National Institute Of Materials Physics - Romania

Fabrication aspects of PdO thin films and coatings are reviewed here. The work provides and organizes the up-to-date information on the methods to obtain the films. In recent years, the interest in Pd oxide for different applications has increased. Since Pd can be converted into PdO, it is instructive to pay attention to the preparation of the pure and the alloyed Pd films, heterostructures, and nanoparticles synthesized on different substrates. The development of PdO films is presented from the early reports on coatings' formation by oxidation of Pd foils and wires to present technologies. Modern synthesis/growth routes are gathered into chemical and physical categories. Chemical methods include hydrothermal, electrochemical, electroless deposition, and coating methods, such as impregnation, precipitation, screen printing, ink jet printing, spin or dip coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD), while the physical ones include sputtering and cathodic arc deposition, laser ablation, ion or electron beam-induced deposition, evaporation, and supersonic cluster beam deposition. Analysis of publications indicates that many as-deposited Pd or Pd-oxide films are granular, with a high variety of morphologies and properties targeting very different applications, and they are grown on different substrates. We note that a comparative assessment of the challenges and quality among different films for a specific application is generally missing and, in some cases, it is difficult to make a distinction between a film and a randomly oriented, powder-like (granular), thin compact material. Textured or epitaxial films of Pd or PdO are rare and, if orientation is observed, in most cases, it is obtained accidentally. Some practical details and challenges of Pd oxidation toward PdO and some specific issues concerning application of films are also presented.

Recently, much research has focused on the search for new mixed donor-acceptor layers for applications in organic electronics. Organic heterostructures with layers based on the generation 1 poly(propylene thiophenoimine) (G1PPT) dendrimer, N,N '-diisopropylnaphthalene diimide (MNDI), and a combination of the two were prepared and their electrical properties were investigated. Single layers of G1PPT and MNDI and a mixed layer (G1PPT:MNDI) were obtained via spin coating on quartz glass, silicon, and glass/ITO substrates, using chloroform as a solvent. The absorption mechanism was investigated, the degree of disorder was estimated, and the emission properties of the layers were highlighted using spectroscopic methods (UV-Vis transmission and photoluminescence). The effects of the concentration and surface topographical particularities on the properties of the layers were analyzed via atomic force microscopy. All of the heterostructures realized with ITO and Au electrodes showed good conduction, with currents of the order of mA. Additionally, the heterostructure with a mixed layer exhibited asymmetry in the current-voltage curve between forward and reverse polarization in the lower range of the applied voltages, which was more significant at increased concentrations and could be correlated with rectifier diode behavior. Consequently, the mixed-layer generation 1 poly(propylene thiophenoimine) dendrimer with N,N '-diisopropylnaphthalene diimide can be considered promising for electronic applications.

Chitosan, a naturally occurring biopolymer derived from chitin, has emerged as a highly promising instrument for the production and application of metal nanoparticles. The present review delves into the several functions of chitosan in the development and operation of metal nanoparticles, emphasizing its aptitudes as a green reducing agent, shape-directing agent, size-controlling agent, and stabilizer. Chitosan's special qualities make it easier to manufacture metal nanoparticles and nanocomposites with desired characteristics. Furthermore, there is a lot of promise for chitosan-based nanocomposites in a number of fields, such as metal removal, water purification, and photoacoustic, photothermal, antibacterial, and photodynamic therapies. This thorough analysis highlights the potential application of chitosan in the advancement of nanotechnology and the development of medicinal and environmental solutions.

The development of two-dimensional (2D) materials has gained significant attention due to their unique properties and potential applications in advanced electronics. This study investigates the fabrication and characterization of Fe-doped SnSe semiconductors using an optimized chemical vapor deposition (CVD) method. Fe doping was achieved by dissolving FeCl3 in deionized water, applying it to SnSe powder, and conducting vacuum drying followed by high-temperature CVD at 820 degrees C. Structural and morphological properties were characterized using optical microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). Results revealed differently shaped flakes, including rectangles, discs and wires, influenced by Fe content. Micro-Raman spectroscopy showed significant vibrational mode shifts, indicating structural changes. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Sn-Se and Fe-Se bonds. Electrical characterization of the memristive devices showed stable switching between high- and low-resistance states, with a threshold voltage of 1.6 V. These findings suggest that Fe-doped SnSe is a promising material for non-volatile memory and neuromorphic computing applications.

MoS2 has proven its efficacy in flexible electronics, transistor devices, and various biological and chemical applications. However, it is still challenging to achieve large-area MoS2 monolayers with desired material quality and electrical properties to fulfill the requirement for practical applications. Moreover, the main strategy for the preparation of a 2D heterostructure it is based on the sequential stacking of the layered materials using wet or dry transfer methods which introduces many defects. This paper presents an economically viable and straightforward two-step methodology to obtain MoS2 thin films, encompassing magnetron sputtering deposition of Mo and subsequent annealing in a sulfur-rich environment. This approach successfully yielded MoS2 thin films on Si\SiO2 substrates. Additionally, heterostructures consisting of few layer graphene (FLG) and MoS2 were directly obtained using the same method. The utilization of grazing incidence X-ray diffraction verified the formation of the hexagonal MoS2 phase, a finding further confirmed by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) investigations revealed the successful sulfurization process, with surface-bound oxides forming only subsequent to air exposure. Comprehensive assessment involving X-ray reflectivity, atomic force microscopy and XPS collectively inferred the fabrication of thin films comprised of a small number of MoS2 layers covering the entire substrate. Electrical assessments exhibited an electrical hysteresis, demonstrating its potential for memristor applications. Overall, this study outlines a cost-effective fabrication method for producing nanoscale MoS2 thin films with excellent properties, avoiding the use of toxic gases such as H2S. These findings contribute to the potential development of cutting-edge applications.

The development of kesterite (Cu2ZnSn(S,Se)4, CZTSSe) thin films for photovoltaic applications is highly necessary, given their composition of Earth-abundant, environmentally friendly elements and their compatibility with established photovoltaic technologies. This study presents a novel synthesis approach for CZTSSe films with varied S/(S+Se) ratios, ranging from 0.83 to 0.44, by a two-step magnetron sputtering deposition/annealing process. The first step consists in an initial deposition of stacked Mo/SnS2/Cu layers, which, upon thermal treatment in a sulfur atmosphere, were transformed into Cu2SnS3 (CTS) films. In the second step, further deposition of ZnSe and subsequent annealing in a tin and selenium atmosphere resulted in the formation of a CZTSSe phase. These processes were optimized to fabricate high-quality and single-phase CZTSSe films, thereby mitigating the formation of secondary phases. Characterization techniques, including scanning electron microscopy, demonstrated a clear correlation between decreased S/(S+Se) ratios and enhanced film densification and grain size. Moreover, grazing incidence X-ray diffraction and Raman spectroscopy confirmed a compositional and structural transition from close to CZTS to nearly a CZTSe phase as the S/(S+Se) ratios decreased. This study advances kesterite-based solar cell technology by enhancing the structural properties and crystallinity of the absorber layer, necessary for improving photovoltaic performance.

Recently, a smart strategy for two-dimensional (2D) materials synthesis has emerged, namely space-confined chemical vapor deposition (CVD). Its extreme case is the microreactor method, in which the growth substrate is face-to-face stacked on the source substrate. In order to grow 2D transition metal dichalcogenides by this method, transition metal oxides, dispersed in very small amounts on the source substrate, are used as source materials in most of the published reports. In this paper, a colloidal dispersion of MoS2 in saline solution is used and MoS2 nanosheets with various shapes, sizes (between 5 and 60 mu m) and thicknesses (2-4 layers) have been synthesized. Small MoS2 flakes (regular or defective) are present on the surface of the nanosheets. Catalytic sites, undercoordinated atoms located at the edges of MoS2 flakes and nanosheets, are produced in a high number by a layer-plus-island (Stranski-Krastanov) growth mechanism. Several double-resonance Raman bands (at 147, 177, 187, 225, 247, 375 cm(-1)) are assignable to single phonon processes in which the excited electron is elastically scattered on a defect. The narrow 247 cm(-1) peak is identified as a topological defect-activated peak. These findings highlight the potential of defect engineering in material property optimization, particularly for solar water splitting applications.

We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram -negative (Escherichia coli ) bacteria, as well as to the opportunistic yeast Candida albicans.

Magneto-optical measurements enable the identification of Fe2+ and Fe3+ in the R and S blocks of BaFe12O19 Mhexaferrite powder obtained by sol -gel processing, followed by thermal annealing at 900 C for 3 hours. The ferromagnetic phase is evidenced by the spin-majority configuration (Fe3+) due to their unpaired electrons between d -d orbitals, while the Fe2+ in the low spin possesses diamagnetic behavior strongly dependent on the surrounded crystal field. Additionally, the irradiation with gamma rays changes the ratio between Fe2+/Fe3+, mainly on the surface of BaFe12O19 nanocrystals. These changes were confirmed by X-ray Photoelectron Spectroscopy measurements, in which the concentration of Fe2+ increased from 69% to 82%, while the one of Fe3+ decreased from 31% to 18%. he thermoluminescent measurements reveal the same changes of Fe3+ in Fe2+ by electron capturing during irradiation, which is released as a red emission after recombination processes. The changes are explained by the increasing of some Fe-O bonds along the c-axis, mainly due to breaking a part of these bonds. The X-ray analysis confirms the changing of the parameters for the BaFe12O19 hexagonal structure.

Considering the increasing need for sustainable and economical energy storage solutions, the integration of layered materials such as MoS2 into these systems represents an important step toward enhancing energy sustainability and efficiency. Exploring environmentally responsible fabrication techniques, this study assesses wrinkled MoS2 thin films synthesized from distinct Mo and MoS2 targets, followed by sulfurization conducted in a graphite box. We utilized magnetron sputtering to deposit precursor Mo and MoS2 films on Si substrates, achieving thicknesses below 20 nm. This novel approach decreases sulfur by up to tenfold during sulfurization due to the confined space technique, contributing also to avoiding the formation of toxic gases such as SO2 or the necessity of using H2S, aligning with sustainable materials development. Thinner MoS2 layers were obtained post-sulfurization from the MoS2 precursors, as shown by X-ray reflectometry. Raman spectroscopy and grazing X-ray diffraction analyses confirmed the amorphous nature of the as-deposited films. Post-sulfurization, both types of films exhibited crystalline hexagonal MoS2 phases, with the sulfurized Mo showing a polycrystalline nature with a (100) orientation and sulfurized MoS2 displaying a (00L) preferred orientation. The X-ray photoelectron spectroscopy results supported a Mo:S ratio of 1:2 on the surface of the films obtained using the MoS2 precursor films, confirming the stoichiometry obtained by means of energy dispersive X-ray spectroscopy. Scanning electron microscopy and atomic force microscopy images revealed micrometer-sized clusters potentially formed during rapid cooling post-sulfurization, with an increased average roughness. These results open the way for the further exploration of wrinkled MoS2 thin films in advanced energy storage technologies.