National Institute Of Materials Physics - Romania

A deeper understanding of the coupling at the interface of multiferroics heterostructures is being achieved by the use of synchrotron radiation techniques. Here, the authors use k-resolved soft X-ray photoemission spectroscopy and first principles calculations to investigate the band structure of several multiferroic heterostructures, isolating the distinct signature of the interface. Physics of the multiferroic interfaces is currently understood mostly within a phenomenological framework based on screening of the polarization field and depolarizing charges. Additional effects still unexplored are the band dependence of the interfacial charge modulation and the associated changes of the electron-phonon interaction, coupling the charge and lattice degrees of freedom. Here, multiferroic heterostructures of the colossal-magnetoresistance manganite La1-xSrxMnO3 buried under ferroelectric BaTiO3 and PbZrxTi1-xO3 are investigated using soft-X-ray angle-resolved photoemission. The experimental band dispersions from the buried La1-xSrxMnO3 identify coexisting two-dimensional hole and three-dimensional electron charge carriers. The ferroelectric polarization modulates their charge density, affecting the coupling of the 2D holes and 3D electrons with the lattice which forms large Frohlich polarons inherently reducing mobility of the charge carriers. Our k-resolved results on the orbital occupancy, band filling and electron-lattice interaction in multiferroic oxide heterostructures modulated by the ferroelectric polarization disclose most fundamental physics of these systems needed for further progress of beyond-CMOS ferro-functional electronics.

In the present work, new luminescent lanthanide complexes with extended mesomorphic range were prepared by coordination to lanthanide ions (Eu3+, Sm3+ and Tb3+) of the new 4-pyridone based organic ligands (L) with 3,4-(7-n) and 3,5-di(alkyloxy)benzyl (8-n) mesogenic groups and variable length (n = 12 or 14 carbon atoms) onto the benzyl unit. The cumulative results of the elemental analyses as well as the H-1, C-13 NMR and IR spectroscopies support the structure of the organic derivatives and their lanthanide complexes [LnL(3)(NO3)(3)] (9-n/Ln and 10-n/Ln) described in this work. These complexes show characteristic lanthanide solid state emission, both at room and elevated temperatures corresponding to crystalline, glassy or liquid crystal states. The long range SmA phases displayed by all complexes were supported by a combination of characterization methods, including: differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and variable-temperature powder X-ray diffraction (XRD). This work shows that the number, substitution pattern and length of flexible alkoxy chains are important parameters to control the phase-transition characteristics of the lanthanide complexes. Complexes with 3,4-disubstituted pattern (9-n/Ln) show higher clearing temperatures (nearly 60 degrees C for Eu3+, 70 degrees C for Sm3+ and 85 degrees C for Tb3+ complexes) compared to their counterparts with 3,5-disubstituted pattern (10-n/Ln). Moreover, complexes 9-n/Ln crystallize when cooling their LC phase while complexes 10-n/Ln are stable in glassy state at room temperature as a consequence of the different close interdigitated molecular packing evidenced by XRD measurements. Dielectric spectroscopy was employed to detect the changes of order degree specific to each phases (crystalline, LC or isotropic). The variation of dielectric constant and the electrical conductivity versus temperature shows three transition intervals for selected complexes 10-14/Sm and 10-14/Tb, which delimit the main intervals: 45-60 degrees C, 90-110 degrees C; 140-160 degrees C corresponding to the Cr-1-Cr-2, Cr-2 - SmA and SmA-Iso transitions, and agree very well with the DSC results. The change of characteristic time, obtained by Havriliak-Negami fit function, with temperature also provides a very good correlation with the DSC and POM results. (C) 2022 Elsevier B.V. All rights reserved.

This paper presents the results concerning monotropic nematic liquid crystals 4-pentylphenyl 40-alkyl benzoate (5PnB) (n = 3 or 5 carbon atoms in the alkyl chain). Their mesophase properties were supported by images of the polarized optical microscopy. Molecular dynamics in the bulk samples or in the composites prepared with aerosil A380 was investigated by broadband dielectric spectroscopy in a large temperature range, appropriately chosen. Thermo gravimetric and infrared investigations were additionally performed. The data were compared with those of structurally related nematics like cyanophenyl pentyl benzoates, which have a cyan group instead of the pentyl chain. The dielectric spectra of the bulk 3P5B and 5P5B demonstrate a dielectric behavior with several relaxation processes as expected for nematic liquid crystals. The temperature dependence of the relaxation rates (and of the dielectric strength) seems to have two distinguished regimes. Thus, in the isotropic state, at higher temperatures the data obey the Vogel-Fulcher-Tammann law, whereas an Arrhenius law is fitted at lower temperature, in a close similarity to the behavior of a constrained dynamic glass transition. Samples with a high density of silica (larger than 7 g aerosil/1 g of 5PnB) were prepared to observe a thin layer adsorbed on the particle surface; it was estimated that almost each guest 5PnB molecule interacts with the aerosil surface. For the composites only one main relaxation process is observed at frequencies much lower than those for the corresponding bulk, which was assigned to the dynamics of the molecules in the surface layer. Infrared spectroscopy shows that these molecules interact with the surface by the ester carbonyl group leading to the monolayer self-assembly at liquid-solid interface. We note once more the importance of the functional unit(s) for the interaction with the hydroxyl groups on the aerosil surface. (c) 2022 Elsevier B.V. All rights reserved.

ZnO nanostructures were electrochemically synthesized on Cu and on chemical vapor deposited (CVD)-graphene/Cu electrodes. The deposition was performed at different electrode potentials ranging from -0.8 to -1.2 V, employing a zinc nitrate bath, and using voltametric and chronoamperometric techniques. The effects of the electrode nature and of the working electrode potential on the structural, morphological, and optical properties of the ZnO structures were investigated. It was found that all the samples crystallize in hexagonal wurtzite structure with a preferential orientation along the c-axis. Scanning electron microscopy (SEM) images confirm that the presence of a graphene covered electrode led to the formation of ZnO nanowires with a smaller diameter compared with the deposition directly on copper surface. The photoluminescence (PL) measurements revealed that the ZnO nanowires grown on graphene/Cu exhibit stronger emission compared to the nanowires grown on Cu. The obtained results add another possibility of tailoring the properties of such nanostructured films according to the specific functionality required.

In this work, we report the preparation of nanostructured electrodes based on dense arrays of vertically-aligned copper (Cu) nanowires (NWs) to be subsequently covered by cadmium telluride (CdTe) thin films, with great potential to be used within "substrate"-type photovoltaic cells based on A(II)-BVI heterojunctions. In particular, the multi-step preparation protocol presented here involves an electrochemical synthesis procedure within a supported anodic aluminum oxide (AAO) nanoporous template for first generating a homogeneous array of vertically-aligned Cu NWs, which are then further embedded within a compact CdTe thin film. In a second stage, we tested three deposition methods (vacuum thermal evaporation, VTE; radio-frequency magnetron sputtering, RF-MS; and electrochemical deposition, ECD) for use in obtaining CdTe layers potentially able to consistently penetrate the previously prepared Cu NWs array. A comparative analysis was performed to critically evaluate the morphological, optical, and structural properties of the deposited CdTe films. The presented results demonstrate that under optimized processing conditions, the ECD approach could potentially allow the cost-effective fabrication of absorber layer/collecting electrode CdTe/Cu nanostructured interfaces that could improve charge collection mechanisms, which in turn could allow the fabrication of more efficient solar cells based on A(II)-BVI semiconducting compounds.

Direct current (DC) and radio frequency (RF) magnetron sputtering methods were selected for conducting the deposition of structural materials, namely ceramic and metallic co-depositions. A total of six configurations were deposited: single thin layers of oxides (Cr2O3, SiO2) and co-deposition configurations (50:50 wt.%) as structural materials (W, Be)-(Cr2O3, SiO2), all deposited on 304L stainless steel (SS). A comprehensive evaluation such as surface topology, thermal desorption outgassing, and structural/chemical state was performed. Moreover, mechanical characterization evaluating properties such as adherence, nano indentation hardness, indentation modulus, and deformation relative to yielding, was performed. Experimental results show that, contrary to SiO2 matrix, the composite layers of Cr2O3 with Be and W exhibit surface smoothing with mitigation of artifacts, thus presenting a uniform and compact state with the best microstructure. These results are relevant in order to develop future dense coatings to be used in the fusion domain.

Cerium-doped Lutetium-Yttrium Oxyorthosilicate (LYSO:Ce) is one of the most widely used Cerium-doped Lutetium based scintillation crystals. Initially developed for medical detectors it rapidly became attractive for High Energy Particle Physics (HEP) applications, especially in the frame of high luminosity particle colliders. In this paper, a comprehensive and systematic study of LYSO:Ce ([Lu((1-x))Y-x](2)SiO5 : Ce) crystals is presented. It involves for the first time a large number of crystal samples (180) of the same size from a dozen of producers. The study consists of a comparative characterization of LYSO:Ce crystal products available on the market by mechanical, optical and scintillation measurements and aims specifically, to investigate key parameters of timing applications for HEP.

Electrospun polymeric fibers present an emerging alternative for the development of flexible electronics, enabling applications in wearable sensors and biosensors for continuous monitoring, and actuators for tissue engineering. The possibility to prepare sub-micrometric polymeric scaffolds, their processing for increasing the conductivity, their modification with different materials, conductive polymers and biomolecules in order to obtain functional flexible electrodes, allows the development of innovative devices for healthcare, and biomedical applications. In this review, the impact of metallized electrospun polymeric fibers in electrochemical (bio)sensors and actuators is discussed. A relation between their structure and functionality is provided, alongside with an overview of the different methods to obtain functional conductive fibers.

We report in this paper on the monolayer composites thin films that have the magnetic spinel CoFe2O4 and the piezoelectric perovskite BNT-BT0.08 as constituent phases. Composite thin films of CoFe2O4 and BNT-BT0.08, with molar ratios of 0.5:1, 1:1 and 1.5:1, have been deposited by spin coating method from a sol precursor, mixture type, of CoFe2O4 and BNT-BT0.08. The monolayer thin films, deposited on Si/SiO2/TiO2/Pt substrate, were characterized using selected methods, such as: X-ray diffraction, scanning electron microscopy, atomic force microscopy/piezoelectric force microscopy, dielectric spectroscopy, and vibrating sample magnetometer. X-ray diffraction demonstrated the two phases: cubic CoFe2O4 and rhombohedral BNT-BT0.08. Furthermore, the Si/ SiO2/TiO2/Pt/BNT-BT0.08/CoFe2O4 monolayers show a simultaneous enhancement of both the magnetization and coercivity with the increase of the magnetic phase, accompanied by a decrease of the dielectric constant. The obtained results reveal that the investigated monolayer structures present superior properties compared to those of bilayer composites.

This is the first report regarding the effect of gamma irradiation on chitosan-coated magnesium-doped hydroxyapatite (x(Mg) = 0.1; 10 MgHApCh) layers prepared by the spin-coating process. The stability of the resulting 10 MgHApCh gel suspension used to obtain the layers has been shown by ultrasound measurements. The presence of magnesium and the effect of the irradiation process on the studied samples were shown by X-ray photoelectron spectroscopy (XPS). The XPS results obtained for irradiated 10 MgHApCh layers suggested that the magnesium and calcium contained in the surface layer are from tricalcium phosphate (TCP; Ca-3(PO4)(2)) and hydroxyapatite (HAp). The XPS analysis has also highlighted that the amount of TCP in the surface layer increased with the irradiation dose. The energy-dispersive X-ray spectroscopy (EDX) evaluation showed that the calcium decreases with the increase in the irradiation dose. In addition, a decrease in crystallinity and crystallite size was highlighted after irradiation. By atomic force microscopy (AFM) we have obtained images suggesting a good homogeneity of the surface of the non-irradiated and irradiated layers. The AFM results were also sustained by the scanning electron microscopy (SEM) images obtained for the studied samples. The effect of gamma-ray doses on the Fourier transform infrared spectroscopy (ATR-FTIR) spectra of 10 MgHApCh composite layers was also evaluated. The in vitro antifungal assays proved that 10 MgHApCh composite layers presented a strong antifungal effect, correlated with the irradiation dose and incubation time. The study of the stability of the 10 MgHApCh gel allowed us to achieve uniform and homogeneous layers that could be used in different biomedical applications.