First direct observation of Dirac fermions in graphite

S.Y. Zhou,1, 2 G.-H. Gweon,1 J. Graf,2 A.V. Fedorov,3 C.D. Spataru,1, 4

R.D. Diehl,5 Y. Kopelevich,6 D.-H. Lee,1, 2 Steven G. Louie,1, 2 and A. Lanzara1, 2
arXiv:cond-mat/0608069v1 [cond-mat.str-el] 2 Aug 2006

1
Department of Physics, University of California, Berkeley, CA 94720, USA
2
Materials Sciences Division, Lawrence Berkeley
National Laboratory, Berkeley, CA 94720, USA
3
Advanced Light Source, Lawrence Berkeley National
Laboratory, Berkeley, California 94720, USA
4
Chemical Sciences Division, Lawrence Berkeley
National Laboratory, Berkeley, CA 94720, USA
5
Department of Physics and Materials Research Institute,
Penn State University, University Park, Pennsylvania 16802, USA
6
Instituto de Fisica Gleb Wataghin,
Universidade Estadual de Campinas,
Unicamp 13083-970, Campinas, Sao Paulo, Brasil
(Dated: February 4, 2008)

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 Originating from relativistic quantum field theory, Dirac fermions have been
recently applied to study various peculiar phenomena in condensed matter
physics, including the novel quantum Hall effect in graphene [1, 2], magnetic
field driven metal-insulator-like transition in graphite [3, 4], superfluid in 3 He
[5], and the exotic pseudogap phase of high temperature superconductors [6, 7].
Although Dirac fermions are proposed to play a key role in these systems, so far
direct experimental evidence of Dirac fermions has been limited. Here we re-
port the first direct observation of massless Dirac fermions with linear dispersion
near the Brillouin zone (BZ) corner H in graphite, coexisting with quasiparti-
cles with parabolic dispersion near another BZ corner K. In addition, we report
a large electron pocket which we attribute to defect-induced localized states.
Thus, graphite presents a novel system where massless Dirac fermions, quasi-
particles with finite effective mass, and defect states all contribute to the low
energy electronic dynamics.
For most condensed matter systems, the physics is formulated in terms of the nonrela-
tivistic Schrodinger equation, and the low energy excitations are quasiparticles with finite
effective mass. For some special systems, e.g. graphene/graphite, where the dispersion is ex-
pected to be linear near the Fermi energy EF and touch EF only at one point (Dirac point),
the physics is described by the relativistic Dirac equation with the speed of light replaced
by the Fermi velocity vF . The low energy excitations in this case are Dirac fermions, which
have zero effective mass and a vanishing density of states at the Dirac point. These massless
quasiparticles are proposed to be responsible for various anomalous phenomena observed in
these systems [1, 2, 3, 8]. So far, transport experiments in graphene have shown results in
agreement with the presence of Dirac fermions [1, 2]. Phase analysis of quantum oscillations
in graphite has also suggested coexistence of both Dirac fermions and quasiparticles with
finite effective mass [9]. Here we report the first direct observation of massless Dirac fermions
coexisting with quasiparticles with finite effective mass in graphite, by using angle resolved
photoemission spectroscopy (ARPES). ARPES provides the advantage of directly probing
the electronic structure with both energy and momentum information, not accessible by any
other measurement.
Figure 1(a) shows an ARPES intensity map measured near the BZ corner H. The out-of-
plane momentum kz is 0.5 c , where c is the reciprocal lattice constant (see supplemental

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information for extraction of kz values). Following the maximum intensity in this map, a
linear -shaped dispersion can be clearly observed. The dispersion can be better extracted by
following the peak positions in the momentum distribution curves (MDCs), momentum scans
at constant energies, shown in panel b. Here, two peaks in the MDCs disperse linearly and
merge near EF . The Fermi velocity extracted from the dispersion is 0.910.15106 m s1 ,
similar to a value 1.1106 m s1 reported by a magnetoresistance study of graphene [2].
We note that at low energy near EF , this linear dispersion is also observed along other cuts
through the H point, with similar Fermi velocity. This linear and isotropic dispersion is in
agreement with the behavior of Dirac fermions.
Another way of probing the linear and isotropic dispersion is to study the intensity maps
at constant energy. At EF (Figure 2(a)), the intensity map shows a small object near H.
The details of this small object will be discussed later. With increasing binding energy, this
object expands and shows a circular shape (panels b-c). We note that only the circular
shape in the first BZ is clearly observed. This is attributed to the dipole matrix element
[10], which suppresses or enhances the intensity in different BZs. However, taking the three
fold symmetry of the sample, this circular shape in the first BZ is expected to extend to
other BZs and thus the electronic structure is isotropic near H. As the energy increases to
-0.9 eV, the constant energy map slightly deviates from the circular shape (see arrow in
panel d). This deviation increases with binding energy and a trigonal distortion is clearly
observed at -1.2 eV (panel e). This trigonal distortion is determined by the relevant tight
binding parameters for graphite and further studies to analyze this trigonal distortion are
in progress. Overall, Figure 2 shows that from EF to -0.6 eV, the electronic structure is
isotropic in the kx -ky plane. Similarly, the Fermi velocity measured within the first BZ is
1.0106 m s1 with a 10% variation along different directions, consistent with the circular
constant energy maps shown here. Combining the results of Figures 1 and 2, we conclude
that from EF to -0.6 eV, the dispersion shows a cone-like behavior near each BZ corner H,
similar to what is expected for graphene (panel f).
To resolve the details of the low energy dispersion and the small object at EF (Figure
2(a)), we show in Figure 3(a) an intensity map measured near H with lower photon energy to
give better energy and momentum resolution. In the intensity map, one can distinguish two
bands dispersing linearly toward EF , as also clear in the MDCs (panel b) where two peaks
can be observed for all binding energies. The extracted dispersion (open circles in panel

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a) from MDCs (panel b) shows two bands dispersing linearly toward EF , with a minimum
separation of 0.0200.004 A1 at EF . This linear dispersion near the H point, as well as the
isotropic electronic structure shown in Figure 2 from EF to -0.6 eV, is a basic characteristic
of Dirac quasiparticles, which points to the presence of Dirac quasiparticles in the low energy
excitations near the H point in graphite. Furthermore, from the extracted dispersions, the
Dirac point is extrapolated to be 5020 meV above EF , and thus the small object observed
at EF is a hole pocket. Assuming an ellipsoidal shape for the hole pocket [11], the hole
concentration is estimated to be 3.11.31018 cm3 , from the 0.020 A1 separation of the
peaks at EF . This hole concentration is in agreement with reported values [11, 12, 13]. The
presence of holes with Dirac fermion dispersion is further supported by the angle integrated
intensity (panel c), which is proportional to the occupied density of states, barring the
matrix element. In this energy range, a linear behavior, similar to what is expected for
Dirac fermions, is observed. In addition, the energy intersect is at 50 meV above EF , in
agreement with the Dirac point energy extrapolated from the dispersions.
Figures 1 to 3 show that near the H point, the low energy excitations in graphite are
massless Dirac fermions characterized by linear and isotropic cone-like dispersion, in agree-
ment with transport measurements in graphite where Dirac fermions are suggested to coexist
with quasiparticles which have finite effective mass [9]. To gain direct insight on the different
types of quasiparticles, ARPES can provide a unique advantage by directly measuring the
effective mass as well as accessing its momentum dependence. Figure 4(a) shows the inten-
sity map near another high symmetry point in the BZ corner, the K point. The dispersion
(open circles) shows a parabolic behavior, in sharp contrast to the linear behavior observed
near the H point (Figures 1 and 3). This parabolic dispersion points to the presence of quasi-
particles with finite effective mass. To determine the effective mass, we first extract the low
energy dispersion, then fit the MDC and EDC dispersions (panels b, c) with a parabolic
function. In both cases, the effective mass is determined to be 0.0690.015 me , where me is
the free electron mass. This effective mass measured by ARPES shows some difference with
values reported by transport measurements [12, 13, 14], 0.052 and 0.038 me for electrons
and holes respectively. This difference may be due to the fact that transport measurements
are not momentum selective, and therefore the mass measured is the average mass over all
kz values. On the other hand, ARPES is momentum selective and the value for the effective
mass is for this specific kz value only. Taking this into account, the agreement between

4
these measurements is reasonable. In summary, the data presented so far show that the low
energy excitations in graphite change from massless Dirac fermions with linear dispersion
near H (Figures 1-3) to quasiparticles with parabolic dispersion and finite effective mass
near K (Figure 4(a)).
We now discuss another interesting feature observed in graphite, i.e., a large electron
pocket near EF . Figure 4(d) shows the intensity map measured in the same experimental
conditions as Figure 4(c) except at a different spot. In panel d, a strong and large electron
pocket within 50 meV below EF is the dominant feature. Weak signatures of the parabolic
band (as in panel c) can still be observed, as the MDC at EF (panel e) demonstrates.
Here, in addition to the two main peaks (black arrows) corresponding to the electron pocket,
a central weak peak (gray arrow) corresponding to the top of the parabolic band can also
be distinguished. From the separation ( 0.1 A1 ) between the two main peaks at EF ,
the electron concentration is determined to be 8.00.71019 cm3 , which is an order of
magnitude higher than the values reported [12, 13]. Moreover, from the dispersion (panel
d), the effective mass is extracted to be 0.42 0.07 me , which is also much larger than any
mass reported by transport measurements [12, 13, 14].
This large electron pocket, though position dependent, is observed in most of the samples
measured, and thus it represents an important feature associated with graphite. We propose
defect-induced localized states as a possible explanation for this large electron pocket, based
on the following reasons. First, the electron concentration and effective mass measured for
this electron pocket are much larger than reported values. Second, although the parabolic
band in panels a and c is observed in all the samples measured and in different spots (averaged
over 100 m) within the same sample, this large electron pocket strongly depends on the
spot position within the same sample. Third, STM shows that zigzag edges can induce a
peak in the local density of states at an energy ( -0.03 eV) similar to the electron pocket
observed here [15]. In fact, it has been shown that low concentration of defects (e.g. edge
states, vacancies, etc.) can induce self-doping to the sample [16, 17]. If this interpretation
is correct, then further studies on this large electron pocket may shed light on the magnetic
properties of nano-graphite ribbons, since it has been proposed that some defect-induced
localized states are magnetic [18, 19].
In conclusion, we report the low energy electronic dynamics of graphite, where massless
Dirac fermions, quasiparticles with finite effective mass, as well as defect-induced localized

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states all have important contributions. These low energy electronic properties are important
in understanding the exotic properties not only in graphitic systems, but also in other
strongly correlated systems where Dirac fermion dynamics may be important.
Supplementary information
High resolution ARPES data have been taken at Beamlines 12.0.1 and 7.0.1 of the Ad-
vanced Light Source (ALS) in Lawrence Berkeley National Lab with photon energies from
20 to 155 eV with energy resolution from 15 to 65 meV. Data were taken from single crystal
graphite samples at a temperature of 25 K. Throughout this paper, the kz values are esti-
mated using the standard free-electron approximation of the ARPES final state [20, 21, 22].
The inner potential needed for extracting the kz value was determined from the periodicity
of the detailed dispersion at the Brillouin zone center A using a wide range of photon
energies from 34 to 155 eV. The consistency of the kz values is confirmed by the degeneracy
of the bands near H and a maximum splitting near K (Figure 5), both in agreement with
band structure [23, 24, 25].

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Acknowledgments

We thank A. Castro Neto, V. Oganesyan, A. Bill, K. McElroy, C.M. Jozwiak, and D.

Garcia for useful discussions; E. Domning and B. Smith for beam line 12.0.1 control soft-
ware. This work was supported by the National Science Foundation through Grant No.
DMR03-49361, the Director, Office of Science, Office of Basic Energy Sciences, Division of
Materials Sciences and Engineering of the U.S Department of Energy under Contract No.
DEAC03-76SF00098, and by the Laboratory Directed Research and Development Program
of Lawrence Berkeley National Laboratory under the Department of Energy Contract No.
DE-AC02-05CH11231.

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FIG. 1: Linear -shaped dispersion near the BZ corner H. (a) ARPES intensity map taken
near the H point (photon energy h=140 eV, kz 0.50 c ), along a cut through H and perpendicular
to kx (see red line in the BZ shown in panel c). The inset shows a schematic diagram of the Dirac
cone dispersion near EF in the three dimensional E-kx -ky space. (b) MDCs from EF to -2.0 eV.
The MDCs are normalized to have the same amplitude and displaced by the same amount so that
the dispersion can be directly viewed by following the peak positions at each energy. The dotted
lines are guides to the eyes for the linear-dispersing peaks in the MDCs. (c) Three dimensional BZ
for graphite with high symmetry directions relevant for this paper highlighted with red, green and
blue lines.

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FIG. 2: Constant energy maps taken near the H point, showing that the electronic
structure is isotropic in the kx -ky plane from EF to -0.6 eV. (a-e) ARPES intensity maps
near H (h=140 eV, kz 0.50 c ) taken at energies from EF to -1.2 eV. The circles are guides for
the circular intensity pattern near the H point. Arrows in panels d and e point to deviation from
the circle. (f) Schematic diagram of the dispersion for graphene near six BZ corners in the three
dimensional E-kx -ky space.

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FIG. 3: Detailed low energy dispersion near the H point shows that low energy exci-
tations are Dirac fermions with the Dirac point slightly above EF . (a) ARPES intensity
map near the H point (h=65 eV, kz 0.45 c ) along AHL direction (green line in the BZ shown
in Figure 1(c)). The open blue circles in panel a show the MDC dispersion. The dotted straight
lines are guides for the linear dispersion. (b) MDCs at energies from EF to -0.2 eV for data shown
in panel a. The blue circles denote the MDC peak positions. Note that, similar to Figure 2, the
intensity of the band is strongly enhanced in the first BZ (HA direction), due to the dipole
matrix element [10]. (c) Angle integrated intensity taken near H (h=140 eV, kz 0.50 c ). An
overall linear behavior is observed, with some small additional intensity near -0.05 eV. The origin
of this additional intensity is unclear and needs further investigation. The inset shows the expected
density of states for Dirac quasiparticles. The shaded area shows the occupied density of states.

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FIG. 4: Detailed dispersion near K, which shows that quasiparticles with finite effective
mass and defect-induced localized states also contribute to the low energy electronic
dynamics. (a) ARPES intensity map near K (h=50 eV, kz 0.08 c ) along KM direction
(blue line in the BZ shown in Figure 1(c)). The open circles are the dispersions extracted from
MDCs. (b) MDCs from EF to -50 meV for data in panel a. The open circles mark the peaks
clearly resolved in the data. The inset shows the MDC dispersion from -10 to -50 meV, with the
parabolic fit used to extract the effective mass. (c) Closer view of data shown in panel a with
the energy distribution curve (EDC) dispersion (dotted line). (d) Intensity map near the K point
measured in some parts of the sample, which shows an additional large electron pocket. The open
circles are dispersions extracted from EDCs shown in panel f. (e) MDC at EF from data shown in
panel d. The black arrows point to the peaks from the large electron pocket which are separated
by 0.1 A1 , while the gray arrow points to the peak from the band. (f) EDCs from k0 to k12 ,
as indicated in panel d. Open circles are the peak positions for the large electron pocket.

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FIG. 5: Dispersions measured near H and K, showing the general consistency of the
extracted kz values. (a) Dispersions near H (h=140 eV, kz 0.50 c ) along HH direction,
showing that the bands are degenerate. (b) Dispersions near K (h=80 eV, kz 0.07 c ) along
direction parallel to HH , where the bands split into bonding (BB) and antibonding (AB) bands.

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