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(Qingbin Zheng, Jang-Kyo Kim (Auth.) ) Graphene For
(Qingbin Zheng, Jang-Kyo Kim (Auth.) ) Graphene For
1 3
Qingbin Zheng Jang-Kyo Kim
Leibniz Institute of Polymer Research Department of Mechanical and Aerospace
Dresden Engineering
Dresden The Hong Kong University of Science and
Germany Technology
Kowloon
Hong Kong SAR
Springer Science+Business Media LLC New York is part of Springer Science+Business Media (www.
springer.com)
Preface
progress for CVD-grown graphene achieved so far, these important challenges must
be overcome before the industry applications.
Owing to the scalability of production and the convenience in processing,
graphene oxide (GO) has been considered an important precursor for the fabrication
of TCs. GO sheets are hydrophilic and can produce stable and homogeneous colloidal
suspensions in aqueous and various polar organic solvents due to the electrostatic
repulsion between the negatively charged GO sheets. These GO dispersions are easy
to be processed to produce TCs on a substrate. Transparent conducting films (TCFs)
containing GO or chemically reduced GO sheets have been deposited via several
well-established techniques, including spin or spray coating, transfer printing, dip
coating, electrophoretic deposition, and the Langmuir–Blodgett (L–B) assembly,
followed by chemical reduction and/or thermal annealing.
While there are some books that specialize in fabrication processes and properties
of graphene and GO, very few books are available specifically dealing with the
following topics for their application in transparent conductors: (i) how to produce
TCs by using CVD grown graphene, (ii) how to synthesize GO with different size
and control their surface functionalities to enhance the electrical conductivity,
(iii) how to incorporate these nanostructured materials into thin films with layered
structure, and (iv) how to improve the conductivity and transparency. In light of the
authors’ experiences on graphene fabrication and application for TCs in the past few
years, this book is aimed to provide a comprehensive overview of traditional and
novel techniques in producing and functionalizing graphene for highly conductive
transparent thin films. It will offer a systematic presentation of the principles,
theories, and technical practices behind the structure–property relationship of the
thin films, which we believe to be the key for the development of high-performance
TCs.
The book is intended primarily for an audience of graduate students, research
scientists, and professors in the area of carbon materials, transparent conductors,
and related fields, as well as to professionals from the electronic and chemical
manufacturing industries. Nanotechnology, as an emerging new subject, has been
established as a major in postgraduate level in many universities and research
institutes. This book would be well suited as a textbook for an intermediate level
class in nanotechnology and/or materials science and engineering as part of such
a program or as a stand-alone course. It will be accessible equally to readers with
either science or engineering background. At the same time, the unique perspectives
provided in the applications of graphene as TCs will serve as a useful guide for
design and fabrication of these thin film materials for specific applications.
The authors are grateful for the assistance, discussion, and encouragement
offered during the preparation of this book by past and current colleagues and
friends, including Dr. B Zhang, Prof. QZ Xue, Prof. ZG Li, Prof. PC Ma, Prof.
JH Yang, Dr. J Li, Dr. ZD Huang, Dr. Y Geng, Dr. X Shen, Dr. XY Lin, as well
as the research group members who produced the research outputs quoted in this
book. Dr. Zheng was partly supported by the Hong Kong University of Science &
Technology (HKUST) Postgraduate Studentships (PGS), Finetex-HKUST R & D
Center at HKUST, Research Grant Council (RGC) of Hong Kong, Shanghai Pujiang
Preface vii
Talent Project, and the Alexander von Humboldt Foundation during the course of
completing this book. The authors specially thank Prof. E. Mäder, Dr. SL Gao, Dr.
HS Qi, Dr. C Scheffler, and Dr. U Gohs at Leibniz Institute of Polymer Research
Dresden (IPF) for stimulating discussion on this book. The authors are also grateful
to Drs. David Packer, Ho Ying Fan, and Kanchan Kumari at Springer for their kind
reviewing and processing of our manuscript.
ix
x Contents
2.3.3 Elimination of Sonication������������������������������������������������������� 45
2.3.4 Size Separation Methods��������������������������������������������������������� 47
2.4 Structures of Graphene and GO���������������������������������������������������������� 51
2.5 Properties of Graphene and GO���������������������������������������������������������� 55
2.5.1 Electrical/Electronic Properties����������������������������������������������� 55
2.5.2 Thermal Properties������������������������������������������������������������������ 63
2.5.3 Optical Properties�������������������������������������������������������������������� 67
2.5.4 Mechanical Properties������������������������������������������������������������� 68
2.6 Common Tools for Characterization of Graphene
and Its Derivatives������������������������������������������������������������������������������� 73
2.6.1 Atomic Force Microscopy������������������������������������������������������� 73
2.6.2 Scanning Electron Microscopy (SEM)����������������������������������� 74
2.6.3 Transmission Electron Microscopy (TEM)����������������������������� 74
2.6.4 Scanning Tunneling Microscope (STM)��������������������������������� 76
2.6.5 Raman Spectroscopy��������������������������������������������������������������� 79
References���������������������������������������������������������������������������������������������������� 81
4.3 Hybridization��������������������������������������������������������������������������������������� 138
4.3.1 Hybridization with CNTs�������������������������������������������������������� 138
4.3.2 Hybridization with Metal Wires��������������������������������������������� 151
4.3.3 Hybridization with Metal Grids���������������������������������������������� 157
4.4 Using UL-GO�������������������������������������������������������������������������������������� 158
4.4.1 Solution Casting of UL-GO���������������������������������������������������� 158
4.4.2 Dip Coating of UL-GO����������������������������������������������������������� 159
4.4.3 L–B Assembly of UL-GO������������������������������������������������������� 161
References���������������������������������������������������������������������������������������������������� 173
Index������������������������������������������������������������������������������������������������������������������ 215
Acronyms and Symbols
Acronyms
PANI Polyaniline
PDMS Polydimethylsiloxane
PDP Plasma display panel
PEDOT/PSS Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
PEI Polyethyleneimine
PEG Polyethylene glycol
PET Polyethylene terephthalate
PLD Pulsed laser deposition
PMMA Poly(methyl methacrylate)
PmPV Poly(m-phenylene vinylene-co-2,5-dioctyloxy-pphenylene vinylene)
P 2O 5 Phosphorus pentoxide
POPT Poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5-thienylene)
PPA Polyphosphoric acid
PPV Poly(para-phenylene vinylene)
PPy Polypyrrole
PTs Polythiophenes
PVDF Polyvinylidene fluoride
PVP Poly(4-vinylphenol)
RAM Radar absorbing materials
rGO Reduced graphene oxide
RF Radio frequency
RP Rear-projection
SAED Selected area electron diffraction
SE Secondary electrons
SEM Scanning electron microscope
SDS Sodium dodecyl sulfate
S-GO Small graphene oxide
SRL Self-release layer
SPL Sound pressure level
STM Scanning tunneling microscope
SWCNT Single-walled carbon nanotube
TCs Transparent conductors
TCFs Transparent conductive films
TCOs Transparent conducting oxides
THD Harmonic distortion
ToF-SIMS Time-of-flight secondary ion mass spectrometry
UL-GO Ultralarge graphene oxide
UHV Ultra-high vacuum
UV-Vis Ultraviolet–visible spectroscopy
VAPE Vacuum arc plasma deposition
VL-GO Very large graphene oxide
WHM Width-at-half-maximum
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
xvi Acronyms and Symbols
Symbols
TCFs, which are optically transparent and electrically conductive thin layers, are
necessary components in many modern devices [1]. TCFs have been used in a wide
variety of optoelectronic devices, such as touch screens, liquid crystal displays
(LCDs), organic light-emitting diodes (OLEDs), solar cells, sensors, etc. [2, 3]. It is
reported that the market for TCFs in 2012 was ~ US$ 3.9 billion and it will grow to
nearly US$ 10 billion by 2019 (Fig. 1.1a) [4]. LCD is by far the largest user of TCF
materials (Fig. 1.1b). It is estimated that ~ 290 million displays will be produced in
2014 and the demand for TCF materials will continuously increase [5]. Different
applications may require differing TCF materials because each application has its
own set of optoelectronic parameters and requirements [6, 7]. Table 1.1 shows rep-
resentative examples of applications and the corresponding TCFs chosen for them.
Flat-panel displays and touch screens need TCFs as the front electrode. Except low
electrical resistance and high transparency, etchability is another very important
consideration to form patterns in transparent conductor (TC) electrodes. By virtue
of its easy etchability, indium tin oxide (ITO) is favored over other TC oxide ma-
terials. The low temperature required for ITO films is another vital advantage for
color displays where the TC is deposited on thermally sensitive organic dyes [7].
Another good example is the low-emissivity glass window that can improve the
energy efficiency of buildings. Because the free electrons reflect infrared radia-
tion for wavelengths longer than the plasma wavelength, it should be long enough
(~ 2 µm) in cold weather so that most of the solar spectrum can be transmitted. Due
to the suitable plasma wavelength of > 1.6 µm with excellent durability and low
cost, fluorine-doped tin oxide (FTO) is the best material for this purpose [7]. How-
ever, a short plasma wavelength (≤ 1 µm) is needed in hot climates so that the near-
infrared portion of the incident sunlight can be reflected out of the building. Silver
and titanium nitride are widely used for this application due to their short plasma
wavelengths of 0.4 and 0.7 µm, respectively [7]. TCFs serve as the front electrodes
in thin-film solar cells. Thermal stability and low cost are the primary selection
criteria. For thermally sensitive solar cells, TCFs need to be deposited on flexible
Fig. 1.1 Transparent conductive film markets (US$ millions). a Forecast of TCF markets [4].
b Flat-panel display and transparent conductor markets. ITO indium tin oxide, TCO transparent
conducting oxides, OLED organic light-emitting diodes, RP rear-projection, PDP plasma display
panel, LCD liquid crystal displays, CCFL cold cathode fluorescent lamp, CRT cathode ray tube,
FPD flat-panel display [11]
steel or plastic substrates. Due to the low temperature deposition requirement, ITO
or ZnO is chosen for this purpose [7]. Electrochromic mirrors and windows have
been widely used in automobiles and smart windows with electrically controllable
transmission. The main considerations are chemical inertness, high transparency,
Table 1.1 Selection criteria for various transparent conductors (TCs) [7]
Applications Sheet Transparency Plasma Thermal Mechanical Chemical Deposition Toxicity cost
resistance wavelength stability stability stability temperature
Flat-panel Low High – – Good Good Low Low –
displays
Touch screens Low High – Good Good Low Low –
Low-emissivity – High Long when Good Good – – Low Low
windows cold and short
when hot
Solar cell Low High – Good – – Low (≤ 200̊C) Low Low
Electrochromic – High – – – Good – – Low
mirrors and
windows
Defrosting Low High – – Good – – – Low
windows
1.1 Applications of Transparent Conductive Films (TCFs)
and low cost, making tin oxide an ideal choice for this purpose [8]. Defrosting win-
dows are required in many areas, such as the display windows in supermarkets and
windshields or windows in airplanes. Low cost and durability are the main factors
and tin oxides are widely used for this application [7]. Laboratory ovens are often
constructed entirely of TCF-coated glass because they need to be transparent while
possessing high temperature stability, chemical and mechanical durability, and low
cost. Static dissipation TCFs are used to dissipate static charges that often grow
excessively on cathode ray tubes (CRT), computer monitors, xerographic copiers,
and television tubes. The main concern here is the mechanical and chemical dura-
bility, although the sheet resistance can be relatively high [7]. In order to prevent
the eavesdropping on computers and communications, electromagnetic shielding
TCFs are used to block the stray signals by detecting electromagnetic signals pass-
ing through windows [9]. Invisible security circuits can be used for both military
and consumer applications [10]. Very high transparency is the most important factor
for this special purpose. In order to improve the durability of glass, TCFs with good
abrasion resistance are needed.
Hence, different sets of parameters are desired for a wide variety of applications
based on different TCFs [6, 7]. Especially, there are rapidly growing markets for
flexible TCFs such as flexible displays [12], flexible touch screens [13], printable
electronics [14, 15], OLEDs [16], and thin-film photovoltaics [17, 18]. Figure 1.2
shows examples of flexible organic optoelectronic devices like OLEDs and organic
photovoltaics (OPVs). OLEDs consume power to emit light, while OPVs absorb
light to store energy for future power output. OLEDs can be used to create digital
displays, such as TV screens, computer monitors, and portable systems [19]. Their
unique flexible and lightweight nature makes them an excellent candidate for use in
emerging technologies, such as roll-up displays. OPV devices convert solar energy
to electrical energy and are promising candidates for meeting the increasing future
energy demands [18]. Flexible and lightweight OPVs can be incorporated into ev-
eryday products, such as clothing, backpacks, and other wearable apparel.
ITO has been the dominant material for TCF applications. It has a huge global
market worth US$ 3 billion in 2010 with a 20 % growth rate annually [1]. The lim-
ited supply of indium and ever-increasing demands, however, have pushed the price
of ITO up continuously [20]. Due to the brittleness of ITO, to apply it in flexible
devices is prohibitively difficult [6]. Several types of new TCF materials, includ-
ing conductive polymers [21, 22], metallic nanowires [23, 24], carbon nanotubes
(CNTs) [2], and graphene films [25] have been developed as alternative transparent
electrode materials. Graphene, a rapidly rising star on the horizon of materials sci-
ence [26], is considered the most interesting material to replace ITO benefited from
its exceptional mechanical, optical, and electrical properties [6].
1.2 Transparent Conducting Oxides (TCOs) 5
Fig. 1.2 Examples of flexible organic optoelectronic devices. a Example of an organic light-
emitting diode (OLED) display (LG Display’s 5″ plastic-based flexible OLED prototype panel)
[27]. b Example of an organic photovoltaic (OPV) device [28]
1.2.1 ITO
TCOs, which belong to a unique class of materials that exhibit both high trans-
parency and electrical conductivity, have been well studied for decades [29]. ITO
is a solid solution of indium(III) oxide (In2O3) and tin(IV) oxide (SnO2), and has
6 1 Introduction to Transparent Conductive Films
Fig. 1.3 Transparent conducting ITO thin films grown by a pulsed laser deposition method. a, b
AFM images of ITO films with thicknesses of 40 nm a and 200 nm b, respectively. c, d Effect of
film thickness on sheet resistance c and transparency d [40]
been the dominant material for producing TCFs owing to their excellent electrical
conductivity and optical transparency [1]. Several fabrication methods, including
magnetron sputtering [30], radio frequency sputtering [31], molecular beam epitaxy
[32], screen printing [33], pulsed laser deposition (PLD) [34], sol-gel techniques
[35], spray pyrolysis [36], and electron beam evaporation [37], have been devel-
oped to produce ITO films. Additional high-temperature annealing is usually need-
ed for the solution-based methods to achieve certain transmittance ( T) and resis-
tance standard. ITO nanowires [38] or ITO nanoparticles [39] have been deposited
via solution-based deposition techniques. Figure 1.3a–b shows the typical atomic
force microscopy (AFM) images of ITO films grown by the PLD method. The root-
mean-square roughness of the ITO films with thicknesses of 40 and 200 nm were
2.8 and 0.5 nm, respectively. The higher surface roughness for the thinner film was
attributed to the formation of islands. It is also noticed that the roughness increased
again when the films were thicker than 200 nm due to the crystallinity [40]. It is seen
from Fig. 1.3c that the sheet resistance initially decreased with an increase in film
thickness and remained almost constant for films up to 870 nm thick. Figure 1.3d
shows the variation of optical T and reflectance as a function of film thickness. The
optical T was above 80 % for films with thickness from 40 to 300 nm in the visible
range (~ 400–700 nm), while the reflectance was relatively low [40], which is why
ITO has been the dominant TCF material.
1.2 Transparent Conducting Oxides (TCOs) 7
1.2.2 ITO Substitutes
Due to the limited nature of world indium reserves, it is widely believed that a
severe shortage of indium may occur in the near future [41]. This means that a
long-term stable supply of ITO might be difficult to satisfy the expanding TCF
markets. Hence, developing other TCO alternatives to ITO becomes critically im-
portant. A number of low-cost alternatives have been proposed recently [1]. TCOs
that contain a reduced amount or no indium, such as Al- and Ga-doped ZnO (AZO
and GZO) and ZnO–In2O3–SnO2 (or Zn–In–Sn–O) multicomponent oxides, have
attracted much attention [41]. Table 1.2 shows typical TCO materials developed as
ITO substitutes. For example, ITO has been prepared on amorphous substrates at
a temperature below 200 °C by direct current (DC) magnetron sputtering deposi-
tion (MSD) for LCD applications. ITO TCFs possess low resistivity in the order
of 10−4 Ω cm and thicknesses of approximately 15–100 nm. Due to the toxicity
of cadmium and the required high temperature heat treatment, it is practically dif-
ficult to use cadmium oxide-based and titanium oxide-based TCO materials under
such circumstances [42]. For titanium oxide and titanium oxide-based TCO TCFs,
a high temperature procedure (> 300 °C) is required to reach a low resistivity [43].
Three different kinds of binary compounds (ZnO, In2O3, and SnO2) and multicom-
ponent oxides composed of any combination of these binary compounds may pos-
8 1 Introduction to Transparent Conductive Films
Fig. 1.4 Stability of resistivity of Al-doped ZnO (AZO) in a humid environment. a Resistivity as a
function of exposure time for AZO films prepared by pulsed laser deposition ( PLD). b Normalized
resistivity as a function of exposure time for AZO thin films prepared by (radio frequency ( rf) and
direct current ( dc)) magnetron sputtering deposition ( MSD) and PLD. (Reprinted with permission
from [45]. Copyright (2008) by Elsevier)
sibly be employed as TCFs in LCDs. The usage of indium could also be reduced
by synthesizing multicomponent oxides that contain less indium, e.g., ZnO–In2O3,
In2O3–SnO2, and Zn–In–Sn–O [44]. The required optoelectrical properties could be
achieved by magnetron sputtering (MS) and vacuum arc plasma deposition (VAPE)
under optimized deposition conditions [44]. Thus, these multicomponent oxides
with an appropriate composition are potential candidates for TCFs in LCDs [41].
The amount of indium used can be reduced to approximately half.
Indium-free oxides, such as ZnO, SnO2, and ZnO–SnO2 multicomponent oxides,
are another solution to avoid the use of indium [41]. However, due to the difficulty
of producing low resistivity TCFs at a low temperature and the patterning problems,
impurity-doped SnO2 and SnO2-based materials are unsuitable for use in LCDs. The
current indium-free candidate is impurity-doped ZnO, such as AZO and GZO [41].
In addition, AZO possesses superior electrical stability upon exposure to humid
environments [1, 45]. Figure 1.4a shows the electrical stability of the AZO films
prepared with different thicknesses and Al contents, revealing the importance of
these factors. The stability of resistivity was improved as the thickness increased
while the resistivity was dependent on the deposition method, which influenced
the crystallinity of deposited AZO films. It is also worth noting that the stability
was relatively independent of substrate deposition temperatures ranging from 68
to 200 °C. Figure 1.4b shows normalized resistivity (ρ/ρI, referenced to the initial
resistivity) as a function of exposure time for 200-nm-thick AZO films. It is found
that the AZO films were sufficiently stable for use in practical TCF applications,
irrespective of the deposition method [45].
However, there are still several critical weaknesses in these TCOs, namely (i) ev-
er-increasing material cost due to the limited availability of the elements needed, such
1.3 Transparent Conducting Polymers 9
as In, Zn, and Sn, on the earth, (ii) TCO being inherently unable to be etched, pat-
terned, or processed at high temperatures, (iii) TCOs being unable to satisfy property
requirements for emerging applications, such as flexible devices (e.g., flexible LCDs
and organic solar cells) due to its brittle nature, (iv) susceptibility to ion diffusion
into polymer layers, (v) low transparency in the near-infrared region, and (vi) current
leakage caused by structural defects [46–50]. In addition to light weight, high flex-
ibility, and low cost, the TCFs required for the next generation optoelectronic devices
should be compatible with the available large-scale manufacturing processes [51].
1.3.1 Polythiophene (PT)
Owing to the good electrical properties and environmental stabilities, PT has re-
ceived much attention from the scientific communities [57]. PTs are conjugated
polymers that can be used for a variety of applications, such as electrical conduc-
tors, nonlinear optical devices, polymer LEDs, and smart windows [72]. New types
of PTs with enhanced properties were developed for certain devices by devising
new design strategies. For example, the electronic properties of solution-process-
able conjugated PTs were modified using self-assembled silane molecules [73].
The electrical conductivities of ultrathin PT films increased by up to six orders of
magnitude by doping with hydrolized fluoroalkyl trichlorosilane (FTS). Because
the interband optical absorption of the polymers in the doped state was drastically
reduced, the doped PT films were highly transparent in the visible range (Fig. 1.6).
The PT films were very stable in vacuum and nonpolar environments because the
dopants within the porous polymer matrix were partially cross-linked via a silane
self-polymerization mechanism [73]. The interaction of the silanol groups with po-
10 1 Introduction to Transparent Conductive Films
Fig. 1.5 Molecular structures of PT, PPV, PANI, PPy, and PEDOT. PT polythiophene, PPV
poly(para-phenylene vinylene), PANI polyaniline, PPy polypyrrole, PEDOT poly(3,4-ethyl-
enedioxythiophene). (Reprinted with permission from [53, 57]. Copyright (2013, 1998) by
Elsevier)
A conducting polymer of the rigid-rod polymer family with high levels of crystal-
linity, PPV has been used in many TCF applications, such as LEDs and photovoltaic
devices, owing to its excellent stability, processability, and optoelectrical properties.
The polymer can be easily doped to form electrically conductive materials, and
thus its electronic and physical properties are easily modified by adding functional
groups [74]. PPV was firstly used as the emissive layer in polymer-based LEDs
in 1989 [75]. PPV synthesized using a solution-processable precursor polymer
(Fig. 1.7) had advantages of easy processing and reduced tendency for crystalliza-
tion [75]. Since then, a large number of PPV derivatives have been synthesized for
TCF applications [76–78].
Table 1.3 Electrical conductivities of PT, PPV, PPy, PANI, and PEDOT prepared by various processing conditions [53]
Conducting polymers Processing conditions Conductivity (S/cm) References
PT Solid-state macromolecular self-assembly 1000 McCullough et al. [58]
PPV Prepared electrochemically from p-xylene-bis(diethylsulphonium chloride) 0.001 Cirpan et al. [59]
in a solvent-electrolyte couple
PPy Deposition in a polymerizing solution of pyrrole using FeCl3 as the oxidiz- 0.1 Avlyanov et al. [60]
ing agent on PET substrates
PPy Deposition in a polymerizing solution of pyrrole using FeCl3 as the oxidiz- 200 Avlyanov et al. [60]
ing agent, with sodium anthraquinone-2-sulfonate and 5-sulfosalicylic acid
as the additives, on PET substrates
PANI Deposition in a 4 M H3PO4 polymerizing solution of aniline using NH4VO3 2–6 Avlyanov et al. [61]
as the oxidizing agent on glass substrates, followed by washing with 1 M
1.3 Transparent Conducting Polymers
HCl
PANI Casting of camphorsulfonic acid-doped PANI solutions mixed with 850 Lim et al. [62]
crystallinity-promoting additives on PET substrates
PEDOT Coating of a commercial aqueous PEDOT/PSS product on PET substrates 0.01–0.06 Hohnholz et al. [63]
PEDOT Coating of a commercial aqueous PEDOT/PSS product mixed with EG as 0.6–1.8 Hohnholz et al. [63]
the additive on PET substrates
PEDOT Casting of polymerizing solution of methanol-substituted 3,4-ethylene- 900 Ha et al. [64]
dioxythiophene using ferric tosylate as the oxidizing agent and various
alcohol solvents containing a weak base, imidazole, on glass substrates
PEDOT Vapor phase polymerization using ferric tosylate as the oxidizing agent 1000 Winther-Jensen et al. [65]
with the addition of a weak base, pyridine, in oxidant solutions on PET
substrates
PEDOT Coating of an aqueous PEDOT/PSS product on glass substrates, followed 1325 Xia et al. [66]
by treatment with hexafluoroacetone
PEDOT Coating of an aqueous PEDOT/PSS product on glass substrates, followed 1362 Alemu et al. [67]
by immersion in methanol
11
Table 1.3 (continued)
12
PT polythiophene, PPV poly(para-phenylene vinylene), PANI polyaniline, PPy polypyrrole, PEDOT poly(3,4-ethylenedioxythiophene)
Introduction to Transparent Conductive Films
1.3 Transparent Conducting Polymers 13
Fig. 1.7 Synthetic route for synthesis of PPV. (Reprinted with permission from [75]. Copyright
(1990) by Nature Publishing Group)
1.3.3 Polypyrrole (PPy)
PPy is a Nobel Prize-winning organic polymer (in Chemistry, 2000) formed by po-
lymerization of pyrrole [79]. PPy films darken in air due to oxidation, while doped
ones are blue or black depending on the degree of polymerization and film thick-
ness. As seen from Table 1.4, the electrical conductivity of PPy thin films increased
by three orders of magnitude when the dopant anion was varied from chloride to
anthraquinone-2-sulfonate [60]. This finding is attributed mainly to the dopant
anions containing fused aromatic rings, enabling the PPy films to have a higher
conductivity than those doped with smaller or bulky dopant anions. Hydrophobic
surface was found to be able to enhance the conductivity of PPy films when a chlo-
ride dopant anion was used [80]. The conductivity was also sensitive to the type of
solvents used for PPy. For example, the PPy thin films cast from PPy dissolved in
bulkier alcohol (e.g., oleyl alcohol) had a higher conductivity than that dissolved in
alcohol, such as methanol [81].
1.3.4 Polyaniline (PANI)
PANI is a conducting polymer of the semiflexible rod polymer family, which has
been extensively studied over the past 50 years, focusing mainly on improving its
electrical conductivity [82]. The dependence of color and electrical conductivity
on different oxidation states or doping levels makes PANI a suitable candidate for
sensors and electrochromic devices [83, 84]. Camphorsulfonic acid-doped PANI
1.3 Transparent Conducting Polymers 15
thin films casted from the PANI’s m-cresol solution showed a higher conductivity
than those casted from the PANI’s chloroform solution [85]. M-cresol facilitated
the extension of the dissolved PANI polymer chains, while chloroform caused the
dissolved PANI polymer chains to coil [86]. The extended conformation of PANI
also improved the mobility of the charge carriers [87], whereas the vapor-phase
secondary doping, such as m-cresol and o-chlorophenol, enhanced the conductiv-
ity of PANI [88]. PANI also has significant advantages over inorganic silicon- and
metal-oxide-based memory materials for the production of both volatile and non-
volatile memory devices [89]. Their dimensions as well as electrical properties can
be easily tailored by controlling the chemical synthesis procedure, producing novel
materials with electrical memory capabilities [90]. Moreover, due to its excellent
electrical conductivity and mechanical stability, PANI finds emerging technological
applications, including rechargeable batteries, solar cells, corrosion devices, and
OLEDs [89].
1.3.5 Poly(3,4-ethylenedioxythiophene) (PEDOT)
Table 1.4 Fabrication of SWNT TCs prepared using different approaches [101]
Dispersion method Solvents or surfactant Fabrication Doping agent T (%) Rs (Ω/sq) σ DC / σ Op Ref.
method
Using specific solvents DCE Dip or spray – 80 340 4.7 Song et al. [107]
coating
DCE Spin coating HNO3 80 85 18.8 Yim et al. [108]
SCA Transfer printing – 90.9 60 64.1 Hecht et al. [109]
1
Non-covalent functionalization SDS Transfer printing SOCl2 87 160 16.3 Zhang et al. [19]
SDS Spin coating HNO3 85 80 27.8 Geng et al. [103]
SDS Transfer printing HNO3+ SOCl2 80 115 13.9 Jackson et al. [110]
Oligothiophene-TN-PEG Spin coating HNO3+ SOCl2 71 59 17.1 Jo et al. [111]
Triton X-100 Transfer printing SOBr2 77.6 56 24.9 Wang et al. [106]
CBs Transfer printing HNO3 82 76 23.8 Liu et al. [112]
DCE dichloroethane, SCA superacid chlorosulfonic acid, SDS sodium dodecyl sulfate, TN-PEG terminated poly(ethylene glycol), CBs carbonaceous by
products
Introduction to Transparent Conductive Films
1.4 Transparent Conducting Metals 17
1.4.1 Metal Nanogrids
1.4.2 Metal Nanowires
As noted above, the fabrication of metal nanogrids is very costly [24]. Thus, ran-
domly distributed metal NWs made of especially copper and silver nanowires (Cu
and Ag NWs) [97, 98] have been investigated as another candidate for TCFs. Cu
NWs were synthesized in gram quantity in aqueous solution and they were assem-
bled into flexible films [101]. The scanning electron microscope (SEM) image in
Fig. 1.9a shows long wires of 90 ± 10 nm in diameter and 10 ± 3 μm in length. The
as-produced Cu NW films exhibited a very low sheet resistance ( Rs) of 15 Ω/sq
at a T of 65 %, along with good stability upon exposure to air for 1 month or after
bending for 1000 cycles. The films consisting of Ag NWs with higher aspect ratios
and uniform dimensions (Fig. 1.9b) [98] significantly improved the optoelectrical
properties, i.e., 20 Ω/sq at ~ 80 % specular T and 8 Ω/sq at 80 % diffusive T in the
visible spectral range. Analogous to metal nanogrids discussed above, their high
Fig. 1.8 Metal nanogrids as TCs. a Scanning electron microscope (SEM) image of Au nanogrids
synthesized via a nano-imprinting technique. b Average transmittance plotted as a function of
sheet resistance ( Rs) of Au nanogrids. (Reprinted with permission from [96]. Copyright (2007)
by Wiley)
18 1 Introduction to Transparent Conductive Films
Fig. 1.9 Randomly distributed metal nanowires and carbon nanotubes as TCs. a SEM image of
Cu NWs 90 ± 10 nm in diameter and 10 ± 3 μm in length (with inset showing Cu nanowires with
spherical copper particles attached at one end (scale bar = 200 nm)) [97]. b SEM image of Ag NW
films [98]; and c SEM and d AFM images of single-walled carbon nanotube (SWNT) thin film
deposited on glass [99]. (Reprinted with permission from [97–99]. Copyright (2010, 2009) by
Wiley and ACS)
manufacturing and material costs are the main challenges for metal NWs to replace
ITO-based TCFs [24].
CNTs have been regarded as the ultimate candidate for high-quality TCFs for more
than two decades due to their unique mechanical, electrical, optical, and electro-
chemical properties along with extremely high aspect ratios (~ 1000) [19, 99, 100].
Figure 1.9c and d present the SEM and AFM images of single-walled carbon nano-
tube (SWNT) films uniformly deposited on a glass surface. After treatment with
fuming sulfuric acid, the TCFs yielded Rs values of 100 and 300 Ω/sq at transparen-
cies of 70 and 90 %, respectively. One of the main challenges of producing CNT-
based TCs through a solution process is poor dispersion caused by the high aspect
ratio, large specific area, and strong van der Waals attraction [101]. Three major
strategies have been performed to disperse CNTs in liquid media, i.e., (i) using spe-
cific solvents, (ii) non-covalent functionalization by surfactants, and (iii) covalent
1.5 Transparent Conducting Carbon 19
1.5.2 Graphene
Fig. 1.10 Outstanding optoelectrical properties of graphene [119]. a Transmittance for differ-
ent TCs (graphene [121], single-walled carbon nanotubes (SWNTs) [103], indium tin oxide (ITO)
[122], ZnO/Ag/ZnO [123], and TiO2/Ag/TiO2 [124]). b Transmittance ( T) versus sheet resistance
( Rs) for different TCs. Blue rhombuses: roll-to-roll graphene TCFs based on chemical vapor depo-
sition (CVD)-grown graphene [121]; red line: ITO [122]; grey dots: metal nanowires [122]; green
triangles: SWNTs [103]. (Reprinted with permission from [119]. Copyright (2010) by Nature
Publishing Group)
where = Z 0 1/ ε=0 c 377 Ω is the free-space impedance, ε 0 is the free space elec-
tric constant, and c is the speed of light. For graphene sheet, σ 2D = nµ e , where
n is the number of charge carriers and μ is the mobility. For an ideal single layer
graphene, the transparency can reach up to 97.7 % with a sheet resistance of ~ 6 kΩ/
sq. The sheet resistance can be further reduced to ~ 400 Ω/sq without sacrificing
the transparency by a chemical doping treatment [120]. In additional, as compared
in Fig. 1.10a, graphene shows a higher transparency over a wider wavelength range
References 21
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graphene films have higher mechanical strength, flexibility, and chemical stability
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Chapter 2
Synthesis, Structure, and Properties
of Graphene and Graphene Oxide
2.1 Introduction
Table 2.1 Synthesis of graphene. (Reprinted with permission from [15]. Copyright (2014) by
Elsevier)
Method Figure/illustration Images Advantages Disadvantages References
No defects for
Epitaxial
every single Discontinuous Sutter et al. 17
growth
graphene island
Potentially suitable
Total organic
for mass Many defects Yang et al. 19
synthesis
production
total organic synthesis of polyaromatic hydrocarbons (PAH) [14] and the chemical
route to produce reduced graphene oxide (rGO) sheets. At present, the chemical
method has emerged to be a viable route to afford graphene-based single sheets in
considerable quantities [14].
Table 2.1 summarizes the relative advantages and disadvantages of the above
synthesis methods in term of the feasibility to scale-up the process for mass pro-
duction, materials and production costs, and the presence of defects. The detailed
fabrication processes of these methods are described in Sect. 2.2.
2.2 Synthesis Methods of Graphene and Graphene Oxide 31
2.2.1 Mechanical Cleavage
Fig. 2.1 Micromechanically exfoliated graphene: optical images of a thin graphite, and b few-
layer graphene and single-layer graphene ( lighter purple contrast) on a ~ 300 nm SiO2 layer.
Yellow color indicates thicker samples whereas bluish and lighter contrast indicates thinner
samples. (Reprinted with permission from [4]. Copyright (2010) by Elsevier)
32 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
surface, which may limit the carrier mobility [25]. This technique is neither scalable
nor capable of mass production, even though the samples of graphene thereby ob-
tained could be useful for fundamental studies to characterize their chemistries and
properties.
2.2.2 Epitaxial Growth
on the substrate. One of the major advantages of the epitaxial and CVD growth
techniques is their high compatibility with the current complementary metal–ox-
ide–semiconductor (CMOS) technology. A typical weakness is that controlling the
film thickness is difficult and secondary crystals are easily formed [51], although
some progress has been made to grow uniform graphene layers using the CVD
method [52]. Another important disadvantage is the need of expensive substrate
materials for graphene growth, considerably limiting its applications for large-scale
production. Nevertheless, the CVD approach has emerged as an important method
for mass production of graphene with less structural and electronic disorder or de-
fects, making it an excellent potential for TC applications.
34 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Graphene Grown on Ni
The formation of FLG on transition metal surfaces has been known for nearly a
half century [53, 54]. The typical process for CVD of graphene onto Ni film is
shown in Fig. 2.2a. In general, the polycrystalline Ni films deposited on SiO2/Si
are first annealed at 900–1000 °C under H2 and Ar flow to grow a smooth surface.
The Ni films are then exposed to a H2 and CH4 mixture so that the carbon atoms
can dissolve into the Ni film to form a solid solution. Finally, the substrate is cooled
down in an Ar atmosphere. As the solubility of carbon atoms decreases as the
temperature goes down, the carbon atoms diffuse out from the Ni–C solid solu-
tion during cooling and precipitate onto the Ni surface to form graphene films.
Fig. 2.2 Graphene grown on a Ni substrate. a Illustration of graphene growth in three different
stages [56]. b Schematic of full-wafer scale deposition of graphene layers on polycrystalline Ni
by chemical vapor deposition (CVD). c E-beam-evaporated Ni film of thickness 100 nm on a
10 cm diameter Si/SiO2 wafer. d Atomic force microscopy (AFM) image of a Ni film after CVD
of graphene layers [55]. (Reprinted with permission from [56, 58]. Copyright (2009, 2013) by
Springer and ACS)
2.2 Synthesis Methods of Graphene and Graphene Oxide 35
Figure 2.2b shows the wafer-scale graphene synthesis on evaporated Ni films [55].
About 10 cm diameter Si/SiO2 wafers were used as the substrate to deposit 100-nm-
thick Ni films (Fig. 2.2c). It is found that using diluted methane was key to the
growth of single-layer graphene (Fig. 2.2d), whereas concentrated methane led to
the growth of multilayer graphene.
Graphene Grown on Pd
Graphene islands can also be in situ grown on another metal surface, such as
Pd(111), using the CVD method [57]. Figure 2.3a, b shows the scanning tunneling
microscope (STM) images of graphene islands grown on a Pd(111) surface using
ethylene at 968 K. The size of the graphene islands largely varied between 200 and
2000 Å, which are common, especially near the Pd step edges or spanning across
the multiple terraces. The STM image in Fig. 2.3c presents the ordered honeycomb
structure in the graphene island formed by the precipitation of carbon atoms. A
periodicity of ~ 20 Å was observed from the surface height profile (Fig. 2.3d), which
was measured along the white line in Fig. 2.3c. Due to the superposition of the
Fig. 2.3 a–c Scanning tunneling microscope (STM) images of graphene on Pd(111) acquired in
situ during growth. d Surface height profile along the white line shown in c; and e atomic model
showing the orientation of graphene. (Reprinted with permission from [57]. Copyright (2009)
by ACS)
36 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
honeycomb lattice of graphene and the hexagonal lattice of Pd (111), these super-
structures are of Moiré patterns [57]. Figure 2.3e shows the atomic model of such
a commensurate Moiré superstructure and the determined epitaxial relationship
between the monolayer graphene and Pd(111).The method of growing graphene
islands on a Pd surface opened up a new avenue of preparing metal-semiconducting
graphene structures and metal-doped graphene-based devices.
Graphene Grown on Cu
Due to the grain boundaries of Ni or Pd surface, the grown graphene films usu-
ally contain both monolayer and few-layer graphene [58]. Because carbon has ex-
tremely low solubility in Cu, Cu has become a potentially outstanding substrate for
the growth of monolayer graphene [54]. Ruoff’s group at the University of Texas
at Austin first reported the growth of high-quality monolayer graphene on poly-
crystalline Cu foils, which attracted great attention due to the advantages of good
control of graphene layers, low cost, and ability to transfer [10]. The Cu foil was
annealed at 1000 °C in a hydrogen atmosphere. A mixture of H2/CH4 was then in-
troduced into the system to initiate graphene growth on the Cu foil. The system was
cooled down to room temperature after a continuous graphene layer was formed
[10]. The SEM image in Fig. 2.4a clearly shows Cu grains with color contrast. The
high-resolution SEM in Fig. 2.4b indicates that these Cu surface steps were formed
during thermal annealing. The darker flakes indicate multilayer graphene, while
the wrinkles originated from the different thermal expansion coefficients between
graphene and Cu. The wrinkles went across the Cu grain boundaries, confirming
that the graphene film was continuous. The inset of Fig. 2.4b shows TEM images
of single and bilayer graphene. The grown graphene films can be transferred to an-
other substrate using various transfer methods. Figure 2.4c, d shows the transferred
graphene film on a SiO2/Si or glass substrate. It is seen that the graphene film on
the glass substrate was optically uniform. The quality and uniformity were evalu-
ated by Raman spectroscopy and Fig. 2.4e–g shows the SEM and optical images
with the corresponding Raman spectra. The Raman spectra (Fig. 2.4g) indicated by
a red circle has a G-to-2D intensity ratio (IG/I2D) of ~ 0.5 and a symmetric 2D band
centered at ~ 2680 cm−1 with a full width at half maximum (FWHM) of ~ 33 cm−1,
confirming the monolayer graphene [10]. The blue circle and green arrow represent
bilayer- and trilayer-graphene sheets, respectively.
2.2.5 Chemical Methods
The most common source of graphite used for oxidation is flake graphite, which can
be produced by removing heteroatomic contaminations from naturally occurring
graphite [60]. Due to the spaces between graphene layers in graphite, the intercalat-
ing agents are able to reside between the graphene layers under chemical reactions,
forming graphite intercalation compound (GIC) [61]. The experiments to investi-
gate the insertion of additional chemical species between the basal planes have been
performed extensively since the successful formation of the first intercalation com-
pound using potassium [51]. GICs have layered compounds with different stages,
which are defined as the number of graphitic layers in between adjacent planes
of intercalant [51]. Figure 2.6a–d shows the structures of second- to fifth-stage
bromide GICs, which correspond to approximate compositions of C16Br2, C24Br2,
C32Br2, and C40Br2 [62].
The interlayer spacing of GIC can increase from 0.34 nm to more than 1 nm
depending on the intercalant, leading to a significant reduction in the van der Waals
forces between adjacent sheets [61]. The weak van der Waals forces make GICs
much easier to be further exfoliated, offering a possible route to fabricate single
layer graphene or graphene oxide (GO). The interlayer spacing in GICs can be ex-
panded by thermal shock (~ 1000 °C) to produce expanded graphite (EG). As shown
in Fig. 2.6e, the halogen intercalants, such as iodine chloride (ICl) (to form Stage-2
ionic GIC) and iodine bromide (IBr) (to form Stage-3 ionic GIC), can be introduced
into the host material of highly ordered pyrolytic graphite (HOPG) and sequentially
to form layered structures [63]. Upon high-temperature annealing, the volume of
the obtained Stage-2 and Stage-3 GICs (Fig. 2.6f, g) increases rapidly due to the
volatilization of the IBr or ICl intercalants between the graphene layers [63].
Graphite oxide was first prepared almost 150 years ago by Brodie, who treated
graphite repeatedly with potassium chlorate and nitric acid [64]. The oxidizing agent
2.2 Synthesis Methods of Graphene and Graphene Oxide 39
was changed to a mixture of sulfuric acid, nitric acid, and potassium chlorate [64]. A
less hazardous and more efficient method for graphite oxidation was later devised by
Hummers and Offeman [65], who employed a mixture of sodium nitrate, potassium
permanganate, and concentrated sulfuric acid. The latter two modified methods are
at present most widely employed [66]. Graphite oxide in water hydrolyzes to form
40 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.6 Interlayer ordering in graphite intercalation compounds (GICs) with different stages and
the expanded graphite (EG) [61–63]. a–d Second to fifth stage structure of bromine-intercalated
GICs. The dashed lines indicate bromine intercalate layers; the solid lines indicate carbon layers
[61, 62]. e 3D computer-generated molecular models of highly ordered pyrolytic graphite (HOPG)
( top), iodine bromide (IBr) Stage-3 GIC ( middle), and chloride (ICl) Stage-2 GIC ( bottom).
f Photographs of HOPG ( top), Stage-3 GIC ( middle), and Stage-3 EG ( bottom). g Photographs of
HOPG ( top), Stage-2 GIC ( middle), and Stage-2 EG ( bottom) [63]. (Reprinted with permission
from [61, 63]. Copyright (2002, 2011) by Springer and Nature Publishing Group)
negatively charged thin platelets that consist of single- to multilayer carbon. Mono-
layer graphite oxide is now widely acknowledged and recognized as GO [20, 67].
The term “sheets” usually indicate monolayer to several layers, while “platelets”
is often used to describe thicker multilayer GO or rGO [68]. Figure 2.7 shows the
2.2 Synthesis Methods of Graphene and Graphene Oxide 41
process involved in the exfoliation of graphite oxide into individual GO sheets. The
exfoliation is facilitated by rapid heating [69] or ultrasonic agitation [70, 71], while
excessive ultrasonication often results in breakage or fragmentation along with a
significant reduction in lateral dimensions of GO sheets [72, 73]. Individual GO
sheets can be viewed as graphene decorated with oxygenated functional groups on
the basal plane and around the edges [74]. Due to the ionization of carboxyl groups
present at the edges, GO can be electrostatically stable to form a colloidal suspen-
sion [70] in water, alcohols, and certain organic solvents [75] without surfactants.
To restore the inherent electrical conductivity of graphene, GO should be re-
duced either in solutions [20, 71, 77–79] or after films are formed on a substrate
(Fig. 2.8a). Many different reducing agents have been identified, including hydra-
zine [20, 80, 81], dimethylhydrazine [67], hydroquinone [82], hydrogen iodine (HI)
[83, 84], and NaBH4 [85, 86]. The reduced GO sheets become less hydrophilic and
instantly aggregate in the solution because of the removal of oxygenated groups
(Fig. 2.8b–d). However, charge-stabilized colloidal dispersions were obtained by
raising the pH value during reduction, even for deoxygenated sheets [87]. More
recently, the reduction step was further improved by preparing dispersions directly
in anhydrous hydrazine [80, 81, 88]. It should be noted, however, that anhydrous
hydrazine is highly toxic and potentially explosive, thus a great caution should be
exercised when using it.
The solution-based exfoliation method involves direct exfoliation of natural
graphite (NG) flakes in organic solvents, such as methanesulfonic acid (MSA)
[90], ionic liquids [91], benzylamine (BA), N-methyl-2-pyrrolidone (NMP),
and N,N-dimethylacetamide (DMA) with the addition of NaOH [92]. Disper-
sion and exfoliation of graphite are simultaneously achieved with the aid of
sonication and the sonication energy required for exfoliation is balanced by the
42 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.8 Reduction of graphene oxide (GO). a Oxidation of graphite to GO and reduction to
reduced graphene oxide (rGO) [14]. b–d Aberration-corrected TEM images of the following mate-
rials. Scale bar, denoting 2 nm, is valid for all images. b Single suspended sheet of graphene.
c Single suspended sheet of GO. d Suspended monolayer of rGO [89]. (Reprinted with permission
from [14, 89]. Copyright (2011, 2010) by Elsevier and Wiley)
2.3 Preparation of Large-Size GO
Fig. 2.10 SEM images of ultralarge graphene oxide (UL-GO) sheets. a Large graphene oxide
(GO) sheets obtained via a mild oxidation and sonication method [103]. b UL-GO sheets obtained
by avoiding sonication process [104]. (Reprinted with permission from [103, 104]. Copyright
(2010, 2009) by ACS)
2.3.3 Elimination of Sonication
Efficient and highly reproducible chemical methods have been developed which
involve intercalation, thermal exfoliation, and chemical oxidation to produce gram-
scale large-size GO sheets, up to ~ 50–200 µm in lateral size with a yield exceeding
50 % [107, 108]. The UL-GO stable suspension was obtained through oxidation and
washing processes without any sonication step. It is found that the GO size produced
through chemical method mainly depended on three factors: namely, (i) to control the
degree of oxidation; (ii) to completely eliminate damaging ultrasonication process;
46 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.11 Transparent graphene films produced via a simple solution casting of exfoliated plate-
lets from edge-selectively functionalized graphite ( EFG). a Schematic presentation of pristine
graphite, EFG in solid state and EFG in dispersed solution. b As-cast EFG film. c Heat-treated
EFG ( HEFG) film on a SiO2 surface. (Reprinted with permission from [106]. Copyright (2011)
by ACS)
and (iii) to use the inherently large NG flakes as the precursor material [109]. Be-
cause the use of large graphite flakes as the precursor material does not necessarily
guarantee large-size GO sheets, the pre-exfoliation process and the use of exfoliated
graphite are necessary to avoid the damaging ultrasonication process, and thus en-
sure minimum breakage of the GO sheets during fabrication. As shown in Fig. 2.12a,
the fabrication process includes three steps: (i) intercalation of acid molecules into
NG to obtain GICs, (ii) expansion of the interlayer space by thermal shock at a
high temperature (~ 1000 °C), and (iii) chemical oxidation by modified Hummers’
method. Graphite was sufficiently exfoliated before oxidation, thus individual GO
sheets were easily obtained by gentle shaking. Figure 2.12b, c shows that the sizes of
the as-prepared GO sheets varied from several to hundreds of micrometers.
To further understand the effects of ultrasonication, thermal shock expansion,
degree of oxidation, and precursor NG flake size on final GO size, well-planned
parallel experiments were performed [109]. As shown in Fig. 2.13, different
2.3 Preparation of Large-Size GO 47
Fig. 2.12 a Flow chart for the synthesis of ultralarge graphene oxide ( UL-GO) [110]. b–c SEM
images of as-prepared graphene oxide (GO) sheets deposited on a Si substrate at b low and c
high magnifications [107]. GIC graphite intercalation compound. (Reprinted with permission from
[107, 110]. Copyright (2011, 2012) by ACS and RSC)
Fig. 2.13 Effects of processing and material parameters on the size of final graphene oxide
(GO) sheets. The flowchart shows the preparation of GO sheets from nano-graphene ( NG) flakes
based on three different approaches. (Reprinted with permission from [109]. Copyright (2014) by
Elsevier)
High-Speed Centrifugation
Several different size groups 4 of GO sheets were obtained after sequential high-
speed centrifugation of GO polydispersion, and Fig. 2.14 shows the flow chart for
the sequential centrifugation at gradually slower speeds. Typically, the unsorted,
as-prepared GO dispersion was centrifugated initially at 8000 rpm for 40 min, di-
viding GO into supernatant and precipitate, and the supernatant was collected to
label as “small GO” (S-GO). The precipitate was re-dispersed for the second run
of centrifugation at 6000 rpm for 25 min, producing supernatant and precipitate.
The supernatant obtained in this run was designated as “large GO” (L-GO). The
precipitate was re-dispersed in water for the third run of centrifugation at 4000 rpm
for 25 min, producing “very large GO” (VL-GO) (supernatant) and “ultralarge GO”
(UL-GO) (precipitate). Figure 2.15 presents the area distributions of the different
2.3 Preparation of Large-Size GO 49
Fig. 2.14 Flow chart for high-speed centrifugation method. (Reprinted with permission from
[110]. Copyright (2012) by RSC)
groups obtained, namely, S-GO, L-GO, VL-GO, and UL-GO, which were measured
by counting more than 200 sheets for each group.
Fig. 2.15 Size distributions of a UL-GO, b VL-GO, c L-GO, and d S-GO; and e average areas of
graphene oxide (GO) sheets. UL-GO ultralarge graphene oxide, VL-GO very large graphene oxide,
L-GO large graphene oxide, S-GO small graphene oxide. (Reprinted with permission from [107,
110]. Copyright (2011, 2012) by ACS and RSC)
Fig. 2.16 Density gradient separation method: schematic a and picture b of separation of reduced
graphene oxide (rGO) sheets into different sizes via density gradient centrifugation [111]; and
c area sorting of polyethyleneglycol-functionalized graphene oxide (GO) after density gradient
separation [73]. (Reprinted with permission from [111, 73]. Copyright (2010, 2008) by ACS and
Springer)
groups with decreasing GO size [112]. Thus, the technique involves selective pre-
cipitation of GO sheets with sizes larger than 40 μm2 at a pH of 4.0 which contain
larger hydrophobic planes and fewer hydrophilic oxygenated groups. The zeta po-
tentials of GO dispersions decreased with increasing pH because of the ionization
of –COOH functional groups, see Fig. 2.17a. GO dispersions became stable when
their zeta potential values were lower than about − 30 mV. It is worth noting that
there was a “pH window” between 3.34 and 4.24, where the zeta potential of the
large GO was higher than − 30 mV, and that of the small GO was lower than this
value. By controlling the pH value of a GO dispersion, one can realize the fraction-
ation of GO sheets (Fig. 2.17b).
a
/DUJHVL]H*2
6PDOOVL]H*2
Fig. 2.17 pH-assisted selective sedimentation method. a Zeta potentials of large and small gra-
phene oxide (GO) aqueous dispersions as a function of pH value. b SEM images of unsorted GO
before fractionation, large and small GO monolayers after fractionation. (Reprinted with permis-
sion from [112]. Copyright (2011) by ACS)
edge can also be directly determined by TEM, which is capable of producing mov-
ies of the dynamics of carbon atoms at the edge of a hole in a suspended graphene
sheets (Figs. 2.19h, i) [118]. As the first truly 2D crystal, it is particularly important
to understand the mechanisms of the stability of graphene. By means of atomistic
Monte Carlo simulations based on a very accurate many-body interatomic potential
for carbon [119], it is found that that ripples spontaneously appear arising from
thermal fluctuations with a size distribution peaked at about 80 Å (Figs. 2.19j, k), a
reflection of the multiplicity of chemical bonding in carbon [120].
The structure of GO is largely different from that of pristine graphene because
of the attachment of oxygenated functional groups. The nonstoichiometric chemi-
cal composition of GO makes it a challenging task to determine the structure of GO
[64]. One of the most credible and well-known models of GO was proposed by Lerf
[74] and Klinowski [65, 122], who focused on a nonstoichiometric and amorphous
structure. As schematically shown in Fig. 2.20a, b, three major features includ-
ing graphitic regions (with an original honeycomb structure), disordered regions
2.4 Structures of Graphene and GO 53
Fig. 2.18 2D building material for other dimension carbon materials. (Reprinted with permission
from [121]. Copyright (2007) by Nature Publishing Group)
(with high oxidation), and defect regions (with holes) are presented on GO sheets.
The oxygenated functional groups attached on GO sheets have been studied using
different characterization techniques, such as high-resolution TEM, STM, XRD,
XPS, and Fourier transform infrared spectra analyzer (FT-IR) [64].
It is found that partial oxidation was thermodynamically favored over complete
oxidation according to both experimental observations and density functional cal-
culations [123]. The variations in the degree of oxidation caused by the difference
in graphite source or oxidation procedure may cause considerable modifications in
the structure and properties of GO. In addition, the precise nature and distribution
of these oxygenated groups were determined by the level of coverage and GO size
[65, 124]. A low O/C ratio is normally associated with a large GO area, suggesting
that a smaller GO contains relatively more oxygenated groups given the GO surface
area [124]. It is also found that the epoxide to alcohol ratio increased with more
oxidation [123]. Characterizing the degree of oxidation is necessary to understand
the structure–property relationships because the optical and electrical properties of
GO are controlled mainly by π-electrons from the sp2 carbon atoms [125].
To reveal further structural information, the surface of GO was examined [90, 91]
under an STM. Although the hexagonal lattice of the sheets was partially preserved,
the GO sheets were distinguishable from pristine graphene by the appearance of
54 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.19 Structure of graphene. a–c Schematics of crystal structure a, Brillouin zone b and dis-
persion spectrum (c) of graphene [116]. d–g Raman imaging results from edges with angles d 30°,
e 60° ( zigzag), f 90°, and d 60° ( armchair) [117]. h, i Aberration-corrected TEM image of h an
armchair, and i zigzag configurations of carbon atoms at the edge of a hole in graphene [118]. j, k
A representative configuration of graphene j and the bond length distribution k [120]
2.5 Properties of Graphene and GO 55
Fig. 2.20 Structure of GO sheets. a Structural model [128]. b 3D view [124] of graphene oxide
(GO) showing hydroxyl and epoxy groups on the basal plane and carboxylic acid groups mainly at
the edges. c STM image of a GO monolayer on a highly oriented pyrolytic graphite (HOPG) sub-
strate, taken under ambient conditions (oxidized regions are marked by the line contours) [129].
d AFM image of a GO monolayer deposited on a SiO2 substrate, showing a backfolded edge [129].
e AFM section profiles along the three different lines in d, showing a mono-, bi-, and trilayer struc-
ture [129]. STM scanning tunneling microscope, AFM atomic force microscopy. (Reprinted with
permission from [124, 128, 129]. Copyright (2012, 2009, 2007) by ACS)
bright regions that correspond to the destruction of ordered lattice features due to
the presence of oxygenated functional groups (Fig. 2.20c). Because of the oxygen-
ated functional groups, the thickness of a monolayer GO sheet is much thicker than
~ 0.34 nm of an ideal monolayer of graphene. The thickness of a monolayer GO
sheet is shown ~ 1 nm, while that of double layer GO is ~ 2 nm (Fig. 2.19d, e).
However, the thickness of GO sheets may largely vary depending on the degree of
oxidation [20, 126, 127].
2.5.1 Electrical/Electronic Properties
Table 2.4 Comparison of electrical properties of pristine graphene, GO, and rGO
Type of graphene or Carrier mobility (cm2 Sheet resistance (Ω/ References
GO v−1 s−1) sq)
Graphene 2000–200,000 30–1000 [8, 45, 121, 132, 133,
143 ],
GO Insulator >1012 [141]
rGO 1–200 103–107 [104, 128, 141,
144–146]
paradox, and weak antilocation [130, 131]. The carrier mobility of graphene can
reach up to 200,000 cm2 v−1 s−1 when graphene is suspended on a clean surface,
which can be extremely useful for ultrafast electronics and optoelectronics [132]. In
reality, however, its mobility is largely limited to 2000–15,000 cm2 v−1 s−1 because
of the presence of microscopic ripples, scattering, and defects [8, 121, 133]. Since
graphene is a zero gap semimetal, many efforts have been directed towards opening
a band gap using several methods, such as narrowing 2D graphene to 1D nanorib-
bon, forming nanomesh and hydrogen patterning [134–137]. An on/off ratio of over
104 was observed in very narrow GNRs [138]. Due to the high charge mobility, the
quantum Hall effect was observed even at room temperature [139].
In sharp contrast, however, the electrical properties of GO sheets are significant-
ly different from those of the pristine graphene. The long-range conjugated network
of the graphitic lattice is the main reason for the excellent conductivity of pristine
graphene sheets, while the functional groups and defects on GO sheets break the
conjugated structure and localized π-electrons [140]. As compared in Table 2.4, ow-
ing to the much reduced carrier mobility, GO film is insulating with Rs values typi-
cally higher than about 1012 Ω/sq [141]. The reduction of GO is the key to restore
the excellent electrical conductivities of graphene. Chemical and thermal reduction
methods are known as the two main strategies to reduce GO [142]. The relation
between sheet resistance ( Rs) (unit: Ω/sq) and bulk conductivity (σ) (unit: S/m) can
be described by the following equation:
1
Rs = (2.1)
σt
Chemical Reduction
Chemical reduction is based on the chemical reactions with GO and the requirement
for equipments is not critical, making the method easy and cheap to reduce GO for
mass production [142]. Chemical reduction involves the exposure of GO sheets to
reducing agents. The commonly used reducing agents are summarized in Table 2.5.
Being a common antioxidant, hydrazine is known to be an effective reducing agent
because it scavenges oxygen while it is chemically broken down to nitrogen and
2.5 Properties of Graphene and GO 57
water. Although hydrazine has been one of the most widely used agents in industry,
it is highly toxic and dangerous, especially the anhydrous hydrazine, thus extreme
care has to be taken in using it.
Figure 2.21a shows the fabrication process of rGO by hydrazine. The direct
dispersion of hydrophobic graphite or graphene sheets in water without the assis-
tance of dispersing agents has generally been considered to be an insurmountable
challenge. To avoid the serious aggregation of GO after reduction, soluble poly-
mer surfactants [71] or ammonia [87, 126, 144] have been employed to retain the
colloidal state in water. Li et al. [87] discovered that it is easy to produce stable
aqueous rGO dispersions by adding ammonia to the reaction solution to increase the
pH value (Fig. 2.21b). This method is a facile approach to large-scale production
of aqueous rGO dispersions without the need of polymeric or surfactant stabilizers,
making it possible to process graphene materials using low-cost solution processing
techniques [87]. The derivatives of hydrazine, such as dimethylhydrazine [67] and
phenylhydrazine [147], were also shown effective reducing agents for GO. Metal
hydride, such as NaBH4, was shown comparable with hydrazine as a reducing agent
[148, 149]. It is also found that an additional dehydration process using concentrat-
ed sulfuric acid at 180 °C after reduction by NaBH4 further improved the reduction
efficiency of GO [148].
However, these chemicals are not suitable for the reduction of GO films, espe-
cially for those needing high flexibility for applications in flexible devices, because
of the stiffening effect and disintegration of the films during reduction. Figure 2.22a
shows optical photographs of the reduction process by immersing GO films into
58 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.21 Chemical reduction by hydrazine. a Scheme showing the chemical route to the synthesis
of aqueous graphene dispersions. 1 Oxidation of graphite ( black blocks) to graphite oxide ( lighter
colored blocks) with greater interlayer distance. 2 Exfoliation of graphite oxide in water by soni-
cation to obtain graphene oxide (GO) colloids stabilized by electrostatic repulsion. 3 Controlled
conversion of GO colloids to conducting graphene colloids through deoxygenation by hydrazine
reduction. b Effect of ammonia on dispersion state of CCG sheets, characterized by measuring
average particle sizes over a long period of time. The photographs shown in the inset were taken
2 days after the reduction reaction was complete with ( left) and without ( right) ammonia [87]
different reducing agents (like NaBH4, N2H4, and HI) for different durations [83]. It
is observed that the bubbles appeared when GO films were immersed into NaBH4
and N2H4 solution, indicating that they reacted with GO to produce gases. The GO
films were broken down to small graphene debris after 16 h reaction. However,
immersion of GO films in HI acid solution hardly generated bubbles around them.
The films in the HI acid solution maintained their integrity very well even after a
long reaction time. Due to the advantage of HI reduction, Moon et al. [84] produced
HI-reduced GO films on a PET substrate (Fig. 2.22b).
2.5 Properties of Graphene and GO 59
Fig. 2.22 a Optical photographs of reduction process by immersing a graphene oxide (GO) film
into different reducing agents for different durations at room temperature [83]. b Flexible GO
film ( left) and HI-reduced GO thin films on a polyethylene terephthalate (PET) substrate [84].
(Reprinted with permission from [83, 84]. Copyright (2010) by Elsevier and Nature Publishing
Group)
Thanks to the extremely fast and efficient reduction abilities, the use of metal
and acid mixture for reduction of GO has gained much attention recently [151, 154].
The reduction is achieved by fast electron transfer between the metal and GO, and
the evolution of nascent hydrogen as the active reducing agent [159]. For example,
a mixture of aluminum powder (10 mm) and hydrochloric acid produced rGO with
a C/O ratio of 18.6 and an electrical conductivity of 2100 S/m [151]. The following
study shows that iron powder (10 mm) in the presence of hydrochloric acid (Fe/
HCl) [152], zinc powder in hydrochloric acid (Zn/HCl) [153], solid zinc filings and
sulfuric acid (Zn/H2SO4) [154], tin(II) chloride in hydrochloric acid (Sn(II)/HCl)
[155], aluminum foil and hydrochloric acid (Al foil/HCl) [156], and magnesium in
hydrochloric acid (Mg/HCl) [157] were all effective reducing agents of GO, which
60 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
offered one of the shortest reaction times to obtain rGO. Metal–alkaline, such as
aluminum or zinc metals in alkaline environments, was also shown to reduce GO
[156, 158]. For example, zinc powder in the presence of ammonia solution success-
fully reduced GO in 10 min at room temperature [158]. Similarly, the reduction of
GO was also achieved with aluminum foil and zinc powder in sodium hydroxide
(Al foil/NaOH, Zn/NaOH) solution [156].
Apart from chemical reduction using various reducing agents, several other
strategies, including photocatalyst reduction, electrochemical reduction, and sol-
vothermal reduction, have been explored recently [142]. Photocatalyst reduction is
based on the photochemical reactions with the assistance of a photocatalyst such as
TiO2 [160, 161]. It is proposed that charge separation occurs on the surface of TiO2
particles upon UV-irradiation. Because the holes are scavenged to produce ethoxy
radicals, the electrons accumulate within the TiO2 particles and interact with GO
sheets to reduce functional groups [162]. Electrochemical reduction is usually car-
ried out in a normal electrochemical cell using an aqueous buffer solution at room
temperature without special chemical agents [163, 164]. The reduction of GO is
achieved mainly by the electron exchange between GO and electrodes, thus the use
of toxic reducing agents like hydrazine and producing byproducts can be avoided.
Solvothermal reduction is normally performed in a sealed container so that the tem-
perature is maintained above solvent’s boiling point [165, 166]. Particularly in the
hydrothermal process, the overheated supercritical water plays the role of reducing
agent and the physiochemical properties can be controlled by pressure and tempera-
ture, offering a green chemistry alternative to organic solvents [165].
Thermal Reduction
Significant research has also been conducted for thermal reduction of GO into a
more pure form of graphene to restore the sp2 carbon structure and thus increase
the electrical conductivity [167]. It is found that the carriers traveling across rGO
thin films are scattered or trapped by sp3 carbon sites, defects, sheet junctions, and
other structural imperfections and impurities [64]. The large variation of electrical
conductivities can be explained by percolation transport. Mattevi et al. [167] inves-
tigated the role of residual oxygen and sp2 carbon fraction on electrical conductivi-
ties of thermally reduced GO. Figure 2.23a shows the evolution of carbon bonds in
GO thin films as a function of annealing temperature in ultrahigh vacuum (UHV).
It is suggested that GO undergoes structural changes due to the loss of oxygen and
the carbon atoms in the basal plane may also rearrange.
Figure 2.23b shows the plot of conductivities of rGO films as a function of sp2-
carbon fraction as well as the data for 100 % sp2-bonded materials like graphene
and polycrystalline graphite for comparison. A high conductivity 1.25 × 103 S cm−1
of polycrystalline graphite at a sp2 fraction of ~ 0.87 in reduced GO was estimated
by extrapolating the experimental data [64]. Even a minimum conductivity
~ 6 × 103 S cm−1 was also suggested for a monolayer graphene [168], if the sp2 frac-
tion were to increase above 0.9. The inset of Fig. 2.23b shows the structural model
2.5 Properties of Graphene and GO 61
for the essential features of transport through an rGO sheet at different stages of re-
duction. Since the sp2 clusters are isolated by oxygen atoms (indicated by dots), the
GO film is insulating prior to reduction. As reduction restores sp2 carbon in GO, the
transport barrier between the clusters narrows, allowing small fraction of carriers to
hop or tunnel among sp2 sites. Upon further reduction of GO, better connectivity is
formed among the original sp2 domains by forming new, smaller sp2 clusters along
with concurrent formation of structural defects. Percolation among the sp2 clusters
dominates the transport at higher sp2 fractions. Percolation is found to occur at sp2
fraction of 0.6 from the fit and it is in reasonable agreement with the theoretical
threshold values for conduction among 2D disks [169].
Based on the above discussion, it is obvious that the heating temperature
significantly affects the reduction of GO [126, 170, 171]. Table 2.6 presents thermal
reduction of GO carried out under different processing conditions, such as anneal-
ing temperature and atmosphere. It is shown that the C/O ratio was no more than
9 if the temperature was less than 500 °C, while the C/O ratio could be higher than
62 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
repair the defects in rGO sheets, Lopez et al. [178] exposed rGO to a carbon source,
such as ethylene, at an elevated temperature of 800 °C. The results showed that the
vacancies were partially “repaired” and the conductivity of the individual rGO sheet
reached up to 350 S/m. Su et al. [179] discovered that rGO sheets functionalized
by aromatic molecules produced a highly graphitic material with a conductivity as
high as 1314 S/cm after thermal annealing at 1000 °C, which is attributed to a simi-
lar defect-healing effect. Although reduction of GO at high annealing temperatures
is effective, there are also obvious drawbacks, such as large energy consumption,
critical treatment conditions, and inability to apply for substrates with a low melting
point, e.g., glass and polymer [142].
2.5.2 Thermal Properties
increasing the degree of reduction, reaching about 42 W/mK when the O/C ratio
was 0.05, see Table 2.7. The inverse relationship between the thermal conductivity
and the O/C ratio is attributed to the increase in phonon scattering with increasing
oxygenation [201]. It is also worth noting that GO showed an increasing thermal
conductivity in response to an external tensile stress, an entirely opposite trend to
those shown by other nanostructured materials, including pristine graphene.
The thermal conductivities of multilayer graphene and GO sheets were measured
using the thermal flash technique [159]. It was shown that the multilayer graphene
comprising 30–45 layers had a thermal conductivity similar to bulk graphite,
whereas that of 3-layer GO was higher than that of bulk graphite. The enhance-
ment in thermal conductivity of multilayer GO than graphite is attributed to the
intercalating oxygen atoms that introduced covalent bridges between the interlay-
ers for interaction [200]. Due to the intrinsic properties of the individual graphene
sheets and the highly aligned structure of GO papers (GOPs) and graphene papers
(GPs), these flexible materials also show unique thermal properties [204]. Thermal
conductivities of GOPs and GOPs modified by divalent ions, Mg2+ and Ca2+, were
measured using a laser flash method. Their thermal conductivities were 3.91, 32.05,
and 61.38 W/mK, respectively [205] (see Table 2.7), indicating that the modifica-
tion of GOP with these metal ions gave rise to significant enhancements in thermal
2.5 Properties of Graphene and GO 65
Table 2.7 Thermal conductivities of graphene, GO, rGO, graphene, and GO papers in comparison
with CNTs at room temperature
Material Method Thermal conductivity References
(W/mK)
Single-layer graphene Confocal micro- 4840–5300 Balandin et al. [186]
Raman spectroscopy
Suspended graphene Confocal micro- 4100–4800 Ghosh et al. [188]
Raman spectroscopy
Suspended graphene Thermal measurement 3000–5000 Seol et al. [189]
method
Graphene on SiO2 Thermal measurement 600 Seol et al. [189]
method
Few-layer graphene Raman optothermal ~ 1300–2800 Ghosh et al. [190]
(2–4 layer)
Suspended graphene Raman optothermal ~ 2500 Cai et al. [46]
Suspended graphene Raman optothermal 1500–5000 Jauregui et al. [191]
Suspended graphene Raman optothermal 600 Faugeras et al. [192]
Suspended graphene Raman optothermal 1100 Murali et al. [193]
Graphene Theory: valence force 2000–5000 Nika et al. [194]
field, Boltzmann
transport equation
Graphene Theory: relaxation- 1000–5000 Nika et al. [195]
time approximation
Graphene Theory: molecular 8000–10,000 Evans et al. [196]
dynamics, Tersoff
Graphene Theory: Boltzmann 1400–2400 Lindsay et al. [197]
transport equation
Graphene Theory: ballistic ~ 4000 Munoz et al. [198]
rGO Electrical four-point 0.14–2.87 Schwamb et al. [199]
measurement
rGO Thermal flash 2180–2275 Mahanta et al. [200]
technique
GO Thermal flash 18–776 Mahanta et al. [200]
technique
Graphene Molecular dynamics 2188 Shen et al. [201]
simulation
rGO Molecular dynamics 42a Shen et al. [201]
simulation
GO Molecular dynamics 8.9b Shen et al. [201]
simulation
Graphene paper Laser flash method 313 Wu et al. [202]
Graphene paper Light flash system 178 Xiang et al. [203]
Graphene paper Self-heating method 1434 Xin et al. [204]
GO paper Laser flash method 3.91 Yu et al. [205]
Mg2+ modified GO Laser flash method 32.05 Yu et al. [205]
paper
Ca2+ modified GO Laser flash method 61.38 Yu et al. [205]
paper
66 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
2.5.3 Optical Properties
For normal incidence light, the optical transmittance ( T) and reflectance ( R) are
given as follows:
1
T= (1+ πα)− 2 , (2.3)
2
1 2 2
R= π α T, (2.4)
4
where
=α 2 π e2 / hc ≈ 1/ 137. (2.5)
e is the electron charge, c the light speed, and h is the Planck’s constant. Combining
Eqs. (2.3) and (2.5) yields the opacity of graphene:
Fig. 2.25 Optical properties of graphene. a Optical image of a 50 µm aperture partially covered
by monolayer and bilayer graphene sheets [216]. b Transmittance spectrum of single-layer gra-
phene ( open circles). (Inset) Transmittance of white light as a function of number of graphene
layers [216]. c UV–vis spectra of roll-to-roll layer-by-layer transferred graphene films on quartz
substrates [45]. d Optical image of graphene with one, two, three, and four layers [217]
temperature. A thicker film normally has a lower transparency because of the higher
degree of absorption of light (Fig. 2.26e). The adsorption of small particles on the
quartz substrate surface may also be partly responsible for the darkening of rGO
films after the thermal treatment.
2.5.4 Mechanical Properties
a b c
ϵŶŵ;ŶŽŶͲƌĞĚƵĐĞĚͿ
e
ϲŶŵ
dƌ ϴ Ŷŵ
ĂŶ
Ɛ
ŵŝ Ϯϳ Ŷŵ
Ʃ
ϰϭ Ŷŵ
ĂŶ
ĐĞ
;й
Ϳ
tĂǀĞůĞŶŐƚŚ;ŶŵͿ
Fig. 2.26 Characterization of optical properties of GO solution and GO films: digital images of
a GO and b rGO dispersions [171]; c UV−Vis spectra of GO and rGO dispersions [218]; d pho-
tograph of rGO films with different thicknesses ( black scale bar is 1 cm) obtained after thermal
treatment at 1100°C [141]; and e optical transmittance spectra of the films in d with their thick-
nesses indicated [141]. GO graphene oxide, rGO reduced graphene oxide. (Reprinted with permis-
sion from [141, 171, 218]. Copyright (2008, 2010, 2011) by ACS, Elsevier and Wiley)
70 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
a b
ŝŐnjĂŐ
e сϭ͘ϬϴdWĂ
ƌŵĐŚĂŝƌ
f
сϭ͘ϬϮdWĂ
g h
Fig. 2.27 Mechanical properties of graphene sheets, graphene oxide (GO), and GO papers. a SEM
image of a graphene sheet spanning an array of circular holes (scale bar = 3 mm). b Schematic of
nanoindentation on suspended graphene [220]. c Graphene molecular model with chiral angles
between 0 and 30° [222]. d Young’s modulus of graphene with different chiral angles [222].
2.5 Properties of Graphene and GO 71
many parameters that affect the Young’s modulus of graphene, such as the chirality
[222], the presence of defects and wrinkles [223], and functionalization [226, 231].
Figure 2.27c shows the molecular model for graphene with chiral angles vary-
ing from 0 (zigzag) to 30º (armchair), showing that the Young’s modulus varied in
a narrow range from 1.086 TPa for the zigzag configuration to 1.050 TPa for the
armchair configuration (Figs. 2.27d). This observation agreed with the previous
proposal in that the elastic properties of graphene with a hexagonal structure should
be relatively independent of the loading direction and thus the Young’s modulus
should not be greatly affected by the chirality [222].
Mechanical properties of one to three layers of GO sheets were investigated
by AFM [234]. The measured Young’s modulus of a monolayer GO sheet was
207.6 GPa, which is much lower than the pristine graphene, due to the oxygenated
functional groups which adversely alter the “perfect” 2D structure of monolayer
graphene [220, 234]. To better understand the effects of defects and functionaliza-
tion on mechanical properties of graphene sheets, molecular dynamics (MDs) and
molecular mechanics (MMs) simulations were performed to evaluate the Young’s
modulus, shear modulus, and wrinkling properties of pristine graphene and GO
sheets [223, 229, 235]. The simulation results show that the Young’s modulus was
dependent on the presence of Stone–Wales defects, degree of functionalization, and
the molecular structure of functional groups (Fig. 2.27e). The presence of Stone–
Wales defects caused the graphene sheet to wrinkle which affected only the initial
part of the stress–strain curves due to straightening of wrinkles, but a small number
of defects had only a negligible influence on Young’s modulus of graphene. The
shear modulus and critical wrinkling strain was also reduced once oxygen-contain-
ing functional groups were introduced (Fig. 2.27f). It is found that the change in
the molecular structure of graphene sheet was associated with the binding energy
between the functional groups and GO. The altered structure of graphene sheets
caused their instability. Hydrogen [236] or methyl [237] groups showed similar
reduction in mechanical properties of graphene sheets.
GO paper, which are a “paper-like” material made by flow directed or self-assem-
bled GO sheets, is another useful GO-based material [238]. GO papers have many
potential applications, such as protective layers, chemical filters, supercapacitors,
adhesive layers, electronic or optoelectronic components, and molecular storage
[180, 238–241]. The mechanical properties of GO papers have also been extensive-
ly studied, for example, tightly packed GO papers fabricated by vacuum filtration
showed an average elastic modulus of ~32 GPa [238]. Compare with those prepared
by vacuum filtration, the GO papers obtained at a liquid/air interface by evaporating
the hydrosol of GO showed a similar tensile strength but a slightly lower modulus
[241]. Chemical cross-linking by using divalent ions [239] or polyallylamine [240]
e Stress–strain curve of graphene sheets containing a row of Stone–Wales defects along with
morphological changes with increasing strain [223]. f Shear stress–strain curves for pristine gra-
phene and GO sheets functionalized with carboxyl and hydroxyl groups [222]. g Tearing tough-
ness of GO papers with different size groups [224]. h Cross-sectional SEM images and schematic
of self-assembly process of GO sheets with different sizes (S-GO in the left panel and UL-GO in
the right panel) [124]. SEM scanning electron microscope, S-GO small graphene oxide, UL-GO
ultralarge graphene oxide. (Reprinted with permission from [124, 220, 222, 223, 224]. Copyright
(2012, 2008, 2010, 2014) by ACS,Science Publishing Group and Elsevier)
72 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Table 2.8 Young’s modulus of pristine graphene from representative experimental and theoretical
investigations. (Reprinted with permission from [221]. Copyright (2013) by RSC)
Method E (TPa)a
Nanoindentation measurements [220] 1.02
Phonon dispersion measurements [225] 1.01
Ab initio computations [226] 1.05
Density functional theory [227] 1.05
First principles calculations [228] 1.01
MD and MM simulation [229] 1.05–1.09
Empirical force constant calculations [230] 1.13
Atomistic Monte Carlo simulations [231] 1.04
Continuum elasticity theory and tight-binding atomistic simulations [232] 0.92
Energetic model [233] 0.90
a
Because the Young’s modulus for a 2D sample is just force/length, elastic properties of graphene
in some references are reported in N/m, which are converted to TPa by taking effective thickness
as 0.34 nm. MD molecular dynamics, MM molecular mechanics
a b
ĚŐĞͲƚŽͲĞĚŐĞŝŶƚĞƌĂĐƟŽŶ
&ĂĐĞͲƚŽͲĨĂĐĞŝŶƚĞƌĂĐƟŽŶ
'KƐŚĞĞƚƐ
c d ĚŐĞͲƚŽͲĞĚŐĞŝŶƚĞƌĂĐƟŽŶ
&ĂĐĞͲƚŽͲĨĂĐĞŝŶƚĞƌĂĐƟŽŶ 'KƐŚĞĞƚƐ
e f
Fig. 2.28 3D model snapshots of graphene oxide ( GO) sheets a without water and c with inter-
calated water molecules; and 2D schematics of GO paper models with functional groups bonded
between adjacent GO sheets through hydrogen bonds b directly and d mediated by water mol-
ecules. e extrapolation of modulus values; and f plots of two different components of deformation
as a function of GO length. (Reprinted with permission from [124]. Copyright (2012) by ACS)
Various techniques, such as AFM, SEM, high-resolution TEM, STM, Raman spec-
troscopy, XRD analysis, FTRI spectroscopy, and UV-vis spectroscopy, have been
successfully used for the characterization of graphene and its derivatives. Two or
more techniques are usually combined together to map the complete picture of their
morphologies, structures, and properties. Some of these techniques are discussed in
the following sections.
AFM was the first technique used to establish that optically identified graphene
(Fig. 2.29a) was indeed one-atom thick monolayer (Fig. 2.29b). A typically 0.4-nm-
thick monolayer graphene was observed on crystalline graphite using an intermittent
74 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.29 AFM images of graphene, GO, and rGO. a Single layer graphene was first observed
by Geim et al. [8]. A few layer flake is shown, with optical contrast enhanced by an interfer-
ence effect at a carefully chosen thickness of oxide [8]. b AFM image of single-layer graphene.
Notice the folded part of the film near the bottom, exhibiting a differential height of ~ 0.4 nm [8].
c–f Height c and e and corresponding phase d and f tapping mode AFM images of unreduced
c and d and chemically reduced e and f GO nanosheets deposited from aqueous dispersions onto
2.6 Common Tools for Characterization of Graphene and Its Derivatives 75
contact AFM mode [8]. The measured thicknesses of GO and rGO were 1.0 and
0.6 nm, respectively (Fig. 2.29c–f) [244]. Besides imaging and thickness detection,
AFM was also used for the study of mechanical, frictional, electrical, magnetic,
and even elastic properties of graphene sheets and flakes [220]. Although the AFM
technique can successfully determine the surface morphology on a nanometer scale,
it is cumbersome for imaging large area graphene [14]. In addition, the samples
freshly cleaved HOPG. The images were recorded in the attractive regime of tip sample inter-
action. Superimposed onto each image is a line profile taken along the marked red line [244].
AFM atomic force microscopy, GO graphene oxide, rGO reduced graphene oxide, HOPG highly
ordered pyrolytic graphite
76 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.31 a, b High-resolution transmission electron microscopy (TEM) images of solution cast
a monolayer and b bilayer graphene (scale bar 500 nm). c Electron diffraction pattern of the sheet
in a, with the peaks labeled by Miller–Bravais indices. d, e Electron diffraction patterns taken from
the positions of the black d and white spots e, respectively, of the sheet shown in b, using the same
labels as in c. The graphene is clearly one layer thick in d and two layers thick in e. f–h Diffracted
2.6 Common Tools for Characterization of Graphene and Its Derivatives 77
used for AFM characterization need to be deposited on a very flat substrate, such as
Si wafer, freshly cleaved mica, and quartz [245].
SEM is routinely used to image nanomaterials and has become a standard, easy-
to-use instrument capable of clearly describe the morphologies of graphene or
GO layers [245]. A variety of imaging modes, including backscattered electrons
(BSE), secondary electrons (SE), auger electrons, X-ray, and cathodoluminescence,
are produced when an electron beam impinges on a sample. These signals can be
selectively collected and combined to generate images. The BSE signal is sensitive
to atomic composition of the specimen, while the SE signal can generate high-
resolution images but is sensitive to surface charging. It is found that SEM images
with good contrast was difficult to obtain for graphene or GO, while a relatively low
accelerating voltage delivered the best result on a 300 nm thick SiO2/Si substrate
(Fig. 2.30) [107]. The main drawbacks of SEM imaging are that it works only
for samples deposited on electrically conducting substrates and the graphene/GO
samples are easily damaged by acceleration voltages [245].
intensity taken along the 1–210 to − 2110 axis for the patterns shown in c–e, respectively [93]. i
Aberration-corrected, high-resolution TEM image of graphene sheet [249]. j High-resolution TEM
image of a GO sheet with corresponding selected area electron diffraction pattern (SAED) in the
inset [126]. (Reprinted with permission from [93, 126, 249]. Copyright (2008, 2011, 2008) by
Nature Publishing Group, Elsevier and ACS)
78 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
STM was developed in 1981 by Gerd Binnig and Heinrich Rohrer at the Interna-
tional Business Machines Corporation (IBM) [250]. The inventors earned the Nobel
Prize in Physics in 1986 [251]. Since STM is able to image surfaces with resolu-
tion up to 0.1 nm in lateral and 0.01 nm in depth, individual atoms within materials
are routinely imaged and manipulated [252]. Recently, STM is also used to image
or manipulate single-layer graphene sheets [253–256]. As shown in Fig. 2.32, in
situ atomic-resolution STM is able to reveal the atomic structure of the graphene
nanoribbon. The graphene nanoribbon is ~ 15 -nm wide and its axis has a crystal-
lographic orientation close to the zigzag direction (Fig. 2.32a). The STM image also
reveals an atomically flat and defect-free structure in the central region (Fig. 2.32b)
and position-dependent superstructures near the edges (Fig. 2.32c). Except for
imaging graphene, STM is also able to manipulate free-standing graphene sheets
[256]. As illustrated in Fig. 2.32d, the Z-V spectroscopy mode STM can control the
deformation of free-standing graphene’s nanoripples. The nanoripples were con-
trolled by the means of attractive electrostatic force, repulsive interatomic force,
and restoring force of graphene itself.
2.6.5 Raman Spectroscopy
The Major features of the Raman spectra for graphite and graphene are the G band
at ~ 1584 cm−1 and the G’band at ~ 2700 cm−1 [257]. The positions and relative peak
heights of the G and G’bands indicate the number of graphene layers. As shown
in Fig. 2.33a–c, the location of the G peak for a single layer graphene is 3–5 cm−1
higher than that of bulk graphite, while the G’peak shows a significant change in
both shape and intensity as the number of layers decreases. For bulk graphite, the G’
band is comprised of two components. The low and high shift are roughly 1/4 and
1/2 of the G peak intensities, respectively. For a single-layer graphene, the G’band
shows a single sharp peak and the intensity is roughly four times the G peak.
The Raman spectroscopy is also an important tool to investigate the surface
chemistries of GO and rGO [76]. Because of the presence of isolated double bonds
that resonate at frequencies higher than that of the G-band of graphite, the G-band
peak of UL-GO was upshifted from 1581 to 1607 cm−1, see Fig. 2.33d, f [258,
259]. The corresponding G-band after the thermal reduction (rUL-GO) occurred at
1590 cm−1, a reflection of the recovery of the hexagonal network of carbon atoms
containing defects. Due to the possibility of charge transfer reaction between the
(host) carbon in graphene and the (guest) chloride [260], the G-band of chemically
reduced C-rUL-GO at 1587 cm−1 was marginally downshifted. The high electro-
negativity of chloride species encouraged carbon–chloride interactions that in turn
triggered charge transfer reactions and created holes in graphene. The G band is
Raman active for sp2-hybridized carbon-based material, while the D band is acti-
vated only if the defects participate in the double resonance Raman scattering near
K point of Brillouin zone [261]. Hence, the intensity ratio of ID/IG is often used for
estimating the sp2 domain size of graphite-based materials. The ID/IG ratio of rUL-
GO was notably lower than UL-GO (Figs. 2.33e), indicating that the thermal reduc-
tion process removed the functional groups and recovered the graphitic structure.
However, the ID/IG ratio increased after the chemical treatments that again altered
the graphene structure.
Besides the G and D bands, there are two other Raman bands, called 2D and
D + G at 2600–3000 cm−1 (Fig. 2.33f), which are often ignored due to their weak
intensities compared to the D and G bands. The 2D band is Raman active for
crystalline graphitic materials and is sensitive to the band in the graphitic elec-
tronic structure, while the combination mode of D + G band is induced by disorder
[261]. These two bands were employed to distinguish the electronic conjugation of
UL-GO obtained at different stages of reduction and treatments. The intensity ratio
I2D/ID + G shown in Fig. 2.33g was more sensitive to the change in electronic con-
jugation from UL-GO to rUL-GO than the ID/IG ratio (Figs. 2.33e), as a reflection
of the recovery of graphitic electronic conjugation. The reduction of the I2D/ID + G
ratio corresponding to the modification from rUL-GO to C-rUL-GO indicates that
the newly doped functional groups, such as –Cl, –SOCl, and –COOH, introduced
disorder again [76].
80 2 Synthesis, Structure, and Properties of Graphene and Graphene Oxide
Fig. 2.33 Raman spectra of graphite, graphene, GO, and rGO. a Comparison of Raman spectra at
514 nm for bulk graphite and graphene. Evolution of the spectra b at 514 nm and c 633 nm with
the number of layers [257]. d, f Raman spectra for NG, UL-GO, reduced rUL-GO, and chemically
doped, reduced C-rUL-GO. e, g The corresponding D/G and 2D/(D + G) intensity ratios [76]. GO
graphene oxide, rGO reduced graphene oxide, NG nano-graphene, UL-GO ultralarge graphene,
rUL-GO reduced ultralarge graphene oxide, C-rUL-GO carbon reduced ultralarge graphene oxide.
(Reprinted with permission from [76, 257]. Copyright (2011, 2006) by ACS and APS)
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Chapter 3
Fabrication of Graphene-Based Transparent
Conducting Thin Films
3.1 Introduction
Chemical vapor deposition (CVD)-grown graphene and graphene oxide (GO) have
been the main starting materials to produce graphene-based transparent conductors
(TCs) [1, 2]. For the CVD-grown graphene, the underlying substrates need to be
removed so that the graphene sheets can be transferred onto the device substrates.
Several strategies have been developed to transfer graphene sheets and they include
the etching and stamping method [3, 4], thermal release method [5], photoresist
method [6], roll-to-roll transfer method [7], and general method [8]. Another low-
cost route to produce graphene-based TCs on a large scale is to synthesize GO
thin films and then reduce them. The ease of solution process of GO sheets due to
their high solubility in aqueous solutions has made it a more viable and favorable
approach [2]. Once a GO dispersion is produced, GO films can be formed on a
substrate using different deposition techniques, including electrophoretic deposi-
tion (EPD), spin coating, spray coating, dip coating, transfer printing, Langmuir–
Blodgett (L–B) assembly, rod coating, and inkjet coating [1].
3.2.1 Etching Method
After graphene is grown on a metal substrate as described in Sect. 2.2, graphene needs
to be transferred to the device substrate via a post-transfer process, which usually in-
volves two main steps: (i) etching of the metal substrate and (ii) transfer of graphene
onto the target substrate. The removal of growth substrate, such as Cu and Ni, is usu-
ally performed by immersing the substrate with the graphene film into the etching
bath until a free-standing graphene membrane floating on the solution can be readily
observed [9–11]. The typical etching recipes include FeCl3 [3], HCl [12], HNO3 [13],
Fe(NO3)3 [10], and (NH4)2SO8 [7]. It should be noted that reactions during etching of
© Springer Science+Business Media New York 2015 95
Q. Zheng, J.-K. Kim, Graphene for Transparent Conductors,
DOI 10.1007/978-1-4939-2769-2_3
96 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.1 Etching method to transfer CVD-grown graphene. a Flow chart of the synthesis, etch-
ing, and transfer processes for the large-scale and patterned graphene films. b A centimeter-scale
graphene film grown on a Ni(300 nm)/SiO2(300 nm)/Si substrate. c A floating graphene film after
etching the nickel layers in 1 M FeCl3 aqueous solution [3] RT Room temperature, HF Hydroflu-
oric acid, BOE Buffered oxide etchant. (Reprinted with permission from [3]. Copyright (2009) by
Nature Publishing Group)
Cu with nitric acid lead to the formation of H2 bubbles which cause cracking in the
graphene film. It is also found that HCl or HNO3 releases corrosive vapor and the
etching rate of copper is very slow. Since FeCl3 is able to etch the copper or nickel
without forming gaseous products or precipitates, it has been widely used recently [3].
Figure 3.1a shows the typical etching transfer process by using FeCl3 (or acids). After
graphene was grown on nickel substrate, an aqueous FeCl3 solution was used as an
oxidizing etchant to remove the nickel layers. It is found that FeCl3 etches the nickel
layers effectively within a mild pH range without forming gaseous products or pre-
cipitates. The graphene film can be separated from the substrate within a few minutes.
3.2 CVD-Grown Graphene-Based TCs 97
Figure 3.1b and c show the graphene film grown on nickel substrate before and after
FeCl3 etching, respectively. It is seen that the graphene film floating on the surface of
the solution is then ready to be transferred to any kind of substrates [3].
3.2.2 Stamping Method
Fig. 3.2 Etching and stamping method to transfer CVD-grown graphene. a Transferring and pat-
terning of graphene films grown on a metal/SiO2/Si wafer [9]. b Graphene transfer by polyethyl-
ene terephthalate (PET)/silicone [12]. (Reprinted with permission from [9, 12]. Copyright (2010,
2013) by ACS and Elsevier)
98 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
stamping method. The polymer supports such as soft PDMS stamps and thermal-re-
lease tapes are first attached to the graphene films grown on metal substrates. After
soaking in water with gentle ultrasonication for several minutes, the polymer sup-
port/graphene/metal layers are detached from SiO2 by water intervening between
metal and SiO2. The metal layers were then removed by soaking in FeCl3 solution.
The resulting graphene film on the polymer support is ready to be transferred onto
arbitrary substrates, such as poly(ethylene terephthalate) (PET) film or rubber sub-
strate [9]. A two-layer structure consisting of PET and silicone was also developed
to transfer graphene grown by chemical vapor deposition onto various rigid and
flexible substrates through dispersive adhesion [12]. As shown in Fig. 3.2b, three
essential steps, which include adhesion of the PET/silicone to the graphene/Cu,
etching of the Cu layer, and transferring of released graphene film, are involved in
the PET/silicone transfer process. The advantage of the two-layer structure is that
it only takes a few seconds to transfer graphene from PET/silicone to the target
substrates [12].
Kang et al. [4] modified the transfer technique by inking the stamp process,
enabling the transfer of single-layer graphene onto a Si/SiO2 substrate in a pattern
defined by the geometry of the PDMS stamp. As shown in Fig. 3.3a, large-scale gra-
phene was grown on Cu foil which was then laminated onto a microscale-patterned
PDMS stamp. The Cu foil was removed by etching with (NH4)2 S2O8 (ammonium
persulfate) solution, and the PDMS stamp was thoroughly rinsed with distilled (DI)
water. The raised features in the stamp were “inked” with graphene that has the
same pattern as the PDMS stamp, which was then transferred to the target substrate
by pressing and gently removing the PDMS mold. Figure 3.3b shows the microscale
features of graphene on a SiO2 substrate, presenting graphene patterns over a large
area of 20 × 1000 µm, confirming the technique’s capability to transfer large-area
patterns. The transfer mechanism is that the adhesion between the graphene and the
target substrate is higher than that of the PDMS/graphene interface [4, 15]. Gra-
phene films with a variety of shapes were transferred onto different substrates using
the same technique, such as poly(4-vinylphenol) (PVP; Fig. 3.3c, d).
To realize the transferring of graphene onto arbitrary substrates, a general meth-
od was developed to perform reliable transfer [8]. This general method relies on
a sacrificial “self-releasing” polymer layer placed between a conventional PDMS
elastomer stamp and the graphene film. As shown in Fig. 3.4a, the general method
employs a polymer thin film—“self-release layer” (SRL)—which is inserted be-
tween the elastomer stamp and the graphene sheet. The work of adhesion between
the SRL and the stamp has to be smaller than that between the graphene and the
destination substrate, making dry transfer of the release polymer/graphene bilayer
thermodynamically favorable. The SRL protects graphene from the contamination
by the low-molecular weight siloxane oligomers present in the PDMS stamp. After
patterning by oxygen plasma, a 0.2–1.0-mm thick SRL is spun-cast over the gra-
phene and brought into conformal contact with the PDMS stamp, then the excess
graphene is removed by oxygen plasma. The Cu substrate is subsequently etched
3.2 CVD-Grown Graphene-Based TCs 99
Fig. 3.3 Inking elastomeric stamp method. a Schematics of the fabrication procedure for trans-
ferred micro-patterned graphene electrode-based organic field effect transistor using rubrene sin-
gle-crystal semi-conductor. b An optical microscope image of patterned graphene electrodes on
a SiO2 layer fabricated by stamping method and a magnified view of patterned graphene in inset.
c An optical microscope image of graphene patterned electrode fabricated on PET/graphene/PVP
layer and the transparent PET/graphene/PVP/patterned graphene structure in inset. d A scanning
electron microscope (SEM) image of the hexagonal arrays of graphene electrodes micro-patterned
onto a SiO2 substrate. (Reprinted with permission from [4]. Copyright (2011) by Wiley)
off to transfer the polymer/graphene bilayer to the stamp. Through the graphene
face, the stamp is brought into contact with the destination substrate. After baking
for several minutes to enhance the conformal contact and adhesion, the stamp is
lifted off, leaving the release polymer/graphene bilayer on the destination substrate.
The SRL is then dissolved to obtain the graphene film transferred on the substrate.
Figure 3.4b–e shows the images of transferred graphene films onto SiO2/Si and
organic polymer substrates. The graphene films transferred using the SRL is largely
intact at the optical length (Fig. 3.4b), while the film transferred without the SRL
is highly fragmented (Fig. 3.4c). The atomic force microscopy (AFM) image in
Fig. 3.4d shows that the integrity of the graphene monolayer is preserved and no
cracks or contaminant residues are found. More importantly, the patterned graphene
films can be placed to align to features, allowing the integration of graphene into
more complex device structures. For example, millimeter-sized graphene pads were
transferred onto a polymer film while aligned with the underlying gold source–
drain electrode array (Fig. 3.4e).
100 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.4 A general stamping method for transferring graphene. a Schematic of the SRL method-
ology in combination with a pick-and-place elastomer stamp. b, c Optical images of a centime-
ter-sized graphene film successfully transferred to a 300-nm thick SiO2/Si substrate b and failed
transfer when the SRL is not present c. d AFM images of graphene film on SiO2/Si at low and high
( inset) magnifications (inset z-scale is 3 nm). e Digital camera image of pre-patterned graphene
films transferred to an organic semiconductor device structure. CVD chemical vapor deposition.
(Reprinted with permission from [8]. Copyright (2013) by Nature Publishing Group)
3.2 CVD-Grown Graphene-Based TCs 101
Since there is strong adhesion between gold and carbon materials [16, 17], a ther-
mal release method was developed recently using gold and thermal releasing tapes
[5]. Figure 3.5a–c shows the schematic flowchart of the transfer-printed graphene
patterns through gold-stamp-assisted exfoliation, including three steps. Firstly, mi-
crometer-scale line features with different sizes were patterned on the surface of a
highly ordered pyrolytic graphite (HOPG) disk using a photolithographic technique
followed by an oxygen plasma-etching process. Secondly, a gold film was depos-
ited onto the patterned HOPG disk surface, where a thermal releasing tape was
used to peel off the gold film together with the graphene patterns. Finally, the gold
film with graphene patterns was pressed onto the target substrate. The thermal tape
was released and removed from the gold film after heating, and the gold film was
etched away using an etchant solution [5]. Figure 3.5d,e shows the atomic force
microscopy (AFM) images of graphene patterns on a silicon substrate, displaying
different graphene thicknesses over the printed line patterns, ranging from 0.8 to
2.5 nm (Fig. 3.5f). The histogram of the average thickness shown in Fig. 3.5g sug-
gests that most of the graphene patterns had thicknesses about 1–3 nm. Although
the thermal release method is complex and costly, its major advantage is that it can
create graphene patterns for electronic applications [5].
3.2.4 Photoresist Method
Figure 3.6a; presents the procedure employed to fabricate graphene device arrays
based on the photoresist method. Graphene is grown on a Cu- or Ni-coated Si wafer
substrate, which is used to fabricate a large-scale device array with a simple photo-
lithography process [6]. The device consists of two large pads connected by a thin
strip. The photoresist covering the devices acts as a protective layer and oxygen
plasma etch is used to remove unwanted photoresist residue and graphene. After
the exposure to a continually refreshed etchant solution to remove Cu/Ni in the
unprotected areas and beneath the connecting photoresist/graphene strips, two large
pads of graphene/Cu laminate connected by a narrow channel of graphene can be
obtained. Figure 3.6b, c shows the optical image of the fabricated device, indicating
that there exhibits a clear undercut around the edges of Cu/Ni as well as the intact
graphene channel. Figure 3.6d provides the differential interface contrast image of
a long graphene channel, confirming that the surface of the device channel is very
clean without any visible residue underneath. The inset shows that the graphene
channel has a uniform Raman signature over a large area, further confirming the
high quality of the device channel.
102 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.6 Fabrication of graphene device array. a Schematic of device fabrication procedure (see
main text for details). b Bright field optical image of a typical sample substrate after fabrication.
c Close-up bright field image of the same sample. Graphene connecting the copper pad is just
visible ( boxed). Inset: Image of the device channel. d Differential interference contrast image of
a longer device. Upper inset: Raman spectra across the length of the graphene strip are highly
uniform. Lower inset: Bright field image of the sample. PR Photoresist, RIE Reactive ion etching.
(Reprinted with permission from [6]. Copyright (2009) by ACS)
The flexibility of both the grown graphene and the underlying substrate allows roll-
to-roll transfer of larger-scale graphene thin films where thermal release tapes are
used as the supporting film [7, 18]. Figure 3.7a presents three essential steps consti-
tuting the roll-to-roll transfer process, including the adhesion of polymer supports
to the graphene film/Cu substrate laminate, etching of the Cu substrate, and release
of the graphene layers [7, 19]. Figure 3.7b presents the corresponding photographs
of the process. The graphene film is attached to a thermal release tape by applying
a soft pressure between two rollers followed by etching the copper foil with an
etchant. After rinsing with DI water to remove residual etchant, the graphene film is
ready to be transferred to any kind of flat or curved substrate surface. By inserting
the graphene film/thermal release tape laminate between the rollers together with a
target substrate, successful transfer from the tape to the target substrate is achieved
with exposure to mild heat. Multilayer graphene films can be prepared by repeat-
ing these steps on the same substrate to achieve enhanced optoelectrical properties.
Figure 3.7c shows the 30-in. multilayer graphene film transferred to a roll of PET
substrate. Graphene-based touch screens can be assembled after the assembly with
electrodes and spacers (Fig. 3.7d, e). Figure 3.7f shows the optical transmittance of
the graphene films with different numbers of stacked layers, implying that the trans-
104 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.7 Roll-to-roll transfer of graphene films. a Schematic of the roll-based production of gra-
phene films grown on a Cu foil. b Roll-to-roll transfer of graphene films from a thermal release
tape to a PET film at 120 °C. c A transparent large-area graphene film on a 35 in. PET sheet. d An
assembled graphene/PET touch panel showing outstanding flexibility. e A graphene-based touch
screen panel connected to a computer with control software. f UV–vis spectra of graphene films on
quartz substrates. The inset shows the UV spectra of graphene films with and without HNO3 dop-
ing. The corresponding optical images are shown in the right inset. g Sheet resistances of graphene
films transferred to a ploy (methylmethacrylate) (PMMA) substrate [7]
3.3 Fabrication of GO-Based TCs 105
Compared with Ni and Pd, Cu is the most promising CVD catalytic substrate to
grow continuous layers of high quality graphene over large areas. This is due to the
very low carbon solubility in Cu and its catalytic activity toward hydrocarbon gas-
ses. CVD-grown graphene has less wrinkles and grain boundaries than chemically
derived graphene and therefore excellent optoelectrical properties can be achieved.
In spite of the significant progress made so far, there are still some important chal-
lenges. First, it is very important to grow large and controllable grain size graphene,
such as single-grain graphene with wafer scale size [20]. This will definitely require
a better understanding and optimization of the growth process. Second, CVD-grown
graphene with controllable number of layers is critically important for technological
implementation, especially for large area electronics [18]. For example, bilayer and
trilayer graphene may offer functions and properties different from monolayer gra-
phene. Due to the smaller interlayer distance and possible AB stacking, bilayer and
trilayer graphene will likely have superior electrical properties. Third, reducing the
manufacturing cost is a very important component for future industrial applications.
The cost may be reduced by low-temperature graphene growth or direct growth on
arbitrary substrates without any post-transfer process. Last but not the least, an easy,
reliable, and scalable transfer method is an urgent challenging issue. The aforemen-
tioned transfer methods all seem complex, expensive, and time consuming. CVD-
grown graphene then has the potential to replace ITO as the ubiquitous TCs if the
above challenges are overcome.
Electrophoretic
deposition
3
Spin coating
Spray coating
Fabrication of Graphene-Based Transparent Conducting Thin Films
Table 3.1 (continued)
Method Schematic figure Advantages Disadvantages References
3.3
Simple and cheap process Randomly stacked GO Lee et al. [27], Dong
sheets et al. [28]
Dip coating
L–B assembly
107
Table 3.1 (continued)
108
Rod coating
3
Inkjet printing
3.3.1 Electrophoretic Deposition
The EPD technique includes a broad range of industrial processes where charged
particles in suspension move toward an electrode of opposite charge by an electric
field and deposit to form a compact film [39]. EPD is a versatile technique that can
be applied to solid powder particles with diameters ranging from micro- to nanome-
ters, and requires a suitable medium for the formation of a stable suspension. It has
many advantages, including facile process, short processing time, cost effective-
ness, and potential scaling up [40]. Due to the relatively high density, good chemi-
cal stability, and low conductivity, organic solvents such as alcohols and ketones are
commonly used. However, organic solvents are usually toxic and flammable, thus
an aqueous medium that is cheaper and environmental friendly is often used for the
deposition of sensitive materials [41].
The EDP technique was applied to fabricate a variety of GO-based thin films
[23, 42, 43]. When a direct current (DC) voltage is applied, GO sheets dispersed in
a suspension migrate toward the positive electrode and form a solid thin film. The
deposition rate is influenced by several processing parameters, such as the con-
centration of GO suspension, the applied DC voltage, and the conductivity of the
substrate. By modifying the deposition time, the film thickness can be controlled.
As shown in Fig. 3.8a, b, the color of the GO films changed from light to dark
brown with increasing thickness, especially after the reduction of GO using KOH
and hydrazine. It is also found that wrinkling occurred along the boundaries be-
tween the individual GO sheets after reduction (Fig. 3.8c, d).
The fabrication of TCs using large-area GO sheets via EPD was specifically
investigated [23, 44]. Reduced graphene oxide (rGO) was obtained using the in-
trinsic EPD process without the addition of chemical agents or high-temperature
treatments [18]. It is shown that the prepared GO films can be electrochemically
reduced by an explicit constant potential reduction step. During the EPD process,
the oxygen-containing functional groups of GO were substantially removed. The
final films showed improved electrical conductivities and low adhesion to the sub-
strate for easy detachment. The conductivity of the rGO film was 1.43 × 104 S m−1,
which is much higher than the GO paper obtained by the filtration method, which
was 0.53 × 10−3 S m−1 [45]. Ishikawa et al. [44] deposited GO sheets obtained from
exfoliation of graphite oxide on a SiO2/Si substrate by an EPD process. The optimal
conditions with an EPD voltage of 10 V for 5 min resulted in a few layers of reduced
graphene with no wrinkles and reduction was confirmed by the XPS analysis. Its
sheet resistance was 4.59 × 104 Ω/sq at a transmittance of 83.8 %.
Although the technique enjoys a number of advantages in the preparation of thin
films, such as high deposition rate, good thickness controllability, and simplicity of
scaling up, its applicability is limited to only electrically conductive substrates, such
as ITO-coated glass, Cu, Ni, Al, stainless steel, and p-type Si. For the same reason,
it cannot be applied to flexible insulating plastic substrates. In addition, the stack-
ing quality of GO sheets is rather difficult to control, making this method unable to
produce uniform deposition over a large surface area [1].
3.3.2 Spin Coating
One of the most convenient and popular methods developed to deposit uniform
thin films on a flat substrate is spin coating. It involves the dropping of an excess
amount of solution on a substrate and rotating at a high speed to spread the fluid
over the entire substrate surface by a centrifugal force. The desired thickness of the
film can be controlled by rotating speed and the concentration of the GO solution.
GO films were deposited on quartz substrate and the deposition behaviors were
studied after different reduction processes [20]. Due to the fast dynamics of deposi-
tion by spin coating and the flexible nature of GO sheets, a significant degree of
disorder was noted from the measurement of film thickness. It is found that rGO
films reduced by hot hydrazine solution resulted in fragmentation and delamina-
tion of the films. Thermal annealing of GO films under nitrogen flow, argon flow,
and vacuum at temperatures ranging from 400–1100 °C were also investigated. The
results indicate that a thermal graphitization procedure was most effective for re-
duction, producing films with sheet resistances as low as 100–1000 Ω/sq with 80 %
transmittance. Wu et al. [46] produced GO film via spin coating and used them as
transparent conductive anodes for an organic photovoltaic (OPV) cell. After reduc-
tion by a combination of hydrazine and high temperature annealing (400–1100 °C),
3.3 Fabrication of GO-Based TCs 111
Fig. 3.9 Spin coating of graphene oxide (GO) film. a Schematic of modified spin-coating tech-
nique. b AFM height image of a GO film. (Reprinted with permission from [47]. Copyright (2008)
by ACS)
the optical transmittance of the best films was higher than 80 %, while the sheet
resistance varied from 5 kΩ/sq to 1 MΩ/sq. A modified spin coating technique [43]
was also devised as shown in Fig. 3.9a. It is found that accelerated solution evapora-
tion by blowing dry nitrogen while spin-casting resulted in continuous films with
GO sheets lying fairly flat on the surface (Fig. 3.9b).
3.3.3 Spray Coating
Spray coating is a type of painting technique where a spraying device based on forced
air is used to apply the coating material through air onto the substrate surface. The
method is fast, scalable, and facile to operate, and ideally suited to producing elec-
trodes for liquid-crystal displays (LCDs) [26, 48], as well as conductive graphene
coatings on various substrates [49]. Once the graphene colloids are dried after the
deposition, they are not re-dispersible in water, resulting in a water resistant coating.
Due to the high aspect ratio of the graphene sheet, spray coating technique can
produce a continuous conducting network, which is thin and transparent. An rGO
coating was produced on a glass slide, achieving a sheet resistance of 2.0 × 107 Ω/
sq with a transmittance higher than 96 % [45]. GO–hydrazine dispersions were also
spray deposited to produce large rGO films [21]. The GO–hydrazine dispersion was
prepared by mixing GO dispersion with an excess amount of hydrazine monohy-
drate, as shown in Fig. 3.10. Therefore, rGO dispersion was sprayed onto preheated
substrates to form rGO films with a sheet resistance of 2.2 × 103 Ω/sq and a transmit-
tance of 84 %. Although the technique holds advantages of simple and fast process
and low cost, it is very difficult to avoid partial aggregation and crumpling or wrin-
kling of GO/rGO sheets generated during the coating process [1].
112 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.10 Schematic of rGO film fabrication by spray deposition. (Reprinted with permission
from [26]. Copyright (2010) by Elsevier)
3.3.4 Dip Coating
Dip coating involves three steps, that is, immersion of a substrate into a tank con-
taining a coating material, removal of the substrate from the tank, and draining of
the coating material.
3.3 Fabrication of GO-Based TCs 113
Fig. 3.11 Schematic illustration of layer-by-layer (LbL) assembly of an rGO film consisting
of alternate layers of negatively charged rGO–COO− and positively charged rGO–NH3+. EDC
N-ethyl-N′-(3-dimethyl aminopropyl)carbodiimide methiodide. (Reprinted with permission from
[27]. Copyright (2011) by RSC)
The coated substrate is then dried using forced air or by baking. By changing
the durations of these three steps, the thickness of the film can be easily controlled.
Graphene films of 10 nm thickness were obtained with a high transparency and
conductivity after coating with GO, followed by thermal reduction [50]. Pretreated
hydrophilic quartz substrates were immersed into a hot, aqueous GO dispersion to
coat GO films. Scrolled or folded GO sheets were observed arising from the film
fabrication, which is detrimental to transparency. Su et al. [51] reported the fabrica-
tion of rGO films by dip-coating the cleaned quartz substrates with large-size GO
sheets in a standard Piranha process, which were annealed at an elevated tempera-
ture in 20 % H2/Ar. The obtained rGO films showed a sheet resistance of 188 kΩ/sq
with 98 % transparency. A novel layer-by-layer (LbL) sequential assembly of posi-
tively and negatively charged rGO sheets was developed based on the dip-coating
method to avoid folding of graphene sheets during deposition [27]. As illustrated in
Fig. 3.11, this approach employed the concept of electrostatic attraction between the
two oppositely charged suspensions of rGO sheets, which allowed the preparation
of multilayer rGO films with a tunable thickness, resistance, and transmittance by
controlling the number of bilayers.
114 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
3.3.6 Langmuir–Blodgett Method
Fig. 3.12 Transfer-printing process of reduced graphene oxide (rGO ) films. a Transfer-printing
process of rGO and the finished rGO films with different thicknesses [53]. b Schematic diagrams
( left) and the corresponding optical microscope images ( right) depicting the PDMS-based soft
transfer-printing process of rGO [52]. (Reprinted with permission from [52]. Copyright (2009)
by Wiley)
on the surface of a given subphase (usually water) are compressed by moving the
two opposing barriers toward each other to increase the surface pressure and thus
the density of GO sheets. The surface pressure is a measure of the GO density on the
water surface, which in turn controls the quality of L–B assemblies. Prior to deposi-
tion, a platinum plate is used to monitor the surface pressure during the compres-
sion and isothermal curves are recorded to identify the target pressure (Fig. 3.13b)
[54]. The prepared substrate is immersed into the water and pulled out at a desired
speed once the desired surface pressure is reached, realizing uniform deposition of
a layer of GO sheets. The L–B assembly method offers several unique advantages
over the other coating techniques: (i) the layered architecture of the films could be
accurately controlled by simply varying the L–B assembly parameters, including
surface pressure and pulling speed of the substrate, (ii) the LbL deposition process
is amenable to assembling any combination of molecular carbon layers on a sub-
strate, thus capable of tailoring the properties and structures of the films, (iii) the
assembly process is operative at room temperature with high throughputs, which
favors automation and mass production [1].
116 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
a Pressure Dipper
measure plate b
Barriers
c d e
50 µm 50 µm 50 µm
f g h
Fig. 3.13 L–B assembly of GO films. a L–B trough equipped with two movable Teflon barriers,
pressure measurement plate, and dipper for film transfer onto solid substrates [54]. b A typical
isothermal curve recorded during compressing of GO sheets prior to film transfer [54]. c–h SEM
images of GO sheets deposited on a polyester slide by drop casting c. d, e Spin coating d and L–B
assembly e [24]. f Close-packed monolayer GO sheets as the first layer. g, h Double layers with
a dilute top layer g, and double layers with a high-density top layer h prepared by L–B assembly
[34]. (Reprinted with permission from [1]. Copyright (2014) by Elsevier)
relatively free of wrinkles or folds. It is also claimed that the L–B method can pro-
duce a large-area flat monolayer GO with much higher surface coverage on the sub-
strate with an accurately controlled thickness [55]. It is also possible to stack double
layers or multilayers of GO by sequential, LbL coating. As shown in Fig. 3.13f, the
first layer is collected at close-packed density, which was either aged in air over-
night or baked in an oven to enhance its adhesion to the substrate. Due to the repul-
sion from both their neighbors and those in the underlayer, the second layer of GO
tends to be wrinkled. Figure 3.13g, h show the double layers of GO with low- and
high-packing density for the second layer, respectively. The heavy degree of folding
and wrinkling of the second layer with high-packing density (Fig. 3.13h) suggests
strong repulsion between the two layers [34].
3.3.7 Rod Coating
The rod coating method is a scalable technique for making solution-processed thin
films, and has been widely used in the coating industry to prepare liquid thin films
[36]. Coating is done using a Meyer rod which is a metal bar with a wire wrapped
around its surface. The wire is used to draw a solution over a substrate surface. A
wet film is left when the Meyer rod is rolled over the substrates, which is then dried
to obtain a solid film. The thickness of the final dry film can be controlled by the
diameter of the wire wrapped around the bar and the concentration of the fluid.
The preparation of the coating fluid is critically important because the coating fluid
should possess a low surface tension and carry sufficient coating material, that is,
GO sheets. Rod coating can be performed in a scalable way for roll-to-roll produc-
tion in industry [56].
Wang et al. [36] demonstrated to fabricate a large-scale GO film on a PET sub-
strate in a controllable manner using the rod-coating technique (Fig. 3.14a). After
room-temperature reduction, highly flexible rGO films were used to assemble 4.5-
in. touch screens (Fig. 3.14b). The thickness of GO films was controlled from a
single layer to tens of layers by adjusting the concentration of GO solution or the
diameter of the rod wire. The film thickness is shown to increase with increasing
GO concentration from 0.05 to 1 mg/mL, see Fig. 3.14c–f. The GO films reduced
using hydrogen with the assistance of a small amount of a palladium (Pd) cata-
lyst had a sheet resistance ranging 1.68–20.1 kΩ/sq with a transmittance ranging
64.6–92.6 %.
3.3.8 Inkjet Printing
Inkjet printing is a process involving propelling droplets of ink onto papers, plastics,
or other substrates, and possesses many advantages, such as direct writing, additive
patterning, low cost, and scalability for large area manufacturing [57]. Kong et al.
[58] directly printed the rGO electrode onto flexible polymeric materials by inkjet
118 3 Fabrication of Graphene-Based Transparent Conducting Thin Films
Fig. 3.14 Rod coating of rGO films. a Rod-coating setup. b A flexible touch screen fabricated
using an rGO/PET film as electrode. c–f AFM images and height profiles of the GO films fabri-
cated by rod coating with 0.2-mm-thick rod wires with different concentrations of GO dispersions,
0.05 mg/mL c, 0.1 mg/mL d, 0.2 mg/mL e, 1 mg/mL f. (Reprinted with permission from [36].
Copyright (2012) by Wiley)
Fig. 3.15 Inkjet-printed rGO films. a Digital images of the vials containing GO and rGO aque-
ous dispersions (TX-100 = Triton-X100 surfactant). b Inkjet-printed GO film lifted from the PET
surface.c AFM image of rGO film obtained by reduction of the film in b with ascorbic acid.
(Reprinted with permission from [59]. Copyright (2010) by Wiley)
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59. Dua, V., Surwade, S. P., Ammu, S., Agnihotra, S. R., Jain, S., Roberts, K. E., Park, S., Ruoff,
R. S., & Manohar, S. K. (2010). All-organic vapor sensor using inkjet-printed reduced gra-
phene oxide. Angewandte Chemie-International Edition, 49, 2154–2157.
Chapter 4
Improvement of Electrical Conductivity
and Transparency
4.1 Introduction
[7]. One of the most effective approaches to reduce the number of intersheet tunnel-
ing barriers is producing large-size graphene sheets. Another successful approach is
to bridge these intersheet junctions with 1D highly conducting nanofillers, such as
single-walled nanotubes (SWNTs), metal nanowire (NW), and nanogrids that can
facilitate the restoration of the inherent electrical conductivities while sacrificing
a little of the transparency of graphene. Apart from reducing the intersheet contact
resistance, the intercalation of conducting fillers between the GO layers may bring
about another important benefit by forming 3D conductive networks through the
film thickness [8].
4.2 Chemical Doping
It is demonstrated that the Br2 vapor treatment enhanced the electrical conductivity
of graphite nanoplatelets (GNPs) by increasing the ionic component of Br function-
alities [9]. The GNPs were prepared by thermal expansion of graphite intercalation
compounds (GIC) following by ultrasonication. The thickness and diameter of the
produced GNPs were estimated to be 4.5 nm and 46 µm on average, respectively
[9]. GNPs were then exposed to Br2 vapor at room temperature in a closed desic-
cator for varying durations. The uptake of Br by GNP was evidenced by a weight
increase, through the increases in both intercalation complexes and covalent C–Br
groups. Figure 4.1a shows the changes in weight and Br atomic concentration as a
function of bromination duration. The weight increased rapidly with bromination
duration and then stabilized or decreased slightly after about 10 h, which may be
caused by the dynamic process of absorption and desorption of Br atoms into graph-
ite. Br was absorbed rapidly because of the ample availability of doping/reactive
sites in the GNPs for treatments below 10 h. Further treatment did not induce ad-
ditional absorption upon saturation of these sites, which can be attributed to gradual
changes in the nature and balance of the C–Br bond types. Another evidence for Br
uptake was the increase in Br atomic concentration.
An effective way to measure the extent of intercalation is the (002) d-spacing of
graphite, which can be performed by X-ray diffraction (XRD) spectra. As shown in
Fig. 4.1b, the peak corresponding to the 3 h treatment differs in position and breadth
from those corresponding to the other bromination durations. Table 4.1 shows that
with a 3 h treatment the d-spacing exhibited a minimum while the width-at-half-max-
imum (WHM) of the peak showed a maximum. The disorder of graphite crystals
during the intercalation process was responsible for the broadened peak and low d-
spacing after the 3 h treatment. Two possible types of bonds, that is, charge transfer
complexes and covalent bonds, were distinguished by time-of-flight secondary ion
mass spectrometry (ToF-SIMS) as shown in Fig. 4.1c. The atomic bromine had two
4.2 Chemical Doping 125
Fig. 4.1 Chemical doping of graphite nanoplatelet (GNP ). a Weight changes and Br atomic con-
centration determined by XPS as a function of bromination duration. b XRD spectra of brominated
graphite with different treatment durations. c ToF-SIMS spectra of brominated GNP. XPS X-ray
photoelectron spectroscopy. (Reprinted with permission from [9]. Copyright (2007) by Elsevier)
isotopic peaks at molar masses 79 and 81 with an intensity ratio of 50.5:49.5; Br2
showed a triplet at 158, 160, and 162 with a respective intensity ratio of about 1:2:1;
CBr exhibited a doublet at 91 and 93; and C2Br exhibited a doublet at 103 and 105 [9].
126 4 Improvement of Electrical Conductivity and Transparency
Table 4.1 XRD results with bromination duration. (Reprinted with permission from [9]. Copyright
(2007) by Elsevier)
Duration (h) 0 1 3 10 72 168
d-spacing (Å) 3.342 3.355 3.348 3.361 3.361 3.361
WHM (°) 0.345 0.365 0.5 0.335 0.32 0.32
WHM width-at-half-maximum
Considerable progress has been made to enhance the electrical conductivities of thin
films made from carbon nanotubes (CNTs) while maintaining their high transmit-
tance through chemical doping treatments before graphene thin films became popu-
lar. Various techniques, including simple immersion of CNT films in HNO3 [10],
SOCl2 [11], HNO3 followed by subsequent treatments by SOCl2 [12] or SOBr2,
[13] have been developed. CNT films were fabricated using CNT dispersion con-
taining sodium dodecyl sulfate (SDS) and washed using HNO3 [10], which showed
an excellent conductivity with a negligible change in transmittance in the visible
light range. Since HNO3 can efficiently remove the residual SDS among CNTs and
also enhance the metallicity of the CNTs, the electrical conductivity of the CNT
TCFs is significantly improved [10]. A combined room-temperature treatment with
HNO3 and SOCl2 was also shown to be an effective approach to reduce the sheet re-
sistivity through the formation of acyl chloride functional groups [12]. As shown in
Fig. 4.2, the sheet resistance decreased after the initial exposure to HNO3 for 3 h and
further decreased after the treatment with SOCl2. Immersion of the film in SOCl2
and complete drying with gentle nitrogen flow leads to instant improvement in the
conductivity while longer immersion times (2 weeks in SOCl2) did not provide
any further change in conductivity. An interesting result was reported that the CNT
films modified using SOBr2 outperformed the counterparts modified using SOCl2
[13]. The observation was attributed to the formation of new conducting paths be-
Table 4.2 Sheet resistances of SWNT films with different numbers of layers measured before
and after chemical treatments. (Reprinted with permission from [13]. Copyright (2008) by Wiley)
Pristine (Ω sq−1) SOCl2 (Ω sq−1) SOBr2 (Ω sq−1)
One layer 5.04 × 103
4.23 × 103
4.02 × 103
Two layers 456 322 298
Three layers 303 187 168
Four layers 184 76 56
tween CNTs via S atoms when SOBr2 was used, while SOCl2-induced conductivity
was mainly due to the formation of SWNT/SOCl2 charge-transfer complexes. In
contrast to SOCl2, SOBr2 is a relatively larger molecule, which may cause larger
binding energy between Br and SWNTs than that of Cl and SWNTs. Table 4.2 com-
pares the sheet resistances of the SWNT films before and after different chemical
treatments. It is noticed that the sheet resistance gradually decreased with increasing
number of layers, consistent with the fact that sheet resistance is determined by film
thickness.
Because graphite, CNTs, and graphene share essentially the same chemical struc-
ture, it is not surprising that chemical doping would also be an important strategy
for improving the optoelectrical properties of graphene films [14–19]. Several dif-
ferent acids and halogenating agents, like HNO3 [15], SOCl2 [20], SOBr2 [17], or
AuCl3 [14, 16, 19] have been successfully employed for treating rGO films.
Graphene is classified as a zero-band-gap semiconductor, where the density of
states vanishes at the Dirac point [15]. As a result, undoped graphene has a low
carrier density and thus a high sheet resistance. Chemical doping is an effective
approach to tailor the electrical properties of graphene because it can increase the
carrier concentration [2]. The chemical doping of graphene can be divided into two
categories including surface transfer doping and substitutional doping, see Sect. 4.1
for further details of these doping methods.
Nitric Acid
Acid treatment, especially using nitric acid, is a simple and effective way to realize
the surface transfer doping. HNO3 is known to be a p-type dopant, that is, electron
acceptor, for graphitic materials. As shown in Eq. (4.1), an electron is transferred
from graphene to HNO3 when a charge-transfer complex is formed [15]:
+
6HNO3 + 25C → C25 NO3− • 4HNO3 + NO 2 + H 2 O (4.1)
128 4 Improvement of Electrical Conductivity and Transparency
(2010, 2011) by ACS and W QP
Elsevier)
W QP
:DYHOHQJWK QP
The charge transfer results in a shift of the Fermi level, leading to an increased car-
rier concentration and a decreased sheet resistance, see Fig. 4.3a. It is also found
that the interlayer doping yielded better optoelectrical properties than the last-layer
doping (Fig. 4.3b) due to the more efficient doping effect [15]. Besides the doping
effect, nitric acids can also clean the graphene film surface, leading to an improved
optical transparency (Fig. 4.3c) [20].
Thionyl Chloride
Apart from nitric acids, halogenating agents have been popularly used to realize
charge transfer. For example, it was shown that the exposure to SOCl2 induced
functional groups on graphene surface, which acted as electron acceptors thus in-
creasing the hole density in graphene [20]. The sheet resistance of the resulting gra-
phene decreased by 50–80 % depending on the type of graphene [20]. The chlorine
decorated along the edges and the basal plane of graphene increased the number of
holes in the conjugated sp2 network. The p-type doping of graphene due to SOCl2
has been further confirmed by electronic structure calculations, which indicated a
Fermi level shift into the valence band and the results are shown in Fig. 4.4d–f [11].
4.2 Chemical Doping 129
Fig. 4.4 SOCl2 doping of graphene. a Equilibrium structure of a SOCl2 molecule adsorbed on a
pyrene molecule, which represents a graphene or CNT segment. b Total change density of the sys-
tem in a plane. c Different charge densities in the same plane, indicating regions of charge deple-
tion and accumulation with respect to a superposition of neutral atoms. (Reprinted with permission
from [11]. Copyright (2005) by ACS)
,QWHQVLW\ &RXQWV
from [20]. Copyright (2011) &2
by ACS)
& 2
2& 2
&G
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2& 2 & 2
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were 15, 36, and 8 %, which were drastically reduced to 9, 4, and 3 %, respectively,
after the thermal treatment. SOCl2 doping induced a strong peak at 286.1 eV at-
tributed to C–S [3], with about 15 % signal composition. It is also worth noting that
the –COOH group increased from 3 to about 10 % after SOCl2 doping. Previous
theoretical [23] and experimental [24] studies reveal that proper carboxyl function-
alization of CNT was beneficial to improving the electrical conductivity. As such,
the increase in –COOH functional group possibly helped stabilize the p-doping ow-
ing to the electron-deficient property of doped CNT or graphene. It is suspected
that the sheet resistance may start to increase again if the –COOH concentration is
too high because of the deterioration of the π–π conjugation structure in graphene.
Thus, a proper control of the SOCl2 doping parameters, such as concentration and
immersion time, is of critical importance to achieve the highest possible electrical
conductivity.
Figure 4.6 shows the S 2p, N 1s, and Cl 2p spectra of the SOCl2-doped rGO film.
In the S 2p spectrum (Fig. 4.6a), the peak at ~ 169.5 eV can be attributed to S with
an oxidation state VI (SO42−) and SO covalent bonds [25]. An additional peak oc-
curred at ~ 163.6 eV, identical to that of an organic C–S bond [26], indicating that
–C–S–C– bonds existed in the SOCl2-doped rGO film. The possibility of covalent
cross-linking between the rGO sheets through –C–S–C– bonds may also contrib-
ute to the enhanced electrical conductivity. In the N 1 s spectrum (Fig. 4.6b), the
components near 395–405 eV are attributed to the NO, CN groups that originated
mainly from the previous HNO3 treatment, confirming the attachment of N atoms
on graphene surface via covalent bonding. Although the treatment by HNO3 was
likely to introduce some defects on rGO, it appeared not to cause detrimental ef-
fect on the electrical properties of rGO films. This is because the dangling bonds or
defects formed by HNO3 are immediately passivated by –OH or –COOH groups.
Once –OH or –COOH groups are in contact with SOCl2, a nucleophilic substitution
by chloride takes place. The ionic bonds with –Cl or –SOCl groups can improve the
conductivity of the rGO films. The Cl 2p core level spectrum (Fig. 4.6c) revealed
two nonequivalent chlorine sites from the 3/2 and 1/2 levels, which are separated
by 1.4 eV due to spin–orbit coupling. The components are located at 202.0 and
200.4 eV corresponding to covalent C–Cl bonds in the organic chlorocarbon com-
pound [27]. The p-type doping associated with –Cl led to the formation of charge
transfer complexes in the rGO sheets, resulting in a charge redistribution in the sys-
tem that in turn increases the rGO’s electrical conductivity [9]. In summary, SOCl2
doping introduced –Cl or –SOCl functional groups with a strong electronegativity
onto the rGO surface which served as electron acceptors to improve the electrical
conductivity.
SOBr2 doping also showed desired effects of enhanced electrical conductivity
and transparency of graphene films [17]. The mechanisms behind the improvemens
in these characteristics were identified by establishing the correlation with the sur-
face chemistry of the thin films. In a typical process, the thermally reduced GO film
was subject to two additional processes: namely, (i) dipping in a HNO3 bath (70 %)
for 3 h and drying with gentle nitrogen flow; and (ii) dipping in a SOBr2 bath for 24
h and drying with gentle nitrogen flow. The deconvoluted C1s spectra taken before
132 4 Improvement of Electrical Conductivity and Transparency
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mission from [20]. Copyright
(2011) by ACS) 62
&6
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b
12
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c
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4.2 Chemical Doping 133
a b
&&
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Fig. 4.7 XPS curve fitting of C1s a and Br 3d b spectra of SOBr2-doped rGO. (Reprinted with
permission from [17]. Copyright (2011) by Elsevier)
and after thermal reduction were all essentially similar to those shown in Fig. 4.5
because the materials and process employed were similar. Major differences arose
when the rGO films were subjected to additional treatments using HNO3 and SOBr2
and the corresponding XPS results are shown in Fig. 4.7a and Table 4.4.
The deconvoluted Br 3d spectrum in Fig. 4.7b shows that there were two types of
C–Br bonds, namely the charge-transfer complexes and the covalent bonds, similar
to the C–Cl bonds in thionyl chloride-doped rGO films. The intense Br 3d compo-
nent at a core-level binding energy of ~ 70.1 eV is typical of C–Br covalent bonds,
whereas the less intense component with a lower binding energy of ~ 69.3 eV is
assigned to ionic bromine [13]. These two different types of C–Br bonds were con-
firmed by the ToF-SIMS analysis. The p-type doping associated with –Br led to the
formation of charge transfer complexes in the rGO sheets, giving rise to enhanced
electrical conductivities of rGO films [9]. A nucleophilic substitution by bromide
takes place once –OH or –COOH groups are in contact with SOBr2. Then, the rGO
sheets form ionic bonds with –Br or –SOBr groups, further contributing to the con-
ductivity of graphene films.
Figure 4.8 shows the resulting sheet resistance values of the rGO films measured
at different stages. The sheet resistance of the rGO films changed from 104–106 to
100–2000 Ω/sq after the thermal treatment, which is about three orders of magni-
tude different. After the doping treatments, it was further reduced by about 20–50 %
to 50–1600 Ω/sq depending on the film thickness. To further explain the enhanced
Table 4.4 Elemental compositions of GO, thermally reduced GO, and SOBr2-doped rGO.
(Reprinted with permission from [17]. Copyright (2011) by Elsevier)
Element (atom %) C N O S Br
GO 71.91 0.49 27.48 0.11 –
Thermally reduced GO 80.91 0.52 18.43 – –
SOBr2-doped rGO 71.40 2.93 16.79 4.80 4.08
GO graphene oxide, rGO reduced graphene oxide
134 4 Improvement of Electrical Conductivity and Transparency
6KHHWUHVLVWDQFH Ω/VT
with permission from
[17]. Copyright (2011) by
Elsevier)
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electrical conductivities, the carrier type and sheet carrier concentrations at differ-
ent stages were determined by a Hall measurement system using the Van der Pauw
method. The results are summarized in Table 4.5, showing that the graphene films
remained as a positive carrier, that is, hole carrier, throughout the whole processes.
The sheet carrier concentration increased by about three orders of magnitude after
thermal treatment due to the removal of the oxygenated functional groups and the
graphitization; and it further increased by nearly 200 % due to the chemical doping.
Auric Chloride
AuCl3 is also known to be an effective p-type chemical doping agent to reduce the
sheet resistance of graphene TCFs [14, 16]. The Raman spectroscopy of the AuCl3-
doped graphene indicates that AuIII was reduced to Au particles by charge transfer
from graphene to AuIII [16]. It is proposed that graphene was p-doped through the
following reactions when nitromethane is used as the solvent [16]:
Table 4.5 Carrier type and sheet carrier concentration of graphene films at different stages.
(Reprinted with permission from [17]. Copyright (2011) by Elsevier)
Sample As prepared rGO film After thermal treatment After SOBr2 treatment
(cm−2) (cm−2) (cm−2)
38.7 nm thick + 2.30 × 1011 + 2.66 × 1014 + 5.64 × 1014
78.0 nm thick + 7.11 × 1011 + 3.63 × 1014 + 7.09 × 1014
rGO reduced graphene oxide
4.2 Chemical Doping 135
Fig. 4.9 AuCl3 doping of graphene films. a The top steps indicate layer-by-layer (LbL) doping and
the bottom steps indicate the topmost layer doping. b Sheet resistance and transmittance of vari-
ous samples as a function of the number of graphene layers. PET polyethylene terephthalate, ITO
indium tin oxide. (Reprinted with permission from [14]. Copyright (2010) by ACS)
136 4 Improvement of Electrical Conductivity and Transparency
the pristine single graphene sheet showed a large sheet resistance of 725 Ω/square
with a remarkable transmittance of 97.6 % at 550 nm. Regardless of the thickness,
the sheet resistance was greatly reduced by about 80 % with AuCl3 doping (see filled
circle). It is also worth noting that the transmittance was slightly decreased com-
pared with pristine graphene films due to the light scattering from the Au nanopar-
ticles formed during the reduction reaction [14, 28]. The Au-doped graphene films
had at least a few folds higher electrical conductivities than those obtained after ni-
tric acid treatment. However, the electrical conductivities of the AuCl3-doped films
were essentially similar regardless of whether the individual graphene layers were
doped or only the top layer of the multilayer graphene films was doped.
5V ΩVT
of exposure to air [17].
b Sheet resistance change as
a function of time under vari-
ous conditions [14].
c Bending stability test
results for four-layer pristine
(top), HNO3-doped (middle)
and Au-doped (bottom)
graphene films [14]. LbL
layer-by-layer. (Reprinted
with permission from [14]. 7UDQPLWWDQFH
Copyright (2010) by ACS) b
c
138 4 Improvement of Electrical Conductivity and Transparency
4.3 Hybridization
CVD Method
CVD method CVD grown CNT film is transferred – 0.735 90 4.7 Li et al. [41]
on top of graphene film using a glass
rod
GO powders mixed with oxygen – – 0.24 86 10.0 Tung et al. [33]
functionalized SWNTs in anhydrous
hydrazine followed by spin coating
Graphene and CNT mixture in water – – 0.1 80 16.0 King et al. [42]
with sodium cholate (NaC) surfactant
followed by transfer printing
Dry powders of GO and SWCNTs – – 0.954 88.6 3.2 Huang et al.
are dispersed directly in anhydrous [34]
hydrazine followed by spin coating
GO film formed at pentane–water Carboxylic acid functionalized SWNT Hydrazine vapor 3.1 73 0.36 Chen et al. [35]
interface and transferred to substrate film formed at pentane–water interface (Aldrich) at 70 °C
and transferred to substrate overnight
Electrostatic self-assembly, aminated Electrostatic self-assembly, nega- Hydrazine mono- 151 93 0.034 Kim et al. [37]
substrate immersed into negatively tively charge GO film immersed in hydrate solution
charged GO solution positively charged aminated MWNT for 1 day at 80 °C,
solution thermally annealed
for 60 min at
500 °C in an argon
atmosphere
Electrostatic self-assembly, nega- Electrostatic self-assembly, positively Hydrazine solution, 8 81 0.21 Hong et al. [38]
tively charged rGO (or GO) solution charged MWNT-NH3 solution spin 95 °C for 1 h
spin coated on top of MWNT film coated on piranha solution cleaned
143
substrate
Table 4.7 (continued)
144
Deposition method of graphene or Deposition method of CNT layer Reduction method Rs (kΩ/sq) T σ DC / σ OP Reference
GO layer
Bubble deposition method, adhesion Bubble deposition method, adhesion – – – – Azevedo et al.
of the film to the substrate of the film to the GO film [39]
L–B assembly, GO on water surface L–B assembly, SWNTs on water sur- – 0.56 86 4.3 Zheng et al.
assembled onto substrate face assembled onto GO film [30]
GO graphene oxide, rGO reduced graphene oxide, CVD chemical vapor deposition, CNT carbon nanotubes, SWNT single-walled nanotubes, L–B
Langmuir–Blodgett
4
Improvement of Electrical Conductivity and Transparency
4.3 Hybridization 145
a b
s
ŐƌĂƉŚĞŶĞ
EdĮůŵ
'ƌĂƉŚĞŶĞ
ƚĐŚŝŶŐ
ϭĐŵ
Fig. 4.11 Hybridization of chemical vapor deposition (CVD)-grown graphene and carbon nano-
tubes (CNT). a Schematic for the assembly of the graphene/CNT composite film. b Graphene/CNT
composite film floating on water surface. (Reprinted with permission from [41]. Copyright (2010)
by ACS)
Solution Mixing
coating method. For the film formed with one and five layers, the sheet resistance
reached as low as 954 and 254 Ω/sq, respectively. However, increasing the number
of spin-cast layers meant thicker films with increasingly reduced optical transmit-
tance from 88.8 to 58.7 %.
Since GO sheets are amphiphilic in nature, they can form thin films at organic sol-
vent–water interfaces based on a self-assembly process [43, 44]. Chen et al. [35]
presented an ethanol-assisted self-assembly method for the quick formation of GO/
CNT composite thin films with tunable composition, transmittance, and surface
resistivity at pentane–water interface. As shown in Table 4.6, ethanol serves as a
nonsolvent when it is injected into the aqueous solution containing GO or carbox-
ylic acid functionalized SWNTs. The injected nonsolvent (ethanol) has a significant
influence on the stability of GO in water, providing a driving force to allow GO or
SWNTs to aggregate at the water–pentane interface. GO/SWCNT (SWCN Single-
walled carbon nanotubes) composite thin films were produced based on the self-
assembly process at the water–pentane interface. Reduced GO/SWCNT composite
films had a much lower surface resistivity of 3.1 kΩ/sq at 73 % transmittance than
the neat rGO thin films, 8.3 kΩ/sq at 72 % transmittance.
Electrostatic Self-Assembly
Fig. 4.12 Electrostatically self-assembled reduced graphene oxide (rGO)/CNT hybrid films.
a Illustration of deposition of positively charged PEI functionalized rGO and negatively charged
MWNTs on a silicon wafer or ITO-coated glass substrate. [36] SEM images of b the first rGO
layer and c the first bilayer deposited on a silicon substrate [36]. d Fabrication of rGO/MWNT
hybrid layer on a substrate [37]. (Reprinted with permission from [36, 37]. Copyright (2010, 2009)
by ACS)
The BDM
The BDM is another simple method to precisely order and deposit GO films onto
any substrates [39]. The BDM is based on the confinement of nano-objects in the
core of water bubbles. The core thickness decreases under drainage and change the
interference phenomena and the film color. There are mainly four major steps for
the BDM process (Table 4.6): (i) formation of bubbles using GO or GO/CNT hybrid
solution in a closed chamber, (ii) start of water drainage, (iii) deposition of films on
the substrate, and (iv) fast evaporation of the residual water after the busting of the
bubbles. The BDM can produce densely packed monolayer to multilayer GO sheets
as well as GO/CNT composite thin films in ambient conditions. However, it should
be noted that this method is incompatible with large-scale production and is only
suitable for fundamental studies.
148 4 Improvement of Electrical Conductivity and Transparency
L–B Assembly
It is well known that the L–B assembly technique is the most sophisticated and ac-
curately controllable among all available techniques to fabricate GO/CNT hybrid
films, where amphiphilic ultralarge graphene oxide (UL-GO) and functionalized
SWNTs are consecutively deposited via an LbL manner [30]. The deposition of
SWNT layers is a crucial part of the whole process, thus the fabrication of COOH-
functionalized SWNTs needs special attention. Due to the strong van der Waals
forces between SWNTs, they are highly insoluble and aggregated, making pristine
SWNTs unsuitable for the L–B assembly. The conventional solution is to apply non-
covalent functionalization, including wrapping SWNTs with a variety of surfactant
or polymers, such as poly(m-phenylene vinylene-co-2,5-dioctyloxy-pphenylene
vinylene) (PmPV) [45] or poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5-thienylene)
(POPT) [46], to avoid the formation of insoluble bundles. However, these additives
are insulating and difficult to be completely eliminated after the film formation,
which is harmful to electrical conductivity of the films due to the additional con-
tact resistance between them [13]. In the absence of surfactant treatment, SWNTs
can also be dispersed using special solvents [47], such as N-methyl-2-pyrrolidone
(NMP) [48], N,N-Dimethylform (DMF) [49], o-dichlorobenzene (DCB) [50], and
dichloroethane (DCE) [45], but they are unsuitable for the L–B assembly because
of their high boiling points [48–50] or toxic nature [45, 50]. Hence, carboxylic
moieties were introduced non-uniformly along the SWNTs length, making them
amphiphilic and ready for the L–B assembly.
The XPS results of the COOH– functionalized SWNTs shown in Fig. 4.13a con-
firmed COOH– functional groups upon sulfuric acid and nitric acid (typically 3: 1
volume ratio) treatments [30]. Typically, the COOH– functionalized SWNTs were
dispersed in a 1:3 water/methanol solution before spreading. The surface pressure–
area isotherm curves in Fig. 4.13b shows the changes in slope due to the phase
transitions of the SWNT monolayer from gas to condensed liquid and to a solid
state at ~ 2 and ~ 10 mN/m, respectively. There were also small shifts of the gas–liq-
uid and liquid–solid phase transition points toward a smaller area with increasing
the cycles probably because of the loss of a small amount of material from the
monolayer after each cycle [43]. The COOH– functionalization was effective in
dispersing the bundles into individual SWNTs (Fig. 4.13c). Alternate monolayers
of GO and SWNTs were deposited on the substrate one after another by carefully
controlling the surface pressure.
The scanning electron microscope (SEM; Fig. 4.14b) images suggest partial-
ly wrinkled edges when the GO sheets were squeezed toward each other during
compression and pullout. The transmission electron microscope (TEM) image and
the corresponding selected area electron diffraction (SAED) pattern (Fig. 4.14c)
confirmed the primarily amorphous nature of the GO sheets [17]. Due to the amphi-
philic GO and SWNT surfaces, strong bonds were formed though π–π interactions
and van der Waals forces when the SWNT layer was deposited on the GO layer
[51]. The SWCNTs functioned as conductive bridges connecting the separate GO
sheets.
4.3 Hybridization 149
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plots of three sequential com-
pression/expansion cycles in
the L–B assembly process,
confirming highly reversible &2
&G
UGF\FOH
by RSC)
F
Fig. 4.14 Fabrication of GO/SWNT hybrid films via an L–B assembly process: schematic a,
SEM b, and TEM c images of a monolayer of GO; schematic d, SEM e, and TEM f images for
one bilayer GO/SWNT hybrid film, with SWNTs bridging GO sheets; schematic g, and SEM h, i
images of four bilayers GO/SWNT hybrid film. (Reprinted with permission from [30]. Copyright
(2012) by RSC)
The typical surface morphologies of the GO/SWNT hybrid thin films with four
bilayers are shown in Figs. 4.14h, 4.14i and 4.15a. Figure 4.15b shows the mean
surface roughness values of the hybrid films as a function of number of bilayers be-
fore and after thermal treatment. As the film thickness increased, the surface rough-
ness presented a generally increasing trend. Because of the deposition of porous
SWNT monolayer and flat GO layer, there were sudden surges and drops in rough-
ness. Due to the graphitization effect, the thermal reduction generally decreased
the surface roughness with less significant drops and surges. The compaction of
the films resulting from the removal of oxygenated functional groups and graphi-
tization during annealing were mainly responsible for the reduction in roughness.
After thermal treatment, the 30-nm-thick hybrid films had a surface roughness of
~ 10 nm, which is far lower than those prepared by other coating techniques, typi-
4.3 Hybridization 151
cally ~ 35 nm for the hybrid films with a similar thickness [34]. The GO/SWNT hy-
brid films without additional doping treatments delivered excellent sheet resistance
ranging 180–560 Ω/sq with an optical transmittance ranging 77–86 % depending on
the number of hybrid layers.
Thanks to the high electrical conductivity and optical properties, metal NW films
are considered promising materials for TC applications [52]. The sheet resistances
of Au NW [53, 54], Ag NW [55, 56], and Cu NW films [57–59] are comparable
to or lower than commonly used indium tin oxide (ITO) films at the same optical
transmittance. However, the low oxidation resistance, poor adhesion to the sub-
strate, the existence of porous open spaces, and low stability in harsh environments
of metal NW films limit their application as TCs [52]. One possible way to address
these problems is the hybridization of metal NWs or nanogrids with rGO. Vertically
grown metal NWs can reduce the contact resistance, while metal nanogrids can
bridge the rGO sheets, both decreasing the electrical resistance.
152 4 Improvement of Electrical Conductivity and Transparency
ZnO Nanorods/NWs
Silver NWs
Graphene layer Deposition method of graphene Deposition method Rs (Ω/sq) T (%) σ DC / σ OP Reference
layer of Ag NWs layer
CVD grown graphene on copper foil Plasma etching and transfer Drop casting 22 88 129.8 Chen et al. [68]
CVD grown graphene on copper foil Modified dry transfer Spin coating 24 91 162.7 Kholmanov et al. [63]
CVD grown graphene on copper foil HNO3 etching and transfer Spin coating 225 91.3 18.0 Liu et al. [69]
CVD grown graphene on copper foil HNO3 etching and transfer Spin coating 32.5 81.5 53.9 Liu et al. [69]
CVD grown graphene on copper foil HNO3 etching and transfer Spin coating 30.4 71.2 33.5 Liu et al. [69]
CVD grown graphene on copper foil Ammonium persulfate etching Spin coating 34.4 92.8 143.9 Lee et al. [70]
4
and transfer
CVD grown graphene on copper foil FeCl3 and transfer Drop casting 16 91.1 246.9 Xu et al. [62]
CVD grown graphene Etching and transfer Spin coating 33 94 181.8 Lee et al. [71]
Gold-decorated rGO Spin coating Spin coating 1460 91 4.1 Kholmanov et al. [65]
Gold-decorated rGO Spin coating Spin coating 86 85 25.9 Kholmanov et al. [65]
Gold-decorated rGO Spin coating Spin coating 26 83 74.3 Kholmanov et al. [65]
GO Spin coating Spin coating – – 44 Liu et al. [72]
GO Spray coating Bar or spray 24.8 92 178.5 Moon et al. [73]
coating
Ag NW-rGO mixture solution Dip coating – 86 80 18.6 Tien et al. [66]
Ag NW-rGO mixture solution Transfer printing – 27 80 59.1 Zhang et al. [74]
GO L–B assembly Spin coating 48 91.2 83.3 Shi et al. [75]
GO L–B assembly Spin coating 13 71.9 80.9 Shi et al. [75]
GO Soaking in GO solution fol- Bar coating 14 88 204.0 Liang et al. [67]
lowed by rinse and blow-dry
CVD chemical vapor deposition, GO graphene oxide, rGO reduced graphene oxide, NW nanowire, L–B Langmuir–Blodgett
Improvement of Electrical Conductivity and Transparency
4.3 Hybridization 155
Fig. 4.17 Ag nanowire (NW)/graphene hybrids for TCFs. a Schematic illustration of Ag NW/gra-
phene films fabrication [63]. b Schematic of reduced graphene oxide (rGO)/Au nanoparticle (NP)/
Ag NW hybrid film preparation [65]. c Schematic of the fabrication process of the 2D AgNW/
rGO hybrid nanomaterials prepared through a two-step reduction process by sodium borohydride
(NaBH4) and ethylene glycol [66]. d Schematic illustration of the fabrication of a Ag NW/GO net-
work on a glass substrate at room temperature [67]. (Reprinted with permission from [63, 65–67].
Copyright (2012, 2013, 2014) by ACS and Elsevier)
156 4 Improvement of Electrical Conductivity and Transparency
Kholmanov et al. [52] found that the rGO film could act as an oxidation resistant
layer for Cu NWs. The rGO film acts as a conductive and continuous transparent
film that fills in the open spaces between the NWs, and as a cover that protects the
NWs from harsh environments. As shown in Fig. 4.18a, the deposition process of
rGO films onto the Cu NW films includes spin coating of rGO solution (left side
of Fig. 4.18b), spray coating of NW solution (right side of Fig. 4.18b) and dry
transfer of the hybrid film. rGO and Cu NWs were produced by spin and spray
coating, respectively (Fig. 4.18c). By spin coating of a layer of Poly(methyl meth-
acrylate) (PMMA) on the rGO films (Fig. 4.18d), the delaminated PMMA/rGO
films were then transferred on the Cu NW films using a dry transfer method [63,
76]. By removing the PMMA layer with acetone, the final rGO/Cu NW hybrid films
were obtained (Fig. 4.18e) which showed much lower sheet resistances than the
neat rGO films with the same transmittances after thermal annealing, see Fig. 4.18f.
Since the lateral size of rGO platelets was as large as several micrometers, they can
Fig. 4.18 Reduced graphene oxide (rGO)/Cu nanowire (NW) hybrid films for TCs. a Schematic
of preparation of rGO/Cu NW hybrid films. b Photographs of GO aqueous dispersion and Cu NWs
dispersed in IPA. c rGO (top) and Cu NW (bottom) films on glass substrates. d PMMA/rGO film
delaminated from the glass substrate in NaOH aqueous solution. e Photograph of rGO/Cu NW
films on a glass substrate after the PMMA layer was removed. f Sheet resistance versus transmit-
tance of the neat Cu NW and rGO/Cu NW hybrid films. g, h SEM images of individual rGO plate-
lets g and rGO/Cu NW film h. (Reprinted with permission from [52]. Copyright (2013) by ACS)
4.3 Hybridization 157
bridge two or more disconnected Cu NWs separated by any distance smaller than
the lateral size of the platelet (Fig. 4.18g), leading to higher electrical conductivities
of the hybrid films (Fig. 4.18h).
The sheet resistance of metal nanogrids was also reduced by incorporating gra-
phene to form hybrid TCFs [77]. As shown in Fig. 4.19a, metal grids were formed
on a transparent substrate, followed by the transfer of CVD grown graphene on a
sacrificial PMMA layer to the top of the grid. Hybrid transparent electrodes were
formed once the sacrificial PMMA layer was removed by etching. Although the
metal nanogrids themselves are opaque, they can form thin transparent percolation
networks, making them conductive and highly transparent (Fig. 4.19b). To evaluate
the flexibility of the TCFs, the thin films fabricated on PET substrates were bent
multiple times (Fig. 4.19c). The flexibility test results showed that the sheet resis-
Fig. 4.19 a Schematic and b SEM image of graphene/metal nanogrids hybrid TCFs. c Image of
a hybrid electrode on the PET substrate bent around a cylinder of d = 1 cm. d Sheet resistance of
hybrid electrodes as a function of bending cycle. (Reprinted with permission from [77]. Copyright
(2011) by ACS)
158 4 Improvement of Electrical Conductivity and Transparency
tances of the hybrid films increased by 20–30 % after the initial 50 bending cycles,
originating from the graphene film itself (Fig. 4.19d). It is worth noting that the
sheet resistance stabilized even up to 500 bending cycles because the weak areas on
the graphene did not survive during the initial bending and changed their forms to
stabilize upon further cycles [77].
4.4 Using UL-GO
Table 4.9 Comparison of optoelectrical properties of UL/GO-based TCFs assembled with differ-
ent approaches
Size of Deposition Reduction method Rs (kΩ/ T σ DC / σ OP Reference
UL-GO method of sq)
(µm) UL-GO
~ 20 Solution Thermal annealing, 0.52 63 1.4 Bae et al.
casting 600 °C in argon for [84]
3h
~ 20 Solution Thermal annealing, 3.110 90 1.1 Bae et al.
casting 600 °C in argon for [84]
3h
Up to ~ 200 Dip coating HI aqueous solution 19.1 79 0.079 Zhao et al.
(55 %) at 100 °C for [1]
30 s
Up to ~ 1–5 Dip coating Thermal annealing, 1005 98 0.018 Su et al.
20 % H2, 800 °C, 2h [85]
Up to Dip coating Thermal annealing, 413 98.1 0.047 Su et al.
~ 20–100 20 %H2, 900 °C, 2h [85]
Up to Dip coating Thermal annealing, 188 98 0.099 Su et al.
~ 1000 20 %/H2, 1000 °C, 2h [85]
Up to ~ 200 L–B Thermal annealing, 0.5 90 6.97 Zheng
assembly 1100 °C in argon, et al. [20]
0.5 h
Up to ~ 200 L–B HI solution (57 %), 1.1 91 3.55 Lin et al.
assembly 90 °C, 10 min [86]
UL-GO ultralarge graphene oxide, L–B Langmuir–Blodgett
PMMA (HEFG/PMMA) film was transferred to a PET film. HEFG on PET (HEFG/
PET; Fig. 20d) was obtained once PMMA was removed in acetone. The optical
transmittances of the HEFG/PET TCFs were in the range of 63–90 % with sheet
resistances of 0.52–3.11 kΩ/sq. It should be noticed that the edge of the HEFG film
was much thicker than the central part due to the nonuniform evaporation during
the solution casting process.
Zhao et al. [1] produced GO-based TCFs by using GO sheets with different areas,
finding that the sheet resistance was strongly correlated to the GO area. The GO films
were fabricated using a dip-coating method on a liquid/air interface (Fig. 4.21a) and
reduced by HI acid (Fig. 4.21b). The sheet resistance of the rGO films decreased
with increasing the area of GO sheets at the same transmittance because of the de-
crease in the number of intersheet tunneling barriers. A reduction in sheet resistance
by one order of magnitude was achieved when the area of GO sheets increased
from ~ 100 to ~ 7000 µm2 (Fig. 4.21c). For example, at a transmittance of ~ 78 %,
160 4 Improvement of Electrical Conductivity and Transparency
Fig. 4.20 Solution casting of edge-selective functionalization of graphite (EFG) for the produc-
tion of large-area uniform graphene films. (Reprinted with permission from [84]. Copyright (2011)
by ACS)
the TCF made from sample I (~ 7000 µm2 in area) had a sheet resistance of ~ 840 Ω/
sq while the TCF made from sample II (~ 1000–3000 µm2 in area) and sample III (
~ 100–300 µm2 in area) had sheet resistance of ~ 5.6 and ~ 19.1 Ω/sq, respectively.
Because three types of TCFs were reduced under the same condition, it is believed
that the lower sheet resistance of sample I was mainly due to the increase in aver-
age sheet area and consequent decrease in the number of intersheet tunneling bar-
riers in a continuous rGO film [1]. A similar trend was also found by Su et al. [85].
As shown in Table 4.9, the sheet resistance of the TCF prepared from the UL-GO
sheets with typical sizes approximately a millimeter after 1 h sonication was signifi-
cantly lower than those prepared from the sample ll GO (S-GO) sheets with typical
lateral sizes ~ 1–5 μm after 6 h sonication and those from the L-GO with typical
sizes 20–100 μm after 2 h sonication.
4.4 Using UL-GO 161
Fig. 4.21 TCFs produced from UL-GO sheets. a, b Optical images of GO films produced by dip
coating a before and b after HI acid reduction. c Sheet resistance and transmittance at 550 nm of
TCFs assembled with GO sheets with different sizes. (Reprinted with permission from [1]. Copy-
right (2010) by ACS)
S-GO and UL-GO dispersions were obtained after three consecutive runs of centrifu-
gation for the L–B assembly. The sizes of S-GO and UL-GO sheets were around 3
and 50 μm, respectively. The typical surface pressure–area isotherm monitored us-
ing a tensiometer during the L–B assembly is shown in Fig. 4.22. The changes in the
slope corresponded to the phase transition of GO sheets from gas to condensed liquid
and to solid state (Fig. 4.22a). An initial gas phase existed where the surface pressure
remained basically constant (stage a). The pressure began to increase as the compres-
sion continued (stage b). The GO sheets were about to touch one another, tiling over
the entire surface. The surface pressure increased because of the electrostatic repulsion
between the GO sheets, leading to slight darkening of the monolayer color due to the
increase in material density on the water surface. When the monolayer was compressed
beyond the close-packed stage, a further increase in surface pressure ensued (stage c)
because the GO sheets began to fold along their edges instead of overlapping on top
of another. Partial overlapping and wrinkling happened at a higher pressure (stage d).
162 4 Improvement of Electrical Conductivity and Transparency
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Fig. 4.22 Isothermal curves of the UL-GO. a Surface pressure vs. area plot showing the corre-
sponding four stages (a–d) of the formation of GO monolayers in L–B assembly. b Isotherm plots
of two sequential compression/expansion cycles, showing essentially overlapped two curves over
the whole area, except at the early stage of compression. (Reprinted with permission from [20].
Copyright (2011) by ACS)
Control of GO Structure
It was found that the GO structure in the TC films can be controlled by varying the
L–B assembly parameters such as surface pressure and pulling speed [20, 87]. Sev-
eral unique microscopic morphologies, such as wrinkles, folds and overlaps, were
observed as a result of the interactions between the neighboring GO sheets when
they were brought together side by side during the L–B assembly. The wrinkles,
folds, and overlaps are undesirable as they reduce the optical transparency of the
GO films [88]. For S-GO, the rigid S-GO sheets collected from the L–B assembly
were free of wrinkles, while other deposition methods, such as drop-casting, spin-
coating, and spraying, usually produced wrinkled sheets [89]. The packing den-
sity increased continuously as the surface compression increased from (a) isolated
S-GO sheets, to (b) close-packed S-GO sheets, (c) over-packed GO sheets with
folded edges, and (d) over-packed S-GO sheets with folded edges and overlapping
on top of another (Fig. 4.23) [44].
UL-GO sheets tend to be softer and more flexible than S-GO sheets due to the
large sizes ranging from a few tens to ~ 200 μm, presenting microscopic morpholo-
gies distinct from those observed in S-GO sheets depending on the pressure ap-
plied (Fig. 4.24). With increasing the surface pressure or the packing density, the
typical features varied from: (a) isolated UL-GO sheets, (b) close-packed UL-GO
sheets, (c) overlapped UL-GO sheets with some wrinkles, to (d) overlapped UL-
GO sheets with extensive wrinkles. It is worth noting that at a high surface pressure
the UL-GO sheets tended to wrinkle while the S-GO sheets were more susceptible
to overlapping. For example, the UL-GO films collected at a low surface pressure
(0 to ~ 10 mN/m) consisted of dilute, well isolated, flat individual UL-GO sheets
(Fig. 4.24a, b). The UL-GO sheets were forced to squeeze each other with increas-
ing the surface compression beyond the close-packed region, leading to overlapping
and buckling. Figure 4.24c, d shows typical graphene oxide wrinkles (GOWs) with
different degrees of wrinkling. The hydrogen bonds present between the carboxylic
acid edge groups encouraged the interactions between UL-GO edges, preventing
them from sliding and producing wrinkled UL-GO. Due to the irregularly shaped
polyhedrons with polydisperse sizes of UL-GO sheets, they would squeeze each
other from random directions, resulting in random wrinkling orientations. In view
of the fact that these wrinkles tended to be aligned along the contact lines of neigh-
boring sheets, the source of wrinkling was confirmed to be caused by buckling
developed under in-plane compression.
Different pulling speeds were found an important parameter in controlling the
degree of wrinkling. A much higher degree of wrinkling was observed at a high pull-
ing speed of 1.0 mm/min for UL-GO films, designating it “concentrated GOWs”
(CGOWs), see Fig. 4.24e, f. The L–B transfer of flat GO sheets is a self-assembly
process whose quality depends on the evaporation of water molecules trapped be-
tween the UL-GO sheets and substrate. Wrinkle-free S-GO films could be produced
(Fig. 4.23) because the S-GO allowed water to evaporate easily. However, the rela-
tively larger size of UL-GO often entrapped the water droplets between the UL-GO
sheets and the capillary force induced by water evaporation caused wrinkling of the
164 4 Improvement of Electrical Conductivity and Transparency
Fig. 4.23 SEM images of S-GO sheets collected on a Si substrate at different stages of surface
pressure. The packaging density increases from a isolated S-GO sheets, to b close-packed S-GO
sheets, c over-packed S-GO sheets with folded edges, and d over-packed S-GO sheets with over-
lapping. e and f Over-packed S-GO sheets at a high magnification. (Reprinted with permission
from [20]. Copyright (2011) by ACS)
4.4 Using UL-GO 165
Fig. 4.24 a–d SEM images of UL-GO sheets collected on a Si substrate at different stages of sur-
face pressure at a pulling speed of 0.1 mm/min. The packaging density increases from a isolated
UL-GO sheets, to b close-packed UL-GO sheets, c overlapped UL-GO sheets with some wrinkles,
and d overlapped UL-GO sheets with extensive wrinkles. e, f SEM images of UL-GO sheets at
stage d of the surface pressure curve at a pulling speed of 1.0 mm/min: concentrated GO wrinkles
(CGOWs): taken at e low and f high magnifications. (Reprinted with permission from [20]. Copy-
right (2011) by ACS)
166 4 Improvement of Electrical Conductivity and Transparency
Fig. 4.25 Schematics for the generation of concentrated graphene oxide wrinkles (CGOWs) due
to capillary forces. UL-GO ultralarge graphene oxide. (Reprinted with permission from [20].
Copyright (2011) by ACS)
sheets [90, 91]. In particular, if a high pulling speed were to be applied, there would
be too short a time for the UL-GO sheets to relax into a flat state and transfer onto
the substrate. Due to the capillary force and gravity (Fig. 4.25), the trapped water
caused wrinkling during the transfer process. This explains why the UL-GO sheets
assembled at a high pulling speed and a high surface pressure became CGOWs after
transfer.
It is reported that GO nanoribbons can be produced by plasma etching of GOWs
[92]. By accurate control of the plasma etching conditions, single- or double-layer
GO nanoribbons were obtained so that the top layers of GOWs acted as the sac-
rificial layers. The method of producing GOWs by L–B assembly offers a facile
and environment-friendly approach to prepare large-size GOs with controllable
amounts of wrinkles on their surface.
Other than using a fast pulling speed, the compression of the films can also cause
wrinkling even before deposition. Another way of controlling the GO structure in
4.4 Using UL-GO 167
Fig. 4.26 a Schematic of the formation of carbon nanoscroll (CNS)-like structures and the loose–
dense pattern during the LB process. b–d TEM b, optical microscope image c, and AFM image d
of CNS-like structures transferred onto a glass substrate. (Reprinted with permission from [87].
Copyright (2010) by Elsevier)
the L–B assembly was proposed by Gao et al. [87]. It is found that the L–B method
is a highly efficient fabrication approach for producing carbon nanoscrolls (CNSs)
using functionalized GO sheets (Fig. 4.26a). The CNSs had a tubular structure with-
out caps at its ends (Fig. 4.26b) and aligned parallel to the moving barriers of the
LB equipment, exhibiting a loose-dense pattern during the LB compression process
(Fig. 4.26c–d). A possible formation mechanism of the CNS-like structure is that the
scrolling of a GO sheet is determined by the competition between the free energy
and the elastic energy [93]. The overlapping of GO sheets decreases the free energy
while the bending increases the elastic energy. It follows then that stable CNSs can
be spontaneously formed when the van der Waals energy gain overweighs the bend-
ing energy. When moving the barriers, the functionalized GO sheets are bent due
to the compression force. Once a close-packed monolayer is formed, the edge of
GO sheets starts to scroll upon further compression. Thus, the CNS-like structure is
formed near the barriers, which expands into the center of the trough. The CNS-like
structure and bundles pack closely and align parallel to the moving barriers with the
progress of the assembly. The simultaneous formation of the CNS-like structure and
the collapse of CNS monolayer result in the loose–dense pattern.
Because CNS, GOWs, and CGOWs have no caps at their ends, it may be easier
to encapsulate functional molecules or nanomaterials in the internal cavities of GOs
than in CNTs [94, 95]. In addition, the interlayer distance of the wrinkles can also
be tailored to better accommodate the intercalants of various sizes [87]. The UL-GO
sheets with high-density wrinkles, such as CNS, GOWs, and CGOWs, are con-
sidered promising candidates for many applications, including hydrogen storage,
supercapacitors, biosensors, and nanomechanical devices. Table 4.10 summarizes
168 4 Improvement of Electrical Conductivity and Transparency
Table 4.10 Various GO structures obtained at different pulling speeds and surface pressures [20, 87]
Type of GO Pulling speed Surface pressure Structure Potential applications
(mm/min) (mN/m)
S-GO 0.1–1.0 Any Flat GO Nanoelectronic devices
UL-GO 0.1 0–15 Flat GO Micro- and Nanoelec-
tronic devices
UL-GO 0.1 > 20 GOWs Fabrication of GO
nanoribbons
UL-GO 1.0 > 20 CGOWs Hydrogen stor-
age, microcircuit
interconnects
Functionalized 0.1–1.0 ~ 50 CNSs Field effect transistors,
GO biosensors, and nanome-
chanical devices
GO graphene oxide, UL-GO ultralarge graphene oxide, GOWs graphene oxide wrinkles, CGOWs
concentrated graphene oxide wrinkles, CNSs carbon nanoscrolls
various GO structures that can be obtained by varying pulling speeds and surface
pressures, along with their potential applications.
Surface Morphology
The electrostatic repulsion between the ionized carboxylic and phenol hydroxyl
groups facilitate the formation of GO colloidal solution in water [96]. When the
second GO layer is deposited on top of the first layer, these two layers are likely
to experience both electrostatic repulsion and van der Waals attraction. It should
be noted that the scaling law of van der Waals potential versus separation depends
on the geometry of the interaction bodies [43]. When the GO sheets are brought
together in a face-to-face manner, they can be treated as two parallel plane and their
van der Waals potential then scales with (1/d2), where d is the distance between the
two GO sheets. Besides van der Waals force, the residual π-conjugated domains
can also contribute to the attraction between the GO sheets. These attractive forces
dominate and lead to successful LbL deposition of GO sheets. However, the elec-
trostatic repulsion that GO sheets experience from both their neighbors and those
already deposited can cause wrinkling. Since the substrate is no longer flat due to
the presence of GO sheets deposited previously, wrinkling becomes serious when
depositing a large number of layers [43].
Figure 4.27 shows the typical surface morphologies of as prepared UL-GO and
rUL-GO films after thermal treatment on a quartz substrate. The corresponding ar-
ithmetical mean roughness, root mean square roughness, and peak-to-peak rough-
ness values are summarized in Fig. 4.28a–c, while the thicknesses of the depos-
ited UL-GO films measured using atomic force microscopy (AFM) are plotted in
Fig. 4.28d. It is noted that the surface roughness of both films increased consistently
4.4 Using UL-GO 169
Fig. 4.27 AFM images of UL-GO films consisting of two layers a, b and eight layers c, d of
monolayer GO sheets taken before a, c and after thermal treatment b, d. (Reprinted with permis-
sion from [20]. Copyright (2011) by ACS)
with increasing the number of GO layers. Instead of a linear increase, the parabolic
increase may indicate that the wrinkles have been accumulated after the deposi-
tion of each GO layer deteriorating the flatness of the films. The surface roughness
was consistently reduced after the thermal treatment which removed oxygenated
functional groups and graphitization of the films [17, 97]. Although the wrinkles
and defects cannot be completely removed after thermal treatment, the surface
roughness of the films produced by L–B assembly was much lower than the films
produced by other techniques. It is interesting to note that the average thickness of
the films made from one layer of UL-GO was ~ 1.9 nm, which is about 50 % larger
than the literature value [98, 99]. This observation is not surprising because the
corresponding roughness of the film was about 1 nm due to wrinkling of UL-GO
sheets [20].
The effects of substrate material on UL-GO film morphology and surface rough-
ness were also investigated [86]. To study the morphology of UL-GO on a soft sub-
strate, such as PET, the substrate surface needs to be made hydrophilic for proper
wetting to take place by water and efficient deposition of UL-GO. One effective way
170 4 Improvement of Electrical Conductivity and Transparency
5D QP
U8/*2
of a arithmetical mean, Ra;
b root mean square, Rq; c
peak-to-peak roughness, Rpp;
and d film thickness as a
function of number of layers. b
5T QP
(Reprinted with permission
from [20]. Copyright (2011)
by ACS)
c
5SS QP
7KLFNQHVV QP
d
1XPEHURIOD\HUV
to modify the PET surface is using oxygen plasma, for enhanced hydrophilicity of
PET. Figure 4.29a shows the contact angles and the AFM images of the PET substrate
surfaces obtained at different stages. It is found that the oxygen plasma treatment en-
hanced the hydrophilicity of the PET substrate, reducing the contact angle from 69
to 22°. The oxidation effect during the oxygen plasma treatment process endowed
the PET surface with moieties of polar groups, which in turn reduced the C/O ratio
while increasing the surface energy. Once a UL-GO layer was deposited on the PET
substrate, the contact angle increased notably from 22° to 74.5°, due mainly to the
amphiphilic GO sheets that had both hydrophilic groups (–COOH, –OH, and C = O)
and hydrophobic (C–C, C–H) groups. The contact angle increased to 103.2° after HI
reduction due to the removal of the oxygenated groups, and dropped back to 83.5°
after the chemical doping with HNO3 and SOCl2 introducing of new functionalities.
Figure 4.29b summarizes the corresponding thickness and mean roughness val-
ues of the UL-GO films on the PET substrate. Similar to UL-GO films on the quartz
substrate, the average thickness of the film increased with increasing the number
of GO layers. It is worth noting that the initially very high roughness of the film
rapidly decreased with the increasing number of layers due possibly to the flattened
PET substrate surface on the microscopic scale. From the AFM images shown in
Fig. 4.29a, it is seen that the sharp peaks were removed by the deformation caused
by the attractive forces between the hydrophilic PET surface and the amphiphilic
UL-GO sheets. The larger the number of UL-GO layers, the larger the deformation
and the more flattening of the sharp peaks, which helped mitigate the overall sur-
face roughness [86].
4.4 Using UL-GO 171
Figure 4.30 shows the comparison of optical and electrical properties of UL-GO
films with different numbers of layer obtained at different stages of treatment. As
expected, a thicker film resulted in a higher degree of absorption of light and thus
a lower transparency at all treatment stages (Fig. 4.30a). The transparency was sig-
172 4 Improvement of Electrical Conductivity and Transparency
Fig. 4.30 Optoelectrical properties of L–B assembled ultralarge graphene oxide (UL-GO) films.
a Comparison of optical and electrical properties between UL-GO films of different numbers of
layers taken at different stages of treatment (transmittance measured at 550 nm wavelength). b
Sheet resistance at different stages. c Sheet resistance and transmittance measured at 550 nm for
transparent conductors consisting of rS-GO, rUL-GO, and C-rUL-GO. (Reprinted with permission
from [20]. Copyright (2011) by ACS)
nificantly deteriorated after the thermal treatment due to the reduction of GO and
the adsorption of impurity particles on the other side of quartz substrates, while part
of the lost transparency was restored after the chemical treatments [17]. However,
the removal of these impurities after acid treatment contributed to the improvement
of transparency. There appeared to be a strong interaction between the rUL-GO and
quartz substrate after thermal treatment arising from the graphitization effect of the
high-temperature annealing. After the thermal treatment, the sheet resistance of the
rUL-GO films was in the range of 277–605 Ω/sq for film thickness 3.7–18.5 nm
(Fig. 4.30b). The sheet resistance was further reduced by 30–50 % to 197–459 Ω/sq
after the chemical treatments.
To evaluate whether these properties remained stable, which is critical for practi-
cal applications [15], the sheet resistance of the chemically doped, reduced ultra-
large graphene oxide (C-rUL-GO) film was measured after 4 months of exposure
to ambient air (Fig. 4.30b). It was found that the sheet resistance increased by about
10–30 % after exposure depending on the film thickness. The loss of ameliorating
chloride functional groups I was mainly responsible for the degradation of the elec-
References 173
trical conductivity. Because the acyl chloride groups were reactive with water, it was
likely that the functional groups doped on the graphene film may have reacted with
moisture present in air during ageing. Employing a protective coating could reduce
the possibility of decomposition and thus retain the improved electrical conductiv-
ity [29]. The sheet resistance values are compared between the films made from
GO sheets of two different sizes using the same processing conditions, as shown in
Fig. 4.30c. The rUL-GO sheets showed a much lower sheet resistance than the rS-
GO sheets, by a remarkable one order of magnitude, for a given transmittance of the
films. The reduced number of intersheet tunneling barriers in a continuous rUL-GO
film because of the large area of GO sheets was responsible for this observation [1].
References
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Chapter 5
Application of Graphene-Based Transparent
Conductors (TCs)
5.1 Introduction
As graphene has several potential advantages over indium tin oxide (ITO) including
weight, robustness , flexibility, chemical stability, and cost, many applications, such
as touch panels, displays, solar cells, organic light-emitting diode, transistors and
other new areas, have been demonstrated [1]. Although the application of graphene
for transparent conductors (TCs) is still in its early stage and the performances of
some devices presented in this book are in a preoptimized state, the unique func-
tional characteristics can make graphene a strong candidate to replace the currently
commercially dominant TC materials [2]. These devices, with their functional,
structural, and mechanical requirements, where graphene has been considered to
apply are discussed in this chapter.
5.2 Touch Screen
A touch screen is an electronic visual display that detects the presence and location
of a touch [2]. A variety of touch-screen technologies, such as resistive, surface
acoustic wave, capacitive, surface capacitance, projected capacitance, has been de-
veloped [3]. The most commonly used touch screens are the resistive and capacitive
types, which require a sheet resistance of ~ 300–1500 Ω/sq at a transparency of
~ 86–90 % [4]. Graphene has several advantages including flexibility, wear resis-
tance, chemical durability, and low toxicity (Fig. 5.1a–b) compared to the tradi-
tional ITO. Based on the successful fabrication of graphene films, with outstanding
sheet resistance and transparency, and a large size of tens of centimeters, Bae et al.
[5] incorporated them into touch-screen panel devices (Fig. 5.1b). It is revealed that
the touch-screen display made from graphene outperformed that of ITO in terms
of the applied strain. The former touch screen could handle twice as much strain as
conventional ITO-based devices (Fig. 5.1c) [5]. The graphene-based panel resisted
up to 6 % strain, which is limited mainly by the silver electrode and not by graphene
itself, while the ITO-based touch panel easily broke at just 2–3 % strain.
© Springer Science+Business Media New York 2015 179
Q. Zheng, J.-K. Kim, Graphene for Transparent Conductors,
DOI 10.1007/978-1-4939-2769-2_5
180 5 Application of Graphene-Based Transparent Conductors (TCs)
Fig. 5.1 a Structure of graphene-based resistive-type touch screen [6]. b Image of flexible touch
screen based on graphene films. c Electromechanical properties of graphene-based touch-screen
devices compared with ITO/PET electrodes in tension. The inset shows the resistance change with
compressive and tensile strains applied to the upper and lower graphene/PET panels, respectively [5]
5.3 Displays 181
5.3 Displays
Nearly 1.7 billion display device panels are produced annually [4] as major compo-
nents for mobile phones, televisions, laptops, desktops, machine interfaces, moni-
tors, etc. Transparent electrodes have critical functions in display devices, such as
liquid crystal displays (LCD) and light-emitting diode (LED) [4] and the functions
in these displace devices are discussed as follows.
An LCD is a thin, flat electronic visual display, which consists of thin films of opti-
cally transparent polymers with micrometer-sized liquid crystal (LC) droplets placed
within the pores of the polymer [7]. Due to its ability to switch from translucence to
opacity, the LCD has become an attractive material for display applications. Although
ITO was the conventional transparent conductive film (TCF) material to apply the
electric field across the LCD, the development was hindered by its instability and
poor flexibility. Blake et al. [8] demonstrated LCDs with electrodes made of graphene
that showed excellent performance with a high contrast ratio. Figure 5.2a shows the
schematic diagram of LCDs fabricated with mechanically exfoliated monolayer gra-
phene. Planar-aligned LCDs were fabricated using graphene-on-glass films, which
were first located using an optical microscope (Fig. 5.2f, g) and then were further
identified as monolayer graphene using Raman microscopy. The LC director was re-
oriented by applying an AC (square-wave) voltage across the cells. By placing an op-
tical microscope between the crossed polarizers while keeping the rubbing direction
oriented 45° with respect to the polarizers, the electro-optic properties were observed.
As shown in Fig. 5.2b–e, i, a strong change in the transmission was observed both
in white and monochromatic lights above the expected threshold voltage of around
0.9 Vrms. Figure 5.2h shows a control sample with an opening in the metallization (Cr/
Au) not covered by graphene. It is suggested that the graphene had no negative effect
on LC alignment because the whole graphene electrode area changed uniformly. The
contrast ratio was better than 100 under white light, showing that graphene could in-
deed function as a transparent electrode for LCDs [8]. In addition, graphene showed
additional advantages of chemical stability and mechanical flexibility [7].
5.3.2 Light-Emitting Diodes
LEDs have received great interests as they can be used in many areas such as flash-
lights, traffic signals, and text and video displays [7]. It is expected that both the
LED TV and LED backlights market will grow steadily in the future. ITO has been
the dominant material for LED applications. However, the price fluctuations and
its ceramic nature have greatly limited the future development. Novel TCF mate-
rial with outstanding optoelectrical and mechanical properties is urgently needed
182 5 Application of Graphene-Based Transparent Conductors (TCs)
Fig. 5.3 a Processes of batch fabrication of GaN-based LEDs with patterned MLG electrodes; b
schematic cross-sectional view of GaN-based LED structure with a transparent MLG electrode;
and c–f optical micrographs of GaN LEDs with transparent MLG electrodes. c Large-area pat-
terned multiple LED devices and d an individual LED. e LED with tip probes attached before
applying the input current and f after applying an input current of 100 μA [9]
to replace ITO in LED devices. It was recently demonstrated that patterned multi-
layer graphene (MLG) could be used for a large-scale fabrication of GaN LEDs [9].
Figure 5.3a shows the fabrication process of the LED devices with MLG electrodes
where the chemical vapor deposition (CVD)-synthesized graphene film was used
as a top anode for GaN LEDs. Figure 5.3b shows the schematic cross-sectional
view of the LED, which consists of an MLG anode, an active luminescent layer (p-
GaN/multiple quantum wells (MQW)/n-GaN), a Cr/Au cathode, undoped GaN, and
the sapphire substrate. Figure 5.3c–d presents large-scale, batch-processed multiple
devices with patterned MLG electrodes. The optical micrographs of an MLG elec-
trode LED before (Fig. 5.3e) and after (Fig. 5.3f) applying an input current show
that blue light emission is clearly visible even at a low input current of 100 μA [9].
Graphene thin films were used as transparent electrodes for organic light-emitting
diodes (OLEDs) [10]. It is shown that the electrical and optical performance of a
small molecule OLED on graphene was similar to that of control devices on an
ITO, although there were marked differences in total thickness of the optical stack.
It is believed that graphene is a viable alternative to ITO [10, 11], while further
184 5 Application of Graphene-Based Transparent Conductors (TCs)
5.4 Solar Cells
Many kinds of graphene-based solar cells, including dye-sensitized solar cells [12],
organic bulk-heterojunction (BHJ) photovoltaic cells [13], hybrid ZnO/poly(3-hexyl-
thiophene) (P3HT) solar cells [14], Si Schottky junction solar cells [15], and InGaN
p–i–n solar cells [16], have been developed recently [7]. One important advantage
of graphene-based solar cell is that graphene can be used for flexible photovoltaic
device applications. Arco et al. [17] demonstrated a feasible, scalable, and an effec-
tive method to employ CVD-grown graphene as a highly transparent, continuous,
and flexible electrode for organic photovoltaic (OPV) cells. As shown in Fig. 5.4a,
graphene films were synthesized by CVD and transferred to transparent substrates.
The TCFs were then evaluated in organic solar cell heterojunctions (TCE/poly-3,4-
ethylenedioxythiophene:poly styrenesulfonate (PEDOT:PSS)/copper phthalocya-
nine/fullerene/bathocuproine/aluminum). The key to success was the continuous
nature of the CVD graphene films. The comparison study shows that graphene offers
comparable performance with ITO. Graphene solar cells demonstrated an outstand-
ing capability to operate under bending conditions up to 138°, whereas the ITO-
based devices displayed cracks and irreversible failure with 60° bending [17].
A major challenge to successful implementation in these applications is the
difficulty to effectively separate photogenerated electron–hole pairs and transfer
the separated charge carriers to the electrodes [7]. Graphene-based materials have
shown controllable surface and interfacial properties as well as tailored work func-
tions via functionalization during synthesis and/or posttreatment [7, 18, 19]. Be-
cause the potential created by the different work functions helps to separate the
exciton pairs, it is important to facilitate better transport of charge carriers to each
electrode, which can be achieved by an additional functional layer [19]. Choe et al.
[13] reported the application of MLG films grown by the CVD method to OVP
cells. Figure 5.4b shows the device structure of a photovoltaic cell with graphene as
a transparent and conducting electrode. The cross-sectional transverse electromag-
netic mode (TEM) image of the photovoltaic cell (Fig. 5.4c) presents distinctive
interfaces formed between the layers of the individual components. It is shown that
the optimized cell structure with an inserted TiOX layer enhanced the power conver-
sion efficiency up to 2.58 ± 0.45 % (Fig. 5.4d–e).
5.5 Transistors
Since graphene has rapidly evolved from the exclusive domain of condensed-matter
physicists to explore by pioneers in a variety of scientific and engineering commu-
nities, graphene-based transistors have attracted much interest [20]. It is well known
that graphene is now considered as an option for post-silicon electronics. Due to
5.5 Transistors 185
Fig. 5.4 a Implementation of continuous, highly flexible, and transparent graphene films obtained
by CVD as transparent conductive electrodes (TCE) in OVP cells [17]. b Schematic diagram of
photovoltaic device structure with MLG electrodes and a hole-blocking TiOX layer. c TEM cross-
sectional image of a photovoltaic device. The insets show HRTEM images near the TiOX layer
( top) and near the MLG films ( bottom). d J–V curves of photovoltaic devices with 1000 °C-grown
MLG electrodes ( circles) and with ITO electrodes ( diamonds). The curves without TiOX layer
( filled symbols) are compared to the ones with TiOX layer ( open symbols). e PCEs for graphene-
electrode photovoltaic devices in comparison with those for the ITO-electrode photovoltaic
devices with and without TiOX layers (pristine) [13] PCE Power conversion efficiency. (Reprinted
with permission from [13, 17]. Copyright (2010) by Elsevier and ACS)
Fig. 5.5 a Schematic illustration of the fabrication of OFETs with patterned graphene electrodes. b
Transfer characteristics of pentacene-based OFETs with graphene and Ag electrodes. c Transfer char-
acteristics of pentacene-based OFETs with graphene and Cu electrodes [21]. d Schematic illustration
of the approach to fabricate patterned graphene electrodes [25]. e Structure of the CuPc monolayer
transistor device with metal electrodes protected by a 50 nm layer of silicon dioxide [23]. f OM and
5.6 Other Applications 187
5.6 Other Applications
AFM images of a representative device. The average thickness of a monolayer graphene is ~ 0.8 nm,
and the gap size between the graphene ends is ~ 100 nm. Inset is the height profile across the nanogap
[24]. (Reprinted with permission from [21, 23, 24, 25]. Copyright (2008, 2010, 2009) by Wiley)
188 5 Application of Graphene-Based Transparent Conductors (TCs)
and human body. Due to the light weight, resistance to corrosion, flexibility, and
processing advantages, electrically conducting composites have become popular to
replace conventional metal-based EMI shielding materials [28, 29]. Graphene is an
excellent choice for high-performance EMI shielding in the form of either sheets
[26], papers [30–32], polymer-based composites, or coatings [33–36] because of
its high conductivity, saturation velocity, flexibility, and mechanical strength [37].
Monolayer graphene prepared by the CVD method was found able to serve as an
ultrathin, transparent, weightless, and flexible EMI shield [26]. The measurement
setup for the EMI shielding effectiveness (SE) of monolayer graphene is shown in
Fig. 5.6a–b. The results show that the monolayer CVD graphene has an average SE
value of 2.27 dB, corresponding to ~ 40 % shielding of incident waves (Fig. 5.6c),
while the defective graphene provided almost no shielding effect (Fig. 5.6d). It
is suggested that manufacturing an ultrathin, transparent, weightless, and flexible
EMI shield by a single or a few atomic layers of graphene would be tremendously
important for portable electronic devices, transparent electronics and displays, au-
tomobiles, and EM field isolation in 3D ICs [26]. It was also demonstrated that
patterned graphene/insulator stacks could be used as tunable far-infrared notch fil-
ters (Fig. 5.6e–f), which could lead to the development of transparent mid- and
far-infrared photonic devices such as detectors, modulators, and three-dimensional
metal material systems [37].
Freestanding graphene papers also show excellent and specific EMI SE [30–32].
Gupta et al. [31] demonstrated that MnO2 decorated graphene nanoribbons (GNRs)
in paper form possessed outstanding microwave shielding properties. MnO2 in
GNRs effectively enhanced the electronic polarization, interfacial polarization,
and anisotropy energy in the presence of microwaves. A maximum SE of − 57 dB
in the Ku band, that is, 12–18 GHz, was achieved for a 3.0-mm-thick sample. By
using nickel pellet as a catalyst template during the CVD synthesis, Zhang et al.
[32] developed a polymer-free process for synthesis of three-dimensional graphene
structures and graphene papers. The obtained graphene papers with thickness below
100 µm already showed excellent EMI SE. For example, the graphene paper with
thickness of 50 µm showed 60 dB EMI SE.
Recently, efforts have also been made for the development of high-performance
EMI shielding graphene/polymer nanocomposite materials [33–36]. For example,
Chen et al. [36] developed a graphene/poly(dimethyl siloxane) (PDMS) foam com-
posite. As shown in Fig. 5.7a–b, the fabricated graphene/PDMS foam composite
is lightweight, flexible, and highly porous. The results show that its SE is as high
as 30 dB in the 30 MHz–1.5 GHz frequency range and 20 dB in the X-band fre-
quency range. Kim’s group [35] in HKUST further found that self-aligned rGO/
epoxy nanocomposites (Fig. 5.7c) with highly anisotropic mechanical and electri-
cal properties present high-performance EMI shielding with a remarkable shield-
ing efficiency of 38 dB. It is proposed that the relatively high shielding efficiency
is associated with two unique features of the composites: namely, (i) the aligned
rGO sheets contributed positively to shield the electromagnetic waves that emanate
through the thickness direction (Fig. 5.7d), and (ii) the capability of absorbing the
5.6 Other Applications 189
Fig. 5.6 Schematic drawings of the measurement setup for the electromagnetic interference shield-
ing effectiveness of graphene. a Waveguide measurement system (frequency range: 2.2–7 GHz)
with two waveguide-to-coaxial adapters and a vector network analyzer. b Measurement setup
using a horn antenna, a TEM cell, and a vector network analyzer. The SE, absorbance loss (AL),
and reflectance loss (RL) of c a monolayer graphene, and d defective graphene [26]. e Extinc-
tion in transmission, 1-T/T0, using a single layer of unpatterned graphene in the far-infrared and
terahertz wavelength range for undoped graphene on quartz without ( gray squares) and with ( red
squares) the polymer buffer layer underneath, and for doped graphene on quartz with the polymer
buffer layer ( green squares). Solid lines are corresponding fitted curves. Inset: schematic of the
measurement. f Fitted Drude weight and scattering width as a function of graphene layer number
in the stacked devices [37]
190 5 Application of Graphene-Based Transparent Conductors (TCs)
incidental electromagnetic waves by polarization in the electric field due to the high
charge storage capacities of the rGO/epoxy composites [35].
5.6.2 Functional Glasses
Most functional glass products would not have the desired functional properties
without proper coatings. The unique properties of graphene offer the opportuni-
ties for improving functionalities of glass. Nowadays, graphene/glass defoggers
(Fig. 5.8a) are fabricated, revealing that the graphene-based heating system has
a better heating efficiency in term of temperature vs. power density than any
other existing heating systems [38]. Figure 5.8b shows the assembly process of a
graphene/glass defogger. The results show that the graphene/glass defoggers had
(with different power densities). d Saturated temperature vs. electrical power density of graphene
and Cr thin-film defoggers. e Schematics of direct scattering, trapping–desorption process of ambi-
ent gases and thermal energy transfer between molecules and electrode surface for graphene and
Cr thin-film defoggers [38]. f Schematic diagram of extremely rapid growth process on glass sub-
strates at a low temperature without using metal catalyst. g Optical images of graphene-like carbon
based films with different thicknesses obtained for different growing periods [40]
5.6 Other Applications 191
Fig. 5.8 a Schematic of heat transfer in a graphene defogger, showing substrates and expected tem-
perature profile over the cross-section. b Layer-by-layer (LbL) transfer process of graphene on to
glass substrate. c Temperature profile of two defoggers reaching the similar saturated temperature
192 5 Application of Graphene-Based Transparent Conductors (TCs)
shorter response times and higher saturated temperatures than Cr/glass defoggers
(Fig. 5.8c–d), which can be explained by the competition between direct scattering
and trapping–desorption of ambient gases (Fig. 5.8e) [39]. Because the adsorption
energies of ambient gases like O2, N2, and H2O in graphene are relatively low, the
thermal accommodation coefficient is also low. The novel interfacial property opens
a new possibility for a variety of flexible and transparent heating systems, such as
outdoor displays and vehicle front-window defrosters and defoggers [38]. It is also
reported that transparent and conductive graphene-like carbon films were deposited
on a glass substrate at a low temperature by a fast and noncatalytic growth method,
see Fig. 5.8f, g [40]. The fabrication process is extremely rapid and performed on a
2 in. wide scale dielectric substrate at a relatively low temperature (< 550 °C) with-
out using a metal catalyst, so that the damaging and expensive transfer processes of
graphene-based films could be avoided, making it compatible with current fabrica-
tion technologies [40].
5.6.3 Transparent Loudspeakers
Since the invention of loudspeaker more than a century ago, many kinds of loud-
speakers have been proposed and commercialized [41]. The next generation display
devices require transparent and flexible loudspeakers for new audio environments.
Because graphene is electrically conducting and has a low mass density, it is an
ideal building material for small, efficient, high-quality broad-band audio speakers
[42, 43]. Xu et al. fabricated graphene-based loudspeakers by transferring the gra-
phene film on the PVDF piezoelectric film [44], demonstrating that the graphene-
based loudspeaker could be a practical magnet-free loudspeaker by simply apply-
ing an audio frequency field through it. Compared with the commercial thin-film
speakers, graphene-based film loudspeakers can generate sound with a wide fre-
quency range, a high sound pressure level (SPL) and low total harmonic distortion
(THD), and has much less power consumption [44]. Especially, it is transparent
and superior to those made from commercial films such as aluminum-based films.
Figure 5.9a shows the structure and the sound generation mechanism of a graphene-
based PVDF thin-film speaker. Once a time variable voltage is applied to the gra-
phene electrodes, an audio frequency vibration on the PVDF piezoelectric film is
produced by the attractive and repulsive forces between the internal charges as the
external field varies. A photograph of the graphene-film loudspeaker is shown in
Fig. 5.9b. This kind of transparent and flexible film loudspeakers has wide potential
applications, especially in transparent and flexible devices [44].
5.6.4 Transparent Heaters
Fig. 5.9 a Schematic illustration of the structure and function. b Photograph of a graphene-based
thin-film loudspeaker connected to the sound source and amplifier. (Reprinted with permission
from [44]. Copyright (2013) by AIP)
flexible film heaters have attracted growing interest [45, 46]. Although ITO has
been widely used to prepare transparent heating films, the drawbacks of ITO,
including limited availability of indium, intolerance to acid or base and fragil-
ity under mechanical bending, limit its future applications [12]. The exceptional
optoelectrical and thermal properties of graphene offer many advantages for pro-
ducing transparent heaters [47]. It is suggested that the CVD-grown large-scale
graphene films could be used for the fabrication of transparent heaters [45, 47]. As
illustrated in Fig. 5.10a, graphene films were placed on a polyethylene terephthalate
(PET) substrate and the copper layer was used to enhance the contact with graphene
at the edges. Figure 5.10b–c shows the fabricated graphene-based heater, indicating
the highly transparent and flexible nature. The time-dependent temperature results
194 5 Application of Graphene-Based Transparent Conductors (TCs)
Fig. 5.10 a A schematic structure of a transparent, flexible graphene heater combined with a plas-
tic substrate and Cu electrodes. b An optical image of the assembled graphene-based heater show-
ing its outstanding flexibility. c An infrared picture of the assembled graphene-based heater while
applying an input voltage under bending conditions. d Temperature profiles of graphene-based
heaters with two different doping agents and an ITO-based heater measured using an infrared scan-
ner. e Mechanical stability test results of the graphene-based heater. (Reprinted with permission
from [47]. Copyright (2011) by ACS)
(Fig. 5.10d) show that the graphene-based heater had a faster heating rate and a
more homogeneous temperature distribution than the ITO-based heater. Due to the
flexibility of graphene-based heater (Fig. 5.10e), it can be used on a curved window
surface or a rollable screen [47].
5.6.5 Transparent Actuators
FLG-driven actuator captured by the digital single lens reflex (DSLR) camera in the states of volt-
age e “OFF” and f “ON”. The manuscript images through the FLG-driven actuator is compared in
g and h, each corresponding to the voltage “OFF” and “ON,” respectively [51]
5.6 Other Applications 195
Fig. 5.11 a Operating principle of graphene-based actuator. b Displacement of the actuator based
on three-layer graphene electrodes. The actuator is maintained for 10 s per single voltage level from
0.3 to 3.0 kV as a sine wave of frequency 0.5 Hz. c Performance of the actuator when the input
voltage is applied from 0 to 3 kV [50]. d Preparation of FLG-driven actuator. e–h Photographs of
196 5 Application of Graphene-Based Transparent Conductors (TCs)
graphene-based actuator was able to generate the motion along the thickness direc-
tion while it has outstanding durability and robustness. At a frequency of 0.5 Hz
in a button-like motion, the high displacement of 1050 µm was achieved for a
100-µm-thick graphen-based actuator (Fig. 5.11b–c). In addition, it is shown that
the graphene-based actuator could still work well even under 25 % stretching while
preserving its electrical and mechanical properties. It is suggested that the gra-
phene-based actuator could be used for functional touch-screen panel devices [50].
Hwang et al. [51] also fabricated a transparent dielectric elastomer actuator driven
by few-layer-graphene (FLG) electrode. The silicone elastomer substrate was sand-
wiched between the two layers of FLG electrodes to form the transparent actuator,
see Fig. 5.11d. The FLG-driven actuator had an optical transparency of over 57 % at
a wavenumber of 600 nm, and produced bending displacement performance rang-
ing from 29 to 946 µm as functions of frequency and voltage, demonstrating its
application feasibility in variable focus lens and opto-electro-mechanical devices,
see Fig. 5.11e–h [51].
5.6.6 Transparent Sensors
Sensors are essential components of many electronic and optoelectronic devices, and
if these sensors are made transparent, they could lead to the development of skin-
like multifunctional sensors [52]. Due to the excellent stretchability and transparen-
cy, graphene is an excellent candidate to realize a new class of human-interface de-
vices [53, 54]. Bae et al. [54] demonstrated a graphene-based strain sensor that was
capable of monitoring the motion of body parts. As shown in Fig. 5.12a, graphene-
based transparent strain sensors were fabricated on a flexible plastic or stretchable
rubber substrate using reactive ion etching and stamping techniques. Figure 5.12b
shows a rosette gauge of graphene fabricated on a thinner PDMS substrate. The
graphene strain sensor had high transparencies of 75–80 % over wavelengths rang-
ing 400–700 nm, see Fig. 5.12c. A motorized tensile machine (Fig. 5.12d) was used
to apply an uniaxial tensile strain to a thin-film material so that the piezoresistive
properties of the graphene strain sensors were investigated in tension. The presence
of a strong van der Waals force between graphene and the PDMS substrate allowed
the same strain level in graphene as in the PDMS film. The measurement results
(Fig. 5.12e) indicate a nonmonotonic resistance change against tensile strain up to
7.1 %, attributed to the presence of defects, disorders, and micro-cracks in graphene
[54]. It is also demonstrated that the transparent rosette gauge on a stretchable and
wearable hand glove was able to detect the bending motion of a finger.
Graphene woven fabrics (GWFs) were utilized to design highly sensitive strain
sensors for human motion monitoring [52]. GWFs were obtained by atmospheric-
pressure CVD growth on crisscross copper meshes, as shown in Fig. 5.13a. After
the copper meshes were etched away in FeCl3/HCl solution, GWFs were transferred
to a composite film consisting of a medical tape and PDMS. The GWF/PDMS/tape
was dried and connected to silver wires with silver paste on both ends to obtain
5.6 Other Applications 197
Fig. 5.12 a Schematic representation of various steps in fabrication process; b transparent gra-
phene strain sensor; c transmittance spectrum for wavelength ranging 400–700 nm and Raman
spectrum of graphene film (inset); d graphene strain sensor fixed in motion controller under
stretching test, and the initial distance (~ 0 %) and final distance (~ 7.1 %) between the two fixed
points (inset), and e variation of resistance with respect to stretching up to ~ 7.1 % of graphene
strain sensor. (Reprinted with permission from [54]. Copyright (2013) by Elsevier)
the final GWF strain sensor. The assembled transparent sensor exhibited relatively
good sensitivity to follow human skin deformation (Fig. 5.13b). Its relative resis-
tance change could be 10 times at 2 % strain or 104 times at 8 % strain, and also
could be 0.07 time at 2 % strain depending on deformation strain which was formed
by the motions, and these values are large enough for ordinary instruments to detect
the motion signals (Fig. 5.13c). Weak motions were chosen to test the resistance
change, including hand clenching, phonation, expression change, blink, breath, and
198 5 Application of Graphene-Based Transparent Conductors (TCs)
Fig. 5.13 Transparent graphene strain sensors for human motion monitoring: a schematic illustra-
tions of fabrication procedure of a human motion sensor based on GWF/PDMS/medical tape film;
b images of GWF/PDMS/tape at various positions; and c relative change of resistance between 0
and 2 % strain. (Reprinted with permission from [55]. Copyright (2014) by Wiley)
pulse. Due to the distinctive features of high sensitivity and reversible extensibility,
the transparent GWF-based piezoresistive sensors can find wide potential applica-
tions, such as robotics, fatigue detection, and body monitoring [55].
5.6.7 Transparent Supercapacitors
The high specific surface area, excellent chemical stability, and outstanding electri-
cal conductivities make graphene an ideal material for the next generation energy
storage devices [56]. Stretchable and transparent supercapacitors with highly stable
performance can open up new possibilities for multifunctional applications of elec-
tronics in various energy, biomedical, and wearable optoelectronic systems [57].
However, most of the existing electrodes are either brittle (e.g., ITO), or with poor
transparency (e.g., conducting polymers) [57]. Graphene films that are optically
5.6 Other Applications 199
graphene films produced by vacuum filtration had high optical transparencies and
homogeneous morphology, see Figs. 5.14a–c. For the film of ~ 25 nm in thickness,
a specific capacitance of 135 F/g was obtained at a transmittance of ~ 70 %. Trans-
parent and stretchable graphene-based supercapacitors were also developed by
Chen et al. [57] where wrinkled graphene (WE) films were stretched to avoid the
reduction in electrical conductivity. As shown in Fig. 5.14d–g, highly transparent
(up to 60 % at 550 nm) and stretchable multilayer WE sheets were transferred onto
a polydimethylsiloxane (PDMS) substrate. The WE films were used as both the
current collector and active electrodes, which showed high transparency of 57 %
and flexibility of up to 40 % strain. Even after the films were stretched to 40 %
strain, their capacitance–voltage (CV) profiles and charge/discharge performance
(Fig. 5.14h) as well as the specific capacitance (Fig. 5.14i) were almost unchanged.
The mechanical cycleability was also measured by stretch/unloading tests of 40 %
strain for over 100 cycles (Fig. 5.14j–k). Both the CV curves and charge/discharge
characteristics remained almost unchanged, confirming highly stretchable and me-
chanically durable graphene-based transparent supercapacitors [57].
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Chapter 6
Conclusions and Perspectives
Table 6.1 Comparison of optoelectrical properties of graphene- and graphene oxide (GO)-based
TCFs collected from representative references. (Reprinted with permission from [2]. Copyright
(2014) by Elsevier)
Fabrication Comments Rs (Ω/sq) T (%) σ DC / σ OP References
method/film
type
CVD Ni substrate 1000 90 3.48 Reina et al. [4]
Ni substrate 280 80 5.70 Kim et al. [3]
Ni substrate 1350 91 2.89 Wang et al. [7]
Cu substrate 350 90 9.96 Li et al. [8]
Cu substrate 200 85 11.1 Cai et al. [9]
L–B deposition Expandable graphite, 1.5 × 105 92 0.03 Li et al. [10]
exfoliated with DMF
High temperature 4.0 × 106 95 0.0018 Kim et al. [11]
annealing
Electrophoretic GO films are electro- 4.59 × 104 83.8 0.044 Ishikawa et al. [12]
depostion chemically reduced
during EPD
Transfer High temperature 6848 82 0.27 Wang et al. [13]
printing annealing
Chemical reduction 3.0 × 104 80 0.05 Liu et al. [14]
Chemical reduction 3500 85 0.64 Mattevi et al. [15]
+ high temperature
annealing
Chemical reduction 1.0 × 105 65 0.008 Eda et al. [16]
+ high temperature
annealing
Chemical reduction 7.0 × 104 65 0.011 Eda et al. [17]
+ high temperature
annealing
Graphite, exfoliated in 2000 75 0.61 Green et al. [18]
sodium cholate solution
Spin coating High temperature 1000 80 1.60 Becerril et al. [19]
annealing
High temperature 800 82 2.26 Wu et al. [20]
annealing
High temperature 5000 80 0.32 Wu et al. [21]
annealing
High temperature 1750 70 0.55 Liang et al. [22]
annealing
Spray coating Graphite exfoliated with 5000 90 0.697 Blake et al. [23]
DMF
Dip coating Chemical reduction 1000 85 2.23 Zhao et al. [24]
Chemical reduction 1.1 × 10 4
87 0.23 Zhu et al. [25]
High temperature 1800 70 0.54 Wang et al. [26]
annealing
High temperature 8000 70 0.12 Zhao et al. [27]
annealing
Chemical reduction 11 × 106 95 0.0007 Kim et al. [28]
+ high temperature
annealing
Conclusions and Perspectives 207
with halogen elements [3–6], the complex and expensive transfer process of gra-
phene limits their large scale applications. For example, the CVD method usually
requires specific substrate materials, such as copper and nickel, which have to be
etched away after the graphene growth. The high cost of the metal substrates, the
ultrahigh vacuum conditions necessary for the CVD growth, and the extra steps
208 6 Conclusions and Perspectives
required for graphene transfer to the target substrates significantly restrict the wide
application of the CVD method [4]. In particular for the next generation flexible
electrodes and circuits, the CVD-grown graphene needs roll-to-roll transfer equip-
ment [5], making it highly dependent on initial infrastructural investments. In addi-
tion, several other challenges must be overcome before the industrial application of
CVD grown graphene is realized. These challenges include (i) growth of graphene
with large and controllable grain sizes, such as single-grain graphene with wafer
scale size; (ii) CVD growth of graphene with controllable number of layers; (iii)
reduction of the synthesis cost by low temperature growth or direct growth on any
metal substrates without posttransfer processes; and (iv) developing easy, reliable,
and scalable transfer processes.
Facile and inexpensive methods for fabricating graphene-based TCFs are highly
desirable to achieve the standard quality to replace ITO. Since graphene oxide (GO)
dispersions are easy to be obtained and deposited on a substrate in a controllable
manner, GO can provide a practical route toward the low-cost and scalable produc-
tion of TCFs with tunable optoelectrical properties. GO-based TCFs are known to
be cheaper and easier to scale up than the CVD-grown graphene, and are thus ap-
pealing for applications where cost reduction is essential. Although many studies
have been dedicated to the development of GO-based TCFs, their applications in
real products are still in their infant stage. This is because the assessment of com-
petition on the materials/manufacturing costs and relative functional performance
between the TCFs produced using different materials and techniques are ongoing.
There is still large room for improvements in the two major functional criteria.
This book offers an overview of the research and development expended thus
far on the synthesis and property measurements of GO-based TCFs with particular
emphasis on the principles of different techniques devised for GO synthesis and de-
position, as well as their influences on the corresponding optoelectrical properties
of TCFs. To produce GO-based TCFs, GO or rGO sheets have been deposited via
several well-established techniques, including spin or spray coating, transfer print-
ing, dip coating, electrophoretic deposition, and L–B assembly, followed by further
chemical reduction and/or thermal annealing. When comparing these approaches,
the L–B assembly is found to be the only technique that can realize layer-by-layer
(LbL) deposition of GO sheets, ensuring accurate control of the film thickness
upon repeated depositions. The optoelectrical properties of the final products can
be optimized by varying the deposition parameters, such as surface pressure and
pulling speed.
A few strategies have been successfully adopted as the postdeposition treatments
to improve the optoelectrical properties of graphene or rGO films, and thus to fully
exploit their fascinating properties. These strategies include: (i) doping with acids,
especially diluted nitric acid; (ii) doping with nitrogen or halogenating agents, such
as SOBr2, SOCl2 and AuCl3 solutions; (iii) use of large size GO sheets; (iv) hybrid-
ization with carbon nanotube (CNTs), metal nanowires (NWs), or nanogrids. Nota-
ble examples with high conductivity ratios based on the techniques include the use
of large-size GO sheets with a conductivity ratio of 7.0 [32], GO/CNT hybrid TCFs
prepared by solution mixing with a conductivity ratio of 16.0 [36], CVD grown
Conclusions and Perspectives 209
graphene/CNT hybrid film with a conductivity ratio of 34.0, rGO or graphene hy-
bridized with Ag NWs with a conductivity ratio of 246.9 [41], and graphene hybrid-
ized with nanogrids with a conductivity ratio of 174.2 [42]. It should also be noted
that apart from using large-size GOs and hybridizing with CNTs, metal NWs like
Ag NWs or Cu NWs, or nanogrids that function as bridges between the isolated GO
sheets, the conductivity of graphene-based TCFs can be further improved though
simple doping treatments by immersing the TCFs into halogenating agents, like
AuCl3, SOCl2, or SOBr2.
After the reduction of GO films, additional treatments have been applied sepa-
rately or in a series of two or more processes. For example, it is found that the
acid treatment helped remove the impurities present on graphene films as well as
substrate surfaces, while the dopant functional groups arising from the halogenat-
ing agents and nitrogen increased the carrier densities in rGO films. It is also found
that the TCFs made from ultralarge graphene oxide (UL-GO) sheets showed a much
lower sheet resistance than that of small size GO sheets, by one to two orders of
magnitude for a given transmittance of the film. Due to the increase in sheet area
of GO from several to thousands of μm2, the reduction in the number of inter-sheet
tunneling barriers in a continuous rGO film was responsible for this observation.
Besides employing large size GO sheets, producing pure rGO sheets with a minimal
number of defects is another efficient approach for improving the optoelectrical
properties of TCFs. The purpose of avoiding defects is to eliminate any noncarbon
atoms that may disrupt the perfect hexagonal pattern of graphene, which is essential
for establishing solid conducting networks in rGO.
Hybridizing rGO sheets with highly conducting 1D materials, such as CNTs,
metal nanowires, or nanogrids is shown to be another particularly attractive op-
tion to improve the optoelectrical properties. The conducting 1D nanofillers or
nanogrids can bridge isolated rGO sheets, where the extended conjugated network
structure serve as fast electronic conducting channels. However, there are still some
challenges in the process and use of these hybrid thin films. For example, weak
bonds are formed between GO and CNTs because CNTs are usually physisorbed
onto the hydrophilic surface of GO sheets, resulting in high contact resistance at the
junctions. After high temperature reduction, the bonds between GO and CNTs can
be even more deteriorated, necessitating the functionalization of these nanocarbons
to allow covalent bonds to form between them, as proposed by molecular dynamics
(MD) simulations [43, 44]. The rGO hybrids with metal nanowires and nanogrids
also have potential issues that need to be addressed, such as high contact resistance,
poor environmental stability, lack of scalable fabrication and uniformity, and elec-
trical shorts due to the large aspect ratios of these hybrid fillers.
In summary, doped metal oxides, such as ITO and fluorine tin oxide (FTO) ,
have well served for over 60 years for TCF applications. However, these materi-
als suffer from several drawbacks including brittleness, lack of chemical stability,
and high manufacturing cost. Emerged over the last 20 years, conducting polymers
have potential to solve the issues inherent to doped metal oxides. Unfortunately,
however, conducting polymers suffer from poor environmental stability and no-
ticeable color. CNTs have shown excellent potential for commercial use in TCF
210 6 Conclusions and Perspectives
applications, but the similar challenges, including the unacceptably large surface
roughness and high cost, still exist. Metallic NWs and nanogrids also possess high
electrical conductivities, however, the large film apertures require the combination
with another more continuous, transparent electrode material.
With about 10 years of short history of the discovery of graphene, extensive
and in-depth research efforts have been directed toward understanding the charac-
teristics and properties of graphene and its derivatives. Thanks to these strenuous
efforts, graphene is now finding a number of useful applications as sensors and
actuators, additives and free-standing electrode materials for energy conversion
and storage devices, conducting and strong nanofillers to reinforce composites, and
especially TCFs for various optoelectronic devices, like touch screens, liquid crys-
tal displays (LCDs), organic photovoltaics (OPV) cells, and organic light emitting
diodes (OLEDs). It is proven that graphene is an attractive alternative to currently
dominant ITO for TCF applications. CVD grown graphene films show excellent
electrical conductivity, but they cannot be produced in sufficient quantities. GO
based TCFs have more defects and possess lower electrical conductivity, but they
are capable of mass production with low cost. Nevertheless, many challenges are
still ahead, such as the relatively low conductivity, before full-scale industrial ap-
plications of these materials are realized. If these desirable attributes are not to be
compromised with others weaknesses, producing large-size GO sheets from natu-
ral graphene flakes and reduction to defect-free or near defect-free rGO sheets to
achieve recovery of their inherent electrical conductivities are among the ongo-
ing issues that need to be addressed. The relatively little understanding of their
long-term functional durability to sustain the desired optoelectrical properties and
structural stability under different service environments is another challenging issue
that has seldom received attention. As the existing synthesis methods are becoming
matured, future research efforts should also focus on developing novel processing
technologies that were previously inconceivable and exploiting exciting properties
of graphene-based TCFs in new applications, especially for a revolutionary new
breed of transparent and flexible electronics [2].
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Index
Symbols B
π-conjugated domains, 168 Bending energy, 167
Bending motion, 196
A Binary compounds, 7
Abrasion resistance, 4 Binding energy, 127, 133
Absorbance loss (AL), 189 Biosensors, 167, 168
Absorption Body monitoring, 197
and desorption, 124 Boiling point, 148
of electromagnetic radiation, 187 Bromination, 124, 125
optical Bromination duration, 124, 125
of polymers, 9 Bubble deposition method (BDM), 138, 147
AB stacking, 105 Buckling, 163
Accumulation, 114, 129 Bulk-heterojunction (BHJ), 184
charge, 129
Active electrodes, 200 C
Acyl chloride, 126, 172 Capacitance-voltage (CV), 200
Adsorption energy, 190 Capacitive type, 179
Aluminum-doped zinc oxide (AZO), 7, 8 Capillary force, 163, 166
Ammonium persulfate, 98, 153 Carbonaceous byproducts (CB), 19
Amorphous substrates, 7 Carbon nanoscrolls (CNSs), 167
Amphiphilic Carbon nanotubes (CNTs), 4, 18, 19
GO sheets, 115, 146, 170 chemical structure of, 127
UL-GO, 148 doping of, 126
Anhydrous hydrazine, 145 hybridization with, 138, 146, 208, 209
Anisotropy energy, 188 Carboxyl groups, 123
Aqueous solution, 95, 96, 138, 146, 156 Carrier concentration, 127, 128, 134
Arithmetical mean roughness, 168 Carrier type, 134
Aromatic ring, 14, 129 Catalyst template, 188
Ascorbic acid, 119 Catalytic activity, 105
Aspect ratio, 17, 18, 111, 209 Cathode ray tubes (CRT), 4
Atomic concentration, 124, 129 Cellulose/ester membrane, 114
Atomic force microscopy (AFM), 101 Centrifugal force, 110
Audio frequency field, 192 Charge accumulation, 129
Electrophoretic deposition, 95, 105, 109, 110, Graphite nanoplatelet (GNP), 124
205, 208 Graphitic materials, 127
Electrostatic repulsion, 161, 168 Graphitization, 110, 134, 150, 169, 172
Electrostatic self-assembly, 138, 146 Gravity, 166
Energy efficiency, 1
Energy storage, 198 H
Epitaxial growth, 19 Halogenating agents, 127, 128, 208, 209
Equilibrium structure, 129 Harmonic distortion, 192
Etchant solution, 101 Heating rate, 193
Etching bath, 95 Height profile, 118, 187
Etching method, 95, 97 Highly ordered pyrolytic graphite (HOPG),
Etching rate, 96 101
High temperature annealing, 6, 110, 172
F Human interface devices, 196
Face-to-face manner, 168 Human motion monitoring, 196, 197
Fatigue detection, 197 Human skin deformation, 196
Feature resolution, 114 Hybridization, 205, 208
Fermi level, 128 Hydrazine, 110
Few-layer-graphene (FLG), 196 Hydrocarbon gas, 105
Field effect transistors, 168 Hydrogen bonds, 105, 163
Flat panel display (FDP), 2 Hydrogen floride (HF), 152
Flexibility, 9, 103, 114, 153, 157, 181, 188, Hydrogen storage, 167, 168
194, 200 Hydrophilic, 158, 170, 209
Flexible Hydrophobic, 14, 170
EMI, 188 Hydroxyl groups, 168
film heaters, 193
GO sheets, 110 I
polyethylene naphthalate (PEN), 152 Impedance of free space, 20
polymeric materials, 118 Indium-doped cadmium-oxide (ICO), 7
steel or plastic substrates, 1 Indium-free oxides, 8
substrates, 145 Indium tin oxide (ITO), 4, 5
TCFs, 4 Industry applications, 19
touch screen-based graphene films, 180 Infrared heat lamp, 118
Fluorine tin oxide (FTO), 209 Infrared scanner, 194
Fluoroalkyl trichlorosilane (FTS), 9, 13 Ink droplets, 118
Free energy, 167 Inkjet printing, 105, 117
Front electrodes, 1 In-plane compression, 163
Fullerene, 19, 184 Input voltage, 194, 195
Functional glasses, 190 Insulator
Functional groups, 10, 123, 134, 148, 169, stacks, 188
173, 209 Intelligence devices, 194
Functionalization, 209 Intensity ratio, 125
Interfacial polarization, 188
G Interlayer distance, 105, 167
Gaseous product, 96 Intermediate transfer processes, 115
Glass slide, 111, 182, 200 Intersheet junctions, 123, 124, 158
Grain boundaries, 105 Invisible security circuits, 4
Grain size, 105, 208 Ion diffusion, 9
Graphene, 4, 19, 20, 95 Ionic bond, 131, 133
Graphene nanoribbons (GNR), 188 Ionic bromine, 133
Graphene oxide wrinkles (GOW), 163, 166 Ionic liquid, 15
Graphene patterns, 98, 100–102 Isopropanol (IPA), 15
Graphene woven fabrics (GWFs), 196 Isothermal curve, 115, 116, 162
Graphite intercalation compounds (GIC), 124 Isotopic peaks, 125
218 Index