Thermodynamics and kinetics of Pb intercalation under graphene on SiC(0001)

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

doi:10.1016/j.carbon.2023.01.029

Thermodynamics and kinetics of Pb intercalation under graphene on SiC(0001)

Journal Article · Tue Jan 17 00:00:00 EST 2023 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2023.01.029· OSTI ID:1969482

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

SiC-supported graphene intercalated by a two-dimensional Pb monolayer can provide an appealing platform for spintronic applications. Such a monolayer structure is thermodynamically ultrastable, as observed in recent experiments. However, important fundamentals such as the structure of intercalated phases, locations of intercalated atoms, thermodynamic preference for intercalation, and intercalation pathways for this system have not yet been understood conclusively. Here, in this work, extensive density functional theory calculations are performed to assess Pb intercalation thermodynamics and kinetics under graphene on SiC(0001). We find that intercalation of isolated Pb atoms is strongly disfavored over adsorption on top of graphene. However, intercalation of complete Pb layers in the gallery between SiC and graphene buffer layer is strongly favored over supported Pb monolayers and moderately favored over formation of supported large three-dimensional Pb islands. We also find that initiation of intercalation either by individual Pb atoms directly penetrating graphene or by hopping under a static graphene step edge is energetically prohibitive at experimental temperatures. Consequently, more complex intercalation pathways are operative and further analyzed. We demonstrated that once an intercalated Pb monolayer forms around a graphene step edge, a facile Pb mass transport by Pb vacancy-mediated diffusion can be triggered for continued growth of the intercalated monolayer.

View Accepted Manuscript (DOE)

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

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

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

OSTI ID:: 1969482

Alternate ID(s):: OSTI ID: 1961504

Report Number(s):: IS-J-11,040

Journal Information:: Carbon, Journal Name: Carbon Vol. 205; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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