National Institute Of Materials Physics - Romania

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.

In this work, new information concerning the optical properties of black phosphorus (BP) sheets chemically/electrochemically functionalized with diphenyl amine (DPA) and its macromolecular compound (poly(diphenylamine) (PDPA)) in the absence/presence of phosphotungstic acid (PTA) is reported. Raman scattering and FTIR spectroscopy studies indicate that the interaction of BP with PTA leads to the elimination of the PxOy layer onto the surface of the BP sheets. In the case of the chemical interaction of BP with DPA, the reaction product corresponds to DPA chemically functionalized BP sheets having an imino-phosphorane (IP) structure. The electrochemical oxidation of BP sheets chemically functionalized with DPA in the presence of PTA leads to an increase in the weight of P-N bonds as a consequence of the generation of PDPA doped with the PTA heteropolyanions, as shown by FTIR spectroscopy and Raman scattering. This process is evidenced by a shift of the Raman line from 362 cm(-1) to 378 cm(-1), assigned to the A(1g) mode. This change was explained by taking into account the compression of the layers containing P atoms, which is induced by PDPA macromolecular chains. The decrease in the intensity of the PL spectra of DPA as well as PDPA, in the presence of BP, indicates that BP acts as a PL quenching agent for these compounds. A preferential orientation of the PDPA doped with the PTA heteropolyanions on the surface of BP sheets is highlighted by the variation of the binding angle of the PDPA on the surface of BP sheets from 44.7 degrees to 39.9 degrees.

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.

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.

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.

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.

Carbon quantum dots (CQDs) derived from biomass, a suggested green approach for nanomaterial synthesis, often possess poor optical properties and have low photoluminescence quantum yield (PLQY). This study employed an environmentally friendly, cost-effective, continuous hydrothermal flow synthesis (CHFS) process to synthesise efficient nitrogen-doped carbon quantum dots (N-CQDs) from biomass precursors (glucose in the presence of ammonia). The concentrations of ammonia, as nitrogen dopant precursor, were varied to optimise the optical properties of CQDs. Optimised N-CQDs showed significant enhancement in fluorescence emission properties with a PLQY of 9.6% compared to pure glucose derived-CQDs (g-CQDs) without nitrogen doping which have PLQY of less than 1%. With stability over a pH range of pH 2 to pH 11, the N-CQDs showed excellent sensitivity as a nano-sensor for the highly toxic highly-pollutant chromium (VI), where efficient photoluminescence (PL) quenching was observed. The optimised nitrogen-doping process demonstrated effective and efficient tuning of the overall electronic structure of the N-CQDs resulting in enhanced optical properties and performance as a nano-sensor.

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.

The ability of TiO2 to generate reactive oxygen species under UV radiation makes it an efficient candidate in antimicrobial studies. In this context, the preparation of TiO2 microparticles coated with Ca- and Cu-based composite layers over which Cu(II), Cu(I), and Cu(0) species were identified is presented here. The obtained materials were characterized by a wide range of analytical methods, such as X-ray diffraction, electron microscopy (TEM, SEM), X-ray photoelectron (XPS), and UV-VIS spectroscopy. The antimicrobial efficiency was evaluated using qualitative and quantitative standard methods and standard clinical microbial strains. A significant aspect of this composite is that the antimicrobial properties were evidenced both in the presence and absence of the light, as result of competition between photo and electrical effects. However, the antibacterial effect was similar in darkness and light for all samples. Because no photocatalytic properties were found in the absence of copper, the results sustain the antibacterial effect of the electric field (generated by the electrostatic potential of the composite layer) both under the dark and in light conditions. In this way, the composite layers supported on the TiO2 microparticles' surface can offer continuous antibacterial protection and do not require the presence of a permanent light source for activation. However, the antimicrobial effect in the dark is more significant and is considered to be the result of the electric field effect generated on the composite layer.