Modern Electronic Materials 2 (2016) 95105

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Modern Electronic Materials

journal homepage: www.elsevier.com/locate/moem

Carbon nanotubes: Sensor properties. A review

Irina V. Zaporotskovaa, , Natalia P. Borozninaa, Yuri N. Parkhomenkob, Lev V. Kozhitovb
a
Volgograd State University, 100 Universitetskii Prospekt, Volgograd 400062, Russia
b
National University of Science and Technology MISiS, 4 Leninskiy Prospekt, Moscow 119049, Russia

A R T I C L E I N F O A BS T RAC T

Keywords: Recent publications dealing with dealing with the fabrication of gas and electrochemical biosensors based on
Carbon nanotubes carbon nanotubes have been reviewed. Experimental and theoretical data on the working principles of
Sensor properties nanotubes have been presented. The main regularities of the structure, energy parameters and sensor
Sensors on the basis of carbon nanotubes properties of modied semiconducting systems on the basis of cabon nanotubes have been studied by analyzing
Boundary modied nanotubes
the mechanisms of nanotubule interaction with functional groups (including carboxyl and amino groups),
Carboxyl group
metallic nanoparticles and polymers leading to the formation of chemically active sensors. The possibility of
Amino group
using boundary modied nanotubes for the identication of metals has been discussed. Simulation results have
been reported for the interaction of nanotubes boundary modied by and NH2 groups with atoms and
ions of potassium, sodium and lithium. The simulation has been carried out using the molecular cluster model
and the MNDO and DFT calculation methods. Sensors fabricated using this technology will nd wide
application for the detection of metallic atoms and their ions included in salts and alkali.

Introduction areas such as additives to polymers and catalysts, in autoelectron

The current stage of research into the nanotubular forms of
materials is characterized by a great interest to their synthesis
methods, improvement of these synthesis methods, study of the
properties and attempts of industrial applications of these nanomater-
ials. Systems of this type attract interest thanks to a combination of
multiple properties that cannot be achieved in conventional single
crystal and polycrystalline structures. Nanomaterials are dened as
materials the sizes of which in at least one dimension are in the 1
100 nm range [13]. Their shapes may be zero-dimensional (0D) and
one-dimensional (1D) nanostructures. 0D nanostructures include, for
example, quantum dots [1]. Quantum dots were used as a structural
material for multiple applications including memory modules, quan-
tum lasers and optical sensors. The discovery of carbon nanotubes (1D
nanostructures) is one of the most important achievements of the
advanced science. This existence form of carbon is intermediate
between graphite and fullerenes. However, many of nanotube proper-
ties are drastically dierent from those of the abovementioned forms of
carbon. Therefore nanotubes (or nanotubulenes) should be considered
as a new material with unique physicochemical properties showing
good promise for a wide range of applications [48].
Carbon nanotubes (CNT) can nd applications in a great number of
emission for cathode rays of lighting components, at displays, gas
discharge tubes in telecommunication networks, absorption and
screening of electromagnetic waves, energy conversion, lithium battery
anodes, hydrogen storage, composite materials (llers or coatings),
nanoprobes, sensors, supercapacitors etc. [9,10]. The great variety of
the new unconventional mechanical, electrical and magnetic properties
of nanotubes can become the starting point for a breakthrough in
nanoelectronics.
As a nanotube is a surface structure, its whole weight is concen-
trated in its surface layers. This feature is the origin of the uniquely
large unit surface of tubulenes which in turn predetermines their
electrochemical and adsorption properties [11]. The high sensitivity of
the electronic properties of nanotubes to molecules adsorbed on their
surface and the unparalleled unit surface providing for this high
sensitivity make CNT a promising starting material for the develop-
ment of superminiaturized chemical and biological sensors [12,13].
The operation principle of these sensors is based on changes in the VI
curves of nanotubes as a result of adsorption of specic molecules on
their surface. The use of CNT in sensor devices is one of their most
promising applications in electronics. These sensors should have high
sensitivity and selectivity, as well as fast response and recovery.
Below we provide a review of recent works that dealt with the

Peer review under responsibility of the National University of Science and Technology MISiS.

Corresponding author.
E-mail addresses: irinazaporotskova@gmail.com (I.V. Zaporotskova), n.z.1103@mail.ru (N.P. Boroznina), parkh@rambler.ru (Y.N. Parkhomenko),
kozitov@misis.ru (L.V. Kozhitov).

http://dx.doi.org/10.1016/j.moem.2017.02.002
Received 5 December 2016; Accepted 10 January 2017
2452-1779/ 2017 The National University of Science and Technology MISiS. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
I.V. Zaporotskova et al. Modern Electronic Materials 2 (2016) 95105

development of CNT based sensors and study of their working

mechanisms, and generalize available theoretical and experimental
literary data on the alkaline metal sensitivity of carbon tubulenes
boundary modied by functional groups.

Structural features of carbon nanotubes

Carbon nanotubes were discovered and described by S. Injima,

Japan, in 1991. One of the amazing phenomena associated with the
nanotubes is the dependence of their properties on their shape.
Nanotubes are elongated cylindrical structures with diameters of 1 to
several dozens of nanometers and lengths of up to several microns Fig. 2. Main parameters of nanotube lattice: OA = h = na1 + ma2 is the chiral vector
consisting of one or several hexagonal graphite planes rolled in tubes. specied by the unit vectors 1 and 2; is the chiral angle, = is the lattice unit cell
Their surface consists of regular hexagonal carbon cycles (hexagons) vector and is the translation vector.
[410]. Depending on nanotube synthesis conditions, one- or multi-
layered tubulenes with open or closed terminations may form. Ch = n a1 + m a 2, (1)
The structure of tubulenes is typically described in terms of innite
as well as the tube diameter dt, the chiral angle and the basic
cylindrical surfaces accommodating carbon atoms interconnected into
translation vector T (Fig. 2).
a single network with hexagonal cells, i.e. the sp2-network. The mutual
The vector Ch connects the two crystallographically equivalent
orientation of the hexagonal network and the longitudinal axis of a
states O and A on a two-dimensional (2D) graphene plane in which
nanotube determines an important structural property of the tubulene,
carbon atoms are located. Fig. 2 shows the chiral angle of a zig-zag
i.e. its chirality. The chirality of a nanotube is described by two integers
type nanotube ( = 0) and the unit vectors a1 of a2 of the hexagonal
(n and m) that locate the hexagon of the network which will match after
lattice. The angle = 30 arc deg corresponds to an arm-chair tubulene.
nanotube rolling with the hexagon that is in the origin of coordinates.
The pairs of the symbols (n,m) specify dierent methods of graphene
The chirality of a nanotube can also be uniquely specied by the angle
surface rolling to a nanotube. The dierences in the chiral angle and
( is the orientation angle or the chiral angle) formed by the
the tube diameter dt cause dierences in the properties of the CNT. In
nanotube rolling direction and the direction of the common edge of two
the (n,m) notation system used for exactly specifying the chiral vector
adjacent hexagons. There are multiple nanotube rolling options, but of
Ch, the notation (n,m) in Eq. (1) refers to chiral symmetry tubulenes,
special interest are those which do not distort the structure of the
(n,0) refers to zig-zag tubulenes and (n,n) refers to arm-chair
hexagonal network. These optional rolling directions are those at the
tubulenes. The higher the value of n the greater the diameter of the
angles = 0 and 30 arc deg corresponding to the (n, 0) and (n, n)
tube.
chiralities, respectively. The orientation (or rolling) angle determines
In the terms of the (n,m) indexes, the diameter of a tubulene can be
the electrical properties of CNT. They can exhibit either metallic or
written as follows:
semiconductor conductivity types. However, most nanotubes are
1/2
semiconductors with a 0.1 to 0.2 eV band gap. Controlling their band 3 ac c(m 2 + mn + n 2 )
structure one can obtain a variety of electronic devices [10]. dt = Ch / = ,

It is a common practice to subdivide the CNT in two types, i.e. the
achiral and chiral ones. The chiral tubulenes have a screw symmetry, where acc is the dierence between the nearest carbon atoms
while the achiral ones have a cylindrical symmetry and are further (0.1421 nm for graphite) and h is the length of the chiral vector Ch.
divided in two types. In one of the achiral CNT types, two edges of each The chiral angle is specied by the following expression:
hexagon are parallel to the cylinder axis. These are the so-called zig- 3m
zag nanotubes (Fig. 1a). In the other type of the achiral CNT two edges = tan1 .
m + 2n
of each hexagon are perpendicular to the cylinder axis, these being the
so-called arm-chair nanotubes (Fig. 1b). To study the properties of the CNT as one-dimensional (1D)
Generally, the CNT can be described by specifying the chiral vector systems one should specify the lattice vector oriented along the
Ch: tubulene axis orthogonally to the chiral vector Ch (Fig. 2). The vector

Fig. 1. Idealized models of () zig-zag and (b) arm-chair monolayer nanotubes.

96
I.V. Zaporotskova et al.
of a chiral tubulene can be written as follows:
(2m + n )a1 (2n + m )a 2
T= . mechanism, attempts were made to accelerate gas desorption by
dk
whereas the following statement is true for dk:
d if n m is not a multiple of 3d
dk =
3d if n = m is a multiple of 3d
where d is the greatest common divisor of (n, m).
Gas sensors based on carbon nanotubes
As a nanotube is a surface structure, its whole weight is concen-
trated in the surface of its layers. This feature is the origin of the
uniquely large unit surface of tubulenes which in turn predetermines
their electrochemical and adsorption properties. The extremely high
adsorption capacity of the CNT and the excellent sensitivity of the CNT
properties to atoms and molecules adsorbed on their surface [8]
provide the possibility of designing sensors on the basis of nanotubes
[1214]. Currently, several types of gas sensors (detectors) on the basis
of the CNT are discussed in literature:
sorption gas sensors;
ionization gas sensors;
capacitance gas sensors;
resonance frequency shift gas sensors. We will consider these types
of sensors in detail.
Sorption gas sensors
Sorption gas sensors are the largest group of gas sensors [13]. Their
main operation principle is adsorption during which an adsorbed gas
molecule transfers an electron to or takes it from a nanotube. This
changes the electrical properties of the CNT, and this change can be
detected. There are gas sensors based on pure CNT including mono-
and multilayered ones, as well as those based on CNT modied by
functional groups, metals, polymers or metal oxides.
It is well known that monolayer CNT are sensitive to gases, e.g.
NO2, NH3 and some volatile organic compounds due to a change in the
conductivity of the nanotubes as a result of gas molecule adsorption on
their surface [15,16]. A sensor was designed [16] for detecting gases
and organic vapors at room temperature the detection limit of which
was as low as 44 ppb for NO2 and 262 ppb for nitrotoluene. The
recovery time of that sensor was ~10 h due to the high bond energy
between the CNT and some gases. Then [17] this recovery time was
reduced to 10 min by exposing to UV radiation which facilitated the
desorption of gas molecules.
The same gases were detected with another sensor [18] based on a
eld-eect transistor in which the conducting channel was one
semiconducting monolayer CNT. The response time of the device was
within a few seconds, and the response dened as the ratio between the
resistivity before and after gas exposure was approx. 1001000 ppm
for NO2. Three models were proposed for explaining the action of that
sensor:
charge transfer between a nanotube and a molecule adsorbed on its
surface;
molecular strobing of nonpolar molecules e.g. NO2 which shift the
conduction threshold of the CNT;
change of the Schottky barrier between the nanotube and the
electrodes [19,20].
In transistor based sensors the energy barrier of CNT adsorption for
dimethylmethylphosphonate [21], NH3 [22] or NOx [23] can be
reduced by applying positive bias to the gate. This causes electron
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Modern Electronic Materials 2 (2016) 95105
tunneling through a narrow barrier.
To reduce the sensor recovery time after gas detection by a sorption
heating sensor detectors. The operation of a monolayer CNT based
sensor for NH3 detection was analyzed [24]. Gas exposure leads to
electron transfer from NH3 to the tube resulting in the formation of a
spatial charge region on the surface of the semiconductor CNT and
hence an increase in its electrical resistivity. The device reached
saturation at a concentration of ~40 ppm. The sensor recovered
completely to the initial state at 80 C. Fabrication of sensor detectors
by template printing followed by annealing in air at dierent tempera-
tures for 2 h was reported [25]. Those sensors were used for NH3
detection. After 10 min gas exposure at room temperature the sensor
resistivity increased by 8% compared to the initial level. The conduc-
tion type of the CNT changed from semiconducting at moderate
temperatures ( < 350 ) to metallic at high temperatures ( > 350 C).
The possibility of fabricating multilayered CNT (MCNT) based
sensors was discussed [26,27]. The resistivity of the sensor proved to
change due to the p conductivity type in semiconducting MCNT and the
formation of Schottky barriers between nanotubes having metallic
conductivity type and those having semiconductor conductivity type
during gas adsorption. An electrochemical gas sensor was designed on
the basis of modied multilayered CNT lms for Cl2 detection [28]. The
sensors surface which was the cathode was exposed to chlorine gas,
and the resulting galvanic eect was measured. The nanotubes acted as
the microelectrode. The recovery time of that sensor was ~150 s.
Another sensor on the basis of ultrathin CNT lms [29] was used for
NO2 and NH3 detection at room temperature. The authors proposed a
method of synthesizing ~5 nm thick lms with a high density of
nanotubes ensuring high sensitivity and reproducibility of the sensor,
i.e. 1 ppm for NO2 and 7 ppm for NH3. Gas desorption was accelerated
by UV exposure.
Gas sensors on the basis of oriented CNT were described [30]. The
resistivity of the CNT lms declined after NO2 exposure and increased
after NH3, ethanol and C6H6 exposure. A nanotube lm can be
described as a network of highly ecient resistors consisting of the
resistances of every single CNT and the resistivity of the sites and
tunnels between adjacent nanotubes. A vertical transport type detector
was suggested [31] on the basis of regular CNT arrays for an NH3 gas
sensing. The detector had high sensitivity and response time (less than
1 min) and good recovery at atmospheric pressure and room tempera-
ture. It provided NH3 detection in the 0.16% range.
CNT modication by functional groups, metal nanoparticles, oxides
and polymers changes the electronic properties of the nanotubes and
increases their selectivity and response to specic gases. Noteworthy,
the interaction of target molecules with dierent functional groups or
additives varies signicantly. CNT are often modied by adding the
carboxyl group . This group creates reactive sections at the
terminations and the side walls of the CNT where active interaction
with various compounds occurs. For example, it was shown [32] that
sensors synthesized from carboxylated monolayer CNT were sensitive
to CO with a 1 ppm detection limit whereas pure monolayer CNT did
not respond to this gas. The NO2 gas sensitivity of monolayer CNT
functionalized by the amino group NH2 was studied [33]. The amino
group acts as a charge transfer agent of the semiconducting CNT that
increases the number of electrons transferred from the nanotube to the
NO2 molecule.
There are also gas sensors on the basis of CNT functionalized by
polymers that show good performance at room temperature [34,35].
They can be used as conductometric, potentiometric, amperometric
and volt-amperometric converters for the detection of a wide range of
gases. it was shown [36] that eld eect transistors based on monolayer
CNT modied by polyethyleneimine can be used as gas sensors with
improved response and selectivity for NO2, CO, CO2, CH4, H2 and O2.
These sensors were able to detect less than 1 ppm NO2 within a
response time of 12 min. It was demonstrated [37] that functionalized
I.V. Zaporotskova et al.
monolayer CNT with attached poly(sulfonic acid m-aminobenzene)
have higher sensitivity to NH3 and NO2 compared with carboxylated
nanotubes. These systems exhibited sensitivity to 5 ppm NH3. CNT
modication by polymers also improves their sensitivity to organic
compound vapors. A compact wireless gas sensor was designed [38] on
the basis of monolayer CNT + polymethylmetacrylate (PMMA). The
sensor exhibited a fast response (25 s) and an increase in resistivity by
100 orders of magnitude after exposure to dichloromethane, chloro-
form and acetone vapors. The sensor recovered to the initial state
immediately after gas removal. The sensors action mechanism was
accounted for by polymer response to the adsorption of organic vapors
by PMMA and charge transfer from polar organic molecules adsorbed
on the surface of the nanotubes. The working principle of an integrated
system on the basis of monolayer CNT and polymer cellulose was
described [39]. A cellulose layer was applied to the surface of the
conducting CNT which was used as a gas sensor for the detection of
benzene, toluene and xylene vapors.
There are gas sensors based on CNT modied by metallic nano-
particles [40]. The working principle of a sensor on the basis of
monolayer CNT with palladium (Pd) nanoparticles for hydrogen
detection at room temperature was described [41]. The response time
of the sensor was 510 s, the recovery time being ~400 s. Adsorbed H2
molecules are known to dissociate at room temperature into hydrogen
atoms that are dissolved in Pd and reduce the metal work function. As a
result the carrier concentration in the nanotubes decreases and their
conductivity drops. The process is reversible for dissolved atomic
hydrogen can react with atmospheric oxygen to form OH. This causes
the formation of water which eventually leaves the Pd-CNT system and
the initial conductivity of the sensor is restored. Two methods of
monolayer CNT functionalizing by palladium for the fabrication of
hydrogen detectors was described [42]. Nanotubes can be either
chemically functionalized by Pd or coated with sputtered metal lms.
In another work [43] an H2 nanosensor functionalizing method was
developed that implied electrodeposition of Pd particles on monolayer
CNT. The sensor exhibited a good room temperature response. The
detection limit was 100 ppm, the recovery time being 20 min.
Other metals can also be used for the design of CNT based gas
sensors. Sensors on the basis of multilayered nanotubes functionalized
by Pt or Pd were fabricated [44,45]. They showed good H2 sensitivity
and recovery at room temperature. The response and recovery times
were 10 min for CNT functionalized by Pd and 15 min for CNT
functionalized by Pt. Another hydrogen detector was designed on the
basis of monolayer CNT decorated by gold particles [46]. The eect of
point heterocontacts between CNT and gold microwires on the detec-
tion of NH3 and NO2 with fast response and recovery was demon-
strated [47]. The working mechanism of the probe was based on the
formation of a thin conducting channel between Au and a nanotube
and a change in the resistivity of the tubulene. Gas detectors on the
basis of monolayer nanotubes modied by Au, Pt, Pd and Rh were
reported [48]. The dierence in the catalytic activity of the metal
nanoparticles determines the selectivity of the sensors for 2, CH4, CO,
H2S, NH3 and NO2. The working principle of a high-eciency gas
sensor based on MCNTPt composite material sensitive to toluene
C7H8 was described [49]. The sensor responses at a concentration of
1 ppm and 150 C were measured. The eciency of the sensor was
noticeably higher than that of earlier described sensors [50].
There were also reports on the fabrication of gas sensors on the
basis of CNT and nanostructured metal oxides [5056]. Sensors
modied by SnO2 or TiO2 were sensitive to NO2, CO, NH3 and ethanol
vapors at low working temperatures. Nanotubes in metal oxide
matrices produced the main conducting channels which eciently
changed the conductivity of the composite material during gas adsorp-
tion. The recovery time of the sensors depended on the energy of the
bond between gas molecules and the CNT surface. A sensor on the basis
of MCNT coated by SnO2 was described [57] that exhibited a good
response to oil gas and ethanol vapors and recovered within a few
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Modern Electronic Materials 2 (2016) 95105
seconds at 335 C. The sensors response grew with gas concentration.
The high sensitivity and low resistivity of that system was accounted for
by the specic features of its electron transfer mechanism. Electrons
move through SnO2 grains in MCNT that have a low resistivity.
Furthermore, the sensors gas response could increase due to the
formation of the pn junction between the nanotubes and the SnO2
nanoparticles [58]. Acetone and NH3 can be detected with TiO2 +
MCNT composition sensors fabricated using the sol gel method [59].
Sensors on the basis of SnO2TiO2 oxide mixture and MCNT
embedded into thin SnO2TiO2 lms were described [60]. The
response and recovery times of those sensors were less than 10 s at
working temperatures of 210400 C. The improved sensor character-
istics and the lower working temperatures can be attributed to an
enhancement of the pn junction inuence in addition to the grain
boundary eects.
An interesting working principle of a CNT based sensor device was
demonstrated by a scientists team of the Research Center at the
Toulouse University, France [61]. They found a signicant dependence
of microwave radiation transmission pattern in a material containing
two-layered nanotubes on the concentration of impurities in atmo-
sphere [61]. Specimens of two-layered nanotubes ~2 nm in diameter
and ~10 m in length that had high purity and high reproducibility of
the electric, magnetic and optical parameters were introduced in a
powdered form into the cavity of a silicon waveguide mounted on a thin
dielectric membrane. The membrane material had a dielectric constant
close to unity and a high microwave radiation transmission coecient
in the 1110 GHz range. To study the sensor characteristics the
authors exposed the device to nitrogen at a 5 atm pressure for 16 h.
Experimental data on the microwave radiation transmission coecient
and the wave phase shift in the abovementioned frequency range
demonstrated substantial changes in these parameters as a result of gas
sorption. The recovery time to the initial device parameters was several
hours at room temperature. However, this time decreased by many
times if the device was heated.
Many researchers dealt with CNT based gas sensors containing
various surface defects. For example, CNT based sensors doped with
boron and nitrogen were described [62]. These sensors were used for
detecting low NO2, CO, C2H4 and H2O concentrations at room
temperature and at 150 C. It was found that nitrogen doped CNT
were more sensitive to nitrogen dioxide and carbon oxide while boron
doped tubes exhibited better sensitivity to ethylene. All the nanotubes
were highly sensitive to humidity variations. Another study [63] dealt
with sensors on the basis of monolayer CNT containing vacancy surface
defects formed as a result of high temperature exposure (300800 C).
Measurements of the sensitivity of those sensors to NO2, NH3 and H2
showed higher sensitivity of defect containing sensors compared to
defect free ones at room temperature. The authors hypothesized [63]
that part of gas molecules are adsorbed on nanotube surfaces while
others penetrate into openings produced on nanotube walls as a result
of high temperature exposure (Fig. 3).
Thus, sorption sensors on the basis of CNT exhibit high sensitivity
but are not free from a number of disadvantages:
inability to identify gases with low adsorption energies;
lack of selectivity;
high nanotube sensitivity to variations of ambient conditions
(humidity, temperature and gas owrate);
long exposure time (from decades of seconds to several minutes);
long sensitive element recovery time (from several minutes to
several hours);
possible irreversible changes of CNT conductivity due to chemisorp-
tion.
Ionization gas sensors
The problem of detecting gas molecules with low adsorption
I.V. Zaporotskova et al.
Fig. 3. (a) Model of sensor on the basis of monolayer CNT modied by defects and (b)
SEM image of CNT on sensor.
energies was resolved by using ionization gas sensors. The working
principle of these sensors is based on the determination of gas
ionization parameters during accelerated ion collision with gas mole-
cules. Due to the absence of adsorption and chemical interaction
between the sensitive element and the tested gas one can identify
gases with low adsorption energies. However, ionization type gas
sensors do not nd general application due to the following disadvan-
tages:
unacceptable weight and dimensions;
high operation voltages ((102103 V) and hence high power con-
sumption.
The use of CNT as one of the sensor electrodes is a key to partial
solution of these problems. The design of these sensors includes an
anode in the form of an array of vertically arrange CNT, an aluminum
cathode and a 150 m thick glass insulation layer inserted between the
anode and the cathode. If voltage is applied between the anode and the
cathode the nanotubes induce high electric eld at their terminations
due to their high aspect ratio [64,65]. These conditions are favorable
for the formation of self-sustained electrode discharge at lower voltages
required. Results for NH3, CO2, N2, O2, He and Ar gas detection with
these sensors were reported [66]. It was found that with an increase in
gas concentration the breakdown voltage of the sensors changed but
slightly while the discharge current increased linearly for each gas. This
is accounted for by the inuence of the volume concentration of gas
molecules on the discharge current and the dependence of the break-
down voltage primarily on electric eld magnitude and the bond energy
of gas molecules.
Thus, the low power consumption and breakdown voltage, high
selectivity and process compatibility with standard microelectronics
technologies as well as compact dimensions of planar ionization
99
Modern Electronic Materials 2 (2016) 95105
sensors on the basis of CNT show good promise for their general use.
However, their wide application is hindered by the necessity of using
high sensitivity signal processing devices and degradation of the CNT
sensitive element due to coronary discharges.
Capacitance gas sensors
One more type of sensors in which CNT arrays are used as sensitive
elements are capacitance gas sensors. A capacitance sensor was
described [67] the sensitive element of which was an array of
misoriented nanotubes grown on a SiO2 layer. The rst plate of the
sensor was a CNT array, the other plate being silicon. If external
voltage is supplied between the two plates, high magnitude electric eld
is generated at the CNT terminations causing polarization of adsorbed
molecules and an increase in the capacity. High sensitivity of that
sensor to vapors of benzene, hexane, heptanes, toluene, isopropyl
alcohol, ethanol, chlorobenzene, methyl alcohol, acetone and dinitro-
toluene was demonstrated [68]. The main drawback of capacitance gas
sensors are irreversible CNT changes caused by gas chemisorption
necessitating sensitive element regeneration or replacement. Moreover,
sensors of this type cannot perform well at high humidity and therefore
their application areas are further restricted.
Resonance frequency shift gas sensors
A change in the electrical properties of the CNT during their
interaction with gases was used as a basis for the development of
resonance frequency shift gas sensors [69,70]. The sensitive elements
of these sensors can be disk resonators with nanotubes grown on the
outer surfaces of the disks. When the CNT on the resonator are exposed
to gases the dielectric permeability of the disk with the nanotubes
changes resulting in a shift of its resonance frequency. Because of the
dierence in the frequency shifts caused by dierent gases these
sensors exhibit good sensitivity and selectivity. This allows detecting
a large number of gases at low concentrations including NH3, CO, N2,
He, O2 and Ar. A drawback of this type of sensors is the necessity of
using additional equipment for analyzing the dielectric permeability
and resonance frequency.
Electrochemical and biological sensors on the basis of CNT
A special group of sensors are electrochemical and biological
sensors (biosensors) that contain CNT. Their typical working principle
is based on oxidation and reduction reactions occurring during the
interaction with biomolecules. Electrochemical sensors with CNT have
found general application in biomedical research [71].
Electrochemical sensors and biosensors were studied [72] the
electrodes of which were CNT modied by redox polymers acting as
catalysts of the electron transfer reaction between biomolecules and the
basis of the electrode, i.e. nanotubes [73]. This combination of CNT
with polymer improves the electrical conductivity and mechanical
strength of the hybrid material. Redox polymers can be selected from
dierent groups of polymers capable of reversible oxidation and
reduction reactions, e.g. azine group polymers (phenazines, phenothia-
zines, phenoxazines etc.) [7478]. These biosensors allow detecting
glucose, ethanol, hydrogen peroxide, nitride, sorbitol, uric and ascorbic
acids, dopamine etc. An amperometric device for glucose detection was
described [79]. Glucose oxidase was introduced into a composite
material and attached to the terminations of the sensor CNT by
creating amide bonds between the Nacetylglucosamine residues and
the carboxyl groups of the modied nanotubes. Glucose was oxidized
by oxygen under the catalytic eect of glucose oxidase, the reaction
product being gluconolactone and hydrogen peroxide. The concentra-
tion of the product hydrogen peroxide is proportional to the initial
glucose concentration. Therefore the sensor signal caused by hydrogen
peroxide in the sample was used for characterizing glucose concentra-
I.V. Zaporotskova et al.
tion. If the composite material contained 10 wt% glucose oxidase the
device signal was linearly proportional to glucose concentration in the
05.4 g/l range, the glucose detection limit being approx. 0.11 g/l
[80].
Biosensors on the basis of CNT arrays are also suitable for the
analysis of deoxyribonucleic or ribonucleic acids (DNA or RNA). For
this application the sensor nanotubes are modied by oligonucleotides
e.g. guanine. The abovementioned valuable property originates from
the ability of oligonucleotides to readily bind with respective comple-
mentary DNA or RNA nucleotides. The signal characterizing the
content of DNA or RNA in the sample is measured using the complex
[Ru(bpy)3]2+ compound which detects guanine oxidation. A decrease
in the density of CNT on the sensor surface causes an increase in the
sensor sensitivity [81]. The study showed that guanine oxidation
produced a far higher signal in that sensor compared to a graphite
electrode signal. The detection limit for a 21-term oligonucleotide was
2 g/l, the DNA detection limit being 170 g/l [82].
Boundary modied CNT as active components of sensor
devices
Carboxylated CNT
Sensors can also be based on boundary modied CNT. This can be
for example an atomic force microscope the probe of which has a
chemically modied nanotube with a specially selected functional
group. Experiments were reported [83] in which CNT were obtained
with one of the boundaries being modied by an attached carboxyl
group. In the experiments the authors used a multilayered nanotube
attached to the golden pyramid of the microscopes silicon cantilever.
The nanotube termination was truncated in an oxygen containing
atmosphere by applying voltage between the tube and mica surface
with a niobium layer sputtered on it. A carboxyl group (, Fig. 4)
formed at the open nanotube termination. It was reported [34,84] that
carboxylated CNT are sensitive to ethanol vapors and NO, and NO2
gases. If necessary the carboxyl group can be substituted for other
functional groups using methods applied in organic chemistry. The
probe with the modifying group interacts with specimen surfaces
having dierent chemical compositions in dierent manners. Thus
the probe of an atomic force microscope tted with a nanotube and a
specially selected chemical group becomes chemically sensitive. It is
logical to assume that the use of modied CNT as sensors may not be
restricted to gas detection. Other chemical elements, e.g. metals, can
also be sensed. It is also possible to dierentiate between metal atoms
and their ions contained in salts and alkali.
The mechanism of functional group attachment to a
Fig. 4. Nanotube with functional chemical group as probe of cantilever of scanning
atomic force microscope. Shown is probe movement for measurement of interaction
energy between functional group and specimen surface.
100
Modern Electronic Materials 2 (2016) 95105
Fig. 5. Model of semi-innite CNT (6, 0) with edge functional carboxyl group.
monolayer semi-innite carbon tubulene was studied [86] and the
activity of this modied system to several metals was investigated. Zig-
zag (6,0) type tubulenes were simulated within the molecular cluster
model using a semiempirical calculation method (MNDO) [87,88] and
the DFT calculation method [89]. One of the cluster boundaries was
terminated by pseudoatoms for which hydrogen atoms were selected,
and a carboxyl group was attached to the carbon atom at the other CNT
termination (Fig. 5). Specic features were identied in the spatial
orientation of the carboxyl group relative to the nanotube boundaries,
as well as its geometry and inner charge distribution.
The mechanism of functional group attachment to a
selected carbon atom at an open nanotube boundary was simulated
by stepwise approximation of the carboxyl group position with a
0.01 nm step along a perpendicular line drawn towards the tube
boundary and oriented to a C atom [90]. As a result the formation of
a chemical bond between the nanotube and was observed
testifying to the possibility of monolayer CNT functionalizing by
carboxyl groups for providing highly sensitive chemically active probes
on their basis.
Then the authors studied the interaction mechanism between
potassium, sodium and lithium atoms with terminal oxygen and
hydrogen atoms of the carboxyl group. The process was simulated by
stepwise approximation of the selected metal atoms to the O or H atom
of the functional group. Potential energy surface proles were plotted
for the nanotube + metal atom system (Fig. 6). Each prole
had a minimum corresponding to the formation of bonds at specic
distances. Table 1 summarizes the calculation results characterizing the
main parameters of , Li and Na atom attachment to the terminal
atoms of the carboxyl group that modies an open CNT boundary. As
the interaction distances corresponding to the minima in the energy
proles are quite large one can assume that the interaction between the
functional group atoms and the selected metal atoms is the weak Van-
der-Waals one. This is an important result conrming the possibility of
multiple reusing of these probes without destruction which could
otherwise be caused by chemical interaction with the selected alkaline
metal atoms.
The authors further studied the scanning of an arbitrary surface
containing sodium, potassium or lithium atoms to be initialized and
determined the sensitivity of CNT with terminal functional groups to
I.V. Zaporotskova et al. Modern Electronic Materials 2 (2016) 95105

Fig. 7. Simulation of scanning of an arbitrary surface area containing Na atom (shown

as purple ball). Dashed line shows sodium atom migration relative to nanotube with
Fig. 6. Energy proles of interaction between CNT modied by carboxyl group functional carboxyl group. Green balls in the gure show carbon atoms, red balls are
and Na, K and Li depending on distance between (a) metal atoms and hydrogen atom of oxygen atoms and white ones are hydrogen atoms.
the group and (b) metal atoms and oxygen atom of the group.

ism whereby the boundary of a monolayer CNT is modied by a

Table 1
functional carboxyl group resulting in the formation of a sensor that
Main Parameters of , Li and Na Attachment to the Terminal O and H Atoms of Carboxyl
Group that Modifies CNT (6, 0).
was later fabricated in the course of experiments and proved to be
sensitive to some gases [8385]. The sensor responded to the presence
Interatomic Bond rint, nm int, eV of ultrane quantities of materials, and this shows good promise for its
applications in chemistry, biology, medicine etc. The use of chemically
MNDO DFT
modied nanotubes in atomic force microscopy is a way to the
Na 0.22 -4.23 -3.21 fabrication of probes with clearly specied chemical characteristics.
Na 0.18 -3.03 -1.77
K 0.25 -4.00 -4.3
K 0.18 -2.41 -1.04 Carbon nanotubes boundary modied by amino group
LiO 0.20 -5.45 -4.39
LiH 0.19 -5.90 -4.62 As noted above, a carboxyl group can be substituted for other
functional groups using methods applied in organic chemistry, e.g. for
Notations. Hereinafter: rint is the interaction distance between the metal atom or the O
(or H) atom of the functional group and int is the energy of the respective interaction.
the quite abundant and well studied amino group NH2. The reactivity
of the amino group originates from the presence of an unshared pair of
selected chemical elements. The process was simulated by stepwise electrons. The interaction of monolayer CNT functionalized by NH2
approximation of the selected metal (ion) atoms to the functional group group with NO2 gas was studied [91]. It was shown that the amino
that was parallel to the modied nanotube boundary (Fig. 7). Analysis group acts as a charge transfer agent in the semiconducting CNT and
of the interaction energy proles plotted based on the calculations hence the number of electrons transferred from the nanotubes to the
(Fig. 8) showed that the modied tubulene became chemically sensitive NO2 molecule increases.
to the selected metals. The energy proles had typical minima There is a report [92] on an investigation of amino group attach-
indicating the formation of stable interaction between elements and ment to an open boundary of semiconducting monolayer CNT forming
the CNT + COOH system. The binding energies are summarized in a chemically active probe for sensor devices and the interaction
Table 2. The results substantiate the possibility of using modied CNT between simulated boundary modied systems with atoms and ions
as sensors for some elements and radicals. Their presence can be of metals. The authors simulated the attachment of an amino group to
experimentally detected by controlling the change in the potential in an open boundary of a semi-innite CNT (6, 0). Analysis of the
the probing system based on a nanotube with a functional group. potential energy surface proles plotted for the nanotube + N2
These theoretical studies provided an explanation of the mechan- system revealed the formation of a chemical bond between CNT and
the functional group.

101
I.V. Zaporotskova et al. Modern Electronic Materials 2 (2016) 95105

Fig. 8. Proles of energy interaction between (a) atoms or (b) ions of metal (K, Li, Na)
and CNT + system obtained by simulation of scanning. r = 0 is the point under the
hydrogen atom of the carboxyl group. Fig. 9. Proles of energy interaction of CNT (6, 6) modied by amino group with (a) Na,
K and Li metal atoms and (b) Li+, Na+ and K+ ions calculated using MNDO method.
Table 2
Main parameters of interaction of carboxylated CNT (6, 0) with metal atoms and ions as Table 3
determined by surface scanning. Main parameters of , Li and Na attachment to CNT (6, 6) modified by amino group.

Atom/Ion rs-int, nm s-int, eV Interatomic Bond rint, nm int, eV

Na 0.3 -0.64 MNDO DFT

Na+ 0.26 -1.73
K 0.25 -1.77 Na 0.16 -1.90 -2.43
K+ 0.28 -1.76 0.16 -3.60 -3.22
Li 0.3 -0.93 Li 0.18 -1.17 -1.0
Li+ 0.3 -1.63 Na+ 0.12 -2.78 -3.21
K+ 0.20 -5.54 -4.30
Notations. Hereinafter: rs-int and s-int are the distance and energy of sensor interaction, Li+ 0.15 -2.15 -3.39
respectively.

Analysis of the charge distribution in the system showed that the
carbon atom of the nanotube to which the amino group is attached
acquires the charge q = +0.2. The negative charge acquired by the
nitrogen atom of the functional group suggests that the attachment of
N2 to the tubulene boundary causes a transfer of electron density
from the carbon atom of the nanotube to the nitrogen atom of the
amino group. This activates the sensor working mechanism according
to which the resultant system acting as a sensor has a dierent
concentration of charge carriers that triggers conductivity in the
nanosystem.
The authors studied the interaction mechanism between potassium,
sodium and lithium atoms and monolayer CNT functionalized by
amino group. The process was simulated by stepwise approximation
of the selected metal atoms to the H atom of the functional group. The
potential energy surface proles plotted for the nanotube + NH2metal
atom system (Fig. 9) have minima corresponding to the presence of
interaction at specic distances. Table 3 summarizes the calculation
results characterizing the main parameters of , Li and Na atom
attachment to the boundary modied CNT system. The presence of the
weak Van-der-Waals interaction indicates the possibility of multiple
reusing of these probes. Moreover, a probing system based on
nanotubes modied by functional groups may undergo a charge in
the height of the Schottky barrier between the nanotube + N2 system
and the sensor device electrodes as a result of the interaction with
metal atoms, and this change will be detected during sensor operation.
The interaction parameters obtained using various theoretical methods
(MNDO and DFT) proved to be in a good agreement conrming the
correctness of the results. Analysis of the charge state of the system
showed that the electron density is transferred from the metal atoms to
the probe system. This leads to an increase in the concentration of
charge carriers and changes the electrical properties of the system.
The authors studied the sensor properties of the probe fabricated on

102
I.V. Zaporotskova et al.
Table 4
Main parameters of interaction of CNT (6, 0) modified by amino group with sodium,
potassium and lithium atoms and ions as determined by arbitrary surface scanning
simulation.
Atom/Ion rs-int, nm s-int, eV
MNDO DFT
K 0.20 -5.47 -5.21
Li 0.20 -2.25 -2.00
Na 0.19 -3.12 -3.48
Na+ 0.12 -2.05 -2.23
K+ 0.14 -5.54 -5.15
Li+ 0.15 -2.15 -2.36
the basis of CNT modied by amino group for sodium, potassium and
lithium atoms and ions by simulating the scanning of a surface
containing selected atoms (or ions). Analysis of the results showed
that tubulenes with functional amino groups become sensitive to the
selected elements. The interaction energies are summarized in Table 4.
Thus, the experimental and theoretical results conrm the possibi-
lity of using CNT modied by amino and carboxyl groups as sensors for
specic elements and radicals. Their presence can be experimentally
detected by controlling the change in the potential of the probing
system based on a nanotube with a functional group. The resultant
sensor element will be highly selective: as can be seen from Tables 3
and 4, the interaction energies of the sensor system with dierent
elements are dierent. Therefore the system response to the presence
of atoms or their ion will also be dierent.
Summary
Experimental and theoretical studies showed that CNT are an
extremely promising material for further use in the eld. Further
development of nanotube technologies will provide new physical
objects the properties of which will be of great scientic and practical
interest. Thanks to their unique structure and properties the CNT can
be used as active elements of sensors for the detection of numerous
materials including gases, organic compounds etc. CNT modication by
functional groups, metal nanoparticles, polymers and metal oxides
greatly increase the selectivity of the detectors fabricated on their basis.
Their high electric catalytic activity and fast electron transfer combined
with high stability of nanotube compounds with redox polymers
provide for CNT application as electrochemical biosensors. Current
investigations focus on the search for new modifying additives that will
improve the parameters of CNT based sensors. This review aims at
stressing not only the unique physicochemical properties of sensor
components but also possible synergistic eects that may occur as a
result of CNT modication by chemically active groups and particles.
Sensors fabricated on their basis will have high selectivity and response
to the presence of ultrane quantities of materials, e.g. metals included
in salts and alkali, and this shows good promise for their use in
chemistry, biology, medicine etc.
References
[1] V.D. Blank, A. Seepujak, E.V. Polyakov, D.V. Batov, B.A. Kulnitskiy, Yu.
N. Parkhomenko, E.A. Skryleva, U. Bangert, A. Gutirrez-Sosa, A.J. Harvey, Growth
and characterisation of BNC nanostructures, Carbon 47 (14) (2009) 31673174.
http://dx.doi.org/10.1016/j.carbon.2009.07.022.
[2] Yu. M. Shulga, V.N. Vasilets, S.A. Baskakov, V.E. Muradyan, E.A. Skryleva, Yu.
N. Parkhomenko, Photoreduction of graphite oxide nanosheets with vacuum
ultraviolet radiation, High. Energy Chem. 46 (2) (2012) 117121. http://
dx.doi.org/10.1134/S0018143912020099.
[3] A.A. Eliseev, A.V. Lukashin, Funktsionalnye nanomaterialy [Functional nanoma-
terials], Fizmatlit, Moscow, 2010, p. 456.
[4] A.L. Ivanovskii, Kvantovaya khimiya v materialovedenii. Nanotubulyarnye formy
veshchestva [Quantum chemistry in materials science. Nanotubular forms of
matter], UrORAN, Ekaterinburg, 1999, p. 176.
[5] M.S. Dresselhaus, G. Dresselhaus, P.C. Eklund, Science of Fullerenes and Carbon
103
Modern Electronic Materials 2 (2016) 95105
Nanotubes, Academic Press, Inc, New York, 1996, p. 965 https://www.elsevier.
com/books/science-of-fullerenes-and-carbon-nanotubes/dresselhaus/978-0-12-
221820-0.
[6] R. Saito, M.S. Dresselhaus, G. Dresselhaus, Physical Properties of Carbon
Nanotubes, Imperial College Press, 1999, p. 251.
[7] P. Kharris, Uglerodnye nanotruby i rodstvennye struktury. Novye materialy XXI
veka [Carbon nanotubes and related structures. New materials of the 21st century],
Tekhnosfera, Moscow, 2003, p. 336.
[8] I.V. Zaporotskova, Uglerodnye i neuglerodnye nanomaterialy i kompozitnye
struktury na ikh osnove: stroenie i elektronnye svoistva [Carbon and non-carbon
nanotubes and composite structures on their basis: structure and electronic
properties], Izd-vo VolGU, Volgograd, 2009, p. 490.
[9] M.S. Dresselhaus, G. Dresselhaus, P. Avouris, arbon Nanotubes: Synthesis,
Structure, Properties, and Application, Springer-Verlag, 2000, p. 464.
[10] P.N. Dyachkov, Elektronnye svoistva i primenenie nanotrubok [Electronic prop-
erties and applications of nanotubes], BINOM, Laboratoriya znanii, Moscow, 2010,
p. 488.
[11] A.V. Eletskii, Sorption properties of carbon nanostructures, Phys. Usp. 47 (11)
(2004) 11191154. http://dx.doi.org/10.1070/PU2004v047n11ABEH002017.
[12] K.F. Akhmadishina, I.I. Bobrinetskii, I.A. Komarov, A.M. Malovichko, V.K. Nevolin,
V.A. Petukhov, A.V. Golovin, A.O. Zalevskii, Flexible biological sensors based on
carbon nanotube lms, Nanotechnol. Russ. 8 (1112) (2013) 721726. http://
dx.doi.org/10.1134/S1995078013060025.
[13] Zhang Wei-De, Zhang Wen-Hui, Carbon nanotubes as active components for gas
sensors, J. Sens. 2009 (2009) 16. http://dx.doi.org/10.1155/2009/160698.
[14] A. Boyd, I. Dube, G. Fedorov, M. Paranjape, P. Barbara, Gas sensing mechanism of
carbon nanotubes: from single tubes to high-density networks, Carbon 69 (2014)
417423. http://dx.doi.org/10.1016/j.carbon.2013.12.044.
[15] J. Zhao, A. Buldum, J. Han, J.P. Lu, Gas molecule adsorption in carbon nanotubes
and nanotube bundles, Nanotechnology 13 (2) (2002) 195200. http://dx.doi.org/
10.1088/0957-4484/13/2/312.
[16] J. Li, Y. Lu, Q. Ye, M. Cinke, J. Han, M. Meyyappan, Carbon nanotube sensors for
gas and organic vapor detection, Nano Lett. 3 (7) (2003) 929933. http://
dx.doi.org/10.1021/nl034220x.
[17] R.J. Chen, N.R. Franklin, J. Kong, J. Cao, Th. W. Tombler, Zhang Yu, H. Dai,
Molecular photodesorption from single-walled carbon nanotubes, Appl. Phys. Lett.
79 (14) (2001) 22582260. http://dx.doi.org/10.1063/1.1408274.
[18] J. Kong, N.R. Franklin, C. Zhou, M.G. Chapline, S. Peng, K. Cho, H. Dai, Nanotube
molecular wires as chemical sensors, Science 287 (5453) (2000) 622625. http://
dx.doi.org/10.1126/science.287.5453.622.
[19] J. Zhang, A. Boyd, A. Tselev, M. Paranjape, P. Barbara, Mechanism of NO2
detection in carbon nanotube eld eect transistor chemical sensors, Appl. Phys.
Lett. 88 (12) (2006) 123112. http://dx.doi.org/10.1063/1.2187510.
[20] T. Helbling, R. Pohle, L. Durrer, C. Stampferc, C. Romana, A. Jungena,
M. Fleischerb, C. Hierolda, Sensing NO2 with individual suspended single-walled
carbon nanotubes, Sens. Actuators B: Chem. 132 (2) (2008) 491497. http://
dx.doi.org/10.1016/j.snb.2007.11.036.
[21] J.P. Novak, E.S. Snow, E.J. Houser, D. Park, J.L. Stepnowski, R.A. McGill, Nerve
agent detection using networks of single-walled carbon nanotubes, Appl. Phys. Lett.
83 (19) (2003) 40264028. http://dx.doi.org/10.1063/1.1626265.
[22] N. Peng, Q. Zhang, Y.C. Lee, O.K. Tan, N. Marzari, Gate modulation in carbon
nanotube eld eect transistors-based NH3 gas sensors, Sens. Actuators B: Chem.
132 (1) (2008) 191195. http://dx.doi.org/10.1016/j.snb.2008.01.025.
[23] M. Lucci, A. Reale, A. Di Carlo, S. Orlanducci, E. Tamburri, M.L. Terranova,
I. Davoli, C. Di Natale, A. DAmico, R. Paolesse, Optimization of a NOx gas sensor
based on single walled carbon nanotubes, Sens. Actuators B: Chem. 118 (12)
(2006) 226231. http://dx.doi.org/10.1016/j.snb.2006.04.027.
[24] N.H. Quang, M. Van Trinh, B.-H. Lee, J.-S. Huh, Eect of NH3 gas on the electrical
properties of single-walled carbon nanotube bundles, Sens. Actuators B: Chem. 113
(1) (2006) 341346. http://dx.doi.org/10.1016/j.snb.2005.03.089.
[25] H.-Q. Nguyen, J.-S. Huh, Behavior of single-walled carbon nanotube-based gas
sensors at various temperatures of treatment and operation, Sens. Actuators B:
Chem. 117 (2) (2006) 426430. http://dx.doi.org/10.1016/j.snb.2005.11.056.
[26] O.K. Varghese, P.D. Kichambre, D. Gong, K.G. Ong, E.C. Dickey, C.A. Grimes, Gas
sensing characteristics of multi-wall carbon nanotubes, Sens. Actuators B: Chem.
81 (1) (2001) 3241. http://dx.doi.org/10.1016/S0925-4005(01)00923-6.
[27] L.H. Nguyen, T.V. Phi, P.Q. Phan, H.N. Vu, C. Nguyen-Duc, F. Fossard, Synthesis of
multi-walled carbon nanotubes for NH3 gas detection, Physica E. 37 (12) (2007)
5457. http://dx.doi.org/10.1016/j.physe.2006.12.006.
[28] G. Sun, S. Liu, K. Hua, X. Lv, L. Huang, Y. Wang, Electrochemical chlorine sensor
with multi-walled carbon nanotubes as electrocatalysts, Electrochem. Commun. 9
(9) (2007) 24362440. http://dx.doi.org/10.1016/j.elecom.2007.07.015.
[29] C. Piloto, F. Mirri, E.A. Bengio, M. Notarianni, B. Gupta, M. Shaei, M. Pasquali,
N. Motta, Room temperature gas sensing properties of ultrathin carbon nanotube
lms by surfactant-free dip coating, Sens. Actuators B: Chem. 227 (2016) 128134.
http://dx.doi.org/10.1016/j.snb.2015.12.051.
[30] L. Valentini, C. Cantalini, I. Armentano, J.M. Kenny, L. Lozzi, S. Santucci, Highly
sensitive and selective sensors based on carbon nanotubes thin lms for molecular
detection, Diam. Relat. Mater. 13 (48) (2004) 13011305. http://dx.doi.org/
10.1016/j.diamond.2003.11.011.
[31] N.D. Hoa, N. Van Quy, Y. Cho, D. Kim, An ammonia gas sensor based on non-
catalytically synthesized carbon nanotubes on an anodic aluminum oxide template,
Sens. Actuators B: Chem. 127 (2) (2007) 447454. http://dx.doi.org/10.1016/
j.snb.2007.04.041.
[32] D. Fu, H. Lim, Y. Shi, X. Dong, S.G. Mhaisalkar, Y. Chen, S. Moochhala, L.-J. Li,
Dierentiation of gas molecules using exible and all-carbon nanotube devices, J.
I.V. Zaporotskova et al.
Phys. Chem. C 112 (3) (2008) 650653. http://dx.doi.org/10.1021/jp710362r.
[33] T.H. Tran, J.-W. Lee, K. Lee, Y.D. Lee, B.-K. Ju, The gas sensing properties of
single-walled carbon nanotubes deposited on an aminosilane monolayer, Sens.
Actuators B: Chem. 129 (1) (2008) 6771. http://dx.doi.org/10.1016/
j.snb.2007.07.104.
[34] Y. Zhou, Y. Jiang, G. Xie, X. Du, H. Tai, Gas sensors based on multiple-walled
carbon nanotubes-polyethylene oxide lms for toluene vapor detection, Sens.
Actuators B: Chem. 191 (2014) 2430. http://dx.doi.org/10.1016/
j.snb.2013.09.079.
[35] S.F. Liu, S. Lin, T.M. Swager, An organocobalt-carbon nanotube chemiresistive
carbon monoxide detector, ACS Sens. 1 (4) (2016) 354357. http://dx.doi.org/
10.1021/acssensors.6b00005.
[36] P. Qi, O. Vermesh, M. Grecu, A. Javey, Q. Wang, H. Dai, S. Peng, K.J. Cho, Toward
large arrays of multiplex functionalized carbon nanotube sensors for highly
sensitive and selective molecular detection, Nano Lett. 3 (3) (2003) 347351.
http://dx.doi.org/10.1021/nl034010k.
[37] E. Bekyarova, M. Davis, T. Burch, M.E. Itkis, B. Zhao, S. Sunshine, R.C. Haddon,
Chemically functionalized single-walled carbon nanotubes as ammonia sensors, J.
Phys. Chem. B 108 (51) (2004) 1971719720. http://dx.doi.org/10.1021/
jp0471857.
[38] J.K. Abraham, B. Philip, A. Witchurch, V.K. Varadan, C.C. Reddy, A compact
wireless gas sensor using a carbon nanotube/PMMA thin lm chemiresistor, Smart
Mater. Struct. 13 (5) (2004) 10451049. http://dx.doi.org/10.1088/0964-1726/
13/5/010.
[39] J. Im, E.S. Sterner, T.M. Swager, Integrated gas sensing system of swcnt and
cellulose polymer concentrator for benzene, toluene, and xylenes, Sensors 16 (2)
(2016) 183. http://dx.doi.org/10.3390/s16020183.
[40] A. Abdelhalim, A. Abdellah, G. Scarpa, P. Lugli, Metallic nanoparticles functiona-
lizing carbon nanotube networks for gas sensing applications, Nanotechnology 25
(5) (2014) 055208. http://dx.doi.org/10.1088/0957-4484/25/5/055208.
[41] J. Kong, M.G. Chapline, H.J. Dai, Functionalized carbon nanotubes for molecular
hydrogen sensors, Adv. Mater. 13 (18) (2001) 13841386. http://dx.doi.org/
10.1002/1521-4095(200109)13:18 < 1384::AID-ADMA1384 > 3.0.CO;2-8.
[42] I. Sayago, E. Terrado, M. Aleixandre, M.C. Horrillo, M.J. Fernndez, J. Lozano,
E. Lafuente, W.K. Maser, A.M. Benito, M.T. Martinez, J. Gutirrez, E. Muoz, Novel
selective sensors based on carbon nanotube lms for hydrogen detection, Sens.
Actuators B: Chem. 122 (1) (2007) 7580. http://dx.doi.org/10.1016/
j.snb.2006.05.005.
[43] S. Mubeen, T. Zhang, B. Yoo, M.A. Deshusses, N.V. Myung, Palladium nanopar-
ticles decorated single-walled carbon nanotube hydrogen sensor, J. Phys. Chem. C
111 (17) (2007) 63216327. http://dx.doi.org/10.1021/jp067716m.
[44] M.K. Kumar, S. Ramaprabhu, Nanostructured Pt functionlized multiwalled carbon
nanotube based hydrogen sensor, J. Phys. Chem. B 110 (23) (2006) 1129111298.
http://dx.doi.org/10.1021/jp0611525.
[45] M.K. Kumar, S. Ramaprabhu, Palladium dispersed multiwalled carbon nanotube
based hydrogen sensor for fuel cell applications, Int. J. Hydrog. Energy. 32 (13)
(2007) 25182526. http://dx.doi.org/10.1016/j.ijhydene.2006.11.015.
[46] S.M. Seo, T.J. Kang, J.H. Cheon, Y.H. Kim, Y.J. Park, Facile and scalable fabrication
of chemiresistive sensor array for hydrogen detection based on gold-nanoparticle
decorated SWCNT network, Sens. Actuators B: Chem. 204 (2014) 716722. http://
dx.doi.org/10.1016/j.snb.2014.07.119.
[47] G.V. Kamarchuk, I.G. Kolobov, A.V. Khotkevich, I.K. Yanson, A.P. Pospelov,
I.A. Levitsky, W.B. Euler, New chemical sensors based on point heterocontact
between single wall carbon nanotubes and gold wires, Sens. Actuators B: Chem.
134 (2) (2008) 10221026. http://dx.doi.org/10.1016/j.snb.2008.07.012.
[48] A. Star, V. Joshi, S. Skarupo, D. Thomas, J.-C.P. Gabriel, Gas sensor array based on
metal-decorated carbon nanotubes, J. Phys. Chem. B 110 (42) (2006)
2101421020. http://dx.doi.org/10.1021/jp064371z.
[49] Y.J. Kwona, H.G. Naa, S.Y. Kanga, S.-W. Choib, S.S. Kimb, H.W. Kima, Selective
detection of low concentration toluene gas using Pt-decorated carbon nanotubes
sensors, Sens. Actuators B: Chem. 227 (2016) 157168. http://dx.doi.org/
10.1016/j.snb.2015.12.024.
[50] I. Hafaiedh, W. Elleuch, P. Clement, E. Llobet, A. Abdelghani, Multi-walled carbon
nanotubes for volatile organic compound detection, Sens. Actuators B: Chem. 182
(2013) 344350. http://dx.doi.org/10.1016/j.snb.2013.03.020.
[51] E.H. Espinosa, R. Ionescu, B. Chambon, G. Bedis, E. Sotter, C. Bittencourt,
A. Felten, J.-J. Pireaux, X. Correig, E. Llobet, Hybrid metal oxide and multiwall
carbon nanotube lms for low temperature gas sensing, Sens. Actuators B: Chem.
127 (1) (2007) 137142. http://dx.doi.org/10.1016/j.snb.2007.07.108.
[52] Y. Chen, C. Zhu, T. Wang, The enhanced ethanol sensing properties of multi-walled
carbon nanotubes/SnO2 core/shell nanostructures, Nanotechnology 17 (12) (2006)
30123017. http://dx.doi.org/10.1088/0957-4484/17/12/033.
[53] J. Wang, L. Liu, S.-Y. Cong, J.-Q. Qi, B.-K. Xu, An enrichment method to detect low
concentration formaldehyde, Sens. Actuators B: Chem. 134 (2) (2008) 10101015.
http://dx.doi.org/10.1016/j.snb.2008.07.010.
[54] C. Bittencourt, A. Felten, E.H. Espinosa, R. Ionescu, E. Llobet, X. Correig, J.-
J. Pireaux, WO3 lms modied with functionalised multi-wall carbon nanotubes:
morphological, compositional and gas response studies, Sens. Actuators B: Chem.
115 (1) (2006) 3341. http://dx.doi.org/10.1016/j.snb.2005.07.067.
[55] B.-Y. Wei, M.-C. Hsu, P.-G. Su, H.-M. Lin, R.-J. Wu, H.-J. Lai, A novel SnO2 gas
sensor doped with carbon nanotubes operating at room temperature, Sens.
Actuators B: Chem. 101 (12) (2004) 8189. http://dx.doi.org/10.1016/
j.snb.2004.02.028.
[56] N.D. Hoa, N.V. Quy, Y.S. Cho, D. Kim, Nanocomposite of SWCNTs and SnO2
fabricated by soldering process for ammonia gas sensor application, Phys. Status
Solidi A 204 (6) (2007) 18201824. http://dx.doi.org/10.1002/pssa.200675318.
104
Modern Electronic Materials 2 (2016) 95105
[57] Y.-L. Liu, H.-F. Yang, Y. Yang, Z.-M. Liu, G.-L. Shen, R.-Q. Yu, Gas sensing
properties of tin dioxide coated onto multiwalled carbon nanotubes, Thin Solid
Films 497 (12) (2006) 355360. http://dx.doi.org/10.1016/j.tsf.2005.11.018.
[58] N. Van Hieu, L.T.B. Thuy, N.D. Chien, Highly sensitive thin lm NH3 gas sensor
operating at room temperature based on SnO2/MWCNTs composite, Sens.
Actuators B: Chem. 129 (2) (2008) 888895. http://dx.doi.org/10.1016/
j.snb.2007.09.088.
[59] M. Snchez, R. Guirado, M.E. Rincn, Multiwalled carbon nanotubes embedded in
sol-gel derived TiO2 matrices and their use as room temperature gas sensors, J.
Mater. Sci. : Mater. Electron. 18 (11) (2007) 11311136. http://dx.doi.org/
10.1007/s10854-007-9144-5.
[60] N. Van Duy, N. Van Hieu, P.T. Huy, N.D. Chien, M. Thamilselvan, J. Yi, Mixed
SnO2/TiO2 included with carbon nanotubes for gas-sensing application, Physica E
41 (2) (2008) 258263. http://dx.doi.org/10.1016/j.physe.2008.07.007.
[61] M. Dragoman, K. Grenier, D. Dubuc, L. Bary, R. Plana, E. Fourn, E. Flahaut,
Millimeter wave carbon nanotube gas sensor, J. Appl. Phys. 101 (10) (2007)
106103. http://dx.doi.org/10.1063/1.2734873.
[62] J.-J. Adjizian, R. Leghrib, A.A. Koos, I. Suarez-Martinez, A. Crossley, Wagner Ph,
N. Grobert, E. Llobet, Ch. P. Ewels, Boron- and nitrogen-doped multi-wall carbon
nanotubes for gas detection, Carbon 66 (2014) 662673. http://dx.doi.org/
10.1016/j.carbon.2013.09.064.
[63] J. Kim, S.-W. Choi, J.-H. Lee, Y. Chung, Y.T. Byun, Gas sensing properties of
defect-induced single-walled carbon nanotubes, Sens. Actuators B: Chem. 228
(2016) 688692. http://dx.doi.org/10.1016/j.snb.2016.01.094.
[64] Z. Hou, D. Xu, B. Cai, Ionization gas sensing in a microelectrode system with
carbon nanotubes, Appl. Phys. Lett. 89 (21) (2006) 213502. http://dx.doi.org/
10.1063/1.2392994.
[65] W.A. De Heer, A. Chtelain, D. Ugarte, A carbon nanotube eld-emission electron
source, Science 270 (5239) (1995) 11791180. http://dx.doi.org/10.1126/
science.270.5239.1179.
[66] N. De Jonge, Y. Lamy, K. Schoots, T.H. Oosterkamp, High brightness electron beam
from a multi-walled carbon nanotube, Nature 420 (6914) (2002) 393395. http://
dx.doi.org/10.1038/nature01233.
[67] J.T.W. Yeow, J.P.M. She, Carbon nanotube-enhanced capillary condensation for a
capacitive humidity sensor, Nanotechnology 17 (21) (2006) 54415448. http://
dx.doi.org/10.1088/0957-4484/17/21/026.
[68] E.S. Snow, F.K. Perkins, E.J. Houser, S.C. Badescu, T.L. Reinecke, Chemical
detection with a single-walled carbon nanotube capacitor, Science 307 (5717)
(2005) 19421945. http://dx.doi.org/10.1126/science.1109128.
[69] S. Chopra, A. Pham, J. Gaillard, A. Parker, A.M. Rao, Carbon-nanotube-based
resonant-circuit sensor for ammonia, Appl. Phys. Lett. 80 (24) (2002) 46324636.
http://dx.doi.org/10.1063/1.1486481.
[70] S. Chopra, K. McGuire, N. Gothard, A.M. Rao, A. Pham, Selective gas detection
using a carbon nanotube sensor, Appl. Phys. Lett. 83 (11) (2003) 22802282.
http://dx.doi.org/10.1063/1.1610251.
[71] V.A. Buzanovskii, Electrochemical sensors based on carbon nanotubes and their
use in biomedical research, Biomeditsinskaya khimiya 57 (6) (2011) 1231. http://
dx.doi.org/10.18097/pbmc20125801012.
[72] M.M. Barsan, M.E. Ghica, C.M.A. Brett, Electrochemical sensors and biosensors
based on redox polymer/carbon nanotube modied electrodes, Anal. Chim. Acta
881 (2015) 123. http://dx.doi.org/10.1016/j.aca.2015.02.059.
[73] A. Chen, S. Chatterjee, Nanomaterials based electrochemical sensors for biomedical
applications, Chem. Soc. Rev. 42 (12) (2013) 54255438. http://dx.doi.org/
10.1039/C3CS35518G.
[74] R. Pauliukaite, M.E. Ghica, M.M. Barsan, C.M.A. Brett, Phenazines and polyphe-
nazines in electrochemical sensors and biosensors, Anal. Lett. 43 (1011) (2010)
15881608. http://dx.doi.org/10.1080/00032711003653791.
[75] H.-J. Liu, D.-W. Yang, H.-H. Liu, A hydrogen peroxide sensor based on the
nanocomposites of poly(brilliant cresyl blue) and single walled-carbon nanotubes,
Anal. Methods 4 (5) (2012) 14211426. http://dx.doi.org/10.1039/C2AY05881B.
[76] M.E. Ghica, Y. Wintersteller, C.M.A. Brett, Poly(brilliant green)/carbon nanotube-
modied carbon lm electrodes and application as sensors, J. Solid State
Electrochem. 17 (6) (2013) 15711580. http://dx.doi.org/10.1007/s10008-013-
2040-4.
[77] V. Pieri, M.M. Barsan, M.E. Ghica, L. Falciola, C.M.A. Brett, Synthesis char-
acterization and inuence of poly(brilliant green) on the performance of dierent
electrode architectures based on carbon nanotubes and poly(3,4- ethylenediox-
ythiophene), Electrochim. Acta 98 (2013) 199207. http://dx.doi.org/10.1016/
j.electacta.2013.03.048.
[78] M.E. Ghica, C.M.A. Brett, Poly(brilliant green) and poly(thionine) modied carbon
nanotube coated carbon lm electrodes for glucose and uric acid biosensors,
Talanta 130 (2014) 198206. http://dx.doi.org/10.1016/j.talanta.2014.06.068.
[79] Y. Lin, F. Lu, Y. Tu, Z. Ren, Glucose biosensors based on carbon nanotube
nanoelectrode ensembles, Nano Lett. 4 (2) (2004) 191195. http://dx.doi.org/
10.1021/nl0347233.
[80] M.D. Rubianes, G.A. Rivas, Carbon nanotubes paste electrode, Electrochem.
Commun. 5 (8) (2003) 689694. http://dx.doi.org/10.1016/S1388-2481(03)
00168-1.
[81] J.E. Koehne, H. Chen, A.M. Cassell, Q. Ye, J. Han, M. Meyyappan, J. Li,
Miniaturized multiplex label-free electronic chip for rapid nucleic acid analysis
based on carbon nanotube nanoelectrode arrays, Clin. Chem. 50 (10) (2004)
18861893. http://dx.doi.org/10.1373/clinchem.2004.036285.
[82] M.L. Pedano, G.A. Rivas, Adsorption and electrooxidation of nucleic acids at carbon
nanotubes paste electrodes, Electrochem. Commun. 6 (1) (2004) 1016. http://
dx.doi.org/10.1016/j.elecom.2003.10.008.
[83] S.S. Wong, E. Josevlevich, A.T. Wooley, C.L. Cheung, C.M. Lieber, Covalently
I.V. Zaporotskova et al.
functionalized nanotubes as nanometer-sized probes in chemistry and biology,
Nature 394 (1998) 5255. http://dx.doi.org/10.1038/27873.
[84] J. Mklin, T. Mustonen, K. Kords, S. Saukko, G. Tth, J. Vhkangas, Nitric oxide
gas sensors with functionalized carbon nanotubes, Phys. Status Solidi B 244 (11)
(2007) 42984302. http://dx.doi.org/10.1002/pssb.200776118.
[85] L.V. Kozhitov, N.Kh. Vet, A.V Kostikova, I.V. Zaporotskova, V.V. Kozlov, The
simulation of carbon material structure based on polyacrylonitrile obtained under
IR heating, Mod. Electron. Mater. 2 (1) (2016) 1317. http://dx.doi.org/10.1016/
j.moem.2016.08.003.
[86] I.V. Zaporotskova, N.P. Polikarpova, D.E. Vilkeeva, Sensor activity of carbon
nanotubes with a boundary functional group, Nanosci. Nanotechnol. Lett. 5 (11)
(2013) 11691173. http://dx.doi.org/10.1166/nnl.2013.1704.
[87] M.J.S. Dewar, W. Thiel, Ground states of molecules. The MNDO method.
Approximations and parameters, J. Am. Chem. Soc. 99 (15) (1977) 48994907.
http://dx.doi.org/10.1021/ja00457a004.
[88] A.A. Voityuk, Application of the MNDO method to investigation of properties and
105
Modern Electronic Materials 2 (2016) 95105
reactivity of molecules, J. Struct. Chem. 29 (1) (1988) 120146. http://dx.doi.org/
10.1007/BF00750187.
[89] W. Koch, M. Holthausen, A chemists Guide to Density Functional Theory, Wiley-
VCH, Weinheim, 2001, p. 313 http://eu.wiley.com/WileyCDA/WileyTitle/
productCd-3527303723.html.
[90] N.P. Polikarpova, I.V. Zaporotskova, D.E. Vilkeeva, D.I. Polikarpov, Sensor
properties of carboxyl-modies carbon nanotubes, Nanosyst.: Phys. Chem. Math. 5
(1) (2014) 101106 http://nanojournal.ifmo.ru/en/wp-content/uploads/2014/
02/NPCM51_P101-106.pdf.
[91] T.H. Tran, J.-W. Lee, K. Lee, Y.D. Lee, B.-K. Ju, The gas sensing properties of
single-walled carbon nanotubes deposited on an aminosilane monolayer, Sens.
Actuators B 129 (1) (2008) 6771. http://dx.doi.org/10.1016/j.snb.2007.07.104.
[92] N.P. Polikarpova, I.V. Zaporotskova, S.V. Boroznin, P.A. Zaporotskov, About using
carbon nanotubes with amino group modication as sensors, J. Nano Electron.
Phys. 7 (4) (2015) 04089 (3 pp) http://essuir.sumdu.edu.ua/bitstream/
123456789/44562/1/Polikarpova_Carbon_nanotube.pdf.