Impedance spectroscopic studies of sol–gel derived barium strontium titanate thin films

In the present work electroceramic thin films of barium strontium titanate (Ba_1?xSr_xTiO₃ – BST) were deposited on stainless steel substrates by sol–gel technique. Homogeneous Ba_0.6Sr_0.4TiO₃ thin films as well as spatially inhomogeneous BST thin films exhibiting artificial gradients in composition normal to the growth surface were deposited. Both up- and down-graded BST films were fabricated by depositing successive layers with Sr mole fraction x ranging from x = 0.5 to x = 0.3. In the present study the tool of impedance spectroscopy has been used to study the dielectric properties of BST thin films at room temperature. To analyze the impedance spectroscopy data the Nyquist (Z″ vs. Z′) plots as well as the simultaneous representation of the imaginary part of impedance and electrical modulus (Z″, M″) vs. frequency were used. Experimental data were fitted using the CNLS fitting method. Agreement between experimental and simulated data was established. The data indicated that the thin film samples fabricated can be represented by an equivalent circuit with two relaxation frequencies.     

Influence of annealing temperature on the structural and anti-corrosion characteristics of sol–gel derived,spin-coated thin films

Recently, an aqueous particulate sol–gel process using metallic chloride precursors was introduced to synthesize zirconium titanate. In this paper, the effect of annealing temperature on the structural and corrosion protection characteristics of spin-coated thin films obtained from this sol–gel system was investigated. Based on scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and spectroscopic reflectometry studies, it was found that the flatness and thickness of the thin films were decreased by increasing the annealing temperature. Also, the corrosion protection of stainless steel AISI 316L provided by the prepared coatings, as analyzed by electrochemical potentiodynamic polarization experiments in a simulated body fluid, was improved in this order: 500 °C-annealed sample<900 °C-annealed sample<700 °C-annealed sample, attributed to a compromise between the defect density and the adhesion of the films to the substrate.     

Characterization of low-temperature solution-processed indium–zinc oxide semiconductor thin films by KrF excimer laser annealing

We have employed KrF excimer laser annealing (ELA) treatment on sol–gel derived indium–zinc oxide (IZO) precursor films to develop a method of low thermal-budget processing. As-coated IZO sol–gel film was dried at 150 °C and then annealed using KrF excimer laser irradiation under ambient air. The laser irradiation energy density was adjusted to 150, 250, 350, and 450 mJ/cm² to investigate the effects of laser irradiation energy density on the microstructure, surface morphology, optical transmittance, and electrical properties of laser annealed IZO thin films. Results of GIXRD and TEM-SAED indicated that the ELA IZO thin films had an amorphous phase structure. The surface characteristics and electrical properties of laser annealed IZO thin films were significantly affected by the laser irradiation energy density. It was found that the dried IZO sol–gel films irradiated with a laser energy density of 350 mJ/cm² exhibited the flattest surface, the highest average optical transmittance in the visible region, and the best electrical properties among all ELA samples.     

Synthesis and characterization of sol–gel derived calcium hydroxyapatite thin films spin-coated on silicon substrate

The goal of this study was to demonstrate that sol–gel processing route is suitable for the fabrication of calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, CHA) thin films on Si substrate by spin-coating technique. The substrate was spin-coated by precursor sol solution 1, 5, 15 and 30 times. The samples were annealed after each spin-coating procedure at 1000 °C for 5 h in air. In the sol–gel process ethylendiamintetraacetic acid and 1,2-ethandiol, and triethanolamine and polyvinyl alcohol were used as complexing agents and as gel network forming agents, respectively. The coatings were characterized using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) and Raman spectroscopies, profilometry and the contact angle measurements (CAM). It was demonstrated, that properties of calcium hydroxyapatite thin films depend on spinning and annealing times.     

Effects of annealing temperature on the microstructure,optical, ferroelectric and photovoltaic properties of BiFeO3 thin films prepared by sol–gel method

Bismuth ferrite thin films were prepared via sol–gel spin-coating method and the effects of annealing temperature on microstructure, optical, ferroelectric and photovoltaic properties have been investigated. The results show that the bismuth ferrite thin films annealed at 550 °C is single phase and the grain size increases with the rise of annealing temperature. The band gap of bismuth ferrite thin films annealed at 550–650 °C is between 2.306 eV and 2.453 eV. With the rise of the annealing temperature, the remnant polarization gradually decreases and the coercive electric field increases. The short circuit photocurrent density decreases with the rise of annealing temperature, and the open circuit photovoltage and the power conversion efficiency of bismuth ferrite thin films annealed at 550 °C are higher than the thin films annealed at higher temperature.     

Sol–gel derived undoped and boron-doped ZnO semiconductor thin films: Preparation and characterization

We report the influence of boron doping concentration on the microstructure, electrical and optical properties of solution-processed zinc oxide (ZnO) thin films. The B doping concentration in the resultant solutions was varied from 0 to 5 at%, and the pH value of each synthetic solution was adjusted to 7.0. XRD measurements, SEM observations, and SPM examinations revealed that boron doping produced ZnO thin films consisting of a fine grain structure with a flat surface morphology. Moreover, ZnO thin films doped with B raised the texture coefficient along the (002) plane. All B-doped ZnO (ZnO:B) thin films exhibited higher transparency than that of the undoped ZnO thin film in the wavelengths between 350 and 650 nm. The optical band gap and Urbach energy of the ZnO:B thin films were higher than those of the undoped thin film. According to electrical transport characteristics, the 1% B-doped ZnO thin film exhibited the highest Hall mobility of 17.9 cm²/V s, the highest electron concentration of 1.2×10¹⁵ cm⁻³, and the lowest electrical resistivity of 2.2×10² Ω cm among all of the ZnO:B thin films.     

Effects of annealing temperature on structure and electrical properties of sol–gel derived 0.65PMN-0.35PT thin film

0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (0.65PMN-0.35PT) thin films were deposited on Pt/Ti/SiO₂/Si substrates annealed from 550 to 700 °C using sol-gel process. The effects of annealing temperature on microstructure, insulating, ferroelectric and dielectric properties were characterized. The result reveals that 0.65PMN-0.35PT thin films possess a polycrystalline structure, matching well with the perovskite phase despite the existence of a slight pyrochlore phase. The film samples annealed at all temperatures exhibit relatively dense surfaces without any large voids and the grain size increases generally with the increase of the annealing temperature. Meanwhile, pyrochlore phase is considerably generated because of the deformation of perovskite phase caused by volatilization of Pb at an excessive high-temperature. The film annealed at 650 °C exhibits superior ferroelectricity with a remanent polarization (P_r) value of 13.31 μC/cm², dielectric constant (ε_r) of 1692 and relatively low dielectric loss (tanδ) of 0.122 at 10⁴ Hz due to the relatively homogeneous large grain size of 130 nm and low leakage current of approximately 10^-6 A/cm².     

Transparent semiconductor zinc oxide thin films deposited on glass substrates by sol–gel process

Transparent semiconductor ZnO thin films were spin-coated onto alkali-free glass substrates by a sol–gel process. The influence of ZnO sols synthesized via different solvents (2-ME, EtOH or IPA) on the surface morphologies, microstructures, optical properties and resistivities of the obtained films were investigated. The as-coated films were annealed in ambient air at 500 °C for 1 h. X-ray diffraction results showed all polycrystalline ZnO thin films to have preferred orientation along the (0 0 2) plane. The surface morphologies, optical transmittances and resistivity values of the sol–gel derived ZnO thin films depended on the solvent used. The ZnO thin films synthesized with IPA as the solvent exhibited the highest average transmittance 92.2%, an RMS roughness of 4.52 nm and a resistivity of 1.5 × 10⁵ Ω cm.     

Multilayer zirconium titanate thin films prepared by a sol–gel deposition method

Zirconium titanate multilayer thin films were prepared by an aqueous particulate sol–gel process followed by spin coating. The obtained structures were studied by transmission electron microscope, scanning electron microscope, atomic force microscope, and spectroscopic reflection analyses. According to the results, sound thin films up to three layers were developed, accompanied by an increase in thickness and roughness by increasing the number of the layers. It was also found that the coatings consist of globular nanoparticles with an average diameter of 50 nm. Considering the contribution of roughness to biological responses, the optimization of the surface characteristics to meet an optimal performance seems to be a challenging issue, which demands future studies.     

Ultrahydrophobic silica films by sol–gel process

Wettability of solid surfaces is a crucial concern in our daily life as well as in engineering and science. The present research work describes the room temperature (27 °C) synthesis of adherent and water repellent silica films on glass substrates using vinyltrimethoxysilane (VTMS) as a hydrophobic reagent by a single step sol–gel process. The silica sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS), methanol (MeOH), water (H₂O) constant at 1:14.69:5, respectively, with 0.01 M NH₄F throughout the experiments and the VTMS/TEOS molar ratio (M) was varied from 0 to 0.97. The effects of M on the surface structure and hydrophobicity have been researched. The static water contact angle as high as 144° and water sliding angle as low as 14° was obtained for silica film prepared from M = 0.97. The hydrophobic silica films retained their hydrophobicity up to a temperature of 255 °C and above this temperature the films became superhydrophilic. The prepared silica films were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier Transform Infrared (FT-IR) spectroscopy, humidity test and static and dynamic water contact angle measurements.     

Effect of annealing temperature on ferroelectric electron emission of sol–gel PZT films

In this work, the influence of annealing temperature on the ferroelectric electron emission behaviors of 1.3-μm-thick sol–gel PbZr_0.52Ti_0.48O₃ (PZT) thin film emitters was investigated. The results revealed that the PZT films were crack-free in perovskite structure with columnar-like grains. Increasing annealing temperature led to the growth of the grains with improved ferroelectric and dielectric properties. The remnant polarization increased slightly from 35.3 to 39.6 μC/cm² and the coercive field decreased from the 56.4 to 54.6 kV/cm with increasing annealing temperature from 600 to 700 °C. The PZT film emitters exhibited remarkable ferroelectric electron emission behaviors at the threshold voltage above 95 V. The film annealed at 700 °C showed a relatively lower threshold voltage and higher emission current, which is related to the improved ferroelectric and dielectric properties at higher annealing temperature. The highest emission current achieved in this work was around 25 mA at the trigger voltage of 160 V.     

Corrosion protection by zirconia-based thin films deposited by a sol–gel spin coating method

This paper focuses on the structure and corrosion behavior of 316L stainless steel coated by inorganic ZrO₂, hybrid ZrO₂–PMMA, and combined inorganic–hybrid films. The coatings were deposited by a particulate sol–gel spin-coating route, using carboxymethyl cellulose as a nanoparticle dispersant. The electrochemical evaluations were conducted in a simulated body fluid, via potentiodynamic polarization and impedance spectroscopic experiments. According to the results, the hybrid coating presented a better corrosion protection compared to the inorganic coating, due to a lesser density of structural defects. However, the best corrosion resistance was found for a combined coating which consists of an inorganic bottom layer and a hybrid top layer, due to a desirable compromise of good adhesion and low defect density.     

Structural and electrical properties of sol–gel-derived Al-doped bismuth ferrite thin films

Al-doped BiFeO₃ (BiFe_(1?x)Al_xO₃) thin films with small doping content (x=0, 0.05, and 0.1) were grown on Pt(111)/TiO₂/SiO₂/Si substrates at the annealing temperature of 550 °C for 5 min in air by the sol–gel method. The crystalline structure, as well as surface and cross section morphology were studied by X-ray diffraction and scanning electron microscope, respectively. The dielectric constant of BiFeO₃ film was approximately 71 at 100 kHz, and it increased to 91 and 96 in the 5% and 10% Al-doped BiFeO₃ films, respectively. The substitution of Al atoms in BiFeO₃ thin films reduced the leakage current obviously. At an applied electric field of 260 kV/cm, the leakage current density of the undoped BiFeO₃ films was 3.97×10^?4 A/cm², while in the 10% Al-substitution BiFeO₃ thin films it was reduced to 8.4×10^?7 A/cm². The obtained values of 2P_r were 63 μC/cm² and 54 μC/cm² in the 5% and 10% Al-doped BiFeO₃ films at 2 kHz, respectively.     

Optical properties of Nb-doped TiO2 thin films prepared by sol–gel method

In this work, we studied optical properties of pure and Nb-doped TiO₂ synthesized using a sol–gel method and deposited as thin films by spin-coating followed by annealing in air at 500 °C for 1 h. The surface elemental composition was derived from X-ray photoelectron spectra, while structure and surface morphology were investigated using X-ray diffraction and atomic force/scanning electron microscopy. Finally, the optical properties were investigated by means of UV–vis spectrophotometry and spectroscopic ellipsometry.The Nb content was determined from XPS measurements to vary between 1.8 and 4.3 at%. The XRD patterns of the deposited thin films, with a maximum thickness of about 56 nm, showed no diffraction peaks. As proven both by microscopy and spectroscopic ellipsometry studies doping TiO₂ with Nb modified the surface morphology of the samples; the grain size is increasing while the surface roughness decreases with the increase in Nb content. This is accompanied by a decrease in the refractive index and an increase of the extinction coefficient.     

Formation and characterization of p-type semiconductor CuCrO2 thin films prepared by a sol–gel method

This study adopted the sol–gel method to synthesize p-type semiconductor CuCrO₂ films and analyzed the effects of an annealing treatment, under a controlled argon atmosphere by changing the temperature and time, on the phase transformation, micro- and nano-structure, composition, and semiconductor properties of thin films. In the Cu–Cr–O phase transformation system, CuO, Cr₂O₃, and CuCr₂O₄ were the intermediate phases of the reaction for forming CuCrO₂: in the metastable state reaction process, the composite phases changed into a single phase, CuCrO₂; in the stable-state reaction process of CuCrO₂, carbon elements of precursors were released and eliminated; and finally the optoelectronic properties of the CuCrO₂ thin film were adjusted and changed. The CuCrO₂ thin film possessed cell- and polygon-like shaped microstructures. The carbon content in the CuCrO₂ film decreased, so the copper, chromium, and oxygen contents increased accordingly. The optical band gap of CuCrO₂ thin film increased from 2.81 eV to 3.05 eV, while the resistivity decreased. The nanoscale crystal was identified which also of the delafossite CuCrO₂ structure. Using the sol–gel method to prepare the CuCrO₂ thin films, an appropriate annealing temperature and time were helpful in forming the single-phase CuCrO₂; the decrease of precursor elements in the thin film could enhance the band gap and the conductivity of the material.     

Systematic investigation of the annealing temperature and composition effects on the dielectric properties of sol–gel BaxSr1−xTiO3 thin films

In this work, Ba_xSr_1?xTiO₃ sol–gel thin films (x = 0.7, 0.5 and 0.3) deposited on Pt/Si substrate and post-annealed at different temperatures have been investigated. A systematic study of the structure, microstructure and dielectric properties has been achieved for each composition. To our knowledge, for the first time, a systematic effect of post-deposition annealing temperature and composition is reported. For each Ba/Sr ratio, higher annealing temperature leads to crystallinity improvement and to grain growth. A shift of the ferroelectric to paraelectric transition toward the bulk Curie temperature with the increase of the annealing temperature is shown. These results are correlated with the increase of the permittivity, tunability and dielectric losses measured on MIM capacitors at low frequency. Moreover, the high frequency results, between 800 MHz and 30 GHz, are in very good agreement with low frequency measurements, and show a huge tunability up to 80% under 600 kV/cm.     

Electrohydrodynamic atomization deposition of PZT sol–gel slurry and sol infiltration on the films

This paper reports the use of a deposition technique, called electrohydrodynamic atomization, for producing PZT films from a composite sol–gel slurry. PZT slurries of different powder concentrations were prepared, and then atomization deposition of them was carried out and resultant films examined. It was observed that large splats with well-mixed PZT particles in sol and fine PZT clusters with dry PZT particle agglomeration can be deposited using this technique. In particular, intermediated sol infiltration process on the EHDA deposited film under optimized atomization condition was also studied. It was found that the film with sol infiltration process become more dense and the electrical properties (P_r, ?_r) were improved compared with that without sol infiltration after EHDA deposition.     

The study of BiCrxFe1−xO3 thin films synthesized by sol–gel technique

Cr-doped bismuth ferrite (BiCr_xFe_1?xO₃, BCFO) thin films were prepared by a sol–gel method with the value of x varying from 0 mol% to 10 mol%. The structures of the BCFO thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis was employed to represent the surface and cross-sectional morphologies of the thin films. Dielectric, electrical, ferroelectric and magnetic properties were measured by HP4294A, Keithley 4200, RT6000 and 6700 Magnet Controller at room temperature, respectively. The dielectric behaviour and insulation are improved in 3% Cr-doped BFO thin film which may be due to the reduced concentration of oxygen vacancies by 3% Cr doping.     

Sol–gel derived amorphous/nanocrystalline MgZnO thin films annealed by atmospheric pressure plasma jets

This paper reports the characterization of sol–gel derived MgZnO thin films annealed by atmospheric pressure plasma jets (APPJs). Mg_xZn_1−xO films exhibit high transparency (> 80%) in the visible light wavelength region. When 20 at% Mg is incorporated into the film, the optical bandgap reveals a blue shift from ~3.25 to ~3.5 eV and the resistivity increases by three to four orders of magnitude, owing to the substitution of Mg atoms into the Zn lattice sites. The absorption band edge becomes sharper and the bandgap becomes slightly narrower as the APPJ treatment time increases. This can be attributed to slight grain growth in the films. When the material is amorphous/nanocrystalline, the quantum confinement effect causes a slight decrease in the bandgap as the grain size increases, resulting in slope alteration at the absorption edge. Compressive stresses caused by the difference in the thermal expansion coefficients between the film and the substrate are generated during the drying process. This leads to surface wrinkling on the sol–gel derived Mg_0.2Zn_0.8O thin films.     

Morphological,structural and ellipsometric investigations of Cr doped TiO2 thin films prepared by sol–gel and spin coating

Pure and chromium doped titanium dioxide (TiO₂) thin films at different atomic percentages (0.5%, 1.3% and 2.9%) have been elaborated on ITO/Glass substrates by sol–gel and spin–coating methods using titanium (IV) isopropoxide as a precursor. The surface morphology of films was investigated by scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM), the structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission microscopy (HRTEM). SEM and HRTEM show homogenous and polycrystalline films. XRD patterns indicate a phase transition from anatase to anatase-rutile leading to expand the absorption band of TiO₂ molecules around 520 cm⁻¹ in FTIR spectra. The optical constants such as the refractive index (n), the extinction coefficient (K) and the band gap (E_g) as well as the film thickness are determined using spectroscopic ellipsometry technique and Fourouhi–Blommer dispersion model. Results show three major changes; (i) the thickness of pure TiO₂ layer is 54 nm, which linearly decreases when the layer is doped with chromium and reaches 33 nm for a doping concentration of 2.9%, (ii) the band gap energy (E_g) is also linearly reduced from 3.24 eV to 2.80 eV when the Cr-doping agent increases, and, (iii) a phase transition from anatase to anatase-rutile is observed causing an increase in values of n(λ) for wavelength greater than 350 nm.