National Institute Of Materials Physics - Romania

The growth and thermal stability of textured iridium thin films used as bottom electrode in electronic devices based on ferroelectric materials were investigated. The thin films were grown using the dc magnetron sputtering technique. The Ir layers directly deposited on SiO2/Si substrates present a mixed (111) and (200) orientations, while the films grown on Ti seed layers exhibit a strong preferred (111) orientation favoured by good matching with the titanium lattice. The substrate temperature during the growth of iridium/titanium stack has a significant effect on the surface morphology of the iridium layer and its thermal stability. The as-grown surface of 20-nm-thick Ir films is smooth, having a root-mean-square (rms) roughness of 0.7 nm. After thermal annealing the Ir film shows an increased surface roughness due to the formation of agglomerations. The change in the surface morphology of the Ir layer is due to titanium diffusion and its oxidation. Thicker and better crystallised iridium thin films annealed in oxygen atmosphere at 700 A degrees C show a good thermal stability with only a slight modification of the surface morphology. Within the limits of experimental error, there is no change in the electrical resistivity before and after thermal annealing. The rms roughness has not varied significantly and the XPS investigation shows no traces of titanium oxide on iridium surface. Ir/Ti stack deposited under the optimum conditions could be successfully used as electrode in devices based on oxide thin films.

The adsorption of L-cysteine from ethanol solutions on GaAs(1 0 0) surfaces has been studied by XPS and density-functional theory (DFT). XPS data reveal that the formation of the adsorbate involves preferentially the As-sites for p-GaAs(1 0 0) and the Ga-sites for n-GaAs(1 0 0). The adsorbed species show different orientations of the functional groups to the surface for the different substrates. DFT calculations performed for both Ga-dimers and As-dimers terminated surfaces show that the adsorption is energetically favourable on both substrates. However, the adsorption energy is more negative on top of Ga-atoms. Here an important contribution for the stabilization of the adsorbate is the interaction of the functional groups with the surface. The parallel orientation found for the Ga-bound species by DFT calculations is in good agreement with the shift in the binding energy of the NH2/NH3+ species observed by XPS analysis.

Effects of the self-assembled layers of biphenyl 4,4'-dithiol (BPDT) and 1,8-octanedithiol (ODT) on the chemical and electronic properties of p-doped GaAs (111)-As terminated substrate, (p-GaAs(111)B), were investigated in order to evidence whether the hydrocarbon moiety plays a role in tailoring the semiconductor surface properties. The electrochemical properties of the BPDT and ODT coated p-GaAs(111)B substrates were studied by Electrochemical Impedance Spectroscopy (EIS). The structural and chemical changes caused by the dithiolate layers formed on p-GaAs(111)B substrates were monitored by Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) investigations, respectively. The XPS data showed that BPDT and ODT bind to pGaAs(111)B via the thiol group. The ODT layer provides better protection against the further oxidation in air of p-GaAs(111)B substrate compared to the BPDT layer. The EIS investigations are in good agreement with XPS results, pointing to better insulating properties of the ODT layer compared to the BPDT layer in the electron transfer at the electrode/solution interface. The results evidenced that backbone plays an important role in tailoring the properties of p-GaAs(111)B substrate. (C) 2016 Elsevier B.V. All rights reserved.

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

A new synthesis method based on the electrochemical reduction of alpha,alpha,alpha',alpha'-tetrabromo-p-xylene in the presence of single-walled carbon nanotubes (SWNTs) is used to obtain composites of carbon nanotubes (CNTs) functionalized with poly(para-phenyl-enevinylene) (PPV). To separate the effects of metallic and semiconducting CNTs on their interaction with PPV, the experiments are carried out with SWNTs enriched in semiconducting (S, 99%) and metallic (M, 98%) tubes. Significant changes in the relative intensity and shift of the radial breathing vibrational mode are reported in the Raman spectra of the as-prepared SWNTs samples, i.e., as mixtures of metallic (33%) and semiconducting (66%) entities and SWNTs enriched in M tubes (98%) that result from the electrofunctionalization with PPV. This different behavior originates in the noncovalent and covalent functionalization of SWNTs enriched in M and S SWNTs tubes with PPV, respectively. A gradual decrease in the absorption of the infrared (IR) bands of PPV situated in the spectral range of 750-1000 cm(-1) as a result of the increase of the polymer weight on the blank Au support is reported. The electrofunctionalization of the as-prepared SWNTs induces position changes of the PPV IR absorption bands. In the presence of S-enriched SWNTs, a significant increase in the absorbance of the two IR bands peaked at 1452 and 1471 cm(-1), which are assigned to the vibrational modes of the phenyl ring stretching and the quinoid structure of the PPV, respectively, is reported. This results from the covalent bonding of the PPV macromolecular chains onto the surface of the SWNTs enriched in S tubes. Our results also demonstrate that the photoluminescence quenching effect reported for the PPV/SWNTs composites is due to the metallic nanotubes.

The possibility to intercalate noble gas atoms below epitaxial graphene monolayers coupled with the instability at high temperature of graphene on the surface of certain metals has been exploited to produce Ar-filled graphene nanosized blisters evenly distributed on the bare Ni(111) surface. We have followed in real time the self-assembling of the nanoblisters during the thermal annealing of the Gr/Ni(111) interface loaded with Ar and characterized their morphology and structure at the atomic scale. The nanoblisters contain Ar aggregates compressed at high pressure arranged below the graphene monolayer skin that is decoupled from the Ni substrate and sealed only at the periphery through stable C-Ni bonds. Their in-plane truncated triangular shapes are driven by the crystallographic directions of the Ni surface. The nonuniform strain revealed along the blister profile is explained by the inhomogeneous expansion of the flexible graphene lattice that adjusts to envelop the Ar atom stacks.

The Peierls transition of polycrystalline CuGeO3 samples was investigated by thermal and magnetic investigations. We find that spin disorder induced by chain breaking and grain boundaries has similar effects to doping but without suppressing the spin-Peierls transition temperature or the spin-Peierls gap.

Aluminum doped zinc oxide (AZO) thin films were obtained by pulsed laser deposition on (001) SrTiO3 (STO) on a range of substrate temperatures during ablation between 300 degrees C and 600 degrees C. A hexagonal system lying on a cubic one should be difficult to be obtained in epitaxial form. The geometrical selection of the AZO growth on (001) STO is not giving a unique preferential orientation. Two orientations, c-axis (along [001]) and 110, have been observed experimentally with different ratios at different substrate temperature. Discussions are made with respect to the temperature dependence of lattice mismatch between the two cases and the cubic surface of the substrate, and to the substrate surface morphology and terminating atomic layer composition. The 110 AZO is the main phase at deposition temperature of 550 degrees C, while for other substrate temperatures the 001 is the preferential orientation. The conductive character of 110 AZO thin film have been inferred from both ellipsometry spectra and current-voltage measurements. Excepting the samples deposited at 300 degrees C, the lowest resistivity is recorded for the samples with 110 AZO as the main phase. (C) 2015 Elsevier B.V. All rights reserved.

Gallium antimonide (GaSb) is the basis of the most photovoltaic and thermophotovoltaic (TPV) systems and its innovative technological aspects based on modern ultra-high vacuum techniques are in trend for device achievement. The real surface of GaSb is modified by technological processes that can conduce to problems related to the reproducible control of its surface properties. The GaSb surface is reactive in atmosphere due to oxygen presence and exhibits a native oxide layer. The evolution of native oxides during the ion sputtering, chemical etching and thermal annealing processes for preparing the surface is presented in detailed way. Ratios of surface constituents are obtained by Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS). Moreover, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Atomic Force Microscopy (AFM) and Low-Energy Electron Diffraction (LEED) are used for characterization. The surface stoichiometry is changed using a specific etchant (e.g. citric acid) at different etching time and is analyzed by ARXPS, SEM, EDS and AFM methods. The experimental results provide useful information regarding surface native oxides characteristics on n-GaSb(100) to be taken into account for development of low resistance contacts for TPV devices based on GaSb alloy. (C) 2015 Elsevier B.V. All rights reserved.

We report a study on the biocompatibility vs. thickness in the case of titanium nitride (TiN) films synthesized on 410 medical grade stainless steel substrates by pulsed laser deposition. The films were grown in a nitrogen atmosphere, and their in vitro cytotoxicity was assessed according to ISO 10993-5 [1]. Extensive physical-chemical analyses have been carried out on the deposited structures with various thicknesses in order to explain the differences in biological behavior: profilometry, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and surface energy measurements. XPS revealed the presence of titanium oxynitride beside TiN in amounts that vary with the film thickness. The cytocompatibility of films seems to be influenced by their TiN surface content. The thinner films seem to be more suitable for medical applications, due to the combined high values of bonding strength and superior cytocompatibility.