Permanent photodoping of plasmonic gallium-ZnO nanocrystals

This work was supported by the Latvian Council of Science in the framework of FLPP (Plasmonic oxide quantum dots for energy saving smart windows, lzp-2018/1-0187). Tanel Käämbre acknowledges financial support for the XPS instrumentation maintenance from the Estonian Centre of Excellence in Research project “Advanced materials and high- technology devices for sustainable energetics, sensorics and nanoelectronics” (TK141).Donor dopants in oxide semiconductors are compensated not only by valuable electrons but also by other point defects, leading to a decrease in electric conductivity and infrared absorption. We demonstrate that the electron compensation mechanism in Ga doped ZnO nanocrystals can be promoted by photodoping. Unexpectedly, the electrons from photodoping are stable in the open air for months.Latvian Council of Science lzp-2018/1-0187; Estonian Centre of Excellence in Research TK141; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Facile synthesis of magnetically separable CoFe2O4/Ag2O/Ag2CO3 nanoheterostructures with high photocatalytic performance under visible light and enhanced stability against photodegradation

Riga Technical University supported the preparation of this manuscript from the Scientific Research Project Competition for Young Researchers No. ZP-2016/7. The authors wish to kindly acknowledge the financial support of HZB, Estonian Research Council (PUT1096, PUT735 and IUT2-25) and Estonian Centre of Excellence in Research Project “Advanced materials and high-technology devices for sustain-able energetics, sensorics and nanoelectronics” TK141 (2014–2020.4.01.15-0011).We have developed magnetically separable and reasonably stable visible light active photocatalysts containing CoFe2O4 and mixture of Ag2O/Ag2CO3 nanoheterostructures. Obtained ternary nanoheterostructures outperform previously reported magnetically separable visible light photocatalysts, showing one of the highest visible light photocatalytic dye degradation activities in water by a magnetically separable photocatalyst. Photocatalytically active part is Ag2O/Ag2CO3 whereas the CoFe2O4 mainly has stabilizing and magnetic separation functions. The Ag2CO3 phase junction on Ag2O nanoparticle surface were obtained by straightforward phase transformation from silver oxide to silver carbonate in air due to ambient CO2. The phase transformation was followed using X-ray diffraction (XRD), and hard X-ray photoelectron spectroscopy (HAXPES) measurements.Riga Technical University No. ZP-2016/7; Estonian Research Council (PUT1096, PUT735 and IUT2-25); Estonian Centre of Excellence in Research TK141 (2014–2020.4.01.15-0011); Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Atomic layer deposited nanolaminates of zirconium oxide and manganese oxide from manganese(III)acetylacetonate and ozone

Producción CientíficaAtomic layer deposition method was used to grow thin films consisting of ZrO2 and MnOx layers. All depositions were carried out at 300 ºC. Some deposition characteristics of the manganese(III)acetylacetonate and ozone process were investigated, such as crystallinity and the dependence of growth rate on the deposition temperature. All films were partly crystalline in their as-deposited state. Zirconium oxide contained cubic and tetragonal phases of ZrO2, while the manganese oxide was shown to consist of cubic Mn2O3 and tetragonal Mn3O4 phases. All the films exhibited nonlinear saturative magnetization with hysteresis, as well as resistive switching characteristics.Fondo Europeo de Desarrollo Regional (projects TK134 and TK141)Ministerio de Economía, Industria y Competitividad (project TEC2017-84321-C4-2-R)Estonian Research Agency (projects PRG4 and PRG753

Identification of Active Sites for Oxygen Reduction Reaction on Nitrogen- and Sulfur-Codoped Carbon Catalysts

This research was financially supported by ERA.Net RUS Plus funding mechanism (Project HeDoCat) and by the European Regional Development Fund project TK134.Nitrogen- and sulfur-codoped carbon catalysts were prepared as electrocatalytic materials for the oxygen reduction reaction (ORR). Herein, we propose a novel and effective one-pot synthetic approach to prepare a NS-doped carbon catalyst by using the mixture of graphene oxide and multi-walled carbon nanotubes as a carbon support. Successful NS-doping of carbon and formation of the catalytically active sites were confirmed by X-ray photoelectron spectroscopy and with energy dispersion spectroscopy. The ORR activity of NS-codoped carbon was investigated by using a rotating disc electrode method. The NS-doped carbon shows superior ORR performance in alkaline media, and the electrocatalytic mechanism for the reduction of oxygen was well explained by density functional theory calculations of graphene sheets.ERA.Net RUS Plus Project HeDoCat; ERDF TK134; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Resonant Soft X-ray Spectroscopic Studies of C60 and Related Materials

This thesis addresses the electronic structure of molecular and correlated solids using resonant inelastic soft X-ray scattering (RIXS), non-resonant X-ray emission, photoemissionand X-ray absorption spectroscopies. The use of monochromatised synchrotron radiation and improved energy resolution for X-ray emission have made it possible to elucidate the normal state transport properties and to get further insight into the electron-vibration coupling in fullerenes and the related compounds. The latter is particularly important in order to understand the physical mechanism of superconductivity in fullerene materials. The characteristic intermolecular charge transfer times in K3C60 are found to be longer than the X-ray scattering time-scale (a few femtoseconds). The slow intermolecular charge transport emphasizes that the reduced fullerene compounds can not be treated as simple metals, but rather as systems with strong electron correlation. The electron structure and the bonding character of the more covalent transition metal (V, Ti, Nb) fullerides have been addressed. Evidence indicating the existence of chemical bond between the metal atom(s) and C60 is presented, and the nature of the bond is discussed by comparing RIXS spectroscopic measurements and theoretical predictions. The (crystal) momentum conservation is discussed by comparing the spectroscopic data of a quasi-1D (carbon nanotubes) and quasi-2D (graphite) systems. Finally, the intra-atomic electron-electron correlation is discussed in the case of double core-hole state photo-excitation and de-excitation processes. RIXS including intermediate states with two core vacancies has been observed for the first time in the soft X-ray region

Synthesis of P-Type and N-Type Nickel Ferrites and Associated Electrical Properties

We used sol-gel auto combustion to synthesize nickel ferrites of p-type and n-type conductivity by controlling the relative amounts of nickel and iron during synthesis. The obtained samples have been characterized by XRD, FE-SEM, electrical measurements and XPS. We observe huge differences in the effect of grain size on the electrical resistivity between the p-type and the n-type material when the grain size increases from nano to micro scale during annealing at temperatures from 900 oC to 1300 oC. The observed resistivity decrease (due to grain size) is four orders of magnitude in the the n-type nickel ferrite, whereas the p-type material remains virtually unaffected. We rationalize this drastic difference to stem from a reverse contrast of the surface (grain shell) versus bulk (grain core) conductivity between p- and n-type ferrite. With the grain shells in p-type the easier charge carrier path the effect of scatter at grain boundaries is accordingly diminished, whereas in the n-type charge transport properties are controlled by (the number of) grain boundaries in a conduction path

Resonant inelastic X-ray scattering at the K edge of oxygen and fluorine in insulators

Here we present the results of a study of the electronic structure using the resonant inelastic scattering process at the F 1s photoabsorption edge in LiF and O 1s edge of MgO crystals. In case of excitations in the sub-threshold region, the Raman-type linear dispersion of X-ray fluorescence peak was observed for the studied compounds. In LiF, the narrowing of the X-ray fluorescence peak is observed at pre-threshold excitation, which can be related to the creation of a core exciton, but no core excitons were identified in MgO

The electronic structure of ionic liquids based on the TFSI anion : A gas phase UPS and DFT study

The valence bands of [EMIM][TFSI], [DEME][TFSI] and [PYR1,4][TFSI] gas-phase ion pairs have been investigated using ultraviolet photoelectron spectroscopy (UPS). The photoelectron spectra are interpreted by using several density functional and ab initio calculation methods. Although the experimental vapor phase spectra are similar, the different calculation methods make different predictions about the HOMO molecular state of the ion-pairs of the ionic liquids. The HOMO state of the [DEME][TFSI] ion-pair is due to the TFSI anion, while in [EMIM][TFSI] it is due to the EMIM cation. However, it is difficult to make conclusive assignments for the [PYR1,4][TFSI] ionic liquid. All calculation methods predict the LUMO to be of cationic origin in all the studied ion-pairs

Visible light to switch-on desorption from goethite

Switching adsorption–desorption by visible light could provide the possibility for a wide range of applications that require controlled release-on-demand. Here, we demonstrate a visible-light controlled desorption behavior in aqueous suspensions for the first time. We observed cationic dye adsorption on amphoteric goethite α-FeOOH in the dark and release during visible light exposure at a pH value slightly over the isoelectric point of goethite. During this process, the dye does not degrade. Desorption is triggered by local heating due to light absorption in narrow band gap goethite, α-FeOOH

Adsorption-induced gap states of h-BN on metal surfaces

The formation of hexagonal boron nitride (h-BN) monolayers on Ni(111), Rh(111), and Pt(111) has been studied by a combination of x-ray emission, angle-resolved valence band photoemission, and x-ray absorption in search for interface-induced gap states of h-BN. A significant density of both occupied and unoccupied gap states with N 2p and B 2p characters is observed for h-BN/Ni(111), somewhat less for h-BN/Rh(111) and still less for h-BN/Pt(111). X-ray emission shows that the h-BN monolayer is chemisorbed strongly on Ni(111) and very weakly on Pt(111). We associate the gap states of h-BN adsorbed on the transition metal surfaces with the orbital mixing and electron sharing at the interface because their density increases with the growing strength of chemisorption