National Institute Of Materials Physics - Romania

Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10-4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.

Novel (1-x) SrFe12O19 - x BNT-BT0.08 (x = 0; 0.5; 0.8; 1) nanocomposites were explored in this study. The samples were produced by sol-gel method and compacted by conventional sintering. The composition, morphology, local structure, dielectric and magnetic properties were investigated by X-ray diffraction, Transmission Electron Microscopy, Impedance Analysis, Mossbauer spectroscopy, and SQUID magnetometry. The desired composition and the presence of the magnetoplumbite SrFe12O19 and perovskite BNT-BT structures were verified by X-ray diffraction. Irregular morphology and large size distributions are evidenced in the electron microscopy micrographs. The reported room temperature dielectric constants in this study are the highest values obtained in multiferroic composites at room temperature: giant dielectric constants (similar to 1.3 x 10(6)) were obtained, relative to 0.13 x 10(4) in BNT-BT. The hyperfine parameters allowed the identification of the Wyckoff positions of the Fe ions corresponding closely to the theoretical case. The hard magnetic character of the SrFe12O19 phase is evidenced from the magnetic measurements. For the first time in multifermic composites, superdielectric characteristics are evidenced at room temperature.

The paper aims to identify the CO2 interaction mechanism for chemical sensors based on Gd-doped SnO2, SnO2 and Gd2O3 powders deposited as thick sensitive layers. The low reactivity of CO2 conferred by the thermodynamic stability and chemical inertia can be offset by the presence of relative humidity. The sensitive powders were prepared by wet chemical co-precipitation method. The Gd concentration was varied from 1% to 20 at% in order to determine the limit for Gd integration as a doping ion prior to chemical segregation as a secondary phase. Analytical transmission electron microscopy points to a homogeneous Gd doping of the nanostructured SnO2 powders for low doping concentrations and the formation of a nanocomposite based on SnO2 as main phase and cubic Gd2O3 as secondary phase for the highly doped samples. The electrical resistance is either influenced by the density of oxygen vacancies, or is the result of compensation for two opposite behaviours into the SnO2- Gd2O3 nanocomposite structures. The CO2 exposure to humid atmosphere determines distinct behaviours cor-responding to SnO2 and Gd2O3 as constitutive elements. The associated CO2 interaction mechanism is based on simultaneous DC electrical resistance and Contact Potential Difference measurements, which allow decoupling the ionosorption from the dipolar processes, thus highlighting specific chemical interactions on the SnO2 and Gd2O3 surfaces.

Due to the currently worldwide petrochemical feedstock shortage, the ethylene synthesis from renewable non-oil sources becomes of high interest. The catalysts were prepared in two steps: (i) formation of spheres containing the carbon-coated Mn core by hydrothermal method, (ii) formation of the Si-Zr oxide shell by sol-gel method. The prepared catalysts were characterized by N2 physisorption, SEM-EDX, XRD, XPS, and NH3-TPD. The catalytic results have shown that Fe, Zn or Ni modified Mn core exhibited superior activity compared to the catalysts containing only Mn in the core. With 75% yield and 98% ethanol conversion at 350 degrees C and WHSV of 1.4 h-1, MnNi@SiZr was the best catalyst. These results are due to an increased number of acid sites compared to the other materials and an optimal ratio of weak/medium acid sites. Our findings suggest new lines for developing active and stable catalysts for ethylene synthesis from ethanol.

Undoped and Zn-doped ITO (ITO:Zn) multifunctional thin films were successfully synthesized using the sol-gel and dipping method on three different types of substrates (glass, SiO2/glass, and Si). The effect of Zn doping on the optoelectronic, microstructural, and gas-sensing properties of the films was investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), spectroscopic ellipsometry (SE), Raman spectroscopy, Hall effect measurements (HE), and gas testing. The results showed that the optical constants, the transmission, and the carrier numbers were correlated with the substrate type and with the microstructure and the thickness of the films. The Raman study showed the formation of ITO films and the incorporation of Zn in the doped film (ITO:Zn), which was confirmed by EDX analysis. The potential use of the multifunctional sol-gel ITO and ITO:Zn thin films was proven for TCO applications or gas-sensing experiments toward CO2. The Nyquist plots and equivalent circuit for fitting the experimental data were provided. The best electrical response of the sensor in CO2 atmosphere was found at 150 degrees C, with activation energy of around 0.31 eV.

The high-k-based MOS-like capacitors are a promising approach for the domain of non-volatile memory devices, which currently is limited by SiO2 technology and cannot face the rapid downsizing of the electronic device trend. In this paper, we prepare MOS-like trilayer memory structures based on high-k ZrO2 by magnetron sputtering, with a 5% and a 10% concentrations of Zr in the Zr-ZrO2 floating gate layer. For crystallization of the memory structure, rapid thermal annealing at different temperatures between 500 degrees C and 700 degrees C was performed. Additionally, Al electrodes were deposited in a top-down configuration. High-resolution transmission electron microscopy reveals that ZrO2 has a polycrystalline-columnar crystallization and a tetragonal crystalline structure, which was confirmed by X-ray diffraction measurements. It is shown that the tetragonal phase is stabilized during the crystallization by the fast diffusion of oxygen atoms. The capacitance-voltage characteristics show that the widest memory window (Delta V = 2.23 V) was obtained for samples with 10% Zr annealed at 700 degrees C for 4 min. The charge retention characteristics show a capacitance decrease of 36% after 10 years.

The manipulation of magnetic anisotropy represents the fundamental prerequisite for the application of magnetic materials. Here we present the vectorial magnetic properties of nanostructured systems and thin films of Fe and FeCo prepared on linearly trenched Mo templates with thermally controlled periodicity. The magnetic properties of the nanosystems are engineered by tuning the shape, size, thickness, and composition parameters of the thin films. Thus, we control coercivity, magnetization, orientation of the easy axis of magnetization, and the long-range magnetic order of the system in the function of the temperature. We distinguish magnetic components that emerge from the complex morpho-structural features of the undulating Fe or FeCo nanostructured films on trenched Mo templates: (i) assembly of magnetic nanowires and (ii) assembly of magnetic islands/clusters. Uniaxial anisotropy at room temperature was proven, characterized, and explained in the case of all systems. Our work contributes to the understanding of magnetic properties necessary for possible further applications of linear systems and undulated thin films.

Antiferroelectric random access memory (AFERAM) is one of the newest alternative non-volatile memory technologies to emerge in recent years. ZrO2-based antiferroelectric films are exceptionally well-suited for memory applications with very high cycling endurance (>10(10)) and low operating voltages (< 2 V). Lightly alloying ZrO2 with HfO2 is performed to assess AFERAM device performance with back-end-of-line compatible thin film Zr1-xHfxO2 (x <= 0.13) capacitors. The transition fields associated with antiferroelectric behavior are reduced with more Hf incorporation, yielding a larger magnitude switching polarization and memory window. Cycling endurance beyond 10(10) cycles is conducted on thin film capacitors where wake-up in AFERAM first leads to an increase, then a decrease in the memory window at a cumulative cycle number found to be dependent on the amount of Hf-incorporation. Hf-incorporation into ZrO2 is demonstrated to be a feasible way to improve the memory window in ZrO2-based AFERAM.

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.

Gallium telluride (GaTe) is a van der Waals semiconductor, currently adopted for photonic and optoelectronic devices. However, the rapid degradation of GaTe in air, promoted by Te vacancies, is detrimental for device applications. Here, it is demonstrate that the surface oxidation of GaTe can be unexpectedly exploited for expanding the breadth of applications of GaTe. Specifically, the formation of a nanoscale sub-stoichiometric wide-band-gap Ga2O3 skin, promoted by Te vacancies, over narrow-band-gap GaTex upon air exposure is beneficial for electrocatalysis, photocatalysis, and gas sensing . In particular, the Heyrovsky step (H-ads + H+ + e(-) -> H-2) of hydrogen evolution reaction in an acidic medium is barrier-free for the sub-stoichiometric gallium-oxide/gallium-telluride heterostructure, which also enables a significant reduction of costs with respect to state-of-the-art Pt/C electrodes. In the photocatalytic process, the photo-generated electrons migrate from GaTe to Ga2Ox skin, which acts as the chemically active side of the interface. Moreover, the Ga2O3/GaTe heterostructure is a suitable platform for sensing of H2O, NH3, and NO2 at operational temperatures extended up to 600 degrees C (useful for gas detection in combustion processes), mainly due to the increased area of charge redistribution after adsorption achieved upon oxidation of GaTe.