Depth-dependent local structures in thin films unraveled by grazing-incidence X-ray absorption spectroscopy

A method of using X-ray absorption spectroscopy together with resolved grazing-incidence geometry for depth profiling of atomic, electronic or chemical local structures in thin films is presented. The quantitative deconvolution of thickness-dependent spectral features is performed by fully considering both scattering and absorption formalisms. Surface oxidation and local structural depth profiles in nanometric FePt films are determined, exemplifying the application of the method.

Effects of mechanical properties, residual stress and indenter tip geometry on instrumented indentation data in thin films

In this work, an axisymmetric two-dimensional finite element model was developed to simulate instrumented indentation testing of thin ceramic films deposited onto hard steel substrates. The level of film residual stress (sigma(r)), the film elastic modulus (E) and the film work hardening exponent (n) were varied to analyze their effects on indentation data. These numerical results were used to analyze experimental data that were obtained with titanium nitride coated specimens, in which the substrate bias applied during deposition was modified to obtain films with different levels of sigma(r). Good qualitative correlation was obtained when numerical and experimental results were compared, as long as all film properties are considered in the analyses, and not only sigma(r). The numerical analyses were also used to further understand the effect of sigma(r) on the mechanical properties calculated based on instrumented indentation data. In this case, the hardness values obtained based on real or calculated contact areas are similar only when sink-in occurs, i.e. with high n or high ratio VIE, where Y is the yield strength of the film. In an additional analysis, four ratios (R/h(max)) between indenter tip radius and maximum penetration depth were simulated to analyze the combined effects of R and sigma(r) on the indentation load-displacement curves. In this case, or did not significantly affect the load curve exponent, which was affected only by the indenter tip radius. On the other hand, the proportional curvature coefficient was significantly affected by sigma(r) and n. (C) 2010 Elsevier B.V. All rights reserved.

Residual stresses in titanium nitride thin films obtained with step variation of substrate bias voltage during deposition

In this work, a series of depositions of titanium nitride (TiN) films on M2 and D2 steel substrates were conducted in a Triode Magnetron Sputtering chamber. The temperature; gas flow and pressure were kept constant during each run. The substrate bias was either decreased or increased in a sequence of steps. Residual stress measurements were later conducted through the grazing X-ray diffraction method. Different incident angles were used in order to change the penetration depth and to obtain values of residual stress at different film depths. A model described by Dolle was adapted as an attempt to calculate the values of residual stress at each incident angle as a function of the value from each individual layer. Stress results indicated that the decrease in bias voltage during the deposition has produced compressive residual stress gradients through the film thickness. On the other hand, much less pronounced gradients were found in one of the films deposited with increasing bias voltage. (C) 2010 Elsevier B.V. All rights reserved.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Study of phase transition in (Pb,Ba)TiO(3) thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb(1-x)Ba(x)TiO(3) thin films (x=0.40 and 0.60) as a function of temperature. The dielectric study on single phase compositions revealed that a diffuse-type phase transition occurred upon transformation of the cubic paraelectric to the tetragonal ferroelectric phase in all thin films, which showed a broadening of the dielectric peak. Diffusivity was found to increase with increasing barium contents in the composition range under study. In addition, the temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted as a breakdown of the local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broadbands in some temperature intervals above the paraferroelectric phase transition temperature suggest a diffuse-type phase transition. (C) 2008 American Institute of Physics.

Diffraction gratings fabricated in DLC thin films

This work presents the fabrication of two-dimensional diffraction gratings in diamond-like carbon (DLC) thin films, with applications in computer-generated holography and micro optics. In order to achieve high diffraction efficiency and to have a very simple manufacturing process, the device is designed to modulate only the phase of an incoming coherent monochromatic laser beam (632.8 nm, HeNe laser). This modulation is obtained by implementing a binary microrelief in the DLC film, responsible for generating a localized optical path difference of half a wavelength. This microrelief is obtained by anisotropic reactive ion etching of the DLC surface in an oxygen based plasma. The DLC layer was grown by reactive magnetron sputtering, using a methane-based plasma chemistry. AFM measurements show a low-level surface roughness of less than 1% of the operation wavelength, and optical characterization shows a good quality of the reconstructed diffraction patterns. (C) 2010 Elsevier B.V. All rights reserved.

Modeling of Plastic Deformation Effects in Ferromagnetic Thin Films

To explain the magnetic behavior of plastic deformation of thin magnetic films (Fe and permalloy) on an elastic substrate (nitinol), it is noted that unlike in the bulk, the dislocation density does not increase dramatically because of the dimensional constraint. As a result, the resulting residual stress, even though strain hardening is limited, dominates the observed magnetic behavior. Thus, with the field parallel to the stress axis, the compressive residual stress resulting from plastic deformation causes a decrease in remanence and an increase in coercivity; and with the field perpendicular to the stress axis, the resulting compressive residual stress causes an increase in remanence and a decrease in coercivity. These elements have been inserted into the model previously developed for plastic deformation in the bulk, producing the aforementioned behavior, which has been observed experimentally in the films.

Influence of gold nanoparticles on optically stimulated effects in TeO(2)-ZnO and GeO(2)-PbO amorphous thin films

We have found photoinduced second harmonic generation at wavelength 1064 nm during bicolor Nd:YAG laser coherent treatment of TeO(2)-ZnO and GeO(2)-PbO amorphous films. The maximally achieved second order susceptibility was equal to about 1.02 pm/V. Correlation of the induced second order susceptibility with local sample heating and induced birefringence may indicate an occurrence of local phase transitions from amorphous glass-like phase to non-centrosymmetry metastable phases. (C) 2010 Elsevier B.V. All rights reserved.

Nanostructured europium oxide thin films deposited by pulsed laser ablation of a metallic target in a He buffer atmosphere

Nanostrucured europium oxide and hydroxide films were obtained by pulsed Nd:YAG (532 nm) laser ablation of a europium metallic target, in the presence of a 1 mbar helium buffer atmosphere. Both the produced film and the ambient plasma were characterized. The plasma was monitored by an electrostatic probe, for plume expansion in vacuum or in the presence of the buffer atmosphere. The time evolution of the ion saturation current was obtained for several probe to substrate distances. The results show the splitting of the plume into two velocity groups, being the lower velocity profile associated with metal cluster formation within the plume. The films were obtained in the presence of helium atmosphere, for several target-to-substrate distances. They were analyzed by Rutherford backscattering spectrometry, x-ray diffraction, and atomic force microscopy, for as-deposited and 600 degrees C treated-in-air samples. The results show that the as-deposited samples are amorphous and have chemical composition compatible with europium hydroxide. The thermally treated samples show x-ray diffraction peaks of Eu(2)O(3), with chemical composition showing excess oxygen. Film nanostructuring was shown to be strongly correlated with cluster formation, as shown by velocity splitting in probe current versus time plots. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3457784]

Pressure-induced electrical and structural anomalies in Pb(1-x)Ca(x)TiO(3) thin films grown at various oxygen pressures by chemical solution route

Lead calcium titanate (Pb(1-x)Ca(x)TiO(3) or PCT) thin films have been thermally treated under different oxygen pressures, 10, 40 and 80 bar, by using the so-called chemical solution deposition method. The structural, morphological, dielectric and ferroelectric properties were characterized by x-ray diffraction, FT-infrared and Raman spectroscopy, atomic force microscopy and polarization-electric-field hysteresis loop measurements. By annealing at a controlled pressure of around 10 and 40 bar, well-crystallized PCT thin films were successfully prepared. For the sample submitted to 80 bar, the x-ray diffraction, Fourier transformed-infrared and Raman data indicated deviation from the tetragonal symmetry. The most interesting feature in the Raman spectra is the occurrence of intense vibrational modes at frequencies of around 747 and 820 cm(-1), whose presence depends strongly on the amount of the pyrochlore phase. In addition, the Raman spectrum indicates the presence of symmetry-breaking disorder, which would be expected for an amorphous (disorder) and mixed pyrochlore-perovskite phase. During the high-pressure annealing process, the crystallinity and the grain size of the annealed film decreased. This process effectively suppressed both the dielectric and ferroelectric behaviour. Ferroelectric hysteresis loop measurements performed on these PCT films exhibited a clear decrease in the remanent polarization with increasing oxygen pressure.

Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Leakage current, ferroelectric and structural properties in Pb(1-x)Ba(x)TiO(3) thin films prepared by chemical route

Single-phase perovskite structure Pb(1-x)Ba(x)TiO(3) thin films (x = 0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO(2)/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature Suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage Current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively. (C) 2008 Elsevier Ltd. All rights reserved.

Alpha element abundances and gradients in the Milky Way bulge from FLAMES-GIRAFFE spectra of 650 K giants

Aims. We present the analysis of the [alpha/Fe] abundance ratios for a large number of stars at several locations in the Milky Way bulge with the aim of constraining its formation scenario. Methods. We obtained FLAMES-GIRAFFE spectra (R = 22 500) at the ESO Very Large Telescope for 650 bulge red giant branch (RGB) stars and performed spectral synthesis to measure Mg, Ca, Ti, and Si abundances. This sample is composed of 474 giant stars observed in 3 fields along the minor axis of the Galactic bulge and at latitudes b = -4 degrees, b = -6 degrees, b = -12 degrees. Another 176 stars belong to a field containing the globular cluster NGC 6553, located at b = -3 degrees and 5 degrees away from the other three fields along the major axis. Stellar parameters and metallicities for these stars were presented in Zoccali et al. (2008, A&A, 486, 177). We have also re-derived stellar parameters and abundances for the sample of thick and thin disk red giants analyzed in Alves-Brito et al. (2010, A&A, 513, A35). Therefore using a homogeneous abundance database for the bulge, thick and thin disk, we have performed a differential analysis minimizing systematic errors, to compare the formation scenarios of these Galactic components. Results. Our results confirm, with large number statistics, the chemical similarity between the Galactic bulge and thick disk, which are both enhanced in alpha elements when compared to the thin disk. In the same context, we analyze [alpha/Fe] vs. [Fe/H] trends across different bulge regions. The most metal rich stars, showing low [alpha/Fe] ratios at b = -4 degrees disappear at higher Galactic latitudes in agreement with the observed metallicity gradient in the bulge. Metal-poor stars ([Fe/H] < -0.2) show a remarkable homogeneity at different bulge locations. Conclusions. We have obtained further constrains for the formation scenario of the Galactic bulge. A metal-poor component chemically indistinguishable from the thick disk hints for a fast and early formation for both the bulge and the thick disk. Such a component shows no variation, neither in abundances nor kinematics, among different bulge regions. A metal-rich component showing low [alpha/Fe] similar to those of the thin disk disappears at larger latitudes. This allows us to trace a component formed through fast early mergers (classical bulge) and a disk/bar component formed on a more extended timescale.

Effect of Mn concentration and atomic structure on the magnetic properties of Ge thin films

This work reports on the magnetic properties of Ge(100-x)Mn(x) (x=0-24 at. %) films prepared by cosputtering a Ge+Mn target and submitted to cumulative thermal annealing treatments up to 500 degrees C. Both as-deposited and annealed films were investigated by means of compositional analysis, Raman scattering spectroscopy, magnetic force microscopy, superconducting quantum interference device magnetometry, and electrical resistivity measurements. All as-deposited films (either pure or containing Mn) exhibit an amorphous structure, which changes to crystalline as the annealing treatments are performed at increasing temperatures. In fact, the magnetic properties of the present Ge(100-x)Mn(x) films are very sensitive to the Mn content and whether their atomic structure is amorphous or crystalline. More specifically: whereas the amorphous Ge(100-x)Mn(x) films (with high x) present a characteristic spin glass behavior at low temperature; after crystallization, the films (with moderate Mn contents) are ferromagnetic at room temperature. Moreover, the magnetic behavior of the films scales with their Mn concentration and tends to be more pronounced after crystallization. Finally, the semiconducting behavior of the films, experienced by previous optical studies, was confirmed through electrical measurements, which also indicate the dependence of the resistivity with the atomic composition of the films. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3520661]