National Institute Of Materials Physics - Romania

Integrating two-dimensional transition-metal dichalcogenides with graphene is attractive for low-power memory and neuromorphic hardware, yet sequential wet transfer leaves polymer residues and high contact resistance. We demonstrate a complementary metal-oxide-semiconductor (CMOS)-compatible, transfer-free route in which an atomically thin amorphous MoS2 precursor is RF-sputtered directly onto chemical vapor-deposited few-layer graphene and crystallized by confined-space sulfurization at 800 degrees C. Grazing-incidence X-ray reflectivity, Raman spectroscopy, and X-ray photoelectron spectroscopy confirm the formation of residue-free, three-to-four-layer 2H-MoS2 (roughness: 0.8-0.9 nm) over 1.5 cm x 2 cm coupons. Lateral MoS2/graphene devices exhibit reproducible non-volatile resistive switching with a set transition (SET) near +6 V and an analogue ON/OFF approximate to 2.1, attributable to vacancy-induced Schottky-barrier modulation. The single-furnace magnetron sputtering + sulfurization sequence avoids toxic H2S, polymer transfer steps, and high-resistance contacts, offering a cost-effective pathway toward wafer-scale 2D memristors compatible with back-end CMOS temperatures.

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.

A facile and versatile strategy to obtain NPs@ZnAlO nanocomposite materials, comprising controlled-size nanoparticles (NPs) within a ZnAlO matrix is reported. The mono-(Au, Ni) and bimetallic (Ni-Au) NPs serving as an active phase were prepared by the polyol-alkaline method, while the ZnAlO support was obtained via the thermal decomposition of its corresponding layered double hydroxide (LDH) precursors. X-ray diffraction (XRD) patterns confirmed the successful fabrication of the nanocomposites, including the synthesis of the metallic NPs, the formation of LDH-like structure, and the subsequent transformation to ZnO phase upon LDH calcination. The obtained nanostructures confirmed the nanoplate-like morphology inherited from the original LDH precursors, which tended to aggregate after the addition of gold NPs. According to the UV-Vis spectroscopy, loading NPs onto the ZnAlO support enhanced the light absorption and reduced the band gap energy. ATR-DRIFT spectroscopy, H2-TPR measurements, and XPS analysis provided information about the functional groups, surface composition, and reducibility of the materials. The catalytic performance of the developed nanostructures was evaluated by the photodegradation of bisphenol A (BPA), under simulated solar irradiation. The conversion of BPA over the bimetallic Ni-Au@ZnAlO reached up to 95% after 180 min of irradiation, exceeding the monometallic Ni@ZnAlO and Au@ZnAlO catalysts. Its enhanced activity was correlated with good dispersion of the bimetals, narrower band gap, and efficient charge carrier separation of the photo-induced e-/h+ pairs.

This study presents annealing time variation as an alternative approach for tuning structural and ionic defects in SnO2 nanoparticles (NPs) synthesized by a modified Pechini method, to modulate charge transfer and the formation of reactive oxygen species (ROS), enabling a correlation of these with photocatalytic activity. Structural refinements of the X-ray diffraction (XRD) data, combined with Raman and infrared (IR) spectroscopy, revealed that the samples adopted a tetragonal P42/mnm symmetry, with a distinct short-range structural order (associated with intraoctahedral [SnO6] distortions), which strongly depends on the annealing time. Field emission scanning electron microscopy (FE-SEM), scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (STEM/EDX), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) analyses showed the formation of homogeneous NPs smaller than 50 nm in the SnO2 samples, with a surface area between 12.072 and 14.102 m2 g-1. The presence of unusual reduced Sn3+ species associated with oxygen vacancies (VO) was evidenced by electron paramagnetic resonance (EPR) spectroscopy, and Sn2+ was characterized by Sn MNN Auger electron emission. The amount of these defects also depends on the annealing time. The synergistic effect and the photocatalytic mechanism were then elucidated. The degree of intraoctahedral [SnO6] distortions and the amounts of Sn3+:VO defects play a fundamental role in the charge transfer mechanism to modulate ROS generation during photoexcitation, as indicated by the photohydroxylation of terephthalic acid (TA) and in situ spin-trapping EPR measurements. Specifically, we show the formation of two main ROS, center dot OOH and center dot OH, which leads to a different photocatalytic pathway in SnO2 NPs. In conclusion, our study enlightens and uncovers the importance of choosing appropriate conditions for materials processing to fine-tune structural and electronic properties to design other functional materials.

The development of titania-based hybrid nanostructures with enhanced visible-light photocatalytic activity has been a key research area recently. The present study addresses current limitations of the TiO2 based composite photocatalyst by newly-experimental designing of flower-like multifunctional hybrid nanostructure with visible light capability through Ferrihydrite (Fh) surface TiO2 functionalization. Here, we present a versatile nanocompartimentalization process of which, core anatase TiO2 nanoparticles are emebeded into Fh lamellar shell. Physico-chemical properties related to the chemical structure and morphology of the prepared nanomaterials were comprehensively analysed using complementary analytical techniques, such as powder X-Ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FE-SEM), Ultra-High Resolution Transmission Electron Microscopy (UHR-TEM), X-Ray Photoelectron Spectroscopy (XPS) and soft X-Ray Absorption Spectroscopy (XAS). The conducted visible-light-driven photocatalytic water splitting tests highlights significant enhancement in the Oxygen Evolution Reaction (OER) performance for TiO2-Fh core-shell nanoheterostructure of 25.6 mu mol/L of molecular oxygen after 60 min of visible light irradiation (AM1.5G), and a photocatalytic water oxidation activity rate of 341.3 mu mol L-1 g-1h-1. The biocompatibility assessment of the developed core-shell structures combined with their enhanced photocatalytic water oxidation activity under visible light illumination suits them as excellent candidates for the development of sustainable environmental remediation technologies.

CuO is a p-type semiconductor that can be found useful in various applications, sensing, photocatalysis or photovoltaics. Better material performance can be achieved by doping. In our study the doping was done using Cr ions and implantation method. Thin film samples were characterised with X-ray photoelectron spectroscopy (XPS) technique to study chemical properties of the films' surface and to determine the in-depth compositional profile of the films before and after annealing of an implanted sample. Spectroscopic ellipsometry was used to extract the dielectric function of CuO thin films. Depolarization measurements are shown as a useful method to quickly study differences between similar samples. XPS measurements proved that before annealing there is a peak of Cr concentration in depth of the sample, which is no longer present after annealing. Measurement of film resistance as function of temperature in range of 150-300 degrees C resulted with 0.82 eV bandgap. Electronic structure obtained with density functional theory calculations (DFT) showed that with Cr doping the energy band gap narrows and the material should become metallic.

This paper presents the synthesis of La2Ti2O7 nanoparticles by the sol-gel method starting from lanthanum nitrate and titanium alkoxide (noted as LTA). Subsequently, the lanthanum titanium oxide nanoparticles are modified with noble metals (platinum) using the chemical impregnation method, followed by a reduction process with NaBH4. The comparative analysis of the structure and surface characteristics of the nanopowders subjected to thermal treatment at 900 degrees C is conducted using Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray fluorescence (XRF), ultraviolet-visible (UV-Vis) spectroscopy, as well as specific surface area and porosity measurements. The photocatalytic activity is evaluated in the oxidative photodegradation of ethanol (CH3CH2OH) under simulated solar irradiation. The modified sample shows higher specific surfaces areas and improved photocatalytic properties, proving the better conversion of CH3CH2OH than the pure sample. The highest conversion of ethanol (29.75%) is obtained in the case of LTA-Pt after 3 h of simulated solar light irradiation.

Nb2C MXene, obtained from Nb2AlC by Al3+ etching and exfoliation, was characterized using XRD, HRTEM and AFM, with the data confirming the crystallinity of the sample and the 2D morphology of the sheets with an average layer thickness of 1.5 nm. Surface analysis using XPS revealed the presence of structural defects, and NH3- and CO2-TPD profiles confirmed the low density of acid and basic sites in the range of tens of mu mol gcatalyst-1 of weak and moderate strengths. The combination of acid and basic sites in close proximity on the solid surface was responsible for the remarkable catalytic activity of Nb2C MXene in promoting aldolic condensation with high turnover frequencies of up to 855 h-1, which was comparable to the values of benchmark catalysts, such as MgO or HZSM-5. Nb2C MXene also catalyzed the aerobic oxidative aniline coupling to azo- and azoxy-benzene and hydrogenation of azoxybenzene to azobenzene.

Spin asymmetry is detected in clean Pt(001)-hex by spin-resolved photoelectron spectroscopy even in absence of external sample magnetization. Magnetization of the sample immediately after preparation yields a consistent remnant spin asymmetry in the direction of the applied magnetic field. The surfaces were also characterized by low energy electron diffraction, scanning tunneling microscopy and high resolution core level x-ray photoelectron spectroscopy, allowing one to quantify the surface component, attributed to the last surface layer enriched in electrons. The explanation of the spin asymmetry induced by electron accumulation into the last monolayer is sketched by using band ferromagnetism criteria. The orientation of the spin asymmetry in the nonmagnetized sample coincides with the direction of the rows of the hex reconstruction, while in the magnetized sample it is aligned with the direction of the external magnetizing field. A strong variation of the spin asymmetry as function of the binding energy near the Fermi level, whose amplitude depends also on the median emission angle, suggests a spin textured state in this energy range or the presence of a Stoner gap

A synthetic rational design of core-shell magnetic nanomaterials has garnered significant attention for their potential in photocatalysis and adsorption applications. This study presents the synthesis and characterization of a TiO2-based core-shell photocatalyst functionalized with FexOy co-catalyst for the efficient adsorption and degradation of synthetic methylene blue dye. The chemical synthesis technique involved a three-step process consisting in the preparation of TiO2 nanoparticles followed by surface nanocompartmentalization with a ferrihydrite layer exhibiting a flower-like morphology and lastly the calcination of the resulting composite at 400 degrees C to produce a magnetic core-shell nanomaterial. Comprehensive physicochemical characterization was performed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultra-high-resolution transmission electron microscopy (UHR-TEM) to elucidate the structural and morphological properties of the synthesized materials. Photodegradation experiments were conducted under both UV and Visible light irradiation using methylene blue as a model contaminant. The results revealed remarkable photocatalytic performance, with nearly instantaneous adsorption of the dye onto the catalyst surface, followed by efficient photodegradation. Detailed investigations confirmed that the adsorption process occurred at an exceptionally rapid rate, which was attributed to the unique surface functionalization and nanocompartmentalized structure of the core-shell material.