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Journal of the Physical Society of Japan 88, 114704 (2019)

https://doi.org/10.7566/JPSJ.88.114704

Identification of Twinning-induced Edges on the Cleaved Graphite Crystal Surface

Fumihiko Matsui1+, Seiji Makita1, Hiroyuki Matsuda1, Takuji Ohigashi1,2,
Hiroyuki Yamane3, and Nobuhiro Kosugi2,4
1
Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan
2
SOKENDAI (The Graduate University for Advanced Studies), Okazaki, Aichi 444-8585, Japan
3
RIKEN SPring-8 Center, Sayo, Hyogo 679-5148, Japan
4
Institute of Materials Structure Science, KEK, Tsukuba, Ibaraki 305-0801, Japan
(Received August 27, 2019; accepted September 6, 2019; published online October 8, 2019)
Edges on the cleaved graphite crystal surface were found to be preferentially oriented perpendicularly to the hexagonal
perimeter facet of the graphite single crystal assigned to the zig-zag-type edge. The crystal orientation was determined
by observing the Brillouin zone in the photoelectron angular distribution of the valence band. Straight edges seen on the
cleavage plane were aligned along the armchair atomic arrangement direction. These features were revealed to be formed
at the twinned domain boundaries along the ½1120  direction.

a wide solid angle without changing the position and

1. Introduction
Crystals have preferential facets and edges which are
mainly determined by the kinetics during growth, the
energetics at equilibrium,1) and the mechanics at cleavage.2)
Furthermore, defects and entangled twinned domains result
in the unexpected shape of the crystal.3,4) Therefore, the
relationship between the crystal shape and the orientation is
not obvious unless the crystal formation conditions are known.
Graphite has been a perfect playground for studying such
basic science. Palache investigated the shape of natural
graphite crystals and found that f1011g is a preferred facet
in addition to van der Waals cleavage planes {0001}.5)
Jaszczak presented a photograph of “barrel-shaped” graphite
 and {0001} facets.6) Note that the
single crystal with f1011g

h1010i direction is along the zig-zag type edge of the

graphite lattice, and the f1010g 
plane includes the h1010i
and [0001] axes. Thus, natural graphite crystals are likely to
have a hexagonal shape formed by the zig-zag type edges. On
the other hand, graphite crystal flakes can be obtained as a
precipitate from iron–carbon alloys.7) In fact, crystal size
minimization and shape control are the important technology
in the steelmaking industry, and the growth of graphite
precipitates has been intensively studied. Spherical poly-
crystalline graphite microstructures are formed in the ductile
cast iron by the addition of various kinds of dopants.8–10)
Microscopic techniques such as scanning transmission
electron microscope (STEM)11) and scanning probe micro-
scope (SPM)12) reveal the local atomic arrangements, while
diffraction techniques combined with focused beams and=or
projection type detectors are powerful for characterization of
small and=or multidomain crystal structures. X-ray diffrac-
tion (XRD) and transmission electron diffraction (TED) are
suitable for bulk structural analysis, while low energy
electron diffraction (LEED) and photoelectron diffraction
(PED) are suitable for surface structural analysis. We have
successfully determined the atomic arrangement at the edge
of monolayer and bilayer graphene flakes13,14) and the steps
of graphite cleaved surface15–17) by PED. Fermi surface
pattern observation by two-dimensional momentum-resolved
photoelectron spectroscopy can be used to identify the
orientation of graphite crystals.18) We have developed an
acceptance-cone-tunable (ACT) photoelectron spectrometer
that can acquire photoelectron intensity distribution data of
114704-1
orientation of the sample.19) We found that edges on the
cleaved graphite crystal surface were preferentially oriented
perpendicularly to the hexagonal perimeter facet of the
graphite single crystal. From the observation of the Brillouin
zone in the photoelectron angular distribution of the valence
band, these straight edges along the ½1120  armchair
direction were assigned to twinned domain boundaries.
2. Experimental Details
Graphite flakes used in this study were purchased from
Covalent Materials Corporation. The selected hexagonal
crystals were mounted on a sample holder and cleaved just
before introducing them to ultrahigh vacuum for measure-
ments. Valence band dispersion was measured by the ACT
photoelectron spectrometer at the linear polarization soft
x-ray beamline BL6U of the UVSOR Synchrotron, Japan.19)
The ACT photoelectron spectrometer consists of a mesh-type
electrostatic lens for wide-solid-angle photoelectron collec-
tion, a mechanical deflecting input lens, and a concentric
hemispherical analyzer. The axis of the spectrometer was
positioned at 60° off from the incident light. The acceptance
angle cone of the analyzer was extended to 3 Å−1 by
applying the bias voltage between the sample surface and the
mesh-type electrostatic lens. The incident photon beam size
was 300 and 40 µm in horizontal and vertical directions,
respectively. The surface quality was checked by x-ray
photoelectron spectroscopy (XPS) measurements. No con-
tamination was detected. The C 1s core level peak was
asymmetric with the Doniac–Šunjić tail at the high binding
energy side, which in this case is characteristic of the sp2
graphite metallic surface.
3. Results and Discussion
Figure 1 shows an optical microscopic image of a mm
sized graphite single crystal surface taken after the all
photoemission measurements. The inset shows the atomic
arrangement, assuming that the hexagonal perimeter facets
are along the zig-zag-type edge of the graphite lattice.
Note that the straight lines appearing at the cleavage plane
is mostly perpendicular to the edge of the hexagonal
crystal. This suggests that the crystal grown edge and the
straight lines appearing at the cleavage plane have different
origins.
©2019 The Physical Society of Japan
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J. Phys. Soc. Jpn. 88, 114704 (2019) F. Matsui et al.

2nd layer

1st layer 3rd layer

armchair edge
200 μm

zig-zag edge

_
[1120]
_
[1010]
beam size:
{1120}

{10

300x40 μm2
_ }
10
_

Fig. 1. (Color online) An optical microscopic image of a mm sized graphite single crystal surface taken after the all measurements. Insets show schematic
drawings of atomic arrangements and orientation.

(a) Μ′ Κ Γ Κ Μ′ (b) Μ Γ Μ perpendicular to the horizontal plane including the incident

0
π
linearly polarized X-ray, and sample surface normal and
σ2,3 KΓK axes, a band dispersion along the MΓM symmetry axis
4
was obtained as shown in Fig. 2(b). Degenerate 2 and 3
σ3
Binding Energy (eV)

bands along the ΓK axis are split into two at M points. The
8 σ3 series of iso-energy cross section of the band dispersion
12 shown in Figs. 2(c)–2(e) was obtained from three-dimen-
σ2 sional volume data. Note that the photoelectron intensity
16 outside the hexagon is darker than the inside due to the effect
σ2 of the photoelectron structure factor.20,21) The interior of the
20 σ1 hexagon is the first Brillouin zone. The center of the hexagon
corresponds to the surface normal direction. By comparing
24 the orientation of Brillouin zone and the hexagonal graphite
2 1 0 1 2 1 0 1 crystal, the hexagonal perimeter facet of the graphite single
Wave number (Å-¹)
crystal was confirmed to be the zig-zag-type edge. This
(c) Μ (d) (e) matches well with the widely accepted crystallographic
assignments. However, the edges on the cleaved graphite
Γ
crystal surface oriented perpendicularly to the hexagonal
Κ
perimeter facet was assigned to the armchair-type edge. This
raises the mystery of the formation of lines that appear
perpendicularly to the zig-zag facet.
The advantage of using the ACT spectrometer is that the
Fig. 2. The valence band dispersion of graphite along (a) the KΓK and iso-energy cross section of complete Brillouin zone from
(b) MΓM symmetry axes. (c) The series of iso-energy cross section of the selected areas on the sample are easily obtained. We
band dispersion. The photon energy was 100 eV. Dotted hexagon indicates sometimes observed Brillouin zone overlap from several
the Brillouin zone.
different facets. This occurs when the x-ray irradiated area
crosses the domain boundary. Figure 3 shows the series of
Figure 2(a) shows the valence band dispersion of graphite cross section of band dispersions in which contributions from
along the KΓK symmetry axis. Parabolic π and 1 bands five different facets were observed. The photon energy was
consisting of 2pz and 2s atomic orbitals, respectively are 50 eV. The bias voltage of 500 V was applied between the
observed at binding energies from 0 to 8 eV and from 14 to sample and the mesh-type electrostatic lens. The same data
22 eV, respectively. The photon energy was 100 eV. By were used in Figs. 3(a)–3(c) and 3(d)–3(f ), but with different
applying a bias voltage of 500 V between the sample and the contrast. The small points near the center of Fig. 3(d) and the
mesh-type electrostatic lens, photoelectrons emitted between triangles in Fig. 3(e) indicate the presence of inclined facets.
M0 directions (2:56 Å−1, 28° off from the surface normal The triangle has one side whose intensity is strong due to the
direction) was acquired at once. By scanning the deflector above-mentioned photoelectron structure factor effect.20,21)
114704-2 ©2019 The Physical Society of Japan
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J. Phys. Soc. Jpn. 88, 114704 (2019) F. Matsui et al.

(a) (b) (c) with step bunching along the boundaries of the SiC(110n)=
(0001) plane pairs. STEM images clearly show that multi-
layer graphene is continuously merged at such end regions.22)

4. Conclusion
In conclusion, we found straight lines on the cleaved
graphite crystal surface preferentially oriented perpendicu-
larly to the hexagonal perimeter facet of the graphite single
crystal. The crystal orientation was determined by observing
the Brillouin zone in the photoelectron angular distribution of
the valence band. The hexagonal perimeters were assigned to
the zig-zag-type edge, while the straight lines seen on the
(d) (e) (f) cleavage plane were aligned along the armchair atomic
Binding Energy 0.0-0.2 eV 1.0-1.2 eV 2.0-2.2 eV arrangement directions. We revealed that the twinned domain
boundaries appear along the ½1120  direction. This finding
Fig. 3. (Color online) (a)–(c) The series of iso-energy cross section of the explains the preferential alignment of the straight line
band dispersion. (d)–(f ) Same as (a)–(c) but with different contrast. Dotted features perpendicular to the crystal perimeter facets.
hexagons indicate the Brillouin zone from different facets. The arrows
 direction.
indicates the π band from the (0001)0 facet at the ½1011 Acknowledgment The authors would like to thank Dr. Peter Baltzer and
Ms. Mitsuse Matsuki-Baltzer of MB Scientific AB for their fruitful assistance and
suggestions for the development of the present ACT spectrometer. We also thank
(a) _ the staff of the UVSOR-III Synchrotron for their support in development of the
[1120]
200 μ m present ARPES system. F.M. acknowledge the support by the Ministry of
Education, Culture, Sports, Science and Technology, Grant-in-Aid for Scientific
Research (B) No. 17H02911.

_ +
[1010]
_ _
(b) [1011] [0001] [1010]
(0001) (00 01)’ _ 15859 (2013).
[1120]
20.1°
Fig. 4. (Color online) (a) An optical microscopic image of a mm sized
graphite single crystal surface. Inclined facet along ½1120  axis was
observed. (b) Schematic diagram of atomic arrangement showing the cross
 directions. The ½1120
section of the {0001} facets at [0001] and h1011i  and
 directions indicated in (a) correspond to those indicated in (b).
h1011i
This allows us to determine the first Brillouin zone and the
facet normal direction.
We found an inclined facet along ½1120  axis in another
piece of the cleaved graphite sample as shown in Fig. 4(a).
Figure 4(b) shows the atomic arrangement at the f1010g  Phenom. 195, 347 (2014).
 
plane. The ½1120 and ½1010 directions indicated in
Fig. 4(a) correspond to those indicated in Fig. 4(b). This
(0001)0 facet with the inclined angle of 20.1° seems to be
corresponding to the one of Brillouin zone and the π band
indicated by arrows in Figs. 3(d)–3(f ). Note that there is no
need to break and rearrange the C–C chemical bonds when
creating facets {0001} at h1011i direction. One explanation
of the straight lines appearing on the cleavage plane along the
armchair-type bonding direction is the formation of twin
domains. Mechanical compressive strain during growth can
induce such inclined facets along the ½1120 axis.
It is noteworthy that edges formed at twin boundaries
 axis are also observed in multilayer
along the graphite ½1120
graphene epitaxially grown on the SiC(0001) vicinal surface
matui@ims.ac.jp
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