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Freestanding n-Doped Graphene via Intercalation of Calcium and Magnesium into the Buffer Layer–SiC(0001) Interface

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    Freestanding n-Doped Graphene via Intercalation of Calcium and Magnesium into the Buffer Layer–SiC(0001) Interface
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 15, 6464–6482
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    https://doi.org/10.1021/acs.chemmater.0c01729
    Published July 15, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The intercalation of epitaxial graphene on SiC(0001) with Ca has been studied extensively, yet precisely where the Ca resides remains elusive. Furthermore, the intercalation of Mg underneath epitaxial graphene on SiC(0001) has not been reported. Here, we use low energy electron diffraction, X-ray photoelectron spectroscopy, secondary electron cutoff photoemission, and scanning tunneling microscopy to elucidate the physical and electronic structures of both Ca- and Mg-intercalated epitaxial graphene on 6H-SiC(0001). We find that Ca intercalates underneath the buffer layer and bonds to the Si-terminated SiC surface, breaking the C–Si bonds of the buffer layer, i.e., “freestanding” the buffer layer to form Ca-intercalated quasi-freestanding bilayer graphene (Ca-QFSBLG). The situation is similar for the Mg-intercalation of epitaxial graphene on SiC(0001), where an ordered Mg-terminated reconstruction at the SiC surface is formed and Mg bonds to the Si-terminated SiC surface are found, resulting in Mg-intercalated quasi-freestanding bilayer graphene (Mg-QFSBLG). Ca-intercalation underneath the buffer layer has not been considered in previous studies of Ca-intercalated epitaxial graphene. Furthermore, we find no evidence that either Ca or Mg intercalates between graphene layers. However, we do find that both Ca-QFSBLG and Mg-QFSBLG exhibit very low work functions of 3.68 and 3.78 eV, respectively, indicating high n-type doping. Upon exposure to ambient conditions, we find Ca-QFSBLG degrades rapidly, whereas Mg-QFSBLG remains remarkably stable.

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    Supporting Information

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    • Elucidation of all Ca- and Mg-intercalation steps of EMLG, along with detailed tables outlining parameters of the component fits including the omitted first intercalation steps; Ca-intercalation of H-QFSBLG—LEED, XPS (C 1s and Si 2p core level spectra), and SECO measurements; measured C 1s graphene line shapes for Ca- and Mg-intercalated EMLG (i.e Ca- and Mg-QFSBLG) are compared to theoretical line shapes for highly doped graphene; O 1s and Ca 2p XPS spectra for Ca-intercalated EMLG and H-QFSBLG; STM micrographs of Ca deposition on top of EMLG, as well as the method for cleaning the graphene surface of excess Ca; detailed STM micrographs of the dark and postintercalation bright features; C 1s and Si 2p core level spectra of the attempted Mg-intercalation of H-QFSBLG; O 1s and Mg 2p core level spectra of Mg-intercalated EMLG; Mg 2p spectra of H-QFSBLG; effect of long-term ambient exposure of Mg-QFSBLG via lab-based C 1s/Si 2p XPS spectra and Raman mapping spectra; and Si 2p and C 1s core levels of the Mg-intercalated sample in Figure 8b (PDF)

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    Cite this: Chem. Mater. 2020, 32, 15, 6464–6482
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c01729
    Published July 15, 2020
    Copyright © 2020 American Chemical Society
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