National Institute Of Materials Physics - Romania

The commercially ubiquitous liquid electrolytes for lithium-ion batteries have several shortcomings in terms of safety. Therefore, development of solid electrolytes, especially those that are glass-based, has been gaining increasing interest in recent times. However, the fundamental understanding of the changes in the glass structure and the corresponding changes in the properties due to the addition of dopants is necessary for the development of glasses. Therefore, here, we report a study on the role of vanadium on the glass structure, ionic conduction, crystallization behavior, and other properties of lithium silicate-based glasses (23Li(2)O-2.64K(2)O-2.64Al(2)O(3)-71.72SiO(2)) as a solid electrolyte for high-temperature Li-ion battery applications. Furthermore, we proposed a mathematical model to describe/quantify the ion-conducting channels' connectivity in glasses. The experimental glass structures were assessed using Si-29, V-51, Al-27 nuclear magnetic resonance, Fourier transform infrared, and ultraviolet-visible spectroscopy techniques. The ionic conductivity was measured by impedance spectroscopy, and the crystallization behavior was studied by optical microscopy and X-ray diffraction. Furthermore, molecular dynamics simulations were also used to gain structural insights of the glasses. In the designed compositions, the addition of vanadium decreased the overall concentration of Li+ ions. However, the results revealed that the ionic conductivity improved with the addition of vanadium in spite of a decrease in the number of charge carriers. This suggests that vanadium makes the pathways easier for the conducting ions. Thus, we conclude that vanadium modifies the conduction channels to promote better hoping of the ions from one site to another.

Hybrid perovskites based solar cells have demonstrated high conversion efficiency but poor long-term stability. This study reports on the results obtained after doping the CH3NH3PbI2.6Cl0.4 mixed halide perovskite with imidazolium (C3N2H5+, denoted IM) on the "A site" position of a perovskite, to improve photovoltaic performances and stability of hybrid perovskite solar cells. The perovskite films were investigated exhaustively by different characterization techniques: X-ray diffraction, Atomic Force Microscopy, Scanning Electron Microscopy, UV-Vis, X-ray Photoelectron Electron Paramagnetic Resonance spectroscopies, Impedance Spectroscopy and Incident Photon-to-Electron Conversion Efficiency. The photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The amount of IM inserted in the perovskite play a key role on the film properties. The calculated new tolerance factors according to the "globularity factor" are experimentally proved and thus at doping concentrations greater than 20% for CH3NH3PbI2.6Cl0.4 perovskite the 3D structure is no longer obtained. However, below this value, the IM substituted perovskite film possesses an improved film quality and crystallinity as compared to the pristine film. Substituting MA+ with IM+ provides a favorable way to reduce recombination processes and shows great potential to achieve high stability, and an improved charge generation, resulting in increased PCE values. We find that the optimal percentage of imidazolium incorporation to achieve better stability of solar cells is 6%.

Polarization switching in ferroelectric films is exploited in many applications, such as non-volatile memories and negative capacitance field affect transistors. This can be inhomogeneous or homogeneous, depending on if ferroelectric domains are forming or not during the switching process. The relation between the polarization switching, the structural quality of the films and the negative capacitance was not studied in depth. Here, Pb(Zr0.2Ti0.8)O-3 (PZT) layers were deposited by pulse laser deposition (PLD) and sol-gel (SG) on single crystal SrTiO3 (STO) and Si substrates, respectively. The structural quality was analyzed by X-ray diffraction and transmission electron microscopy, while the electric properties were investigated by performing hysteresis, dynamic dielectric measurements, and piezo-electric force microscopy analysis. It was found that the PZT layers grown by PLD on SRO/STO substrates are epitaxial while the layers deposited by SG on Pt/Si are polycrystalline. The polarization value decreases as the structure changes from epitaxial to polycrystalline, as well as the magnitude of the leakage current and of the differential negative capacitance, while the switching changes from homogeneous to inhomogeneous. The results are explained by the compensation rate of the depolarization field during the switching process, which is much faster in epitaxial films than in polycrystalline ones.

The frequency and temperature dependence of dielectric properties of CH3NH3PbI3 (MAPI) crystals have been studied and analyzed in connection with temperature-dependent structural studies. The obtained results bring arguments for the existence of ferroelectricity and aim to complete the current knowledge on the thermally activated conduction mechanisms, in dark equilibrium and in the presence of a small external a.c. electric field. The study correlates the frequency-dispersive dielectric spectra with the conduction mechanisms and their relaxation processes, as well as with the different transport regimes indicated by the Nyquist plots. The different energy barriers revealed by the impedance spectroscopy highlight the dominant transport mechanisms in different frequency and temperature ranges, being associated with the bulk of the grains, their boundaries, and/or the electrodes' interfaces.

Ge2Sb2Te5 (GST-225) is a chalcogenide material with applications in nonvolatile memories. However, chalcogenide material properties are dependent on the deposition technique. GST-225 thin films were prepared using three deposition methods: magnetron sputtering (MS), pulsed laser deposition (PLD) and a deposition technique that combines MS and PLD, namely MSPLD. In the MSPLD technique, the same bulk target is used for sputtering but also for PLD at the same time. The structural and optical properties of the as-deposited and annealed thin films were characterized by Rutherford backscattering spectrometry, X-ray reflectometry, X-ray diffraction, Raman spectroscopy and spectroscopic ellipsometry. MS has the advantage of easily leading to fully amorphous films and to a single crystalline phase after annealing. MS also produces the highest optical contrast between the as-deposited and annealed films. PLD leads to the best stoichiometric transfer, whereas the annealed MSPLD films have the highest mass density. All the as-deposited films obtained with the three methods have a similar optical bandgap of approximately 0.7 eV, which decreases after annealing, mostly in the case of the MS sample. This study reveals that the properties of GST-225 are significantly influenced by the deposition technique, and the proper method should be selected when targeting a specific application. In particular, for electrical and optical phase change memories, MS is the best suited deposition method.

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Composites of magnetite (Fe3O4) nanoparticles dispersed in a polydimethylsiloxane (PDMS) matrix were prepared by a molding process. Two types of samples were obtained by free polymerization with randomly dispersed particles and by polymerization in an applied magnetic field. The magnetite nanoparticles were obtained from magnetic micrograins of acicular goethite (alpha-FeOOH) and spherical hematite (alpha-Fe2O3), as demonstrated by XRD measurements. The evaluation of morphological and compositional properties of the PDMS:Fe3O4 composites, performed by SEM and EDX, showed that the magnetic particles were uniformly distributed in the polymer matrix. Addition of magnetic dispersions promotes an increase of thermal conductivity compared with pristine PDMS, while further orienting the powders in a magnetic field during the polymerization process induces a decrease of the thermal conductivity compared with the un-oriented samples. The shape of the magnetic dispersions is an important factor, acicular dispersions providing a higher value for thermal conductivity compared with classic commercial powders with almost spherical shapes.

The lack of order in amorphous chalcogenides offers them novel properties but also adds increased challenges in the discovery and design of advanced functional materials. The amorphous compositions in the Si-Ge-Te system are of interest for many applications such as optical data storage, optical sensors and Ovonic threshold switches. But an extended exploration of this system is still missing. In this study, magnetron co-sputtering is used for the combinatorial synthesis of thin film libraries, outside the glass formation domain. Compositional, structural and optical properties are investigated and discussed in the framework of topological constraint theory. The materials in the library are classified as stressed-rigid amorphous networks. The bandgap is heavily influenced by the Te content while the near-IR refractive index dependence on Ge concentration shows a minimum, which could be exploited in applications. A transition from a disordered to a more ordered amorphous network at 60 at% Te, is observed. The thermal stability study shows that the formed crystalline phases are dictated by the concentration of Ge and Te. New amorphous compositions in the Si-Ge-Te system were found and their properties explored, thus enabling an informed and rapid material selection and design for applications.

The structural role of V in 28Li(2)O-72SiO(2) (in mol%) lithium silicate glass doped with 0.5 mol% V2O5 was assessed using Si-29 and V-51 Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V2O5 used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V2O5 addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the Si-29 NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V2O5 acting as network former, capable to form various QVn tetrahedral units (for n = 0, 1, and 2) in the glasses. These QVn units, which are similar to phosphate units, scavenge the Li+ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.

This Special Issue was devoted to developments made in Physical Vapour Deposited (PVD) biomedical coatings for various healthcare applications. The scrutinized PVD methods were Radio-Frequency Magnetron Sputtering (RF-MS), Cathodic Arc Evaporation, Pulsed Electron Deposition and its variants, Pulsed Laser Deposition, and Matrix Assisted Pulsed Laser Evaporation (MAPLE), due to their great promise especially in the dentistry and orthopaedics. These methods have yet to gain traction for industrialization and large-scale application in biomedicine. A new generation of implant coatings can be made available by the (1) incorporation of organic moieties (e.g., proteins, peptides, enzymes) into thin films by innovative methods such as combinatorial MAPLE, (2) direct coupling of therapeutic agents with bioactive glasses or ceramics within substituted or composite layers via RF-MS, or (3) by innovation in high energy deposition methods such as arc evaporation or pulsed electron beam methods.