Journal of Electronic Materials (2022) 51:207–213

https://doi.org/10.1007/s11664-021-09278-9

ORIGINAL RESEARCH ARTICLE

Carbon Nanotube and Polyacrylonitrile Nanofiber Devices for Sensing

Applications
Narendra Kumar1 · Pardeep Kumar2 · Naveen Kumar Navani3 · Sanjeev Kumar Manhas1

Received: 20 March 2021 / Accepted: 5 October 2021 / Published online: 3 November 2021
© The Minerals, Metals & Materials Society 2021

Abstract
In this paper, a novel technique is presented to fabricate aligned polymer-wrapped semiconducting carbon nanotube (CNT)-
based devices to overcome the issues that arise in randomly oriented CNT network devices. It is challenging to make the
CNT-based devices with straight polymer-wrapped CNTs. Straight CNTs have better conductivity than the bended ones.
Therefore, we have fabricated simple electrodes of a square pad with the conventional lithography process. Subsequently,
dispersed single-walled CNTs (SWNT)-polyacrylonitrile is used to fabricate aligned nanofiber by an electrospinning system
on the fabricated electrodes. The average diameter of the fabricated nanofiberr is found to be 100 nm. The current–voltage
(I–V) characteristics are investigated for the fabricated devices. The I–V characteristics are similar to those of a back-to-
back Schottky diode. The Schottky barrier height and ideality factor of the nanofiber devices are found to be 431 meV and
4.1, respectively. Therefore, the multiple current transport mechanisms (thermionic emission, tunneling, generation-recom-
bination, and leakage) contribute to the current through the nanofiber device. Applications of the devices can include gas
sensors, biosensors, and other CNT-based device electronics applications.
Graphic Abstract

Keywords Alignment · current transport · nanofiber devices · Schottky barrier height · semiconducting carbon nanotube

Introduction
* Sanjeev Kumar Manhas
samanfec@iitr.ac.in Semiconducting carbon nanotubes (CNTs) are found to
be superior materials to fabricate nanoelectronic devices.1
1
Department of Electronics and Communication Single-walled CNTs (SWNTs) are one dimensional (1D)
Engineering, Indian Institute of Technology (IIT), Roorkee,
structures. They are similar to the molecular wire struc-
Uttarakhand 247 667, India
2
ture and hence can be used for large-scale manufacturing
Centre of Nanotechnology, Indian Institute of Technology
of CNT-based devices.2 CNTs have high mobility and high
Roorkee, Roorkee, Uttarakhand 247 667, India
3
thermal ­c onductivity3,4 and have excellent mechanical
Department of Biotechnology, Indian Institute of Technology
strength due to the fact that the carbon atoms are connected
(IIT), Roorkee, Uttarakhand 247 667, India

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through the s­ p2 bonds. The s­ p2 bonds are stronger than the
sp and s­ p3 bonds.5 Also, CNTs have Young’s moduli with
a very high terapascal r­ ange6 and have a tensile strength of
gigapascal range.7 In addition, CNTs have a high current
carrying capacity and support ballistic transport.8,9 Carrier
transport occurs in the CNTs through their surfaces. Due to
this, CNTs can be easily functionalized.10 Moreover, CNTs
have a very high surface area to volume ratio.11 Due to these
excellent properties, CNT-based devices can be an alterna-
tive to silicon-based complementary metal–oxide semicon-
ductor (CMOS) technologies. Nenkova et al.12 have used
CNT-polyacrylonitrile (CNT-PAN) film for biosensing. For
fabricating CNT-based devices without degradation in the
conductivity of the CNTs, it is better to align the CNTs.
CNTs can be aligned by the di-electrophoresis method in
CNT suspension.13,14 However, alignment of the polymer-
wrapped CNTs is difficult to obtain by the di-electrophoresis
method. CNTs can be aligned by the tip of an atomic-force
microscopy (AFM) which is not only used to align the CNTs
but can even change the position of CNTs on the substrate.15
However, the alignment of CNTs by AFM results in a small
yield and is quite involved. The AFM tip may get damaged
during CNT alignment. To overcome CNT alignment diffi-
culties, Bourourou et al.16 used the electrospinning process
to fabricate a CNT-PAN nanofiber film electrode for catechol
detection. We used the electrospinning process to fabricate
CNT-PAN nanofiber devices, in which the few nanofibers
are aligned between the metal electrodes.
Semiconducting carbon nanotubes with metal contact
devices are similar to those of the semiconductor–metal con-
tact. The semiconducting CNTs and aluminum (Al) metal
form the Schottky junction. As both ends of the CNTs are
connected to identical metal pads, two Schottky junctions
are formed. Therefore, the devices have symmetrical I–V
characteristics.17,18 The current conduction through the
metal–semiconductor device is due to a multiple-current
conduction mechanism through the junction. The contribu-
tion in the current conduction mechanism can be due to ther-
mionic emission (TE), tunneling (TU), generation-recom-
bination (GR), and leakage (RL) currents. The multiple
transport mechanisms through the Schottky contact are due
to the defects and inhomogeneities at the metal–semiconduc-
tor interface. The Schottky diode parameters are attributed
to the current transport mechanism through the devices.19
In this paper, we present a novel technique whereby
SWNT-PAN nanofiber is aligned between the simple square
pad electrodes made of Al. Aluminum is first deposited on
the glass substrate, and the conventional lithography pro-
cess is used to make Al square pad electrodes. Nanofiber is
made by the electrospinning process using the SWNT-PAN.
The Schottky barrier (SB) height is then calculated at the
SWNTs–metal electrode contact. Subsequently, the current
conduction mechanism through the device is investigated.
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N. Kumar et al.
This is a cost-effective and simple method for the fabrication
of nanofiber devices.
The paper is organized as follows: Section II describes the
sample preparation, PAN–SWNT dispersion, and fabrica-
tion of nanofiber and nanofiber devices. Section III provides
results and a discussion of the nanofiber device, and finally,
the conclusion is presented in section IV.
Experimental Detail
Glass micro-slides are cut into 2.5 cm × 2.5 cm pieces to
fabricate the devices. The glass substrate is sonicated in
acetone for 10 min, and then the sample is cleaned with iso-
propyl alcohol (IPA) and deionized (DI) water. The chemi-
cally cleaned glass substrate is dried with a nitrogen air gun
and heated at 100°̊C to remove the moisture. Further, the Al
layer of thickness 200 nm is deposited on the glass substrate
by an electron beam physical vapor deposition system (HHV
Pvt. Ltd, India, model no. 12A4D). The system is kept at a
base pressure of 1 × ­10−5 m bar for the deposition process.
The deposition pressure is maintained below 4 × ­10−5 m bar.
Figure 1(a) shows the schematic diagram of the deposited Al
on the glass substrate. Thereafter, the photoresist is coated
by a spin coater (model spinNXG-P2, Apex Instruments Pvt.
Ltd., India) on the Al-deposited substrate as shown in the
schematic in Fig. 1(b). Subsequently, the Al-deposited sub-
strate is patterned with a laser writer (photolithography sys-
tem, model Microtech LW 405B) and developed; the pattern
is shown in the schematic in Fig. 1(c). The patterned sample
is etched with Al etchant. The schematic after the etching Al
is shown in Fig. 1(d). Figure 1(e) shows the schematic of the
final structure after removing the acetone.
The patterned sample has a regular square pad dimen-
sion of 100 µm × 100 µm, as shown in Fig. 2. The square
pad electrodes have a space of 7 µm between them. The two
consecutive square pads are used to make the devices. The
separation between two consecutive devices is 50 µm.
Further, a quantity of 3.33% PAN and 0.33% SWNTs
(Intelligent Materials Pvt. Ltd., a division of Nanoshel LLC,
USA) are taken. SWNTs are dispersed in dimethylforma-
mide (DMF) using a probe sonicator for 1 h. The schematic
diagram before and after the dispersion of the SWNTs is
shown in Fig. 3(a) and (b). Thereafter, PAN is dissolved in
DMF at 70°̊C under stirring. The schematic diagram before
and after dissolving the PAN is shown in Fig. 3(c) and (d).
Dispersed SWNTs are mixed in dissolved PAN solution as
shown in the schematic in Fig. 3(e).
The prepared suspension is placed in the syringe attached
to the electrospinning system (model ESPIN NANOPECO)
as shown in the schematic diagram in Fig. 4. The suspen-
sion flow rate is fixed at a constant rate through the needle
and thus forms the nanofiber. The nanofiber is collected on
Carbon Nanotube and Polyacrylonitrile Nanofiber Devices for Sensing Applications 209

Fig. 1  Schematic diagram of fabrication of electrodes by the lithography process. (a) Aluminum deposited; (b) photoresist coated; (c) structure
after patterning and developing; (d) etched aluminum; and (e) final structure of the electrodes on the glass substrate.

the fabricated simple pad electrodes. During the fabrica-
tion process of nanofiber, high voltage is applied across the
electrospinning system. The nanofiber device's morphology
characterization is done by field emission scanning elec-
tron microscopy (FESEM, Carl Zeiss Ultra Plus). Also, the
nanofiber device composition is characterized by X-ray pho-
toelectron spectroscopy (XPS, model PHI 5000 VersaProbe
III, Physical Electronics). The fabricated nanofiber devices are
characterized by a Keithley 4200 semiconductor characteriza-
tion system (SCS).
Results and Discussions
The fabrication of long, aligned, and textured nanofiber by
the electrospinning process is demonstrated. In this pro-
cess, initially, a single jet of fluid is ejected from the noz-
zle tip's apex. Subsequently, the fluid at the nozzle tip is
charged electrostatically. The electrostatic charge on fluid
at the nozzle tip converts fluid into the well-known Taylor
cone. Due to the presence of an electric field, the fluid jet

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accelerates and becomes thin. The radial repulsion charge
on the fluid tries to expand the jet radius and stretches the
jet in the axial direction. Due to the stretching of the jet,
there is a decrease in the radius of the jet and the radial
forces from the charge increase enough to overcome the
cohesive forces of the fiber. Consequently, the single jet is
Fig. 2  Microscopic image of the fabricated array of Al pad electrodes
for nanofiber devices on glass substrate.
Fig. 3  Schematic diagram of (a) CNTs in DMF, (b) CNT suspension, (c) PAN in DMF, (d) PAN solution, and (e) CNT-PAN suspension.
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N. Kumar et al.
split into multiple filaments and collected on the substrate
as fibers. This process of jet splitting is known as splaying.
Moreover, the number of the subsidiary jet determines the
diameter of the fiber.20–22
The parameters conductivity, surface tension, viscosity,
tip-to-collector distance, the electric potential at the tip,
temperature, air velocity, and humidity in the electrospin-
ning chamber determine the morphology of the fabricated
nanofiber. The parameters conductivity, surface tension, and
viscosity are the physical properties of the materials that are
material-dependent. Therefore, these cannot be controlled
for the material, and the rest of the parameters can be con-
trolled for the fabrication of nanofiber.22
The process parameters are optimized for the PAN and
SWNT-PAN nanofibers. Figure 5 shows the SEM image
of the only PAN nanofiber synthesized on the Al foil. The
SWNT-PAN nanofiber SEM image is shown in Fig. 6. The
average diameter of the fabricated nanofiber is 100 nm. The
SWNT-PAN nanofiber is synthesized on the fabricated Al
square pad electrodes. The nanofiber is connected to the Al
pad electrodes as in SEM image in Fig. 7. The density of
the nanofiber connected between the Al pads is controlled
by time: the higher the nanofiber density, the higher the
number of CNTs between the electrodes. This enhances the
power consumption of the devices. Therefore, the minimum
Carbon Nanotube and Polyacrylonitrile Nanofiber Devices for Sensing Applications 211
Fig. 4  Schematic diagram of the fabrication of nanofiber by the elec-
trospinning system.
Fig. 5  SEM image of the PAN nanofiber fabricated on the Al foil.
number of CNTs is required between the electrodes. It is
better to align nanofiber between the Al electrodes for better
device performance for biosensing.
XPS analysis of the fabricated SWNT-PAN nanofiber is
carried out to analyze the bonding of the atoms. The high-
resolution XPS analysis of the C 1s spectrum of SWNT-PAN
nanofiber indicates that the spectrum de-convoluted into
three Gaussian sub-spectra as shown in Fig. 8. The de-con-
voluted peak of C 1s has the peaks ­CI, ­CII, and C
­ III at 284.8
eV, 285.6 eV, and 288.8 eV, respectively. The sub-spectrum
of ­CI with a peak at 284.8 eV represents the C–C, C=C, and
C–H bonds within the nanofiber. C–C, C=C, and C–H bonds
Fig. 6  SEM image of the SWNT-PAN nanofiber fabricated on the Al
foil.
Fig. 7  SEM image of the SWNT-PAN nanofiber device. The aligned
SWNT-PAN nanofiber between Al metal pads.
are related to the CNTs and PAN. The sub-spectrum of ­CII
indicates the CN group, which is centered at 285.6 eV, and
the ­CIII sub-spectrum at 288.8 eV shows the C=O bond in
the SWNT-PAN nanofiber. Therefore, from the XPS analy-
sis, it is clear that SWNT-PAN nanofiber does not make any
other complex compound.23,24
Figure 9 shows the measured I–V characteristics of the
nanofiber-based fabricated device. The direct-current (DC)
sweep voltage (amplitude of −3 V to 3 V with a step voltage
of 0.1 V) is applied to characterize the fabricated nanofiber
devices. The device current is in the range of ­10−7 A. To
verify that the current flows through the CNTs, we apply
the same voltage sweep across the device fabricated with
only PAN nanofiber and across the fabricated electrodes. A
negligible current flow is found through the PAN nanofiber.
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Fig. 8  High-resolution XPS spectra of C 1s of the fabricated SWNT-
PAN nanofiber device.
Fig. 9  Current–voltage characteristics of the fabricated device. The
device is fabricated by placing the SWNT-PAN nanofiber between Al
pad electrodes.
The I–V characteristics of the SWNT-PAN nanofiber device
are symmetric in both forward and reverse bias. The sym-
metrical current through the device shows characteristics
like two Schottky diodes connected back-to-back, like a con-
ventional semiconductor device. The structure is also like
the conventional semiconductor and metal junction. Metal
semiconductor metal contacts have a double Schottky barrier
at both ends of the semiconductor.25 Similarly, a Schottky
contact is made between semiconducting SWNTs and metal
electrodes in nanofiber devices. For a Schottky diode, the
current equation is based on the thermionic transmission
(TE) theory given in Refs. 26 and 27 as
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N. Kumar et al.
Fig. 10  Linear fitting parameters of I–V characteristics of the fabri-
cated device.
[ ( ) ]
qV
I = Is exp −1 (1)
nkT
( ) qV
ln(I) = ln Is + (2)
nkT
( q𝜑 )
Is = AA∗ T 2 exp − SB (3)
kT
where Is, n, ϕSB, and Rs represent the reverse saturation cur-
rent, ideality factor, zero bias SB height, and series resist-
ance of the diode, respectively. A is the metal–semiconduc-
tor contact area, and A* is Richardson’s constant (7.21 A/
cm2 ­K2 for CNTs).28 V denotes the applied voltage across the
diode, K is the Boltzmann constant, and T is the diode oper-
ating temperature in Kelvin. The above equation is based on
the thermionic theory that is applicable to find the Schottky
diode parameters.29
Figure 10 shows the ln(I) plot with respect to the voltage
of the fabricated nanofiber device. The plot data is used to
find the Schottky diode parameters of the device by using the
linear fitting method. The left semi-log plot shows the linear
fitting of the experimental data of the nanofiber device. The
numerical values of the slope and the intercept of the linear
fitting data are obtained from the semi-log plot as 9.3 ­V−1
and −24.6, respectively. The slope and intercept of the lin-
ear fitting data are compared with (2). From the intercept,
the value of Is = 2 × ­10−11 A is calculated for the fabricated
device. The numerical value of the Is is substituted into (3),
and the SB height is obtained as 431 meV for the nanofiber
device (assuming a diameter ~ 100 nm × contact length ~
50 µm, then the contact area is in the order of ~ 5 × 1­ 0−10
Carbon Nanotube and Polyacrylonitrile Nanofiber Devices for Sensing Applications 213
­cm2). Also, from the slope, the value of ideality factor of
4.1 is obtained. The current transport mechanism through
the junction can be explained based on the value of the ide-
ality factor. For the Schottky diode, the current transport
is attributed to the TE, TU, GR, and RL currents. For the
ideality factor 1, the TE current dominates all other currents.
However, the ideality factor for our device of 4.1 is greater
than 1. Hence, the current transport through the nanofiber
device is not dominated by the TE current. However, it is
attributed to the multiple current transport mechanisms (TE,
TU, GR, and RL) of the current through the device.19 The
nanofiber devices fabricated here can be used for gas sen-
sors, biosensors, and other electronic device applications
such as CNTFET and CNT-based diodes.
Conclusion
Carbon nanotube-PAN-based nanofiber devices are fab-
ricated on glass substrate by the electrospinning process.
Metal pads of aluminum are fabricated by the conventional
lithography process, and these pads are used to fabricate
the nanofiber devices. The fabricated devices have an aver-
age nanofiber diameter of 100 nm. The fabricated devices
display electrical properties similar to that of the back-to-
back Schottky diode. Thermionic emission theory is used to
calculate the Schottky diode parameters of the device. The
SB height and ideality factor of the device are calculated
to be 431 meV and 4.1, respectively. The ideality factor of
the device indicates multiple current transport mechanisms
(thermionic emission, tunneling, generation-recombina-
tion, and leakage) contributing to the current through the
nanofiber device. The fabrication technique of the devices
is simple and cost-effective. The electrode metal Al is also
cost-effective for nanofiber devices. The application of the
nanofiber devices can include gas sensing, bio-sensing, and
other electronic device applications.
Conflict of interest The authors declare that they have no conflict of
interest.
References
1. S.J. Tans, A.R.M. Verschueren, and C. Dekker, Nature 393, 49
(1998).
2. S.J. Tans, M.H. Devoret, H. Dai, A. Thess, R.E. Smalley, L.J.
Geerligs, and C. Dekker, Nature 386, 474 (1997).
3. T. Durkop, S.A. Getty, E. Cobas, and M.S. Fuhrer, Nano Lett. 4,
35 (2004).
4. S. Berber, Y.-K. Kwon, and D. Tomanek, Phys. Rev. Lett. 84, 4613
(2000).
5. P.A. Tran, L. Zhang, and T.J. Webster, Adv. Drug Deliv. Rev. 61,
1097 (2009).
6. M.M.J. Treacy, T.W. Ebbesen, and J.M. Gibson, Nature 381, 678
(1996).
7. M.-F. Yu, O. Lourie, M.J. Dyer, K. Moloni, T.F. Kelly, and R.S.
Ruoff, Science 287, 637 (2000).
8. B.Q. Wei, R. Vajtai, and P.M. Ajayan, Appl. Phys. Lett. 79, 1172
(2001).
9. A. Javey, J. Guo, Q. Wang, M. Lundstrom, and H. Dai, Nature 424,
654 (2003).
10. S.E. Baker, K.-Y. Tse, E. Hindin, B.M. Nichols, T.L. Clare, and
R.J. Hamers, Chem. Mater. 17, 4971 (2005).
11. T.-T. Wu, Y.-Y. Chen, and T.-H. Chou, J. Phys. D. Appl. Phys. 41,
085101 (2008).
12. R. Nenkova, D. Ivanova, J. Vladimirova, and T. Godjevargova,
Sensors Actuators B Chem. 148, 59 (2010).
13. K. Bubke, H. Gnewuch, M. Hempstead, J. Hammer, and M.L.H.
Green, Appl. Phys. Lett. 71, 1906 (1997).
14. N. Kumar, N.K. Navani, and S.K. Manhas, IEEE Trans. Electron
Devices 66, 2789 (2019).
15. P. Avouris, T. Hertel, R. Martel, T. Schmidt, H.R. Shea, and R.E.
Walkup, Appl. Surf. Sci. 141, 201 (1999).
16. M. Bourourou, M. Holzinger, F. Bossard, F. Hugenell, A. Maaref,
and S. Cosnier, Carbon 87, 233 (2015).
17. A. Bezryadin, A.R.M. Verschueren, S.J. Tans, and C. Dekker,
Phys. Rev. Lett. 80, 4036 (1998).
18. M. H. Yang, K. B. K. Teo, W. I. Milne, and D. G. Hasko, Appl.
Phys. Lett. 87, 253116 (2005).
19. E. Arslan, Ş. Altindal, S. Öz̧celik, and E. Ozbay, J. Appl. Phys.
105, 023705 (2009).
20. Y.M. Shin, M.M. Hohman, M.P. Brenner, and G.C. Rutledge,
Appl. Phys. Lett. 78, 1149 (2001).
21. G. Taylor, Proc. R. Soc. London. Ser. A. Math. Phys. Sci. 280, 383
(1964).
22. D.H. Reneker, and I. Chun, Nanotechnology 7, 216 (1996).
23. M. Holc, R. Zaplotnik, M. Mozetic, and A. Vesel, IEEE Trans.
Plasma Sci. 46, 3669 (2018).
24. J.F. Moulder, W.F. Stickle, P.E. Sobol, and K.D. Bomben, X-Ray
Photoelectron Spectroscopy (Eden Prairie Minnesota: Perkin-
Elmer Corporation, 1992).
25. D.J. Coleman, J. Appl. Phys. 43, 1812 (1972).
26. S.-Y. Lee and S.-K. Lee, Nanotechnology 18, 495701 (2007).
27. S. M. Sze and K. K. Ng, Physics of Semiconductor Devices John
Wiley & Sons, Inc., Hoboken, New Jersey USA (2006).
28. S. Koné, H. Schneider, K. Isoird, F. Thion, J. Achard, R. Issaoui,
S. Msolli, and J. Alexis, Diam. Relat. Mater. 27–28, 23 (2012).
29. E.H. Rhoderick, J. Phys. D. Appl. Phys. 5, 1920 (1972).
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