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Preparation and characterization of

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its application in FET
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Journal of Physics and Chemistry of Solids ()

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Contents lists available at ScienceDirect

Journal of Physics and Chemistry of Solids

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

Preparation and characterization of semiconductor GNR-CNT

nanocomposite and its application in FET
Sedighe Salimian a,n, Mohammad Esmaeil Azim Araghi a, Ahmad Nozad Golikand b
a
b

Faculty of Physics, Kharazmi University, 49 Mofateh Avenue, Tehran 15719-14911, Iran

Material Research Center, Metalogy Group, Tehran, Iran

art ic l e i nf o

a b s t r a c t

Article history:
Received 5 November 2015
Received in revised form
21 December 2015
Accepted 2 January 2016

So far, little is known about the experimental potential of graphene nanoribbon-carbon nanotube (GNRCNT) heterostructure as a semiconductor nanocomposite. The present work examined the structural
features, topography and electronic properties of GNR-CNT nanocomposite by using Raman spectroscopy,
transmission electron microscopy, scanning tunneling microscopy and spectroscopy (STS). The homogenous semiconductor GNR-CNT nanocomposites were produced under optimized synthesis conditions.
The narrow band gap was exhibited by optimization of the reduction step. The STS of the micro-scale
surface of the nanocomposite shows local density of state in selected areas that represent the 0.08 eV
band gap of a homogenous nanocomposite. The potential of the semiconductor nanocomposite was
considered for application in stacked graphene nanoribbon-eld effect transistors (SGNR-FETs). A simple
method of device fabrication is proposed based on a semiconductor stacked GNR nanocomposite. The
high hole mobility and rectifying effect of the pn junction of the SGNR nanocomposite on TiO2 are
demonstrated. The optimal thickness for the back gate TiO2 dielectric for the tested devices was 40 nm.
This thickness decreased leakage current at the pn junction of the SGNR/TiO2 interface, which is promising heterojunction for optoelectronics. The thickness of gate dielectric and quantum capacitance of
the gate was investigated at the low 40 nm thickness by calculating the mobility. In the proposed SGNRFET, holes dominate electrical transport with a high mobility of about 1030 cm2/V s.
& 2016 Published by Elsevier Ltd.

Keywords:
Graphene nanoribbon
Nanocomposite
Rectifying effect
pn junction
Quantum capacitance

1. Introduction
After publication of the study by Geim and Novoselov et al. in
2004 [1], graphene has been regarded as a new material for fundamental and practical study because of its unique mechanical,
thermal, optical and electrical properties that include high mobility at room temperature [24]. Graphene is a zero band gap semimetal with nite minimum conductivity [5], which is a major
problem for electrical applications. The electronic band structure
of graphene is intrinsically different from that of a semiconductor
with a band gap and metal with a high density of state (DOS) at
the Fermi level. Graphene has a conical shape for conduction and a
valence band having zero band gap and zero DOS at the Fermi
level. This gives rise to linear energy dispersion and massless Dirac
fermions that produce exceptional properties such as high conductivity and mobility [6]. These unique behaviors make graphene
a good candidate for the next generation of electronic devices;
however, graphene cannot be used effectively for eld effect
n

Corresponding author.
E-mail address: std_salimian@khu.ac.ir (S. Salimian).

transistors because it has a poor On/Off ratio. Thus, a major challenge with graphene is to open a well-dened band gap to solve
the problem of low On/Off current proportion. In nanosized graphene structures, connement geometry and increased edge to
area ratio inuence their electronic properties and promise interesting physical properties for electrical and optical device applications. Quantum connement can be increased by preparing a 1D
strip of graphene nanoribbon to increase the graphene band gap
[710], downscaling the width of the GNR and decreasing the
mobility to less than that for a graphene sheet [11,12].
GNRs have been prepared using methods such as unzipping,
top-down lithography, and bottom-up processes like the synthesis
of GNR from a molecular precursor [1215]. Magda et al. [15]
observed the highest band gap of 2.3 eV using STS in which they
deposited monomer precursors on the metal surface. Furthermore,
lithographic and plasma unzipping methods [16] usually produce
rough GNR edges that decrease carrier mobility because GNR
mobility is limited by line edge roughness scattering [17]. The
difference in mobility results from the difference in the methods
used to create the GNR. A better method would be one using
chemical approaches to produce smoother edges. The highest

http://dx.doi.org/10.1016/j.jpcs.2016.01.001
0022-3697/& 2016 Published by Elsevier Ltd.

Please cite this article as: S. Salimian, et al., J. Phys. Chem. Solids (2016), http://dx.doi.org/10.1016/j.jpcs.2016.01.001i

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mobility reported thus far for monolayer GNR on a SiO2 substrate

was produced by chemical vapor deposition and measured
200500 cm2/V s [18]. Although chemical synthesis could be useful for large volume production, nding an isolated single layer of
GNR in a large amount of nanocomposite would mean costly device fabrication.
Research on the preparation of GNR and consideration of its
potential continues. No reports thus far have investigated the application of GNR to large volume production. Our research underlines the importance of obtaining a carbon based nanocomposite with the characteristics of a semiconductor in order to
develop new electronic devices. The present study used the
longitudinal unzipping approach for GNR preparation [9,13,19,20].
This method is inexpensive with cost-effective chemical process,
high yield and stable aqueous solution. The synthesis yield is a
carbon nanocomposite with a GNR-CNT heterostructure. Utilizing
an isolated single layer GNR for this production requires expensive
device fabrication. The present study investigated a new potential
of GNR-CNT nanocomposite and optimized chemical synthesis to
achieve carbon nanocomposite semiconductor with narrow band
gap of about 0.08 eV. Then the produced GNR nanocomposite was
used in a simple fabrication method and its potential was investigated for semiconductor carbon nanostructure FETs. The
carrier mobility achieved by the SGNR was higher than those
previously reported for GNR. The TiO2 was used for the back gate
dielectric. The synthesized GNR nanocomposite was highly
p-doped and a strong rectifying effect was shown for SGNR-FET on
n-type TiO2. This indicates that the FET is appropriate for optoelectronic applications like pn junction diodes. In addition, according to our previous research, SGNR nanocomposite is a compelling semiconductor for sensor application and exible electronics [21]. Although the band gap was three times greater than the
thermal energy at room temperature and the On-state increased,
the On/Off ratio remained low for transistor applications. This
could be as a result of the high concentration of GNR edges in the
nanocomposite, which creates Off leakage current. The proposed
GNR-CNT nanocomposite is a promising material with a simple
fabrication approach [21] in technology.

2. Exprimental
2.1. GNR-CNT nanocomposite preparation
In this study, GNRs were synthesized by chemical unzipping of
multiwall carbon nanotubes (MWCNTs) [13] based on Hummers
method [22]. The preparation procedure was followed as explained by Kosynkin et al. [13]. The main difference between the
synthesis used in current study and Kosynkin et al.'s synthesis is in
the size of used MWCNTs. We also investigated the potential of
GNR-CNT nanocomposite as a semiconductor carbon nanostructure, in large volume production, instead of single layer GNR
as the considered material. Patterning the graphene sheet into a
ribbon with a width of o10 nm opens an effective band gap from
the quantum connement effect [15,23,24]. The width of the GNR
formed by chemical unzipping depends on the diameter of the
nanotubes from which the GNRs originated. Therefore, raw
MWCTs o8 nm was used in diameter for unzipping. All chemicals
except the MWCNT were purchased from Merck (Germany).
MWCNTs were acquired from Neutrino (Iran).
Preparation of graphene nanoribbons based on unzipping CNTs
involves two steps: rstly, preparation of oxidized graphene nanoribbon (GONR) and secondly reduction of GONR. Two-step
synthesis of GNR, with the ratio and exact amount of each
chemical used in the samples A through F, are presented in
Tables 1 and 2. The nanoribbons obtained by this technique have

Table 1
Synthesis conditions for the preparation of GONR samples A through F.
Sample

MWCNT/KMnO4

H2O2 (ml)

A
B
C
D
E
F

(15 mg/75 mg); 1/5

1/5
1/5
1/5
(15 mg/135 mg); 1/9
1/9

0.5
0.5
0.5
0.5
1
1

Table 2
Synthesis conditions for the preparation of GNR samples A through F.
NH4OH (ml) N2H4
H2O (ml)

Sample GONR composite

(mg)

DI (ml)

A
B
C
D

12.5
30
15
15

15

60

75
75
75
30
75
45
1% SDS (in 75 cc
45
DI)
1% SDS (in 75 cc 120
DI)
75
135

75
30
45
45
120
135

much smoother edges than those which are made by conventional lithographic means.
In a typical procedure for GONR preparation (Table 1), 15 mg of
95% MWCNTs with diameters of o8 nm were suspended in 15 ml
of 98% concentrated sulfuric acid treated with 500 wt% potassium
permanganate (KMnO4) (Fig. 1(a)). The solution was heated in an
oil bath up to 70 C to consume the KMnO4. Heating process was
as follows:
1. At rst, the reaction was heated at 55 C for 30 min. The progress of the reaction was checked by preparing two test tubes.
One tube containing 1 ml of deionized (DI) water and 23 drops
of hydrogen peroxide (30%) was used to monitor the reaction
progress in which several drops (4 or 5) of the reaction mixture
were added to the test tube; if the color of the solution was
yellow/brown, the reaction was complete.
2. The second test tube containing 1 ml of DI water only was used
to check the level of permanganate consumption; a red hue
solution indicates permanganate consumption and a complete
reaction.
3. It is also remarkable to notice that there is important information in the color of the reaction mixture itself; when the color
went from black to dark brown with disappearing of the green
color of permanganate in acid, the reaction was completed.
4. Since the reaction was not complete after 30 min at 55 C (the
permanganate was not entirely consumed), continued heating
was required. The temperature was increased to 65 C and was
then stabilized. Subsequently, the reaction progress was
checked again using the test-tube procedure. Finally, when the
reaction appeared nearly complete, the temperature was increased and maintained consistently to 70 C and the solution
was stabilized.
5. Then the mixture was cooled by pouring it into an ice bath and
adding hydrogen peroxide (H2O2) (30%) to prevent precipitation
of insoluble MnO2.
6. After 3 h of centrifuging at 4000 rpm, the solution was washed
several times with DI water followed by ethanol/hydrochloric
acid. Finally, the cleaned GONR-CNT nanocomposite was collected by centrifuging.
For GNR preparation, reduction of GONR in aqueous of

Please cite this article as: S. Salimian, et al., J. Phys. Chem. Solids (2016), http://dx.doi.org/10.1016/j.jpcs.2016.01.001i

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Fig. 1. (a) The schematic of the reaction process (b) The synthesis yield is a carbon nanocomposite with GNR-CNT heterostructures (left side) and different types of unzipped
CNTs (right side).

ammonium hydroxide (NH4OH) (27%) and hydrazine monohydrate

(N2H4
H2O) (98%) can be done with or without surfactant (Table 2,
Fig. 1(a)). Here we used Sodium Dodecyl Sulfate (SDS) surfactant
for samples D and E in which 1% SDS was prepared in 75 ml DI.
The reduction steps were as follows:
1. The collected GONR nanocomposite, from step 5 (Table 1), was
added to a ask of 75 ml DI water (with or without SDS).
2. NH4OH and N2H4
H2O were added to the mixture, which was
then immersed in an oil bath at 90 C.

the TiO2/silicon substrate. In order to achieve a continuous deposition of nanocomposite layer on a hard substrate, it is necessary
to deposit a thick layer. The channel thickness was about 100 mm.
A shadow mask covered the channel and 50 nm of source-drain
aluminum electrodes were evaporated on the top. A schematic of
the devices is shown in Fig. 2(a). Fig. 2(b) shows the absence of
metal contact between the source and the drain using an optical
microscope.

3. Results and discussions

After 1 h of reduction without stirring, the dark GNR-CNT nanocomposite sediment was washed (Fig. 1(b)), centrifuged and
dried by using the same method which was used for GONR. The
reaction process and produced nanocomposite are shown schematically in Fig. 1.

Since reduction affects the basic structure of the material

(MWCNT), characteristic changes were revealed by STS, STM and
Raman identications and measurements to determine which
samples were semiconductors under different synthesis conditions (Table 2).

2.2. Device fabrication

3.1. GNR-CNT nanocomposite characterization
After cleaning the silicon substrate using the RCA method, the
TiO2 was evaporated using an electron beam gun on (100) silicon
at about 30, 40, 60 nm. To reduce agglomeration, the nanocomposite suspension was sonicated at room temperature for
5 min. After centrifuging and washing the GNR in DI water, one
spot of viscous GNR was spin-coated at 3000 rpm for 1 min onto

Raman spectra was recorded at ambient temperature using a

standard backscattering geometry with 785 nm excitation wavelength produced by a high-power laser diode source capable of
supplying 50 mW of power. We used transmission electron microscopy (TEM, model Philips EM208S) operated at 100 kV to

Fig. 2. (a) Schematic of devices (cross section); (b) channel under optical microscopy (top view).

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Fig. 3. Raman spectra of samples A through F excited with 785 nm laser radiation; raw MWCNT and GONR nanocomposites before and after reduction (GNR).

image the nanoribbons structure. Scanning tunneling spectroscopy (STM, model DME Doalscope) measurements were performed for the topographic and spectroscopic measurements.
The Raman spectrum of GNR-CNT nanocomposites is shown in
Fig. 3 by presence of three main peaks; G (1580 nm), D (1350 nm),
and 2D (2700 nm) [2528]. D band and 2D band, both are second

order double resonances including one and two phonon scattering

respectively [37]. D band presents the disorder and defect in a
sample or at the edge of a graphene sample. In unzipping process,
broad D band in GONR also can be originated from oxygen-containing functional groups which reduce, in width and intensity,
after adding reduction agents. Lower D-band intensity in GNR in

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Fig. 5. RBM modes, excited with 785 nm laser radiation, of raw MWCNT and GONR
nanocomposites of sample A before and after reduction (GNR).

Fig. 4. Agglomeration caused by hydrophobicity after GONR reduction.

comparison to that of GONR shows that the reduction has occurred as a result of the reducing agents. Therefore, when GNRs'
D-band intensity is higher than that of MWCNTs, it would mainly
originate from GNRs' open edges (Fig. 3, Sample A). Hydrazine
reduction produced an agglomeration of unzipped GNR-CNT nanocomposites caused by hydrophobicity (Fig. 4) [32,33]. The GNRs
attached to each other at the edges producing an extended graphene layer with GNR building blocks [35,36]. It can cause the
creation of narrow band gap in GNR-CNT nanocomposite. Thus,
2D-band intensity decreases with increasing reduction agents
(Fig. 3, Samples E and F).
The ratio of D band and G band represents the mount of disorder in carbon nanostructure samples. Thus, D band evaluate the
quality of carbon-based materials by comparing IG/ID ratio [15].
Table 3 shows the intensity values for ID/IG and ID/I2D which are
commonly used to evaluate the quality of carbon material [15]. It
shows that the lowest defect intensity, the highest 2D peak ratio
(ID/I2D 3) and the highest reduction (lower D-band intensity in
GNR in comparison to GONR) were found in sample A which indicate successive opening reaction and reduction in synthesis
process.
In general, the Radial Breathing Modes (RBM) are carbon nanotube identication peaks located below 400 nm [2931]. This is
unique quantum behavior and appears in single wall carbon nanotubes [38]. However, the breathing vibration in few-walled CNTs
cannot be neglected [39]; the radial vibrations of multiple tubes
make the weak RBM mode, which can be detected using Raman
spectroscopy. The diameter of the CNT is therefore of great
Table 3
Intensity ratios of main peaks in the Raman spectra of samples A through F.
Sample

ID/IG

ID/I2D

A
B
C
D
E
F

0.3
0.57
1
1
0.58
1.2

3
10

23

signicance and a higher diameter pushes the radial vibration

beyond the detection limit, whereas a lower diameter means it
appears clearly when using Raman spectroscopy. RBM modes in
MWCNT (o8 nm) are therefore observable due to their low diameter size and few-walled inner vibration; especially when the
inner shell is less than 2 nm [38]. In this experiment, the RBM
modes of sample A decreased after unzipping MWCNT (Fig. 5),
which shows that the unzipping of MWCTs was carried out
successfully.
Fig. 6 shows TEM images of the transformation of MWCNTs into
nanoribbons after unzipping. The reduced graphene nanoribbons
show single layer and multi-layer GNRs. Dark sections appear due
to the agglomeration of GNRs and CNTs in the carbon grid and
folded-in areas of the sheet. In Fig. 6(f), the remaining MWCNTs
are shown together with the GNRs. This shows that the nal
product of the unzipping process is a mixture of extended GNRs
and MWCNTs. As it was mentioned previously, reduction produces
an agglomeration which is caused by hydrophobicity and GNRs
attached at the edges producing an extended graphene layer
[35,36]. Then the extended GNR (Fig. 6(g)) included small GNR
building blocks.
Scanning tunneling spectroscopy (STS) and Microscopy (STM)
were used to study large-scale areas (micro-to-micro), on three
different samples: A, B and D. Samples A and B were selected from
Table 3, because they showed respectively the least number of
defect, the narrowest D peak after reduction and they both have
the highest intensity for 2D peak (Fig. 3). In addition, sample D
was selected to investigate surfactant effect in nanocomposite.
Figs. 7, 8 and 9 show the STS and STM of stacked fragments of
GNR-CNT nanocomposites (A, B and D) drop casted onto aluminum foil.
The tunneling current of the samples versus bias voltage was
measured using STS; it is an average of current measured in specic area. The measurements show nonlinear IV curves in different places on sample A (Fig. 7(b) and (c)). The numerical derivation dI/dV denes the local density of state (DOS) (Fig. 7(d)).
From this result, it can be understood that the interference of
electron waves produced DOSs at measured positions. Fig. 7
(d) shows the decrease the dI/dV signal that can be attributed to
the decrease in DOS at the edges of the area [10]; the dI/dV curve
is related to the scanned area (1 mm2) (Fig. 7(a)). A gap-like feature
was observed at about 0.08 eV between two arrows in the graphene tunneling spectrum of sample A (Fig. 7(d)). This gap was

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Fig. 6. TEM images of the stepwise opening of MWCNTs to form GNRs. The dark parts are carbon grid: (a) and (b) raw MWCNTs; (c) and (d) oxidized graphene nanoribbons;
(e) reduced graphene nanoribbons; (f) reduced graphene nanoribbons (left side) showing GNR sheet and (right side) agglomerated raw MWCNT; (g) highly transparent GNR
partially folded onto itself.

found to arise from suppression of electronic tunneling to graphene states near the Fermi level [34].
This is promising band gap for carbon nanotechnology and
indicates that homogenous GNR-CNT heterostructure nanocomposites with optimized narrow band gap can be used to develop easy strategies for device fabrication.
The reduction step plays an important role in decreasing oxidization and the amount is critical for preventing agglomeration
and producing homogenous nanocomposite. A lower reduction
amount (30 ml) was tested for sample B for comparison with
sample A (75 ml) (Table 2). Fig. 8 shows that the tunneling IV
curve has a linear aspect (Fig. 8(b)) and there are energy states at
the Fermi level of DOS (dI/dV curve) which are CNT mid-gap states
(Fig. 8(c)); the dI/dV curve is related to the red square scanned
area (0.05 mm2) (Fig. 8(a)). This behavior indicates that reduction

was not complete. As long as there is a high concentration of

oxidized CNT in the nanocomposite, the GNR-CNT nanocomposite
band structure does not have band gap.
According to Table 2, sample D contained more reductant in a
surfactant solution (45 ml of reduction in 1% SDS surfactant solution)
than sample B (30 ml of reduction in 75 ml DI water) to prevent agglomeration. The STS of sample D shows nonlinearity of an insulator
(Fig. 9) which could be an effect of the surfactant used. Vibration in the
tunneling IV curve is instrumental noise related to the nanometer
range of the selected scale area (400 nm2, green line). A large area
(0.036 mm2, red line) has a lower vibrational effect.
3.2. Electrical measurement of SGNR-FET
As sample A showed semiconductor characteristics, it was
chosen for device fabrication. The electrical characterization of

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Fig. 7. (a) STM image of GNR nanocomposite of sample A drop casted on Al foil at 1 mm2 area scale. Two triangle bars show the material thickness on top of Al substrate is
about 50 nm. (b) and (c) nonlinear IV curve of selected areas. (d) Derived IV (dI/dV); DOS shows sample A is a semiconductor nanocomposite; the insect shows a gap-like
feature of sample A with narrow energy gap at about 0.08 eV.

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Fig. 8. (a) STM images of GNR nanocomposite of sample B drop casted on Al foil at 0.05 mm2 area scale. Red square shows selected area for measurement. (c) Linear IV curve
and (d) Derived IV (dI/dV); DOS of sample B included CNT mid-gap states around fermi level with no energy gap.

devices was performed using HP instrument. The channel resistance of sample A showed nonlinear behavior at about 106 .
This amount of resistance was expected because of the small
diameter of the raw CNTs used. Dayen et al. [40] also reported
channel resistance for GNR in the range of 40700 k at 300 K.
The charge carrier density was controlled using a gate eld
rather than a source drain eld. The thickness of the gate dielectric
must decrease [4143]; however, for graphene on a SiO2 substrate,
scattering electrons using the optical phonons of the substrate had
a greater effect at room temperature than scattering the graphene
phonons. TiO2 is a high-k material with a low band gap. High-k
materials can decrease charged impurity scattering from the increased screening effect and improve gate charge control on the
channel because of higher gate capacitance [42, 48,50].
Sample B was next spin-coated onto the three substrates devices 1, 2 and 3 with 30 nm, 40 nm and 60 nm evaporated TiO2,
respectively (Fig. 10). The electrical performance of the SGNR-FETs
varied according to the thickness of the TiO2. Fig. 10(b) shows a
smooth cross-section of device 2 with 40 nm TiO2. The bright lines
at the top are evaporated TiO2. At low roughness, the 40 nm
sample had a low scattering center at the SGNR/TiO2 interface. The
evaporated TiO2 thickness was conrmed using an interferometer.

The contribution of current from the holes in Fig. 11 indicates that

the holes dominated transport.
The band gap at 0.08 eV is about three times larger than the
thermal energy at room temperature. It appears that the superposition of electrical properties of the GNRs in the SGNR had a
constructive effect in the On-state (mA current range) and a destructive effect in the Off-state (Fig. 11). Utilizing the narrow band
gap graphene stack for FET increased the mobility of the SGNRFET, but is not a guarantee of improvement of Off-state performance. Off leakage could be the result of the variability in the band
gap and edge effects [8,44] from the combined GNRs in the
nanocomposite.
One of the most efcient ways to determine the semiconductor
behavior of materials is assessing pn junction characteristics [52].
In Fig. 12, a pn junction diode was inserted at the interface to
allow for different densities for the carriers at the SGNR/TiO2
junction having an asymmetric IV curve. The semiconductor behavior of SGNR upon formation of pn junction on TiO2 thin lm
(Fig. 12) conrms the band gap characteristic (Fig. 7(d)) of sample
A. Fig. 12 shows the rectifying behavior at the SGNR/TiO2 interface
after application of source-drain voltage and constant applied back
gate voltages (VBG 10 V, 0 V, 10 V). The pn junction diode with

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Fig. 9. Red (0.036 mm2) and green (400 nm2) squares are two different sizes of
selected areas of sample D; nonlinear IV curve of measured squares originates
from surfactant effect and vibrations are instrumental noise related to the nanometer range of the measured scale size.

the lowest leakage current is shown in Fig. 12(b). The current shift
(prole does not pass zero current at zero V source-drain) for
positive and negative back gate voltage is from the effect of charge

Fig. 11. Electrical transport curves of SGNR-FETs; VBG v.s. ISD for VSD 0.5 V.

carriers induced by the back gate eld effect. Fig. 13 shows this
effect on charge carrier concentration. By applying zero and negative back gate voltages, the (p-doped) higher p-doped GNR stack
and the (n-doped) higher n-doped TiO2 dielectric were produced

Fig. 10. Cross-section images of Si substrate with TiO2 deposits of about: (a) 30 nm (b) 40 nm (c) 60 nm.

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Fig. 12. Rectifying IV curves, VSD v.s. ISD at VBG  10, 0, 10 V and TiO2 of (a) 30 nm (b) 40 nm (c) 60 nm.

at the junction. In a positive (negative) biased channel, the junction is in forward (reverse) bias.
The schematic energy band diagram of the SGNR/TiO2 heterojunction shown in Fig. 14 corresponds to that shown in Fig. 12(b).
The main difference between the narrow band gap SGNR and the
wide band gap TiO2 is caused by the hole barrier [51]. In reverse
bias, the minority charge carriers ow through the junction from
both directions; in forward bias, just one direction of the majority
charge carrier ows across the junction. Holes require more energy to pass this potential barrier.
Table 4 shows the increased number of electrons and the hole
mobility of device 2 compared to the other two devices. All three
devices operated at the quantum capacitance limit (QCL) when QC
was less than their classical capacitance (CC) [49]. The equivalent
circuit is shown in Fig. 15. QC was calculated using Eq. (1)
[45,46,47] which shows that QC is in the QCL regime, Cinsulator was
calculated using Eq. (2) and mobility was calculated using Eq. (3):

CQ = e 2

2eVch
2

( vf )

(1)

Cinsulator =

COX CQ
COX + CQ

L g m
W CiVD

(2)

(3)

4. Conclusion
In this research we synthesized a GNR-CNT nanocomposite by
chemical unzipping of CNT for potential use as a carbon nanostructure semiconductor. The CNTs were converted into the GNRs
through longitudinal unzipping. Measurement of the structural
and elemental properties was done by Raman spectroscopy, TEM,
STM and STS. Controllable reduction is a specic requirement for
preparation of semiconductor carbon nanocomposites. Although
complete unzipping and complete reduction are difcult to perform on CNTs, partial synthesize is sufcient to achieve a homogenous semiconductor by optimizing synthesis; in this case, optimizing the mount of reductant. The energy gap of optimized

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Table 4
Electrical parameters of devices.
Device

le (cm2/V s)

lh (cm2/V s)

1; TiO2 (30 nm)

2; TiO2 (40 nm)
3; TiO2 (60 nm)

102
223
74

354
1030
1030

Fig. 15. Equivalent circuit for dielectric and graphene interface.

Fig. 13. Effect of back gate on charge carrier concentration at SGNR/TiO2 junction.

nanocomposite using STS in micro scale size was observed at

0.08 eV above the Fermi level. This narrow band gap in spite of
unzipping small-size MWCNTs is likely to be because of the producing an extended graphene ribbon with GNR building blocks.
The semiconductor GNR was utilized as a channel for the eld
effect transistor with a TiO2 dielectric. Asymmetry in ambipolar
graphs of the SGNR-FET shows that holes dominated electrical
transportation with higher mobility (1030 cm2/V s) as calculated
using equivalent circuit and quantum capacitance. The negative
voltage of the back gate induced high density in the charge carriers at the SGNR/TiO2 interface and formed a pn junction diode
with low leakage current. The suggested band diagrams describe
the process of charge transferring well. It is a promising low cost
proposed structure for optoelectronic applications requiring
stacked GNRs with high charge carrier mobility. This characteristic
should help pave the way toward development of GNR nanocomposite-based semiconductor nanotechnology. Research on
GNR-CNT nanocomposites is a step toward developing this material for practical applications and is attractive for mass-scale production of GNRs in combination with CNTs which can be applicable for ease of device fabrication.

Acknowledgments
The rst author is grateful to the University of Kharazmi and
Material Research Center for nancial support for this research
work.

References

Fig. 14. Energy band diagram of a SGNR/TiO2 heterojunction of device 2 at:

(a) equilibrium; (b) reverse bias; (c) forward bias.

[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.
V. Grigorieva, A.A. Firsov, Science 306 (2006) 666669.
[2] W.J. Yu, X. Duan, Sci. Rep. 3 (2013) 1248.
[3] C.N.R. Rao, K.S. Subrahmanyam, H.S.S. Ramakrishna Matte, A. Govindaraj, Mod.
Phys. Lett. B 25 (2011) 427451.
[4] F. Perreault, A. Fonseca de Faria, M. Elimelech, Chem. Soc. Rev. 44 (2015)
58615896.
[5] M.W. Lin, C. Ling, Y. Zhang, H.J. Yoon, M.M.C. Cheng, L.A. Agapito, N. Kioussis,
N. Widjaja, Z. Zhou, Nanotechnology 22 (2011) 265201.
[6] F. Akbar, M. Kolahdouz, S. Larimian, B. Radfar, H.H. Radamson, J. Mater. Sci.:
Mater. Electron. 26 (2015) 43474379.
[7] H. Owlia, P. Keshavarzi, Mat. Sci. Semicon. Proc. 39 (2015) 636640.
[8] M. Poljak, K.L. Wang, T. Suligoj, Solid State Electron. 108 (2015) 6774.
[9] L. Jiao, L. Zhang, X. Wang, G. Diankov, H. Dai, Nature 458 (2009) 877880.
[10] S.H. Phark, J. Borme, A.L. Vanegas, M. Corbetta, D. Sander, J. Kirschner,

Please cite this article as: S. Salimian, et al., J. Phys. Chem. Solids (2016), http://dx.doi.org/10.1016/j.jpcs.2016.01.001i

67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
Q5114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132

12

1
2
3
4
5
6
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11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66

S. Salimian et al. / Journal of Physics and Chemistry of Solids ()

Nanoscale Res. Lett. 7 (2012) 255.

[11] X. Wang, Y. Ouyang, X. Li, H. Wang, J. Guo, H. Dai, Phys. Rev. Lett. 100 (2008)
206803.
[12] Y. Yang, R. Murali, IEEE Electron Dev. Lett. 31 (2010) 237239.
[13] D.V. Kosynkin, A.L. Higginbotham, A. Sinitskii, J.R. Lomeda, A. Dimiev,
B. Katherine Price, J.M. Tour, Nature 458 (2009) 872876.
[14] H. Sde, L. Talirz, O. Groning, C.A. Pignedoli, R. Berger, X. Feng, K. Mllen,
R. Fasel, P. Rufeux, Phys. Rev. B 91 (2015) 045429.
[15] G.Z. Magda, X. Jin, I. Hagymsi, P. Vancs, Z. Osvth, P. Nemes-Incze, C. Hwang,
L.P. Bir, L. Tapaszt, Nature 514 (2014) 608611.
[16] I.M. Fernandez, D. Wang, Y. Zhang, Nano Lett. 12 (2012) 61756179.
[17] J.H. Chen, W.G. Cullen, C. Jang, M.S. Fuhrer, E.D. Williams, Phys. Rev. Lett. 102
(2009) 236805.
[18] A. Behnam, A.S. Lyons, M. Bae, E.K. Chow, S. Islam, C.M. Neumann, E. Pop, Nano
Lett. 12 (2012) 44244430.
[19] A. Sinitskii, A. Dimiev, D.V. Kosynkin, J.M. Tour, ACS Nano 4 (2010) 54055413.
[20] L. Jiao, L. Zhang, L. Ding, J. Liu, H. Dai, Nano Res. 3 (2010) 387394.
[21] M. Asad, S. Salimian, M.H. Sheikhi, M. Pourfath, Sens. Actuators A-Phys. 232
(2015) 285291.
[22] W.S. Hummers Jr, R.E. Offeman, J. Am. Chem. Soc. 80 (1958) 1339.
[23] R. Sako, H. Hosokawa, H. Tsuchiya, IEEE Electron Dev. Lett. 32 (2011) 11704692.
[24] L.F. Huang, G.R. Zhang, X.H. Zheng, P.L. Gong, T.F. Cao, Z. Zeng, J. Phys.: Condens. Matter 25 (2013) 055304.
[25] Y. You, Zh Ni, T. Yu, Z. Shen, Appl. Phys. Lett. 93 (2008) 163112.
[26] M.S. Dresselhaus, A. Jorio, A.G. Souza Filho, R. Saito, Phil. Trans. R. Soc. A 368
(2010) 53555377.
[27] A.C. Ferrari, D.M. Basko, Nat. Nanotechnol. 8 (2013) 235.
[28] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri,
S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Phys. Rev. Lett. 97
(2006) 187401.
[29] S. Costa, E. Borowiak-Palen, M. Kruszynska, A. Bachmatiuk, R.J. Kalenczuk,
Mater. Sci.-Poland 26 (2008) 433441.
[30] M.S. Dresselhaus, A. Jorio, M.A. Pimenta, An. Ac. Bras. Cie nc. 78 (2006)
423439.
[31] H. Telg, M. Fouquet, J. Maultzsch, Y. Wu, B. Chandra, J. Hone, T.F. Heinz,

C. Thomsen, Phys. Status Solidi B 245 (2008) 21892192.

[32] S. Pei, H.M. Cheng, Carbon 50 (2012) 32103228.
[33] S. Park, J. An, J.R. Potts, A. Velamakanni, Sh Murali, R.S. Ruoff, Carbon 49 (2011)
30193023.
[34] Y. Zhang, V.W. Brar, F. Wang, C. Girit, Y. Yayon, M. Panlasigui, A. Zettl, M.
F. Crommie, Nat. Phys. 4 (2008) 627630.
[35] F. Cataldo, G. Compagnini, G. Patan, O. Ursini, G. Angelini, P.R. Ribic,
G. Margaritondo, A. Cricenti, G. Palleschi, F. Valentini, Carbon 48 (2010)
25962602.
[36] C.Y. Moon, Y.S. Kim, E.C. Lee, Y.G. Jin, K.J. Chang, Phys. Rev. B 65 (2001) 155401.
[37] J.S. Chen, V. Stolojan, S.R.P. Silva, Carbon 84 (2015) 409418.
[38] R. Kamalakannan, K. Ganesan, S. Ilango, N. Thirumurugan, V.N. Singh,
M. Kamruddin, B.R. Mehta, A.K. Tyagi, Appl. Phys. Lett. 98 (2011) 192105.
[39] K.N. Cheng, Y.H. Lin, G.R. Lin, Laser Phys. 23 (2013) 045105.
[40] J.F. Dayen, A. Mahmood, D.S. Golubev, I.R. Jeune, P. Salles, E. Dujardin, Small 4
(2008) 716720.
[41] L. Liao, X. Duan, Mater. Sci. Eng.: R: Rep. 70 (2010) 354370.
[42] J.H. Chen, C. Jang, M. Ishigami, S. Xiao, W.G. Cullen, E.D. Williams, M.S. Fuhrer,
Solid State Commun. 149 (2009) 10801086.
[43] M. Akbari Eshkalak, R. Faez, S. Haji-Nasiri, Phys. E: Low Dimens. Syst. Nanostruct. 66 (2015) 133139.
[44] M. Poljak, M. Wang, E.B. Song, T. Suligoj, K.L. Wang, Solid State Electron. 84
(2013) 103111.
[45] J. Xia, F. Chen, J. Li, N. Tao, Nat. Nanotechnol. 4 (2009) 505509.
[46] S. Drscher, P. Roulleau, F. Molitor, P. Studerus, C. Stampfer, K. Ensslin, T. Ihn,
Phys. Scr. T 146 (2010) 014009.
[47] S. Luryi, Appl. Phys. Lett. 52 (1988) 501503.
[48] S.K. Jang, J. Jeon, S.M. Jeon, Y.J. Song, S. Lee, Solid State Electron. 109 (2015)
811.
[49] M.A. Khayer, R.K. Lake, IEEE Trans. Elect. Dev. 56 (2009) 22152223.
[50] F. Schwierz, Nat. Nanotechnol. 5 (2010) 487496.
[51] L. Hans, Solid Surface, Interfaces and Thin Films, Fifth ed., Springer, New York,
2010.
[52] D.T. Phan, G.S. Chung, J. Phys. Chem. Solids 74 (2013) 15091514.

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