LbL Fabricated Poly(Styrene Sulfonate)/TiO2 Multilayer Thin Films for Environmental Applications

Fabrication of multilayer ultrathin composite films composed of nanosized titanium dioxide particles (P25, Degussa) and polyelectrolytes (PELs), such as poly(allyl amine hydrochloride) (PAH) and poly(styrene sulfonate sodium salt) (PSS), on glass substrates using the layer-by-layer (LbL) assembly technique and its potentia application for the photodegradation of rhodamine B under ultraviolet (UV) irradiation has been reported. The polyelectrolytes and TiO2 were deposited on glass substrates at pH 2.5 and the growth of the multilayers was studied using UV/vis speccrophotometer. Thicknes measurements of the films showed a linear increase in film thickness with increase in number of bilayers. The surface microstructure of the thin films was characterized by field emission scanning electron microscope. The ability of the catalysts immobilized by this technique was compared with TiO2 films prepared by drop casting and spin coating methods. Comparison has been made in terms of film stability and photodegradation of rhodamine B. Process variables such as the effect of surface area of the multilayers, umber of bilayers, and initial dye concentration on photodegradation of rhodamine B were studied. Degradation efficiency increased with increase in number of catalysts (total surface area) and bilayers. Kinetics analysis indicated that the photodegradation rates follow first order kinetics. Under maximum loading of TiO2, with five catalyst slides having 20 bilayers of polyelectrolyte/TiO2 on each, 100 mL of 10 mg/L dye solution could be degraded completely in 4 h. The same slides could be reused with the same efficiency for several cycles. This study demonstrates that nanoparticles can be used in wastewater treatment using a simple immobilization technique. This makes the process an attractive option for scale up.

RF Sputtered Er2O3 Thin Films as High-k Gate Dielectrics for Germanium MOS Devices

We report the material and electrical properties of Erbium Oxide (Er2O3) thin films grown on n-Ge (100) by RF sputtering. The properties of the films are correlated with the processing conditions. The structural characterization reveals that the films annealed at 550 degrees C, has densified as compared to the as-grown ones. Fixed oxide charges and interface charges, both of the order of 10(13)/cm(2) is observed.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol-gel route

Sol-gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn1-xLixO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400-500 degrees C. Ferroelectricity in Zn0.85Li0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C-V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P-s) and coercive field were 0.15 mu C/cm(2) and 20 kV/cm, respectively, confirming the presence of ferroelectricity.

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr0.53Ti0.47O3 (PZT), (Pb0.90La0.10)TiO3 (PLT10) and (Pb0.80La0.20)TiO3 (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance-voltage (C- V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C-V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 degrees C for 10 min. The phase transition temperature [T-c] of PLT20 increased from 115 degrees C to 120 degrees C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 degrees C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Investigations on magnetron sputtered ZnO thin films and Au/ZnO Schottky diodes

Magnetron sputtering is a promising technique for the growth of oxide materials including ZnO, which allows deposition of films at low temperatures with good electrical properties. The current-voltage (I-P) characteristics of An Schottky contacts on magnetron sputtered ZnO, films have been measured over a temperature range of 278-358K. Both effective barrier height (phi(B,eff)) and ideality factor (n) are found to be a function of temperature, and this behavior has been interpreted on the basis of a Gaussian distribution of barrier heights due to barrier height inhomogeneities that prevail at the interface. Density of states (DOS) near the Fermi level is determined using a model based on the space charge limited current (SCLC). The dispersion in both real and imaginary parts of the dielectric constant at low frequencies, with increase in temperature is attributed to the space charge effect. Complex impedance plots exhibited two semicircles, which corresponds to bulk grains and the grain boundaries. (c) 2006 Elsevier B.V. All rights reserved.

Electrical and structural properties of zirconia thin films prepared by reactive magnetron sputtering

Thin films of ZrO2 were prepared by reactive magnetron sputtering. Annealing of the films exhibited a drastic change in the properties due to improved crystallinity and packing density. The root mean square roughness of the sample observed from atomic force microscope is about 5.75 nm which is comparable to the average grain size of the thin film which is about 6 nm obtained from X-ray diffraction. The film annealed at 873 K exhibits an optical band gap of around 4.83 eV and shows +4 oxidation state of zirconium indicating fully oxidized zirconium, whereas higher annealing temperatures lead to oxygen deficiency in the films and this is reflected in their properties. A discontinuity in the imaginary part of the AC conductivity was observed in the frequency range of tens of thousands of Hz, where as, the real part does not show such behavior.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO2 thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO2 films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO2 films was estimated by Tauc's method at different annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

The effect of pressure and W-doping on the properties of ZnO thin films for NO2 gas sensing

Pure and W-doped ZnO thin films were obtained using magnetron sputtering at working pressures of 0.4 Pa and 1.33 Pa. The films were deposited on glass and alumina substrates at room temperature and subsequently annealed at 400oC for 1 hour in air. The effects of pressure and W-doping on the structure, chemical, optical and electronic properties of the ZnO films for gas sensing were examined. From AFM, the doped film deposited at higher pressure (1.33 Pa) has spiky morphology with much lower grain density and porosity compared to the doped film deposited at 0.4 Pa. The average gain size and roughness of the annealed films were estimated to be 65 nm and 2.2 nm, respectively with slightly larger grain size and roughness appeared in the doped films. From XPS the films deposited at 1.33 Pa favored the formation of adsorbed oxygen on the film surface and this has been more pronounced in the doped film which created active sites for OH adsorption. As a consequence the W-doped film deposited at 1.33 Pa was found to have lower oxidation state of W (35.1 eV) than the doped film deposited at 0.4 Pa (35.9 eV). Raman spectra indicated that doping modified the properties of the ZnO film and induced free-carrier defects. The transmittance of the samples also reveals an enhanced free-carrier density in the W-doped films. The refractive index of the pure film was also found to increase from 1.7 to 2.2 after W-doping whereas the optical band gap only slightly increased. The W-doped ZnO film deposited at 0.4 Pa appeared to have favorable properties for enhanced gas sensing. This film showed significantly higher sensing performance towards 5-10 ppm NO2 at lower operating temperature of 150oC most dominantly due to increased free-carrier defects achieved by W-doping.

ZnO nanocrystalline thin films: a correlation of microstructural, optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol-gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 A degrees C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60-80 nm in size is really an aggregate of many small crystallites of around 10-20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10(-5)-10(-6) (Omega cm)(-1). The optical study showed that the spectra for all samples give the transparency in the visible range.

Growth and Modification of Cluster-Assembled Thin Films

Thin film applications have become increasingly important in our search for multifunctional and economically viable technological solutions of the future. Thin film coatings can be used for a multitude of purposes, ranging from a basic enhancement of aesthetic attributes to the addition of a complex surface functionality. Anything from electronic or optical properties, to an increased catalytic or biological activity, can be added or enhanced by the deposition of a thin film, with a thickness of only a few atomic layers at the best, on an already existing surface. Thin films offer both a means of saving in materials and the possibility for improving properties without a critical enlargement of devices. Nanocluster deposition is a promising new method for the growth of structured thin films. Nanoclusters are small aggregates of atoms or molecules, ranging in sizes from only a few nanometers up to several hundreds of nanometers in diameter. Due to their large surface to volume ratio, and the confinement of atoms and electrons in all three dimensions, nanoclusters exhibit a wide variety of exotic properties that differ notably from those of both single atoms and bulk materials. Nanoclusters are a completely new type of building block for thin film deposition. As preformed entities, clusters provide a new means of tailoring the properties of thin films before their growth, simply by changing the size or composition of the clusters that are to be deposited. Contrary to contemporary methods of thin film growth, which mainly rely on the deposition of single atoms, cluster deposition also allows for a more precise assembly of thin films, as the configuration of single atoms with respect to each other is already predetermined in clusters. Nanocluster deposition offers a possibility for the coating of virtually any material with a nanostructured thin film, and therein the enhancement of already existing physical or chemical properties, or the addition of some exciting new feature. A clearer understanding of cluster-surface interactions, and the growth of thin films by cluster deposition, must, however, be achieved, if clusters are to be successfully used in thin film technologies. Using a combination of experimental techniques and molecular dynamics simulations, both the deposition of nanoclusters, and the growth and modification of cluster-assembled thin films, are studied in this thesis. Emphasis is laid on an understanding of the interaction between metal clusters and surfaces, and therein the behaviour of these clusters during deposition and thin film growth. The behaviour of single metal clusters, as they impact on clean metal surfaces, is analysed in detail, from which it is shown that there exists a cluster size and deposition energy dependent limit, below which epitaxial alignment occurs. If larger clusters are deposited at low energies, or cluster-surface interactions are weaker, non-epitaxial deposition will take place, resulting in the formation of nanocrystalline structures. The effect of cluster size and deposition energy on the morphology of cluster-assembled thin films is also determined, from which it is shown that nanocrystalline cluster-assembled films will be porous. Modification of these thin films, with the purpose of enhancing their mechanical properties and durability, without destroying their nanostructure, is presented. Irradiation with heavy ions is introduced as a feasible method for increasing the density, and therein the mechanical stability, of cluster-assembled thin films, without critically destroying their nanocrystalline properties. The results of this thesis demonstrate that nanocluster deposition is a suitable technique for the growth of nanostructured thin films. The interactions between nanoclusters and their supporting surfaces must, however, be carefully considered, if a controlled growth of cluster-assembled thin films, with precisely tailored properties, is to be achieved.

Spectroscopic ellipsometry investigations of the optical properties of manganese doped bismuth vanadate thin films

The optical properties of Bi(2)V(1-x)MnxO(5.5-x) (x=0.05, 0.1, 0.15 and 0.2 at.%) thin films fabricated by pulsed laser deposition on platinized Silicon Substrates were Studied in UV-visible spectral region (1.51-4.17 CV) using spectroscopic ellipsometry. The optical constants and thicknesses of these films have been obtained by fitting the ellipsometric data (Psi and Delta) using a multilayer four-phase model system and a relaxed Lorentz oscillator dispersion relation. The surface roughness and film thickness obtained by spectroscopic ellipsometry were found to be consistent with the results obtained by atomic force and scanning electron microscopy. The refractive index measured at 650 nm does not show any marginal increase with Mn content. Further, the extinction coefficient does not show much decrease with increasing Mn content. An increase in optical band gap energy from 2.52 to 2.77 eV with increasing Mn Content from x = 0.05 to 0.15 was attributed to the increase in oxygen ion vacancy disorder. (C) 2009 Elsevier Ltd. All rights reserved.

Multilayer single-component thin films and microcapsules via covalent bonded layer-by-layer self-assembly

Fabrication of single-component multilayer thin films still remains a challenging task via the layer-by-layer (LbL) approach. In this communication, we report the self-assembly of single-component multilayer thin films on flat and colloidal substrates through glutaraldehyde mediated covalent bonding.