National Institute Of Materials Physics - Romania

In this study, six different donor-pi-acceptor1-pi-donor-acceptor2 type random co-polymers containing benzodithiophene as a donor, benzooxadiazole (BO), and thieno[3,4-c]pyrrole-4,6-dione (TPD) as acceptor, have been synthesized and characterized. In addition to the acceptor core ratio at different values, the effect of aromatic bridge structures on the optical, electronic, and photovoltaic properties of six different random co-polymers is investigated by using thiophene and selenophene structures as aromatic bridge units. To investigate how the acceptor unit ratio and replacement of aromatic bridge units impact the structural, electronic, and optical properties of the polymers, density functional theory (DFT) calculations are carried out for the tetramer models. The open-circuit voltage (VOC), which is strongly correlated with the HOMO levels of the donor material, is enhanced with the increasing ratio of the TPD moiety. On the other hand, the short-circuit current (JSC), which is associated with the absorption ability of the donor material, is improved by the increasing ratio of BO moiety with the pi-bridges. BO moiety dominant selenophene pi-bridged co-polymer (P4) showed the best performance with a power conversion efficiency (PCE) of 6.26%, a JSC of 11.44 mA cm2, a VOC of 0.80 V, and a fill factor (FF) of 68.81%. Synthesis and design of six new D - pi - A1 - pi - D - A2 type copolymers performed. Density functional theory (DFT) calculations are carried out. All polymers showed good solubility in common organic solvents. The effect of the acceptor core ratio and aromatic bridging units on polymers is revealed. OSCs containing P4 donor polymer achieved a maximum PCE of 6.26%. image

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactive inorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been the deliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization, confer antioxidant properties, and impart antimicrobial effects, marking significant contributions to the field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertainties posed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroid hormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. This comprehensive overview of CICECO-hub ' s significant contributions to the forefront inorganic biomaterials across all research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures), follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, and testing protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes (scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated bone regeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctional examples of successful biomedical applications and effective translations to the market of bone grafts for advanced therapies.

Background/Objectives: A biocomposite based on magnesium-doped hydroxyapatite and enriched with amoxicillin (MgHApOx) was synthesized using the coprecipitation method and is presented here for the first time. Methods: The stability of MgHAp and MgHApOx suspensions was evaluated by ultrasound measurements. The structure of the synthesized MgHAp and MgHApOx was examined with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The crystalline structure was determined by X-ray diffraction. The FTIR data were collected in the range of 4000-400 cm-1. The morphology of the nanoparticles was evaluated by scanning electron microscopy (SEM). Furthermore, the biocompatible properties of MgHAp, MgHApOx and amoxicillin (Ox) suspensions were assessed using human fetal osteoblastic cells (hFOB 1.19 cell line). The antimicrobial properties of the MgHAp, MgHApOx and Ox suspension nanoparticles were assessed using the standard reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922 and Candida albicans ATCC 10231. Results: X-ray studies have shown that the biocomposite retains the characteristics of HAp and amoxicillin. The SEM assessment exhibited that the apatite contains particles at nanometric scale with acicular flakes morphology. The XRD and SEM results exhibited crystalline nanoparticles. The average crystallite size calculated from XRD analysis increased from 15.31 nm for MgHAp to 17.79 nm in the case of the MgHApOx sample. The energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis highlighted the presence of the constituent elements of MgHAp and amoxicillin. Moreover, XPS confirmed the substitution of Ca2+ ions with Mg2+ and the presence of amoxicillin constituents in the MgHAp lattice. The results of the in vitro antimicrobial assay demonstrated that MgHAp, MgHApOx and Ox suspensions exhibited good antimicrobial activity against the tested microbial strains. The results showed that the antimicrobial activity of the samples was influenced by the presence of the antibiotic and also by the incubation time. Conclusions: The findings from the biological assays indicate that MgHAp and MgHApOx are promising candidates for the development of new biocompatible and antimicrobial agents for biomedical applications.

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.

Blending carbon particles (CPs) and nanoscale bioactive cerium dioxide is a promising approach for designing composites for biomedical applications, combining the sorption and antioxidant potentials of each individual component. To address this issue, it is crucial to assess the correlation between the components' ratio, physicochemical parameters, and biofunctionality of the composites. Thus, the current research was aimed at fabricating C@CeO2 composites with different molar ratios and the examination of how the parameters of the composites affect their bioactivity. XRD, X-ray photoelectron spectroscopy, and electron microscopy data verified the formation of C@CeO2 composites. CeO2 nanoparticles (NPs) of 4-6 nm are highly dispersed on the surfaces of amorphous CPs. The presence of CeO2 NPs on the carbon surface decreased its adsorption potential in a dose-dependent manner. Besides, the coexistence of carbon and CeO2 in a single composite promotes some redox interactions between O-functionalities and Ce3+/Ce4+ species, resulting in changes in the chemical state of the surface of the composites. These observations suggest the strong connection between these parameters and the biofunctionality of the composites. The presence of CeO2 NPs on the surface of carbon led to a significant increase in the stability of the prepared composites in their aqueous suspensions. The enhancement of bioactivity of the newly prepared C@CeO2 compared to bare carbon and CeO2 was validated by testing their pseudomimetic (catalase/peroxidase-like and superoxide dismutase-like), antiamyloid, and radioprotective activities.

Cylindrical magnetic nanowires (NWs) have gained significant interest as building-blocks of spintronics devices and magnetic sensors thanks to their geometry-tunable magnetic properties and anisotropy. While the synthesis and compositional control of NWs have seen major improvements in recent years, considerable challenges remain for the characterization of local magnetic features at the nanoscale. Here, we demonstrate non-perturbative field distribution mapping and minimally invasive magnetic imaging with scanning nitrogen-vacancy magnetometry. This enables a sensitivity down to 3 mu T Hz-1/2 used to localize ultra-scaled magnetic defects with lateral dimensions below 50 nm. The imaging reveals the presence of magnetic inhomogeneities in correspondence of periodical geometrical modulations/anti-notches in axial magnetized nanowires that are largely undetectable with standard metrology. The features induce local fluctuations of the NWs' magnetization orientation that are sensed by SNVM and compared with magnetic force microscopy. Finally, the strong magnetic field confinement in the nanowires is leveraged to study the interaction between the stray magnetic field and the fluorescence generated by two nitrogen-vacancies contained in the probe sensor, thus clarifying the contrast formation mechanisms. We report on magnetic imaging capability with non-perturbative field distribution mapping and minimally invasive magnetic sensing using scanning nitrogen-vacancy magnetometry in axial magnetized nanowires.

The development of thin films of chromium-doped hydroxyapatite (20CrHAp) deposited on silicon substrate by the spin coating method was realized for the first time. A coherent investigation of the physicochemical properties of 20CrHAp thin films was also carried out for the first time. The obtained thin films were studied by various techniques such as, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) investigations and fractal analysis. By scanning electron microscopy (SEM) studies were obtained valuable information about the surface morphology of the 20CrHAp thin films. The zeta potential (ZP), Dynamic light scattering (DLS) and ultrasound measurements (US) were used in order to evaluate the stability of 20CrHAp suspension. The ratio between the hydrodynamic diameter obtained by DLS and the particle diameter obtained by SEM was 1.6. The SEM results on 20CrHAp thin films suggested that the sample possess a conglomerate of nanoparticles unevenly distributed on their surface. The surface morphology of the 20CrHAp thin films was studied with the aid of atomic force microscopy (AFM). The AFM topography of the 20CrHAp thin film's surface highlighted that the thin films present the morphology of a continuum deposited layer composed of non-uniform particle conglomerates. The presence of hydroxyapatite on the surface of silicium effects on the development of the fungal cells on their surface. Furthermore, our investigation delves into the

The synergistic piezoelectric and osteoconductive properties of barium titanate (BT) and hydroxyapatite (HA) could stir the development of a new generation of synthetic bone graft substitutes, with capability for rapid and safe osseointegration. The research focused on two concurrent approaches for coupling the BT and HA materials: (i) conventional sintering of BT-HA powder mixtures; and (ii) functionalization of pre-sintered BT with HA coatings using magnetron sputtering (MS). Irrespective of the BT/HA ratios ranging from 95/5 to 80/20 wt%, nanocrystalline or highly-crystallized nature of the powders, sub-micron- or micron-sized particle dimensions, and sintering temperature, it was observed that the BT-HA reactivity cannot be prevented above 800 degrees C. At higher temperatures in the range of 1000-1300 degrees C, HA undergoes decomposition and extensively reacts with BT, leading to the formation of several secondary phases such as CaTiO3, Ba2Ca(PO4)2, BaCa6(PO4)4O, BaCa(PO3)4, and beta-Ca2P2O7. As a consequence, the cytocompatibility assessed in fibroblast and osteoblast cell cultures, as well as the piezoelectric response, were significantly altered. Applying HA coatings by MS to the sintered BT ceramics successfully preserved their piezoelectric properties, while also providing an unaltered cytocompatible and osteogenic-prone surface. The HA coatings were fully crystallized at post-deposition annealing temperatures of 550 and 700 degrees C, achieving crystalline qualities comparable to HA powders sintered at 1100 and 1200 degrees C, respectively. No reactivity events between BT and HA were observed. Partial reactivity was only noticeable upon annealing at 1000 degrees C. Therefore, it is suggested that the HA coating of BT is effective in seamlessly coupling the piezoelectric and osteogenic properties of the two constituents without compromise.

Fe, Co and Si powders were exposed to mechanochemical activation by high-energy ball milling for 0, 2, 4, 8 and 12 h. The samples were subsequently characterized by Mossbauer spectroscopy, X-ray powder diffraction (XRPD), magnetic measurements and optical diffuse reflectance spectroscopy. The room temperature Mossbauer measurements were consistent with the occurrence of FeCo2Si and Fe0.5Co0.5Si crystalline phases. The low temperature Mossbauer spectra confirmed the absence of superparamagnetism up to 44 K in the milled system. XRPD patterns supported the phase sequence derived from Mossbauer spectroscopy. The coercive field was found to increase with the ball milling time (BMT). Zero-field-cooling-field-cooling (ZFC-FC) measurements performed at 200 Oe in the temperature range 5-300 K evidenced the transition to the skyrmion phase of the Fe0.5Co0.5Si material below the critical temperature of 44 K. The optical absorption in the UV-Vis-NIR region of the spectrum was found to increase with BMT.

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.