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.
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