National Institute Of Materials Physics - Romania

In the quest for advanced materials suitable for next-generation electronic and optoelectronic applications, tungsten disulfide (WS2) ultrathin films have emerged as promising candidates due to their unique properties. However, obtaining WS2 directly on the desired substrate, eliminating the need for transfer, which produces additional defects, poses many challenges. This paper aims to explore the synthesis of WS2 ultrathin films via physical vapor deposition (PVD) followed by sulfurization in a confined space, addressing the challenge of film formation for practical applications. Precursor layers of tungsten and WS2 were deposited by RF magnetron sputtering. Subsequent sulfurization treatments were conducted in a small, closed, graphite box to produce WS2 films. The physical and chemical properties of these precursor and sulfurized layers were thoroughly characterized using techniques such as X-ray reflectometry (XRR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The findings reveal notable distinctions in film thickness, structural orientation, and chemical composition, attributable to the different precursor used. Particularly, the sulfurized layers from the tungsten precursor exhibited a preferred orientation of WS2 crystallites with their (00L) planes parallel to the substrate surface, along with a deviation from parallelism in a small angular range. This study highlights the necessity of precise control over deposition and sulfurization parameters to tailor the properties of WS2 films for specific technological applications.

The process of N-doping is frequently employed to enhance the properties of carbon quantum dots. However, the precise requirements for nitrogen precursors in producing high-quality N-doped carbon quantum dots (NCQDs) remain undefined. This research systematically examines the influence of various nitrogen dopants on the morphology, optical features, and band structure of NCQDs. The dots are synthesized using an efficient, eco- friendly, and rapid continuous hydrothermal flow technique. This method offers unparalleled control over synthesis and doping, while also eliminating convention-related issues. Citric acid is used as the carbon source, and urea, trizma base, beta-alanine, L-arginine, and EDTA are used as nitrogen sources. Notably, urea and trizma produced NCQDs with excitation-independent fluorescence, high quantum yields (up to 40%), and uniform dots with narrow particle size distributions. Density functional theory (DFT) and time-dependent DFT modelling established that defects and substituents within the graphitic structure have a more significant impact on the NCQDs' electronic structure than nitrogen-containing functional groups. Importantly, for the first time, this work demonstrates that the conventional approach of modelling single-layer structures is insufficient, but two layers suffice for replicating experimental data. This study, therefore, provides essential guidance on the selection of nitrogen precursors for NCQD customization for diverse applications. This manuscript highlights continuous hydrothermal flow synthesis (CHFS) that directly obtains luminescent nitrogen doped carbon quantum dots using a simple precursor, citric acid, whilst varying the N-dopants to systematically engineer carbon dots with varied but controllable optical characteristics. It reports that a common approach of modelling single-layer structures is insufficient, but two layers suffice to reproduce the experimental data. image

Ti-aluminosilicate gels were used as supports for the immobilization of Fe, Co, and Ni oxides (5%) by impregnation and synthesis of efficient photocatalysts for the degradation of beta-lactam antibiotics from water. Titanium oxide (1 and 2%) was incorporated into the zeolite network by modifying the gel during the zeolitization process. The formation of the zeolite Y structure and its microporous structure were evidenced by X-ray diffraction and N-2 physisorption. The structure, composition, reduction, and optical properties were studied by X-ray diffraction, H-2-TPR, XPS, Raman, photoluminescence, and UV-Vis spectroscopy. The obtained results indicated a zeolite Y structure for all photocatalysts with tetracoordinated Ti4+ sites. The second transitional metals supported by the post-synthesis method were obtained in various forms, such as oxides and/or in the metallic state. A red shift of the absorption edge was observed in the UV-Vis spectra of photocatalysts upon the addition of Fe, Co, or Ni species. The photocatalytic performances were evaluated for the degradation of cefuroxime in water under visible light irradiation. The best results were obtained for iron-immobilized photocatalysts. Scavenger experiments explained the photocatalytic results and their mechanisms. A different contribution of the active species to the photocatalytic reactions was evidenced.

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 degrees C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.

This study reports the development of a novel biocomposite for potential applications in the environmental remediation. The hydroxyapatite/sodium bicarbonate (HAp-SB) biocomposite obtained by a cheap method could offer promising characteristics to be used in environmental applications. The obtaining of HAp-SB ceramic composites was studied with the aim of increasing the adsorption efficiency of lead ions from contaminated waters. A composite material (HAp-SB) with good crystallinity that preserves the hexagonal structure of pure hydroxyapatite was obtained. For the powder recovered after decontamination of the lead solution (PbHAp-SB), the XRD model highlighted additional maxima belonging to Ca10(PO4)5(OH)2, Ca0.805Pb4.195(PO4)(OH) and PbH2P2O7. The FTIR spectra of PbHAp-SB are similar to those of HAp-SB composites showing a broadening of the vibration peaks and a slight shift. The XPS and EDS studies illustrated the purity of the HAp-SB sample. Moreover, the presence of lead in the powder recovered after decontamination was also highlighted by XPS and EDS studies. The efficiency of HAp-SB in the adsorption of Pb2+ ions from the contaminated solution was also highlighted by ultrasound studies using double-distilled water as the reference liquid. The adsorption kinetics were investigated with the aid of Langmuir and Freundlich theoretical models. The results demonstrated that the HAp-SB ceramic composite has a strong affinity for the adsorption of Pb2+ ions from contaminated solutions. The removal efficiency of Pb2+ ions was about 92% for the initial Pb2+ concentration above 50 mg/L. The results of the cell viability and cytotoxicity studies demonstrated that HAp-SB nanoparticles did not influence negatively the HeLa cell's viability and did not induce any significant changes of the morphological features of HeLa cells after 24 h of incubation. The batch adsorption results as well as the cytotoxicity assay results suggested that the HAp-SB powder could be successfully used for the removal of Pb2+ from contaminated water.

B doped as well as B and N co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers were synthesized using a one-step laser technique. NiO nanoparticles, graphene oxide platelets, and multiwall carbon nanotubes were used as starting materials for the preparation of the composite layers. H3BO3 was used as B precursor and urea as well as NH3 as N precursors for B and N co -doping of the composite layers. The influence of the nature and concentration of the B and N precursors on the physico-chemical properties of the nanohybrid layers, chemical composition and chemical bonding states, crystalline structure, as well as charge transfer properties was systematically investigated. The relation between the physico-chemical properties and functional characteristics of the nanohybrid layers, photocatalytic removal of water contaminants under simulated sun irradiation conditions was studied, identifying the optimum con-centrations of the dopant precursor materials. The mechanism of the photodegradation process was explored, based of the band structure of the composites. The main intermediates, reactive oxygen species implied in the photocatalytic degradation processes of organic molecules, was investigated through the addition of scavengers to the organic dye test solutions. The highest photocatalytic activities were achieved for B and N co-doped samples synthesised using H3BO3 as B and urea as N precursors.

B doped as well as B and N co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers were synthesized using a one-step laser technique. NiO nanoparticles, graphene oxide platelets, and multiwall carbon nanotubes were used as starting materials for the preparation of the composite layers. H3BO3 was used as B precursor and urea as well as NH3 as N precursors for B and N co -doping of the composite layers. The influence of the nature and concentration of the B and N precursors on the physico-chemical properties of the nanohybrid layers, chemical composition and chemical bonding states, crystalline structure, as well as charge transfer properties was systematically investigated. The relation between the physico-chemical properties and functional characteristics of the nanohybrid layers, photocatalytic removal of water contaminants under simulated sun irradiation conditions was studied, identifying the optimum con-centrations of the dopant precursor materials. The mechanism of the photodegradation process was explored, based of the band structure of the composites. The main intermediates, reactive oxygen species implied in the photocatalytic degradation processes of organic molecules, was investigated through the addition of scavengers to the organic dye test solutions. The highest photocatalytic activities were achieved for B and N co-doped samples synthesised using H3BO3 as B and urea as N precursors.

One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.

Recently, Kittel's theory of ferromagnetic domains in thin films in one dimension, i. e. with the domains extended infinitely over one in-plane direction and with the anisotropy axis oriented perpendicular to the film was revisited by considering the film thickness and unbalanced domains with up and down magnetization, yielding to the computation of magnetic hysteresis [C. M. Teodorescu, Res. Phys. 46 (2023) 106287]. In this work, the above study is extended to samples featuring two-dimensional domain landscapes, for materials with strong magnetic anisotropy, typically characterized by a superunitary ratio between the anisotropy energy and the stray field energy densities. This allows one to compute the most stable structures for vanishing average magnetization < M > together with hysteresis curves for thin films with perpendicular magnetic anisotropy and two-dimensional rectangular domains and also for thin films with in-plane magnetic anisotropy. For two-dimensional films with perpendicular magnetic anisotropy, the most stable structure for < M > = 0 is found to be that with domains infinitely elongated along one in-plane direction, i. e. the one-dimensional case treated in the preceding work. For thin stripes with in-plane magnetization, the domain size l is approximately linear with the stripe lateral size d for low film thickness, while for large film thicknesses it follows a Kittel-like law, but as function of the stripe size l similar to d(1/2). For in-plane magnetized thin films of infinite lateral extent, the most stable structure is the single domain. As for hysteresis curves, the two-dimensional case with perpendicular magnetic anisotropy is shown to evolve from a 2D landscape derived from the checkerboard structure, but with unbalanced domains for magnetization near saturation, towards one-dimensional domain structures for lower magnetization. In some cases and depending also on the demagnetization factor, the one-dimensional case is not reached, and the film exhibit 2D structures on the whole range of the magnetization curve. The hysteresis obtained for thin magnetic stripes with in-plane magnetization also can exhibit a rich structure, with minor cycles on the wings of the magnetization curves evolving towards ,,normal" hysteresis (again, depending on the film thickness, stripe lateral size and demagnetization factor). An infinite thin film with in-plane anisotropy features a steplike magnetization dependence on the applied field.

Thick tungsten oxide layers were prepared electrophoretically in order to be used as photoanodes in photoelectrochemical water oxidation applications. The highest photocurrent density was obtained for a WO3 layer with thickness of similar to 900 nm. Additionally, WO3/BiVO4 and WO3/BiVO4/MIL-101(Fe) heterojunctions have been fabricated using WO3 layer as substrate. WO3/BiVO4 shows an increased value of the electrochemical active surface area indicating that more sites of this photoanode are activated through the formation of the heterojunction. The small V5+ signals observed in the V 2p XPS spectra of these heterojunctions were attributed to the substitution of V5+ atoms with W6+ atoms on the surface of BiVO4. Excessive W doping of the BiVO4 film determined the decrease of the photoelectrochemical performance of WO3/BiVO4 photoanode. The significant improvement of the photoconversion efficiency of the sample decorated with MIL-101(Fe) indicated that this cocatalyst provides sites more efficiently in the photoelectrochemical process. This performance was correlated with the reduced value of the charge transfer resistance at electrode/electrolyte interface obtained from electrochemical impedance spectroscopy investigation.