GRAPHE,NE,

SCIE,NCE,
HANDBOOK
Applications and
Industriahzation

EDITED BY
Mahmood Aliofkh azraei o Nasar Ali
\Tilliam I. Milne . Cengiz S. Ozkan
Stanislaw Mitura . Juana L. Gervasoni

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Library of Congress Cataloging-in-Publication Data

Names: Aliofkhazraei, Mahmood, editor. Ali, Nasar, editor. Milne, W. L (William I.),
I I editor. I Ozkan, Cengiz S., editor. I Mitura,
Stanislaw 1951- editor. I Gervasoni, iuana L., editor.
Title: Graphene science handbook. Applications and industrialization / edited by Mahmood Aliofkhazraei,
Nasar Ali, William l.
Milne, Cengiz S. Ozkan, Stanislaw Mitura, and |uana L. Gervasoni.
Other titles: Applications and industrialization
Description: Boca Raton, FL: CRC Press, Taylor & Francis Group,2016. "2016 Includes bibliographical references
I | and index.
ldentifiers: LCCN 20150429871 ISBN 9781466591222 (hardcover; alk. paper)
I
ISBN i466591331 (hardcover; alk. paper)
Subjects: LCSH: Graphene--Handbooks, manuals, etc. Graphene--lndustrial applications--Handbooks, manuals, etc.
I
Classification: LCC QD341.H9 c683 2016 | DDC 661/.8r6--dc23
LC record available at http://lccn.loc.govl20LS0429g7

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Contents

SfCfrON I Biomaterial

Chapter 1 Design and Applications of 6raphene- and Biomolecuie-Based Nanosensors and Nanodevices.......................... 3

Ke Xu, Preeti Pratap, Mitra Dutta, and Michael Stoscio

Hatef Sadeghi

Chapter 3 Antimicrobial Perspectires for Graphene-Based Nanomaterials ........... ...................21

Archana Ramchandra Deokar, Madhulika Sinha, Ganesh Gollavelli, and Yong-Chien Ling

Maria Caffo, Lucia Merlo, DanieLe Marino, and Gerardo Caruso

Xiaochen Dong, Beibei Zhan, and Wei Huang

Chapter 6 Antibacterial ancl Antifungal Activities of Graphene Nanosheets... ........................... 71

Montee Sawangphruk

D. P. l{ikolelis, Z. H. Ibupoto, G.-P. Nikoleli, and M. Willander

Arzum Erdem, Ece Eksin, and Mihrican Muti

Chapter 9 Graphene-Based Laser Desorption/Ionization Mass Spectrometry tbr Bioanalytical Applications.................. 105

Suresh Kumar Kailasa, Hui-Fen Wu, and Jigneshkumar V. Rohit

Chapter 10 Richness of Graphene-Based Materials in Biomimetic Applications.............. ........125

Bhaskar Garg and Yong-Chien Ling

SECTION II Nanocomposifes

S. Chattelee and B. T. T. Chu

 Contents

Chapter 12 Preparation of Cellulose/Graphene Nanocomposites"...............

..".......,161
Ngut,en Dang Luong and Jukka Sepprilti

chapter 13 Straightforward Routes for the Preparation of Graphene-Based polymer

Nanocomposlres ............ ...............,...175
Giulio Malucelli and Atberro Mariani

Chapter 14 Poiymer Devices with Graphene: Solar Cells and

Ultracapacrtors.................. ........,.191
Agnieszka In-an, Bronislaw Szubzda, andAndrzei Sikora

SECTION lll Electrical/Sensor Devices

chapter 15 Graphene-Based Sensors: current status and Future Trends .........,.....2r1
Gouram Kaley, Amot Singh, and Ahsan Uddin

Chapter 16 E{'fbct of External Electric Fields on the Multifunctional

Applications of Graphene ,,.................235
Zhimin Ao, Qing Jiang, Sean Li, Shixue Dou, and Guoxiu Wanp

chapter 17 Impact of the Structural Properties of Graphene on siC

Surlaces on Their Eiectronic Applications:

Jolanta Borlsiuk and Jakub Soltys

chapter 18 Resistive Nonvolatile Memories Based on Graphene-Reiared

Materials: State of the art..... ......269
P. Bondavalli, D. Ihnatov, D. pribat, and p. Legagneux

chapter 19 Appiications of Graphene-Based Materials in Electronic Devices......,. ......,............279

Gaurav Gupta, Minggang zeng, Argo Nurbawono, wen Huattg,
and Gengchiau Lrang

Chapter 20 Graphene- and Graphene-Oxide_Based Gas Sensors

.....2gg
Vladimir Aroutiounian

SECTION IV New Applications

chapter 21 Graphene-Based Materiars for Fuer cells: Approaches and
Applications. ................313
Junrui Li and Haolin Tans

chapter 22 chemistry and Applications of Supramolecular Graphene

Derivatives ..........,........337
Hugo Bares, Jean-Baptiste Verlhac, and Dario M. Bassani

Chapter 23 Applications of Graphene in Tissue Engineering ........... 353

Eoin Murrat,, Brianna C. Thompson, and Gordon G. Wallace

Domingo Anibal Garcia-Herndndez and Franco Cataldo

I
E

$
&
E

&-- Contents vll

Chapter 25 Graphene Materials in Energy Storage Appiications. ....377

Grzegorz Lota, Krr'*sztof Fic, Ilona Acznik, and Katarzyna Lota

Chapter 26 Applications of Graphene in Fuel/Propellant Combustion .................. 391

Bruce Chehroudi

Chapter 27 Fabrtcation of Graphene-Based Porous Materials and Their Applications in Environmental Fields..... ............399

Zhu-Yin Stti, Ding Zhou, and Bao-Hang Han

Hottgting Hou, Xianxi Liu, and Jinhui Peng

Chapter 29 Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell ........................439

Avijit Ghosh and Anil Verma

 raptrene- and C raphene-Oxide- Based
20 !Gas Sensors
Vladimir Aroutiounian
CONTENTS
20.3 Some Electronic Properties of Pristine (Intrinsic) Grapheme.......
20.8 Acoustic Wave and Functionalized Graphene Gas/Vapor
20.9
Analysis of Experimental Results Obtained for Different Graphene
ABSTRACT
Exceptional physical properties of graphene and possibili-
ties of its electronic applications have evoked a great deal
of research interest for the last few years. From a theoreti-
cal point of view electrons in graphene behave like mass-
less Dirac fermion and equivalent to a massless neutrino in
two dimensions. Therefore, mobility of electrons is realized
effectively in graphene, which is the highest among all sol-
Q1 ids. Graphene exhibits ballistic charge transport properties.
Graphene is actually a semimetal. However, the lack of an
energy gap in its electronic spectra, for example, prevents the
use of graphene in making transistors, logic circuit devices,
and sensors. Several methods have been developed to break
the lattice symmetry in graphene and open an energy gap. The
opening of the bandgap in graphene is a unique phenomenon.
Several versions of gap opening are discussed in the chapter
after a short introduction on the synthesis procedures of gra-
Q2 phene and graphene oxide. The best surface-to-volume ratio
is in graphenelike two-dimensional (2D) materials, every
atom of which may be considered as a surface atom; therefore,
the use of graphene has opened up the opportunity for the
detection of gases and vapors with excellent sensitivity, fast
response time, and high stability. Different types of sensors
are considered. Resides resistive sensors, field-effect transis-
tor, and acoustic wave and functionalized gas/vapor sensors
have been reported.
20.1 INTRODUCTION
Graphene is a zero-bandgap 2D semimetal. "Charge carriers
in graphene exhibit giant intrinsic mobility, have the smallest
rzosoe-cozo.inoo zss
I I
.. .... 301
Sensors ...." 305
Sensors
.."'..'.....306
effective mass (it is zero) and can travel micrometer-long dis-
tances without scattering at room temperature" (Geim 2009).
The unique structural characteristics and exceptional physical
properties of graphene (Table 20.1) have attracted enormous
research interest in the last years (Mikhailov 201 la,b).
Previous volumes of this book and the December 2012
issue of MRS Bulletin (vol. 37, 2012) are focused on fun-
damental functionalities of graphene (Lu et al. 2012). Note
that graphene has shown ultrahigh intrinsic carrier mobility
f ar largor than lirr any othcr material (Morozov et al. 2008,
Mikhailov 201 la,b, Lu et al. 2012) and has potential applica-
tions in high-speed transistor electronics and integrated cir-
cuits. The research group at IBM has demonstrated silicon
carbide (SiC)-based graphene field-effect transistors (FETs)
with a cutoff frequency of more than 300 GHz (Avouris and
Xia2012), which is very important for nanoelectronics. Otsuji Q3
et al. (2012) note that graphene devices will operate in the
terahertz frequency range. A very long spin diffusion length is
typical for graphene. It opens, along with high electron veloc-
ity related to their linear dispersion relation, possibilities to
use graphene for spintronics (Seneor et al.2012).
A half-integer quantum Hall effect for both electron and
hole carriers in graphene has been observed at higher than
helium temperatures (Novoselov et aI.2005, Xiao et al.2011, Q4
Schopfer and Poirier 2012). ln addition, graphene is highly
transparent for visible light (Avouris and Xia 2012). Graphene
can sustain current densities 6 orders of magnitude higher than
copper and shows record thermal conductivity and stiffness
(Geim 2009). Its thermal conductivity is measured at a value
of -5000 W mK-r for a single-layer sheet at room temperature
(RT) (Balandin et al. 2008). It is promising for thermoelectric
applications (Lu et al. 2012, Pop et al. 2012). The excellent
299
02-09-2015 14:22:OS
 300 Craohene Science Handbook

TABLE 20.1
Physical Properties of Graphene
Structural Dimension 2D Clhickness: 0.34 nm)
Young's modulus I TPa
Tensile strength 130 GPa
Bandgap 0 eV (zero-gap semimetal)
I
Electrical conductivity -106 S cm
Intrinsic carrier mobility Up to 200,000-250,000 cm2 V-r sr at low
temperature and -10,000-20,000 cm'? V-t s-'
at room temperature
Thermal conductivity 3000-5000 W m-rK-'
Solubility -2800"C under Ar
4.7t 1.9 pg mL-' in NMP
4.1t 1.4 pg ml-rin DMF
Density 2.2 gcm-3
FIGURE 20.1 The existence of an energy gap between the con-
Soare: Adapted liom lre S. H. et al., Advanced Functional Materitls 21, duction and valence bands makes it possible for graphene to act as
1338-1354. a semiconductor. In pristine graphene, the conical conduction and
valence bands meet at a point-the bandgap is absent. Electrical
fields introduce asynmetry into the bilayered structure (bottom),
yielding tuned bandgap (A). Allowed optical transitions between
breaking strength of graphene is equal to 42 N m-1. Its high
diff'erent subbands of a graphene bilayer are also shown. (Adapted
Young's modulus shows that it is one of the strongest mate-
from Craciun, M. F. et al., Nano Today 6,42-6O.)
rials ever measured. High-efficiency energy conversion and
energy-storage devices based on graphene materials have
been achieved (Cao et al. 2012).The optical properties ofgra-
Anodic bonding (Figure 20.1b) allows sticking a few lay-
phene are also of great interest. Broadband absorption coef- ers of graphite, including single-layer graphene, to a glass
(see, e.g., Shukla et al. 2009). A laser beam can in principle
ficients from UV to near IR region, and sub-picoseconds to
microsecond responses are typical for graphene (Du et al. remove material from a solid surface and prepare graphene
2012). Biosensing and bioimaging applications in enzyme bio- flakes (Miyamoto et al. 2010). The process is called photo-
sensors, immunosensors, DNA biosensors, and cell imaging
exfoliation. Graphite can also be exfoliated in a liquid using
havo bccn reported (Singh ct al. 2011). Although many papors ultrasound to extract graphene layers. The technique can
on gas/vapor sensors made of graphene and graphene oxide be used for the exfoliation of graphite oxide and graphite
(GO) have been published, there is only one review in this intercalated compounds, which have different properties
field (tsasu and Bhattacharyya 2012). This chapter focuses on compared with pristine graphite. There are several ways to
the physical properties and applications of graphene and CO obtain GO and reduced graphene oxide (rGO) (Bonaccorso
gas/vapor sensors. 20r3).
Sensors made of SiC are very promising (Buniatian and
Aroutiounian 2OO7).h is possible to grow graphene on SiC Q6
20.2 SYNTHESIS OF GRAPHENE AND GO
though there are large lattice mismatches between graphene
The preparation, production, placement, and handling and SiC. SiC is annealed in vacuum or argon atmosphere
of graphene and GO have been recently reviewed by above 1000"C. Silicon near the surface of the SiC lattice
Q5 Bonaccorso (2013). A detailed discussion ofthese questions desorbs, and free carbon atoms rearrange itself in a hexagonal
is beyond the scope of this chapter. We will very shortly lattice structure (graphene). An electronic structure modifi-
stop on some questions, which are important for gas sensor cation by hydrogen intercalation in graphene on the carbon
applications. face of SiC is considered by Hiebel et al. (2011). RT mobil-
SingleJayer graphene was first obtained by Novoselov ity (p) of -5800 cm2 V-r s-r on the Si-face has been reported
et al. (2005) using the simplc mcthod of dry cxloliation (thc (Bonaccorso 2013). Growth of epitaxial graphene on SiC
process of splitting of layered materials into atomically thin allows organizing large-scale production of different elec-
sheets in air, vacuum, or inert environment). The splitting tronic devices (microwave devices, light-emitting devices,
can be realized via mechanical and other forces and adhesive and radiation-hard devices) (Buniatian and Aroutiounian
tape. Micromechanical cleavage allows realizing high-quality 2007, Nyakiti et al. 2012, Ruan et al. 2012, Iezhokin et al.
layers, with size limited by the single crystal grains in graph- 2013). The cost of SiC wafers is much higher compared with
ite (up to millimeters). RT mobility of up to 20,000 cm2 V-r s-r that of Si wafers of the same size. One approach to reduce
was measured in graphene layers. Of course, such a method substrate costs is to grow thin SiC layers on sapphire, cost of
is not practical for large-scale devices, but it allows obtain- which today is much lower. Layers produced in this way have
ing basic results and devices as well as understanding of new structural and electronic properties comparable to those on
physical results (Shmavonyan et al. 201 3a,b). bulk SiC.

xzosoe-cozo.inoo soo 02-09-2015 la:22:Og

I I
 Craphene- and Craphene-Oxide-Based Cas Sensors
Carbon can be deposited on a Ni, Co, Ru, Ir, Pt, and Pd
surface by a number of techniques. The carbon source can be
a solid, liquid, or gas (Barlett and McCarty 2012, Bonaccorso
2013).
Chemical exfoliation from graphite powders through the
formation of graphite oxides by oxidation of graphite in solu-
tion is another well-studied fabrication technique. This pro-
cess has low cost, high throughput, chemical versatility, and
scalability to large quantities (Jaber-Ansari and Hersam 2012).
Graphene is a single-element material; therefore, it is eas-
ier to deposit it than a multicomponent system. Versions of
chemical vapor deposition (CVD) of graphene on metals and
dielectrics are described by Bonaccorso (2013). It is unlikely
that very expensive molecular beam or atomic layer epitax-
ial technology is useful for the growth of graphene layers of
high-enough quality. Apart from the above-mentioned meth-
ods for the synthesis of graphene, there are few other synthe-
sis methods. It is also noteworthy that the growth of graphene
on diamond-like carbon film as a substrate is very promising
due to its lower surface trap density.
GO sheets have been recently proposed for the manufac-
ture of graphene. Such single-layer GO sheets can be pro-
duced by sonication of hydrophilic graphite oxide in water.
20.3 SOME ELECTRONIC PROPERTIES OF
PRISTINE (INTRINSIC) GRAPHEME
Electronic properties of graphene are unique and very differ-
ent from many othcr known matcrials (Novoselov et al.2004,
2005, Castro Neto et al. 2009, Geim 2009, Mikhailov 201 1a,b,
Lu et al. 2012). As shown earlier, electron waves propagat-
ing through the honeycomb lattice of graphene completely
lose their effective mass, which results in quasiparticles that
are described by the Dirac-like equation rather than by the
Schrodinger equation. The Dirac electrons behave in unusual
ways in tunneling, confinement, and the integer quantum Hall
effect. The valence band and conduction band of graphene
look like conical valleys and touch the high-symmetry points
of the Brillouin zone. The energy varies linearly with the mag-
nitude of momentum. Linear dispersion relation leads to zero
effective mass near the Dirac point (Geim 2009, Mikhailov
2011a.b. Lu et al. 201 2).
Electron waves in graphene propagate within a layer that is
only one atom thick. which makes graphene very sensitive to
different imperfections and exposure. To manufacture a sensor,
we have to change the resistance of the material in order that it
can bc changed under thc inllucncc ol'some outer lbrcc (electric
or magnetrc field, concentration of gas, illumination, etc.) It was
shown that the Dirac electrons can be controlled by applica-
tion of external electric and magnetic fields or by altering the
sample geometry and/or topology. Usually, the Fermi level can
Q7
be changed by changing the concentration of vacancy defects
or by doping. Graphene can become either n- or p-doped. A
substrate like SiO, has a larger influence on the mobility than
scattering by graphene's own phonons at room temperature. It
leads to a mobilitv of -40.000 cm2 V-r s-l at RT.
xzosoa co2o.indd 301
] |
301
Usually, pristine graphene is poorly sensitive to gas. It
was established that graphene can be decorated with metal
by first adding metal salt precursors to a solution of theGO
and then converting them to metallic nanoparticles. Graphene
can adsorb and desorb various atoms and molecules (e.g.,
H2, NO2, NH,, or OH). Weakly attached adsorbents often
act as donors or acceptors and lead to changes in carrier
concentration. Other adsorbents give rise to localized ("mid-
gap") states, which results in poorly conductive derivatives
(Novcrsclov ct al.2004,200-5, Gcim 2009, Mikhailov 2011a,b,
Lu et al. 2012).
Such changes in the conductivity of graphene are lead-
ing to the possibilities to manufacture different sensors. We
will discuss below the properties of only gas/vapor sensors.
Most of them are operating in the resistive mode, and a
change in resistance under gas/vapor influence can be mea-
sured easily.
20,4 GAS SENSORS MADE OF CRAPHENE
It is shown in Ao et al. (2008) that the aluminum incorporated
into graphene causes a distortion of the energy density dis-
tribution around Al atoms. C atoms surrounding this dopant
attract electrons due to their high electron affinity, whereas a
decrease in electron density on the Al dopant is observed. The
charge redistribution makes Al an active site for CO adsorp-
tion and ultrasensitive carbon oxide detection. This charge Q8
redistribution effect is confirmed by theory. The results show
that the Al-doped graphene has strong chemisorption of CO
molecule by forming an AI-CO bond, whereas CO undergoes
weak physisorption onto intrinsic graphene. Furthermore, the
enhancement of CO sensitivity in the Al-doped graphene is
determined by a large electrical conductivity change after
adsorption, where CO absorption leads to an increase in the
electrical conductivity via introducing large amounts of shal-
low acceptor states. N substitutionally doped graphene syn-
thesized by the CVD method is sensitive to the presence of
CHo and NH. (Wei et al. 2009).
Nitrogen plasma treatment of graphene can remarkably
change its work function (Akada et al.2014).
Graphene can be decorated with metallic nanoparticles by
first adding metal salt precursors to a solution of theGO, and
then converting them to metallic nanoparticles by reduction
(Si and Samulski 2008, Xu et al. 2008, Gotoh et aI.2009).
Other methods include electrochemical deposition of metal-
lic nanoparticles on thin layers of graphene (Sundaram et al.
2008). Composites of graphene with gold (Xu et al. 2008),
ruthcnium (Gotoh ot al. 2009), platinum (Si and Samulski
2008, Xu et al. 2008, Gotoh et al. 2009, Shafiei et al. 2010),
and palladium (Xu et al. 2008, Gotoh et al. 2009) nanopar-
ticles were synthesized by this method.
The catalytic properties of palladium are well known
(Paremuzyan and Aroutiounian 2012). This material is often
used in chemical hydrogen gas sensors (Aroutiounian et al.
2012) due to a hydrogen-induced decrease in the work func-
tion of Pd or Pd-Pt alloy and modification in the distrrbution
of defect states due to gas adsorption. Palladium-decorated
02-09-2015 14:22:09
 302
graphene can serve as a sensor material for hydrogen at lev-
els from O.5Vo to l7o in synthetic air. The incorporation of
Pd nanoparticles increases graphene sensitivity by more
than an order of magnitude compared with pristine graphene
(Lange et al. 2011). Application of palladium in the form of
nanoparticles allows fabricating chemical sensors using a
very small amount of this low-cost material. Performance of
graphene resistive H, sensors made of nanosheets deposited
on SiC substrate has recently been investigated by Chu et al.
(2011). Graphenelike nanosheets with Pd/Au electrode were
investigated as graphene NO, sensors by Ko et al. (2010).
Their sensitivity down to parts-per-billion (ppb) levels, fast
response, recovery, and appreciable selectivity toward NOr in
the presence of commonly interfering gases such as C02, H2O
(saturated vapor), NH, (550 ppm), and O, were observed by
Nomani et al. (2010). Multilayer graphene-Pd sensors with
Au electrode were also investigated by Lange et al. (20i 1) for
H, detection at levels from 0.5 to 17o in synthetic air (see also
Johnson et al. 2010, Wu et al. 2010, Chung 2012a,b, Lee et al.
Qe 2012, Das and Prusta 2013). For 2Vo H, at 40oC, response
time of less than 2 s and a recovery time of 18 s are observed
by Kumar (2011). Deng et al. (2012) reported NOr gas sen-
sors fabricated reduced graphene-conjugated CurO nanowire
mesocrystals. Esfandiar et al. (2013) reported that DNA-
decorated graphene nanomesh can detect several chemical
vapors.
20.5 BANDGAP OPENING IN GRAPHENE
Graphene exhibits ballistic charge transport properties.
However, the lack of an energy gap in its electronic spectra,
for example, prevents the use of graphene in making transis-
tors, logic circuit devices, and sensors. It was discovered that
the graphene band structure is sensitive to lattice symmeffy.
As a result, several methods have been developed to break
this symmetry and open an energy gap. The opening of the
bandgap in graphene is a unique phenomenon.
3.0
-d-" ?o
! rc
1.0
0.5
0.0
Strain (%)
FIG URE 20.2 The bandgap of the fully hydrogenated (Hiype) and doped with B (Btype) bilayer graphene. (Adapted from Boukhvalov,
D.W..Katsnelson.M. I.andLichtenstein.A. I.2008. PhvsicsReviewB71,035427.)
K20508-C020.indd 302
Craohene Science Handbook
Several efforts have been made to open the bandgap of
graphene (see Figure 20.1). One possibility to open the band-
gap in graphene is to use bilayer graphene (Ohta et al. 2006,
Castro et al. 2007, 2010, Zhang et al. 2009, Johnson et al.
2010). The bandgap around 0.25 eV is opened when the
electric field is applied up to 2 V/nm (Zhang et al. 2009).
However, a large external voltage of several tens to hundreds
of volts makes this approach not practical (Guo et al. 2008,
Nanda and Satpathy 2009, Choi et al. 2010). The bandgap
of bilayer graphene can be opened larger (up to 3.3 eV) by
a combination of strain (along the z axis) and electrical field
(Figure 20.2) (Gui et al.20ll, Yang et al.20ll, Zhangetal. Q10
2011a.b).
Graphene made on a Cu fbil can also have the bandgap
under strain. FewJayer graphene sensor developed by Jung
et al. (2009) can detect B, and Jr. Here, a bandgap of 0.2-
0.3 eV was observed. The bandgap in graphene can also be
opened under infrared laser beam or at a high level of humid-
ity 19.26-0.r, eV) (Yavari et al. 2010). Bandgap engineering
of bilayer graphene can be realized by chemical conjugating
double sides of bilayer graphene, one side with an electron-
donating group and the other side with an electron-withdraw-
ing group. The compensated charges not only created a large
bandgap of 0.3 eV by invoking an internally strong local
dipole field in bilaycr graphemc but also removod degeneracy
by shifting the Fermi level within the bandgap.
The bandgap of graphene can be opened by the use of
a quantum confinement effect of carriers by narrowing the
width of graphene to a nanometer scale. Such graphene ts
called nanoribbon (NR). NRs can be fabricated from solu-
tion phase, by e-beam lithography of large-area graphene
or by local heat treatment using atomic force microscopy
(Bonaccorso et al.2O12). A bandgap of -30 meV and corre-
sponding FETs were reported when NRs were prepared (Chen
etal.2007, Li et al. 2008, Jiao et al. 2010, Wei et aI.2010,
Bonaccorso et al. 2012). Sub-1 0 nm NRs with a bandgap of up
to 400 meV were reported by Ponomarenko et al. (2008). NRs
02-09-2015 l4:22:09
I
 Craphene- and Craphene-Oxide-Based Cas Sensors 303

were used as channels in FETs. A direct to indirect bandgap

TABLE 20.2
transition is possible in NR by the application of an exter-
nal bias along the width of NR (Majumdar 2013). It is very Bandgap Opening in Different Structures of Craphene
Qll
promising for applications of graphene in nanophotonics and Lavers and Influences
at terahertz applications. Direct observation of a widely tun- Structure of Craphene Layers Bandgap
able bandgap in bilayer graphene was reported by Zhang et al. and lnfluence (eV) Reference(s)
(2009).
Bilayer graphene and electric field 0.25 Zhmg et al. (2009)
BN-graphene-BN antidot systems (Zhang et al. 2011a'b' Bilayer grapheme, combination of Up to 3.3 Ymg et al. (201l),
Ouhe et al.2012) are also very interesting versions for gra- strain md electric lield Zhmg et al. (201la,b)' Q21
phene applications. The construction of periodic structures Gui et al. (201 l)
such as antidot lattices (Eroms and Weiss 2009, Pedersen Few-la,ver grapheme and gas 0.2-0.3 Jung et al. (2009)

Q12 2009, Vanevic et al. 2009, Balog et al. 2010) and the corre- environment (Bt and J.)
sponding confinement potential for the carriers in pristine Graphene and infrared laser beam 0.26-0.73 Yavari et al. (2010)

grapheme led to the bandgap opening. Unfortunately, the size or high hunidity
in NRs and dots is difficult to control duc to high sensitivity Graphene Moir€ superlattice and 0J3 tsalog ct al. (2010)

to their width, edge geometry, and chemical functionalization hydrogen environment

(Berger 2006, Son et al. 2006, Giovannetti et al. 2007, Lu Half-hydrogenated graphene 0.43 Zhou et al. (2009)
Ql3
2009, Balog et al. 2010). It is also worth noting that the manu- Tunable bandgap and water Up to 0.206 Yavari ct al. (2010)

facture of NRs is still far from being realized in the industry molecules

level.
In nanomesh graphene structure (Guo et aI.2008)' lateral
quantum confinement and localization effects due to edge dis-
order, such as variable edge roughness, were proposed as the
mechanism responsible for the bandgap opening.
Epitaxial growth of graphene on the carbon face of SiC
under vacuum leads to a gap of =0.26 eY, which originates
from the breaking of sublattice symmetry due to the gra-
phene-substrate interaction. As a result of the creation of the
gap, sensors on epitaxially grown graphene for ultrasensitive
NO, detection with extremely high sensitivity were reported
by Pearce et al. (2011).
The hydrogenation of the graphene surface can create a to =0.206 eV can be engineered in graphene by the controlled
stable material with a large energy band (Boukhvalov 2007,
Q14 Sofo et al. 2007, Savchenko et al. 2009). It is crystalline and
retains the hexagonal lattice, but its period becomes mark-
edly shorter than that of graphene' Here' alternating carbon
atoms are pulled out of the plane in opposite directions by
the attached hydrogen atoms. Their concentration controls the
size of the gap in hydrogenated graphene (Elias et al. 2009).
Zhou et al. (2009) showed that the energy gap can be pro-
duced withoutcuttinggraphene into aribbon. They also showed
that the chemical modification of graphene is reversible; the
properties of graphene can be largely restored by annealing
the hydrogenated samples at high temperatures. The hydro-
gen gas, which exposed a graphene sample, is dissociated into
hydrogen ions during hydrogen plasma discharge (Elias et al.
2009). The electrical conductance becomes strongly tempera-
ture dependent, which is connected with electron "hopping"'
because the presence of the gap after the hydrogenation forces
electrons to "hop" from one site to another' Therefore' conduc-
tion mechanism is much more efficient at high temperatures.
From the diffraction image of the new crystal lattice, a notice-
able decrease in the separation between the carbon atoms
caused by hydrogen atoms is seen' The Raman spectroscopy'
which is sensitive to the vibrations of atoms in the crystal lat-
tice (phonons), also shows the evolution of the lattice during
hydrogenation. The reversible hydrogenation of graphene is
important for device applications. A search for optimal ways
of graphene hydrogenation, including chemical methods, is
carried out currently. Patterned adsorption of atomic hydro-
gen onto the Moird superlattice positions of graphene (Balog
et al. 2010) led to a bandgap opening of =0"73 eV, while half-
hydrogenated graphene (Zhou et aI.2009) led to a bandgap of
=0.43 eV. A single hydrogen atom in a 32-carbon-atom slab
generated a gap of about 1.25 eV. A widely tunable bandgap
in bilayer graphene was observed by Zhang et al. (2009).
Yavari et al. (2010) demonstrated that a tunable bandgap up
adsorption of water molecules to the surface of graphene. It
opens a possibility to prepare sensitive humidity sensors'
The earlier reported data on bandgap opening in differ-
ent graphene structures under different influences ate sum-
marized in Table 20.2.
Wo discusscd oarlicr (ArouLiounian et al- 2012) that open-
ing of a tunable bandgap is necessary for the manufacture of
efficient resistive graphene chcmical sensors, as pristine gra-
phene is not a good material for gas sensing. There are other
possibilities to make them.
20.6 DETECTION OF CASES BY
GRAPHENT RESISTIVE SENSORS
The tuning of graphene's sensing properties can be real-
ized by the charge transfer between a gas and graphene. It is
known that NO2, NH3, CO2, CO, H2O, and Ot are active gases.
Adsorption of NO, induced higher doping compared with NO
(Leenaerts 2007). Gautam and Jayatissa (201 1,2012) reported
on NH. and oxygen detection at the substrate preheating tem-
perature in the 150'-200o range. The single-layer graphene
changed the type of conductivity from electronic to hole on
exposure to increased concentration of NOt.
Outstanding results were obtained by Schedin et al.
(2007). Figure 20.3 shows the response of zero-field

02-09-2015 14:22:09
*rorot coro.'noo .*
| |
 304
0 500
r (s)
FIGURE 20.3 Sensitivity of graphene to chemical doping.
Changes in the resistivity p are caused by graphene's exposure to
various gases. The positive (negative) sign of changes is chosen
here to indicate electron (hole) doping. Region I-the device is in
vacuum prior to its exposure; Il-exposure to a 5 L volume of a
diluted chemical; Ill-evacuation of the experimental setup; and
IV-annealing at 150'C. The response time was limited by the gas-
handling system and a several-second delay in lock-in-based mea-
surements, The annealing caused an initial spike-like response in p.
which lasted for a few minutes and was generally irreproducible For
clarity, this transient region between III and IV is omitted, as indi-
Q23 cated in Figure 20.5. (Adapted from Schcdin, F. et a1.,2007. Nature
MateriaLs 6, 652*655.)
resistivity of graphene to NOr, NH3, H2O, and CO in its
concentration of I ppm. As mentioned above, gas molecules
adsorbed by the graphene's surface change the electrical
conductivity of graphene resistive sensors. They are acting
as donors or acceptors. As the whole surface of graphene
is a 2D material, a few extra electrons can cause notable
relative changes in carrier concentration. The adsorbed
gas molecules change the local carrier concentration in
graphene one by one electron, which leads to stepwise
changes in resistance. Therefore, it is possible to increase
the sensitivity to its ultimate limit and detect individual
dopants. The Hall measurements revealed that NOt, HrO,
and iodine acted as acceptors whereas NHi, CO, and etha-
nol were donors. There is the linear response of change of
the local carrier concentration to the concentration of the
gas. It makes the use of graphene-based sensors simple.
Schedin et al. (2007) did not observe notable changes in
the mobility despite additional scatterers and make the con-
clusion that graphene-based gas sensors allow the ultimate
sensitivity to the adsorption of gas molecules, that is, they
have large dynamic range of gas detection. In addition to
NO, and NH,, dinitrotoluene can be detected by graphene
sensors (Fowler et al. 2009). Yoon et al. (2011) reported
a rather fast (10 s) linear response of the sensor to CO2 at
RT and in the concentration range of 10-100 ppm at low
rzosoo co2o.indd 304
] I
Craphene Science Handbook
power consumption. A two-step adsorption/desorption
mechanism for such response was detected. Fast adsorption/
desorption is associated with pristine sites, whereas slow
adsorption/desorption is attributed to the defective sites (Ko
et al. 20ll). It is interesting that the exposure of graphene
to ozone dramatically improved NO, sensing behavior of
graphene (Chung 2ol2a,b). Graphene chemiresistor sensor
for trimethylamine gas was realized by Rapola et al. (2014).
20.7 FIELD-EFFECT TRANSISTOR GAS SENSORS
Characteristics ofFETs are changing upon exposure to differ-
ent gases. It is shown that such FET sensors are very sensitive
and have fast response time, low noise and cost. Rumyantsev
ct al. (2012) discussed thc propcrtics ol' sclectivc gas/vapor
FET sensors made of graphene. It is very important that the
noise spectral density of graphene FETs changed remarkably
under different gases (Figure 20.4).
Vapors of different chemicals (methanol, ethanol, tetra-
hydrofuran, chloroform, acetonitrile, toluene, and methylene
chloride) lead to different forms of the low-frequency noise
spectra of graphene. The same phenomena were detected
earlier for porous silicon gas sensors (Aroutiounian et al.
2008, 2009). A remarkable change in the characteristic fre-
quency of the Lorentzian noise was observed, which is dif-
ferent for different chemicals. Rumyantsev et al. (2012) have
shown that their FET sensors are selective to different gases
without any surface functionalization or fabrication. The
low-frequency noise can be used as the sensing parameter to
enhance selectivity and help in discriminating between dif-
ferent gases. It was also shown for porous silicon gas sensors
Noise in graphene devices
Tetrahydrofuran
107
q
10"
1oo 1ol 102 lo3 104 105
Frequency/(Hz)
FIGURE 20.4 Noise spectral density multiplied by frequency I
versusfrequency/lbr thc devicc in open air and undcr thc influ-
ence of difl'erent vapors. Different vapors induce noise with dif-
ferent characteristic f'requencies f,. The fiequencies, f,, are shown
explicitly tbr two different gases. The difference in the frequency
f is sufficient for reliable identification of different gases with the
same graphene transistor. For comparison, the pure lfnoise depen-
dence is also rndicated. (Adapted from Rumyantsev, S. et a1., 2012.
N ano Le t te rs 12. 229 4-2298.)
02-09'2015 14:22:09
 Craphene- and Craphene-Oxide-Based Cas Sensors 305

by Aroutiounian et al. (2008, 2009). However, some vapors (a) 40

ccc
change the electrical resistance of graphene without change *^**
in the form oftheir noise spectra. Therefore, it is necessary to
Gasoff - ZnO NRs/CCG

20
estimate the response (sensitivity) and selectivity to different
gases very accurately and carefully.
Recently, CO has received great attention because it €
b0
readily exfoliates as single sheets in water and, from these :t
.=
solutions, it is straightforward to produce films. Its chemi- tr
cal reduction increases the conductivity by several orders of
magnitude by the removal of oxygen and recovery of aro-
matic double-bonded carbons. The rGO is both conductive
and has chemically active defect sites making it a promis- -40
ing candidate for the sensors allowing detection of chemical
agents in the ppb range with significant reduction of noise 0 2500 5000 7500 10,000

lcvcl. Wang ot al. (2014) rcportcd reccntly about tho rcaliz'a'

tion of GO hydrogen sensors working without the heating
of their work body. Hafiz et al. (2014) reported about CO,
GO sensors. Lu (2009) investigated rGO-based FET sen-
sors for NO, and NH, detection at a low concentration level.
These gases were diluted in air at RT. FET with intrinsic
GO sheets have no response to these gases. Electron trans-
fer from GO to adsorbed strong oxidizer NOr leads to an
enriched hole concentration and enhanced electrical con-
duction in the rGO sheet annealed at 300'C (Leenaerts
et al. 2008, Lu 2009). Faster response timc and much longer
recovery time are typical for such sensors after annealing
at 300'C in comparison with sensors annealed at 2OO'C'
Response (sensitivity) to NH, is smaller. The sensor was fab-
ricated by dispersing the aqueous GO suspension onto Au
electrodes. Source-drain separation was about 1 pm. Such
electrodes were fabricated using the e-beam lithography on
a silicon wafer. Low-concentration NO, diluted in dry air
starting from I ppm was detected in rCO gas sensors at RT
(Lu 2009).
Two important parameters characterize the response (sen-
sitivity)-the conductance response to molecular adsorbents
lfnoise generally dominates
and low-frequency noise, where
(Robinson et al. 2008). Authors have shown the 10-100-
fold reduction of lf noise in rGO sensors over single-walled
nanotube (SWNT)-based sensors. The noise level in rGO
devices strongly decreases with an increase in film thick-
ness. Figure 3b in Robinson et al. (2008) demonstrates the
Q22
important role of noise reduction in the responses to 0.5 ppb'
2,4-Dinitrotoluene (DNT) is a stimulant for the explosive
TNT. The lower noise levels in the rGO device lead to a nota-
ble increase in the signal{o-noise ratio.
It is important to note that the conductance-based rGO
sensors are sensitive to explosive gases and their stimulants
as well as to the three main classes of chemical warfare
agents and nerve agents. Dependence of change in conductiv-
ity of rGO sensor on the concentration of hydrogen cyanide
(HCN) in nitrogen is linear in double-logarithmic scale from
a minimal detectable level of 70 ppb of HCH:\ (Figure 20.4
in Robinson et al. 2008). Note that the detection of HCN
by carbon nanotube (CNT) sensors is impossible even at a
much higher concentration of HCN. In addition, rGO sensor
is able to detect other stimulants such as organophosphates
(b)
Gas on @ ccc
I
b -10
::
E
r30
0 5000 10,000 15,000
Time (s)
FIGURE 20.5 (a) The response curve of the chemically reduced
graphene sensor to the DMMP vapor under concentrations of
5-80 ppm and (b) response of the sensors versus the concentrations
of DMMP. (Adapted from Hu, N. et al., 2O12. Sensors andActuators
B 163. t07-114.)
(i.e., dimethyl methylphosphonate [DMMP]), aromatics, and
alkane derivatives (i.e., DNT and CEES, respectively). For
example, the response curve of FGO to DMMP is demon- Q15
strated in Figure 20.5 (Hu et al.20l2). Note that the depen-
dence of the response on the concentration of DMMP is linear,
which is very convenient during analysis of measurements in
practice.
Chemical or biological selectivity of sensors are discussed
by Zhu et al. (2010), Singh et al. (2011), and Hu et al' (2012)'
Cuong et al. (20,l0) used MEMS technology fbr the manufac-
ture of back-gated graphene FET sensors.
20.8 ACOUSTIC WAVE AND FUNCTIONATIZID
GRAPHENE GAS/VAPOR SENSORS
Gas/vapor sensing is possible using surface acoustic wave
(SAW) devices. Here, the frequency of operation of the
sensors changes with exposure to gas molecules. The shift
in frequency is proportional to the mass of adsorbed gas/
vapor molecules. SAW chemical sensors lor sensing of Ht
and CO at RT and 40oC, respectively, made of graphene-like

K20508_C020.indd 305 02-092015 14:22109

|
 306 Craohene Science Handbook

(4,, and Cuong et al. (2010). Detection of ethanol, CO, NHr H2O2,
16 80
and NO with appreciable selectivity toward electron donor
60 ppm
gases such as CO and NH, was carried out using such com-
1a
40 ppm posite structures. They have much better response to gases
over ZnO nanorod or GO-based gas sensors alone. Singh
:R
(2013) proposed that probably two different depletion layers
qc8 t0 ppm
were coexisting, one on theZn() surface and the other at the
interface of GO andZnO, which improve the sensitivity of the
4
integrated system. It is possible to use such sensors at RT. Such
a composite sensor has higher gas response, probably, due to
the larger specific surface area of ZnO nanoparticles on GO
islands compared with the use of ZnO alone as a gas sensor.
6000 8000 10,000 The ZnO-GO composite sensor is more selective to reducing
Time (s) gases and shows a poor response to oxidizing gases. Cuong
ct al. (2010) rcportod thc ZnO nanorod-graphenc structures.
(b) 16
Linear fit
Such sensors were able to detect 2 ppm of HrS in oxygen at
RT and nitrogen at 279oC (Figure 20.6). High-efficiency HrS
14 - sensors made of FqO./graphene nanosheets are reported by
t2 Jiang et al. (2014). Sun and Lin (2012) reported a simulation
y=O.1217x+4.9715
model, where it was assumed that the sensing mechanism is
-x R2 = 0.995
o<o 10 based on the variation of conduction of the nanoscale wtre
A< placed between two graphene leads. Other theoretical mod-
8 els should be proposed for an understanding of the compli-
cated physicochemical processes in such systems. All-optical
Mach-Zender interferometric NH, gas grapheme sensor has
been reported by Yao et al. (2014).

20 44 60
DMMP concentration (ppm)
FIGURE 20.6 The sensitivity of ZnO NRs-a chemically con-
verted graphene thin film sensor to HrS gas in (a) oxygen at RT
and (b) nitrogen at 270"C. (Adapted from Cuong, T. V. et al.' 2010.
M a te r ials Le u e rs 64, 241 9 -2482.)
nanosheets deposited on lithium tantalate, were reported by
Arsat et al. (2009). A bandgap of 0.1 eV was opened in such
a graphene-LiTaO, sensor. Other type of mass sensitive sen-
sors is bulk acoustic wave (BAW) sensors (graphene-based
quartz crystal microbalance (QCM) gas/vapor sensors).
Here, the mass is linearly dependent on frequency quite
similar to that of SAW sensors. A down to nanogram change
in the electrode mass can be detected in acoustic wave sen-
sors very efficiently (Yao et al. 2011). High sensitivity and
stability are typical for the mass-sensitive BAW and SAW
devices. SAW made of a single graphene layer was used
for the detection of the noble gases He, Ne, Ar, Kr, and Xe
(Arash et al. 201l).
Functionalization (decoration) of graphene became prom-
Q16
ising for gas detection metal oxides such as TiOr, ZnO, etc.,
leading to dramatically improving the selectivity aspects.
This was demonstrated, for example, by us for CNT sen-
sors (Aroutiounian et al. 2012). For example, we observed
synergetic effect in the TiO,-CNT system-the response
to e-butane which was absent for TiOr and CNT separately.
Such graphene-metal oxide functionalized gas sensors made
of ZnO-nanorod*GO were investigated by Palanisamy et al.
(2012),Yi et al. (201 l), Singh et al. (2012), Sun and Lin (2012)'
20.9 ANATYSIS OF EXPERIMENTAT
RESUTTS OBTAINED FOR DIFFERENT
GRAPHENE SENSORS
The dcvelopment of sensors with high response, short
response, and recovery times, as well as high selectivity is
still necessary. We are today on the stage of collecting infor-
mation about parameters of graphene/GO gas/vapor sensors.
Anyway, the best results for the response tr and recovery ,2
times are today for resistive and functionalized sensors.
Earlier graphene sensors functionalized with catalytically
active Pd or alloys containing Pd provide faster response
and recovery times at hydrogen sensing by graphene-metal
composite layers. Resistive hydrogen sensors working at RT
have /r 10-30 s, but /2 - few min in the detection range
-
40-8000 ppm (Johnson et al. 2010) and 40 and 50-60 s in the
0.5-l7o runge (Lange et al. 201 l). Correspondingly, tt and t,
are equal to 70-100 and 200-300 s during NO2 detection in
the 100-1000 ppm range (Ko et al. 20'l0). In the case of COt
detection, t, and t, were 8 and l0 s in the range 10-100 ppm
(Yoon et al. 20ll). The FET detection of ethanol vapors with
/r = 5-10 s and /2 = 30-40 s was reported by Chen et al.
(2012). The situation with functionalized grapheme-metal
oxide sensors at RT is rather good. /r = 5-6 s and l, = 2-5 s
were reported in the case of CO, and NH. detection (Singh
et al.2012). I, and t, are equal to several min-10-25 min for
other above-reported graphene sensors detecting NO, Hr, 02'
CO, COr, NH, gases, and ethanol vapor. No details of param-
eters (including the selectivity and stability) of sensors to

02-09-20t5 14122t1o
xzosoa cozo.inoc soo
I I
 Craphene- and Craphene-Oxide-Based Cas Sensors
chemical warfare agents and other important toxic gases such
as HrS and O: are available. We think that the development of
graphene gas/vapor sensors is in the beginning. We hope that
valuable parameters for practical applications of such sensors
will be reported in the near future.
20.10 coNctustoN
A brief information about different synthesis procedures for
graphene and GO is given in this chapter. We have reviewed
the recent developments in the field of gas/vapor sensors made
of graphene and GO. Sensing of different gases and vapors
(in particular, NOr, NO, NH3, CO, etc.) is of great practical
interest for industrial, domestic, environmental, medical, and
scicntitic applications. The manulacturc of gas/vapor sensors
demands a detailed knowledge of its sensitivity, selectiv-
ity, stability, interface, mechanical and electrical properties,
transduction efficiency, etc. But in many cases, the lack of an
energy gap in the electronic spectra of pristine graphene, for
example, prevents its use in making transistors, logic circuit
devices, and sensors. Several methods have been developed to
break the lattice symmetry in graphene and open an energy
gap. Note that the opening of the bandgap in graphene is a
unique phenomenon.
Several versions of gap opening are discussed in the chap-
ter. The best surface{o-volume ratio is in grapheneJike 2D
materials. Every atom of graphene, being a surface atom, is
capable of interacting with the target gas or vapor species,
which eventually results in the ultrasensitive sensor response
with the detection capability of even a single molecule of gas/
vapor. In particular, graphene should be doped with P, B, N,
and Hr, as nonmodified graphene is no an ideal material for
gas/vapor sensing. Moreover, B-doped grapheme is a two
orders of magnitude higher sensitive sensor of NO, NOr, or
NH. than N-doped graphene. The response and selectivity of
graphene sensors could be remarkably improved by the intro-
duction of controlled defects and impurities into graphene.
Therefore, the use of graphene has opened up an opportunity
for the detection of gases and vapors with excellent sensitiv-
ity, fast response time, and high stability. It is very important
that gas/vapor sensors made of graphene and GO have mainly
room-temperature operational temperature, and can work
without preheating of work body of the sensor.
Different types of graphene/GO gas/vapor sensors are con-
sidered in this chapter. Besides resistive sensors, FET, norse,
acoustic wave, functionalized sensors, as well as graphene-
based quartz crystal microbalance sensors are reported.
Wc havc discusscd thc possibilities, spccific propcrtics, and
parameters ofdetection ofthe following gases and vapors: Hr,
02, No2, No, cor, co, NH3, H2s, J2, H2o2, so2, chloride,
arsenic, humidity, ethanol, methanol, nonanal, tetrahydrofu-
ran, chloroform, acetonitrile, octanoid acid, hydroquinone,
dinitrotoluene, trimethylamine, dopamine, HCN, DMMP,
DNT, TMA, CEES, noble gases, other chemical warfare
agents, and important gas/vapors.
As the graphene films have lower resistance (typically a
few hundreds of ohms) compared with the metal oxide-based
*rosoe-coro.'noo sot
|
307
gas sensors, graphene/GO sensors can be integrated with ICs
easier. Graphene and its oxides promise the development of
more efficient gas sensors in the near future.
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