National Institute Of Materials Physics - Romania

Electronic structure of LaAlO3/SrTiO3 (LAO/STO) samples, grown at low oxygen pressure and post-annealed ex situ, was investigated by soft-x-ray ARPES focussing on the Fermi momentum (k (F)) of the mobile electron system (MES). X-ray irradiation of these samples at temperatures below 100 K creates oxygen vacancies (V(O)s) injecting Ti t (2g)-electrons into the MES. At this temperature the oxygen out-diffusion is suppressed, and the V(O)s should appear mostly in the top STO layer. The x-ray generated MES demonstrates, however, a pronounced three-dimensional (3D) behavior as evidenced by variations of its experimental k (F) over different Brillouin zones. Identical to bare STO, this behavior indicates an unexpectedly large extension of the x-ray generated MES into the STO depth. The intrinsic MES in the standard LAO/STO samples annealed in situ, in contrast, demonstrates purely two-dimensional (2D) behaviour. The relevance of our ARPES data analysis is supported by model calculations to compare the intensity vs gradient methods of the k (F) determination as a function of the energy resolution ratio to the bandwidth. Based on self-interaction-corrected DFT calculations of the MES induced by V(O)s at the interface and in STO bulk, we discuss possible scenarios of the puzzling 3D-ity. It may involve either a dense ladder of quantum-well states formed in a long-range interfacial potential or, more likely, x-ray-induced bulk metallicity in STO accessed in the ARPES experiment through a short-range interfacial barrier. The mechanism of this metallicity may involve remnant V(O)s and photoconductivity-induced metallic states in the STO bulk, and even more exotic mechanisms such as x-ray induced formation of Frenkel pairs.

Group IV quantum dots (QDs) in HfO2 are attractive for non-volatile memories (NVMs) due to complementary metal-oxide semiconductor (CMOS) compatibility. Besides the role of charge storage centers, SiGeSn QDs have the advantage of a low thermal budget for formation, because Sn presence decreases crystallization temperature, while Si ensures higher thermal stability. In this paper, we prepare MOS capacitors based on 3-layer stacks of gate HfO2/floating gate of SiGeSn QDs in HfO2/tunnel HfO2/p-Si obtained by magnetron sputtering deposition followed by rapid thermal annealing (RTA) for nanocrystallization. Crystalline structure, morphology, and composition studies by cross-section transmission electron microscopy and X-ray diffraction correlated with Raman spectroscopy and C-V measurements are carried out for understanding RTA temperature effects on charge storage behavior. 3-layer morphology and Sn content trends with RTA temperature are explained by the strongly temperature-dependent Sn segregation and diffusion processes. We show that the memory properties measured on Al/3-layer stack/p-Si/Al capacitors are controlled by SiGeSn-related trapping states (deep electronic levels) and low-ordering clusters for RTA at 325-450 degrees C, and by crystalline SiGeSn QDs for 520 and 530 degrees C RTA. Specific to the structures annealed at 520 and 530 degrees C is the formation of two kinds of crystalline SiGeSn QDs, i.e., QDs with low Sn content (2 at.%) that are positioned inside the floating gate, and QDs with high Sn content (up to 12.5 at.%) located at the interface of floating gate with adjacent HfO2 layers. The presence of Sn in the SiGe intermediate layer decreases the SiGe crystallization temperature and induces the easier crystallization of the diamond structure in comparison with 3-layer stacks with Ge-HfO2 intermediate layer. High frequency-independent memory windows of 3-4 V and stored electron densities of 1-2 x 10(13) electrons/cm(2) are achieved.

To enhance the spectral response of solar cells, an experimental study on LaPO4:0.01Ce(3+)/xNd(3+) (x = 0, 2, 4 mol%) was carried out, where structural and morphological properties of the prepared samples were well characterized by the means of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electronic microscope. Additionally, the photoluminescence behavior of phosphors in ultraviolet-visible (UV-VIS) and Near-infrared (NIR) regions were investigated to confirm the energy transfer (ET) from Ce3+ to Nd3+. Moreover, the quantum efficiency of Ce3+/Nd3+-co-doped samples was estimated as high as similar to 172% and the possible ET process was described. Accordingly, the LaPO4:Ce3+/Nd3+ phosphors can convert the UV light (275 nm) into NIR photons (approx. 1059 nm) through the possible two-pathway energy transfer processes from Ce3+ sensitizer ions to Nd3+ activators. Obtained NIR down-conversion emissions are suitable for improving the conversion efficiency of c-Si solar cells.

Despite being the lightest element in the periodic table, hydrogen poses many risks regarding its production, storage, and transport, but it is also the one element promising pollution-free energy for the planet, energy reliability, and sustainability. Development of such novel materials conveying a hydrogen source face stringent scrutiny from both a scientific and a safety point of view: they are required to have a high hydrogen wt.% storage capacity, must store hydrogen in a safe manner (i.e., by chemically binding it), and should exhibit controlled, and preferably rapid, absorption-desorption kinetics. Even the most advanced composites today face the difficult task of overcoming the harsh re-hydrogenation conditions (elevated temperature, high hydrogen pressure). Traditionally, the most utilized materials have been RMH (reactive metal hydrides) and complex metal borohydrides M(BH4)(x) (M: main group or transition metal; x: valence of M), often along with metal amides or various additives serving as catalysts (Pd2+, Ti4+ etc.). Through destabilization (kinetic or thermodynamic), M(BH4)(x) can effectively lower their dehydrogenation enthalpy, providing for a faster reaction occurring at a lower temperature onset. The present review summarizes the recent scientific results on various metal borohydrides, aiming to present the current state-of-the-art on such hydrogen storage materials, while trying to analyze the pros and cons of each material regarding its thermodynamic and kinetic behavior in hydrogenation studies.

This work presents the preparation of W and V co-doped TiO2 nanoparticles (W:TiO2 and W:V:TiO2) using laser pyrolysis technique subsequently modified with noble metals Pt or Pd using chemical impregnation method. By using well defined TiO2 nanoparticles, the enhancement of catalytic activity is expected mainly due to their higher surface area and density defects relative to bulk material. Structural, morphological and optical properties of the as-obtained nanopowders have been characterized by transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, UV-VIS diffuse reflectance spectroscopy and photoluminescence techniques. The phase composition analysis reveals the preponderance of anatase (95%) in addition to ruffle phase, its particle average size ranging from 25 to 30 nm. The TiO 2 based nanomaterials were supplementary modified by noble metals deposition (Pt particles with dimensions of 3-4 nm and spherical Pd crystallites with a diameter between 3 and 9 nm) and their photocatalytic activity was tested in oxidative photo degradation of CH3OH, under simulated solar light. The metal modified samples displayed higher specific surface areas (3-6 times) and improved photocatalytic properties, the W:V:TiO2@Pt material showing better conversion efficiency of CH3OH to CH2O than the reference Degussa P25 sample (1.54 versus 0.90%).

In the last decade orthorhombic hafnia and zirconia films have attracted tremendous attention arising from the discovery of ferroelectricity at the nanoscale. However, an initial wake-up pre-cycling is usually needed to achieve a ferroelectric behaviour in these films. Recently, different strategies, such as microstructure tailoring, defect, bulk and interface engineering, doping, NH3 plasma treatment and epitaxial growth, have been employed to obtain wake-up free orthorhombic ferroelectric hafnia and zirconia films. In this work we review recent developments in obtaining polar hafnia and zirconia-based thin films without the need of any wake-up cycling. In particular, we discuss the rhombohedral phase of hafnia/ zirconia, which under a constrained environment exhibits wake-up-free ferroelectric behaviour. This phase could have a strong impact on the current investigations of ferroelectric binary oxide materials and pave the way toward exploiting ferroelectric behaviour for next-generation memory and logic gate applications. Crown Copyright (c) 2022 Published by Elsevier Ltd. All rights reserved.

Titanium dioxide nanoparticles (TiO2 NPs) are found in several products on the market that include paints, smart textiles, cosmetics and food products. Besides these, TiO2 NPs are intensively researched for their use in biomedicine, agriculture or installations to produce energy. Taking into account that several risks have been associated with the use of TiO2 NPs, our aim was to provide TiO2 NPs with improved qualities and lower toxicity to humans and the environment. Pure TiO2 P25 NPs and the same NPs co-doped with iron (1%) and nitrogen atoms (P25-Fe(1%)-N NPs) by hydrothermal treatment to increase the photocatalytic activity in the visible light spectrum were in vitro evaluated in the presence of human lung cells. After 24 and 72 h of incubation, the oxidative stress was initiated in a time- and dose-dependent manner with major differences between pure P25 and P25-Fe(1%)-N NPs as revealed by malondialdehyde and reactive oxygen species levels. Additionally, a lower dynamic of autophagic vacuoles formation was observed in cells exposed to Fe-N-doped P25 NPs compared to the pure ones. Therefore, our results suggest that Fe-N doping of TiO2 NPs can represent a valuable alternative to the conventional P25 Degussa particles in industrial and medical applications.

The role of Ag addition on the structural, dielectric, and mechanical harvesting response of 20%(xAg - (1 - x)BaTiO3) - 80%PVDF (x = 0, 2, 5, 7 and 27 vol.%) flexible composites is investigated. The inorganic fillers were realized by precipitating fine (similar to 3 nm) silver nanoparticles onto BaTiO3 nanoparticles (similar to 60 nm average size). The hybrid admixtures with a total filling factor of 20 vol.% were embedded into the PVDF matrix. The presence of filler enhances the amount of beta-PVDF polar phase and the BaTiO3 filler induces an increase of the permittivity from 11 to 18 (1 kHz) in the flexible composites. The addition of increasing amounts of Ag is further beneficial for permittivity increase; with the maximum amount (x = 27 vol.%), permittivity is three times larger than in pure PVDF (epsilon(r) similar to 33 at 1 kHz) with a similar level of tangent losses. This result is due to the local field enhancement in the regions close to the filler-PVDF interfaces which are additionally intensified by the presence of silver nanoparticles. The metallic addition is also beneficial for the mechanical harvesting ability of such composites: the amplitude of the maximum piezoelectric-triboelectric combined output collected in open circuit conditions increases from 0.2 V/cm(2) (PVDF) to 30 V/cm(2) for x = 27 vol.% Ag in a capacitive configuration. The role of ferroelectric and metallic nanoparticles on the increasing mechanical-electric conversion response is also been explained.

Owing to its unique biological and physicochemical properties, hydroxyapatite (HAp) represents one of the most extensively studied biomaterials for biomedical applications. It is well known that Candida is currently one of the fungi frequently involved in the onset and development of post-implant infections and, owing to the appearance of antifungal resistance, it is quite difficult to treat despite all the tremendous efforts made in this regard by the scientific world. Therefore, in this context, we report for the first time in this paper, the development and characterization of europium-doped thin films (5EuHAp, x(Eu) = 0.05) on a Si substrate by a spin-coating method. The results of ultrasound (US), zeta (zeta) potential, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR) studies are presented. The XRD studies conducted on 5EuHAp suspension revealed the nanometric dimensions of the particles and sample purity. In addition, a moderate stability of the 5EuHAp suspension was observed. XPS measurements revealed the presence of Eu 3d in the 5EuHAp thin films. In the SEM micrographs, the surface uniformity and the absence of the surface defects could be observed. Moreover, the results of the FTIR studies showed the presence of the vibrational bands specific to the HAp structure in the studied sample. The antifungal activity of the HAp and 5EuHAp suspensions and coatings was evaluated using the Candida albicans ATCC 10231 (C. albicans) fungal strain. The qualitative assays of the antifungal properties of HAp and 5EuHAp coatings were also visualized by SEM and CLSM. The antifungal studies revealed that both 5EuHAp suspensions and coatings exhibited noticeable antifungal activity against C. albicans cells.

Phosphate and tellurite glasses can be used in optics, optoelectronics, magneto-optics, and nuclear and medical fields. Two series of phosphate-tellurite glasses, (50-x)ZnO-10Al(2)O(3)-40P(2)O(5)-xTeO(2) and (40-x)Li2O-10Al(2)O(3)-5TiO(2)-45P(2)O(5)-xTeO(2) (x = 5, 10), were synthesized by a non-conventional wet-route, and the mechanical properties as key performance measures for their application in optoelectronics were investigated. X-ray Diffraction (XRD) measurements revealed the vitreous nature of the investigated materials. Instrumented indentation tests allowed the calculation of hardness (H) and Young's modulus (E) using the Oliver and Pharr model. The influence of increasing the TeO2 content, as well as the substitution of ZnO by Li2O-TiO2, on the variation of hardness, Young's modulus, penetration depth (PD), and fracture toughness (FT) was evaluated in both series. As a general trend, there is a decrease in the hardness and Young's modulus with increasing penetration depth. The addition of Li2O and TiO2 instead of ZnO leads to improved hardness and elastic modulus values. Regarding the H/E ratio, it was found that the samples with lower TeO2 content should be significantly more crack-resistant compared to the higher TeO2 content samples. The H-3/E-2 ratio, being lower than 0.01, revealed a poor resistance of these glasses to plastic deformation. At the same time, a decrease of the fracture toughness with increasing TeO2 content was noticed for each glass series. Based on dilatometry measurements, the thermal expansion coefficient as well as the characteristic temperatures of the glasses were measured. Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray analysis (FESEM-EDX) revealed a uniform distribution of the elements in the bulk samples. The mechanical properties of these vitreous materials are important in relation to their application as magneto-optical Faraday rotators in laser cavities.