National Institute Of Materials Physics - Romania

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.

Porous silica-based materials are a promising alternative to graphite anodes for Li-ion batteries due to their high theoretical capacity, low discharge potential similar to pure silicon, superior cycling stability compared to silicon, abundance, and environmental friendliness. However, several challenges prevent the practical application of silica anodes, such as low coulombic efficiency and irreversible capacity losses during cycling. The main strategy to tackle the challenges of silica as an anode material has been developed to prepare carbon-coated SiO2 composites by carbonization in argon atmosphere. A facile and eco-friendly method of preparing carbon-coated SiO2 composites using sucrose is reported herein. The carbon-coated SiO2 composites were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry, transmission and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, cyclic voltammetry, and charge-discharge cycling. A C/SiO2-0.085 M calendered electrode displays the best cycling stability, capacity of 714.3 mAh center dot g(-1), and coulombic efficiency as well as the lowest charge transfer resistance over 200 cycles without electrode degradation. The electrochemical performance improvement could be attributed to the positive effect of the carbon thin layer that can effectively diminish interfacial impedance.

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.

The crystalline structure and Fe local environment in a Co-doped Ni-Fe-Ga Heusler alloy, prepared by the melt-spinning technique, were investigated by X-ray diffraction (XRD) and EXAFS at room and low temperatures. The characteristic temperatures of the austenite-martensite phase transitions were determined by differential scanning calorimetry via cooling and heating cycles of the alloy ribbons. As shown by room-temperature XRD, the austenitic phase of the alloy has the chemically ordered L2(1) Heusler structure. This was confirmed by EXAFS, although this technique was not able to conclusively distinguish between the L2(1) and B2 structures of the austenite for the analyzed alloy. The low-temperature martensitic phase and its structural evolution towards austenite with increasing temperature were studied by high-energy X-ray diffraction, which evinced the martensite modulation. However, the Fe environment could be fitted by EXAFS with the tetragonal L1(0) structure of the non-modulated martensite. This proves that the martensite modulation has structural effects on a long-range scale, without significant changes in the short-range order around the atoms. The changes in the local structure around iron on martensitic transformation were correlated with changes in the electronic structure, described by XANES spectroscopy at the Fe K edge.

Achieving thermoelectric devices with high performance based on low-cost and nontoxic materials is extremely challenging. Moreover, as we move toward an Internet-of-Things society, a miniaturized local power source such as a thermoelectric generator (TEG) is desired to power increasing numbers of wireless sensors. Therefore, in this work, an all-oxide p-n junction TEG composed of low-cost, abundant, and nontoxic materials, such as n-type ZnO and p-type SnOx thin films, deposited on borosilicate glass substrate is proposed. A type II heterojunction between SnOx and ZnO films was predicted by density functional theory (DFT) calculations and confirmed experimentally by X-ray photoelectron spectroscopy (XPS). Moreover, scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDS) show a sharp interface between the SnOx and ZnO layers, confirming the high quality of the p-n junction even after annealing at 523 K. ZnO and SnOx thin films exhibit Seebeck coefficients (alpha) of similar to 121 and similar to 258 mu V/K, respectively, at 298 K, resulting in power factors (PF) of 180 mu W/m K-2 (for ZnO) and 37 mu W/m K-2 (for SnOx). Moreover, the thermal conductivities of ZnO and SnOx films are 8.7 and 1.24 W/m K, respectively, at 298 K, with no significant changes until 575 K. The four pairs all-oxide TEG generated a maximum power output (P-out) of 1.8 nW (approximate to 126 mu W/cm(2)) at a temperature difference of 160 K. The output voltage (V-out) and output current (I-ou(t)) at the maximum power output of the TEG are 124 mV and 0.0146 mu A, respectively. This work paves the way for achieving a high-performance TEG device based on oxide thin films.

In this work, the photodegradation process of atorvastatin calcium (ATC) is reported as depending on: (1) the presence and the absence of excipients in the solid state; (2) the chemical interaction of ATC with phosphate buffer (PB) having pH equal to 7 and 8; and (3) hydrolysis reaction of ATC in the presence of aqueous solution of NaOH. The novelty of this work consists in the monitoring of the ATC photodegradation by photoluminescence (PL). The exposure of ATC in solid state to UV light induces the photo-oxygenation reactions in the presence of water vapors and oxygen from air. According to the X-ray photoelectron spectroscopic studies, we demonstrate that the photo-oxygenation reaction leads to photodegradation compounds having a high share of C=O bonds compared to ATC before exposure to UV light. Both in the presence of PB and NaOH, the photodegradation process of ATC is highlighted by a significant decrease in the intensity of the PL and photoluminescence excitation (PLE) spectra. According to PLE spectra, the exposure of ATC in the presence of NaOH to UV light leads to the appearance of a new band in the spectral range 340-370 nm, this belonging to the photodegradation products. Arguments concerning the chemical compounds, that resulted in this last case, are shown by Raman scattering and FTIR spectroscopy.

Energy harvesting for Internet of Things applications, comprising sensing, life sciences, wearables, and communications, requires efficient thermoelectric (TE) materials, ideally semiconductors compatible with Si technology. In this work, we investigate the potential of GeSn/Ge layers, a group IV material system, as TE material for low-grade heat conversion. We extract the lattice thermal conductivity, by developing an analytical model based on Raman thermometry and heat transport model, and use it to predict thermoelectric performances. The lattice thermal conductivity decreases from 56 W/(m.K) for Ge to 4 W/(m.K) by increasing the Sn atomic composition to 14%. The bulk cubic Ge0.86Sn0.14 alloy features a TE figure of merit of ZT similar to 0.4 at 300 K and an impressive 1.04 at 600 K. These values are extremely promising in view of the use of GeSn/Ge layers operating in the typical on-chip temperature range.

The Laser-induced Thermionic Vacuum Arc method was applied to optimize magnesium-silver (Mg:Ag) alloys, which can be potentially used as stable metallic cathodes for optoelectronic devices. Besides lowering the cathode work function given by the magnesium that improves the electron injection, Mg:Ag alloys induce a higher electrical conductivity, estimated here to be 3.42 x 10(7) S m(-1) for AgMg3, compared with 2.64 x 10(7) S m(-1), estimated here for Mg thin films. Mg:Ag alloys avoid the critical issue of Mg oxidation for better charge injection in optoelectronic active layers. By improving the Thermionic Vacuum Arc technique with the laser beam, this method enables the control of the silver concentration in these alloys due to photonic processes. The uniformity of metallic thin films, compactness, and high purity are the primary advantages of the Laser-induced Thermionic Vacuum Arc method. (C) 2021 Elsevier B.V. All rights reserved.

The electrochemical behavior and the interaction of the immunosuppressive drug azathioprine (AZA) with deoxyribonucleic acid (DNA) were investigated using voltammetric techniques, mass spectrometry (MS), and scanning electron microscopy (SEM). The redox mechanism of AZA on glassy carbon (GC) was investigated using cyclic and differential pulse (DP) voltammetry. It was proven that the electroactive center of AZA is the nitro group and its reduction mechanism is a diffusion-controlled process, which occurs in consecutive steps with formation of electroactive products and involves the transfer of electrons and protons. A redox mechanism was proposed and the interaction of AZA with DNA was also investigated. Morphological characterization of the DNA film on the electrode surface before and after interaction with AZA was performed using scanning electron microscopy. An electrochemical DNA biosensor was employed to study the interactions between AZA and DNA with different concentrations, incubation times, and applied potential values. It was shown that the reduction of AZA molecules bound to the DNA layer induces structural changes of the DNA double strands and oxidative damage, which were recognized through the occurrence of the 8-oxo-deoxyguanosine oxidation peak. Mass spectrometry investigation of the DNA film before and after interaction with AZA also demonstrated the formation of AZA adducts with purine bases.