NLO properties and their thermal stability of the hybrid films were investigated by in situ second harmonic generation (SHG) measurement. The poled films exhibit large second harmonic coefficient (d₃₃) in the range of 32–41 pm/V at 1064 nm. The aniline group of the AMTES was found to be effective for improving the thermal stability of optical nonlinearity due to the formation of hydrogen bonds between the carbonyl and aniline group, which was confirmed by virtue of FTIR and UV–visible spectra.     

Growth and physical properties of sol–gel derived Co doped ZnO thin film

Zn_1−xCo_xO films were grown on glass by sol–gel spin coating process. The Zn_1−xCo_xO thin films with 10 at.% Co were highly c-axis oriented. The electrical resistivity of the films at 10 at.% Co had the lowest value due to the highest c-axis orientation. XPS and AGM analyses indicated that Co metal clusters weren’t formed, and the ferromagnetism was appeared at room temperature. The characteristics of the electrical resistivity and room temperature ferromagnetism of sol–gel derived Zn_1−xCo_xO films suggest a potential application to dilute magnetic semiconductor devices.     

Sol–gel preparation and characterisation of dense proton conducting Sr3CaZr0.5Ta1.5O8.75 thin films

Dense proton conducting Sr₃CaZr_0.5Ta_1.5O_8.75 films (1.25 μm, with grain size in the 200–400 nm range) were deposited, using the sol–gel method, on Al₂O₃–8%Y₂O₃-stabilised ZrO₂ plates. The obtained gels were characterised by differential and thermogravimetric thermal analysis (DTA–TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results of a study of the structural and electrical properties of Sr₃CaZr_0.5Ta_1.5O_8.75 films deposited on the mentioned substrates are presented herein. The structural data for the gels and films were compared with those obtained for the same material prepared by solid state synthesis. Electrical properties of the sandwich-type structure were investigated by AC impedance conductivity measurements at different temperatures, in both dry and wet 5% H₂/Ar atmospheres. A careful analysis of the impedance spectra for this complex structure was performed, using a model with a series of five electrical circuits, having resistance and capacitance coupled in parallel. The specific responses observed in the impedance spectra were assigned to the corresponding substrate and layer contributions. A significant improvement, by an order of magnitude, in the electrode response was observed in the presence of the interleaving Sr₃CaZr_0.5Ta_1.5O_8.75 proton conducting layer, between the electrode and electrolyte. This enhancement is lost at temperatures above that at which the Sr₃CaZr_0.5Ta_1.5O_8.75 dehydrates and its protonic conductivity diminishes. Considering the structural and electrical characterisation results, these Sr₃CaZr_0.5Ta_1.5O_8.75 sol–gel derived films have a potential use for proton conducting electrolyte or intermediate layer in fuel cells.     

Structure and optical properties of sol–gel derived Gd2O3 waveguide films

Pure and rare earth doped gadolinium oxide (Gd₂O₃) waveguide films were prepared by a simple sol–gel process and dip-coating method. Gd₂O₃ was successfully synthesized by hydrolysis of gadolinium acetate. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structure of Gd₂O₃ films annealed at different temperature ranging from 400 to 750 °C were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that Gd₂O₃ starts crystallizing at about 400 °C and the crystallite size increases with annealing temperature. Oriented growth of (4 0 0) face of Gd₂O₃ has been observed when the films were deposited on (1 0 0) Si substrate and annealed at 750 °C. The laser beam (λ=632.8 nm) was coupled into the film by a prism coupler and propagation loss of the film measured by scattering-detection method is about 2 dB/cm. Luminescence properties of europium ions doped films were measured and are discussed.     

Crystallization behavior and origin of c-axis orientation in sol–gel-derived ZnO:Li thin films on glass substrates

Preferentially, c-axis-oriented lithium-doped zinc oxide (ZnO:Li) thin films were prepared on Pyrex borosilicate glass substrates by a sol–gel method starting from zinc acetate dihydrate, lithium chloride, 2-methoxyethanol and monoethanolamine. Decomposition and crystallization behavior of dip-coated amorphous precursor films during post-annealing treatments were investigated by thermogravimetry–differential thermal analysis (TG–DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), optical transmittance measurements, field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). It was revealed that the films contained the organic compounds at temperatures up to 300°C, which was the key to the transformation from the amorphous to the crystalline state. Thermodynamical consideration of nucleation and crystal growth was made taking account of surface energies of the film and the glass substrate and an interfacial energy between them. Mechanisms underlying the c-axis orientation were proposed based upon the initial orientation due to nucleation and final growth orientation.     

Impact of interface geometric structure on organic–metal interface energetics and subsequent films electronic structure

We present the electronic structure of various pentacene thin films grown on Au(1 1 1), Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces studied by angle-resolved ultraviolet photoemission spectroscopy using synchrotron radiation. A systematic variation of the metal surface such as the substrate metal and its surface symmetry allows a comprehensive discussion on the correlation between the electronic structure and the interface geometric structure. In the monolayer regime, we observed the evidence of the formation of the organic–metal interface state depending on the metal surface, i.e., the interface geometric structure. This evidence is explained by the different organic–metal and intermolecular interactions, which originate from the hybridization of the molecular orbitals with the metal wavefunction. These interface geometric and electronic phenomena can be a seed for the subsequent film growth and resultant films electronic structure.     

Effect of post annealing temperature on structural and optical properties of ZnCdO thin films deposited by sol–gel method

Ternary ZnCdO thin films oriented along c-axis have been successfully deposited on p-Si (1 0 0) substrates using sol–gel spin coating route. To optimize most suitable annealing temperature for the Zn_1−xCd_xO thin films; these films with selected cadmium content x = 0.10 were treated at annealing temperatures from 300 °C up to 800 °C in oxygen ambient after deposition. The structural and optical properties of deposited thin films have been characterized by X-ray diffraction, energy dispersive spectroscopy, atomic force microscopy, UV–Vis spectroscopy, and photoluminescence spectra. The results show that the obtained films possess high crystallinity with wurtzite structure. The crystallite size, lattice parameters, lattice strain and stress in the deposited films are determined from X-ray diffraction analysis. The band gap energy increased as a function of annealing temperatures as observed from optical reflectance spectra of samples. The presence of Cd in the deposited films is confirmed by energy dispersive spectrum and it is observed that Cd re-evaporate from the lattice with annealing. The photoluminescence measurements as performed at room temperature did not exhibit any luminescence related to oxygen vacancies defects for lower annealing temperatures, as normally displayed by ZnO films. The green yellow luminescence associated to these defects was observed at higher annealing temperatures (≥700 °C).     

Structural and optical properties of Ba(Ti1−x,Nix)O3 thin films prepared by sol–gel process

Ba(Ti_1−x,Ni_x)O₃ thin films were prepared on fused quartz substrates by a sol–gel process. X-ray diffraction and Raman scattering measurements showed that the films are of pseudo-cubic perovskite structure with random orientation and the change of lattice constant caused by Ni-doping with different concentrations is very small. Optical transmittance spectra indicated that Ni-doping has an obvious effect on the energy band structure. The energy gap of Ba(Ti_1−x,Ni_x)O₃ decreased linearly with the increase of Ni concentration. It indicates that the adjusting of band gap can be achieved by controlling the Ni-doping content accurately in Ba(Ti_1−x,Ni_x)O₃ thin films. This has potential application in devices based on ferroelectric thin films.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Preparation and characterization of the transparent nanocomposite mirror film for the infrared region by sol–gel method

Transparent mirror coated, SiO₂–Ag/PV P nanocomposites were prepared on the Pyrex glass slides by dip-coating technique. Embedding of the silver (Ag) nanoparticles on silica modified polyvinyl pyrrolidone (PVP) was performed by the sol–gel method. As prepared transparent mirror coated SiO₂–Ag/PV P nanocomposite films were finally characterized for surface morphology, chemistry, and nano size dimensions using various advanced analytical techniques including, UV visible, Fourier transform, infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), dispersive x-ray analaysis (EDAX) and transmission electron microscopy (TEM) analysis. It was found that all the prepared samples were almost uniform particles of Ag nanospheres of 7–8 nm diameters arranged as double paralleled nanowires with an average length of 200–450 nm and diameters of around 20–25 nm.