Increasing the Rate of Magnesium Intercalation Underneath Epitaxial Graphene on 6H-SiC(0001)

Magnesium intercalated 'quasi-freestanding' bilayer graphene on 6H-SiC(0001) (Mg-QFSBLG) has many favorable properties (e.g., highly n-type doped, relatively stable in ambient conditions). However, intercalation of Mg underneath monolayer graphene is challenging, requiring multiple intercalation steps. Here, we overcome these challenges and subsequently increase the rate of Mg intercalation by laser patterning (ablating) the graphene to form micron-sized discontinuities. We then use low energy electron diffraction to verify Mg-intercalation and conversion to Mg-QFSBLG, and X-ray photoelectron spectroscopy to determine the Mg intercalation rate for patterned and non-patterned samples. By modeling Mg intercalation with the Verhulst equation, we find that the intercalation rate increase for the patterned sample is 4.5$\pm$1.7. Since the edge length of the patterned sample is $\approx$5.2 times that of the non-patterned sample, the model implies that the increased intercalation rate is proportional to the increase in edge length. Moreover, Mg intercalation likely begins at graphene discontinuities in pristine samples (not step edges or flat terraces), where the 2D-like crystal growth of Mg-silicide proceeds. Our laser patterning technique may enable the rapid intercalation of other atomic or molecular species, thereby expanding upon the library of intercalants used to modify the characteristics of graphene, or other 2D materials and heterostructures.Comment: 24 pages, 4 figure

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

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 cut-off photoemission and scanning tunneling microscopy to elucidate the physical and electronic structure 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 and Mg bonds to the Si-terminated SiC surface are formed, 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 workfunctions 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.Comment: 58 pages, 10 figures, 4 tables. Revised text and figure

Exfoliation of Quasi-Stratified Bi₂S₃ Crystals into Micron-Scale Ultrathin Corrugated Nanosheets

There is ongoing interest in exploring new two-dimensional materials and exploiting their functionalities. Here, a top-down approach is used for developing a new morphology of ultrathin nanosheets from highly ordered bismuth sulfide crystals. The efficient chemical delamination method exfoliates the bulk powder into a suspension of corrugated ultrathin sheets, despite the fact that the Bi₂S₃ fundamental layers are made of atomically thin ribbons that are held together by van der Waals forces in two dimensions. Morphological analyses show that the produced corrugated sheets are as thin as 2.5 nm and can be as large as 20 μm across. Determined atomic ratios indicate that the exfoliation process introduces sulfur vacancies into the sheets, with a resulting stoichiometry of Bi₂S_2.6. It is hypothesized that the nanoribbons were cross-linked during the reduction process leading to corrugated sheet formation. The material is used for preparing field effect devices and was found to be highly p-doped, which is attributed to the substoichiometry. These devices show a near-linear response to the elevation of temperature. The devices demonstrate selective and relatively fast response to NO₂ gas when tested as gas sensors. This is the first report showing the possibility of exfoliating planar morphologies of metal chalcogenide compounds such as orthorhombic Bi₂S₃, even if their stratified crystal structures constitute van der Waals forces within the fundamental planes