National Institute Of Materials Physics - Romania

Herein we show that the Ti3SiC2 MAX phase can be used as a support for deposition of different amounts of metal oxides (MOx, M = Cu or V) (5, 10 and 20 wt%) for the direct oxidation of methane to formaldehyde using molecular oxygen, at relatively low temperatures and atmospheric pressure. The oxides were deposited using a hydrothermal method at 180 degrees C without affecting the bulk MAX phase structure. However, during the hydrothermal treatment (HT) a thin oxide layer - found to play an important role in the reaction's selectivity- was evidenced by X-ray photoelectron spectroscopy. We thus conclude that the MOx species are responsible for the CH4 activation, while the Ti3SiC2 surface is responsible for the high selectivity to formaldehyde indicating that, Ti3SiC2 has great potential for designing innovative catalysts for direct oxidation of methane using molecular oxygen and at atmospheric pressure.

Laser thin layer deposition technologies were applied to develop organic heterostructures on flexible transparent conductive electrode (TCE). Flexible substrates such as flexible glass (FG), polyethersulfone (PES), amorphous polyethylene terephthalate (PET-A) and biaxially-oriented polyethylene terephthalate (PET-B) were employed to assess the influence of the substrate type on the optical and electrical characteristics of the organic devices. For comparison reason, the organic heterostructures were fabricated on rigid glass substrate and commercially available indium tin oxide (ITO)-coated PET. Hence, flexible and rigid glass substrates were coated with ITO film by pulsed laser deposition (PLD) at low fluence, subsequently a blend layer based on zinc phthalocyanine (ZnPc) and N, N '-bis-(1-dodecyl)perylene-3,4,9,10 tetracarboxylic diimide (AMC14) being deposited by matrix assisted pulsed laser evaporation (MAPLE) on the TCE film. The investigations evidenced that the roughness and the substrate type can strongly influence the properties of the ITO layer deposited by PLD as well as the optical and electrical characteristics of the organic heterostructures based on the blend layer deposited by MAPLE. Thus, the lowest roughness (0.8 nm) and the best Hall mobility (41.9 cm2/V center dot s) were achieved for ITO coatings deposited on flexible glass substrate. Also, the highest current density value (9.3 x 10- 4 A/cm2 at 0.5 V) was reached for the organic heterostructures fabricated on this type of flexible substrate.

The tuning sensitivity towards CO2 detection under in-field-like conditions was investigated using SnO2-sensitive material deposited onto Al2O3 substrates provided with platinum electrodes with interdigital gaps of 100 mu m and 30 mu m. X-ray diffraction, low-magnification and high-resolution transmission electron microscopy, and electrical and contact potential difference investigations were employed to understand the sensing mechanism involved in CO2 detection. The morpho-structural analysis revealed that the SnO2 nanoparticles exhibit well-defined facets along the (110) and (101) crystallographic planes. Complex phenomenological investigations showed that moisture significantly affects the gas sensing performance. The experimental results corroborated the literature evidence, highlighting the importance of Pt within the interdigital electrodes subsequently reflected in the increase in the CO2 sensing performance with the decrease in the interdigital gap. The catalytic efficiency is explained by the distribution of platinum at the gas-Pt-SnO2 three-phase boundary, which is critical for enhancing the sensor performance.

Self-powered near-infrared (NIR) photodetectors are essential for surveillance systems, sensing in IoT electronics, facial recognition, health monitoring, optical communication networks, night vision, and biomedical imaging. However, silicon commercial detectors need external power to operate and cooling to suppress large dark currents. This work demonstrates a new class of CMOS-compatible self-powered NIR photodetector based on ferroelectric 5-nm thick ZrO2 films which do not require cooling and therefore have two key advantages over Si, and at the same time have comparable performance metrics. At room-temperature, under 940 nm wavelength illumination (1.4 mW cm-2 power density, 10 Hz repetition rate), and without any power applied, fast rise and fall times of approximate to 2 and 4 mu s, respectively, are achieved in Al/Si/SiOx/ZrO2/ITO devices, along with responsivity, detectivity and sensitivity values of up to approximate to 3.4 A W-1, 1.2 x 1010 Jones and 4.2 x 103, respectively, far exceeding all other emerging self-powered systems. Furthermore, dual-band NIR detection is shown for different NIR wavelengths, proof-of-concept feasibility being demonstrated for the smart identification of NIR targets. Therefore, it is demonstrated, for the first time, that coupling together the pyroelectric effect, the photovoltaic effect, and the ferroelectric effect is a novel method to significantly enhance the performance of CMOS-compatible ZrO2-based self-powered photodetectors in the NIR region.

Rare-earth doped GdF3 nanocrystals embedded in silica glassy matrix have been prepared by controlled crystallization of the xerogel; the influence of rare-earth ion (Pr, Sm, Eu, Tb, Dy, Er, Yb) and additional Li-codopant on structural and optical properties was discussed. The precipitation of RE-doped GdF3 nanocrystalline phase is the result of Gd-trifluoracetate thermolysis revealed as a strong exothermic peak at around 300 degrees C. Structural analysis of RE-doped SiO2-GdF3 glass-ceramic sample calcined at 525 degrees C showed the occurrence of GdF3 nanocrystals of about 25 nm size, showing hexagonal or orthorombic structure depending on the RE-ion. Under UV-light excitation at 273 nm of Gd3+ ions (S-8(7/2) -> I-6(13/2,15/2) transition), photoluminescence spectra showed characteristic RE3+ luminescence due to the non-radiative energy transfer between the excited Gd3+ and acceptor RE ions; the highest energy transfer (congruent to 80 %) was observed for Tb3+ and lowest (congruent to 21 %) for Sm3+.

We study the dependence of photo-spectral intensity on tri- and multilayers of SiO2/[SiGe [ dSiGe]/SiO2]N with repetitions N = 1 to 10 and thicknesses dSiGe=5-100 nm. Photocurrent analysis reveals a bimodal spectral feature. A comparison of the photocurrent analysis between tri- and multilayers shows that in the multilayer structures, the photo-spectral intensity increases with increasing repetition N. The change in intensity could then be further tuned by changing the thickness of the SiGe layers dSiGe. We attribute the change in intensity to an increase in tensile strain, along with increased Ge atomic concentration and reduced SiGe-nano cluster size.

15 at.% Yb3+:YAG/YAG transparent composite ceramics with a coaxial geometry were synthesized by a ceramic forming method combined with the reactive sintering at 1800 degrees C. Densification peculiarities, microstructure, optical properties, and laser characteristics of composite ceramic samples were studied. Powder mixtures of Yb3+:YAG and YAG stoichiometric compositions demonstrate almost the same densification enabling uniform shrinkage of composite without differential sintering. It was shown that in-line optical transmittance of 15 at.% Yb3+:YAG/YAG composite ceramics reaches 80 % at 1030 nm wavelength. The effective diffusion coefficient of Yb3+ ions in garnet structure has been determined. Efficient laser emission was generated from Yb3+:YAG/YAG composite ceramics with a slope efficiency of eta(sa) = 0.30.

Blending carbon particles (CPs) and nanoscale bioactive cerium dioxide is a promising approach for designing composites for biomedical applications, combining the sorption and antioxidant potentials of each individual component. To address this issue, it is crucial to assess the correlation between the components' ratio, physicochemical parameters, and biofunctionality of the composites. Thus, the current research was aimed at fabricating C@CeO2 composites with different molar ratios and the examination of how the parameters of the composites affect their bioactivity. XRD, X-ray photoelectron spectroscopy, and electron microscopy data verified the formation of C@CeO2 composites. CeO2 nanoparticles (NPs) of 4-6 nm are highly dispersed on the surfaces of amorphous CPs. The presence of CeO2 NPs on the carbon surface decreased its adsorption potential in a dose-dependent manner. Besides, the coexistence of carbon and CeO2 in a single composite promotes some redox interactions between O-functionalities and Ce3+/Ce4+ species, resulting in changes in the chemical state of the surface of the composites. These observations suggest the strong connection between these parameters and the biofunctionality of the composites. The presence of CeO2 NPs on the surface of carbon led to a significant increase in the stability of the prepared composites in their aqueous suspensions. The enhancement of bioactivity of the newly prepared C@CeO2 compared to bare carbon and CeO2 was validated by testing their pseudomimetic (catalase/peroxidase-like and superoxide dismutase-like), antiamyloid, and radioprotective activities.

The ca. 480 Ma Albesti granite (Southern Carpathians, Romania) is characterized by the presence of color zoned blue quartz grains, and is part of the rather extensive European Cambro-Ordovician blue quartz landscape. The color is heat sensitive, fading at temperatures as low as 300degree celsius, inconsistent with the thermally stable, light scattering, nanometric rutile/ilmenite inclusions cited in literature. Extensive X- and Q-band electron paramagnetic resonance (EPR) investigations were carried out, searching for distinctive features of the Albesti quartz that are directly or indirectly involved in the generation of the blue coloration. The analyzed quartz grains were extracted from three granite samples of varying coloration and anisotropy, and the quartz from each rock sample was further separated into colored and colorless fractions. The paramagnetic E' and [AlO4]0 centers, as well as Mn2+ ions localized in traces of amorphous associated minerals at grain boundaries or fissure planes, were observed in all quartz samples. Broad EPR lines associated with the presence of magnetic clusters were observed in the spectra of the white quartz sample and the corresponding colorless one. Isochronal annealing up to 500degree celsius induced the correlated recombination of the E' and [AlO4]0 centers, the strong decrease of the Mn2+ spectrum and the formation of a minority iron oxide phase at the grain boundaries and/or fissure planes. The EPR signature was similar for the colored and the corresponding colorless quartz samples, before and after annealing, showing that the heat sensitive coloration of the Albesti quartz does not directly involve the presence of paramagnetic defects and/or minority magnetic phases.

Design of composite support materials based on Sn-doped TiO2 and carbon is one of the strategies to develop corrosion-resistant and CO-tolerant Pt electrocatalysts for polymer electrolyte membrane (PEM) fuel cells. As the synthesis methodology may have crucial influence on the structural and functional properties of the composites, different preparation routes for the novel support materials are explored and compared. Ti(1-x)SnxO2-C (x: 0.1-0.3) composites with different mixed oxide/carbon ratios were prepared by two sol-gel-based synthesis routes, namely (i) the introduction of a Sn precursor after the formation of the TiO2-rutile nuclei on the carbon backbone (route A), and (ii) simultaneous introduction of Ti and Sn precursors, resulting in good mixing of the Sn- and Ti-sol before the addition of the carbon (route B). The bulk and surface microstructure of the composites and the electrocatalysts obtained by their Pt-loading were investigated in detail. The incorporation of tin into the TiO2-rutile unit cell was confirmed by X-ray powder diffraction and Raman spectroscopy; the results indicated doping levels in good accordance with the amount of tin precursor. The advantages of composites and Pt electrocatalysts obtained via synthesis route B were that they do not contain segregated Sn-0 or SnO2 phases, have a more homogeneous/uniform mixed oxide distribution over the carbon backbone, and the electrochemically active surface area values (similar to 60-80 m(2)/g(Pt)) are twice as high as those of catalysts with similar compositions synthesized by method A. A common feature of the composites prepared by routes A and B was the presence of a tin oxide-rich overlayer identified by X-ray photoelectron spectroscopy. As a consequence, the electrocatalytic behavior of the catalysts was not influenced by the Ti/Sn ratio and was mainly dependent on the synthesis method used in the preparation of composite support materials. Elemental maps confirmed the formation of areas where Pt and the Sn doping element were in atomic proximity to each other, which means a favorable interaction either for the bifunctional mechanism or the electronic ligand effect. An increase in carbon content in composite materials led to an increase in both catalytic activity and long-term stability. The results of electrochemical studies showed that Sn-containing Pt catalysts with a high carbon content (75 wt%) are the most promising for potential use both as an anode and a cathode for PEM fuel cells.