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Available at www.sciencedirect.com

ScienceDirect
journal homepage: www.elsevier.com/locate/carbon

Long-range interactions of bismuth growth

on monolayer epitaxial graphene at room
temperature
H.-H. Chen a, S.H. Su a, S.-L. Chang d, B.-Y. Cheng a, C.-W. Chong a, J.C.A. Huang
M.-F. Lin a,*

a,b,c,*
,

Department of Physics, National Cheng Kung University, Tainan 701, Taiwan

Advanced Optoelectronic Technology Center, National Cheng Kung University, Tainan 701, Taiwan
c
Taiwan Consortium of Emergent Crystalline Materials, Ministry of Science and Technology, Taipei 106, Taiwan
d
Department of Electrophysics, National Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu 30050, Taiwan
b

A R T I C L E I N F O

A B S T R A C T

Article history:

Long-range electronic interaction between Bismuth (Bi) adatoms on graphene formed on a

Received 12 February 2015

4H-SiC (0 0 0 1) substrate are clearly observed at room temperature (T = 300 K). Using scan-

Accepted 17 May 2015

ning tunneling microscopy (STM) and density functional theory (DFT) calculations, we have

Available online 21 May 2015

demonstrated that such oscillatory interaction results mainly from the mediation of
graphene Dirac-like electrons and the effect of the corrugated surface of SiC substrate.
These two factors cause the observed oscillatory interaction with characteristic distribution distances and linear arrangements of Bi adatoms. The present study sheds light on
understanding and controlling the nucleation of adatoms and subsequent growth of
nanostructures on graphene surface.
 2015 Elsevier Ltd. All rights reserved.

1.

Introduction

Understanding how adsorbates interact with each other on an

atomically well-defined surface and controlling their structures are essential to the fabrication of low-dimensional
materials with novel electronic structures. In recent decades,
adsorbateadsorbate interactions have been extensively studied both theoretically [1,2] and experimentally [35], but
almost can be observed only at rather low temperatures.
These interactions have various origins that can be generally
categorized according to their adsorbate separation statistics,
resulting in several possible interaction behaviors as a function of distance between two adsorbates [6]. In particular,
the electronic indirect interaction mediated by surface

electrons exhibits characteristic feature of oscillatory interaction energy. These oscillatory interactions can be observed
directly by scanning tunneling microscopy (STM) [7,8]. The
inability to clarify the interactions between adsorbates prevents the clear identification of the nucleation and growth
of adatoms and limits the development of advanced devices
with nanometer dimensions.
Despite many of the concerns paid to interactions between
adsorbate and a well-defined surface, most studies have
focused on metal surfaces. An atomically well-defined surface with unique properties for the fundamental study of
nucleation and growth of adatoms and invention of highperformance device is of our great interest. Graphene is a
model candidate, owing to its remarkable physical properties

* Corresponding authors at: Department of Physics, National Cheng Kung University, Tainan 701, Taiwan (J.C.A. Huang).
E-mail addresses: jcahuang@mail.ncku.edu.tw (J.C.A. Huang), mflin@mail.ncku.edu.tw (M.-F. Lin).
http://dx.doi.org/10.1016/j.carbon.2015.05.052
0008-6223/ 2015 Elsevier Ltd. All rights reserved.

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[9,10] such as high carrier mobility and Dirac-like electrons.

Additionally, doping of graphene with heavy metals can control the number of carriers and spinorbit coupling (SOC) can
be exploited for fundamental electronic studies and spintronic applications. Charge transfer between metal adatoms
and carbon atoms are also worthy of investigation and may
lead to a distinct graphene electronic structure. To date, many
theoretical [1115] and experimental studies [1619] of adsorbategraphene systems have been performed. Almost all
related experiments have focused on either the adsorbate
graphene interactions or the modified graphene properties
following the adsorption of atoms and molecules, interactions between adatoms had been seldom addressed until
S. M. Binz et al. and Xiaojie Liu et al. reported the deposition
of Fe clusters on graphene [20,21] and Can-Li Song et al.
explored the adsorption of Cs adatoms on graphene [22].
Semimetal bismuth (Bi), being one of the most extensively
studied elements, has received considerable attention
because of its unique electronic properties as a Dirac fermion
gas [23], long Fermi wavelength and small effective electron
mass [24]. Furthermore, Bi can form a narrow band gap semiconductor due to strong quantum confinement effect [25,26]
when it is restricted to nanoscale. Moreover, SOC on a Bi surface results in significant and anisotropic splitting of the
surface-state bands, suggesting possible potential applications for electronic and spintronic devices [23,2527].
In this work, we report our STM study and DFT calculations of Bi adsorption behaviors, Bigraphene and BiBi interactions on monolayer epitaxial graphene (MEG) formed on
Si-terminated 4H-SiC (0 0 0 1) substrate. The observed phenomenon of oscillatory interaction of BiBi adatoms at room
temperature is explained by the mediation of graphene
Dirac-like electrons and the effect of the corrugated surface
of SiC substrate.

2.

Experimental

Experiments were performed in an ultrahigh-vacuum (UHV)

system (JSPM-4500 A/S; JEOL Ltd.) with a base pressure of
2.0 108 Pa. The system consisted of a sample preparation
chamber and a variable temperature STM/AFM observation
chamber equipped with a cooling tank [28,29]. The
Siterminated 4H-SiC (0 0 0 1) single crystal with CMP process
was purchased from Cree, Inc. Siterminated 4H-SiC (0 0 0 1)
substrate was used and cleaned ultrasonically in acetone
and isopropanol before in situ degassing at 600 C in UHV
for several hours. The substrate was then annealed under a
low Si flux at 1000 C to remove the native oxide before
annealing to higher temperatures without Si flux. Graphene
was subsequently formed by thermal annealing in the temperature range of 12001300 C [30]. The temperature of the
sample was measured by a C-type thermocouple located
behind and very close to the sample holder. Moreover, an
infrared thermometer (Cyclops 100B, AMETEK Land, Inc.)
was employed to calibrate the sample temperature. Bi was
deposited on the graphene surface from a Bi rod (diameter
of 2 mm, purity of 99.9999%) by electron bombardment in a
water-cooled commercial evaporator (Omicrometer EFM 3)
at room temperature. The atomic density of the deposited metal

181

was represented in the monolayer (ML) form, corresponding to a

Bi packing density of 1.1 1015 Bi atom/cm2 when proceeding
along the growth plane of graphene [31]. The growth rate was
determined to be approximately 0.0013 ML per minute.
Immediately following deposition, the sample was introduced
into the STM measurement chamber under UHV condition.
STM experiments were conducted at room temperature and
data were collected in a constant current mode. The dI/dV
tunneling spectrum was carried out by holding the tip at a fixed
distance above the surface and using a standard lock-in
technique at liquid nitrogen temperature. A small a.c. modulation voltage of 10 mV at 4.7971 kHz was applied to the tip.
The calculation results were performed within density
functional theory under local density approximation potential (LDA) in the form of Projector augmented-wave method
(PAW) [32,33] implemented in the Vienna Ab initio
Simulation Package (VASP) [33,34] codes. The Wave functions
were expanded by plane wave basis set within energy cutoff
500 eV, and the first Brillouin zone was sampled by a
3 3 1 k-point mesh in the gamma schema. All calculation
parameters were carefully chosen to converge the total
energy to 0.01 eV. Since we represented a 2-D structure on
was inserted between
SiC substrate, a vacuum space of 15 A
periodic images to simulate an isolated system. Based on previous study [35,36], we constructed 4 bilayer silicon carbide
films as the substrate. The buffer layer and monolayer graphene form an AB stacking-like structure on Siterminated
substrate. Both layers were reconstructed.

3.

Results and discussion

Fig. 1a shows a 7 nm 7 nm topographic image of MEG. The

image reveals a well-identified honeycomb lattice of the graphene superimposed onto the 6 6 corrugation buffer layer
structure (white hexagon). According to Fig. 1a, the 6 6
superstructure includes two distinctive regions: the lattice
matched (valley) region and the lattice mismatched (rim)
region [22,37,38]. The dI/dV spectrum of the as-grown MEG
exhibits a local minimum 0.37 eV in Fig. 1b, representing
the Dirac point of graphene [39,40]. Upon Bi deposition, protrusions of approximately 0.24 nm in height are observed
with different coverage of Bi adatoms, as presented in Fig. 2.
At 0.0013 ML, it reveals dispersed protrusions, as illustrated
in Fig. 2a. The interactions of Bi adatoms are pairwise and
additive with increasing Bi coverage. As coverage increased,
the arrangement of the protrusions exhibits linear-like ordering (at 0.0078 ML, Fig. 2b). Moreover, at 0.0092 ML, large scale
linear structures can be detected in STM image, as illustrated
in Fig. 2c, indicating possibly one-dimensional (1D) growth
mode. In order to clarify the BiBi interactions of such structures, the pair distance distribution analysis between Bi adatoms, by analyzing Fig. 2c, is introduced by firstly evaluating
over 18800 interadatom separations from a series of nonoverlapping STM images and then plotting a statistical histogram
N(r) of these separations, as illustrated in Fig. 3a. By comparing the theoretical function with the random distribution
N 0 (r) of interadatom separations r in the absence of BiBi interactions (blue dashed line in Fig. 3a) [29], the pair-correlation
function, in terms of the two-body interaction, can be

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Fig. 1 (a) Atomically resolved STM image (7 nm 7 nm) of MEG on 4H-SiC (0 0 0 1) and the corresponding Fast Fourier
transform (inset). White solid arrow points to a 1 1-G spot and green dashed arrow to a 6 6-SiC spot [36,43]. Imaging
conditions: Vs = 40 mV, I = 0.15 nA. (b) The dI/dVV curve obtained on clean surface of MEG. (A colour version of this figure can
be viewed online.)

Fig. 2 STM image of Bi adatoms on MEG with (a) 0.0013 ML (20 nm 20 nm, Vs = 0.85 V, I = 0.15 nA), (b) 0.0078 ML
(20 nm 20 nm, Vs = 0.74 V, I = 0.15 nA) and (c) 0.0092 ML (17.3 nm 22.3 nm, Vs = 0.84 V, I = 0.15 nA). (A colour version of this
figure can be viewed online.)
described as gr NNr
. Next, the interaction potential E(r)
0
r
between the Bi adatoms is determined by E(r) = kBT ln [(g(r))]
[29], where T denotes the temperature (T = 300 K), and kB
represents the Boltzmann constant.

Fig. 3b plots the interaction potential between Bi adatoms,

E(r), as a function of distance between the interadatom separations r. The interaction potential, E(r), reveals a clearly oscillatory long-range interaction. This oscillatory feature is very

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Fig. 3 (a) Statistical histogram N(r) of separations between

Bi adatoms obtained from a series of STM images recorded
at room temperature. Blue dashed line N 0 (r) represents the
expected distribution in the absence of any interatomic
interactions. Black arrows correspond to the energy minima
in the Fig. 3b. (b) The experimentally derived potential
energy (solid line) is overlaid with two theoretically derived
plots (red and blue dashed lines). The standard deviation of
the mean is shown as the error bar. Inset: k1=2 1:50 nm
measured from experimental interaction potential. Arrows
indicate four potential energy minima at 1.8, 3.3, 4.8 and
6.3 nm. (A colour version of this figure can be viewed
online.)

likely to originate from Friedel oscillations [4]. To verify the origin of the oscillatory feature, the interaction energy is theoretically fitted as follows. The experimental interaction energy
(solid line, Fig. 3b) is overlaid with two theoretical energy plots
(red and blue dashed lines in Fig. 3b) adapted from Hyldgaard
[2] and V. V. Mkhitaryan [14], respectively, with adequate fitting. The first theoretical energy plot (red dashed line in
Fig. 3b) resembles a Shockley surface state fit of a (1 1 1) noble
metal surface and can be formulated as follows [2]:
 
4e sin2kF r 2dF
Er AdF ; r 2
1
2
p
kF r
where dF represents the phase shift, e is the carrier energy,
is the Fermi wave vector, r is the interatomic distance,
kF 2p
kF
and A is a dimensionless value representing the interaction
strength. Hence, the first observed position of minimum

potential energy, at a distance of 1.8 nm, corresponds to the

first favorable distance between the adatoms, and the following minima are observed at intervals of 1.5 nm (which is,
kF/2). Additionally, the amplitude of the interaction strength
decays as 1/r2. The theoretical energy plot is based on Eq. (1)
with A = 0.78 and d = 0, and the measured A is larger than previous values of noble metal surface in the literature [3]. This
difference probably results from the fact that Bi is a strong
scattering element. The phase shift of Fit (1) is zero, which
is smaller than that for the noble metal surface case [4].
This discrepancy may be attributed to fundamental property
differences between graphene Dirac-like electrons and the
electrons of the Shockley surface state of a (1 1 1) noble metal
surface. Notably, Shockley surface-state electrons have a
finite Fermi wave vector [4] but Dirac-like electrons of intrinsic graphene have a very small (almost zero) Fermi wave vector. Only by gating or doping in graphene, finite Fermi wave
vector can be achieved. This issue will be addressed in the following discussions of Fit (2). Furthermore, the first minimum
of potential energy in the theoretical energy plot is less than
25 meV, indicating that the observed distribution of BiBi distances described by Eq. (1) should not be stable at room temperature. Therefore, the description of a conventional twodimensional electron gas description cannot be fully applied
to our study. The second theoretical energy fit (blue dashed
line in Fig. 3b) describes a system with the Berry phase and
nontrivial chiral spectrum, if the states with momenta k
and k are mutually orthogonal and then backscattering is
suppressed [41]. This situation could happen in the case of
doped or gated graphene [10], when the Fermi level is shifted
away from the Dirac points, such that kF 5 0. The doping level
reveals nonzero Fermi momentum and this phenomenon can
be roughly described as [14]:
Er a  2 sindF

cos2kF r dF
p2 kF r3

where dF denotes the phase shift, kF 2p

is the Fermi wave
kF
vector, r is the distance, and a is a constant value that represents the energy scale. The theoretical energy plot is based on
Eq. (2) above with a = 2000 and d = p/2 and the same oscillatory
period and similar potential energy minimum features are
determined. Moreover, the potential energy minima fit better
than those in Fit (1) and the experimentally observed first
energy maximum is about 11 meV, likely originating from a
strong scattering effect of Bi adatom [3]. Notably, the deviation of experiment plot from two theoretical plots is large at
r < 1.5 nm. With a closer examination, experimental E(r)
approximately decays as 1/r at r < 1.5 nm, suggesting that a
possibly electrostatic interaction exists between Bi adatoms.
Such 1/r behavior could be originated from the interaction
between Bi adatom and graphene, and it is similar with previous literature [22]. The two theoretical formula employed
herein do not include the electrostatic interaction, which
could be the reason of large deviation at r < 1.5 nm.
Meanwhile, two interesting features can be observed in
experimental plot. First, the potential wells in the empirical
E(r) in Fig. 3b and the first potential energy minimum,
32 meV in Fit (2), are seemingly not completely sufficient
to keep the Bi atoms at the certain site. We then speculate
that the observed order structure could be a metastable

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phase. Second, compared with previous report [39], one finds

that the Fermi wave vector obtained from Fig. 3b is quite
large, indicating heavily doped graphene. This conflict with
the evaluated Dirac point measured in Fig. 1b. That is, there
are other factors existing in the formation of the observed
oscillatory interaction and it will be addressed in the following discussions.
Based on the above findings, we suggest that not only the
Dirac-like electrons in graphene but also some factors are
responsible for the room-temperature oscillatory interaction
between Bi adatoms. It is noticed that Dirac-like electrons
mainly originate from the doping effect of the underlying
SiC substrate and the charge transfer between graphene
and Bi adatom. By photoemission spectroscopy data and
STM studies, combined with DFT calculations, A. T. S. Wee
and his colleagues have verified very weak interactions
between Bi nanoribbon and MEG [31,42]. Therefore, we suggest that the charge transfer between graphene and Bi should
be a minor effect and the doping effect of SiC substrate is very
likely to play a major role in the contribution of the Dirac-like
electrons [31,42]. Notably, the induced energy difference follows the usual Friedel cos2kF r=r3 dependence, with the resonance behavior entering via the phase shift, as shown in
Eq. (2). For such a reason, the measured p/2 phase shift indicates that the deposition of Bi adatoms on graphene is in
the resonance region [14]. In contrast, Fe clusters that are
deposited on epitaxial graphene [20,21] exhibit FeFe interactions that involve short-range attraction and long-range

repulsion. Such interactions are attributed to sum of dipole

dipole, elastic (substrate) and indirect interactions. On the
other hand, Cs adatoms that are deposited on epitaxial graphene [22] exhibit CsCs long-range electrostatic interaction
mainly caused by significant charge transfer from Cs to epitaxial graphene, which is also coupled with the corrugated
substrate.
Same as previous literature [22], MEG exhibits the unambiguously characteristic 6 6-SiC periodicity in Fig. 1a, indicating the existence of influence of the corrugated
substrate. However, the BiBi interactions herein differ significantly from the behaviors described above and an unexpected Fermi wave vector is extracted from Fig. 3. Therefore,
the effect of corrugated substrate should need a careful investigation for the formation of oscillatory interaction between
Bi adatoms.
Generally, corrugated substrate can be most likely represented as exhibiting the curvature effect, which observably
changes the chemical activity and binding energy of graphene
[38]. A closer examination of the STM image, as illustrated in
Fig. 4a, reveals linear arrangements of Bi adatoms rather
than short-range ordered hexagonal structures with an average interadatom separation of 6 6 superstructure [22], indicating weak influence of 6 6 superstructure. Thus, the
structure of the underlying buffer layer should also be carefully examined instead of a simple consideration of the 6 6
superstructure. DFT calculations are introduced and balland-stick representations of MEG/4H-SiC (0 0 0 1) structures

Fig. 4 (a) Linear Bi structures are represented by several colored lines (red, green and blue), representing different
orientations. (b) Top view and side view ball-and-stick representations of MEG/4H-SiC (0 0 0 1). MEG, C and Si atoms are shown
in different colors. (c) DFT results of two different length variation units on buffer layer structure. (d) Possible orientation with
respect to each Unit 1 due to bond length variation and angle of structure of 90 degrees between Unit 1 and Unit 2. (A colour
version of this figure can be viewed online.)

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are schematically presented in Fig. 4b. As in the literature

[35,36], DFT calculations herein demonstrate reliable structure features. In the structure of MEG/4H-SiC (0 0 0 1), some
bonding length variations are observed in the buffer layer
and such C atoms are marked in red color in Fig. 4b. That
is, the buffer layer reveals bonding length variations around
the C atom due to C atom bonded to Si atom or not, as shown
in left panel of Fig. 4c. Additionally, in Fig. 4a, most linear Bi
structures are indicated by red lines (oriented at 60 with
respect to the green lines and 30 with respect to the blue
lines). Additionally, the blue lines are oriented at 90 with
respect to green lines. The observation of linear arrangements of Bi adatoms along the three different orientations
is adequately consistent with the fact that the deposition of
Bi nanoribbons grown on MEG [42]. Moreover, the average
BiBi interatomic distance obtained from Fig. 2 is 1.8 nm,
which is almost four times the lattice constant along the
[1120] direction of Bi nanoribbon [42]. Furthermore, DFT calculations reveal that the buffer layer clearly exhibit two different bonding length variation units, d1 and d2 of Unit 1 and
Unit 2, respectively. The length ratio d1/d2 is approximately
0.866 obtained from DFT calculations and the statistical
length ratio DRed/DBlue is roughly 0.878 0.008 extracted from
experimental data, as shown in Fig. 4a and c. As described
above, the structure of buffer layer should be an important
reason for the formation of the linear Bi structure and causing
small variations in the interatomic distances between Bi adatoms. With a closer examination of the underlying buffer
layer of SiC, Unit 1 or 2 is oriented at 60 with respect to itself
and 90 with respect to the other, as illustrated in Fig. 4d.
Clearly, the underlying buffer layer of SiC determines the
effect of the corrugated substrate which causes the linear
arrangements of Bi adatoms. Furthermore, the different orientations of the linear structures of Bi adatoms are consistent
with Bi nanoribbons grown on MEG [42]. This detailed investigation provides a route to elucidating the initial nucleation of
Bi adatoms and the subsequent growth of Bi nanoribbons.
However, further DFT calculations and experimental works,
including different coverages and temperature effect, are
needed to carry out in the future.

4.

Conclusion

In summary, this work has demonstrated the long-range

oscillatory interaction of Bi adatoms adsorbed on graphene
formed on 4H-SiC (0 0 0 1) at room temperature. The oscillatory feature resembles much as Friedel oscillations. Using
STM experiments and DFT calculations, such interaction is
explained by the mediation of graphene Dirac-like electrons
and the effect of the corrugated substrate. The mediation of
graphene Dirac-like electrons and the corrugated substrate
are responsible to the observed oscillatory interaction with
characteristic distribution distances and linear arrangements
of Bi adatoms. The approaches adopted in this work are useful for understanding the adatomadatom interactions as
well as the nucleation and growth of adatoms on MEG. The
results could be utilized to realize graphene-based electronic
and spintronic devices down to nanometer dimensions at
room temperature.

185

Competing financial interests

The authors declare no competing financial interests.

Acknowledgments
The authors would like to thank the Ministry of Science and
Technology of the Republic of China, Taiwan, for financially
supporting this research under Contract MOST 103-2119-M006-015. The authors are also grateful for their useful discussion with Ko-Fan Tsai at National Cheng Kung University
(NCKU). Funding was also gratefully received from the
Headquarters of University Advancement at NCKU, which is
sponsored by the Ministry of Education, Taiwan, ROC. Ted
Knoy is appreciated for his editorial assistance.

Appendix A. Supplementary data

Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.carbon.
2015.05.052.

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