National Institute Of Materials Physics - Romania

Controlling the semiconductor-to-metal transition temperature in epitaxial VO2 thin films remains an unresolved question both at the fundamental as well as the application level. Within the scope of this work, the effects of growth temperature on the structure, chemical composition, interface coherency and electrical characteristics of rutile VO2 epitaxial thin films grown on TiO2 substrates are investigated. It is hereby deduced that the transition temperature is lower than the bulk value of 340 K. However, it is found to approach this value as a function of increased growth temperature even though it is accompanied by a contraction along the V4+-V4+ bond direction, the crystallographic c-axis lattice parameter. Additionally, it is demonstrated that films grown at low substrate temperatures exhibit a relaxed state and a strongly reduced transition temperature. It is suggested that, besides thermal and epitaxial strain, growth-induced defects may strongly affect the electronic phase transition. The results of this work reveal the difficulty in extracting the intrinsic material response to strain, when the exact contribution of all strain sources cannot be effectively determined. The findings also bear implications on the limitations in obtaining the recently predicted novel semi-Dirac point phase in VO2/TiO2 multilayer structures.

This paper reports the sensing mechanism of SnO2-CuWO4 mixed oxides towards H2S detection revealed through Pulsed Temperature Mode (PTM). After thick film deposition onto commercial substrates, the final annealing temperature enhances the material reliability through the changes occurred during the experimental conditions. PTM approach represents a tradeoff in terms of sensing mechanism versus sensing performance, in order to get insights about the fundamental aspects. The measurements have been done under dynamic gas flow conditions, in the presence of 50% relative humidity (RH). The gas sensors based on SnO2-CuWO4 exhibit sensor signals higher than 100 to 10 ppm H2S, low cross-sensitivity to common gaseous interfering agents (CO, CH4, NH3, SO2), average selective sensitivity of 8.64 towards the main interfering NO2 gas, moderate response (4 min)/recovery (5 min) transients and power consumption. In order to emphasize the role of moisture towards H2S detection mechanism, the photoacoustic spectroscopic insights were correlated with Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy results. Such approach has shown promising aspects towards further operational sensitive devices. (c) 2017 Elsevier B.V. All rights reserved.

This work is focused on a novel class of hybrid materials exhibiting enhanced optical properties and high surface areas that combine the morphology offered by the vinyl substituted silica host, and the excellent absorption and emission properties of 5,10,15,20-tetrakis(N-methyl-4-pyridyl) porphyrin-Zn(II) tetrachloride as a water soluble guest molecule. In order to optimize the synthesis procedure and the performance of the immobilized porphyrin, silica precursor mixtures of different compositions were used. To achieve the requirements regarding the hydrophobicity and the porous structure of the gels for the successful incorporation of porphyrin, the content of vinyltriacetoxysilane was systematically changed and thoroughly investigated. Substitution of the silica gels with organic groups is a viable way to provide new properties to the support. An exhaustive characterization of the synthesized silica samples was realised by complementary physicochemical methods, such as infrared spectroscopy (FT-IR), absorption spectroscopy (UV-Vis) and photoluminescence, nuclear magnetic resonance spectroscopy (Si-29-MAS-NMR) transmission and scanning electron microscopy (TEM and SEM), nitrogen absorption (BET), contact angle (CA), small angle X ray and neutron scattering (SAXS and SANS). All hybrids showed an increase in emission intensity in the wide region from 575 to 725 nm (Q bands) in comparison with bare porphyrin. By simply tuning the vinyltriacetoxysilane content, the hydrophilic/hydrophobic profile of the hybrid materials was changed, while maintaining a high surface area. Good control of hydrophobicity is important to enhance properties such as dispersion, stability behaviour, and resistance to water, in order to achieve highly dispersible systems in water for biomedical applications.

Gold nanoparticles were decorated on/into the SBA-15 channels covalently functionalized by new class of symmetrical tridentate NNN-pincer ligand. This provides a unique support for stabilization of Au NPs preventing agglomeration due to the strong ligation of pincer ligand. The catalyst proved to be highly active for the reduction of nitroarenes. The kinetics study showed that the rate constant for the current protocol are comparable or larger than the reported ones in literature. The catalyst also showed high recoverability and reusability up to ten times without significant loss of activity and leaching or aggregation of Au NPs (overall TOF = 8798).

Si and Ge nanocrystals in oxides are of a large interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in nanocrystals. In this work, dense Ge nanocrystals suitable for enhanced photoconduction were fabricated from 60% Ge in TiO2 amorphous layers by low temperature rapid thermal annealing at 550 degrees C. An exponential increase of the photocurrent with the applied voltage was observed in coplanar structure of Ge nanocrystals composite films deposited on oxidized Si wafers. The behaviour was explained by field effect control of the Fermi level at the Ge nanocrystals-TiO2 layer/substrate interfaces. The blue-shift of the absorption gap from bulk Ge value to 1.14 eV was evidenced in both photocurrent spectra and optical reflection-transmission experiments, in good agreement with quantum confinement induced bandgap broadening in Ge nanocrystal with sizes of about 5 nm as found from HRTEM and XRD investigations. A nonmonotonic spectral dependence of the refractive index is associated to the Ge nanocrystals formation. The nanocrystal morphology is also in good agreement with the Coulomb gap hopping mechanism of T-1/2 -type explaining the temperature dependence of the dark conduction.

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO2 and inferred for TiO2. In this paper, TiO2 thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 degrees C. The TiO2 films were exposed to different concentrations of CO, CH4, NO2, NH3 and SO2 to evaluate their gas sensitivities. These experiments showed that the TiO2 film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH4 and NH3 exposure indicated typical n-type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated.

The present study is focused on the wet chemical synthesis and the characterization of ZnO-CdS composites. The X-ray diffraction shows that the composites contain ZnO in hexagonal wurtzite structure and CdS in cubic phase. The scanning/transmission electron microscopy images reveal flower-like structures with different sizes depending on the CdS content. The optical investigations on composites reveal that the reflectance spectra disclose two thresholds of similar to 370 nm and similar to 460 nm associated with the ZnO and CdS, respectively. The photocatalytic activity measurements evidenced that the degradation efficiency of RhB in the presence of composites is higher comparatively with pristine ZnO, depending on the catalyst morphology, which varies with CdS content and the pH value of RhB solution. The electron paramagnetic resonance revealed the presence of the paramagnetic point defects in the samples. Thus, the wet chemical approaches are suitable for a large scale production of such ZnO-CdS composites having enhanced photocatalytic activity.

By platinum deposition on a 150 nm thick film of lead zirco-titanate oriented PZT(001), grown on strontium titanate (001) single crystals with a strontium ruthenate buffer layer, which did not show initial preferential out-of-plane orientation of its ferroelectric polarization, a band bending near the interface towards lower energies is observed using photoelectron spectroscopy, by following all core levels from the substrate (Pb 4f, Zr 3d, Ti 2p, O 1s). This is unexpected given the fact that platinum has a larger work function than PZT and a rectifying contact for electrons is expected to be built at the interface. This observation may have two explanations: (i) platinum forms an alloy with elements from PZT yielding a metal with considerable lower work function; (ii) platinum provides electrons to the substrate which are able to compensate the depolarization field generated by the outwards polarization state. Several arguments are brought in favor of the second hypothesis, especially the attenuation of core levels from the substrate which is well described by exponential functions with reasonable values of the photoelectron inelastic mean free path, suggesting the formation of a sharp interface. High resolution transmission electron microscopy confirmed the sharpness of the interface. (C) 2017 Elsevier B.V. All rights reserved.

It is shown that the dielectric and piezoelectric properties of Ba(Ti0.8Zr0.2)O-3-x(Ba0.7Ca0.3)TiO3 (x = 0.45) (BCTZ 45) epitaxial thin films have a nontrivial dependence on film thickness. BCTZ 45 epitaxial films with different thicknesses (up to 400 nm) have been deposited on SrTiO3 by pulsed laser deposition and investigated by different combined techniques: conventional and off-axis X-ray diffraction, high resolution transmission electron microscopy and dielectric and piezoforce microscopy. The changes occurring in epitaxial films when their thickness increases have been attributed to a partial relaxation of misfit strain, driving the induced tetragonal symmetry in very thin films to the original rhombohedral symmetry of the bulk material in the thickest film, which influences directly and indirectly the dielectric and piezoelectric properties.

We have analyzed by transmission electron microscopy silicon and GaAs crystals polished with sandpapers of different grain size. The surface damage induced a crystal permanent convex curvature with a radius of the order of a few meters. The curvature is due to a compressive strain generated in the damaged zone of the sample. Contrary to what was reported in the literature, the only defects detected by transmission electron microscopy were dislocations penetrating a few microns from the surface. Assuming the surface damage as a kind of continuous indentation, a simple model able to explain the observed compressive strain is given.