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Front. Mater. Sci.

China 2010, 4(1): 45–51


DOI 10.1007/s11706-010-0014-3

REVIEW ARTICLE

Properties, synthesis, and characterization of graphene

Liang-Xu DONG, Qiang CHEN (✉)


Laboratory of Plasma Physics and Materials, Beijing Institute of Graphic Communication, Beijing 102600, China

© Higher Education Press and Springer-Verlag Berlin Heidelberg 2010

Abstract Graphene is a wonder material that attracts 2 The properties and applications of
great interests in materials science and condensed matter graphene
physics. It is the thinnest material and also the strongest
material ever measured. Its distinctive band structure and Graphene is one layer of atomic carbon, and its theoretic
physical properties determine its bright application pro- thickness is only 0.34 nm. The theoretical specific surface
spects. This review introduces briefly the properties and area of graphene is up to 2600 m2/g [3]. It has outstanding
applications of graphene. Recent synthesis and characteri- thermal conductivity (3000 W/(m$K)), as well as high-
zation methods are summarized in detail, and the future speed electron mobility (15000 cm2/(V$s)) at room
research direction is also pointed out in this paper. temperature. Its mechanical stress reaches to 1060 GPa
[4], while the density is only 2.2 g/cm3.
Keywords graphene, properties, synthesis, characteriza- Besides, graphene also has many special characteristics,
tion such as bipolar supercurrent, chiral tunneling of relativistic
particles, absence of Anderson location, and anomalous
quantum Hall effect [5]. These unique characters make it
1 Introduction provide a research platform for quantum mechanics and
condensed matter physics. Many phenomena are easily
Since graphene was discovered in 2004, it has attracted observed in graphene, which were only observed in black
great interests because of its outstanding electrical and holes or heavy ion accelerators in previous.
mechanical properties [1]. Graphene is a well-defined two- Moreover, graphene is the strongest material ever
dimensional crystal material, as Fig. 1(a) shows, and it is measured in the world. It is noticed that the graphene
regarded as the elementary structure of carbon-based density is even harder than diamond and about 100 times
materials, such as carbon nanotube, fullerene, and graphite stronger than that of the best steels in the world.
[2]. Before the discovery of graphene, it was once The single graphene layer is a semimetal or zero-gap
considered that the thermodynamic fluctuation does not semiconductor and has excellent electronic properties. The
allow any two-dimensional crystals existence at the finite electron mobility of graphene is very high; it is about 10
temperature. The successful synthesis of single layer times faster than the commercial silicon wafer. Further-
graphene shocked the entire condensed matter physics more, the mobility is little affected by the temperature. Its
community. Then, after the work of graphene was first carrier shows ballistic transport under ambient condition.
published in October 2004, the amount of papers relevant These properties share prominent advantages of gra-
to graphene was more than hundreds published on top phene used in nanoelectronic devices. It is possible using
journals, such as Science and Nature. There is no doubt graphene for ballistic field effect transistor at room
that graphene is a very important discovery after fullerene temperature. The nanoribbon transistors with large on-off
and carbon nanotube. Its distinctive structure and excellent current ratios at room temperature [6] were demonstrated
properties certainly make it being widely used in future. in Fig. 1(b). Graphene makes it possible for this relatively
simple framework to implement complex and new circuit
and becomes the basic electronic material beyond the
silicon age.
However, the current situation is not optimistic, and the
difficulties are still puzzling researchers, such as the
Received November 13, 2009; accepted December 10, 2009 preparation of high-quality large-area graphene, the high
E-mail: chenqiang@bigc.edu.cn stability, and consistence, as well as a simple process. In
46 Front. Mater. Sci. China 2010, 4(1): 45–51

Fig. 1 (a) The structure of graphene; (b) Graphene nanoribbons exhibit the transistor action with large on-off ratios (Reprinted with
permission from Ref. [6])

order to get the size required, we often resort to cut down 3 The synthesis of graphene
graphene to obtain graphene nanoribbons. Graphene
nanoribbons have already been produced using plasma At the beginning, the graphene fabrication is micromecha-
etching, scanning tunneling microscopy (STM) lithogra- nical cleavage from graphite, it is also the method that
phy, and atomic force microscopy (AFM) anodic oxida- graphene was first isolated for property study. This way is
tion, as well as by chemically derived techniques [7]. often referred to as a scotch-tape technique, which relies on
However, a method to produce single-layer graphene destroying Van der Waals force between graphite layers.
structures with well-defined crystallographic edges Geim’s group first isolated graphene from platelets of
remains elusive. Geim [8] forecasted that it might require highly oriented pyrolytic graphite (HOPG) [1]. They first
another 10 years before the first integrated circuits based prepared 5 mm-deep mesas on top of the platelets using dry
on graphene chips to appear. etching in oxygen plasma. The structured surface was then
Another important application is that graphene can be pressed against a 1-mm-thick layer of a fresh wet
used as transparent electrode, which maybe widely used in photoresist spun over a glass substrate. After baking, the
liquid crystal display (LCD), organic light emitting display mesas became attached to the photoresist layer. Then,
(OLED), or organic solar cells in future [9]. Graphene has using scotch tape, they started repeatedly peeling flakes of
an optical transmission rate over 98%, significantly higher graphite off the mesas. Thin flakes left in the photoresist
than that 82%–85% of the standard indium tin oxides were released in acetone. When a Si wafer was dipped in
(ITO) film. Through the reduction processing graphene the solution, some flakes became captured on the wafer’s
demonstrates a low resistance, and it can be reduced surface (as shown in Fig. 2(a)). Although delicate and
furthermore by chemical doping. ITO, on the other hand, time-consuming, the handcraft provides crystals of high
has to trade resistance for transparency. Indeed, if an ITO structural and electronic quality, which can currently reach
electrode is made thin enough to rival the transparency of millimeter size. It is likely to remain the technique of
graphene, its sheet resistance also shall be skyrockets [8]. choice for basic research and for making proof-of-concept
Established on large specific surface area, graphene is devices in the foreseeable future [12]. However, it is
also used as gas detector and biological system. Schedin et obviously not suitable for large-scale preparation due to
al. [10] showed that the micrometer-sized sensors made nonfiguration.
from graphene are capable of detecting individual events The second method for graphene fabrication is chemical
when a gas molecule is attached to or detached from cleavage from graphite, which is an improvement of
graphene’s surface. Mohanty et al. [11] demonstrated the micromechanical cleavage. Graphene made from chemical
interfacing of chemically modified graphene with biologi- cleavage can reap larger quantities. The single sheet is
cal systems to build a novel live-bacterial-hybrid device fabricated from graphite oxide. Due to the existence of
and a DNA-hybridization device with excellent sensitivity. oxide groups, the atomic planes of graphite are partially
Due to the excellent electrical, thermal, and mechanical detached by intercalation. After ultrasonic cleaning for
properties, graphene is expected to be used in high- several hours, these samples are exfoliated to create stable
performance nanoelectronic devices, composite materials, aqueous dispersions of individual sheets, as Fig. 2(b)
field emission materials, gas sensors, energy storage areas, shows. After deposition, graphene oxide can be reduced to
etc. graphene either by means of chemical or by thermal
Liang-Xu DONG et al. Properties, synthesis, and characterization of graphene 47

annealing [13]. Although the thickness is not consistent, large-scale area production. Nowadays, graphene made by
which varies between one and four layers of carbon, the CVD on silicon wafer with nickel layer as catalyst has
optical properties still match to those of graphene achieved centimeter in size. Groups at MIT and in Korea
fabricated by micromechanical cleavage method. The [17,18] have developed a simple method to grow and
small scale size, in tens of microns however, hinders the transfer the high-quality stretchable graphene films using
application of graphene by this method. CVD technology on nickel layer. The mechanism is based
The graphene grown epitaxially on SiC substrates and on precipitation, where Ni and C atoms form a solid
patterned via standard lithographic procedures has been solution in CVD after heating. Since the solubility of C in
proposed as a platform for carbon-based nanoelectronics Ni is temperature-dependent, C atoms precipitate and form
and molecular electronics in recent studies [14,15]. The graphene layer on the Ni surface upon sharply cooling of
epitaxial graphene was produced on the Si terminated the sample (in Fig. 2(d)) [18], and the layer of graphene
(0001) facet of single-crystal 6H-SiC by thermal desorp- depends on the concentration of C precipitated in Ni.
tion of Si [16]. After the surface is oxidized or reduced in However, Li et al. [19] recently fabricated graphene films
H2, samples are heated by electron bombardment in ultra- on copper foils. They concluded that the thickness of
high vacuum (ca. 1.3310–8 Pa) to 1000°C and remove the graphene films were independent on exploring time, and
oxide. Then, samples are heated again to temperatures in the low solubility of carbon in copper made this growth
the range of 1250°C to 1450°C for 1–20 min. After process self-limiting. The precipitation mechanism did not
these processes, thin graphene layers are formed (as shown work on copper substrate. Therefore, the mechanism of
in Fig. 2(c)), and the layer thickness is determined CVD growth graphene needs additional experiments to be
predominantly by the temperature [14]. The shortcoming fully understood.
of the epitaxial graphene on SiC is a lot of defects in the Anyway, this method demonstrates the potential for
layer besides it hard to transfer to other substrates. large area production, and the graphene can be easily
Therefore, this method needs further improvement. transferred to other substrates [20]. Therefore, the CVD
The last method to fabricate graphene is chemical vapor technology has attracted wide attention for large-scale
deposition (CVD). This method has the potential for preparation of graphene. However, graphene obtained by

Fig. 2 (a) Large graphene crystal prepared on an oxidized Si wafer by the scotch-tape technique (Reprinted with permission from Ref.
[12]); (b) Graphene made from chemical cleavage from graphite (Reprinted from Ref. [13]); (c) Low-energy electron diffraction (LEED)
pattern (of three monolayers of epitaxial graphene on 4H-SiC(0001) (C-terminated face) (Reprinted from Ref. [15]) ; (d) Optical image of
Ni film on SiO2/Si, and CVD graphene is grown on the surface of the Ni pattern (Reprinted from Ref. [18])
48 Front. Mater. Sci. China 2010, 4(1): 45–51

this method usually is a mixture of single and multilayer, provides accurate and reliable layer identification for rapid
and how to improve the quality of graphene is the goal of evaluation of the layer range of graphene by different color
the future research work. bands, which opens up the possibility for the nondestruc-
Meanwhile, to realize the graphene-based circuits, tive identification and physical property measurements of
various types of graphene are needed. Thus, modulation graphene with an optical microscope.
of its electrical properties is of great technological SEM is also used for observation of graphene. This
importance. Doping it with other elements is a promising method is similar to optical microscope. Usually, it needs
way to achieve this goal, and the doped graphene might to transfer graphene to silicon wafer with a specific
promise fascinating properties and widespread applica- thickness of SiO2. From the color depth, the layer of
tions. graphene can be estimated. To identify graphene films,
Bekyarova et al. [21] demonstrated a chemical modi- Geim’s group compared the results of optical and SEM
fication of epitaxial graphene (EG) by covalent attachment of large areas on the wafer, trying to find the film
of aryl groups to the basal carbon atoms. The surface visible in SEM but not in optical microscope [1].
modification of EG with nitrophenyl groups was achieved Figure 3(a) shows the flakes, which is easily identifiable on
through the spontaneous reaction of the diazonium salt both SEM and optical images because of a thick region
with the graphene layer. They showed that the chemical nearby. The graphene film gives a more clear contrast in
formation of carbon-carbon bonds offers an alternative SEM.
approach to the control of the electronic properties of AFM is an effective way for the characterization of
epitaxial graphene, and the transformation of the carbon graphene. Though the thickness of graphene is very thin, it
centers from sp2 to sp3 introduces a barrier to electron can easily get the morphological feature using AFM. From
flowing by opening a band gap and allows the generation the step of graphene on substrate, it is possible to estimate
of insulating and semiconducting regions in graphene the number of graphene layer. Due to the differences in tip
wafers. attraction/repulsion between the insulating substrate and
Elias et al. [22] attached atomic hydrogen to each site of semimetallic graphene and under ambient conditions by
the graphene lattice to create graphane, which changes the the preferential adsorption of a thin layer of water on
hybridization of carbon atoms from sp2 into sp3, thus graphene, it is hard to get the theoretical thickness of
removing the conducting p-bands and opening an energy 0.34 nm (which results in an typical thickness ranging from
gap. Hydrogenated graphene realized the function of not 0.6 to 1.0 nm for single layers, as shown in Fig. 3(b) and
only a metal-insulator transition but also an alternative (c)). Therefore, the AFM method for measurement of the
candidate for hydrogen storage material. graphene layer number is not accurate, and it has a very
Groups in the Chinese Academy of Sciences provided a low throughput [26].
CVD technique to produce the N-doped graphene, the first TEM can not only observe the morphological feature of
experimental example of a substitutionally doped gra- graphene but also count the number of graphene layers
phene. They measured the electrical properties of the N- accurately. It is known that the edges of the graphene films
doped graphene, which behaves like an n-type semicon- always fold back, which allows a cross sectional view of
ductor, indicating that the doping can modulate the the films (as Fig. 3(d) shows). The observation of these
electrical properties of graphene. This work provides a edges by TEM provides an accurate way to account the
new experimental instance of graphene and would promote number of layers at multiple locations on the films.
the research and applications of graphene [23]. Besides, TEM is often assisted with electron diffraction
pattern, which shows a hexagonal pattern of the graphene
crystal structure.
4 The characterization of graphene Raman spectroscopy can provide a quick and effective
way for structure and quality characterization of graphene.
Graphene is only one layer of atomic carbon and very The peaks at 1350 cm–1 (noted as D band), 1580 cm–1 (G
transparent, so the characterization method is very band), and 2700 cm–1 (G’ band, also called as 2D band) are
important and difficult. The usual methods include optical presented in the spectrum of the graphene samples. The D
microscope, SEM, TEM, AFM, Raman spectroscopy, etc. band of graphene associates with the existence of defects:
The identification of graphene sheets, down to one layer the lower intensity of D peak, the fewer defects of the
in thickness, is possibly realized through optical micro- graphene layer. It also associates with doping in graphene
scopy via the color contrast caused by the light interference [22]. The G band is E2g mode of graphite, which is due to
effect on the SiO2 substrate, which is modulated by the the sp2-bonded carbon atoms in a two-dimensional
graphene layer [24,25]. Gao et al. [24] developed a total hexagonal graphite layer. The G’ band is a double
color difference (TCD) method to make it possible for resonance Raman process, which involves the scattering
characterization of large-area graphene samples. This of two phonons with opposite momentum around the high
method based on a combination of reflection spectrum symmetry K point in the first Brillouin zone of graphene
and international commission on illumination color space [27–30].
Liang-Xu DONG et al. Properties, synthesis, and characterization of graphene 49

Fig. 3 (a) Images of a thin graphitic flake in optical (left) and scanning electron (right) microscopes. Few-layer graphene is clearly
visible in SEM (in the center) but not in optics (Reprinted with permission from Ref. [1]); (b) AFM image of graphene on SiO2/Si substrate
(Reprinted from Ref. [13]); (c) The height of graphene based on (b) (Reprinted from Ref. [13]); (d) High-magnification TEM image of
graphene (Reprinted from Ref. [17])

From Raman spectroscopy, one can deduce the layers 5 The prospect of graphene
of graphene. As shown in Fig. 4, a further increase in
layer leads to a significant decrease in the relative Graphene research is developing in a very rapid pace.
intensity of the G’ band. At the same time, the G’ band Since the discovery of graphene, the study on graphene is
shall shift to higher wave number and saturate to that of remarkably intense. The amounts of literature on graphene
HOPG, whereas the intensity ratio IG’/IG reduces keep rapidly increasing over the next few years [12]. The
gradually. Thus, Raman spectroscopy can clearly distin- curiosity for the properties of graphene, the aspiration for
guish a single layer, from a bilayer or few (less than 5) its application in transparent electrode, field effect
layers [27]. Due to the advantage of high-throughput and transistor (FET), and sensors, tempt scientists to study
nondestructive identification of graphene layers, Raman graphene with great enthusiasm. However, it seems that the
spectroscopy is wildly used for characterizing graphene difficulty is not easily being solved recently, and the new
recently. challenges shall appear at any moment.
50 Front. Mater. Sci. China 2010, 4(1): 45–51

Fig. 4 (a) Comparison of Raman spectra at 514 nm for bulk graphite and graphene; (b) Evolution of the G’ band at 514 nm with the
number of layers (Reprinted with permission from Ref. [27])

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