National Institute Of Materials Physics - Romania

This study investigates the fabrication of short-wavelength infrared (SWIR) photosensitive amorphous and nanocrystalline Ge1-xSnx:H thin films by magnetron sputtering from separate Ge and Sn targets using different Ar: H mixing ratios as working gas. Amorphous Ge1-xSnx:H films have been obtained on both c-Si and fused quartz substrates at ambient temperature, while dynamic nanocrystallization occurs in-situ when the substrate temperature during deposition is raised to 200 degrees C. Fourier-transform infrared spectroscopy has shown the hydrogen incorporation by detecting an absorption line at 1873 cm(-1), close to the value corresponding to Ge-H bonding, only in the room temperature amorphous films. Based on that, we infer that the hydrogen concentration is very low in the films deposited at high temperature. The higher concentration of hydrogen in the amorphous samples is associated with an increase of the absorption gap to 0.5 eV compared to 0.3 eV in the 200 degrees C samples. In-situ (during deposition) and ex-situ (by subsequent rapid thermal annealing) nanocrystallization have been analyzed by high-resolution transmission electron microscopy, X-ray diffraction and micro-Raman spectroscopy. SWIR spectral photosensitivity up to 2.4 mu m was found to be more than two orders of magnitude improved in hydrogenated amorphous films with high hydrogen content, compared to the nanocrystalline ones that are weakly hydrogenated. These findings demonstrate the potential of hydrogenation to enhance the photoelectric properties of GeSn sputtering films for optoelectronic SWIR infrared applications.

Recently, perovskites have become a hotspot for researchers attempting to exploit metal and oxygen vacancies in structures of the form MTiO3, facilitating the convenient electron/hole migration, thus displaying interesting properties. Magnesium Titanate (MgTiO3) is a prominent part of the perovskite class, exhibiting remarkable electrical, thermal, and chemical properties. Undoped and Mn-doped MgTiO3 samples were obtained using a solid-state reaction starting from previously synthesized MgO and TiO2 powders, which were separately doped with different Mn ion concentrations. The resulting multiphase materials with a major MgTiO3 phase were thoroughly morpho-structurally analyzed employing XRD, STEM, Raman, PL, XPS, and EPR spectroscopy. The electrochemical results indicate that they show superior performance when used as electrode materials for supercapacitor application due to the high defect concentration as shown in EPR and PL spectroscopy and the ferroelectric behavior observed in XPS and XRD. When used in symmetric and asymmetric supercapacitor devices, they show promising results, with specific capacity values reaching up to 109 F/g for the symmetric and 609 F/g for the asymmetric devices, while energy and power density values reached 84.7 Wh/kg and 90.8 kW/kg respectively, proving a great potential in the energy storage field.

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.

In this work, three methods for the synthesis of composites based on poly(ortho-toluidine) (POT) and WS2 are reported: (a) the solid-state interaction (SSI) of POT with WS2 nanoparticles (NPs); (b) the in situ chemical polymerization (ICP) of ortho-toluidine (OT); and (c) the electrochemical polymerization (ECP) of OT. The preparation of WS2 sheets was performed by the ball milling of the WS2 NPs followed by ultrasonication in the solvent N,N'-dimethyl formamide. During the synthesis of the POT/WS2 composites by SSI and ICP, an additional exfoliation of the WS2 NPs was reported. In this work, we demonstrated the following: (a) the ICP method leads to POT/WS2 composites, which contain repeating units of POT in the leucoemeraldine salt (LS) state, while (b) the ECP method leads to POT/WS2 composites, which contain repeating units of POT in the emeraldine salt (ES) state. Capacitances equal to 123.5, 465.76, and 751.6 mF cm-2 in the cases of POT-ES/WS2 composites, synthesized by SSI, ICP, and ECP, respectively, were reported.

Ruthenium-based catalysts were prepared through a deposition-precipitation approach, taking beta zeolites with Si/Al ratios of 12.5, 18.5, and 150, respectively, as supports, and 1-3 wt% loadings of metal. Their activation was performed in the presence of either H2 or NaBH4. The dispersion of the Ru species and the acid-base properties were influenced by both the preparation method and the activation protocol. The catalysts reduced under H2 flow presented well-dispersed Ru(0) and RuOx nanoparticles, while the reduction with NaBH4 led to larger RuOx crystallites and highly dispersed Ru(0). These characteristics exerted an important role in the hydrogenation of levulinic acid (LA) to gamma-valerolactone (GVL). The H2 dissociation occurred via a heterolytic mechanism involving Lewis acid-base pairs associated with RuOx and the framework oxygen (Si-O-Al) located near the zeolite pore edge. The Ru(0) nanoparticles activated the -C=O bond of the LA substrate, while the presence of the carrier zeolite Br & oslash;nsted acid sites promoted the ring-closure esterification of the 4-hydroxyvaleric acid (4-HVA) intermediate to GVL. An optimal combination of these features was achieved for the catalyst with 3 wt% Ru and a Si/Al ratio of 150, which selectively converted LA (XLA = 96.5%) to GVL (SGVL = 97.8%) at 130 degrees C and 10 bars of H2.

Featured Application Optoelectronic devices in space missions.Abstract Transparent conductive oxides are essential materials for many optoelectronic applications. For new devices for aerospace and space applications, it is crucial to know how they respond to the space environment. The most important issue in commonly used low-Earth orbits is proton radiation. This study examines the effects of high-energy proton irradiation (226.5 MeV) on thin films of aluminium-doped zinc oxide (AZO) and indium tin oxide (ITO). We use X-ray diffraction and electron microscopy observations to see the changes in the structure and microstructure of the films. The optical properties and homogeneity of the materials are determined by spectrophotometry and spectroscopic ellipsometry (SE). Analysis of the chemical states of the elements with X-ray photoelectron spectroscopy (XPS) gives insight into what proton irradiation changes at the surface of the oxides. All measurements show that ITO is less influenced than AZO. The proton energy and fluence used in this study simulate about a hundred years in low Earth orbit. This research demonstrates that both transparent conductive oxide thin films can function under simulated space conditions, with ITO showing superior resilience. The ITO film was more homogenous in terms of the total thickness measured with SE, had fewer defects and adsorbates present on the surface, as XPS analysis proved, and did not show a difference after irradiation regarding its optical properties, transmission, refractive index, or extinction coefficient.

Magnesium and its alloys, pure or doped MgO and its solid solutions show an increasing interest for future applications in the field of biomaterials. In this paper, MgO nanoparticles were prepared by sol-gel route starting from magnesium acetylacetonate and 2-methoxyethanol. A complex thermal analysis was used to investigate in situ the decomposition reactions, the gaseous products evolved from the gel precursor of MgO during the thermal treatment procedure, in the temperature range of 293.2-1123.2 K (20-850 degrees C), and crystallization of cubic MgO phase. We found 5 steps for the pyrolysis of the precursor gel and, as gaseous products removed: water, carbon dioxide and fragments of acetylacetone and 2-methoxyethanol. The structure and morphology of the resulting MgO powder were also investigated by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The results of these analyses demonstrated that as-prepared MgO powder show a microstructure consisting of particles with rounded shape and size ranging from 7 to 12 nm and, a structure of cubic phase by heating the gel precursor at 773.2 K (500 degrees C), 1 h in 5%H2/Ar.

Lithium-ion batteries (LIBs) are fundamental to modern technology, powering everything from portable electronics to electric vehicles and large-scale energy storage systems. As their use expands across various industries, ensuring the reliability and safety of these batteries becomes paramount. This review explores the multifaceted aspects of LIB reliability, highlighting recent advancements and ongoing challenges. The importance of safety has been underscored by numerous incidents, such as the well-known smartphone battery explosions and more than 10,000 fires a year at facilities throughout Australia, both linked to LIB failures. These events emphasize the need for robust reliability and safety measures to ensure consistent performance and longevity. Factors like battery chemistry, design, manufacturing, and operating conditions can all influence the reliability of LIBs. Despite their widespread use, the mechanisms of failure, failure rates, and consequences of LIB failures are still not well understood, raising significant safety concerns. Current reliability assessment techniques include experimental methods, computational models, and data-driven approaches. Emerging trends, such as advanced characterization techniques and standardized testing protocols, advocate for improved practices to enhance the reliability and safety of LIBs across all applications.

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.

Hydroxyapatite (HAp), resembling human bone tissue, is a promising biomaterial for dental and hip prosthetics. Incorporating fluorine ions enhances HAp properties, particularly in dental restoration. This new study examines the physicochemical and biological properties of fluorine substituted hydroxyapatite (FHAp) coatings. Structural and morphological properties of the coatings were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The elemental composition of the FHAp coatings was studied using energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy. Fourier Transform Infrared spectroscopy (FTIR) investigations were also conducted. The typical peaks identified in XRD patterns of the FHAp were associated with pure hydroxyapatite with hexagonal structure. The general XPS spectrum of FHAp coatings shows peaks corresponding to the constituent elements of stoichiometric HAp as well as the presence of F that was used as a substituent. Consequently, the FTIR studies results underlined the presence of hydroxyapatite in the FHAp coatings. The SEM images reveal the presence of a uniform and continuous layer of particle conglomerates evenly distributed across the FHAp surface. Valuable information about the FHAp coating's wettability, adhesion and coating thickness were also obtained. Also, the AFM images suggest the absence of the significant irregularities from the surface of the FHAp coatings. Investigations of FHAp coatings reveal promising outcomes for cell viability and proliferation. Detailed analysis of FHAp's 3D surface characteristics and roughness, following ISO 25178-2:2012 standards, highlights their favorable biocompatibility, supporting MG63 cell proliferation. The surface roughness parameters of FHAp coatings were found to vary, with Sa values spanning from 0.029 +/- 0.004 mu m to 0.778 +/- 0.007 mu m, while Sq ranged from 0.035 +/- 0.005 mu m to 0.907 +/- 0.011 mu m. Furthermore, FHAp exhibits skewness (Ssk) from -0.048 +/- 0.006 to 0.195 +/- 0.009, kurtosis (Sku) from -0.600 +/- 0.011 to -1.050 +/- 0.021, and fractal dimension from 2.14 +/- 0.01 to 2.19 +/- 0.01, indicating consistent surface complexity and favorable properties. The Minkowski Functionals mirror the morphological observations from AFM images, emphasizing their dynamic influence on the samples' surfaces.