Iridium oxohydroxide thin coatings have been prepared by a dynamic oxidation electrodeposition method from complex oxalate solutions that induce template effects in the final coating at the nanoscale. The preparation method induces the formation of a oxohydroxide with reproducible stoichiometry and sponge-like quasiamorphous open structure, high ionic mobility, and significant behavior as compared with other reported iridium oxides as derived from X-ray diffraction, XPS, and TGA. Reproducible mixed valence states are also observed and a local rutile structure that allows ion exchange and facile redox changes. Rather significant is the large affinity for organic compounds observed and the behavior as substrate for cell culture, the best observed to date. Optimal cell response seems to be related to such open structure, which suggests this coating as ideal for devices implanted in the nervous system.
A Mn valence instability on La 2/3 Ca 1/3 MnO 3 thin films, grown on LaAlO 3 ͑001͒ substrates is observed by x-ray absorption spectroscopy at the Mn L-edge and O K-edge. As-grown samples, in situ annealed at 800°C in oxygen, exhibit a Curie temperature well below that of the bulk material. Upon air exposure a reduction of the saturation magnetization, M S , of the films is detected. Simultaneously a Mn 2+ spectral signature develops, in addition to the expected Mn 3+ and Mn 4+ contributions, which increases with time. The similarity of the spectral results obtained by total electron yield and fluorescence yield spectroscopy indicates that the location of the Mn valence anomalies is not confined to a narrow surface region of the film, but can extend throughout the whole thickness of the sample. High temperature annealing at 1000°C in air, immediately after growth, improves the magnetic and transport properties of such films towards the bulk values and the Mn 2+ signature in the spectra does not appear. The Mn valence is then stable even to prolonged air exposure. We propose a mechanism for the Mn 2+ ions formation and discuss the importance of these observations with respect to previous findings and production of thin films devices.
We report the development of a Si-based micro thermogenerator build from silicon-oninsulator by using standard CMOS processing. Ultrathin layers of Si, 100 nm in thickness, with embedded n and p-type doped regions electrically connected in series and thermally in parallel, are the active elements of the thermoelectric device that generate the thermopower under various thermal gradients. This proof-of-concept device produces an output power density of 4.5 µW/cm 2 under a temperature difference of 5 K across the hot and cold regions.
We measure the thermal conductivity of a 17.5-nm-thick single crystalline Si layer by using a suspended structure developed from a silicon-on-insulator wafer, in which the Si layer bridges the suspended platforms. The obtained value of 19 Wm(-1) K(-1) at room temperature represents a tenfold reduction with respect to bulk Si. This design paves the way for subsequent lateral nanostructuration of the layer with lithographic techniques, to define different geometries such as Si nanowires, nanostrips or phononic grids. As a proof of concept, nanostrips of 0.5 × 10 μm have been defined by focused ion beam (FIB) in the ultrathin Si layer. After the FIB cutting process with Ga ions at 30 kV and 100 pA, the measured thermal conductivity dramatically decreased to 1.7 Wm(-1) K(-1), indicating that the structure became severely damaged (amorphous). Re-crystallization of the structure was promoted by laser annealing while monitoring the Raman spectra. The thermal conductivity of the layer increased again to a value of 9.5 Wm(-1) K(-1) at room temperature, below that of the single crystalline material due to phonon scattering at the grain boundaries.
Magneto-optical techniques in reflection geometry turn out to be a very efficient tool to study the surface magnetism due to their sensitivity to magnetic and chemical variations across the sample depth. The existence of a surface layer of about one to five unit cells with strongly depressed magnetic properties, when compared with the rest of the film, in La2∕3Ca1∕3MnO3 thin films is shown. These results strongly support previous theoretical predictions as well as recent findings showing the insulating nature of the topmost layers in these materials.
Microstructural features of La2∕3Ca1∕3MnO3 layers of various thicknesses grown on top of (001) LaAlO3 substrates are studied by using transmission electron microscopy and electron energy loss spectroscopy. Films are of high microstructural quality but exhibit some structural relaxation and mosaicity both when increasing thickness or after annealing processes. The existence of a cationic segregation process of La atoms toward free surface has been detected, as well as a Mn oxidation state variation through layer thickness. La diffusion would lead to a Mn valence change and, in turn, to reduced magnetization.
Surface and interface magnetisms in oxide thin films and heterostructures have been a recurrent topic during the past years due to their relevance in the implementation of magnetoelectronic devices. Magneto-optical techniques, such as x-ray magnetic circular dichroism, turn out to be a very efficient tool to study surface magnetism due to their sensitivity to magnetic and chemical variations across the sample depth. Nevertheless, the application of the sum rules for the determination of the spin magnetic moment might lead to uncertainties as large as 40%. To overcome this problem we present an alternative approach consisting in using x-ray magnetic circular dichroism in reflection geometry. Data analysis by using a computer code based on a 4×4 matrix formalism indicates that surface and interface roughnessas are of major relevance for a proper description of the experimental data and a correct interpretation of the results. By using such an approach, we discuss the presence of a narrow surface region with strongly depressed magnetic properties in La2∕3Ca1∕3MnO3 thin films.
Porous materials display enhanced scattering mechanisms that greatly influence their transport properties. Metal-assisted chemical etching (MACE) enables fabrication of porous silicon nanowires starting from a doped Si wafer by using a metal template that catalyzes the etching process. Here, we report on the low thermal conductivity (κ) of individual porous Si nanowires (NWs) prepared from MACE, with values as low as 0.87 W·m−1·K−1 for 90 nm diameter wires with 35–40% porosity. Despite the strong suppression of long mean free path phonons in porous materials, we find a linear correlation of κ with the NW diameter. We ascribe this dependence to the anisotropic porous structure that arises during chemical etching and modifies the phonon percolation pathway in the center and outer regions of the nanowire. The inner microstructure of the NWs is visualized by means of electron tomography. In addition, we have used molecular dynamics simulations to provide guidance for how a porosity gradient influences phonon transport along the axis of the NW. Our findings are important towards the rational design of porous materials with tailored thermal and electronic properties for improved thermoelectric devices.
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