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films. Spray-coated films from pure graphene

dispersion in DMF display transparencies of
∼90% and Rs ∼5 kΩ/䊐 (Figure 4a,b).[13] For
surfactant stabilized graphene dispersions,
both LB and vacuum filtration techniques
can be used.[52,80] Small graphene sheets
stabilized by a surfactant such as DSPE-
mPEG can assemble to form a monolayer
graphene film at the water/air interface.[80]
Therefore, the fabrication of one-, two- or
three layer graphene films can be easily con-
trolled by repeating the LB cycles (Figure 4c).
The decoration of the surface of graphene
with amphiphilic surfactants is very impor-
tant for its stabilization on the water sur-
face with minimal aggregation during film
formation. The accurate control of the film
thickness makes LB a promising approach
for the fabrication of low-cost, large-scale
graphene films (83% transmittance and Rs
Figure 3. (a) Sonication- driven exfoliation of graphite flakes in organic solvents such as
dimethylformamide (DMF), N,N-dimethylacetamide (DMA) and N-methylpyrrolidone (NMP). of 8 kΩ/䊐 have been achieved for a three-
(b) Negatively charged graphene layers from graphite intercalated compound spontaneously layer LB graphene film (Figure 4d,e)). The
dissolved in NMP. Reproduced with permission.[78] Copyright 2008, ACS. (c) Two times interca- higher resistance of these films compared to
lation of graphite with oleum (H2SO4) (teal spheres) and tetrabutylammonium hydroxide (TBA, spray-coated films could be attributed to the
blue spheres) in order and then dispersed in the DMF solution with 1,2-distearoyl-sn-glycero- small size of the graphene sheets and the
3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-5000] (DSPE-mPEG) molecules as presence of surfactant molecules between
the surfactant. Reproduced with permission.[80] Copyright 2010, Nature publishing group.
the graphene layers.[80] Vacuum filtration,
which allows effective removal of most of
poly(m-phenylenevinylene-co-2,5-dioctoxy-m-phenylenevi- the excess surfactant molecules on the filtrated film, has been
nylene) (PmPV) as the surfactant to stabilize the graphene dis- widely employed to produce homogenous CNTs films from the
persion. Since expanded graphite has much larger interlayer surfactant-stabilized CNT dispersions.[52,76] The process allows
spacing compared to natural graphite, solvent molecules can reasonably good nanoscale control over the thin film thick-
easily interpenetrate within the graphitic layers during sonica- ness by simply varying either the concentration or the filtrated
tion. To further improve this exfoliation process, the expansion volume of graphene dispersion.[43,52] Homogenous films can be
of graphite can be carried out by employing oleum as the re- obtained by vacuum filtration on porous cellulose filter mem-
intercalation agent and tetrabutylammonium hydroxide as the branes and subsequent transfer onto glass/or PET substrates
expanding agent. The final suspension of graphene sheets, (Figure 4f, g). In this way, the fabricated graphene films dis-
coated with 2-distearoyl-sn-glycero-3-phosphoethanolamine- play Rs ∼4 kΩ/䊐 and ∼80% transmittance after 500 ºC thermal
N-[methoxy(polyethyleneglycol)-5000] (DSPE-mPEG), can be annealing (Figure 4h).[52] However, the resistance of graphene
produced by sonication in DMF, with 90% of the sheets films prepared by solution-exfoliated graphene is still quite
reported as individual graphene sheets (Figure 3c).[80] high when compared to pristine graphene because of the large
Two factors need to be taken into account when graphene is contact-resistance between the adjacent graphene sheets and
dispersed in organic solvents and/or surfactant solutions: poly- also due to the presence of adsorbed solvent molecules and
dispersity and flake size. The first one is related to the nature surfactants.[13,81]
of the objects present in the solution, i. e. monolayers, bilayers,
multilayers, which ideally would need to be separated before
film formation. Because of the different buoyant densities of the 3.2. Graphene Oxide, a Precursor to Graphene
multilayered graphene compared to mono or bilayer graphene,
density gradient ultracentrifugation (DGU) is a valuable method
3.2.1. Graphene Oxide Preparation
to purify the graphene dispersions by removing the thick flakes.
The narrower the dispersivity of the graphene dispersions, the The low cost method of producing graphene on a large scale
more homogeneous the films obtained, which means signifi- is to reduce graphene oxide (GO) to graphene. GO is made by
cant improvement in transmittance and resistance.[76] oxidizing graphite with strong acids followed by intercalation
and exfoliation in water.[82,83] The downside of this approach
is that, after reduction, some places in the sp2 carbon network
3.1.2. Thin Film Formation
can be irreversibly destroyed leaving sp3 carbons and vacan-
Due to the nature of the liquid phase exfoliated graphene dis- cies which behave as electron traps.[3,49,84] However, due to
persions, spray coating, Langmuir-Blodgett (LB) and vacuum its low cost and easy solution processing, a great number of
filtration are suitable methods of fabricating thin graphene attempts have been made to improve the electronic properties

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morphology (Figure 5c). The absence of post
sonication treatment of the dried GO powder
is undoubtedly favorable to maintain the size
of the initially produced sheets (Figure 5d).

3.2.2. Fabrication of GO Films

Individual sheets of GO can be viewed as
graphene decorated with oxygen-containing
groups on both sides of the plane and around
the edges. The negatively charged sheets
allow the formation of stable colloidal suspen-
sions by electrostatic interactions in water.[43]
GO films can be easily fabricated by spray-
coating,[92] dip-coating,[14] spin-coating,[42]
vacuum filtering[43] and LB[93] techniques.
Similar to graphene dispersions exfoliated
by solution sonication, thin GO films can also
be prepared by vacuum filtration and LB tech-
niques.[43,93,94] The oxygen-containing groups
partially decorate the large hexagonal carbon
network and as a consequence it features the
GO sheets with hydrophobic and hydrophilic
components (Figure 6a).[95,96] Therefore, the
negatively charged sheets form a stable dis-
persion against flocculation or coagulation
when they are confined at the 2D air-water
interface.[93,95,97] The edge-to-edge repulsion
between the single layers prevents them
Figure 4. (a) Light transmittance through an original glass slide, the right side covered with from overlapping. These unique features
graphene film. (b) Scanning electron micrograph (SEM) of a thin graphene film obtained by render GO an interesting material with high
spray-coating from a liquid phase exfoliated graphene dispersion. (a-b) Reproduced with per- stability on the water surface, thus allowing
mission.[13] Copyright 2010, ACS. (c) Photograph of a two- layer graphene film fabricated by the
the fabrication of monolayer GO films using
Langmuir-Blodgett (LB) technique from the surfactant stabilized graphene dispersion (scale [93] It should be noted that the
bar is 10 mm). (d) Transmittances of one-, two-, and three-layer graphene films. (e) Resistance LB technology.
and transparencies of one-, two- and three-layer LB graphene films. (c–e) Reproduced with per- LB method enables the deposition of GO
mission.[80] Copyright 2010, Nature publishing group. (f) Photograph of 6 nm thick graphene films on any arbitrary substrate and the size
film on PET substrate prepared by filtration and transfer process from the surfactant stabilized of the film is only limited by the size of the
graphene water dispersion. (g) SEM image of the surface of graphene film. (h) Transmittance LB vessel. A gradual increase in surface pres-
plotted as a function of Rs for both as-produced and annealed films. (f-h) Reproduced with sure is recorded when the barrier is closed,
permission.[52] Copyright 2010, Wiley-VCH.
as shown in the isothermal surface pressure-
area plot in Figure 6b. The corresponding LB-
of the reduced graphene oxide (RGO), such as the preparation assembled GO films with different densities can be obtained by
of large-sized GO sheets,[2,85–87] chemical doping,[88] and defect dipping the film at different surface pressures (Figure 6c–f). It
repairing.[89,90] is noteworthy that there are no wrinkled structures in the first
The in-plane conductivity in RGO film is much higher than layer GO sheets due to the hydrophilic nature of the silicon sub-
that in the vertical direction because of the large resistance in strate. In theory, thick GO films can be obtained by sequential
the junction between two RGO sheets as shown in Figure 5a.[91] dip-coating, but the newly deposited top layers tend to be wrin-
The preparation of ultra-large GO sheets is interesting because kled.[93] For the application as the transparent electrodes in solar
of the feasible processing and favorability towards reducing cells, graphene multilayers are needed to provide the low resist-
the inter-junction resistance (Figure 5a and b). The Hummers ance and high transmittance. In this case, spin-coating is more
method is modified by replacing the sonication process with convenient as the thickness of the graphene films can be easily
shaking. Subsequently, the ultra-large monolayer graphene adjusted by the spin- coating speed and/or the concentration
sheets can be delaminated via centrifugation of the GO disper- of the GO dispersion.[18] The conventional concentration of GO
sion at different centrifugation speeds. [ 86,87 ] Freeze-drying has in water is lower than 0.5 mg/mL, and it is generally difficult
proven to be a very efficient technique to dry the GO colloid, to achieve a concentrated GO dispersion without the sonication
thus facilitating the re-dispersion process.[86] Due to the incor- process. As mentioned above, the sonication treatment is prone
poration of a significant number of water molecules between to cut the large graphene sheets into small pieces. However, this
the GO sheets, freeze-drying of the GO colloid can keep the process is detrimental to the electronic conductivity of graphene
GO sheets separated from each other, leading to a porous after reduction.[18] Ultracentrifugation can yield a desired

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 www.advmat.de
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Figure 5. (a) Schematic of the resistance of RGO nanosheets between the
two electrodes and the corresponding resistor network model (bottom).
Reproduced with permission.[91] Copyright 2010, Wiley-VCH. (b) Com-
parison of the sheet resistance as function of transmittance (T% at
550 nm) for the electrodes prepared from ultra-large, large, and small
reduced GO sheets after 800 °C thermal reduction (20% H2 in Ar). Repro-
duced with permission.[87] Copyright 2010, ACS. (c) SEM images of the
freeze-dried GO solid foam (inset: digital photographs). (d) SEM images
of GO sheets that were deposited on a Si substrate. (c-d) Reproduced
with permission.[86] Copyright 2010, RSC.
concentration from a diluted GO dispersion. A 10000 rpm
centrifuging speed can yield up to ∼8 mg/mL of GO dispersion,
which is high enough to prepare a ∼100 nm thick GO film.
Figure 6g displays a series of GO films deposited on quartz
substrates, where the leftmost sample is GO and the rest are
high-temperature treated GO films with thickness increasing
from left to right (Figure 6g). Large GO sheets are beneficial
for decreasing the resistance but are unfavorable for fabricating
large area homogenous films, which are always associated with
wrinkled structures as indicated in the atomic force microscope
(AFM) images (Figure 6h,i).[42]
The oxygen content in insulating GO is as high as ∼40 wt%
which badly destroys the sp2 structure.[98] In order to restore
the conductivity, the sp2 structure must be extensively repaired.
Although a number of methods have been established to elimi-
nate the oxygen-containing moieties and recover the electronic
properties. Thermal reduction (or combined with pre-chemical
reduction with N2H4) is currently the most efficient approach
to achieve highly conductive RGO films.[43] Chemical reduction
via N2H4 alone provides a conductivity of < 50 S/cm which is
significantly lower than that of thermally reduced GO films
(∼1000 S/cm).[42,43,99] The most conductive graphene film,
from GO, (∼1800 S/cm) was reported by vacuum annealing at
1100 ºC for three hours. The film shows the Rs of ∼800 Ω/䊐
and transmittance of 82% at 550 nm.[24] Based on the thermally
reduced GO film, repairing the defects is more efficient to fur-
ther improve the conductivity and the mobility.[89,100]
3.3. Conductive Carbon Film from Aromatic Precursors
Carbon films from organic aromatic molecules fabri-
cated by pyrolysis at high temperatures normally show low
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graphitic crystallization compared with thermally reduced GO
films.[21,51,101] The selection of the precursor, the film fabrica-
tion and the high temperature treatment are three important
steps. For instance, ultrathin (∼1 nm) conducting carbon films
can be prepared through self-assembly of 1,1’-biphenyl-4-thiol
(BPT) on a gold surface, electron beam irradiation and pyrolysis
(Figure 7a).[51] During the thermal treatment, cross-linked aro-
matic monolayers undergo a transition to a mechanically stable
graphitic phase (Figure 7b to c). The line profiles across the
regions in Figure 7c give a periodicity of ∼0.35 nm, which is
close to the interplanar spacing of the close-packed planes in
graphite (0.342 nm). The Rs measured after annealing at 927 °C
is ∼100 kΩ/䊐 as shown in Figure 7d (conductivity is ∼20 S/cm).
This resistance value is much higher than that of the defect-free
graphene monolayer and TRGO.[13,51] In order to improve the
graphitic crystallization, large polycyclic aromatic hydrocarbons
(PAHs) were employed as precursors for the fabrication of con-
ductive films (Figure 7e). Typically, PAHs can be spin coated on
a quartz substrate from organic solution and then annealed at
1100 °C, yielding a Rs of ∼1.6 kΩ/䊐 (corresponding conductivity
is ∼206 S/cm) for the as-prepared 30 nm thick films (Figure 7g).
The high conductivity with respect to the pyrolyzed BPT film
can be attributed to the improved graphitic crystal structure as
validated in Figure 7f.[21]
Currently most synthetic methods of graphene nano-
structures (graphene and graphene nanoribbons(GNRs)) estab-
lished so far rely on top-down fabrication protocols. PAHs,
which can be regarded as typical nanographenes consisting of
all sp2 carbons in a two-dimensional framework, have attracted
the attention of synthetic chemists for several decades.[102]
Compared with other graphene materials, these nanogra-
phenes possess obvious advantages in terms of (i) precisely
defined structure, (ii) possible large-scale preparation, and
(iii) tunable solubility and good processability. In particular, a
unique bottom-up approach for the fabrication of GNRs on the
surface with chemical precision through the selection of suit-
able oligophenylene precursors was recently developed. The
concept is to fabricate nano-structured graphene systems by the
self-organization of carefully selected molecular building blocks
(precursor monomers) that react with each other under specific
atmosphere and temperature conditions. By using two thermal
activation steps, the surface-adsorbed monomers are first cou-
pled to linear polymer chains and then planarized into GNRs
by cyclodehydrogenation.[103]
3.4. Chemical Vapor Deposition
3.4.1. CVD Growth Mechanism
For over 40 years the CVD of hydrocarbons on reactive Ni or
transition-metal-carbide surfaces has been known to produce
thin graphitic layers.[4] For graphene growth, in particular,
Pt,[104] Ru,[105,106] Ni[4,54,107] and Cu[25,108,109] have been used
as catalysts with furnace temperatures ranging from 500 to
1000 ºC.[110–112] The CVD growth of graphene on Ni occurs
by a C segregation and/or precipitation processes whereas
graphene on copper grows by a surface adsorption process.
The film formation mechanisms have been extensively studied
Adv. Mater. 2011, 23, 2779–2795