Ferromagnetism in Co-doped ZnO films grown by molecular beam epitaxy: magnetic, electrical and microstructural studies

We studied structural, optical and magnetic properties of high-quality 5 and 15% Co-doped ZnO films grown by plasma-assisted molecular beam epitaxy (MBE) on (0001)-sapphire substrates. Magnetic force microscopy (MFM) and magnetic measurements with SQUID magnetometer show clear ferromagnetic behavior of the films up to room temperature whereas they are antiferromagnetic below 200 K approximately. Temperature dependence of the carrier mobility was determined using Raman line shape analysis of the longitudinal-optical-phonon-plasmon coupled modes. It shows that the microscopic mechanism for ferromagnetic ordering is coupling mediated by free electrons between spins of Co atoms. These results bring insight into a subtle interplay between charge carriers and magnetism in MBE-grown Zn(1-x)CoxO films.Comment: 10 pages, 9 figures, 2 table

Non stoichiometry effect and disorder in Cu2ZnSnS4 thin films obtained by flash evaporation Raman scattering investigation

The cation disorder in Cu2ZnSnS4 thin films grown by flash evaporation of ZnS, CuS and SnS binary compounds has been studied by Raman spectroscopy. Process parameters such as the substrate temperature during the evaporation and the Ar pressure in the post-thermal treatment determined the samples' composition and Raman spectra. As a measure of cation disorder, the half-width and relative intensity of the Raman band peaking at 331-332 cm-1 is analysed. Comparison of the spectra for different samples of known composition showed that the relative intensity of the 331 cm-1 defect peak correlates with the previously reported theoretical prediction about enhancement of antisite defect formation in Cu2ZnSnS4 under "Cu-poor, Zn-rich" conditions. For "Cu-rich, Zn-poor" films, further experimental confirmation was obtained of the previously detected effect of the enhancement of cation disorder under intense optical excitationThis research is supported by the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Program FP7/2007-2013/ under REA grant greement 269167 (PVICOKEST), the Spanish MINECO project (KEST- PV, ENE2010-21541-C03) and the OPTEC grant. RC acknowledges financial support from Spanish MINECO within the program Ramon y Cajal (RYC-2011-08521

Development of a high-resolution spatial inventory of greenhouse gas emissions for Poland from stationary and mobile sources

Greenhouse gas (GHG) inventories at national or provincial levels include the total emissions as well as the emissions for many categories of human activity, but there is a need for spatially explicit GHG emission inventories. Hence, the aim of this research was to outline a methodology for producing a high-resolution spatially explicit emission inventory, demonstrated for Poland. GHG emission sources were classified into point, line, and area types and then combined to calculate the total emissions. We created vector maps of all sources for all categories of economic activity covered by the IPCC guidelines, using official information about companies, the administrative maps, Corine Land Cover, and other available data. We created the algorithms for the disaggregation of these data to the level of elementary objects such as emission sources. The algorithms used depend on the categories of economic activity under investigation. We calculated the emissions of carbon, nitrogen sulfure and other GHG compounds (e.g., CO2, CH4, N2O, SO2, NMVOC) as well as total emissions in the CO2-equivalent. Gridded data were only created in the final stage to present the summarized emissions of very diverse sources from all categories. In our approach, information on the administrative assignment of corresponding emission sources is retained, which makes it possible to aggregate the final results to different administrative levels including municipalities, which is not possible using a traditional gridded emission approach. We demonstrate that any grid size can be chosen to match the aim of the spatial inventory, but not less than 100 m in this example, which corresponds to the coarsest resolution of the input datasets. We then considered the uncertainties in the statistical data, the calorific values, and the emission factors, with symmetric and asymmetric (lognormal) distributions. Using the Monte Carlo method, uncertainties, expressed using 95% confidence intervals, were estimated for high point-type emission sources, the provinces, and the subsectors. Such an approach is flexible, provided the data are available, and can be applied to other countries

Towards the growth of Cu2ZnSn1 xGexS4 thin films by a single stage process Effect of substrate temperature and composition

Cu2ZnSn1-xGexS4 (CZTGS) thin films prepared by flash evaporation of a Zn-rich Cu2ZnSn0.5Ge0.5S4 bulk compound in powder form, and a subsequent thermal annealing in S containing Ar atmosphere are studied. The effect of the substrate temperature during evaporation and the initial composition of the precursor powder on the growth mechanism and properties of the final CZTGS thin film are investigated. The microstructure of the films and elemental depth profiles depend strongly on the growth conditions used. Incorporation of Ge into the Cu2ZnSnS4 lattice is demonstrated by the shift of the relevant X-ray diffraction peaks and Raman vibrational modes towards higher diffraction angles and frequencies respectively. A Raman mode at around 348-351 cm-1 is identified as characteristic of CZTGS alloys for x = [Ge]/([Sn]+[Ge]) = 0.14-0.30. The supply of Ge enables the reduction of the Sn loss via a saccrifical Ge loss. This fact allows increasing the substrate temperature up to 350º C during the evaporation, forming a high quality kesterite material and therefore, reducing the deposition process to one single stageRC acknowledges financial support from Spanish MINECO within the Ramón y Cajal programme (RYC-2011-08521) and VIR for the Juan de la Cierva fellowship (JCI-2011-10782). GB also acknowledges the CSIC-JAE pre-doctoral program, co-funded by the European Social Fund. This work was supported by the Marie Curie-IRSES project (PVICOKEST, GA: 269167), Marie Curie-ITN project (KESTCELL, GA: 316488), DAAD project (INTERKEST, Ref: 57050358), and MINECO projects (SUNBEAM, ENE2013-49136-C4-3-R) (TEC2012-38901-C02-01). A. Scheu is acknowledged for GDOES measurement

Towards the growth of Cu2ZnSn1-xGexS4 thin films by a single-stage process: Effect of substrate temperature and composition

Cu2ZnSn1-xGexS4 (CZTGS) thin films prepared by flash evaporation of a Zn-rich Cu2ZnSn0.5Ge0.5S4 bulk compound in powder form, and a subsequent thermal annealing in S containing Ar atmosphere are studied. The effect of the substrate temperature during evaporation and the initial composition of the precursor powder on the growth mechanism and properties of the final CZTGS thin film are investigated. The microstructure of the films and elemental depth profiles depend strongly on the growth conditions used. Incorporation of Ge into the Cu2ZnSnS4 lattice is demonstrated by the shift of the relevant X-ray diffraction peaks and Raman vibrational modes towards higher diffraction angles and frequencies respectively. A Raman mode at around 348-351 cm-1 is identified as characteristic of CZTGS alloys for x = [Ge]/([Sn]+[Ge]) = 0.14-0.30. The supply of Ge enables the reduction of the Sn loss via a saccrifical Ge loss. This fact allows increasing the substrate temperature up to 350º C during the evaporation, forming a high quality kesterite material and therefore, reducing the deposition process to one single stageRC acknowledges financial support from Spanish MINECO within the Ramón y Cajal programme (RYC-2011-08521) and VIR for the Juan de la Cierva fellowship (JCI-2011-10782). GB also acknowledges the CSIC-JAE pre-doctoral program, co-funded by the European Social Fund. This work was supported by the Marie Curie-IRSES project (PVICOKEST, GA: 269167), Marie Curie-ITN project (KESTCELL, GA: 316488), DAAD project (INTERKEST, Ref: 57050358), and MINECO projects (SUNBEAM, ENE2013-49136-C4-3-R) (TEC2012-38901-C02-01). A. Scheu is acknowledged for GDOES measurement

Towards the growth of Cu2ZnSn1-xGexS4 thin films by a single-stage process : effect of substrate temperatura and composition

Cu2ZnSn1-xGexS4 (CZTGS) thin films prepared by flash evaporation of a Zn-rich Cu2ZnSn0.5Ge0.5S4 bulk compound in powder form, and a subsequent thermal annealing in S containing Ar atmosphere are studied. The effect of the substrate temperature during evaporation and the initial composition of the precursor powder on the growth mechanism and properties of the final CZTGS thin film are investigated. The microstructure of the films and elemental depth profiles depend strongly on the growth conditions used. Incorporation of Ge into the Cu2ZnSnS4 lattice is demonstrated by the shift of the relevant X-ray diffraction peaks and Raman vibrational modes towards higher diffraction angles and frequencies respectively. A Raman mode at around 348-351 cm-1 is identified as characteristic of CZTGS alloys for x = [Ge]/([Sn]+[Ge]) = 0.14-0.30. The supply of Ge enables the reduction of the Sn loss via a saccrifical Ge loss. This fact allows increasing the substrate temperature up to 350º C during the evaporation, forming a high quality kesterite material and therefore, reducing the deposition process to one single stag

Fermi Resonance in Phonon Spectra of Quaternary Chalcohenides of the type Cu2ZnGeS4

The experimental resonant and non-resonant Raman scattering spectra of the kesterite structural modification of Cu2ZnGeS4 single crystals are reported. The results are compared with those calculated theoretically within the density functional perturbation theory. For the majority of lines a good agreement (within 2–5 cm−1) is established between experimental and calculated mode frequencies. However, several dominant spectral lines, in particular the two intense fully symmetric modes, are found to deviate from the calculated values by as much as 20 cm−1. A possible reason for this discrepancy is found to be associated with the Fermi resonant interaction between one and two-phonon vibrational excitations. The modelling of spectra, which takes into account the symmetry of interacting states, allows a qualitative description of the observed experimental findings. Due to the similarity of the vibrational spectra of Cu2A II B IV S4 (A  =  Zn, Mn, Cd; B  =  Sn, Ge, Si) chalcogenides, Fermi resonance is argued to be a general phenomenon for this class of compounds

Nanostructured Silver Substrates With Stable and Universal SERS Properties: Application to Organic Molecules and Semiconductor Nanoparticles

Nanostructured silver films have been prepared by thermal deposition on silicon, and their properties as SERS substrates investigated. The optimal conditions of the post-growth annealing of the substrates were established. Atomic force microscopy study revealed that the silver films with relatively dense and homogeneous arrays of 60–80-nm high pyramidal nanoislands are the most efficient for SERS of both organic dye and inorganic nanoparticles analytes. The noticeable enhancement of the Raman signal from colloidal nanoparticles with the help of silver island films is reported for the first time