Thermodynamics and kinetics of H adsorption and intercalation for graphene on 6H-SiC(0001) from first-principles calculations

Han, Yong; Evans, James W.; Tringides, Michael C.

doi:10.1116/6.0001343

Thermodynamics and kinetics of H adsorption and intercalation for graphene on 6H-SiC(0001) from first-principles calculations

Journal Article · Tue Dec 07 00:00:00 EST 2021 · Journal of Vacuum Science and Technology A

DOI:https://doi.org/10.1116/6.0001343· OSTI ID:1835555

^[1]; ^[1]; Tringides, Michael C. ^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)

Previous experimental observations for H intercalation under graphene on SiC surfaces motivate the clarification of configuration stabilities and kinetic processes related to intercalation. From first-principles density-functional-theory calculations, we analyze H adsorption and intercalation for graphene on a 6H-SiC(0001) surface, where the system includes two single-atom-thick graphene layers: the top-layer graphene (TLG) and the underling buffer-layer graphene (BLG) above the terminal Si layer. Our chemical potential analysis shows that in the low-H coverage regime (described by a single H atom within a sufficiently large supercell), intercalation into the gallery between TLG and BLG or into the gallery underneath BLG is more favorable thermodynamically than adsorption on top of TLG. However, intercalation into the gallery between TLG and BLG is most favorable. We obtain energy barriers of about 1.3 and 2.3 eV for a H atom diffusing on and under TLG, respectively. From an additional analysis of the energy landscape in the vicinity of a step on the TLG, we assess how readily one guest H atom on the TLG terrace can directly penetrate the TLG into the gallery between TLG and BLG versus crossing a TLG step to access the gallery. Finally, we also perform density functional theory calculations for higher H coverages revealing a shift in favorability to intercalation of H underneath BLG and characterizing the variation with H coverage in interlayer spacings.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC02-07CH11358

OSTI ID:: 1835555

Report Number(s):: IS-J--10,670; DE-AC02-07CH11358; DE-AC02-07CH11358

Journal Information:: Journal of Vacuum Science and Technology A, Journal Name: Journal of Vacuum Science and Technology A Journal Issue: 1 Vol. 40; ISSN 0734-2101

Publisher:: American Vacuum Society / AIPCopyright Statement

Country of Publication:: United States

Language:: English

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