Mechanical properties of thin sol-gel films

This thesis presents a study of the mechanical properties of thin films. The main aim was to determine the properties of sol-gel derived coatings. These films are used in a range of different applications and are known to be quite porous. Very little work has been carried out in this area and in order to study the mechanical properties of sol-gel films, some of the work was carried out on magnetron sputtered metal coatings in order to validate the techniques developed in this work. The main part of the work has concentrated on the development of various bending techniques to study the elastic modulus of the thin films, including both a small scale three-point bending, as well as a novel bi-axial bending technique based on a disk resting on three supporting balls. The bending techniques involve a load being applied to the sample being tested and the bending response to this force being recorded. These experiments were carried out using an ultra micro indentation system with very sensitive force and depth recording capabilities. By analysing the result of these forces and deflections using existing theories of elasticity, the elastic modulus may be determined. In addition to the bi-axial bending study, a finite element analysis of the stress distribution in a disk during bending was carried out. The results from the bi-axial bending tests of the magnetron sputtered films was confirmed by ultra micro indentation tests, giving information of the hardness and elastic modulus of the films. It was found that while the three point bending method gave acceptable results for uncoated steel substrates, it was very susceptible to slight deformations of the substrate. Improvements were made by more careful preparation of the substrates in order to avoid deformation. However the technique still failed to give reasonable results for coated specimens. In contrast, biaxial bending gave very reliable results even for very thin films and this technique was also found to be useful for determination of the properties of sol-gel coatings. In addition, an ultra micro indentation study of the hardness and elastic modulus of sol-gel films was conducted. This study included conventionally fired films as well as films ion implanted in a range of doses. The indentation tests showed that for implantation of H⁺ ions at doses exceeding 3x10¹⁶ ions/cm², the mechanical properties closely resembled those of films that were conventionally fired to 450°C.

Mechanical properties of graphene films enhanced by homo-telechelic functionalized polymer fillers via π-π Stacking interactions

© 2015 Elsevier Ltd. All rights reserved. Most researches on graphene/polymer composites are focusing on improving the mechanical and electrical properties of polymers at low graphene content instead of paying attention to constructing graphene's macroscopic structures. In current study the homo-telechelic functionalized polyethylene glycols (FPEGs) were tailored with π-orbital-rich groups (namely phenyl, pyrene and di-pyrene) via esterification reactions, which enhanced the interaction between polyethylene glycol (PEG) molecules and chemical reduced graphene oxide (RGO) sheets. The π-π stacking interactions between graphene sheets and π-orbital-rich groups endowed the composite films with enhanced tensile strength and tunable electrical conductivity. The formation of graphene network structure mediated by the FPEGs fillers via π-π stacking non-covalent interactions should account for the experimental results. The experimental investigations were also complemented with theoretical calculation using a density functional theory. Atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), UV-vis and fluorescence spectroscopy were used to monitor the step-wise preparation of graphene composite films.

Thickness dependence of structure and piezoelectric properties at nanoscale of polycrystalline lead zirconate titanate thin films

Lead zirconate titanate Pb(Zr0.50Ti0.50)O3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/Ti/SiO2/Si substrates to understand the mechanisms of phase transformations and the effect of film thickness on the structure, dielectric, and piezoelectric properties in these films. PZT films pyrolyzed at temperatures higher than 350 °C present a coexistence of pyrochlore and perovskite phases, while only perovskite phase grows in films pyrolyzed at temperatures lower than 300 °C. For pyrochlore-free PZT thin films, a small (100)-orientation tendency near the film-substrate interface was observed. Finally, we demonstrate the existence of a self-polarization effect in the studied PZT thin films. The increase of self-polarization with the film thickness increasing from 200 nm to 710 nm suggests that Schottky barriers and/or mechanical coupling near the film-substrate interface are not primarily responsible for the observed self-polarization effect in our films. © 2013 AIP Publishing LLC.

Thermal, structural and optical properties of NiOx thin films deposited by reactive dc-magnetron sputtering

The NiOx thin films were deposited by reactive dc-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content 5%. The as-deposited NiOx, thin films could represent a two-component system comprising crystalline NiO particles dispersed in an amorphous Ni2O3. Decomposition temperature of the as-deposited NiO, thin films was at about 263 degrees C. After annealed at 400 degrees C for 30 min in air, the surface morphology of the films became very rough due to the decomposition of the Ni2O3, leading to the changes of the optical properties of the NiO, thin films. The reflectivity of the films annealed at 400 degrees C was lower than that of the as-deposited one and the optical contrast was 52% at 405 nm. (c) 2006 Elsevier B.V. All rights reserved.

Fabrication and Infrared Optical Properties of Nano Vanadium Dioxide Thin Films

Vanadium dioxide thin films were fabricated by ion beam sputtering on Si3N4/SiO2/Si after a post reductive annealing process in a nitrogen atmosphere. X-ray Diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were employed to analyze the effects of post annealing temperature on crystallinity, morphology, and composition of the vanadium oxide thin films. Transmission properties of vanadium dioxide thin films were measured by Fourier transform-infrared (FT-IR) spectroscopy. The results showed that the as-deposited vanadium oxide thin films were composed of non-crystalline V2O5 and a tetragonal rutile VO2. After annealing at 400 degrees C for 2 h, the mixed phase vanadium oxide (VOx) thin film changed its composition and structure to VO2 and had a (011) oriented monoclinic rutile structure. When increasing the temperature to 450 degrees C, nano VO2 thin films with smaller grains were obtained. FT-IR results showed that the transmission contrast factor of the nano VO2 thin film was more than 0.99 and the transmission of smaller grain nano VO2 thin film was near zero at its switched state. Nano VO2 thin film with smaller grains is an ideal material for application in optical switching devices.

Optical properties of potassium niobate thin films prepared by the polymeric precursor method

Thin films of potassium niobate were deposited on MgO (100) substrates by the polymeric precursor method and annealing in static air at 600 degreesC for 20 h. The obtained films were characterized by X-ray diffraction, atomic force microscopy (AFM) and the prism coupling method. The phi-scan diffraction evidenced the growth of the films with fourfold symmetry. AFM study shows that the films are homogeneous, dense and present a smooth surface. The refractive index and optical losses were strongly influenced by the degree of crystallinity. (C) 2004 Elsevier B.V. All rights reserved.

Effect of magnesium on the properties of LiNbO3 thin films prepared from polymeric precursors

The effect of magnesium addition on the phase formation, microstructure and electric and ferroelectric properties of LiNbO3 thin films prepared through polymeric precursors was analyzed. By X ray diffraction no secondary phase was observed with the increase of magnesium concentration. Comparing to pure LiNbO3, the addition of 0.5 and 1.0 mol% of Mg+2 increased of the dielectric constant, while 2.0 mol% decreased it. It was noticed that the increase in additive concentration decreases the ferroelectric remanent polarization and increases the coercive field.

Influence of temperature on the microstructure and electrical properties of BBT thin films

The BBT films were prepared by a spin-coating process from the polymeric precursor method (Pechini process). In order to study the influence of the temperature on the BBT microstructure and electrical properties, the films were deposited on platinum coated silicon substrates and annealed from 700degreesC to 800degreesC for 2 hours in oxygen atmosphere. The crystallinity of the films was examined by X-ray diffraction while the surface morphology was analysed by atomic force microscope. The dielectric properties and dissipation factor of BaBi2Ta2O9 films at 1 MHz were observed. The polarization-electric field hysteresis loops revealed the ferroelectric characteristics of BaBi2Ta2O9 thin films.

Structural, dielectric and ferroelectric properties of Nb-doped PZT thin films produced by oxide precursor method

Recently, was proposed a chemical method for preparation of ferroelectric thin films based on oxide precursors. In this work, PZT thin films were prepared to attest the viability of this method for cation-substitution. In this study, a small concentration of Nb (5 mol%) was selected as substitute of B-site in ABO 3 structure of PZT. Dielectric and ferroelectric properties of PZT films were studied as a function of cation-substitution. Results for Nb-PZT were compared with PZT films undoped. The values of dielectric constant, at typical 100 kHz frequency, were 358 and 137, for PZT and Nb-PZT films respectively. Remanent polarizations of these films were respectively 7.33 μ C/cm 2 and 13.3 μ C/cm 2 , while the measured coercive fields were 101 kV/cm and 93 kV/cm. As a result, changes on observed dielectric and ferroelectric values confirm the Nb substitution in PZT thin film produced by oxide precursor method. © 2002 Taylor & Francis.

Effect of magnesium on the properties of LiNbO 3 thin films prepared from polymeric precursors

The effect of magnesium addition on the phase formation, microstructure and electric and ferroelectric properties of LiNbO 3 thin films prepared through polymeric precursors was analyzed. By X ray diffraction no secondary phase was observed with the increase of magnesium concentration. Comparing to pure LiNbO 3, the addition of 0.5 and 1.0 mol% of Mg +2 increased of the dielectric constant, while 2.0 mol% decreased it. It was noticed that the increase in additive concentration decreases the ferroelectric remanent polarization and increases the coercive field. © 2002 Taylor & Francis.

Eumelanin thin films: Solution-processing, growth, and charge transport properties

Eumelanin pigments show hydration-dependent conductivity, broad-band UV-vis absorption, and chelation of metal ions. Solution-processing of synthetic eumelanins opens new possibilities for the characterization of eumelanin in thin film form and its integration into bioelectronic devices. We investigate the effect of different synthesis routes and processing solvents on the growth, the morphology, and the chemical composition of eumelanin thin films using atomic force microscopy and X-ray photoelectron spectroscopy. We further characterize the films by transient electrical current measurements obtained at 50% to 90% relative humidity, relevant for bioelectronic applications. We show that the use of dimethyl sulfoxide is preferable over ammonia solution as processing solvent, yielding homogeneous films with surface roughnesses below 0.5 nm and a chemical composition in agreement with the eumelanin molecular structure. These eumelanin films grow in a quasi layer-by-layer mode, each layer being composed of nanoaggregates, 1-2 nm high, 10-30 nm large. The transient electrical measurements using a planar two-electrode device suggest that there are two contributions to the current, electronic and ionic, the latter being increasingly dominant at higher hydration, and point to the importance of time-dependent electrical characterization of eumelanin films. This journal is © 2013 The Royal Society of Chemistry.

Dielectric properties of Sr0.75Ba0.25Nb 2O6 thin films: Bias field, frequency and temperature dependence

Ferroelectric strontium barium niobate solid solutions had received great attention due to their excellent pyroelectric, electrooptic and photorefractive properties. Furthermore, they usually also present very interesting phase transition characteristics. In this work, polycrystalline single phase Sr 0.75 Ba 0.25 Nb 2 O 6 thin films were prepared by a hybrid chemical method and deposited on Pt/Ti/SiO 2 /Si substrates. The temperature dependence of dielectric constant was measured at different frequencies and bias field levels. The presence of two dielectric dispersion regions with relaxor characteristics was observed at distinct temperature ranges, corresponding to the ferro-paraelectric and to a structural phase transition at low temperatures, respectively. A specific dielectric dispersion region, associated with an incommensurate superstructure frequently observed in bulk samples, was not observed in this films probably due to their small grain sizes. © 2002 Taylor & Francis.

Growth and Characterization of LiCoO₂ Thin Films for Microbatteries

LiCoO₂thin films have been grown by pulsed laser deposition on stainless steel and SiO₂/Si substrates. The film deposited at 600°C in an oxygen partial pressure of 100mTorr shows an excellent crystallinity, stoichiometry and no impurity phase present. Microstructure and surface morphology of thin films were examined using a scanning electron microscope. The electrochemical properties of the thin films were studied with cyclic voltammetry and galvanostatic charge-discharge techniques in the potential range 3.0-4.2 V. The initial discharge capacity of the LiCoO2 thin films deposited on the stainless steel and SiO₂/Si substrates reached 23 and 27 µAh/cm², respectively.

Preparation and characterization of Cd(2)Nb(2)O(7) thin films on Si substrates

Thin Cd(2)Nb(2)O(7) films were grown on single-crystal p-type SiO(2)/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/SiO(2)/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. (c) 2008 Elsevier Ltd. All rights reserved.

Electric and dielectric behavior of CaCu3Ti4O12-based thin films obtained by soft chemical method

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