National Institute Of Materials Physics - Romania

In this work, the ferroelectric and fatigue characteristics of Au/0.5Ba(Zr0.2Ti0.8)O-3-0.5(Ba0.7Ca0.3)TiO3(BCZT)/Si metal-ferroelectric-semiconductor (MFS) structures are investigated. Moreover, the effect of introducing a thin dielectric HfO2-Al2O3 (HAO) layer with different thicknesses between the BCZT layer and the Si substrate on the ferroelectric characteristics in the metal-ferroelectric-insulator-semiconductor (MFIS) configuration is evaluated. It is evidenced that the insertion of the HAO layer with a thickness of 8 nm improves the memory window of the capacitance-voltage (C-V) curves by 106% compared to the value obtained in the MFS structure and reduces the leakage currents. Furthermore, the Au/BCZT/HAO (8 nm)/Si structure shows a remarkable remnant polarization (P-r) of 7.8 mu C/cm(2), with a coercive voltage of 1.9 V. The obtained value for P-r corresponds to a six times enhancement when compared to the value obtained in the Au/BCZT/Si structure. In addition, the fatigue studies reveal that the P-r obtained in the Au/BCZT/HAO/Si structure slightly decreases (3%) with continuous cycling, up to 10(9) cycles. The present work evidences that Au/BCZT/HAO/Si structures are promising for nonvolatile memory applications.

The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.

The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.

In this paper, we investigate the origin of point defects revealed by electron spin resonance (ESR) and photoluminescence (PL) emission in correlation with the photocatalytic activity of ZnO nanocrystals subjected to thermal annealing at various temperatures. Two ESR signals at g similar to 1.96 and similar to 2.003 were consistently observed in all annealed ZnO samples. However, their relative intensities have changed, indicating that the point defect densities were influenced by the annealing temperature. Interestingly, when doping nanoZnO with Cr3+, the Q-band ESR measurements at T = 100 K did show that the g similar to 1.96 signal was completely passivated, suggesting that the origin of the signal lies in the electrons located near the conduction band, i.e. at a shallow-donor level. The intensity of the g similar to 2.003 signal decreased by rising the annealing temperature, and this is attributed to the depopulation of zinc interstitials through the thermally induced migration process and/or recombination with the zinc vacancies. The green PL emission line at similar to 520 nm, which is dominant in the 700 degrees C annealed ZnO sample, shows a correlation with the ESR signal at g similar to 1.96, whose origin is attributed to the radiative transition of the electron from the shallow donor level to the singly ionized zinc vacancy. Furthermore, the high density of the shallow donor electron states was found to be primarily responsible for the high photocatalytic activity in the degradation of methylene blue.

This paper outlines a method of extraction of iron from water in the form of iron oxyhydroxide natural nanoclusters at comparatively low concentrations and varied ranges of pH using zinc acetate salt. The zinc acetate salt dissociates into Zn(2+)and acetate ions in water where Zn(2+)interacts with iron clusters present in a solution of a given iron concentration and pH, while the acetate ion helps in charge-neutralization based coagulation and consequent precipitation of such nanoclusters. The Zn(2+)ions may also lead to the growth of layered zinc hydroxide (LZH) nanosurfaces at pH >= 6 at sufficient loading. The advantage of this method is the active chemical interaction of Zn(2+)with Fe clusters, followed by growth, which ensures that only some added Zn ions remain in the water while the rest precipitate out along with the residual iron oxyhydroxide, especially at higher pH. The solid that precipitated under various different conditions was successfully evaluated by XRD (formation of ferrihydrite-like nanoclusters (n-Fh)), FTIR (the presence of acetate in the solid n-Fh), TEM (the presence of zinc at higher pH), and EXAFS (local structural characterization). ICP analysis of the obtained solid and the corresponding filtrate revealed the removal efficiency of iron and zinc from the solution at various initial concentrations and pH values. This method of extracting soluble Fh-like nanoclusters by charge neutralization appears to be a suitable promising tool for water purification, because ferrihydrite is capable of isolating other adsorbed contaminants from water, along with itself.

GeSn alloys have the potential of extending the Si photonics functionality in shortwave infrared (SWIR) light emission and detection. Epitaxial GeSn layers were deposited on a relaxed Ge buffer on Si(100) wafer by using high power impulse magnetron sputtering (HiPI-MS). Detailed X-ray reciprocal space mapping and HRTEM investigations indicate higher crystalline quality of GeSn epitaxial layers deposited by Ge HiPI-MS compared to commonly used radio frequency magnetron sputtering (RF-MS). To obtain a rectifying heterostructure for SWIR light detection, a layer of GeSn nanocrystals (NCs) embedded in oxide was deposited on the epitaxial GeSn one. Embedded GeSn NCs are obtained by cosputtering deposition of (Ge1-xSnx)(1-y)(SiO2)(y) layers and subsequent rapid thermal annealing at a low temperature of 400 degrees C. Intrinsic GeSn structural defects give p-type behavior, while the presence of oxygen leads to the n-character of the embedded GeSn NCs. Such an embedded NCs/epitaxial GeSn p-n heterostructure shows superior photoelectrical response up to 3 orders of magnitude increase in the 1.2-2.5 mu m range, as compared to performances of diode based only on embedded NCs.

The present work reports for the first time, the employment of ferroelectric ZrO(2)films as energy storage capacitors utilized in pulsed power systems. Furthermore, the effect of insertion of a low permittivity dielectric HfO2:Al2O3(HAO) layer, with a thickness ranging from 2 to 8 nm, on the tunability of ferroelectric and energy storage characteristics of ZrO(2)films is assessed. The increase in thickness of the HAO layer gave rise to distorted ferroelectric loops with decreased polarization, coercive field, and hysteresis loss of the films. These results are correlated with the depolarization field induced by the insertion of the dielectric HAO layer. An optimum combination of high energy density of 54.3 J cm(-3)and good storage efficiency of 51.3% are obtained for the ZrO(2)film capacitors with 2 nm-thick HAO insert layer. These values correspond to an increase of similar to 55% and similar to 92%, from the respective values of pure ZrO(2)film capacitors. In addition, the HAO/ZrO(2)films showed a good fatigue endurance of energy storage performance over 10(9)electric field cycles. The energy storage density obtained from HAO(2 nm)/ZrO(2)film capacitor is found to be higher than that reported for several Pb-based as well as Pb-free ferroelectric ceramic films with complex compositions. The present study demonstrates that simple binary oxides such as ZrO(2)with ferroelectric behavior could be potential candidates for developing high performance energy storage capacitors.

Hematite (alpha-Fe2O3) is a promising and Earth-abundant material for solar fuel production, and Si-doping has been employed as a general strategy to improve its performance. However, an atomistic description that reconciles the modifications that Si-doping induces on the morphology, crystalline lattice, and electronic and magnetic properties of alpha-Fe2O3 has remained elusive. Here we report on the role of electron small polarons in driving the morphological transition from nearly rounded-shaped to nanowire nanocrystals in Si-doped hematite alpha-Fe2O3. Electron small polaron formation is evidenced by the formation of Fe2+ and the increase of FeO6 distortion at increasing Si content. Local analysis via pair distribution function highlights an unreported crossover from small to large polarons, which affects the correlation length of the polaronic distortion from short to average scales. Ferromagnetic double exchange interactions between Fe2+/Fe3+ species are found to be the driving force of the crossover, constraining the chaining of chemical bonds along the [110] crystallographic direction. This promotes the increase in the reticular density of Fe atoms along the hematite basal plane only, which boosts the anisotropic growth of nanocrystals with more extended [110] facets. Our results show that magnetic and electronic interactions drive preferential crystallographic growth in Si-doped alpha-Fe2O3, thus providing new insights for the nanoscale structural design of efficient solar fuel devices.

Melanin is a natural pigment present in almost all biological groups, and is composed of indolic polymers and characterized by black-brown colorization. Furthermore, it is one of the pigments produced by extremophiles including those living in the Antarctic desert, and is mainly involved in their protection from high UV radiation, desiccation, salinity and oxidation. Previous studies have shown that melanized species have an increased capability to survive high level of radiation compared with the non-melanized counterpart. Understanding the molecular composition of fungal melanin could help to understand this peculiar capability. Here, we aimed to characterize the melanin pigment extracted from the Antarctic black fungus Cryomyces antarcticus, which is a good test model for radioprotection researches, by studying its chemical properties and spectral data. Our results demonstrated that, in spite of having a specific type of melanin as the majority of fungi, the fungus possesses the ability to produce both 1,8-dihydroxynaphthalene (DHN) and l 3-4 dihydroxyphenylalanine (L-DOPA) melanins, opening interesting scenarios for the protection role against radiation. Researches on fungal melanin have a huge application in different fields, including radioprotection, bioremediation, and biomedical applications.