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Graphene as Transparent Electrode Material for Organic
Electronics
Shuping Pang, Yenny Hernandez, Xinliang Feng,* and Klaus Müllen*
1. Introduction
Graphene, a two-dimensional atomically thick carbon atom
arranged in a honeycomb lattice, was recently isolated by
repeatedly peeling highly oriented pyrolytic graphite (HOPG)
using sticky tape.[1] Since then, outstanding physical properties
predicted and measured for graphene have been explored for
practical applications such as field-effect transistors,[1–4] chem-
ical sensors[5–7] and composite reinforcement.[8–10] Monolayer
graphene possesses high crystallographic quality and ballistic
electron transport on the micrometer scale with only 2.3% of
light absorption.[11,12] Moreover, the combination of its high
chemical and thermal stability,[13,14] high stretchability,[15–17]
and low contact resistance with organic materials,[13,18,19] offers
tremendous advantages for using graphene as a promising
transparent conductor in organic electronic devices, e.g. solar
cells,[14,16,20,21] organic light emitting diodes (OLEDs),[22–24] liquid
crystal displays (LCDs),[13] touch screens,[25] field effect transis-
tors (FETs)[18,19,26] and spectroelectrochemistry investigation.[27]
Transparent electrodes are an essential part of optoelectronic
devices. Commercially, indium tin oxide (ITO) sets the market
standard for most of these applications. In the emerging area
of thin film solar cells, layers of ITO are widely used as a hole-
collecting electrode with transparencies > 90% at a wavelength
of 550 nm, sheet resistances (Rs) of 10–30 Ω/䊐 and a favorable
work function (∼4.8 eV).[21,28,29,] However, the use of ITO as
a transparent electrode has certain limitations, such as ever
increasing costs due to indium scarcity, complicated processing
requirements and sensitivity to acid and basic environments,
and the high surface roughness. Moreover, ITO is brittle and
can easily crack when used in applications where bending is
involved, such as touch screens, flexible displays and solar
cells.[16] Many of the alternative transparent electrodes, there-
fore, have been developed in order to replace ITO, such as
metal grids and metallic nanowires,[30,31] conductive polymers
like poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS),[32–34] and carbon nanotubes (CNTs).[35–37] Among
these transparent electrode materials, CNTs films exhibit sig-
nificantly high transparency across the whole visible light spec-
trum. One of the critical requirements for CNT films is that the
density of nanotubes must be above the threshold for the for-
mation of a percolation network. Additionally, the conductivity
S. Pang, Dr. Y. Hernandez, Dr. X. Feng, Prof. Dr. K. Müllen
Max Planck Institute for Polymer Research
Ackermannweg 10, D-55128 Mainz, Germany
E-mail: feng@mpip-mainz.mpg.de; muellen@mpip-mainz.mpg.de
DOI: 10.1002/adma.201100304
Adv. Mater. 2011, 23, 2779–2795 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PROGRESS REPORT
of individual CNTs is high, but the high resistance at the nan-
otube-nanotube junctions limits the conductive pathway within
the films.[38–40] Thus, CNTs films are currently not competitive
with ITO as transparent electrodes for practical applications.[41]
The experimental discovery of graphene brought a new
alternative to commercially available ITO electrodes. Although
research is still at its early stages, graphene already offers
several potential advantages over traditional transparent elec-
trodes.[25,42,43] Many groups have already demonstrated the
resilience of graphene-based organic photoelectrical devices.
The excellent performance of various graphene-based electronic
devices gives graphene a realistic chance of being competitive
in transparent and bendable technologies.
2. Properties of Graphene
2.1. Transmittance of Graphene
The theoretical transmittance (T) of a freestanding graphene
can be derived by applying Fresnel equations, in the thin film
limit, for a material with a fixed universal optical conductance[44]
G0 = e2/4h̄ ≈ 6.08 × 10−5/Ω, to give:
T = (1 + 0.5n")−2 ≈ 1 − n" ≈ 97.7%
where α is the fine structure constant, α = e2/h̄ c = 1/137.
The absorbance can be calculated as A = 1- T = πα = 2.3%.
Graphene only reflects < 0.1% of the incident light in the visible
region.[11] Thus, we can take the optical absorption of graphene
layers to be linearly proportional to the number of layers, each
absorbing 2.3% over the visible spectrum (Figure 1c). In a few
layer graphene (FLG) sample, each sheet can be seen as a two-
dimensional electron gas, with little perturbation from the adja-
cent layers, making it optically equivalent to a superposition
of almost non-interacting monolayer graphene (Figure 1d).[45]
The absorption curve of monolayer graphene is flat over a long
range,[27,14] as expected for 2D materials, with a peak in the UV
region (∼250 nm), attributable to inter-band electronic transi-
tion from the unoccupied π∗ states.[43,46]
The optical transmittance of free standing graphene is solely
determined by the value of the fine structure constant.[47] Exper-
imentally, the transmittance of the mechanically exfoliated
graphene (97.7%) is in excellent agreement with the theoretical
result as shown in Figure 1a, c for its perfect sp2 structure.
Graphene synthesized by chemical vapor deposition (CVD)[4,48]
is of high quality and also shows the similar optical trans-
mittance (97.4%) as demonstrated in Figure 1b,d (the small
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decrease of the transmittance has been attributed to contamina-

tion produced during the transfer process). In both the case of Dr. Xinliang Feng joined the
the mechanically exfoliated graphene and the CVD graphene, group of Prof. K. Müllen at
the transmittance linearly decreases as the number of layers the Max Planck Institute for
is increased. Actually, the transmittance of the graphene films Polymer Research (MPIP)
highly depend on the their crystal quality. In the case of ther- and obtained his PhD
mally reduced graphene oxide (TRGO) or cross-linked graphene degree in April 2008. Since
(CLG) from aromatic molecules, the transmittance is much December 2007, he was
higher than that of the pristine graphene due to the presence appointed as project leader
of defects.[49,50] The transmittance is ∼99.0% for TRGO[14] and in MPIP. His current sci-
∼99.5% for CLG[21] per ca. 0.34 nm in thickness. entific interests include the
conjugated oligomers and
polymers, graphene, carbon-
2.2. Resistance of Graphene rich molecules and materials
for electronic and energy-related applications.
In general, Rs of graphene films fabricated by different
approaches strongly depend on their surface morphology Prof. Klaus Müllen
and crystal quality. One of the bottom-up methods to ayn- received his PhD in 1972
thesis conductive carbon films is via the cross-linking of at the University of Basel
carbon-rich molecules on transparent substrates (e.g. quartz). (Switzerland). He pursued
This approach yields to high Rs films due to its low crystal postdoctoral research with
quality.[21,51] Another approach to achieve more conductive Prof. J.F.M. Oth at ETH
graphene film is using liquid exfoliated graphene as the pre- Zurich, where he obtained
cursor, producing the graphene films display Rs ∼5 kΩ/䊐 with his habilitation in 1977.
∼90% transmittance.[13] This resistance is much higher than the After working as a Professor
equivalent value calculated from the single graphene sheet due of Organic Chemistry at
to the non-uniformity of the graphene layers and the large inter- the universities of Cologne
layer resistance.[13] Thermal reduction is widely used to prepare and Mainz, he became a
conductive graphene films from GO due to its simple solution scientific member of the Max
processing and low roughness level.[14,18,42] Although a signifi- Planck Society in 1989 and was appointed Director of the
cant number of defects remain after thermal treatment, the Department for Synthetic Chemistry at the Max Planck
resistance is still comparable to that fabricated from the liquid Institute for Polymer Research. His current research focus
exfoliated graphene dispersion.[52] Nevertheless, the graphene lies on synthetic macromolecular chemistry, supramo-
films prepared by these methods are far below the requirement lecular chemistry, and materials science.
for replacing ITO (Figure 2a). Up to now, the most promising
way to obtain large area and highly conductive graphene films
is the use of CVD.[4,25,48,53,54] The decomposition of carbona-
ceous sources at high temperature and subsequent growth on from the atmosphere.[4,13] Increasing the doping concentration
metallic substrates leads to high quality graphene films which reduces the Rs of graphene films.[13,58–63] It has been shown that
are comparable to the pristine graphene exfoliated from HOPG. graphene can be chemically doped at a level of Ni = 1012 cm−2
The recently reported growth of graphene on copper substrates while maintaining charge carrier mobility of μ = 105 cm2/(V s)
by CVD with subsequent transfer onto bendable substrates ena- or higher.[64–66] Based on these values, the Rs of graphene is:
bled the production of large area graphene films (up to 30 inch)
with Rs ∼275 Ω/䊐 for single layer and ∼40 Ω/䊐 for four-layer Rs = 1/ e :Ni N = 64.2Ω / N
graphene films after p-type doping with HNO3.[25] This is the where N is the number of graphene layers of the film.[24]
first reported method for large-scale graphene film fabrication Simple atomic or molecular doping can directly modify the
which surpasses the “Minimum Industry Standard” with per- charge carrier concentration of graphene.[62,67–69] Polyvinyl
formances superior to common transparent electrodes such as alcohol (PVA) induces n-type doping with Rs values decreasing
ITO and CNTs films (Figure 2a).[55] from ∼4 kΩ/䊐 to ∼400 Ω/䊐 (Figure 2b), while the transmit-
Doping has been reported to be an efficient approach to tance value is not affected.[13] With HNO3 as p-type doping rea-
increase the overall conductivity. It has been documented that gent,[25,70] the Rs of monolayer graphene can be decreased from
organic molecules that act as electron donors or acceptors can 275 Ω/䊐 to 125 Ω/䊐. Four-layer doped graphene films fabricated
modify the electronic structure, which can be distinguished by roll-to-roll process displayed Rs as low as 30 Ω/䊐.[25]
by FET or Raman (2D versus G frequency map) measure-
ments.[56] Additionally, the change of the electronic structure
of graphene because of the present of organic dye molecules
3. Graphene Films Preparation
normally makes graphene (or GO) sheets more visible.[57] In
reality, sample doping seems to be unavoidable as it could So far, the original top-down mechanical exfoliation approach
be induced either by the substrate or by adsorbed molecules has produced the highest quality samples but at extremely low

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3.1. Graphitic Precursors to Graphene

3.1.1. Liquid Phase Exfoliation

The sonication-driven exfoliation of graphite
to produce graphene in organic solvents has
been shown to be an efficient and low-cost
method to produce oxide-free graphene in
solution. A number of organic solvents, with
surface tensions ∼40 mJ/m2, have been identi-
fied to exfoliate graphite to produce graphene
at quantifiable yields (Figure 3a).[13,71–72]
The exfoliation process occurs because of
the strong interaction between the solvent
and the composing layers of graphite, which
means that the energetic penalty for exfolia-
tion is small. Even though the concentra-
tion at which graphene can be dispersed has
jumped from 0.01mg/mL to 1.2 mg/mL in
NMP with low power sonication, the mean
flake size is reduced, thereby increasing
the overall inter-junction resistance of thin
films prepared from these dispersions.[71,73]
The main drawback of the organic solvents
used for exfoliation is their high boiling
points, which makes processing compli-
Figure 1. (a) Transmittance of mechanically exfoliated monolayer and bilayer graphene. (b) A
cated. Aqueous dispersions of high quality
transparent, 35-inch flexible polyethylene terephthalate (PET) sheet supported ultralarge-area
graphene film, which was synthesized by chemical vapor deposition (CVD). (c) Transmittance graphene are therefore desirable for the prep-
spectrum of mechanically exfoliated single-layer graphene (open circles). The red line is the aration of thin films. To this end, graphene
transmittance T = (1 + 0.5πα)−2 expected for two-dimensional Dirac fermions, whereas the has been exfoliated in surfactant-containing
green curve takes into account a nonlinearity and triangular warping of the electronic spectrum solutions. Anionic surfactants such as
of graphene. Inset in (c) Transmittance of white light as a function of the number of graphene 4-dodecylbenzenesulfonic acid and sodium
layers (squares). (d) Ultraviolet–visible (UV–vis) spectra of the CVD graphene films with 1 to
cholate have been reported to successfully
4 layers. The inset in (d) is the comparison of transmittance of a 10 nm thick thermal reduced
graphene film (red), ITO (black) and fluorine tin oxide (FTO, blue). (a,c) Reproduced with exfoliate graphite at a concentration up to
[52,74–76]
permission.[11] Copyright 2008, Science. (b,d) Reproduced with permission.[25] Copyright 2010, 0.3 mg/mL in water.
[ 14]
Nature publishing group. Inset in (d) Reproduced with permission. . Copyright 2008, ACS. Another approach is to expand inter-
layer spacing of graphite through interca-
lation with highly volatile agents and then
simultaneously exfoliate in organic solvents.
Because of its layered structure, graphite
can readily be intercalated using alkali
metals.[77,78] The graphitic intercalated com-
pounds (GICs), such as KC8 and K(THF)
xC24, are easy to exfoliate when exposed to
organic solvents due to the gas evolution
between the graphite layers as indicated in
Figure 3b. The K ions can be easily removed
Figure 2. (a) Transmittance (T%) and sheet resistance (Rs) data reported in the literature from the dispersion by filtration or cen-
for films prepared by CVD, from reduced GO or chemical modified graphene, pristine exfoli-
ated graphene and chemically synthesized graphene. The dash line represents the minimum
trifugation. However, graphene exfoliated
industry standard for transparent electrodes for solar cells. Reproduced with permission.[55] from the GICs is not very stable due to the
Copyright 2010, ACS. (b,c) Sheet resistances of a graphene FETs as a function of gate voltage strong π–π stacking of the relatively large
with n-type doping with polyvinyl alcohol (b) and p-type doping with concentrated HNO3 sheets produced. Long sonication of these
(c), respectively. (b) Reproduced with permission.[13] Copyright 2010, ACS. (c) Reproduced with exfoliated sheets can make the graphene
permission.[4] Copyright 2009, Nature publishing group. scroll to form tubular structures.[77] In order to
stabilize the graphene sheets in the
yields. Therefore, a number of alternative approaches such as organic solvents, surfactants are introduced.[79,80] For
liquid phase exfoliation, thermal reduction of GO and chemical example, expanded graphite was first synthesized by
vapor deposition (CVD) have been explored to produce trans- thermally annealing the expendable graphite at high tem-
parent graphene films. peratures and then sonicated in dichloroethane solution with

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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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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
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Figure 6. (a) Structural model of a GO showing carboxylic acid groups at the edge and epoxy and hydroxy groups mainly on the basal plane.
(b) Isothermal surface pressure/area plot showing the corresponding regions i-iv at which the monolayers were collected. (c-f) SEM images showing
the collected GO monolayers on a silicon wafer at different regions of the isotherm. The packing density can be continuously tuned. Scale bars in
(c)-(f) represent 20 μm. (a-f) Reproduced with permission.[93] Copyright 2010, ACS. (g) Photograph of an unreduced (leftmost) and a series of high-
temperature reduced GO films prepared by spin coating with increasing thickness. (h) and (i) are AFM images of GO film before and after 1100 °C
thermal reduction. White bar in g and h is 1 μm. (g-i) Reproduced with permission.[42] Copyright 2008, ACS.

using carbon isotope labeling in conjunction with Raman spec-
troscopic mapping to track carbon during the growth process
(Figure 8a, b).[113] The difference in the growth mechanisms of
graphene on Ni and Cu foils lies in the significant difference of
the solubility of carbon in these two metals. Since only a small
amount of carbon can be dissolved in Cu, once the surface is
fully covered with graphene the growth terminates. In contrast,
Ni can dissolve more carbon atoms on its surface and hence it
is difficult to achieve uniform graphene films due to precipita-
tion of extra carbon during the cooling-down process. There-
fore, metals with low C solubility such as Cu offer an advantage
over Ni in the large scale growth of monolayer graphene.[113]
3.4.2. Film Transfer and Doping
The application of graphene transparent electrodes in organic
electronics requires an indispensable step involving the transfer
of produced graphene films onto transparent substrates,
like glass, quartz and PET. Transfer processes are common
in the semiconductor industry. Poly(methyl methacrylate)
(PMMA)[114–115], polydimethylsiloxane (PDMS)[4,116] and thermal
release tapes (Jinsung Chemical Co. and Nitto Denko Co)[25]
are mostly used to transfer graphene films onto arbitrary sub-
strates. PMMA can be dissolved with acetone after the PMMA/
graphene membrane has been placed over the target substrate.
PDMS and thermally released tapes are normally employed

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applications. Third, the Rs values reported so

far outperforms the values reported for solu-
tion- processed graphene films.

4. Applications in Organic
Electronics
As already mentioned, using graphene
films as transparent electrode for organic
electronics emerges as a feasible option for
future devices. Although the performances
of some devices presented here are in an un-
optimized state, they still show promising
characteristics that make graphene a strong
candidate for replacing the commercially
available transparent electrodes.
Figure 7. (a) Transmission electron microscopy (TEM) image of a carbon nanosheet obtained
by cross-linking 1,1’-biphenyl-4-thiol (BPT, inset) and then pyrolyzed at 927 °C. (b, c) High reso-
lution transmission electron microscopy (HRTEM) images of non-annealed (b) and annealed 4.1 Solar Cells
(c) biphenyl nanosheets (927 oC), respectively. (d) Summary of sheet resistance as a function
of the annealing temperature. (a-d) Reproduced with permission.[51] Copyright 2010, Wiley-
VCH. (e) Polycyclic aromatic hydrocarbon and the mechanism of the intermolecular condensa- 4.1.1. Organic Solar Cells
tion into graphitic networks. (f) A representative HRTEM image of the scratched sample from To demonstrate how the transparent graphene
graphene film. (g) Sheet resistance and corresponding average conductivity of the graphene
film on quartz as a function of the film thickness. (e-g) Reproduced with permission.[21] Copy-
films performed as electrodes in organic
right 2008, Wiley-VCH. solar cells, the simplest bulk-heterojunction
solar cells consisting of graphene/ (poly[3-
hexylthiophene-2,5-diyl]:[6,6]-phenyl C61
in the dry transfer methods for the deposition of graphene on butyric acid methyl ester) (P3HT:PCBM)/Ag without any buffer
PET substrates (Figure 8c).[116–117] The effective area of graphene layers were studied (Figure 10a).[14] The favorable work function
grown on Cu substrates rapidly increased since first demon- of graphene makes it suitable as the hole-collecting electrode
strated, from a few centimeters to tens of centimeters as shown (Figure 10b), yielding an overall power efficiency of 0.29%.
in Figure 8d-h.[25,116] Comparing the fill factor (FF) and the short circuit current (Isc)
Up to now, Cu substrate is mostly used to grow monolayer with those of the ITO-based solar cells leads to the conclusion
graphene films. The Rs depends on the transfer processes that the low efficiency of the graphene-based device is due to
involving different doping properties (Figure 9a). The resist- the high Rs of the graphene electrode fabricated from PAHs via
ance of the roll-to-roll dry transferred monolayer graphene is the thermally-mediated cross-linking process (∼18 kΩ/䊐 and a
approximately two to three times larger than that of the PMMA- transmittance of 85%).[14]
assisted wet-transferred graphene films. As the number of In general, there are two approaches to improve the effi-
layers increases, the resistance of the dry transferred graphene ciency of graphene-based organic solar cells. One is to decrease
films drops quickly and reaches to ∼40Ω/䊐 of the four layer the resistance of the graphene electrodes, and the other is to
graphene film, which is already similar to the wet-transferred introduce buffer layers (hole- and electron-transporting layers)
graphene. Additionally, the improvement of the conductivity to increase the parallel resistance (Rp, sometimes referred to as
of monolayer graphene films is more effective than the thick shunt resistance, Rsh) of the solar cell (Figure 10c).[118–121] The Rp
graphene film via HNO3 doping. An improvement of 50% in arises from the current leakage through the cell (e.g. recombi-
conductivity is observed for the monolayer graphene, which is nation of the charge carriers), and the series resistance Rs arises
much higher than that of the four- layer graphene film (25%) as from the resistance of the cell materials to the current flow (e.g.
demonstrated in Figure 9a. Excitingly, the undoped four-layer resistance of the electrodes). Normally, the Rs is at least one
graphene film shows ∼90% optical transmittance (550 nm) order of magnitude lower than Rp.[120] Thus, both reducing Rs
and Rs as low as ∼40 Ω/䊐, which can be further improved to and increasing Rp enhance the efficiency of the solar cells.[121]
∼30 Ω/䊐 via HNO3 doping. This transmittance and resistance One of the most efficient approaches to increase the Rp is to
are already superior to common transparent electrodes such as introduce interfacial hole transport/electron blocking and elec-
ITO used for organic electronic applications.[25] tron transport/hole blocking layers between the electrodes and
The production of graphene via CVD has many advantages the active materials. To this end, the new construction of the
over other methods for transparent electrode applications. P3HT/PCBM heterojunction solar cell with PEDOT:PSS and
First of all, CVD is a technique already applied in industry ZnO as the buffer layers was performed (inset in Figure 10d),
which makes the compatibility of the process straightforward. and 0.78% efficiency was achieved. A subsequent experiment
Second, the ability to transfer the thermally grown graphene on with more conductive TRGO films (∼1000 Ω/䊐) provided an
any substrate over large areas is quite important for practical efficiency of 1.12%.[20] However, this efficiency is still much

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Figure 8. Schematic diagrams of the possible distribution of C isotopes in graphene films based on different growth mechanisms for sequential input of
13
CH4 and 12CH4. (a) Graphene with randomly mixed isotopes might occur from surface segregation and/or precipitation. (b) Graphene with separated
isotopes might occur by surface adsorption. (a-b) Reproduced with permission.[113] Copyright 2009, ACS. (c) Schematic illustration for the synthesis
and transfer of large-area graphene or patterned graphene films on an arbitrary substrate. Reproduced with permission.[116] Copyright 2009, ACS.
(d and e) Photographs of the CVD graphene films transferred onto a SiO2/Si substrate (d) and a glass plate (e), respectively. Reproduced with permis-
sion.[48] Copyright 2009, Science. (f and g) Photographs of as-grown graphene film on 3 inch large SiO2/Si/Ni substrate (f) and subsequently transferred
wafer-scale graphene film on a PET substrate (g), respectively. Reproduced with permission.[116] Copyright 2009, ACS. (h) Roll-to-roll transfer of 30 inch
graphene films from a thermal release tape to a PET film. Reproduced with permission.[25] Copyright 2010, Nature publishing group.

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 www.advmat.de
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donors, producing a power efficiency of 1.1% and 1.4%, respec-

tively.[122,123] Moreover, a thin reduced GO layer (2 nm) can be
applied to replace PEDOT:PSS as hole transport and electron
blocking layer in the organic heterojunction solar cells.[124]

4.1.2. Dye-sensitized Solar Cells

Dye-sensitized solar cells (DSSCs), another type of photovoltaic
device, has recently attracted widespread interest due to their
Figure 9. (a) Sheet resistances of transferred graphene films prepared potentially low production costs and relatively high energy
with different transfer (roll-to-roll dry transfer using thermal release tape conversion efficiency. Typically, DSSC consists of a dye- sensi-
and wet transfer using PMMA and doping with HNO3. (b) Comparison tized mesoscopic TiO2 photoanode, a Pt counter electrode, and
of sheet resistances of the different kinds of transparent electrodes, such
an electrolyte with the I−/I3− redox couple in liquid- state (or
as ITO, CNTs and graphene films. Reproduced with permission.[25] Copy-
right 2010, Nature publishing group. hole transport polymer in solid state). The working principle of
the DSSC is shown schematically in Figure 11a.[125] First, the
dye is excited by absorbing the incoming photon and rapidly
lower than that of the ITO-based devices (about 2.50% under injecting an electron into the conduction band (CB) of TiO2.
the same experimental condition) due to their large Rs. In con- Then the electron goes through an external circuit and arrives
trast, it was recently demonstrated that, the more conductive at the counter electrode, where an I3− ion is reduced. Finally,
CVD graphene film with a Rs of 230 Ω/䊐 and a transparency of the dye is regenerated by I−. Similarly, for solid state DSSCs,
72% (550 nm) showed performance comparable with the ITO- the I−/I3− redox is replaced with a solid state polymer (such
based device.[16] Additionally, CVD graphene based solar cells as spiro-OMeTAD1), which can transport holes to the counter
revealed an outstanding ability to operate under bending condi- gold electrodes. Graphene can cover an even larger number of
tions of up to 138°, whereas the ITO-based devices displayed functions in DSSCs. First, as the transparent electrode, solid-
cracks and irreversible failure under bending of 60°. This indi- state DSSCs based on spiro-OMeTAD1 and porous TiO2 (for
cates the great potential of graphene films for flexible photo- electron transport) can be fabricated as shown in Figure 11b.[14]
voltaic applications.[16] The work function of graphene is lower than that of the counter
Besides serving as transparent electrodes, there are still other gold electrode, therefore qualifying for application as the trans-
applications of graphene in organic heterojunction solar cells. parent anode in the DSSCs as indicated in Figure 11c. An effi-
For instance, functionalized graphene can be used as an elec- ciency of 0.26% was obtained when a graphene film with a Rs
tron acceptor to replace PCBM in organic heterojunction solar of 1.8 kΩ/䊐 and transmittance of 72% (550 nm) was used as
cells with poly(3-hexylthiophene) and poly(3-octylthiophene) as anode electrode.[14]
On the other hand, the two-dimensional
graphene bridges in the TiO2 layer can also
serve as the short range transparent conductor
(compare to the ITO transparent electrode) to
quickly collect and transport electrons from
TiO2 to the FTO electrodes (Figure 11d,e). It
was found that the efficiency of DSSCs can be
improved by ∼50% by using graphene-TiO2
composites as the photoanodes compared to
that of the commercial TiO2 (P25) nanopar-
ticles.[126,128] A RGO content of ∼0.6% (equal
to 0.4% graphene) is the currently reported
value to achieve maximum efficiency
(Figure 11f). In the case of high graphene
content in the composite, the dye adsorp-
tion is reduced because the TiO2 starts to be
coated by graphene. At the same time, excess
graphene can act as a recombination center
Figure 10. (a) Illustration of a solar cell configuration; the four layers from bottom to top are instead of providing an electron pathway,
[126,128]
cathode (Ag or Al), P3HT/PCBM, graphene, and quartz substrate, respectively. (b) A schematic which can lead to a short circuit.
representation of charge transfer and transport as an energy level diagram. (a,b) Reproduced The third application for the introduction
with permission.[14] Copyright 2008, ACS. (c) Equivalent circuit for standard solar cell under of graphene in DSSCs is to replace Pt as the
illumination. (d) Current–voltage (I–V) curves of P3HT/PCBM heterojunction solar cells with counter electrode (not as the transparent
ZnO as the electron transfer layer. Reproduced with permission.[20] Copyright 2009, Wiley-VCH.
electrode), due to its high conductivity, high
(e) Photograph of high flexible of CVD graphene on a PET substrate. (f) I–V characteristics of
CVD graphene photovoltaic cells with different bending angles. Insets show the experimental specific surface area and good electrocata-
setup to bend the flexible solar cells. (g) Fill factor (FF) dependence of the bending angles for lytic activity. A hybrid PEDOT:PSS/RGO
CVD graphene and ITO devices. (e-g) Reproduced with permission.[16] Copyright 2010, ACS. composite was used as the counter electrode,

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flexibility. Other applications of graphene, for
example as electron acceptor materials, hole
transport buffer layers, bridge conductors in
TiO2 nanocrystals and counter electrodes in
DSSCs also need to be further explored.

4.2. Organic Light-Emitting Diodes

A solar cell is a device that converts the

energy of incident light into electricity, while
an LED is a device that converts electrical
energy into light. In an OLED, an organic
semiconductor layer emits light when an
electric current passes through it. This layer
of organic semiconductor material is formed
between two charge-injecting electrodes, and
at least one of these electrodes is transparent.
Holes are injected into the highest occupied
molecular orbital (HOMO) from the anode,
while electrons are injected into the lowest
unoccupied molecular orbital (LUMO) from
the cathode. Thus, the work functions of the
anode and cathode should match the HOMO
and LUMO of the light-emitting polymer,
respectively.[130] Although OLEDs are prom-
ising for electronic displays in television
screens, computer monitors, small portable
screens, watches, advertising, information
and indication,[131,132] the chemical instability
and the inferior flexibility of the commercial
ITO electrodes have hindered their develop-
ment and strongly indicate the need to find a
candidate to replace ITO in OLEDs.[133]
The classical OLED with a structure of
Figure 11. (a) Schematic illustration of the working principle of dye-sensitized solar cells anode/PEDOT:PSS/N,N′-di-1-naphthyl-N,N′-
(DSSCs). Graphene can be used as a candidate for FTO replacement, as a bridge in TiO2, or as diphenyl-1,1′-biphenyl-4,4′diamine (NPD)/
counter electrode. Reproduced with permission.[125] Copyright 2009, Wiley-VCH. (b) Illustration tris(8-hydroxyquinoline) aluminum (Alq3)/
of a dye-sensitized solar cell using graphene film as a transparent electrode, the four layers LiF/Al (inset in Figure 12a) was adopted to
from bottom to top are Au, dye-sensitized TiO2, compact TiO2, and graphene film. (c) The investigate the performance when a graphene
energy level diagram of graphene/TiO2/dye/spiro-OMeTAD/Au solar cell. (b,c) Reproduced
with permission.[14] Copyright 2008, ACS. (d) Graphene bridges in TiO2 to capture and transfer
film was used as the transparent electrode.[24]
electrons to the cathode. (e) Electrochemical impedance spectra of different kinds of TiO2 A graphene film with a Rs and transmittance of
layers. (inset: equivalent circuit of the device). The spectra were measured under the illumina- ∼800 Ω/䊐 and 82% (550 nm) was used in this
tion of one sun at open circuit potential. (f) Photocurrent-voltage characteristics of DSSCs study. The turn-on voltage of the OLED with
with different electrodes containing different graphene loading levels. (d–f) Reproduced with graphene as transparent electrode is 4.5 V,
permission.[126] Copyright 2010, ACS. (g) Photocurrent-voltage characteristics of the DSSCs slightly higher than the 3.8 V of the ITO-
with different counter electrodes. Reproduced with permission.[127] Copyright 2008, ACS.
based device. The OLEDs on graphene have
a current drive and light emission intensity
yielding an efficiency of 4.5%, comparable to 6.3% for a Pt- comparable to those of ITO-based devices when the current
based counter electrode.[129] The pure graphene film prepared density is < 10 mA/cm2 as shown in Figure 12a. However, at
from GO also showed promising properties, ∼55% of the value a current density > 10 mA/cm2, the obvious degradation of the
obtained by using Pt as the counter electrode. It has been sug- graphene-based OLEDs, due to the high Rs of graphene, pro-
gested that the efficiency could be further improved by opti- duces a voltage drop in the electrode. More interestingly, the
mizing the device fabrication (Figure 11g).[127] external quantum efficiency (EQE) and the luminous power
For the solar cells, graphene constitutes a significant advance efficiency (LPE) of graphene- based OLEDs nearly match that
towards the production of transparent conductive electrodes. of the ITO-based device, despite the low conductivity of the
Graphene films meet the most important criteria for replacing graphene electrode (Figure 12b).[24]
ITO in organic solar cells, including high yield produc- Additionally, transparent graphene electrodes can also be
tion, high conductivity, good chemical stability, and excellent used in light-emitting electrochemical cells (LEC).[22] An LEC

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Figure 12. (a) Current density (filled symbols) and luminance (open sym-
bols) vs applied forward bias for an OLED employing graphene (squares)
and ITO (circles) as transparent electrodes. OLED device structure is Figure 13. (a) Schematic diagram of a liquid crystal device. 1, glass;
anode/PEDOT:PSS/N,N′-di-1- naphthyl-N,N′-diphenyl-1,1′-biphenyl- 2, monolayer graphene; 3, Cr/Au contact surrounding graphene; 4, align-
4,4′diamine (NPD)/tris(8-hydroxyquinoline) aluminum (Alq3)/LiF/Al as ment layer (polyvinyl alcohol); 5, liquid crystal; 6, alignment layer; 7, ITO;
shown in the inset. (b) External quantum efficiency (EQE) (filled symbols) 8, glass. (b-e) Optical micrographs of a liquid device using green light
and luminous power efficiency (LPE) (open symbols) for an OLED on with different voltages applied across the cells: (b) 8 Vrms; (c) 13 Vrms;
graphene film (squares) and ITO glass (circles). Reproduced with permis- (d) 22 Vrms; (e) 100 Vrms. Overall image is 30 μm and the central hex-
sion.[24] Copyright 2010, ACS. agonal window is covered by graphene. (f) Light transmission through
the liquid crystal device as a function of voltage applied across the cell,
normalized to the maximum transmission. Inset: low voltage measure-
is a device, similar to OLED, where the light-emitting polymer ments. Solid blue curve: in green light, 505 nm, dashed red curve: in white
is blended with an electrolyte. The mobile ions in the electro- light. Reproduced with permission.[13] Copyright 2010, ACS.
lyte migrate when a potential is applied between the electrodes,
forming high charge-density layers at each electrode interface,
ion diffusion easily takes place when ITO serves as the trans-
allowing efficient and balanced injection of electrons and holes.
parent electrode. Recent reports showed that in the case of a
Graphene, used as both the anode and cathode electrodes, can
6 nm thick thermally reduced GO film, the performance of pre-
overcome the problem of the electrochemical side-reaction on
pared LCD device was comparable to that of ITO electrodes.[135]
the traditional metal electrode, showing a promising future in
OLED structures.[22]
4.4 Touch Screens
4.3 Organic Liquid Crystal Displays
A touch screen is an electronic visual display that can detect the
presence and location of a touch, by a finger or other objects,
A liquid crystal display (LCD) is a thin, flat electronic visual
within the display area, thereby permitting the physical interac-
display that use the light modulating properties of liquid crys-
tion with what is shown on the display itself. There are a variety
tals. It consists of thin films of optically transparent polymers
of touch screen technologies, e.g. resistive, surface acoustic
with micrometer-sized liquid crystal (LC) droplets placed within
wave, capacitive, surface capacitance, projected capacitance.[136]
pores of the polymer. Light passing through the LC/polymer is
Resistive and capacitive touch panels are the most common. A
strongly forward scattered, producing a milky film. If the LC
resistive touch screen panel is composed of several layers, the
ordinary refractive index is close to that of the host polymer, the
most important of which are two thin, metallic, electrically con-
application of an electric field results in a transparent state.[134]
ductive layers separated by a narrow gap (Figure 14a). There
The ability to switch from translucent to opaque makes them
are many advantages of graphene-based transparent electrodes
attractive in many applications including computer monitors,
compared to ITO, including brittleness and wear resistance,
televisions, instrument panels, aircraft cockpit displays, sig-
high chemical durability and no toxicity as was discussed above.
nage, etc. Conventionally, ITO on glass is used as a transparent
Recently, graphene produced by CVD, was reported to reach up
electrode to apply the electric field across the LCD. However, the
to 30-inch in size which satisfies the requirements for resistive
instability and poor flexibility hinder its development. The sche-
touch screens in terms of transmittance and Rs (Figure 14b).[25]
matic diagram of LCDs fabricated with mechanically exfoliated
monolayer graphene is shown in Figure 13a.[13] The threshold
voltage of the graphene-based LCDs is around 0.9 Vrms, and
an obvious change in the transmission is observed both in
white and monochromatic light (Figure 13b–e, f). The whole
graphene electrode area changes uniformly, which suggests that
the graphene has no negative effect on the liquid crystal align-
ment. The contrast ratio (between maximum transmission and
the transmission when 100 Vrms is applied across the cell) is
better than 100 under white light, which is outstanding for this
type of cell and demonstrates that graphene could indeed be
used effectively as a transparent electrode for LCDs. The com- Figure 14. (a) Schematic capacitive touch panel. (b) Graphene-based
parison of the chemical stabilities of graphene and ITO also touch screen panel connected to a computer with control software. Repro-
shows a remarkable advantage for graphene electrodes because duced with permission.[136] Copyright 2010, Nature publishing group.

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4.5. Organic Field Effect Transistors
For p-type organic semiconductors, gold is normally used as
the source and drain (S/D) electrodes due to its favorable work
function. Recently, it was reported that the work functions of
Cu and Ag electrodes can be tuned by depositing thin graphene
films on their surface. The modification of the electrodes can
be easily carried out via heating the patterned Cu and Ag elec-
trodes in an ethanol/H2/Ar gas at 700–800 ºC (Figure 15a).[19]
The mobilities of pentacene FETs with the Cu (or Ag)/graphene
as the S/D electrodes were reported to be 10 times higher than
that with pure Cu or Ag contacts (Figure 15b, c). The reason for
this improved performance could be attributed to the decreased
work function of the S/D electrodes and the reduced contact
resistance between the electrodes and the organic semiconduc-
tors after deposition of a thin layer of graphene.[19] To prove
the advantage of the graphene electrodes over normal gold
contacts, full graphene S/D electrodes were also fabricated by
oxygen plasma etching of a TRGO film (Figure 15d). Oxygen
plasma involving an etching process is an efficient way of pat-
terning graphene, and can be used on a large scale (Figure 15
e-g). Solution-based polymer transistors employing P3HT as
semiconductor yield an average hole mobility of 0.04 cm2/Vs,
which is about twice as high as that of gold contact devices.
The lack of nonlinear behavior suggests the presence of an
Ohmic contact between the graphene electrodes and the
P3HT layer.[18] The Rs of the P3HT layer is in the range of
104 MΩ/䊐 to 10 MΩ/䊐, which is significantly higher than that
of the graphene electrode (∼200 Ω/䊐). Therefore, the resistance
of the graphene electrodes is low enough to serve as the S/D
electrodes for OFETs. It should be mentioned that monolayer
graphene can also act as the electrodes in OFETs and photo-
detectors.[13,26,137,138] For instance, monolayer graphene elec-
trodes can be directly prepared by the oxidative cutting of an
individual 2D planar graphene sheet involving electron beam
lithography and oxygen plasma etching (Figure 15h–k). The
mobility of the P3HT transistor is around 0.0014 cm2/Vs.[138]
Besides serving as the electrode material, another promising
application of graphene in OFET field is to mix with semicon-
ducting polymer to improve the performance as well.[139]
4.6 Spectroelectrochemistry Devices
Most of the above-mentioned devices are operated under visible
(Vis) light, such as solar cells, LEDs and LCDs. The ultraviolet
(UV) region also opens the door to currently inaccessible appli-
cations of transparent electrodes. In particular, spectroelectro-
chemical studies have combined a wide range of spectroscopies
with electrochemistry. However, the absorption spectroscopy in
the UV region has been greatly limited since the transparency
of an ITO electrode decreases rapidly for wavelengths shorter
than 350 nm. This weakness, therefore, hinders the detection of
electrochemical species that absorb in the UV region and com-
plicates the analysis of overlapping spectral features associated
with species that absorb across the UV–Vis region. In contrast,
graphene shows a high transparency over a broad wavelength
region. Typically, thermally reduced graphene films, ∼24 nm
thick, exhibit transmittances better than 53% at a wavelength
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PROGRESS REPORT
of 200–800 nm. The conductivity and chemical stability of
graphene films are sufficient for electrochemical and spectro-
electrochemical investigations. Therefore, the spectroelectro-
chemical properties in the entire UV-Vis region of immobilized
nanotubular quasi 1D-excitonic J-aggregates of the amphiphilic
cyanine dye 3,3’-bis(2-sulfopropyl)-5,5’,6,6’-tetrachloro-1,
1’-dioctylbenzimidacarbocyanine (C8S3) can be evaluated. The
results demonstrate that graphene films offer great promise as
ultrathin, optically transparent electrodes that could facilitate
new measurement protocols using combined electrochemical
and spectroscopic methods, particularly in the UV.[27]
5. Conclusion
Graphene is the name given to a one atom thick layer of
carbon. It is mechanically stable, optically transparent, chemi-
cally inert, and an excellent electrical and thermal conductor.
These properties make graphene a promising candidate for
applications in various photoelectronic devices that require con-
ducting and transparent thin films. In many cases (e.g. touch
screens, OLEDs) this also adds fabrication flexibility, in addi-
tion to economic advantages. Current LCDs face major chal-
lenges due to fabrication costs associated with the requirement
of large transparent electrodes. Up to now there have been a
vast number of reports which suggest that graphene is indeed
a promising transparent electrode for organic electronics. Novel
graphene-based transparent electrodes on flexible substrates for
organic electronics show excellent operational flexibility, which
is not accessible with current transparent ITO electrodes. The
industry requirements of Rs and electrode transparency strongly
depend on the application, which means that graphenes with
different values of resistances can be used in different kinds of
electronic devices. Although the electrical conductivity of ther-
mally reduced GO films is significantly lower than that of CVD
graphene, it still works well in OFETs and LCDs. For OLEDs,
TRGO also provides performance comparable to ITO-based
devices, especially at lower applied voltage. For spectroelectro-
chemistry experiments in the UV-Vis region, the high transmit-
tance of graphene makes it clearly superior to ITO electrodes.
However, organic solar cells need highly conductive elec-
trodes in order to efficiently transport carriers and to decrease
the energy loss. For this purpose, the CVD grown graphene
already reaches the basic requirements in terms of resistance
and transmittance. Future research should be directed at opti-
mizing the growth, transfer and doping technologies in CVD
graphene, with the aim of attaining more homogenous, large-
scale and low- cost graphene films on flexible substrates. For
thermally reduced GO films, attention should be focused on
the improvement of conductivity, including the restoration of
a perfect sp2 structure and on making hybrid films with other
more conductive components. One idea is to fabricate reduced
graphene-metal wire hybrid films. In such an electrode struc-
ture, graphene and metal wires can serve as the short-range and
long-range conductor respectively, which should be more effi-
cient in collecting and transporting the carriers to the external
circuits. The availability and easy processability of graphene on
substrates or on liquid phase have already shown to be prom-
ising as a transparent electrode in organic electronics. In our
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Figure 15. (a) Schematic illustration of the fabrication of graphene modified Ag or Cu patterned electrodes. (b) Transfer characteristics of pentacene
FETs with Ag/graphene and Ag electrodes. (c) Transfer characteristics of pentacene FETs with Cu/graphene and Cu electrodes. (a-c) Reproduced with
permission.[19] Copyright 2008, Wiley-VCH. (d) Schematic illustration of the fabrication of patterned graphene electrodes. (e) Optical microscopy (OM)
image of patterned graphene electrodes on a silicon substrate. (f) AFM image of the edge of the patterned graphene electrode. (g) Height profile along
the line in f, showing microchannel etched down to the underlying SiO2/Si substrate. (d-g) Reproduced with permission.[18] Copyright 2009, Wiley-VCH.
(h, i) A schematic of how monolayer graphene sheets function as 2D electrodes to measure the electrical properties of organic semiconductors. (j) OM
and AFM image of a representative device. The gap size between the graphene ends is ∼100 nm. Inset is the height profile across the nanogap. (h,j,k)
Reproduced with permission.[138] Copyright 2009, Wiley-VCH. (i) Reproduced with permission.[137] Copyright 2010, Wiley-VCH.

2792 wileyonlinelibrary.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2011, 23, 2779–2795

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opinion, there will be many improvements in this direction in
the near future, which is exciting for a material that has been
studied for less than a decade. Carbon is once more paving the
way towards new advanced materials, in this case towards light,
flexible, resilient and efficient organic electronic devices.
Acknowledgements
The authors would like to acknowledge DFG Priority Program SPP 1459,
and ERC. Y. Hernandez gratefully acknowledges funding by the Alexander
von Humboldt Foundation.
Received: January 24, 2011
Revised: March 1, 2011
Published online: April 26, 2011
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