Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; Hooper, Daylong; Oakes, Landon; Cohn, Adam P.; Rao, Rahul; Puretzky, Alexander A.; Geohegan, David B.; Maruyama, Benji; Pint, Cary L.

doi:10.1021/acs.jpcc.6b03880

Title: Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

Journal Article · Wed Jun 08 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b03880· OSTI ID:1271889

Share, Keith ^[1]; Carter, Rachel E. ^[1]; Nikolaev, Pavel ^[2]; Hooper, Daylong ^[2]; Oakes, Landon ^[1]; Cohn, Adam P. ^[1]; Rao, Rahul ^[2]; Puretzky, Alexander A. ^[3]; Geohegan, David B. ^[3]; Maruyama, Benji ^[2]; Pint, Cary L. ^[1]

Vanderbilt Univ., Nashville, TN (United States)
Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growth kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1271889

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 26; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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