Comparison of SERS performances of Co and Ni ultrathin films over silver to electrochemically activated Co and Ni electrodes

In this work, the surface-enhanced Raman scattering (SERS) spectra of pyridine (py) on thin films of Co and Ni electrodeposited on an Ag electrode activated by oxidation-reduction cycles (ORC) are presented. The SERS spectra from the thin films were compared to those of py on activated bare transition metal electrodes. It was verified that the SERS spectra of py on 3 monolayers (ML)-thick films of Ni and Co presented only bands assignable to the py adsorbed on transition metal surfaces. It was also observed that even for 50 ML-thick transition metal films, the py SERS intensity was ca. 40% of the intensity from the 3 ML-thick films. The relative intensities of the SERS bands depended on the thickness of the films, and for films thicker than 7 ML for Co and 9 ML for Ni they were very similar to those of the bare transition metal electrodes. The transition metal thin films over Ag activated electrodes presented SERS intensities 3 orders of magnitude higher than the ones from bare transition metal electrodes. These films are more suitable to study the adsorption of low Raman cross-section molecules than are ORC-activated transition metal electrodes.

Indium tin oxide films prepared via wet chemical route

In this work, indium tin oxide (ITO) films were prepared using a wet chemical route, the Pechini method. This consists of a polyesterification reaction between an alpha-hydroxicarboxylate complex (indium citrate and tin citrate) with a polyalcohol (ethylene glycol) followed by a post annealing at 500 degrees C. A 10 at.% of doping of Sn4+ ions into an In2O3 matrix was successfully achieved through this method. In order to characterize the structure, the morphology as well as the optical and electrical properties of the produced ITO films, they were analyzed using different experimental techniques. The obtained films are highly transparent, exhibiting transmittance of about 85% at 550 nm. They are crystalline with a preferred orientation of [222]. Microscopy discloses that the films are composed of grains of 30 nm average size and 0.63 nm RMS roughness. The films' measured resistivity, mobility and charge carrier concentration were 5.8 x 10(-3) Omega cm, 2.9 cm(2)/V s and -3.5 x 10(20)/cm(3), respectively. While the low mobility value can be related to the small grain size, the charge carrier concentration value can be explained in terms of the high oxygen concentration level resulting from the thermal treatment process performed in air. The experimental conditions are being refined to improve the electrical characteristics of the films while good optical, chemical, structural and morphological qualities already achieved are maintained. (C) 2007 Elsevier B.V. All rights reserved.

Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Nanomechanical properties of glass-ceramic films obtained by pressure impregnation of oxide powders on commercial float glass surfaces

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

An improved three-dimensional model for growth of oxide films induced by laser heating

In this paper we consider a three-dimensional heat diffusion model to explain the growth of oxide films which takes place when a laser beam is shined on and heats a metallic layer deposited on a glass substrate in a normal atmospheric environment. In particular, we apply this model to the experimental results obtained for the dependence of the oxide layer thickness on the laser density power for growth of TiO2 films grown on Ti-covered glass slides. We show that there is a very good agreement between the experimental results and the theoretical predictions from our proposed three-dimensional model, improving the results obtained with the one-dimensional heat diffusion model previously reported. Our theoretical results also show the occurrence of surface cooling between consecutive laser pulses, and that the oxide track surface profile closely follows the spatial laser profile indicating that heat diffusive effects can be neglected in the growth of oxide films by laser heating. © 2001 Elsevier Science B.V.

An ellipsometric study of manganese oxide films: In situ characterization of the deposition and electroreduction of MnO2

The electrodeposition of manganese oxide films onto a platinum substrate was investigated by means of in situ ellipsometry. In the thickness range from 0 to 150 nm, the anodic oxide behaves as an Isotropic single layer with optical constants that are independent of thickness. Deviations at higher thickness are explained in terms of anisotropic properties of the film. The electroreduction of thin films (up to ca. 150 nm) in an alkaline electrolyte leads to a decrease in both the refractive index and the extinction coefficient and is accompanied by a thickness increase of ca. 10%. The Mn(IV) to Mn(III) conversion takes place from the oxide/electrolyte interface inwards. © 2004 The Electrochemical Society. All rights reserved.

Densification of Mn-doped tin oxide films by conventional heating and microwave heating treatment

Mn(II) doped SnO2 thin films used for shielding fluoride glasses against corrosion were investigated by x-ray absorption spectroscopy (EXAFS and XANE)S at the Sn and Mn K-edges. The effect of firing treatment on the densification of the films was studied. It has been evidenced a partial change of Mn valence from 2.3 to 2.6 upon heating which is attributed to a change of ratios of two Mn sites: grafted divalent Mn ions at the surface of SnO 2 nanocrystallites and trivalent Mn ions embedded into a substitutional solid solution with Sn. © Physica Scripta 2005.

Atomic resolution studies of oxide superlattices and ultrathin films

The ability to grow ultrathin films layer-by-layer with well-defined epitaxial relationships has allowed research groups worldwide to grow a range of artificial films and superlattices, first for semiconductors, and now with oxides. In the oxides thin film research community, there have been concerted efforts recently to develop a number of epitaxial oxide systems grown on single crystal oxide substrates that display a wide variety of novel interfacial functionality, such as enhanced ferromagnetic ordering, increased charge carrier density, increased optical absorption, etc, at interfaces. The magnitude of these novel properties is dependent upon the structure of thin films, especially interface sharpness, intermixing, defects, and strain, layering sequence in the case of superlattices and the density of interfaces relative to the film thicknesses. To understand the relationship between the interfacial thin film oxide atomic structure and its properties, atomic scale characterization is required. Transmission electron microscopy (TEM) offers the ability to study interfaces of films at high resolution. Scanning transmission electron microscopy (STEM) allows for real space imaging of materials with directly interpretable atomic number contrast. Electron energy loss spectroscopy (EELS), together with STEM, can probe the local chemical composition as well as local electronic states of transition metals and oxygen. Both techniques have been significantly improved by aberration correctors, which reduce the probe size to 1 Å, or less. Aberration correctors have thus made it possible to resolve individual atomic columns, and possibly probe the electronic structure at atomic scales. Separately, using electron probe forming lenses, structural information such as the crystal structure, strain, lattice mismatches, and superlattice ordering can be measured by nanoarea electron diffraction (NED). The combination of STEM, EELS, and NED techniques allows us to gain a fundamental understanding of the properties of oxide superlattices and ultrathin films and their relationship with the corresponding atomic and electronic structure. In this dissertation, I use the aforementioned electron microscopy techniques to investigate several oxide superlattice and ultrathin film systems. The major findings are summarized below. These results were obtained with stringent specimen preparation methods that I developed for high resolution studies, which are described in Chapter 2. The essential materials background and description of electron microscopy techniques are given in Chapter 1 and 2. In a LaMnO3-SrMnO3 superlattice, we demonstrate the interface of LaMnO3-SrMnO3 is sharper than the SrMnO3-LaMnO3 interface. Extra spectral weights in EELS are confined to the sharp interface, whereas at the rougher interface, the extra states are either not present or are not confined to the interface. Both the structural and electronic asymmetries correspond to asymmetric magnetic ordering at low temperature. In a short period LaMnO3-SrTiO3 superlattice for optical applications, we discovered a modified band structure in SrTiO3 ultrathin films relative to thick films and a SrTiO3 substrate, due to charge leakage from LaMnO3 in SrTiO3. This was measured by chemical shifts of the Ti L and O K edges using atomic scale EELS. The interfacial sharpness of LaAlO3 films grown on SrTiO3 was investigated by the STEM/EELS technique together with electron diffraction. This interface, when prepared under specific conditions, is conductive with high carrier mobility. Several suggestions for the conductive interface have been proposed, including a polar catastrophe model, where a large built-in electric field in LaAlO3 films results in electron charge transfer into the SrTiO3 substrate. Other suggested possibilities include oxygen vacancies at the interface and/or oxygen vacancies in the substrate. The abruptness of the interface as well as extent of intermixing has not been thoroughly investigated at high resolution, even though this can strongly influence the electrical transport properties. We found clear evidence for cation intermixing through the LaAlO3-SrTiO3 interface with high spatial resolution EELS and STEM, which contributes to the conduction at the interface. We also found structural defects, such as misfit dislocations, which leads to increased intermixing over coherent interfaces.

Study of reactive sputtering titanium oxide for metal-oxide-semiconductor capacitors

Metal oxide semiconductor (MOS) capacitors with titanium oxide (TiO(x)) dielectric layer, deposited with different oxygen partial pressure (30,35 and 40%) and annealed at 550, 750 and 1000 degrees C, were fabricated and characterized. Capacitance-voltage and current-voltage measurements were utilized to obtain, the effective dielectric constant, effective oxide thickness, leakage current density and interface quality. The obtained TiO(x) films present a dielectric constant varying from 40 to 170 and a leakage current density, for a gate voltage of - 1 V, as low as 1 nA/cm(2) for some of the structures, acceptable for MOS fabrication, indicating that this material is a viable high dielectric constant substitute for current ultra thin dielectric layers. (C) 2009 Elsevier B.V. All rights reserved.

Low-temperature deposition of silicon oxide and silicon nitride by reactive magnetron sputtering

In this study, oxide and nitride films were deposited at room temperature through the reaction of silicon Sputtered by argon and oxygen ions or argon and nitrogen ions at 250 and 350 W with 0.67 Pa pressure. It was observed that for both thin films the deposition rates increase with the applied RF power and decrease with the increase of the gas concentration. The Si/O and Si/N ratio were obtained through RBS analyses and for silicon oxide the values changed from 0.42 to 0.57 and for silicon nitride the Values changed from 0.4 to 1.03. The dielectric constants were calculated through capacitance-voltage curves with the silicon oxide values varying from 2.4 to 5.5, and silicon nitride values varying from 6.2 to 6.7, which are good options for microelectronic dielectrics. (c) 2008 Elsevier Ltd. All rights reserved.

A technique to produce thin cucurbit[6]uril films

We report a methodology to obtain thin films of cucurbit[6]uril, starting from ammoniacal solutions. This technique is very useful for the obtention of modified electrodes or other substrates for sensor purposes. Cucurbit[6]uril is insoluble in most media, and film formation was impossible until now.

Sol-gel preparation of near-infrared broadband emitting Er(3+)-doped SiO(2)-Ta(2)O(5) nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO(2)-Ta(2)O(5) nanocomposite films obtained by the sol-gel process. The films were doped with Er(3+) and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 degrees C. The onset of crystallization and devitrification, with the growth of Ta(2)O(5) nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er(3+)-doped nanocomposite annealed at 900 degrees C consists of Ta(2)O(5) nanoparticles, with sizes around 2 nm, dispersed in the SiO(2) amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the (4)I(13/2)->(4)I(15/2) transition of the Er(3+) ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the (4)I(13/2) levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide. (C) 2010 Elsevier B.V. All rights reserved.

Morphological and structural characterization of CrO2/Cr2O3 films grown by laser-CVD

This work reports on the synthesis of chromium (III, IV) oxides films by KrF laser-assisted CVD. Films were deposited onto sapphire substrates at room temperature by the photodissociation of Cr(CO)(6) in dynamic atmospheres containing oxygen and argon. A study of the processing parameters has shown that partial pressure ratio Of O-2 to Cr(CO)(6) and laser fluence are the prominent parameters that have to be accurately controlled in order to co-deposit both the crystalline oxide phases. Films consistent with such a two-phase system were synthesised for a laser fluence of 75 mJ cm(-2) and a partial pressure ratio of about 1. (c) 2005 Elsevier B.V. All rights reserved.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

Interdiffusion at Sb/Ge interfaces induced in thin multilayer films by nanosecond laser irradiation

Thin films consisting of 3 or 4 Sb and Ge alternating layers are irradiated with single nanosecond laser pulses (12 ns, 193 nm). Real time reflectivity (RTR) measurements are performed during irradiation, and Rutherford backscattering spectrometry (RBS) is used to obtain the concentration depth profiles before and after irradiation. Interdiffusion of the elements takes place at the layer interfaces within the liquid phase. The reflectivity transients allow to determine the laser energy thresholds both to induce and to saturate the process being both thresholds dependent on the multilayer configuration. It is found that the energy threshold to initiate the process is lower when Sb is at the surface while the saturation is reached at lower energy densities in those configurations with thinner layers.