National Institute Of Materials Physics - Romania

Control of structural coupling at complex-oxide interfaces is a powerful platform for creating ultrathin layers with electronic and magnetic properties unattainable in the bulk. However, with the capability to design and control the electronic structure of such buried layers and interfaces at a unit-cell level, a new challenge emerges to be able to probe these engineered emergent phenomena with depth-dependent atomic resolution as well as element- and orbital selectivity. Here, we utilize a combination of core-level and valence-band soft x-ray standing-wave photoemission spectroscopy, in conjunction with scanning transmission electron microscopy, to probe the depth-dependent and single-unit-cell resolved electronic structure of an isovalent manganite superlattice [Eu0.7Sr0.3MnO3/La0.7Sr0.3MnO3] x 15 wherein the electronic-structural properties are intentionally modulated with depth via engineered oxygen octahedra rotations/tilts and A-site displacements. Our unit-cell resolved measurements reveal significant transformations in the local chemical and electronic valence-band states, which are consistent with the layer-resolved first-principles theoretical calculations, thus opening the door for future depth-resolved studies of a wide variety of heteroengineered material systems.

SiGe nanoparticles dispersed in a dielectric matrix exhibit properties different from those of bulk and have shown great potential in devices for application in advanced optoelectronics. Annealing is a common fabrication step used to increase crystallinity and to form nanoparticles in such a system. A frequent downside of such annealing treatment is the formation of insulating SiO2 layer at the matrix/SiGe interface, degrading the optical properties of the structure. An annealing process that could bypass this downside would therefore be of great interest. In this work, a short-time furnace annealing of a SiGe/TiO2 system is applied to obtain SiGe nanoparticles without formation of the undesired SiO2 layer between the dielectric matrix (TiO2) and SiGe. The structures were prepared by depositing alternate layers of TiO2 and SiGe films, using direct-current magnetron sputtering technique. A wide range spectral response with a response-threshold up to similar to 1300 nm was obtained, accompanied with an increase in photo-response of more than two-orders of magnitude. Scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy and grazing incidence x-ray diffraction were used to analyze the morphological changes in respective structures. Photoconductive properties were studied by measuring photocurrent spectra using applied dc-voltages at various temperatures.

Nanoclustered Pd (2 mol%) was used to decorate Zn doped SnO2 (10 mol% Zn) in order to increase its sensing performances. Zn doped SnO2 built from nanoparticles was prepared by a hydrothermal method using a nonionic surfactant -Brij52 and Tripropylamine (TPA) as co-templates. The presence of well-dispersed Zn2+ ions in the SnO2 matrix leads to a nonstoichiometric surface. Pd was deposited by subsequent wet impregnation using hydrazine as reducing agent. The as obtained powders were deposited as thick layers onto commercial substrates, in order to obtain the sensitive structures. The coexistence of a mixture of valence states (Pd-0, Pd2+ and Pd4+) was highlighted on the surface of the as prepared layers. Several aspects have been followed regarding the Zn and Pd dispersion into the SnO2 matrix: the large scale and low scale morphology (SEM and TEM/HRTEM) in relation with the synthesis route, the obtained crystallographic phases (XRD, SAED) and the way in which the Zn2+ ions are inserted into the SnO2 structure (XRD, XPS, EPR), the spatial distribution of the added chemical elements, Zn and Pd (SEM, STEM, EDS). All these morphological and structural aspects, as well as the Pd surface chemistry, have been correlated with the sensing properties of the nanostructured materials under controlled gas atmosphere. Through this study, we could harvest the specific role of the aforementioned loadings towards selective detection of low NO2 concentrations, between 350 ppb to 5 ppm, at low operating temperature of 100 degrees C, for infield conditions.

Copper (Cu) and dysprosium (Dy) co-doped zinc oxide (ZnO) thin films were fabricated by radio frequency magnetron sputtering (RF-magnetron sputtering) using a homemade target having the atomic percentage of Cu and Dy of 1%, onto optical glass substrates and quartz substrates. The structural, morphological, optical, and electrical properties of fabricated ZnO:(Cu, Dy) structures were analyzed and discussed. It was found that all samples have hexagonal Wurtzite structure. Optical transmission measurements indicate values larger than 75% in the 400-2500 nm ranges. The current-voltage characteristics of hybrid heterojunctions based on ZnO:(Cu, Dy) and poly(3-hexylthiophene-2.5-diyl) (P3HT) or copper (II) phthalocyanine (CuPc) thin films were acquired in the dark, in ambient atmosphere, and they exhibit the typical diode behavior, almost free of electrical hysteresis.

In this work, we report a photodegradation process of azathioprine (AZA) highlighted by correlated studies of photoluminescence (PL) and the UV-VIS and IR absorption spectroscopy. The photodegradation process of AZA is observed by the gradual increasing in the intensity of the PL spectrum recorded under the excitation wavelength of 300 nm. This behaviour is accompanied, in the photoluminescence excitation (PLE) spectra, by a gradual intensity decreasing of the PLE band situated in the 250-320 nm spectral range simultaneous with the intensity increasing of the PLE band localized in the 325-425 nm spectral range. Regardless if the immunosuppressive compound is in the state of powder, tablet or solution, the PL and UV-VIS absorption spectroscopy studies have demonstrated that a photodegradation process under UV light takes place. According to the PL studies carried out in ambient and vacuum condition, the photodegradation process of AZA was demonstrated to be influenced by the oxygen from air. The presence of a new IR band with maximum at 1745 cm(-1) confirms the AZA photodegradation pathway proposed in this work.

Semiconducting metal oxide (SMOX)-based gas sensors are indispensable for safety and health applications, for example, explosive, toxic gas alarms, controls for intake into car cabins, and monitor for industrial processes. In the past, the sensor community has been studying polycrystalline materials as sensors where the porous and random microstructure of the SMOX does not allow a separation of the phenomena involved in the sensing process. This led to conduction models that can model and predict the behavior of the overall response, but they were not capable of giving fundamental information regarding the basic mechanisms taking place. The study of epitaxial layers is a definite improvement, allowing clarifying the different aspects and contributions of the sensing mechanisms. A detailed analytical model of the transduction function for n- and p-type single-crystalline/compact metal oxide gas sensors was developed that directly relates the conductance of the sample with changes in the surface electrostatic potential. Combined dc resistance and work function measurements were used in a compact SnO2(101) layer in operando conditions that allowed us to check the validity of our model in the region where Boltzmann approximation holds to determine the surface and bulk properties of the material.

Luminescent europium-doped hydroxylapatite (Eu(X)HAp) nanomaterials were successfully obtained by co-precipitation method at low temperature. The morphological, structural and optical properties were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), UV-Vis and photoluminescence (PL) spectroscopy. The cytotoxicity and biocompatibility of Eu(X)HAp were also evaluated using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide)) assay, oxidative stress assessment and fluorescent microscopy. The results reveal that the Eu3+ has successfully doped the hexagonal lattice of hydroxylapatite. By enhancing the optical features, these Eu(X)HAp materials demonstrated superior efficiency to become fluorescent labelling materials for bioimaging applications.

In the case of DEMO fusion reactor, the divertor should be able to extract a steady heat flux of about 10 MW/m(2). A promising concept is the W-monoblock which should be connected to a CuCrZr or an advanced Cu ODS alloy pipe passing through the W component. Taking into account the optimum operating temperature windows for W and existing Cu-based alloys and the thermal expansion coefficients mismatch of these two materials, a "thermal barrier" interface material is inserted in between in order to mitigate the thermal stresses and to optimize the heat flow through divertor components. In this work we investigate the feasibility to realize such divertor components using materials produced by FAST (field assisted sintering technology). This powder metallurgy technique was used firstly to produce W or W-based composites and the thermal barriers in an almost final shape and then to join the materials in realistic divertor mock-ups. The thermal barrier materials are various Cu-based composites which are included both as single material or as functionally graded components. The interface quality between different materials is investigated by scanning electron microscopy and the heat flow through components is evaluated using simulations.

The influence of the injection of minority charge carriers on the formation of a divalent bistable defect (DBH) having two energy levels of E-v + 0.44 eV and E-v + 0.53 eV in its metastable configuration is investigated. Using forward current injection, the formation temperature of this defect in p-type silicon can be lowered by about 50 degrees C. The production of such bistable defect is enhanced in materials with a high ratio of boron to carbon concentrations. This allows one to conclude that the boron atom is one of the constituents of the defect under study. There is also a correlation between the behavior of the bistable hole traps and a metastable electron trap observed earlier. It is concluded that these traps are related to metastable and stable configurations of the DBH defect, which has inverse occupancy level ordering in its stable configuration.

In this study, CuxCrFeTiV (x = 0.21, 0.44, 1 and 1.7 M ratio) high entropy alloys have been devised for thermal barriers between the plasma facing tungsten tiles and the copper-based heat sink in the first wall of nuclear fusion reactors. The high entropy alloys were produced by ball milling the elemental powders, followed by consolidation with spark plasma sintering. Irradiation of the equiatomic CuCrFeTiV sample was carried out at room temperature with Ai(+) (300 keV) beams with a fluence of 3 x 10(20) at/m(2). Structural changes prior and after irradiation were investigated by scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy, X-ray diffraction and thermal diffusivity. Preliminary results showed the presence of heterogenous and multiphasic microstructures in all samples. Moreover, with the increase of the Cu content it is possible to observe the formation of Cu-rich structures. The diffractogram of the CuCrFeTiV sample revealed major peaks of a BCC crystal structure and minor peaks of a FCC crystal structure. In addition, after irradiation no modifications in the CuCrFeTiV microstructure or in the diffractogram were observed.