In van der Waals (vdWs) materials, the engineering of stacking structures is a powerful method to control the electronic states for novel quantum phenomena or future electronic devices. To change the stacking structure, atomic intercalation is a promising way. This is because the atomic intercalation can modulate the stacking structure without a highly technical protocol nor a limitation for the sample size [1-
4
]. However, there is little knowledge of the atomic dynamics during the intercalation process related to the stacking structures.
Here, we report that Li-intercalation into epitaxial graphene (EG) on SiC (0001) drives topological domain wall motions associated with stacking change in graphene/buffer layers [
5
].
In-situ ultrahigh-vacuum (UHV) aberration-corrected low-energy electron microscopy (LEEM) has been applied to real-time imaging of the Li-intercalation process. The buffer layer and the top graphene layer forming a carbon bilayer configuration (named the bilayer system thereafter) are used for the observation of Li-intercalation dynamics (Fig. 1(a)).
AB
and
BA
stacking domains are alternatively distributed and sandwich topological domain walls (TDWs) in between (Fig. 1(
b
)). The TDWs are topologically protected due to the difference in the number of unit cells in the buffer and graphene layers. The crossing points of multiple TDWs have a topologically protected AA stacking structure. The top of Fig. 1(c) is a dark-field LEEM image of the pristine bilayer system. The dark and bright domains correspond to
AB
and
BA
stacking domains, respectively. They are consistent with the top illustration of Fig. 1(
b
).
We deposited Li on the bilayer system with a low flux rate to capture the Li-intercalation dynamics. At
7
min of the Li-intercalation, Li-intercalation firstly occurred at AA stacking points, which changes the contrast of the bright-field LEEM image to bright dots as shown in stage 1 in Fig 1(c). At
9
min (stage 2 in Fig 1(c)), Li-intercalated domains with the bright contrast grow into
AB
stacking domains (surrounded by or between blue dashed lines in Fig 1(c)). Further Li-intercalation makes the Li-intercalated domains extend into
BA
stacking domains (surrounded by or between red dashed lines in Fig 1(c)) as stage 3 in Fig 1(c). Finally, the Li-intercalated domains cover most areas, whereas they do not combine with each other and are divided by dark lines (
i.e
. TDW regions).
To elucidate the mechanism of the stacking-dependent Li-intercalation, we performed density functional theory calculations. Li adsorption energy into AA,
AB
, and
BA
stackings is in the order of AA <
AB
<
BA
. Thus, it is energetically preferable for Li to intercalate the AA stacking points first and then selectively intercalate
AB
domains instead of
BA
domains as observed in the LEEM snapshots. In addition, we calculated the stable stacking structure of the Li-intercalated bilayer system and figured out that it is AA stacking.
Next, we look into the evolution of the stacking distribution during the Li-intercalation in the stripe microstructure as seen in the pink rectangle regions in LEEM snapshots of Fig. 1(c), with molecular dynamics simulation. When Li-intercalated domains start to grow into
AB
regions, the intercalated regions change their stacking structure to AA (Stage 2 of Fig. 1(d)). Further Li-intercalation changes the
BA
stacking to AA stacking structure. Finally, Li-intercalated domains with AA stacking fill the whole region, while there is a TDW region in between them as shown in Stage 3 of Fig. 1(d). The TDW region can not have AA stacking structure by the topological constraint, and never disappear.
View PDF for the rest of the abstract.
抄録全体を表示