Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates.

Self-assembled monolayers (SAMs) derived of 4-methoxy-terphenyl-3'',5''-dimethanethiol (TPDMT) and 4-methoxyterphenyl-4''-methanethiol (TPMT) have been prepared by chemisorption from solution onto gold thin films and nanoparticles. The SAMs have been characterized by spectroscopic ellipsometry, Raman spectroscopy and atomic force microscopy to determine their optical properties, namely the refractive index and extinction coefficient, in an extended spectral range of 0.75-6.5 eV. From the analysis of the optical data, information on SAMs structural organization has been inferred. Comparison of SAMs generated from the above aromatic thiols to well-known SAMs generated from the alkanethiol dodecanethiol revealed that the former aromatic SAMs are densely packed and highly vertically oriented, with a slightly higher packing density and a absence of molecular inclination in TPMT/Au. The thermal behavior of SAMs has also been monitored using ellipsometry in the temperature range 25-500 degrees C. Gold nanoparticles functionalized by the same aromatic thiols have also been discussed for surface enhanced Raman spectroscopy applications. This study represents a step forward tailoring the optical and thermal behavior of surfaces as well as nanoparticles.

The role of polymer side chains in conferring selectivity to a sensing organic thin-film transistor is investigated. Alkyl-and alkoxy-substituted regioregular polythiophenes are used as active layers, and a set of volatile organic compounds carrying different chemical functionalities are employed as analytes. The responses of both polymer-based transistor and quartz crystal microbalance sensors are evaluated and compared; the sensing mechanisms involving weak interactions between the analyte functionalities and the polymers' side chains are discussed as well.

Ga nanoparticles supported on large band gap semiconductors like SiC, GaN, and ZnO are interesting for plasmon-enhanced UV-emitting solid-state devices. We investigate the influence of the polarity of the SiC, GaN, and ZnO wurtzite semiconductors on the wetting of Ga nanoparticles and on the resulting surface plasmon resonance (SPR) by exploiting real time plasmonic ellipsometry. The interface potential between polar semiconductors (SiC, GaN, and ZnO) and plasmonic nanoparticles (gallium) is shown to influence nanoparticle formation dynamics, geometry, and consequently the SPR wavelength. We invoke the Lippman electrowetting framework to elucidate the mechanisms controlling nanoparticle dynamics and experimentally demonstrate that the charge transfer at the Ga nanoparticle/polar semiconductor interface is an intrinsic method for tailoring the nanoparticle plasmon resonance. Therefore, the present data demonstrate that for supported nanoparticles, surface and interface piezoelectric charge of polar semiconductors also affects SPR along with the well-known effect of the media refractive index.

Metal nanoparticle (NP)-graphene multifunctional platforms are of great interest for exploring strong light-graphene interactions enhanced by plasmons and for improving performance of numerous applications, such as sensing and catalysis. These platforms can also be used to carry out fundamental studies on charge transfer, and the findings can lead to new strategies for doping graphene. There have been a large number of studies on noble metal Au-graphene and Ag-graphene platforms that have shown their potential for a number of applications. These studies have also highlighted some drawbacks that must be overcome to realize high performance. Here we demonstrate the promise of plasmonic gallium (Ga) nanoparticle (NP)-graphene hybrids as a means of modulating the graphene Fermi level, creating tunable localized surface plasmon resonances and, consequently, creating high-performance surface-enhanced Raman scattering (SERS) platforms. Four prominent peculiarities of Ga, differentiating it from the commonly used noble (gold and silver) metals are (1) the ability to create tunable (from the UV to the visible) plasmonic platforms, (2) its chemical stability leading to long-lifetime plasmonic platforms, (3) its ability to n-type dope graphene, and (4) its weak chemical interaction with graphene, which preserves the integrity of the graphene lattice. As a result of these factors, a Ga NP-enhanced graphene Raman intensity effect has been observed. To further elucidate the roles of the electromagnetic enhancement (or plasmonic) mechanism in relation to electron transfer, we compare graphene-on-Ga NP and Ga NP-on-graphene SERS platforms using the cationic dye rhodamine B, a drug model biomolecule, as the analyte.

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Graphene/metal heterojunctions are ubiquitous in graphene-based devices and, therefore, have attracted increasing interest of researchers. Indeed, the literature on the field reports apparently contradictory results about the effect of a metal on graphene doping. Here, we elucidate the effect of metal nanostructuring and oxidation on the metal work function (WF) and, consequently, on the charge transfer and doping of graphene/metal hybrids. We show that nanostructuring and oxidation of metals provide a valid support to frame WF and doping variation in metal/graphene hybrids. Chemical vapour-deposited monolayer graphene has been transferred onto a variety of metal surfaces, including d-metals, such as Ag, Au, and Cu, and sp-metals, such as Al and Ga, configured as thin films or nanoparticle (NP) ensembles of various average sizes. The metal-induced charge transfer and the doping of graphene have been investigated using Kelvin probe force microscopy (KPFM), and corroborated by Raman spectroscopy and plasmonic ellipsometric spectroscopy. We show that when the appropriate WF of the metal is considered, without any assumption, taking into account WF variations by nanostructure and/or oxidation, a linear relationship between the metal WF and the doping of graphene is found. Specifically, for all metals, nanostructuring lowers the metal WF. In addition, using gold as an example, a critical metal nanoparticle size is found at which the direction of charge transfer, and consequently graphene doping, is inverted.

A novel approach based on a molten multicomponent precursor source has been applied for the MOCVD fabrication of high-quality CaCu(3)Ti(4)O(12) (CCTO) thin films on various substrates. The adopted in situ strategy involves a molten mixture consisting of Ca(hfa)(2).tetraglyme, Ti(tmhd)(2)(O-iPr)(2), and Cu(tmhd)(2) [Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane; Htmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = isopropoxide] precursors. Film structural and morphological characterizations have been carried out by several techniques [X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM)], and in particular the energy filtered TEM mapping and X-ray energy dispersive (EDX) analysis in TEM mode provided a suitable correlation between nanostructural properties of CCTO films and deposition conditions and/or the substrate nature. Correlation between the nanostructure and optical/dielectric properties has been investigated exploiting spectroscopic ellipsometry.