Influence of precursor source on sol–gel deposited ZnO thin films properties

Zinc oxide thin films were deposited by sol gel technique on glass substrates using different precursors (zinc acetate, zinc nitrate and zinc chloride). In the present work we investigate the precursor nature influence on structural, morphological, optical, electrical properties and photocatalytic activity of ZnO thin films. For this purpose we have used X-rays diffraction (XRD), atomic force microscopy (AFM), UV–visible spectroscopy and Hall effect measurements for films characterization. The obtained results indicated that ZnO films properties are strongly influenced by the nature of the used precursor as reactant. Films photocatalytic activity was evaluated by the photo-degradation of methylene blue (MB) dissolved in aqueous solution under UV-A light. The obtained results indicated that ZnO thin films prepared from zinc acetate are more efficient than those prepared from zinc nitrate and zinc chloride.     

Dense PLZT films grown on nickel substrates by PVP-modified sol–gel method

We have successfully grown ferroelectric Pb_0.92La_0.08Zr_0.52Ti_0.48O₃ (PLZT) films on base metal foils by chemical solution deposition using sol–gel solutions containing polyvinylpyrrolidone. Under zero-bias field, we measured a dielectric constant of ≈820 and dielectric loss of ≈0.06 at room temperature, and a dielectric constant of ≈1250 and dielectric loss of ≈0.03 at 150 °C. In addition, leakage current density of ≈1.5 × 10^?8 A/cm², remanent polarization of ≈11.2 μC/cm², and coercive field of ≈40.6 kV/cm were measured at room temperature on a ≈3-μm-thick PLZT film grown on LaNiO₃-buffered nickel substrate. Finally, energy density ≈25 J/cm³ was measured from the P–E hysteresis loop at an applied field of 2 × 10⁶ V/cm.     

Preparation and luminescent properties of Eu-doped BaTiO3 thin films by sol–gel process

Eu-doped BaTiO₃ thin films with a pseudo-cubic perovskite structure were successfully fabricated on magnesia substrates at low temperature by using a high-concentration sol–gel process, in which the newly developed gel-aging process on substrate was employed. Film microstructure, crystallinity, sintering properties and photoluminescence (PL) were investigated. The xerogel thin films exhibited strong PL associated with Eu³⁺ ions under ultraviolet excitation at room temperature; the PL was visible to naked eyes. The intensity maximum of PL was reached with doping concentration of about 8 mol%. Sintering above 600 °C caused reduction of europium, resulting in a rapid quenching of Eu³⁺ emission and enhancement of Eu²⁺ emission.     

Influence of pH on ZnO nanocrystalline thin films prepared by sol–gel dip coating method

ZnO nanocrystalline thin films have been prepared on glass substrates by sol?Cgel dip coating method. ZnO thin films have been coated at room temperature and at four different pH values of 4, 6, 8 and 10. The X-ray diffraction pattern showed that ZnO nanocrystalline thin films are of hexagonal structure and the grain size was found to be in the range of 25?C45?nm. Scanning electron microscopic images show that the surface morphology improves with increase of pH values. TEM analysis reveals formation of ZnO nanocrystalline with an average grain size of 44?nm. The compositional analysis results show that Zn and O are present in the sample. Optical band studies show that the films are highly transparent and exhibit a direct bandgap. The bandgap has been found to lie in the range of 3 $\boldsymbol\cdot$ 14?C3 $\boldsymbol\cdot$ 32?eV depending on pH suggesting the formation of ZnO nanocrystalline thin films.     

Influence of annealing temperature and oxygen atmosphere on the optical and photoluminescence properties of BaTiO3 amorphous thin films prepared by sol–gel method

Homogeneous and transparent BaTiO₃ thin films were prepared by sol–gel dip coating method. The prepared BaTiO₃ thin films were annealed in air and O₂ atmosphere at different temperatures. The annealed BaTiO₃ thin films were amorphous in nature. Scanning electron microscopy (SEM) revealed the nucleation and particle growth on the films. Energy-dispersive X-ray (EDX) analysis data revealed the adsorption of oxygen atoms in the BaTiO₃ film. The direct energy band gap was found to vary (3.84–3.58 eV) as functions of annealing atmosphere and temperature. Photoluminescence (PL) revealed intense emission peaks at 393 and 675 nm. Quenching of PL intensity was observed in films annealed at high temperature and in O₂ atmosphere. This is due to reduction in the oxygen vacancy by the adsorption of oxygen in the film. Luminescence spectra also have been related to the results obtained by SEM and EDX analysis. The change in luminescence intensity of BaTiO₃ thin films makes it suitable for optoelectronic temperature sensor applications.     

Effects of preferred orientation on the piezoelectric properties of Pt/Pb(Zr0.3Ti0.7)O3/Pt thin films grown by sol–gel process

Tetragonal lead zirconate titanate (PZT) films with different orientations and 200 nm film thicknesses were prepared on platinized silicon substrates. Types of substrate and control of thermal processes, such as layer-by-layer and one-crystallization heat treatments, result in highly (111) or (100)-oriented PZT films. The piezoelectric, dielectric, and ferroelectric properties of polycrystalline PZT films have been investigated as a function of preferred orientation. The property difference between (111) and (100)-oriented films appears to be induced by the effect of ferroelastic domain existence (90° domain in tetragonal composition). From a modified phenomenological equation, the higher electrostrictive coefficient value of 5.6 × 10⁻² m⁴/C² for (100)-oriented PZT may be responsible for the larger piezoelectric coefficients in (100)-oriented polycrystalline PZT films of 44 pm/V in comparison to (111)-oriented PZT films with about 3.1 × 10⁻² m⁴/C² of Q ₃₃ and 40 pm/V of d _33,f . It was also observed that two (100)-oriented films prepared by different heat treatments showed different values in piezoelectric, dielectric, and ferroelectric properties even though only (100) orientation was characterized for both cases. This process-induced difference may also play an important role in determining both intrinsic and extrinsic contribution to the properties, even though these parameters seem to be more responsible for extrinsic components, such as domain wall motion.     

Influence of Fe dopant concentration and annealing temperature on the structural and optical properties of ZnO thin films deposited by sol–gel method

Nanostructured Fe doped ZnO thin films were deposited onto glass substrates by sol–gel spin coating method. Influence of Fe doping concentration and annealing temperature on the structural, compositional, morphological and optical properties were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV–Vis spectroscopy and photoluminescence (PL) measurements. XRD analysis showed that all the films prepared in this work possessed a hexagonal wurtzite structure and were preferentially oriented along the c-axis. Pure ZnO thin films possessed extensive strain, whereas Fe doped films possessed compressive strain. In the doped films, least value of stress and strain was observed in the 0.5 at.% Fe doped thin film, annealed at 873 K. Average crystallite size was not significantly affected by Fe doping, but it increased from 15.57 to 17.79 nm with increase in annealing temperature from 673 to 873 K. Fe ions are present in +3 oxidation state as revealed by XPS analysis of the 0.5 at.% Fe doped film. Surface morphology is greatly affected by changes in Fe doping concentration and annealing temperature which is evident in the SEM images. The increase in optical band gap from 3.21 to 3.25 eV, with increase in dopant concentration was attributed to Moss–Burstein shift. But increase in annealing temperature from 673 to 873 K caused a decrease in band gap from 3.22 to 3.20 eV. PL spectra showed emissions due to excitonic combinations in the UV region and defect related emissions in the visible region in all the investigated films.     

Effect of Zn doping on structure and ferroelectric properties of PST thin films prepared by sol–gel method

(Pb _y Sr_1−y )Zn _x Ti_1−x O_3−x thin films were prepared on ITO/glass substrate by sol–gel process using dip-coating method. The phase structure, morphology and ferroelectric property of the thin film were studied. All the thin films show the typical perovskite phase structure. Both the crystallinity and c/a ratio of the perovskite phase increases initially and then decreases gradually with doping Zn in the thin film. Ferroelectric properties of the Zn-doped PST thin films, including ferroelectric hysteresis-loop, remnant polarization and coercive force, decrease gradually with increasing Zn. And the effect of Zn on ferroelectric properties is more obvious in PST thin film with high content of Pb than that with low Pb although the high lead thin film exhibits high intrinsic ferroelectric properties.     

Characteristics of CeOx–VO2 composite thin films synthesized by sol–gel process

Pure vanadium dioxide (VO₂) and CeOx–VO₂ (1.5 < x < 2) composite thin films were grown on muscovite substrate by inorganic sol–gel process using vanadium pentaoxide and cerium(III) nitrate hexahydrate powder as precursor. The crystalline structure, morphology and phase transition properties of the thin films were systematically investigated by X-ray diffraction, Raman, X-ray photoelectron spectroscopy, FE-SEM and optical transmission measurements. High quality of the VO₂ and CeOx–VO₂ composite films were obtained, in which the relative fractions of +4 valence state vanadium were above 70 % though the concentrations of cerium reached 9.77 at %. However, much of cerium compounds were formed at the edge of grains and the addition of cerium resulted in more clearly defined grain boundaries as shown in SEM images. Meanwhile, the composite films exhibited excellent phase transition properties and the infrared transmittance decreased from about 70 to 10 % at λ = 4 μm bellow and above the metal–insulator phase transition temperature. The metal–insulator phase transition temperatures were quite similar with about 66 °C of the pure VO₂ and CeOx–VO₂ composite thin films. But hysteresis widths increased with more addition of cerium, due to the limiting effect of grain boundaries on the propagation of the phase transition. Particularly, the CeOx–VO₂ composite film with an addition of 7.82 at % Ce showed a largest hysteresis width with about 20.6 °C. In addition, the thermochromic performance of visible transmittance did not change obviously with more addition of cerium.     

Low-temperature preparation of transparent conductive Al-doped ZnO thin films by a novel sol–gel method

We developed a novel sol–gel method to prepare transparent conductive Al-doped ZnO (AZO) thin film at low temperature. The AZO nanocrystals were prepared by a solvothermal method and then they were dispersed in the monoethanolamine and methanol to form AZO colloids. A (002)-oriented ZnO thin film was used as a nucleation layer to induce the (002)-oriented growth of AZO thin films. The AZO thin films were prepared on Si(100) and fused quartz glass substrates with the (002)-oriented ZnO nucleation layer and annealed at 400 °C for 60 min. All AZO thin films showed (002) orientation. For electrical and optical measurements, the films deposited on glass substrates were post-annealed at 400 °C for 30 min in forming gas (100 % H₂) to improve their conductivity. These samples had high transparency in the visible wavelength range, and also showed good conductivity. A 0.2 mol L^?1 AZO solution with 3 at.% Al content was heated in a Teflon autoclave at 160 °C for 30 min to form AZO nanocrystals, and then the AZO nanocrystals were suspended in the MEA and methanol to obtain the stable AZO colloid. The Al content in the AZO nanocrystals was 2.7 at.%, and the high Al doping coefficient was mainly attributed to the formation of AZO nanocrystals in the autoclave. The AZO thin film using this colloid had the lowest resistivity of 3.89 × 10^?3 Ω cm due to its high carrier concentration of 3.29 × 10²⁰ cm^?3.     

Microstructure and ferroelectric properties of compositionally graded Nd-doped Bi4Ti3O12 thin films prepared by sol–gel method

The compositionally graded Bi_4?xNd_xTi₃O₁₂ (BNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by sol–gel method. Their microstructure, ferroelectric and dielectric properties were investigated. The single-phase upgraded and downgraded BNT films were obtained with (117) preferred orientation. Compared to the homogeneous BNT films prepared by the same conditions, the remanent polarization (P _r) and permittivity (ε _r) of compositionally graded BNT films were significantly enhanced. The upgraded BNT film showed larger 2P _r (34.9?μC/cm²) and ε _r (509), and those of downgraded BNT film were 29.4?μC/cm² and 505. Bi element in the downgraded BNT film accumulated near the interface of film/Pt bottom electrode, which deteriorated the compositional gradient and resulted in decreasing 2P _r and ε _r compared to the upgraded BNT film.     

Orientation-dependent microwave dielectric properties of Ba0.6Sr0.4TiO3 thin films prepared by sol–gel method

Barium strontium titanate (Ba_0.6Sr_0.4TiO₃, BST) thin films have been prepared on the (100) LaAlO₃ single-crystal substrates by sol–gel technique. The X-ray diffraction study indicated that the thin films exhibited (100) preferred orientation and random orientation depending upon the concentration of precursor solution. The nonlinear dielectric properties of the BST films were measured using an interdigital capacitor. The temperature dependence of dielectric constant of the BST thin films was measured at 1 MHz in the temperature range from ?100 to 80 °C. The Curie temperature T _c of the films derived from 0.1, 0.2 and 0.3 M was found to be ?18.5, ?32.5 and ?39.9 °C, respectively. The tunability of BST films with the (100) preferred orientation was 30.74 %, which was much higher than that of thin films with random orientation at the frequency of 10 kHz with an applied electric field of 80 kV/cm. The microwave dielectric properties of the BST thin films were measured by a vector network analyser from 1 to 10 GHz.     

Phase and structural evolution of sol–gel synthesized ZrO2/Si thin films under heat treatment

ZrO₂/Si thin films were fabricated using a sol–gel technique, and the chemical state change and structural evolution from sol to gel to Zr oxide by heat treatment were investigated. The precursor sol was synthesized using a Zr-acetylacetonate (Zr-acac) precursor, spin-coated, dried on Si(100) substrates, and then annealed at 300–700 °C in air. With increased annealing temperature of the sol–gel-derived layer, Zr-acac decomposed into Zr-acetate, an amorphous ZrO₂ phase formed, and crystallization into a tetragonal phase occurred. In addition, the ZrO₂ layer became denser and the interfacial layer between ZrO₂ and Si thickened, whereas the surface morphology was nearly unaffected and remained smooth with root-mean-square values < 4.5 ?.