National Institute Of Materials Physics - Romania

Cerium dioxide (CeO2) thin films with pyramidal nanostructures exhibiting a fractal aspect are suitable for various applications that require a large surface area. An accurate model of these films is valuable not only for optimizing the properties for specific applications but also for predicting and understanding the growth mechanism. In this paper, we present the foundation of a simulation for the growth of CeO2-x nanostructured thin films. We propose a 3-dimensional model of the surface nanostructures and link the morphology with crystallographic orientations and growth modes. To validate our model, we fabricated CeO2_ x thin films with different thicknesses using pulsed laser deposition (PLD) and characterized their morphological and structural properties. The evolution of our films shows the representative features of the Stranski-Krastanov model. The morphology changes from compact and smooth to dendritic with pyramidal nanostructures. The texture of our film also changes with thickness, and the preferential orientations are (111) and (220). Additionally, we characterize the CeO2_ x thin films from the chemical and optical points of view. The stoichiometry of CeO2 is not fully achieved, our thin films present the Ce3+ oxidation state at the surface. The formation of C-type Ce2O3 with fluorite structure can be associated with a small refractive index and small band gap.

The precise control of the magnetic compensation temperature (theta c) in ferrimagnetic garnets is essential for the development of cutting-edge ultrafast customizable spintronic devices. In this work we demonstrate how fine variation in stoichiometry and cation distribution in iron gadolinium garnets significanty influences theta c. Two samples of Gd3Fe5O112 garnets synthesized via a new hydrothermal method and a conventional solid-state reaction, respectively, were considered. The complex study was carried out using a complex approach combining X-ray diffraction, magnetometry, and M & ouml;ssbauer spectroscopy. Atomic-scale analysis revealed with unprecedent accuracy a cationic inversion between Fe3+ ang Gd3+ at octahedral and dodecahedral sites in both samples, and their chemical compositions were determined as Gd2.70Fe4.76O11.9 and Gd2.96Fe4.68O11.5, respectively. These local rearrangements have been shown to have a consistent influence on theta c (290 K and 317 K, respectively) around room temperature, emphasizing the high sensitivity of exchange interactions to internal atomic order. Results clearly illustrate the strong correlation between the processing, atomic configuration and macroscopic magnetic behavior, establishing a new paradigm for the design of garnet-based materials with tunable theta c. The strategy for the accurate determination of cation inversion illustrated in this work exhibits great potential in guiding material innovations for next-generation spintronics.

The morpho-structural and defect properties of SnO2 nanoparticles, obtained by hydrothermal synthesis at 120 degrees C, 140 degrees C and 160 degrees C, using a SnCl2 precursor, were comparatively investigated and correlated with their NO2 sensing performance for in-field conditions. The constructive contributions of the nanoparticle size, faceting and oxygen vacancy concentrations had a positive effect on the sensor performances for the two samples synthesized at lower temperatures. These samples had almost similar, smaller size and the proportion of the more active, higher-index facets over the {110} facets was significantly larger than for the sample prepared at 160 degrees C. The concentration of paramagnetic defects, associated to complexes of oxygen vacancies in the (101) planes at the SnO2 surface, increased with the synthesis temperature decrease. A sensor signal of 74 for the NO2 detection limit of 3 ppm, at the operating temperature of 100 degrees C, under dynamic air flow with in-field-like relative humidity of 50 %, was obtained for the sample grown at 120 degrees C. The sensor signal was about four times higher compared to the 140 degrees C sample with similar size and morphology and about nine times higher than in the case of the 160 degrees C sample. In addition to its high NO2 sensitivity, the 120 degrees C sample had a low sensor response for potential interfering gases as CH4 and CO2 and was relatively stable over a period of 20 months. Our results evidence the direct correlation between the sensing properties and the surface oxygen vacancy complexes and highlight the importance of an in-depth atomic-level investigation approach for the controlled synthesis of an application-oriented material.

The present paper concerns a formalism aimed to describe the behavior and trajectories of complex scalar waves with space-varying amplitude in media characterized by variable refractive index. The classical wave equation is transformed into an eikonal-type equation, without imposing the geometrical optics limit, satisfied by an effective refractive index. The effective index combines the refractive properties of the medium with self-refraction phenomena generated by the space dependence of the wave amplitude. It also induces wave packet dispersion, leading to relations between the group and phase velocities that are particularly relevant in the context of de Broglie waves. The equations of motion are provided, and it is shown that the self-refraction term bends the trajectory of the wave and changes its velocity. The dynamics is dictated by the curvature of the trajectory expressed in terms of the gradient of the effective refractive index. The uncovered findings point toward a possible generalization of geometrical optics with relevant implications for its relation to quantum mechanics, general relativity and transformation optics.

Pnictogen chalcohalide semiconductors are emerging materials with broad potential in energy-related applications, including solar cells, photocatalysis, photodetectors, batteries, supercapacitors, thermoelectric and piezoelectric generators. Their compositional flexibility allows fine tuning of structural and optoelectronic properties. In this study, microcrystalline powders of Sb1-xBixSeI (x = 0-1) were synthesized from binary precursors by a solid-state method in evacuated quartz ampoules. Energy dispersive spectroscopy confirmed the successful substitution of Sb with Bi in Sb1-xBixSeI. The formation of solid solutions was also supported by Raman spectroscopy and X-ray diffraction (XRD). All materials exhibited needle-shaped crystal morphologies and orthorhombic crystal structure (Pnma), regardless of the Bi/Sb ratio. XRD patterns shifted toward smaller angles with increasing Bi content, indicating lattice expansion. Calculated lattice parameters (b and c) increased linearly with Bi incorporation, while the lattice parameter (a) remained constant. Raman spectra exhibited characteristic peaks at 182 cm- 1 for Bi-Se vibration and 209 cm- 1 for Sb-Se vibration, with intensity ratios reflecting Bi content. UV-Vis-NIR diffuse reflectance spectroscopy revealed a direct band gap that decreased from 1.7 eV (SbSeI) to 1.29 eV (BiSeI). Room-temperature photoluminescence measurements exhibited a single emission band, shifting from 1.75 eV to 1.41 eV with increasing Bi content. Ultraviolet photoelectron spectroscopy indicated a shift in the valence band maximum from 0.44 eV (SbSeI) to 1.1 eV (BiSeI). These findings highlight the tunability of Sb1-xBixSeI compounds, offering pathways for optimizing their properties for specific optoelectronic applications.

Synchrotron-based small- and wide-angle X-ray scattering is used to elucidate the structure of low-dimensional lepidocrocite-titanate-based nanofilaments. In the colloidal state, they consist of quantum-confined 1D NFs, loosely associated into nanoribbons, one lepidocrocite sheet thick (about 4 & Aring;), 30-40 & Aring; wide (5-8 NFs), and more than 300 & Aring; long. In the dry state, they reach a final state of extended sheets, stacked three to about twenty high, whose crystallinity increases with stack height, in parallel with a decrease in photocatalytic activity. These findings suggest a kinetic pathway for the self-assembly of initially 1D titanate nanoribbons into 2D and ultimately 3D structures, providing context for a recent body of work on these low-dimensional materials.

Copper is an essential micronutrient for plants, but excessive levels can induce toxicity and impair physiological functions. This study evaluates the toxic effects of copper sulfate (CuSO4) on the germination of common wheat (Triticum aestivum), with emphasis on the gas emission dynamics and oxidative stress biomarkers. Seeds were germinated in agar and exposed to CuSO4 at concentrations of 1 mu M, 100 mu M, 1 mM, and 10 mM; distilled water served as the control. Ethylene and ammonia emissions were quantified using CO2 laser photoacoustic spectroscopy, while electron paramagnetic resonance (EPR) spectroscopy was employed to detect free radicals and Cu2+ complexes. Exposure to Cu concentrations >= 1 mM significantly inhibited germination and biomass accumulation. Enhanced ethylene and ammonia emissions, particularly at 10 mM, indicated stress-related metabolic responses. The EPR spectra confirmed the presence of semiquinone radicals and Cu2+ complexes under higher Cu levels. These results demonstrate that photoacoustic and EPR techniques are effective tools for the early detection of metal-induced phytotoxicity and offer a non-invasive approach to environmental toxicity screening and plant stress assessment.

Superconducting bulk disks, of 20 mm in diameter and similar to 3.5-mm thickness of MgB2 were prepared by spark plasma sintering. Samples are co-added with 10 wt. % hexagonal BN (h-BN) or graphene (G) and other additives (B4C, Te, cubic BN, fullerene C-60, or Repa-C6H10O7Ge2 (GEP)), where h-BN and G are introduced in the composite to provide full machinability by chipping of the composite and the other additives to modify microstructure and superconducting characteristics. Measurements of trapped magnetic field B-tr for a fixed rate of the applied magnetic field decrease (0.00015 T/s) indicate that samples with G show less flux jumps, but a higher thermomagnetic stability is accompanied by lower values of B-tr than for samples with h-BN. The highest maximum B-tr at 12 K for samples added with h-BN or graphene was recorded for MgB2(Te)(0.01) + 10wt.% h-BN (3.48 T) and MgB2(B4C)(0.01) + 10wt.% G (2.73 T), respectively. These values of maximum trapped field were determined for an applied field of - 2.5 and - 1.8 T. Results suggest that machinable MgB2-based composites show potential for bulk superconducting magnet applications.

We report large-scale synthesis of monolayer WS2 films obtained by sulfurization of oxidized magnetron sputtered monolayer W precursors. Literature routes typically require similar to 800 degrees C, well above the 400 degrees C limit imposed by back-end-of-line (BEOL) integration. Here, using an enhanced chemical vapor deposition (CVD) approach, the magnetron sputtered ultrathin W precursor (a W monolayer film, 0.27 nm thick, which in ambient air becomes a WOx monolayer) is sulfurized at the lowest possible temperature (450 degrees C) within a microreactor, which consists of a sandwich-like structure formed by the precursor and a clean Si substrate. The obtained WS2 material has a good crystallinity and uniform morphology across the entire growth substrate, as confirmed by detailed characterization. These results highlight the versatility of the method combining magnetron sputtering and microreactor-CVD, facilitating its applications to wafer-scale synthesis of monolayer WS2, heterogeneously integrated into electronic circuits (a major objective for next-generation electronics and optoelectronics). Additionally, we investigate in detail the properties of WS2 films synthesized from a bilayer W precursor (0.43 nm thick), under the same conditions, and we calculated the frequencies of the second-order Raman scattering modes. For electrical measurements, we fabricated WS2/few-layer-graphene heterostructures, whose atomically clean interface yields reliable, low-resistance contacts. These devices exhibit resistive switching behavior, likely governed by vacancy migration, making it a promising candidate for memristive applications. Our results demonstrate that electronics-grade monolayer WS2 can be synthesized at 450 degrees C, approaching the BEOL requirement of 400 degrees C.

This study presents an environmentally friendly approach for synthesis Ag-TiO2 composite using pulsed reverse current (PRC) electrodeposition from green electrolytes, specifically deep eutectic solvents (DESs). The combination of PRC and DESs offers better control over nanoparticle synthesis while eliminating the need for toxic or expensive precursors, representing a significant advancement in sustainable nanomaterial synthesis. Different electrochemical parameters were adjusted, and their influence on the structure and morphology of the composite was investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). TEM analysis revealed that silver nanoparticles (Ag NPs) are attached to TiO2 nanopowder, with the coexistence of TiO2 and Ag further confirmed by XRD and XPS. The recorded UV-Vis diffuse reflectance spectra (DRS) displayed a broad peak in the range of 400 - 650 nm, associated with the localized surface plasmon resonance (LSPR) of Ag NPs on the semiconductor's surface. The photocatalytic activity of TiO2 nanopowder and Ag-TiO2 composite was evaluated based on the degradation of methyl orange (MO) dye under UV and visible light illumination. Our findings clearly demonstrated that the incorporation of Ag improved the photocatalytic efficiency. The mechanism of MO dye degradation was explored by using various scavengers, revealing that superoxide radicals (center dot O-2(-)) play a dominant role. Furthermore, the incorporation of Ag NPs significantly enhanced the antimicrobial activity of the oxide against both Gram-positive (B. subtilis) and Gram-negative (E.coli) strains.