National Institute Of Materials Physics - Romania

The effect of the annealing temperature on 1% nitrogen-doped WO3 materials was studied, which were then used as electrode materials for high-performance supercapacitor (SC) devices. The supercapacitive performance of the proposed materials was strongly influenced by the doping element and the annealing temperature by directly changing the defect structure of the host material. The 1% N-doped WO3 materials annealed at different temperatures were thoroughly characterized through various characterization techniques, including electron paramagnetic resonance and photoluminescence spectroscopy, giving insight into the effect of N-doping on the defect structure and optical properties of WO3. When the WO3:N materials were used as electrode material in symmetric SCs, the doping element and the annealing temperature improved the electrochemical performance. No booster materials (such as carbon black) were used in the symmetric SC designs, showing increased specific capacitance (102 F/g) and energy density (14.6 W h/kg) values.

This study reports the development of a novel biocomposite for potential applications in the environmental remediation. The hydroxyapatite/sodium bicarbonate (HAp-SB) biocomposite obtained by a cheap method could offer promising characteristics to be used in environmental applications. The obtaining of HAp-SB ceramic composites was studied with the aim of increasing the adsorption efficiency of lead ions from contaminated waters. A composite material (HAp-SB) with good crystallinity that preserves the hexagonal structure of pure hydroxyapatite was obtained. For the powder recovered after decontamination of the lead solution (PbHAp-SB), the XRD model highlighted additional maxima belonging to Ca10(PO4)5(OH)2, Ca0.805Pb4.195(PO4)(OH) and PbH2P2O7. The FTIR spectra of PbHAp-SB are similar to those of HAp-SB composites showing a broadening of the vibration peaks and a slight shift. The XPS and EDS studies illustrated the purity of the HAp-SB sample. Moreover, the presence of lead in the powder recovered after decontamination was also highlighted by XPS and EDS studies. The efficiency of HAp-SB in the adsorption of Pb2+ ions from the contaminated solution was also highlighted by ultrasound studies using double-distilled water as the reference liquid. The adsorption kinetics were investigated with the aid of Langmuir and Freundlich theoretical models. The results demonstrated that the HAp-SB ceramic composite has a strong affinity for the adsorption of Pb2+ ions from contaminated solutions. The removal efficiency of Pb2+ ions was about 92% for the initial Pb2+ concentration above 50 mg/L. The results of the cell viability and cytotoxicity studies demonstrated that HAp-SB nanoparticles did not influence negatively the HeLa cell's viability and did not induce any significant changes of the morphological features of HeLa cells after 24 h of incubation. The batch adsorption results as well as the cytotoxicity assay results suggested that the HAp-SB powder could be successfully used for the removal of Pb2+ from contaminated water.

B doped as well as B and N co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers were synthesized using a one-step laser technique. NiO nanoparticles, graphene oxide platelets, and multiwall carbon nanotubes were used as starting materials for the preparation of the composite layers. H3BO3 was used as B precursor and urea as well as NH3 as N precursors for B and N co -doping of the composite layers. The influence of the nature and concentration of the B and N precursors on the physico-chemical properties of the nanohybrid layers, chemical composition and chemical bonding states, crystalline structure, as well as charge transfer properties was systematically investigated. The relation between the physico-chemical properties and functional characteristics of the nanohybrid layers, photocatalytic removal of water contaminants under simulated sun irradiation conditions was studied, identifying the optimum con-centrations of the dopant precursor materials. The mechanism of the photodegradation process was explored, based of the band structure of the composites. The main intermediates, reactive oxygen species implied in the photocatalytic degradation processes of organic molecules, was investigated through the addition of scavengers to the organic dye test solutions. The highest photocatalytic activities were achieved for B and N co-doped samples synthesised using H3BO3 as B and urea as N precursors.

B doped as well as B and N co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers were synthesized using a one-step laser technique. NiO nanoparticles, graphene oxide platelets, and multiwall carbon nanotubes were used as starting materials for the preparation of the composite layers. H3BO3 was used as B precursor and urea as well as NH3 as N precursors for B and N co -doping of the composite layers. The influence of the nature and concentration of the B and N precursors on the physico-chemical properties of the nanohybrid layers, chemical composition and chemical bonding states, crystalline structure, as well as charge transfer properties was systematically investigated. The relation between the physico-chemical properties and functional characteristics of the nanohybrid layers, photocatalytic removal of water contaminants under simulated sun irradiation conditions was studied, identifying the optimum con-centrations of the dopant precursor materials. The mechanism of the photodegradation process was explored, based of the band structure of the composites. The main intermediates, reactive oxygen species implied in the photocatalytic degradation processes of organic molecules, was investigated through the addition of scavengers to the organic dye test solutions. The highest photocatalytic activities were achieved for B and N co-doped samples synthesised using H3BO3 as B and urea as N precursors.

One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.

Recently, Kittel's theory of ferromagnetic domains in thin films in one dimension, i. e. with the domains extended infinitely over one in-plane direction and with the anisotropy axis oriented perpendicular to the film was revisited by considering the film thickness and unbalanced domains with up and down magnetization, yielding to the computation of magnetic hysteresis [C. M. Teodorescu, Res. Phys. 46 (2023) 106287]. In this work, the above study is extended to samples featuring two-dimensional domain landscapes, for materials with strong magnetic anisotropy, typically characterized by a superunitary ratio between the anisotropy energy and the stray field energy densities. This allows one to compute the most stable structures for vanishing average magnetization < M > together with hysteresis curves for thin films with perpendicular magnetic anisotropy and two-dimensional rectangular domains and also for thin films with in-plane magnetic anisotropy. For two-dimensional films with perpendicular magnetic anisotropy, the most stable structure for < M > = 0 is found to be that with domains infinitely elongated along one in-plane direction, i. e. the one-dimensional case treated in the preceding work. For thin stripes with in-plane magnetization, the domain size l is approximately linear with the stripe lateral size d for low film thickness, while for large film thicknesses it follows a Kittel-like law, but as function of the stripe size l similar to d(1/2). For in-plane magnetized thin films of infinite lateral extent, the most stable structure is the single domain. As for hysteresis curves, the two-dimensional case with perpendicular magnetic anisotropy is shown to evolve from a 2D landscape derived from the checkerboard structure, but with unbalanced domains for magnetization near saturation, towards one-dimensional domain structures for lower magnetization. In some cases and depending also on the demagnetization factor, the one-dimensional case is not reached, and the film exhibit 2D structures on the whole range of the magnetization curve. The hysteresis obtained for thin magnetic stripes with in-plane magnetization also can exhibit a rich structure, with minor cycles on the wings of the magnetization curves evolving towards ,,normal" hysteresis (again, depending on the film thickness, stripe lateral size and demagnetization factor). An infinite thin film with in-plane anisotropy features a steplike magnetization dependence on the applied field.

Thick tungsten oxide layers were prepared electrophoretically in order to be used as photoanodes in photoelectrochemical water oxidation applications. The highest photocurrent density was obtained for a WO3 layer with thickness of similar to 900 nm. Additionally, WO3/BiVO4 and WO3/BiVO4/MIL-101(Fe) heterojunctions have been fabricated using WO3 layer as substrate. WO3/BiVO4 shows an increased value of the electrochemical active surface area indicating that more sites of this photoanode are activated through the formation of the heterojunction. The small V5+ signals observed in the V 2p XPS spectra of these heterojunctions were attributed to the substitution of V5+ atoms with W6+ atoms on the surface of BiVO4. Excessive W doping of the BiVO4 film determined the decrease of the photoelectrochemical performance of WO3/BiVO4 photoanode. The significant improvement of the photoconversion efficiency of the sample decorated with MIL-101(Fe) indicated that this cocatalyst provides sites more efficiently in the photoelectrochemical process. This performance was correlated with the reduced value of the charge transfer resistance at electrode/electrolyte interface obtained from electrochemical impedance spectroscopy investigation.

Motivated by the goal of developing ultralow power, smart and multifunctional nano (micro) electronic devices, research has shown unwavering interest in synthesis methods, architectures and interphase connectivity of composites containing magnetostrictive and piezoelectric phases, known as magnetoelectric (ME) materials. Herein we report on CoFe2O4/0.92Bi0.5Na0.5TiO3-0.08BaTiO3 biphasic ME composites, obtained by sol-gel chemistry, by mixing the precursor sols of the two phases into one precursor sol and further transforming it into gel, with the goal of obtaining homogeneous nanocomposites with magnetoelectric properties. The structural properties, the temperature dependance of dielectric properties, the magnetic and magnetoelectric properties of these biphasic mixtures, with various molar ratios CoFe2O4/ BNT-BT0.08 = 0.5:1, 1:1 and 1.5:1, are investigated. It is observed that the amount of CoFe2O4 and the synthesis in situ of these composites influences their macroscopic properties showing a high difficulty of carrying out an efficient poling resulting in small piezoelectric and magnetoelectric response. It was concluded that the synthesis procedure, the type of architecture and the interphase connectivity are of outmost importance for magnetoelectric properties based on lead-free materials. (c) 2023 Published by Elsevier B.V.

Probing of the free surface ferroelectric properties of thin polar films can be achieved either by estimating the band bending variance under the top-most layer or by studying the extent of the extrinsic charge accumulated outside the surface. Photoemitted or incoming low-energy electrons can be used to characterize locally both properties in a spectromicroscopic approach. Thin ferroelectric lead zirco-titanate (PZT) is investigated by combining low energy/mirror electron microscopy (LEEM/MEM) with photoemission electron microscopy (PEEM) and high-resolution photoelectron spectroscopy (XPS). Significant extrinsic negative compensation charge is proven to accumulate on the surface of the outward polarized thin film, indicated by high MEM-LEEM transition values, up to 15.3 eV, and is correlated with the surface electrostatic potential, which can be partially screened either by electrons interacting with the sample or by soft X-rays through the ejection of secondary electrons and generation of positive charge under the surface. A radiation-induced surface charge compensation effect is observed. The study indicates that air-exposed high quality ferroelectric thin films show large negative surface potentials, determined locally on the surface, which are nevertheless sensitive to beam damage and molecular desorption. These values represent a confirmation of previously estimated surface potential energy values determined from the LEED data on clean surfaces.

Zn1-xFexO nanoparticles with the iron concentrations level in the dilute regime (x = 0.001---0.01) were produced by a sol-gel route from acetate precursors along with an un-doped and 3 at.% Fe-doped reference. The X-ray diffraction of the un-doped and 0.1-1 at.% Fe-doped samples reveal the reflections for only the ZnO wurtzite structure. Fe doping enhances the a-axis lattice constant, the unit cell volume and the microstrain. Iron doping reduces the average crystallite/particle size (confirmed by Scanning Electron Microscopy), improving the surface-to-volume ratio or the concentration of defective surface sites. XPS identifies the iron in both Fe3+ and Fe2+ states. XPS and Fe-57 Mossbauer spectroscopy indicate a broad distribution (distortion) of Fe3+ sites on the surface of ZnO nanoparticles. The blue shift and broadening of the UV emission, and quenching of defect-related photoluminescence in the Fe-doped samples verify the presence of iron in the ZnO lattice and surface intrinsic defects. 0.1-1 at.% Fe-doped ZnO show room temperature ferromagnetism, RTFM, characteristic of dilute magnetic semiconductors, DMS. The magnetization measurements with temperature evidence an antiferromagnetic alignment and an increase of ferromagnetic contribution with Fe doping up to 1 at.%. Zn0.97Fe0.3O reference is a superparamagnetic ZnO/ZnFe2O4 nanocomposite with a blocking temperature of 20 K; HRTEM shows (ultra)fine ZnFe2O4 particles at the surface of ZnO nanoparticles. The analysis of experimental data of 0.1-1 at.% Fe-doped ZnO was done in terms of iron coupling with intrinsic defects, which can generate surface Fe3+ states with geometries similar to the Fe3+ in inverse spinel ZnFe2O4. The superexchange interaction (resembling that in the inverse spinel ZnFe2O4) between the Fe3+ sites with distorted configuration resulting in ferrimagnetism was hypothesised as a possible mechanism of RTFM. Experimental (structural, local chemical, magnetic, optical) and interpretation results can be used to optimize the processing conditions for Fe-doped ZnO to serve as an effective DMS, e.g. for spintronic applications.