2nd International Conference on Green Materials and Environmental Engineering (GMEE 2015)

Graphite Pencil Drawn Lines: A Nanomaterial or Few

Layer Graphene/Graphite Layered Structure
G.Sh. Shmavonyan1 and A.R. Mailian2
1
National Polytechnic University of Armenia, Department of Microelectronics and Biomedical Devices, 105 Teryan str., Yerevan,
0009, Armenia
2
Institute for Informatics, 1 P. Sevak str., 0014, Yerevan, Armenia

Abstract—A non-conventional method of obtaining few-layer structures obtained from disordered graphite bulk by rubbing
graphene (FLG) is suggested, which comprises repeatedly on different substrates.
rubbing bulk graphite against semiconducting and insulating
substrates. The obtained graphene/graphite structures consisting II. EXPERIMENT
of rubbed-off layers behave like a semiconducting material with Samples of graphite thin structures were prepared by series
through-thickness anisotropy of carrier mobility reaching to
of sequential rubbing parent graphite rods against the surface
3000 cm2/V⋅sec at the surface. The structure surface
of insulating and semiconducting substrates along the same
demonstrates more ordered and oriented character containing
FLG. The suggested method allows easily obtaining graphene
path (see inset of Figure 1). We commonly used pencil leads
with pencil directly on paper, as well as graphene-based of H, HB, Fand B hardness, though all types of rods (highly
electronic components and circuits on paper and other substrates, oriented pyrolitic graphite, graphite used in electrical
which could enable flexible and cheap electronics. The observed engineering and chemistry, etc.) showed the same behavior.
phenomenon is universal, does not depend on the substrate As a substrate we mainly used paper for convenience though,
material and could find a widespread application. again, all types of the substrates showed identical results.
In order to peel off layers, the parent graphite rod was
Keywords—graphene; graphite; pencil; drawing
pressed normal to the substrate surface with the pressure of
I. INTRODUCTION ≥1MPa, which is higher than the force required for cleaving
off a flake with the thickness of several atomic layers from the
Graphite thin films are extensively used in electronics bulk.[9] Actually drawing a line is a mechanical modification
(resistors, conducting layers in printed circuits, under-button by combined and continuous operation of cleaving-
contacts, etc.) so far. The interest toward their physical transferring-pressing of flakes. Therefore, we call the drawn
properties increased in recent past as a consequence of the lines Combined Mechanical Modified (CMM) layers and the
discovery of fascinating properties in graphite single layers. In structures containing multiple CMM layers - CMM structures.
timeline, isolation of one-atom-thick layer of carbon was the The advantages of our preparation method lie in the easy way
last one of a triumphant series of obtaining various graphite- to realize and it avoids contamination or surface doping
based low-dimensional materials, such as zero dimensional avoiding the contact with any other material.
carbon fullerene [1], 1D-nanotube [2] and 2D-graphene [3], an
atomically thick basic carbon plane. Graphene is the most The electrical resistance of the structures was measured by
practical structure in this series since its electronic properties a conventional two-probe method, using gold contacts pressed
are easy to control by external factors and it is convenient to on the surface of the structures.
utilize. FLG is a unique material with its own potential for
Raman spectra were measured using a RENISHAW in Via
device applications.[4-6] Mechanical exfoliation is still a
Raman at excitation wavelength of 514 nm, at room
reliable and simple method to obtain FLG flakes with high
temperature. The Raman spectral resolution was better than 4
electronic quality. By this method a layered graphite crystal is
cm-1 and the incident power of the excitation laser light was
rubbed against the substrate surface leaving nanoscale flakes
0.6 W.
attached to it. It is much like drawing by pencil. Then, single
or few-layer flakes are picked up from rubbed off and attached III. RESULTS AND DISCUSSION
to substrate surface set of flakes.[7,8] The whole trace or
graphite thin structure or just the pencil drawn line as a Our experimental observations show that observed
material was disbelieved to have attractive electronic regularities and peculiarities presented hereafter originate
properties and because of that, perhaps, have been overlooked from the surface or surface-adjacent stratum of the CMM
to be studied. On the other hand, we believed its micro-scale structure. First, it was found that the CMM structures behave
thickness ought to alter the behavior of electron gas and it like a solid state material exhibiting a number of interesting
could be an interesting object of investigation. physical properties common to layered fine structures. The
carrier transport is dimensionality dependent. Namely, the
This pioneering report summarizes the experimental study electrical resistance taken from the structure surface
of some basic properties of mechanically exfoliated graphite undergoes drastic change with the number of cleaved and
transferred layers, i.e. with the thickness of the CMM structure

© 2015. The authors - Published by Atlantis Press 12

(Figure 1a). Typically, the conductance became clearly upper layers in the CMM structure, the curve of thickness vs.
detectable after a couple of rubbings. Take for example, number of transferred layers (dN) tends to saturate since dN = ,
samples presented in Figure 1a. At the same pressure, and like the case shown in Figure 2a.
with the same graphite rod, layers on glass, paper and ceramic
substrates exhibited conductance at the 2nd rubbing or transfer, Next characteristic parameter, the carrier mobility is
while layers on ZnO ceramic and plastic substrates at the 3rd deduced from the measured electrical resistance of the
rubbing. structure by

During a few following rubbings the resistance dropped µN = a/enρN = a/enwRNdN, (1)
~1000 times, from several Mohm to several hundred ohm
reaching low-resistance plateau (N>10). Note, that the where e is the charge of an electron, a and w are the length
resistance of the structures never reached that of the bulk. and the width of the structure segment between measuring
Such a behavior is common to the structures on different contacts, respectively, n - the bulk carrier density and RN - the
substrates and different graphite rods, and hence electrical resistance taken from the surface of the CMM
unambiguously reflects the intrinsic properties of graphite structure containing N transferred layers. For instance, for the
(Figure 1a). sample presented in Figure 2 quantitative assess revealed
Following the growth of the structure under optical enhancement in the mobility by a factor of 10s with respect to
microscope, the pre-conduction structure was seen as a field of the ground conducting layer with N=3 (Figure 2b). However,
casual and rare spread spots or wormlike threads (paper one can see apparent discrepancy between this value and sharp
substrate) of several micrometer sizes. This picture should drop in the structure resistance. Consequently, this suggests
mean that initial rubbed off flakes merely filled pores of the anisotropy in the stacking geometry and the mechanism of
substrate (layers 1 and 2, Figure 1b). The ground conducting carrier transport should be different through the structure
layer and structures appearing at further few rubbings (N=2÷5 thickness[13]. Thus, to obtain accurate values for mobility it is
in Figure 1) may have been shaped by chain of randomly necessary to take into account this aspect.
stacked flakes bridging the neighboring graphite filled pores.
Disorder in these layers should strongly limit the
conductance, since the sizes of flakes are close to mean free
path of electrons and therefore boundary scattering is
extremely high. Thus, a CMM structure should consist of
graphite isles attached to the substrate and continuous and
conducting layers sandwiched above. Hereafter we will
examine the behavior of conducting layers shaped at each
rubbing and the whole structure consisting of individual
conducting layers. The rubbing numeration which is the same
for transfer, will be kept unchanged as shown in Figure 1b.
For characterizing the obtained structure, as well as for
understanding the observed regularities one needs to know the
thickness of the structure. The thickness of Nth transferred
layer, as and the total thickness of the conducting stratum in
total structure containing N transferred layers, dN= is possible
to calculate measuring the abraded volume of the parent
graphite rod during rubbing (inset in Figure 1 a, b)[12]. With a
rod having round cross section, the thickness of a single
rubbed off layer can be calculated by =Dl/4L, where lis the
change in the rod length, D - diameter of the rod, L - the
length of transferred layer (inset in Figure 1). As the thickness
of the whole structure increases with successive steps of
rubbing, the upper transferred individual conducting layers
progressively get thinner (Figure 2a). The thickness of Nth FIGURE I. A) TYPICAL DEPENDENCE OF THE ELECTRICAL
transferred layer is estimated by d d inset in Figure 2a. For RESISTANCE OF THE CMM STRUCTURES ON THE NUMBER OF
N=20÷30 corresponding to the region of plateau on resistance TRANSFERRED LAYERS FOR DIFFERENT INSULATING
vs. N curve (Figure 1a), is estimated to range from ~ 1 to 8 nm SUBSTRATES AND SEMICONDUCTING ZnO At Applied Pressure Of P ~
5 MPa. INSET SCHEMATICALLY ILLUSTRATES THE FABRICATION
depending on the surface roughness of substrates and graphite PROCESS OF A CMM STRUCTURE, WHERE TWO ARROWS
hardness. This value is quite reasonable for as the structure INDICATE THE DIRECTION OF THE MOVEMENT OF BULK
becomes thicker the same bonding strength between crystal GRAPHITE ROD DURING RUBBING. B) SCHEMATIC PRESENTATION
planes in both grown structure and parent graphite bulk should OF PACKING OF TRANSFERRED LAYERS IN THE CMM. ON THIS
limit the maximum thickness of a single peeled off flake from EXAMPLE CONDUCTING TAKES PLACE AT THE 2nd RUBBING OR
TRANSFER. VERTICAL ARROWS SHOW THE SURFACES FROM
both sides. Thus, due to tightly packed and ordered stacking of WHICH THE RESISTANCE WAS MEASURED

13
 demonstrate quasi two-dimensionality of carrier transport [12-
15], with an alternate conducting mechanism. Also, such T-
behavior lends support for the model of through-thickness
anisotropy.

FIGURE II. A) TYPICAL DEPENDENCE OF TOTAL THICKNESS OF

THE CONDUCTING LAYER IN THE CMM STRUCTURE (BLACK LINE)
AND THE THICKNESS OF SINGLE RUBBED OFF LAYER (RED LINE)
ON THE NUMBER OF THE TRANSFERRED LAYERS ON PAPER. THE
INSET ILLUSTRATES THE CALCULATION OF THICKNESS OF ONE
RUBBED OFF LAYER. B) TYPICAL DEPENDENCE OF RESISTANCE
OF CMM STRUCTURE ON TOTAL THICKNESS OF CONDUCTING
LAYER AND THE NUMBER OF TRANSFERRED LAYERS COMPARED
WITH CARRIER MOBILITY
FIGURE III. A) TEMPERATURE DEPENDENCE OF ELECTRICAL
RESISTANCE OF VARIOUS CMM STRUCTURES ONA PAPER
To identify the conducting mechanism in the CMM SUBSTRATE. THE STRUCTURE RESISTANCE DECREASES BY
structure, the temperature (T) behavior was studied as well INCREASING THE ORDER OF CURVES.B) THE SAME DEPENDENCE
(Figure 3). As can be seen, the electrical resistance of the IN SEMILOG PLOT OF THE INVERSE TEMPERATURE. THE BARS ON
CMM structure decreases with the increase of the temperature. THE LEFT SIDE PRESENT THE SCALE. THE NUMBERS IN EV
PRESENT THE ACTIVATION ENERGIES CALCULATED FOR LINEAR
There is an obvious difference in the T-dependence between PARTS
thick, i.e. more conductive and thinner (less conductive)
samples. Note, that no metallic-like behavior was observed. Further on, as the surface layers of any ordered graphitic
To understand the nature of the electrical conduction in structure are totally screened from the substrate due to huge
these structures we consider a semilog plot of the inverse anisotropy in in-plane and out-of-plane conductivity and
temperature dependence of inverse resistance for a sources of disorder are reduced significantly at a layer surface
representative samples (Figure 3). In all cases we find that [16-18], we argue that mainly the resistance of the top layer is
ln(1/R) has a similar functional dependence on measured from the contacts pressed on surface. Our
T−1characterized by three regions with distinct slopes observation and measurements too speak about totally
extracted from the plots in Figure 3 a. independent behavior of transferred layers: the resistance of
bottom layers did not change with rubbing upper layers. In
These experimental results expose semiconducting nature addition, concerning the measurements of resistance from the
of the CMM structures and provide clear evidence for layered surface of the CMM structure, the inter-layer screening length
and ordered stacking of the CMM structures. Electronic states to electric field in thin graphite is estimated to be 1.2 nm,
responsible for linear slopes in ln(1/R) vs. 1/T plot do not exist which is about four monolayer thick.[19] This leads to assume
neither in single-layer nor in bulk graphite. They originate over again that the contribution of the surface structure in
from modification of continuous and linear and bands at carrier transport is crucial for the CMM structures.
K point of Brillouin zone under influence of interaction
between basic layers.[11] So, the CMM structures

14
 Explicit features of the layered CMM structure is expected with the highest value of ∼3000 cm2/V⋅sec at the top of the
to reveal by Raman spectroscopy since it is sensitive to the structure.
surface, layer number and structural and stacking order.[19-
22]. Raman spectra of the CMM structures are shown in The overall results testify to a structure promising to
Figure 4, which allow us to conclude that FLG (N = 2÷4) is obtain importance in achieving selective conductivity and high
formed on the CMM structure surface. carrier mobility in the graphite/graphene system.
The suggested method allows easily obtaining graphene
1
2 with pencil directly on paper, as well as designing graphene-
15 00
based electrical components and circuits on paper and other
substrates, which could enable flexible and cheap electronics.
The observed phenomenon is universal, does not depend on
Intensity, a.u.

10 00 the substrate material and could find a widespread application.

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