Letter

pubs.acs.org/NanoLett

A Growth Mechanism for Free-Standing Vertical Graphene

Jiong Zhao,†,‡ Mehrdad Shaygan,§ Jürgen Eckert,†,∥ M. Meyyappan,⊥ and Mark H. Rümmeli*,‡,¶,□
†
IFW Dresden, Institute of Complex Materials, P.O. Box 270116, D-01171 Dresden, Germany
‡
IBS Center for Integrated Nanostructure Physics, Institute for Basic Science (IBS), Daejon 305-701, Republic of Korea
§
Division of IT Convergence Engineering, Pohang University of Science and Technology, Pohang, Republic of Korea
∥
TU Dresden, Institute of Materials Science and the Center for Advancing Electronics Dresden (cfaed), 01062 Dresden, Germany
⊥
NASA Ames Research Center, Moffett Field, California 94035, United States
¶
Department of Energy Science and □Department of Physics, Sungkyunkwan University, Suwon 440-746, Republic of Korea
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ABSTRACT: We propose a detailed mechanism for the

growth of vertical graphene by plasma-enhanced vapor
deposition. Different steps during growth including nucleation,
growth, and completion of the free-standing two-dimensional
structures are characterized and analyzed by transmission
electron microscopy. The nucleation of vertical graphene
growth is either from the buffer layer or from the surface of
carbon onions. A continuum model based on the surface
diffusion and moving boundary (mass flow) is developed to
describe the intermediate states of the steps and the edges of
graphene. The experimentally observed convergence tendency
of the steps near the top edge can be explained by this model.
We also observed the closure of the top edges that can possibly stop the growth. This two-dimensional vertical growth follows a
self-nucleated, step-flow mode, explained for the first time.
KEYWORDS: Vertical graphene, nucleation, step-flow, edge closure

S ingle crystal growth is an old topic typically including two

stages, nucleation, and growth.1 The nucleate has to first
overcome an energy barrier caused by the interfacial mismatch
under supersaturation and then act as the subsequent growth
template. Crystal growth issues have come to the forefront with
the advance of nanotechnology and growth of nanomaterials
for use in the so-called bottom-up scheme.2 The growth
mechanism is clear when discussing the one-dimensional (1D)
growth like whiskers,3 nanowires,4 and nanotubes,5 and they are
often free-standing (self-supported). These growths can be
initiated by atomic clusters, either by the same material
(homogeneous nucleation) or different materials (heteroge-
neous nucleation or catalysts). The surface energy anisotropy
or even surface decoration anisotropy plays an important role
in 1D growth, according to the so-called L−S (liquid−solid) or
V−S (vapor−solid) mechanism;2−5 in the case of nucleation by
catalysts, the growth might probably continue at the interface
between the catalyst and the nanowire (nanotube), according
to the VLS (vapor−liquid−solid) or VSS (vapor−solid−solid)
mechanism.4−6 In contrast, two-dimensional (2D) growth
normally requires additional support (substrate) and the as-
grown thin film is parallel with the substrate.7 The growth
mechanism of vertical free-standing 2D structures has not been
discussed much compared to various techniques for thin film
deposition, which have been well developed. In this report, we
use vertical graphene as an example to investigate its specific
bottom-up growth mechanism. We believe that the present
study on vertical growth of 2D structures will promote the
realization of more types of vertical structures and that an
understanding of the underlying mechanisms will enable
nanostructures for various applications.
It is well-known that sp2 carbon, which is the most stable
elementary form of carbon at room temperature, can lead to
various kinds of layered structures. Among these structures,
graphene is a true 2D material8 with the large anisotropy
between the in-plane and out-of-plane directions providing
possibilities to manage the 2D growth. As reported in
numerous publications, the growth of high quality graphene
(monolayer or few layers) can be carried out by chemical vapor
deposition (CVD) on different substrates such as Cu, Ni, SiC,
and so forth.9−12 Even before the emergence of these
atomically thin carbon layers, there has already been some
work focusing on carbon nanosheets produced by plasma
enhanced CVD (PECVD). The PECVD method proceeds at a
lower temperature and has better control in nanostructure
ordering and higher purity which can easily produce very dense
carbon nanoflakes or carbon nanowalls (CNWs).13−25 The gas
precursors (mainly hydrocarbons) undergo inelastic collisions
with the electrons in the plasma to form free radicals, ions, and
other reactive species. In the presence of metallic catalytic
Received: January 3, 2014
Revised: April 23, 2014
Published: May 2, 2014

© 2014 American Chemical Society 3064 dx.doi.org/10.1021/nl501039c | Nano Lett. 2014, 14, 3064−3071
Nano Letters
Figure 1. Vertical graphene (VG) grown by PECVD. (a) The cross-sectional SEM image of an as-grown vertical graphene sample on the substrate.
Red and blue triangles indicate two interfaces. (b) TEM image of the upper layer of VG, which stems from the carbon onion. Red dashed circle
highlights the position of the carbon onion. (c) TEM image of the bottom layer of VG, which stems from the substrate and buffer layer.
particles, the dissociation of the feedstock gas in the plasma is
not necessary in principle; rather, carbon is produced from
dissociation at the metal catalyst surface as in most cases of
carbon nanotube growth with PECVD. But the carbon
nanowalls can also grow without the use of catalysts, which
means precursor dissociation by the plasma plays an important
role. Various substrates have been shown to enable carbon
nanowall growth, including Si, SiO2, Si3N4, Cu, steel, and so
forth.13,18 The as-grown CNWs usually have tapered structures,
typically 1−3 graphene layers at the top and several layers at
the bottom, standing perpendicular to the substrates. Hence
they are also called vertical graphene (VG), first to indicate the
few layer graphitic nature, and second to differentiate this type
of graphene from graphene deposited parallel to a substrate by
thermal CVD. The vertical graphene can be useful in fuel cells
as catalyst support and as electrodes in energy storage devices
such as lithium ion batteries and supercapacitors. As-grown
structures directly on metal substrates without the aid of
catalysts eliminate the need for binding materials commonly
used to make pastes of reduced graphene oxide for electrode
preparation. The binding materials add to the gravimetric
weight estimation but do not enhance the conductivity and
thus, as-grown VG can be advantageous for intercalation of
other materials useful in batteries and supercapacitors
Compared to the widely studied graphene synthesis by
thermal CVD, the microscopic growth mechanism of vertical
graphene is still not well understood. The nucleation site for
the vertical structure is the first puzzle. Some evidence has been
presented for the formation of a thin carbon film on the
substrate before the onset of vertical growth,14 and the upward
curling force can lead to the takeoff of some top carbon layers
at the grain boundaries that continue to grow perpendicular to
the substrate.26 The electric field in the plasma is also suggested
to assist in aligned vertical growth,26,27 as in the case of PECVD
of carbon nanotubes.28 The plasma appears to play several roles
in nanostructure growth.27 The plasma can produce a relatively
larger chemical potential gradient near the surface through ion
focusing effects and fast delivery of precursors. The plasma
exposure can increase the temperature of the top surface layer.
The diffusion barrier may be reduced by the electric-field
induced polarization effects that in turn will reduce the
adhesion/bonding energy of atoms to the surface. The
nonuniform electric field on the surface can effectively increase
the diffusion coefficient. The complex interplay of such effects,
while providing unique opportunities, makes the understanding
of mechanisms difficult. Second, how are these tapered
structures formed? And where are the active growth sites for
these 2D structures? There are tip growth2 and root growth29
models for 1D structures such as nanowires and carbon
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Letter
nanotubes, but there are more possibilities for 2D growth: at
the contact line between the graphene and substrate, at the free
edges of the graphene (growing larger), as well as at active
steps/edges on the two sides of the graphene wall (growing
thicker).
The samples employed in this study were fabricated by an RF
(radio frequency)-PECVD method. The plasma was ignited by
using a mixture of methane and hydrogen at an RF power of
900 W for a fixed deposition time of 20 min. Different
substrates, including Si and Si covered with a 150 nm film of Au
(thermally deposited) were used. The temperature of the
sample stage ranged from 600 to 1100 °C at growth pressures
between 10−3 Torr and atmospheric pressure. The effects of the
different parameters (temperature, pressure, substrate, RF
power) have been discussed elsewhere.18 A review can be
found in ref 17 on how these parameters influence the final
products. However, all variations induced by the growth
parameters do not alter the major growth mechanism proposed
here but only create different amount of defects or lead to
different growth rates, sizes, and thicknesses. Hence, in the
following discussion we mainly focus on the microscopic
features in the process of vertical graphene growth, disregarding
specific growth conditions.
The scanning electron microscopy (SEM) image in Figure 1a
shows a cross-section view of the as-grown vertical graphene. At
the bottom of the SEM image one can see lines or wrinkle-like
formations on the substrate. These are in effect the tops of
vertical graphene sheets that have emerged perpendicularly to
the VG sheets above the substrate. Above the substrate two
distinct regions or layers can be observed; one layer of VG
sheets sits immediately above the substrate (indicated by a blue
triangle) while another rests on top of the initial layer with its
interface indicated by a red triangle. As we will show below, the
upper layer VG sheets nucleate from carbon onions.
Our detailed investigation is based on low-voltage aberration-
corrected transmission electron microscopy (LVACTEM). A
JEOL 2010F TEM retrofitted with CEOS aberration correctors
working with a 80 kV accelerating voltage was used.30 The
TEM specimen was prepared by mechanically scratching the
surface of the vertical graphene samples and transferring to
TEM grids. The TEM copper grid is put directly onto the
surface of the sample, pressed and scratched, for the manual
mechanical cleavage of the samples. After this process, the
upper layer of vertical graphene can be peeled off and separated
during scratching while the bottom layer of vertical graphene
remains on the substrate. A comparison of the SEM images
(Figure 1a) and TEM images (Figure 1b,c) reveals that the
morphology and size of the vertical graphene samples did not
change. Also, because the top edges of these vertical graphene
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Nano Letters Letter

Figure 2. Nucleation mechanisms and schemes for the VG growth. (a) Low-magnification TEM image for the VG stemmed from substrate and
buffer layer (bottom layer VG). (b) HRTEM image of the buffer layer shows the buffer layer consists of amorphous carbon and graphitic layer on the
surface. There are some mismatches where VG is initialized. (c) TEM image for the VG stemmed from carbon onions (upper layer VG). (d)
HRTEM of the carbon onion that shows the mismatch of graphitic layers at the surface, which initialize the growth of VG. (e) The scheme for
nucleation at curved areas on the buffer layers as well as on the surface carbon onions, the arrows show the growth direction. (f) The scheme for
growth of 1D and 2D nanostructures where the arrows represent the mass supply for growth. (g) The scheme for the nearly completed vertical
graphene with some seamless (straight) edges and some open (nonstraight) edges. The growth history is presented by the dashed lines.

samples are closed or seamless (to be discussed later) between
each neighboring wall that provides more mechanical stability,
the sample preparation process is unlikely to introduce any
folding or damage. Figure 1b shows the TEM image of the
upper layer of vertical graphene which is peeled off during TEM
sample preparation. This kind of vertical graphene has a
bloomed flower shape that originates from a carbon onion
(highlighted by the dashed circle in Figure 1b). In Figure 1c,
the vertical graphene sheets are firmly connected with the
substrate.
The nucleation mechanisms for vertical graphene are
discussed below. There is a ∼20 nm thick buffer layer
(highlighted in blue in the image in Figure 2a) between the
substrate (150 nm thick Au film) and the vertical graphene,
consistent with the SEM analysis by Wang et al.13 The HRTEM
of the area for this buffer layer (Figure 2b) shows that it is
composed of amorphous carbon and graphitic layering on the
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surface. Some mismatches in the graphitic layers can also be
observed. The hypothesis that the vertical graphene stems from
the mismatches and curved areas of graphitic layers31 can be
confirmed (Figure 2e), especially referring to the large
concentration of defects due to the plasma. The amorphous
carbon can be formed due to the catalytic effect of the Au layer,
because metals can act as catalytic decomposition sites for the
carbon sources and easily form amorphous carbon by
PECVD.28 The amorphous carbon is formed because the
carbon deposition rate is greatly enhanced by catalysts and both
the time and temperature are insufficient for the crystallization
of carbon. However, in the regions away from the substrate, the
growth of sp2 carbon still dominates, which is a noncatalyst
growth process. In contrast, the upper layer of vertical graphene
nucleates from the carbon onions (Figure 2c). The formation
of onions by PECVD has been reported by many groups.32,33
Similar to the buffer layer, the onions also serve as active
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Figure 3. (a) Atomistic model of a curved vertical graphene with active growing edges (highlighted with colors). (b) TEM image of a growing
vertical graphene sheet with many curved steps and terraces (highlighted in different colors) on the surfaces. The two wings are curved and
overlapped by itself in the viewing direction. (c) Finite element simulation of the carbon adatom diffusion on the surfaces. The isolines for adatom
concentrations and the mass flowchart (marked by the red arrows) are presented. The scale bar (from white to black) on the right indicates the value
of C0 (higher to lower concentrations of free carbon atoms). The conditions for the simulation are C0 = 10, μ = 1, d = 1, g = 1 and the lateral size of
the graphene is approximately 1, all in arbitrary units. Changes in the absolute values of these parameters do not change the shapes of the isolines and
the mass flow directions. (d) For convenient comparison between the experimental result (panel b) and simulation (panel c), the two wings in the
simulation are folded.

nucleation sites here for the growth of vertical graphene. The
HRTEM (Figure 2d) shows the graphitic layering mismatches
at the outmost six layers of the onions. The graphene layers
then grow in the tangential direction, naturally leading to a
flower shaped vertical graphene structure.
The active edges or steps will play important roles after
nucleation (vertical growth initiation). For graphene grown by
CVD on the substrates, the growing edges are normally zigzag
edges, having a hexagonal polygon structure34 or sometimes
even fractal shapes.35 The growth mode for carbon nanotube
(1D) can be either top or bottom modes (Figure 1f), and the
vertical 2D growth has also several possibilities: growth at the
top edge, on the surface (in the lateral direction), or at the
bottom (Figure 1f). Normally, the presence of the catalyst
particle and its position provide evidence for the growth mode,
top36 or bottom,37 as clarified by in situ experiments.38 If we
just inspect the final vertical graphene products, for example, in
Figure 1c, it is difficult to tell the mechanism as there is no
catalyst left behind, and the edges at the top and at the bottom
are both completely smooth. The folded structures of
graphene39,40 are also one possibility. However, these straight
edges have been previously proved to be closed (seamless)
edges of two monolayer graphene layers18 and a few other
reports also indicate the tendency of edge closure of two
adjacent graphene layers under high temperatures.41−43 The
growth will cease naturally at a closed edge (schematically
shown in Figure 1g). Nevertheless, we are able to find some
intermediate states of the growing vertical graphene among all
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the products. In Figure 3b, there is a typical vertical graphene
during growth, while in Figure 3a the atomic model highlights
the active edges and the curved nature. A series of steps can be
clearly identified on the surfaces, and the terraces are
highlighted in different colors. The steps are not straight but
in a round shape and arch upward. These steps play the same
role as the active edges that mediate the growth of vertical
graphene in the upward direction.
Here we can give further explanation of the step
morphologies and positions. The decomposition rate of the
precursor and the deposition rate of free carbon (adatoms)
onto the substrate as well as the growth rates are quite fast in
PECVD, evidenced by the thick buffer layer. Hence we assume
that the attachment and detachment of carbon adatoms on the
active steps or edges are the rate controlling processes for
graphene growth. Within this quasi-stationary boundary
condition (the diffusion rate is an order of magnitude larger
than the growth rate at the active sites), the concentration of
carbon adatoms on the terraces (surface) of vertical graphene
will be governed by the common 2D diffusion equation
D∇2 C − g C + d = 0 (1)
where C is the local carbon adatom concentration, d is the
carbon deposition rate which is homogeneous over the whole
surface, g is the carbon consuming rate due to growth which is
simplified to be proportional to the local carbon concentration,
and D is the diffusion constant. Consider our subject as a
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Figure 4. (a) The schematic model for the vertical graphene in a cross section view. The steps from the top edge are numbered X0, X1, X2...and so
forth. (b) The simulated result for a moving boundary problem using eq 4. The conditions for the simulations are the same as in the last simulation
in Figure 2c. The initial interval between nearest steps is assumed to be equal (time = 10) and at time = 27, the intervals between nearest steps
(terrace lengths) as a function of their number (counted from the top edge) are presented in the inset. (c,d) Cross section views of two growing
vertical graphene cases. The morphologies are highlighted by red dashed lines. These experimental terrace lengths of growing edges for vertical
graphene (red square in the inset of panel b) match well with the simulated terrace lengths (green circle in the inset of panel b), showing a tendency
of step convergence.

similar shape to the real vertical graphene in Figure 3b (see
Figure 3c), and one side connecting to the substrate has a
constant adatom concentration (C0), (Dirichlet boundary
condition, C = C0, much like contacting to a big carbon supply
tank). The other growing edges obey the Neumann boundary
condition, (∂C/∂x)·n = g0 where n is unit vector in the normal
direction at the boundary and g0 is the net mass flux (growth
rate at the edges) at the boundary. The 2D diffusion equation
can be numerically solved using a finite element method or
other appropriate techniques.
Following this scheme, Matlab Software was used and the
results are presented in Figure 3c. Before simulation, eq 1 can
be recast into a dimensionless form, where C* = gC/d, and eq 1
will become
2
w∇ C * − C * + 1 = 0
where w = D/gl2 and l is a characteristic length scale taken as
√D/g. Diffusion becomes negligible for small values of w (w ∼
0) when concentration becomes constant and the growth will
have no direction. This limiting case is certainly not applicable
in our work. The other limiting condition of large w (w ∼ ∞)
corresponds to the diffusion limit wherein the carbon
consumption due to growth and deposition of carbon directly
on the surface of graphene become negligible. This is not also
appropriate in our case and therefore, intermediate w values (w
∼ 1) would be meaningful to study here. Because we expect C*
= gC/d > 1 (to be discussed later), the boundary concentration
C0 would be large. We discuss a case where values for D, d, and
g were chosen as C0 = 10, D = 1, d = 1, and g = 1. A careful
analysis revealed that other values of w did not change the main
features of the concentration distribution. The shape of the
experimentally observed steps in Figure 3b matches well with
the contour lines of the carbon adatom concentration map in
Figure 3c. This can be understood readily by a simple linear
relationship between the step growth velocity and the local
carbon adatom concentration (also the supersaturation),44
v = K(C − Ceq ) (3)
where Ceq is the equilibrium carbon adatom concentration,
which is determined by the temperature as well as the
formation energy of carbon adatoms (or vancancies) (E) on the
graphene steps,
⎛ E⎞
Ceq ∼ exp⎜ ⎟
(2) ⎝ kT ⎠ (4)
During growth, the shapes of the steps located along the
concentration isolines are stable. Deviations from these isolines
which cause either faster or slower motion of the steps can lead
to negative feedback (because ∂C/∂x < 0, the growth speed is
slower at a faster growing location) and keep the shapes of the
steps. The carbon concentration on the two wings of the
vertical graphene is lower, therefore the step formation is
slower than in the center, hence leading to a round shape for
the steps. (Note in Figure 3a, the vertical graphene sheet is
curved and partially overlapped in the viewing direction,
therefore the sides are folded over, as schematically shown in
Figure 3b.)
We assume that d < gC in our analysis above. If d were larger,
then the carbon adatom flow would be reversed, and the carbon
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Nano Letters Letter

Figure 5. TEM images of some VG edges. (a) The seamless edge has two layers, forming a corner (lower inset, atomic structure of a double layer
seamless edge; upper inset, multislice TEM image simulation for this structure. There is also one incomplete graphene layer on the surface, similar to
what is present in the TEM image. (b) The 12 layer flat seamless edges with a nearly 90° angle corner (lower inset, atomic structure of a 12 layer
seamless edge; upper inset, TEM image simulation for this structure. There are some differences between the image and simulation at the corner
because the VG is not perfect at the corner.) (c) The tapered seamless edge, black triangles indicate the edge closure. (e,f) The nonstraight open
edges, which are in the growing processes.

concentration would be larger at the two wings of the graphene
sheet. In this case, the shapes of the steps are unstable,
deviation from the isolines can be positive feedback (∂C/∂x >
0) and hence enlarge the deviations. Therefore, we can exclude
the possibility that d > gC.
The kinetics of steps can be further elaborated if a time lapse
is included into the boundary conditions. For the simplified 1D
model (cross section view at the center line in the vertical
direction of graphene, Figure 4a) for vertical graphene, the
moving boundary conditions are set and the governing
equations are
⎧ ∂ 2C(x , t )
⎪D − gC + d = 0
⎪ ∂x 2
⎪ dX n
⎪ = KC(X n , t )
⎨ dt
⎪ naturally form a lip−lip connection during growth and the
⎪ C(0, t ) = C0
⎪ are normally nonstraight (Figure 5d−f).
⎪ ∂C(x = X 0)
=0
⎩ ∂x
where Xn are the positions for each step, and X0 stands for the
position of the top edge. With the initial terraces (decided by
nucleation) assumed to be equally distributed, and using a finite
element method to simulate this growth, the step positions as a
function of time can be plotted in Figure 4b. Here, time is
divided into finite periods and the diffusion equation is then
solved under stationary assumptions. The inset of Figure 4b
also shows the different terrace lengths (Ln =Xn − Xn+1) after
some growth. This linear relationship of the terrace length and
the terrace number implies a convergence tendency of all the
steps which starts from the top, and this tendency matches well
with our experimental HRTEM observations (Figure 4c,d).
The above kinetic model and experimental observations
demonstrate that the growth of vertical graphene can be
considered as a step-flow process45 on the basis of nucleation at
the bottom. According to this mechanism, the thickness of
graphene will depend on the number of layers which nucleates
from the bottom. Regarding the size of the vertical graphene,
there are at least two limitations. The first limitation is that two
graphene layers nearby can naturally connect with each other to
form a sealed edge. The seamless edges that have double
graphene layers and 12 layers are shown in Figure 5a,b,
respectively. The atomic structures and multislice TEM image
simulations are presented in the insets. The formation of this
closed structure can lead to the “magic angle” (the integer times
of 30°) that has been reported previously and such sealed edges
are usually zigzag or armchair.18 The tapered edges are more
frequently observed because the neighboring layers can
growth can cease (Figure 5c). In contrast, the growing edges
The bending curvature of the whole vertical graphene can
(5) also affect their sizes. Any local curvatures in sp2 carbon may
possibly cause more defects (like heptagons and pentagons)
during growth and these defects will disturb the diffusion of
free carbon adatoms on the surfaces. In other words, the
diffusion length on surfaces of curved graphene is shorter than
on flat graphene. Therefore, the growth speed at the edges for
curved vertical graphene (Figure 1b) will be slower than for flat
graphene (Figure 1c). Eventually the flat graphene without
curvature can be larger than the highly curved ones under the
same growth conditions, which is confirmed by our TEM
observations. Finally, these seamless edges as well as folded
structures, which are common in few-layered grapheme,46
provide the mechanical support for the free-standing vertical
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Nano Letters
alignment; otherwise, these large ultrathin sheets would easily
bend or scroll. The closure of edges can greatly suppress the
interlayer shear which could occur for open edge graphene. The
bending rigidity for the closed edges (similar to nanotubes) is
at least 1 order of magnitude larger than the open edges.47
In conclusion, our TEM observations reveal the growth
mechanisms for vertical graphene grown by PECVD. The
nucleation occurs at the mismatch of graphitic carbon layers
(surface at buffer layer on the substrate as well as carbon
onions) and the active sites for growth can be the surface steps
as well as the edges at the top. The diffusion of carbon adatoms
on the surfaces of vertical graphene supplies the materials
needed for the growth while the rate controlling step is the
attachment of carbon atoms at the active sites. We developed a
moving boundary model that can describe the motion of the
steps with respect to time. The experimental observations of
the step morphologies and the relative positions of the steps
can thus be explained. Finally, the closure of open edges
determines the final size of the vertical graphene and together
with the overall curvature provide the necessary mechanical
support for vertical alignment.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: M.Ruemmeli@ifw-dresden.de.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
J.Z. thanks the DAAD. Support from the excellence cluster
(CFAED) is gratefully acknowledged. This work was supported
by the Institute of Basic Science (IBS) Korea (EM1304). We
also thank Ms. Y. Woo and Mr. J. Ju for their support with the
TEM facilities at SKKU.
■
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