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Here, we report the electrochemical deposition of lead (Pb) as a model metal on epitaxial graphene fabricated on silicon carbide (Gr/SiC). The kinetics of electrodeposition and morphological characteristics of the deposits were evaluated by complementary electrochemical, physical and computational methods. The use of Gr/SiC as an electrode allowed the tracking of lead-associated redox conversions. The analysis of current transients passed during the deposition revealed an instantaneous nucleation mechanism controlled by convergent mass transport on the nuclei locally randomly distributed on epitaxial graphene. This key observation of the deposit topology was confirmed by low values of the experimentally-estimated apparent diffusion coefficient, Raman spectroscopy and scanning electron microscopy (SEM) studies. First principles calculations showed that the nucleation of Pb clusters on the graphene surface leads to weakening of the interaction strength of the metal-graphene complex, and only spatially separated Pb adatoms adsorbed on bridge and/or edge-plane sites can affect the vibrational properties of graphene. We expect that the lead adatoms can merge in large metallic clusters only at defect sites that reinforce the metal-graphene interactions. Our findings provide valuable insights into both heavy metal ion electrochemical analysis and metal electroplating on graphene interfaces that are important for designing effective detectors of toxic heavy metals. Funding Agencies|VR grant [621-2014-5805]; SSF [SSF GMT14-0077, SSF RMA15-0024]; Angpanneforeningens Forskningsstiftelse [16-541]

Nickel oxide thin films were deposited by a simple and low-cost spray pyrolysis technique using three different precursors: nickel nitrate, nickel chloride, and nickel acetate on corning glass substrates. X-ray diffraction show that the NiO films are polycrystalline and have a cubic crystal structure, although predominantly with a preferred 111-orientation in the growth direction and a random in-plane orientation. The deconvolution of the Ni 2p and O 1s core level X-ray photoelectron-spectra of nickel oxides produced by using different precursors indicates a shift of the binding energies. The sprayed NiO deposited from nickel nitrate has an optical transmittance in the range of 60-65% in the visible region. The optical band gap energies of the sprayed NiO films deposited from nickel nitrate, nickel chloride and nickel acetate are 3.5, 3.2 and 3.43 eV respectively. Also, the extinction coefficient and refractive index of NiO films have been calculated from transmittance and reflectance measurements. The average value of refractive index for sprayed films by nickel nitrate, nickel chloride and nickel acetate are 2.1, 1.6 and 1.85 respectively. It is revealed that the band gap and refractive index of NiO films by using nickel nitrate corresponds to the commonly reported values. We attribute the observed behavior in the optical band gap and optical constants as due to the change of the Ni/O ratio. Funding Agencies|Swedish Research Council [VR 348-2013-6782]; Egyptian Ministry for Higher Education and Scientific Research; Angpanneforeningens Forskningsstiftelse [14-517]; Swedish Research Council (VR) Marie Sklodowska Curie International Career "GREEN 2D FOX" [2015-00679]

In this work, surface functionalization of epitaxial graphene grown on silicon carbide was performed by ion irradiation to investigate their gas sensing capabilities. Swift heavy ion irradiation using 100 MeV silver ions at four varying fluences was implemented on epitaxial graphene to investigate morphological and structural changes and their effects on the gas sensing capabilities of graphene. Sensing devices are expected as one of the first electronic applications using graphene and most of them use functionalized surfaces to tailor a certain function. In our case, we have studied irradiation as a tool to achieve functionalization. Morphological and structural changes on epitaxial graphene layers were investigated by atomic force microscopy, Raman spectroscopy, Raman mapping and reflectance mapping. The surface morphology of irradiated graphene layers showed graphene folding, hillocks, and formation of wrinkles at highest fluence (2 x 10(13) ions/cm(2)). Raman spectra analysis shows that the graphene defect density is increased with increasing fluence, while Raman mapping and reflectance mapping show that there is also a reduction of monolayer graphene coverage. The samples were investigated for ammonia and nitrogen dioxide gas sensing applications. Sensors fabricated on pristine and irradiated samples showed highest gas sensing response at an optimal fluence. Our work provides new pathways for introducing defects in controlled manner in epitaxial graphene, which can be used not only for gas sensing application but also for other applications, such as electrochemical, biosensing, magnetosensing and spintronic applications. (C) 2017 Elsevier B.V. All rights reserved. Funding Agencies|Graphene Flagship [CNECT-ICT-604391]; Swedish Research Council [2015-05876]

Tuning the emission energy of graphene quantum dots (GQDs) and understanding the reason of tunability is essential for the GOD function in optoelectronic devices. Besides material-based challenges, the way to realize chemical doping and band gap tuning also pose a serious challenge. In this study, we tuned the emission energy of GQDs by substitutional doping using chlorine, nitrogen, boron, sodium, and potassium dopants in solution form. Photoluminescence data obtained from (Cl- and N-doped) GQDs and (B-, Na-, and K-doped) GQDs, respectively exhibited red- and blue-shift with respect to the photoluminescence of the undoped GQDs. X-ray photoemission spectroscopy (XPS) revealed that oxygen functional groups were attached to GQDs. We qualitatively correlate red-shift of the photoluminescence with the oxygen functional groups using literature references which demonstrates that more oxygen containing groups leads to the formation of more defect states and is the reason of observed red-shift of luminescence in GQDs. Further on, time resolved photoluminescence measurements of Cl- and N-GQDs demonstrated that Cl substitution in GQDs has effective role in radiative transition whereas in N-GQDs leads to photoluminescence (PL) quenching with non-radiative transition to ground state. Presumably oxidation or reduction processes cause a change of effective size and the bandgap. Funding Agencies|Higher Education Commission Pakistan (HEC) under NRPU [2913/RD]; Graphene Flagship [CNECT-ICT-604391]; Angpanneforeningen Research Foundation; Swedish Research Council [2015-05876]; Rositsa Yakimova