National Institute Of Materials Physics - Romania

In the present work, we report the synthesis and investigations of La0.9K0.1MnO3 and La0.8K0.1Pb0.1MnO3 bulk samples which could be potential magnetocaloric materials for magnetic refrigeration close to room temperature. A flash combustion reaction and sintering at 1200 degrees C for 10 h are used to prepare the bulk materials. Both compounds crystallized into a rhombohedral structure with R3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\overline{3 }$$\end{document}c space group confirmed by X-ray powder diffraction results. Scanning electron microscopy analysis, combined with XRD peak profiles is performed to estimate the particle/crystallite size of the samples. Moreover, the Curie temperature, TC, is found to be higher in lead-rich sample due to the enhancement of the grain size and the Mn3+-O-Mn4+ double exchange (DE) interaction. Therefore, the bulk sample La0.8K0.1Pb0.1MnO3 shows a room temperature phase transition of 289 K as well as a higher saturation magnetization. The La0.8K0.1Pb0.1MnO3 bulk compound exhibits a high and sharp peak in magnetic entropy change up to 5.5 Jkg-1 K-1 under 5 T at the magnetic transition temperature TC. To compare the magnetocaloric performances of the studied compounds, relative cooling power (RCP) was employed. The obtained experimental results revealed that the increase in particle size influences severely the magnetocaloric properties.

Among many iron-based superconductors, isovalently substituted BaFe2(As1-xPx)2 displays, for x approximate to 0.3, apart from the quite usual Second Magnetization Peak (SMP) in the field dependence of the critical current density, an unusual peak effect in the temperature dependence of the critical current density in the constant field, which is related to the rhombic-to-square (RST) structural transition of the Bragg vortex glass (BVG). By using multi-harmonic AC susceptibility investigations in three different cooling regimes-field cooling, zero-field cooling, and field cooling with measurements during warming up-we have discovered the existence of a temperature region in which there is a pronounced magnetic memory effect, which we attributed to the direction of the structural transition. The observed huge differences in the third harmonic susceptibility at low and high AC frequencies indicates the difference in the time-scale of the structural transition in comparison with the timescale of the vortex excitations. Our findings show that the RST influence on the vortex dynamics goes beyond the previously observed influence on the onset of the SMP.

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.

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.

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.

The compounds KBa 1-x Sr x Cr 2 (PO 4 ) 3 (with x = 0.00; 0.25; 0.50; 0.75; 1.00) were synthesized by a solid-state reaction, and they were thoroughly characterized by different spectroscopic and microscopic techniques. Their structures were indexed in a cubic system with a P2 1 3 space group forming a 3D framework built on CrO 6 octahedra and PO 4 tetrahedra sharing vertices leading to identical Cr 2 P 3 O 18 (U) units. The interconnection between the tetrahedral and octahedral groups leads to the formation of two large closed cavities (K, M II )(1) and (K, M II )(2), statistically occupied by K + and M 2+ (M = Ba, Sr) atoms. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr 3+ ions, showing the effects of substituting the Ba 2+ ions with smaller Sr 2+ ions on the dipolar coupling between the Cr 3+ centers. The obtained materials and active carbon were used as electrode materials in hybrid SC devices. At the same time, their electrochemical properties were assessed by potentiostatic electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge measurements, showing promising results with a maximal specific capacitance (3.86 F/g), energy density (343 mWh/kg), and power density (30.9 kW/kg) in the case of KBa 0.5 Sr 0.5 Cr 2 (PO 4 ) 3 , proving them as good candidates for positive and/or negative electrode materials for energy storage applications.

Quaternary multicomponent Cu2BaSnS4 (CBTS) has emerged as a potential absorber material due to its abundant and nontoxic constituents, high absorption coefficient (10-4 cm-1) and suitable bandgap (1.5-2.0 eV) for the solar photovoltaic application. In this study, polycrystalline CBTS thin layers have been deposited by a typical spray pyrolysis technique on glass substrates using different substrate temperatures (Ts = 200, 250, 300 and 350 degrees C) followed by annealing in a sulfur-rich atmosphere at 550 degrees C under an argon flow. The (micro-)structural, compositional, and optical properties of both types of films have been studied. Analysis of x-ray diffractogram (XRD) patterns for all acquired films showed the presence of polycrystalline CBTS alongside various secondary phases, including Cu2SnS3 being predominant. Nonetheless, the XRD of the films deposited at 250 degrees C and annealed at 550 degrees C showed only the CBTS phase. Raman spectroscopy confirm the formation of the trigonal phase of CBTS. The presence of Cu, Ba, Sn and S in CBTS thin films was confirmed by X-ray photoelectron spectroscopy and Energy-dispersive X-ray spectroscopy. Scanning electron micrographs show a smooth and dense structure with enhanced crystallinity and improved uniformity. Overall, the physical properties of CBTS thin films were found to be spray deposition temperature dependent. An appropriate optical band gap of 1.6 to 1.8 eV and a compact structure indicate their prospective for solar cell applications.

Carbon monoxide (CO) is reversibly adsorbed on and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate. All processes are characterized in real time via photoelectron spectroscopy. Adsorption proceeds on different sites/geometries as a function of substrate temperature. Below room temperature, CO is adsorbed on surface Ba. At room temperature, adsorption proceeds on surface oxygen, whereas at high temperatures, "hollow" site adsorption occurs with carbon coordinated with three oxygens, one oxygen initially belonging to CO and two oxygens from the substrate. The amount of CO adsorbed is about one molecule for 10 surface unit cells, which is slightly increased at low temperatures. CO is desorbed if the substrate is heated above the Curie temperature, which is a sign of the definitory role of ferroelectric polarization. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption.