Hermetic carbon coatings of different thicknesses ranging from 1 to 100 nm on a series of optical fibers are characterized with confocal Raman spectroscopy and atomic force microscopy. Standard far‐field Raman spectra in the region of 1,000–2,000 cm−1 were fitted and well reproduced using 5 individual components assigned to different species of graphite‐like and disordered phases. Based on the fitting, a new spectroscopic indicator was proposed:
G*D*true/Δ, where G* and D* and Δ are intensities at the maxima of the graphite‐like G peak and the disorder‐induced D peak and the dip between them, respectively. This indicator provides a measure of soot fraction in carbonaceous materials. A tip‐enhanced Raman scattering (TERS) technique confirmed the complex structure of the first‐order Raman D band assigned to disordered graphitic lattice vibrations. In addition, the TERS method provided convincing evidence for the formation of carbon allotropes, such as carbon nanotubes in the coatings. Possible effects of allotropes on hydrogen and water permeation through carbon coating are discussed in the view of the obtained results.
As-thermal-CVD-synthesized
amorphous carbon (a-C) ultrathin coatings
enable silica optical fibers to be mechanically robust and optically
transparent in aggressive environments. This is achieved by mitigating
both hydrogen diffusion and water ingression onto the fiber surface.
Notwithstanding the advanced performance of CVD-deposited a-C films,
their functionality may suffer from structural and topology defects,
dopants, intrinsic stresses, and other imperfections. In this paper,
we experimentally study the influence of water-anchored edge functional
groups on dc electrical conductivity and Raman scattering of a-C films,
ranging from 10 to 100 nm in thickness, exposed to thermal and electrical
annealing. A series of heating/cooling cycles was found to affect
the disorder D-family bands in the Raman spectra of a-C. In particular,
two new Raman peaks at 1260 and 1400 cm–1, attributed
to carboxyl (COOH) and hydroxyl (C–OH) groups, have been unraveled
through polarization-controlled far-field Raman spectroscopy and tip-enhanced
Raman scattering (TERS) spectroscopy. The TERS technique allows one
to readily resolve the broad disorder D-family bands due to the excitation
of coherent Raman scatters (nanosized graphitic clusters). A temperature-sensitive
and thickness-dependent hysteresis in dc conductivity, observed at
temperatures of above 80 °C, is explained by physical sorption/desorption
of water at the surface of graphite-like crystals through hydrogen
bonding and dissociative absorption of water with the formation of
extra COOH/C–OH groups at the edge defects. The electroheating
leads to a nonuniform distribution of the water-decorated edges owing
to hot spots of a percolated carbon crystals network. This is directly
evidenced by electroassisted TERS mapping of the a-C coating. We believe
that our study will pave a way for the understanding of how water
interacts with amorphous carbon and improve the performance of carbon
coatings in harsh environments.
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