IEEE SENSORS JOURNAL, VOL. 16, NO.
1, JANUARY 1, 2016
Coupled Effects of Film Thickness and Filler
Length on Conductivity and Strain Sensitivity of
Carbon Nanotube/Polymer Composite Thin Films
Rubaiya Rahman, Saeid Soltanian, and Peyman Servati, Member, IEEE
Abstract— The coupled effects of varying composite film
thicknesses and filler lengths on the conductivity and strain
sensitivity of carbon nanotube (CNT)/polymer composite films
are investigated through modeling and experiments. Change
in average intertube distance is calculated statistically through
the Monte Carlo simulations for samples with different CNT
concentrations and film thicknesses for a given filler aspect
ratio. The composite conductivity is then estimated from the
intertube distance with a semi-analytical model based on a
tunneling current. The dependence of conductivity on mechanical
strain is investigated for varying film thickness for strain sensor
applications. A partial alignment of CNTs introduced at film
thicknesses less than the CNT length is observed to have a
significant influence on the composite conductivity and strain
sensitivity, specially at low CNT concentrations. The modeling
results can explain the observed experimental results of con-
ductivity for CNT composites, which illustrate a unique dip in
conduction with increasing thickness. These results are important
for understanding the composite characteristics with different
filler orientations and film thicknesses for a given filler length,
and useful for the design optimization of high performance
composite electronic films for applications in electronic skin and
sensors.
Index Terms— Nanocomposite, carbon nanotube, polymer,
conductivity, modeling, film thickness, sensor.
I. I NTRODUCTION
C ARBON nanotubes (CNTs) have attracted interest
of researchers working in nanoelectronics and
optoelectronics for the last few decades and recently in smart
structure applications. CNTs possess exceptional electrical,
thermal and mechanical properties and high sensitivity that
make them attractive candidates for multifarious application,
i.e. transparent electrodes, photovoltaic devices, flexible
electronics, smart materials, etc. When they are introduced in
an insulating polymer matrix even at a very low amount, the
CNTs can form an electrical percolating network that turns the
insulating matrix to a conducting one [1]. The unique mechani-
cal strength of the CNTs can be understood from the Young’s
Manuscript received August 10, 2015; accepted August 27, 2015. Date of
publication September 14, 2015; date of current version December 10, 2015.
This work was supported by the Natural Sciences and Engineering Research
Council of Canada. The associate editor coordinating the review of this paper
and approving it for publication was Dr. Stefan J. Rupitsch.
The authors are with the Department of Electrical and Computer
Engineering, University of British Columbia, Vancouver, BC V6T 1Z4,
Canada (e-mail: rubaiya11@gmail.com; saeid@ece.ubc.ca; peymans@ece.
ubc.ca).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/JSEN.2015.2478447
1530-437X © 2015 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
77
modulus of individual multi-walled nanotube (MWNT)
(0.27-0.95 TPa) [2] and single-walled nanotube (SWNT)
(0.32-1.47 TPa) [3]. The high Young’s modulus of the
CNTs shows its potential in the applications where composite
reinforcement is necessary or repetitive strain/stress is exerted.
CNTs when embedded in polymers have been reported to
enhance the piezoresistive property of the composites
and show higher sensitivity than the conventional strain
sensors [4].
Generally, in a conductor-insulator composite, if we
gradually increase the number of conductive fillers
(e.g. CNTs), after reaching a certain filler volume fraction
the electrical conductivity of the composite takes a sharp
upturn. At this filler concentration, known as percolation
threshold, the electrical conduction effectively begins through
the percolating conductive filler network. Several parameters
including the type, concentration, aspect ratio, orientation
order, synthesis method, surface modification of CNTs as
well as polymer type and dispersion method influence the
percolation threshold, scaling law exponent and maximum
conductivity of the composite [5]. Most of the experimental
results suggest exponential increase of film conductivity with
the increase of CNT concentration [6], [7]. Larger aspect ratio
and random isotropic orientation of tubes are reported to lower
the percolation threshold, and thus enhance the conductivity
of a CNT film [6], [8], [9]. From the recent studies it has
been suggested that electron tunneling between neighboring
CNTs plays a major role in the electrical conductivity and
piezoresistivity of a CNT/polymer composite [10], [11]. Since
the CNTs rarely make intimate contacts, in contrary to the
assumption in percolation theory, the electrons tunnel through
the polymer molecules present between neighboring CNTs,
given that the intertube gap is sufficiently small [12]. Thus the
composite conductivity is mainly determined by the tunneling
conductivity specially in application where concentration of
CNTs is low, i.e. transparent conductors, strain sensors, etc.
The tunneling current in a CNT-CNT junction is determined
by different factors, i.e. the intertube distance d, energy barrier
height of the polymer λ, the type of CNT, etc. Again the
intertube distance d in a composite film is influenced by the
CNT concentration, aspect ratio, alignment, film thickness, etc.
Thus the film thickness can in turn influence the tunneling
conductivity, which is a major component playing role in
strain sensitivity of composite films. Thin films of CNTs and
CNT/polymer composite films have potential application in
78 IEEE SENSORS JOURNAL, VOL. 16, NO. 1, JANUARY 1, 2016

strain and pressure sensing for structural health monitoring,

damage or deformation detection, fluid flow sensing, artificial
skin, etc. [13]–[16]. To identify local structural damage and to
investigate structures at the component level, a large number
of sensors need to be installed. Thinner composite films can
help in cost reduction of the sensors and allow installation
of large number of sensors in a single monitoring system.
In a CNT/polymer composite film, when the film thickness is
reduced below the filler length, it introduces some alignment
of the fillers which can potentially affect the average intertube
distance and eventually the film conductivity and sensitivity.
Although there has been reports on the effect of film thickness
on the composite conductivity [17], [18], the comparative
effects of film thickness below and above the filler length have
not been reported yet. A thorough understanding of the relative
effect of film thickness and CNT length on the composite
conductivity can help to estimate the sensitivity of composite
films of different thickness. Hence a systematic study on this
coupled effect of film thickness and filler length can help in
design optimization of sensors, but still in need.
In this paper, we present our experimental and numerical
study of the relative effect of film thickness and filler length on
the electromechanical properties of CNT/polymer composites.
We numerically generated composite samples of different
thickness t, CNT volume fraction φ and alignment angle ψ,
then applied Monte Carlo based statistical method to calculate
the average intertube distance d. Then the composite film
conductivity and strain sensitivity was estimated using our
semi-analytical model. In order to verify the numerical results
on the behavior of film conductivity with the varying film
thickness and filler alignment, we carried out experiments with
SWNT/PMMA composite films and compared the experimen-
tal results with the numerical ones.
II. M ETHODOLOGY AND R ESULTS
In this section we first build a number of numerical com-
posite samples containing uniformly dispersed CNTs in order
to analyze the intertube distance. The number of CNTs are
varied to observe the effect of different CNT concentration on Fig. 1. Illustration of (a) a 3D cubic sample of CNT/polymer composite
the average intertube distance. The sample film thickness is and (b) a randomly oriented filler making orientation angles with X-Y and
changed below and above the length of CNTs to observe the X-Z planes.
effect of filler alignment on the intertube gaps introduced by
the sample thickness. Then the composite film conductivity is The concentration of CNTs are determined by the filler volume
obtained using our semi-analytical model. Finally, the strain fraction φ, which is the ratio of total volume of CNTs to the
sensitivity of the films with different thickness under applied volume of composite cell. The alignment order was determined
strain in longitudinal direction is estimated and analyzed. by two orientation angles-θ and ψ, the angles that the fillers
make with the X-Z and X-Y planes respectively, as shown
A. Construction of Numerical Samples of Nanocomposite in Fig. 1(b). We varied the CNT concentration by changing
A three dimensional microstructure sample of CNT/polymer the stick numbers in the unit samples. The cut-off angles θμ
composite is simulated where CNTs are assumed as multi- and ψμ are the maximum angle between an arbitrary filler
walled carbon nanotubes (MWNTs) and randomly dispersed in and the X-Z and X-Y planes respectively. The average value
the polymer matrix. Here, CNTs are considered as penetrable of intertube distance and other numerical data are obtained by
soft-core cylinders with length L = 5μm and diameter Monte-Carlo simulations over large number samples. We also
D = 50nm, hence aspect ratio AR of 100. The sample, varied the thickness of the samples by changing the length
as shown in Fig. 1(a), is simulated as a cubic unit cell of L z while keeping the L x = L y of same length. It is to
(L x × L y × L z ) with a length of 25μm on each side. note that the results of simulations can be influenced by the
The position and orientation of the stick-like fillers is size of the unit cell. Smaller cell size is helpful in reducing
randomly chosen following the method by Hu et al [11]. the computational cost but it generates very unstable results.
RAHMAN et al.: COUPLED EFFECTS OF FILM THICKNESS AND FILLER LENGTH ON CONDUCTIVITY AND STRAIN SENSITIVITY
Fig. 2. A schematic diagram of (a) top view of the CNT network with
electric field applied on it. The percolating cluster is shown within the dashed
line, and (b) a CNT pair with tunneling gap dt between them. The resistance
along the CNTs are denoted as Rc and the tunneling resistance as Rt .
For this work we chose L x = L y = 5L and varying values
of L z for 3D samples. This cell size is sufficiently large to
achieve numerical convergence and stability in the results as
confirmed by literature [4].
B. Analysis of Intertube Distance
As the filler concentration in a composite sample increases,
it decreases the inter-filler gaps. If an electric field is applied
across a CNT/polymer composite sample, the decreased
intertube distance at higher CNT concentration enhances the
probability of electron transfer between neighboring tubes.
In our simulation work, the direction of applied field and
electrical conduction is assumed along X-axis, determined
by the location of electrodes. The neighboring junctions
transferring electrons can build up a conducting bridge from
the left electrode to the right one known as the percolating
cluster. It is shown within the dashed line in Fig. 2(a).
79
Fig. 3. Intertube distance for varying CNT concentration for a random
3D network.
There can be multiple number of percolating clusters making
parallel conductive pathways across the sample.
If voltage is applied across a junction between two neigh-
boring tubes, the electron finds the shortest distance between
these two tubes and tunnels through it if the intertube gap
is below the maximum allowed tunneling gap. The energy
barrier between the tubes, due to the presence of polymer
layer, gets changed in shape under a potential difference and
causes the electrons to tunnel through the barrier [10]. Thus a
small current is generated at the junction. The current through
the entire sample is the summation of these small junction
currents through the conductive pathways. Fig. 2(b) shows a
pair of neighboring CNTs where electron tunneling occurs
between two tubes through the minimum intertube gap dt .
The resistance of the electron’s pathway is represented by a
series resistance comprising the tunneling resistance Rt , and
CNT resistance Rc .
The composite conductivity is primarily influenced by
the tunneling currents. Since electron tunneling occurs only
between the nearest neighbor CNTs, the minimum distance
among the tubes plays significant role in determining the
overall conductivity. In this work, we have used a Monte-Carlo
procedure of large number of simulations to estimate the aver-
age minimum distance between any arbitrary pair of tubes d
in a 3D CNT network for varying CNT concentration and film
thickness. For samples with thickness greater than the length
of the CNTs, the fillers can be oriented in any order inside
the 3D unit cells. Hence both the cut-off angles θμ and ψμ
are set at their highest value, i.e. 90°. and the fillers can
achieve complete randomness in orientation. Fig. 3 shows the
simulation results of intertube distance for varying filler con-
centration in a cubic unit cell with L x = L y = L z = 25 μm.
We can see as CNT volume fraction φ increases, the intertube
distance d decreases in a power law manner, which is similar
to the behavior observed in 2D composite samples [19].
Apart from the filler concentration, the average intertube
distance can vary with the filler aspect ratio or orientation
80
Fig. 4. Schematic diagram of CNT/polymer composite films with different
thicknesses.
Fig. 5. Intertube distance at varying CNT concentration for CNT/polymer
composite films with different thickness.
which in turn can influence the film resistance [19]–[21].
If the sample film thickness is decreased below the filler
length, that will limit the randomness of the fillers and
introduce some alignment, thus reduce the cut-off angle ψμ
to a value below 90°. The schematic diagram in Fig. 4
demonstrates how the alignment order of the CNTs is changed
when the film thickness is decreased below the CNT length,
keeping the number of CNTs per unit volume unchanged. The
change in the CNT orientation affects the average distance
between tubes and thus can influence the conductivity and
sensitivity of the composite film.
We studied the effect of film thickness on the intertube
distance by numerical simulation which is shown in Fig. 5.
Since the CNTs used in our simulation have length of
L = 5μm and diameter of D = 50nm, we varied the film
thickness from 15μm to 50nm to study effect of film thickness
both below and above the CNT length. From the figure we
can see for all film thickness t, the intertube distance d
decreases as the CNT concentration increases. At any CNT
concentration, the d has higher value at lower film thickness,
except when t is close to CNT length L = 5μm. Fig. 6
demonstrates the change in d with thickness. Our simulation
results show that when the film thickness t decreases from
15μm to 5μm the intertube distance increases gradually. But
as t drops slightly from 5μm, d starts decreasing, keeps
lower value for a while, then again starts increasing with the
IEEE SENSORS JOURNAL, VOL. 16, NO. 1, JANUARY 1, 2016
Fig. 6. Intertube distance at varying sample film thickness for different CNT
concentration.
Fig. 7. Intertube distance at varying alignment order of CNTs for different
CNT volume fraction.
decreasing t. This behavior opens up a question of the effect of
the partial alignment on d. Before t is decreased to 5μm, the
fillers are allowed to have full randomness whereas right after
the t is reduced below 5μm, the fillers starts aligning to the
X-Y plane gradually making ψμ less than 90°. Thus at
t = 50nm the composite film becomes almost a quasi-2D
plane making ψμ ≈ 0°. We calculated the cut-off angle ψμ
for t ≤ 5μm and re-plotted the corresponding values of d
in Fig. 7. It shows that the intertube distance reaches the lowest
value at around ψμ = 45°. Therefore, the minimum intertube
distance can be found at partial alignment, not in completely
random or completely aligned CNT network. This behavior
is consistently shown by samples of different concentrations,
whereas the drop in the intertube gap at partial alignment
is more pronounced at lower concentration of fillers. For
example, when ψμ is decreased from 90° to 53°, the intertube
distance decreases from 0.47nm to 0.05nm for φ = 7%
concentration, whereas for the same change in alignment, the
RAHMAN et al.: COUPLED EFFECTS OF FILM THICKNESS AND FILLER LENGTH ON CONDUCTIVITY AND STRAIN SENSITIVITY
drop in the intertube distance for φ = 1.42% is from 7.61nm
to 2.026nm. This behavior can be explained in context of
CNT-CNT junctions that build up the conductive pathway for
percolation. In a highly concentrated random CNT network,
the number of nanotube junctions is high. When a filler is
aligned slightly, it may lose contact with one neighbor filler.
But since each filler is surrounded by many others, it can make
contact with another neighboring filler. Thus the average inter-
tube distance does not get significantly affected by the partial
alignment of fillers, and the percolation continues. However,
higher alignment causes loss of junctions and discontinu-
ity in the network, and results in increasing intertube gap.
In case of low CNT low concentration near percolation thresh-
old, slight alignment of the fillers allows less number of fillers
to build the conducting bridges by reducing gaps between the
neighboring fillers along the direction of conduction. However,
at higher alignment, the low concentrated CNT network also
experiences the loss of junctions like the highly concentrated
networks and d increases.
C. Analysis of Conductivity
The electrical conductivity of a composite is mainly
governed by the tunneling current through the junctions. Hence
the average intertube distance can be used as a key parameter
to estimate the composite conductivity. In order to estimate the
electrical conductivity of the composite samples of different
filler concentrations and film thickness, we used the simulated
data of intertube distance and applied our conductivity model
that we developed analytically in our previous work [22].
In a composite sample, there are usually several number
of percolating clusters making parallel pathways along
the sample. When a voltage is applied across the sample,
it generates potential difference between each tunneling
junction along the percolating pathways that exerts a driving
force on the electrons to tunnel through the barrier. The
resulting junction currents sums up to generate the total
current in the composite sample. Considering a rectangular
tunneling barrier, the tunneling current It through a single
junction, with tunneling distance dt between the neighboring
CNTs, can be expressed as [23],
It = cρ1 ρ2 e−βdt . (1)
Here, ρ1 and ρ2 are the density of states of the two neighboring
CNTs and function of their location, energy E with respect
to their individual Fermi levels and applied voltage V . The
polymer dependent parameter β is given by
√ For an ideal 3D composite sample with uniform filler dis-
2π 2mλ
β= , (2)
h For conductivity estimation using our model, we considered
where, λ = V − E is the height of the energy barrier of the
polymer.
In a conductive pathway, consisting of a number of tunnel-
ing junctions, the current is limited by the junction with the
largest tunneling gap. If the voltage applied across a composite
film is V f , and Ii is the current in the i th pathway, and
there are N number of parallel conductive pathways along
the voltage bias direction, then the total current through the
81
film I f should be the accumulation of the currents passing
through all the parallel pathways,

N 
N
Vf
If = Ii = . (3)
Ri
i=1 i=1
Here, Ri is the resistance of the i th pathway consisting a
number of tunneling (Rt ) and CNT resistances (Rc ).
If the sample CNT/polymer composite film with length L f
and cross-sectional area A f , has a total current I f flowing
through it while the applied voltage across it is V f , we can
calculate the conductivity of the composite by
If L f
σcomp = (4)
Vf Af
Lf 
N
= ( Ii ). (5)
A f Vf
i=1
Now, the current in the i th pathway Ii is mainly determined
by the tunneling current at the junctions present in that
pathway. Hence, it should be proportional to the tunneling
current It , thus should have an exponential relationship with
the tunneling intertube gap. Again, the composite conductivity
has been reported to proportionally increase with the increase
of filler CNT conductivity [4]. Thus, considering the effect of
intertube gap, CNT conductivity, CNT concentration, polymer
energy barrier height, etc., we developed an analytical model
of composite conductivity [22] as follows,
σcomp = σC N T e−(sβd) + σmatri x . (6)
Here, σmatri x is the conductivity of the polymer matrix
without any filler present. The exponential term β includes
the effect of the energy barrier height λ of the polymer by,
√
β ∝ λ (7)
√
= r λ. (8)
Here r = 9.7692nm −1eV −0.5 for the 3D composite model and
is independent of the polymer type. λ is dependent on the type
of polymer. For different polymers the energy barrier height
can vary within a wide range (e.g. for PMMA λ = 0.17 eV
and for epoxy λ = 1.5 eV [21], [24]). The average intertube
distance d is numerically determined for different sample film
thickness and CNT concentrations. The exponent s includes
the effect of filler concentration on the number of junctions
and the number of parallel pathways,
s = mφ n . (9)
tribution we obtained m = 91.7487 and n = 1.0915.
MWNTs with AR=100 and conductivity σcnt = 104 S/m
as the fillers. As the polymer we chose epoxy and PMMA,
since they are widely used by the researchers as compos-
ite materials for their transparency, stretchability, dispersion
property with CNTs, and biocompatibility [9], [11], [15], [20].
We considered the conductivity of the polymer insulators of
about 10−12 S/m [12]. We varied the CNT concentration by
changing the number of fillers in the numerical samples and
82 IEEE SENSORS JOURNAL, VOL. 16, NO. 1, JANUARY 1, 2016

Fig. 8. MWNT/epoxy composite conductivity at varying CNT concentration.

Our model is compared with the literature data based on percolation model
by Hu et al. [20], numerical simulation by Hu et al. [21], and experimental
results by Hu et al. [11] and NCT Co. [25].

estimated the composite conductivity using Eq. (6). The result

for MWNT/epoxy composite is compared with the results
previously reported in the literature [11], [20], [21], [25] as
shown in Fig. 8. Our model shows a close fit to numerical
results while reducing the computational cost significantly.
It shows reasonable comparative values with the theoretical
and experimental results. Our model incorporates the tunneling
current through polymers, unlike the traditional percolation
model. It can estimate the composite conductivity both in sub-
percolation and high CNT concentration region, without know-
ing the percolation threshold from experiment beforehand.
This in effect is a new hierarchical method for estimation of
composite film properties that provides accuracy while having
enhanced ease of computation. However, since this model is
based on the assumption that the CNTs as soft-core penetrable
cylinders, it can predict the electrical behavior of composite
films only under tensile strain, not when they are subjected
to compressive strain. To be able to deal with both the tensile
and compressive strains, the model needs to consider hard-core
bendable structure of fillers so that the geometric change of
the fillers and the corresponding change in the junction areas
as an effect of mechanical compression can be included.
In the next stage the film thickness is varied for each
filler concentration to study the effect of film thickness on
composite conductivity. The result is shown in Fig. 9 for both
MWNT/epoxy and MWNT/PMMA composites. We plotted
σcomp in terms of t/L to understand the relative effect of filler
length and film thickness. As the film thickness is reduced
from 15μm to 5μm, making t/L from 3 to 1, the conductivity
decreases. But just below t/L < 1 it increases sharply which
is due to the lowered d at partial alignment, as shown by our
results on intertube distance. Although the dip in conductivity
is observed near t/L ≈ 1 for both the epoxy and PMMA
polymer matrices, the extent of conductivity fall and rise vary
with the polymer. Hence, the polymer barrier height plays a
significant role here in determining the lowest and highest
Fig. 9. Conductivity of (a) MWNT/epoxy and (b) MWNT/PMMA compos-
ites at varying film thickness to filler length ratio for different CNT volume
fraction.
conductivity achieved by film thickness variation. After t/L is
decreased to a certain extent, σcomp starts dropping again with
lower film thickness. Fig. 10 shows the conductivity plot for
the corresponding cut-off angles ψμ at different t/L both for
CNT/epoxy and CNT/PMMA composites. It shows the highest
σcomp is achieved at around ψμ of 45° to 50°. Thus our sim-
ulation shows that for a given filler concentration and aspect
ratio the highest composite conductivity is obtained at slightly
aligned network rather than at isotropic network. Although this
result contradicts with many reports claiming that maximum
conductivity should occur at complete isotropy [26], [27],
it agrees with the results by Du et al. [9]. This is demon-
strated by Fig. 10(b). We compared our simulation results
for CNT/PMMA composites with the experimental results of
Du et al. Our results show similar pattern of the composite
conductivity with the partial alignment of fillers as found in
Du’s experiment, although it differs in the conductivity value.
The higher value of conductivity shown by the simula-
tion results than that of the experimental ones may be
caused by the CNT agglomerations that we neglected in our
RAHMAN et al.: COUPLED EFFECTS OF FILM THICKNESS AND FILLER LENGTH ON CONDUCTIVITY AND STRAIN SENSITIVITY
Fig. 10. Composite conductivity at varying alignment order of CNTs
for different CNT volume fraction. (a) Numerical estimation of conductiv-
ity of CNT/epoxy composite. (b) Numerical estimation of conductivity of
CNT/PMMA composite compared with experimental data of Du et al. [9].
numerical procedure. Thus our semi-analytical model can
explain and qualitatively confirm the result reported
by Du et al. from the context of intertube distance, while
other models could not do so. Our result indicates that with
composite films slightly thinner than the filler length, causing
partial alignment of the fillers, we can attain significantly
higher conductivity in a composite sample with lower CNT
concentration in comparison to a sample with higher CNT
concentration and random alignment. The rise in conductivity
at partial alignment is more prominent in samples with low
CNT concentration. However, at higher alignment the con-
ductivity drops for all CNT concentration since the conducting
pathway becomes discontinuous.
D. Experimental Verification of Thickness
Effect on Conductivity
To verify our numerical results, we conducted experiments
on CNT/polymer composite films with varying CNT concen-
tration and film thickness. Single walled carbon nanotubes
83
Fig. 11. (a) Dropcasted samples of SWNT/DMF solution. (b) The SEM
image of a SWNT/DMF sample shows good dispersion.
were bought from Cheap Tubes Inc. The CNTs had purity
over 90% with average length of 30μm and outer diameter
of 1.5nm. As the polymer we used PMMA with molecular
weight of 35 × 104 . Dimethylformamide (DMF) was used as
the common solvent for both SWNT and PMMA.
At first, CNT/DMF dispersion of 0.5 mg/ml concentration
was prepared by continuous sonication of the dispersion
for 30 minutes using a Sonics VCX 750 ultrasonic
processor equipped with a 6 mm tip. We added
polyvinylpyrrolidone (PVP) as the surfactant in order to
obtain uniform dispersion. The PVP was added in 1:3 weight
ratio to CNTs. The CNTs were well dispersed in the DMF.
We made some dropcasted samples of the CNT/DMF solution
and used scanning electron microscope (SEM) to check
dispersion of CNTs. Fig. 11(a) shows some dropcasted
samples and Fig. 11(b) shows the SEM image of one of the
samples. We can see CNTs are well dispersed in the sample
and almost no agglomeration present there.
After preparing the CNT/DMF dispersion, PMMA powder
was added to it at different amounts in order to vary the CNT
concentration in the mixture and final CNT/PMMA composite
films. The mixture was first stirred overnight at room temper-
ature in a closed container to obtain a uniform solution. Then
the solution was again stirred in an open container at 80°C
for few hours to evaporate the DMF and attain the desired
viscosity. In the final CNT/PMMA/DMF composite solutions
after evaporation, the PMMA concentration was maintained at
1
6 gm/ml to attain almost the same viscosity for all solutions
with varying CNT concentrations. Uniform viscosity helped to
control the film thickness while changing the spin speed for
samples with varying CNT concentrations. In the next step,
the CNT/PMMA/DMF composite solution was spincoated on
glass substrates. For each batch of composite solution with
different CNT concentrations, we varied the spin speed from
700 to 2000 rpms in order to vary the coated film thickness
within a range of 3 to 60μm. The spincoated samples were
then degassed in a vacuum chamber in order to make sure that
no air bubble stays inside the film. Finally the composite films
were dried in air at 50°C. In the final CNT/PMMA composite
films, the CNT concentration varied from 0.24 to 1.5% in
weight fraction.
In order to examine the CNT distribution inside the polymer
matrix, the as prepared composite films were examined
84
Fig. 12. (a) SWNT/PMMA composite film samples with different film thick-
ness having same CNT concentration. (b) The SEM image of a SWNT/PMMA
film with its surface and edge. The CNTs look well distributed in the polymer
matrix.
Fig. 13. Experimental data of SWNT/PMMA composite conductivity at
varying film thickness for different CNT weight fraction.
by SEM. Fig. 12(a) shows three typical SWNT/PMMA
composite film samples with different film thickness having
same CNT concentration. From the SEM micrograph of a
composite sample, as shown in Fig. 12(b), we can see the
SWNTs are almost uniformly distributed in the PMMA matrix.
After preparation, a large number of samples with different
thickness and CNT weight fraction were measured for con-
ductivity and thickness. The film thickness of the samples was
measured using profilometer. The conductivity of the samples
was measured with four point probe method. The measured
values of the conductivity of films with varying thickness and
different CNT weight fractions are shown in Fig. 13.
IEEE SENSORS JOURNAL, VOL. 16, NO. 1, JANUARY 1, 2016
It was observed that for low CNT concentrations, i.e. CNT
weight fraction 0.24%, 0.26%, 0.28%, the film conductiv-
ity rises immediately after the film thickness is decreased
below 30μm, which is the average length of the SWNTs here.
But it drops after t is reduced further. Thus our experimental
results demonstrate similar pattern of conductivity change with
the varying film thickness. It is interesting to note that the film
with 0.26% CNT weight and 18.9μm thickness is showing
higher conductivity than the film with 0.28% CNT weight
and 34μm thickness despite having lower filler concentration
and lower film thickness. This result is significantly impor-
tant in cost reduction and design optimization of composite
devices based on thin films. However, similar increase in the
conductivity of the films with thickness around 30μm were
not observed for the higher CNT weight fraction. Thus our
numerical prediction of the relative influence of film thickness
and filler length on the composite conductivity is confirmed
by the experimental results.
In the real samples, the length and aspect ratio of the CNTs
are not constant. Hence we used weight fraction (m%) of
CNTs as the CNT concentration parameter for experimental
data. However, for low CNT concentration, as used in the
experiment, the weight fraction and the volume fraction give
very close values. In general, we can convert the volume
fraction φ to weight fraction m by the following relation,
1
m= , (10)
1 + (ρ p /ρc ) × (1/φ − 1)
where, ρ p and ρc are the density of the polymer and CNT
respectively. Since during the experiments it is not practically
feasible to have samples with all the CNTs of same aspect
ratio, chirality, or uniformity in distribution, as assumed in
our simulation work, the measured values do not exactly
match those obtained by the numerical study. Nevertheless,
our experimental results follow almost the same trend as those
obtained by our numerical studies and qualitatively confirm
our numerical result, which is important for designing the
experiments before carrying them out.
E. Analysis of Strain Sensitivity
When tensile strain is applied on a CNT/polymer composite
film, the change in the film dimension causes change in the
orientation angle of most of the tubes in the film, which in turn
changes the intertube distance and the tunneling resistance.
Consequently, this affects the overall film resistance. The
change in resistance in a percolating network of a thin film can
be used to sense the applied strain which can be very helpful
in many practical application, such as, early detection of
structural damage, stretch or deformation reading of artificial
skin, etc. It is to note that, large deformation of the composite
film due to large strain application can cause deformation of
the CNT fillers inside the matrix, leading to change in CNT
properties. But at small strain, the physical change of the
CNTs becomes negligible due to their much higher elastic
modulus than the polymers. Hence the change in the filler
properties can be ignored. In this work, we have used small
strain, less than 5%, as most of the polymers deform plastically
RAHMAN et al.: COUPLED EFFECTS OF FILM THICKNESS AND FILLER LENGTH ON CONDUCTIVITY AND STRAIN SENSITIVITY 85

Fig. 15. Conductivity of MWNT/epoxy composite films (φ = 1.14%) at

Fig. 14. Effect on intertube distance at applied strain, for a CNT concentration applied strain for different film thickness.
φ = 1.14% and different film thickness.

beyond this range. We have numerically studied the effect of

uniaxial strain on the sensitivity of composite films of varying
thickness. The change in film dimension is determined by the
applied strain
and the Poisson’s ratio of the polymer ν. The
sensitivity of a thin film strain sensor is measured in terms of
the gauge factor G F,
R/R0 (R − R0 )/R0 R/R0
GF = = = . (11)
L f /L f 0 (L f − L f 0 )/L f 0

Here R0 and L f 0 are the initial resistance and length of the

film when no strain is applied, and R and L f are the resistance
and length of the film when strain is applied, respectively.
For a given strain
, higher resistance change ratio R/R0
indicates higher gauge factor and better sensitivity. Since we
observed from our results in the previous section that the film
thickness and filler length contribute to the intertube distance
and composite conductivity, the change in the film thickness
should also have impact on the gauge factor of the film. Fig. 16. Resistance of MWNT/epoxy composite films (φ = 1.14%) at applied
For different film thickness t and mechanical strain
, strain for different film thickness.
we numerically calculated the average intertube distance using
the fiber reorientation model [28]. For our numerical study, other curves. Again, with increasing strain, the values of d for
we considered epoxy as the polymer. We used the value of t = 5 and 7μm drop with a power law within this strain range.
ν = 0.4 as the Poisson’s ratio [19]. We then obtained the This exceptional trend of d shown by films with t/L ≈ 1
film conductivity applying our analytical model by Eq. 6. can be explained by the effect of partial alignment of fillers.
From the conductivity and film thickness we calculated the For films with t = 5 and 7μm, the CNTs in unstrained film
film resistance and resistance change ratio for varying strains. can be oriented with full randomness in all X, Y, and Z axes
The film thickness was varied from 1μm to 7μm. With directions. The application of small longitudinal strain aligns
changing t, the number of CNTs in the unstrained (
= 0) the fillers slightly towards X axis direction changing the cut-
composite sample was adjusted to keep the CNT concentration off angle ψμ from 90° to a lesser value. The partial alignment
at φ = 1.14%. The results are shown in Figs. 14-17. The brings the overall CNTs closer and reduces d. For lower film
change in the average intertube distance d with the increasing thicknesses, i.e., t < 5μm or t/L < 1, the CNTs are already
strain is shown in Fig. 14. As we can see, the intertube distance slightly aligned towards the X-Y plane in the unstrained films.
increases almost linearly with the strain for almost all film The application of strain aligns them further and causes the
thickness except when t takes value close to filler length L, intertube distance to increase.
i.e. for t = 5 and 7μm. At these film thicknesses we find The change in film conductivity due to the change in
that the initial intertube distance at
= 0 is higher than the intertube distance with applied strain is shown in Fig. 15.
initial d values for t = 4μm film, unlike the trend shown by We can see the conductivity towards the longitudinal
86
Fig. 17. Resistance change ratio of MWNT/epoxy composite films
(φ = 1.14%) at applied strain for different film thickness.
direction decreases as the strain increases for most of the
film thicknesses except for t = 5 and 7μm, as expected from
the intertube distance pattern. However, for t = 5 and 7μm,
the conductivity starts from a low value at unstrained films,
then rises drastically with the application of strain smaller
than 5%. The corresponding film resistance were calculated
which is shown in Fig. 16. The films with t = 5 and 7μm,
with sharp change in R with strain, show high potential
in sensor application within smaller strain range. The
IEEE SENSORS JOURNAL, VOL. 16, NO. 1, JANUARY 1, 2016
III. C ONCLUSION
We have studied the coupled effect of film thickness and
filler length on the conductivity and strain sensitivity of
CNT/polymer composite films. The partial alignment of fillers
introduced by the film thickness lower than the filler length has
shown to have significant influence on the average intertube
distance of the fillers causing remarkable impact on film
conductivity and resistance change ratio. Our results on CNT
alignment effect show that higher conductivity in composites
can be obtained at low CNT concentration by aligning the
fillers slightly to the direction of conduction, rather than
by increasing filler concentration and keeping the network
random. It indicates that partial alignment of CNTs will allow
low cost composite fabrication with low CNT loading to
achieve the same conductivity offered by highly concentrated
and randomly distributed CNT composite samples. This find-
ing has significant importance for some particular applica-
tions. For example, transparent conductors can be made from
CNT/polymer composites for solar cell applications. Here low
filler concentration is desired to ensure higher transparency
and the conductivity then needs a trade-off. Our study on
composite film thickness shows that conductivity works as
a function of film thickness when the thickness goes below
filler length, and higher strain sensitivity can be obtained
with a thinner film keeping the same CNT concentration. The
results on composite films with thickness close to the filler
length reveals an exceptional trend of conductivity with the
changing strain, that shows potential of this kind of films for
stretchable switching applications. Our results presented here
is broadly applicable to conductive, stick-like filler networks
resistance drops from 1013  to 104 , that is, from almost
insulator to conductor state, within strain application of 10%.
These results show potential of thin composite films with
t/L ≈ 1 for the application of stretchable switches. The
filler concentration can be optimized along with the thickness
of the film to obtain certain design window for specific
switching requirements or polymer-filler combinations.
Finally we calculated the resistance change ratio R/R0
to estimate the strain sensitivity for different film thickness
which is shown in Fig. 17. We can see that, with increasing
[3] M.-F. Yu, B. S. Files, S. Arepalli, and R. S. Ruoff, “Tensile loading of
the film resistance increases resulting in higher absolute
value of resistance change ratio R/R0 . For films with
thickness t < L, the R/R0 values increase gradually and
almost linearly with the strain, and are higher for thinner
films at any strain indicating higher gauge factor. However,
for t = 5 and 7μm, the decreasing resistance with applied
strain results in negative values of R/R0 and drastically
reaches the minimum value of −100% within
≈ 1%. of thin single-wall carbon nanotube networks,” ACS Nano, vol. 2, no. 9,
So it can be said that, films with thickness t < L show good
sensitivity to a broader range of strain, whereas films with
t ≈ L show high potential in sensor application within smaller
strain range. In general, the sensitivity gets higher for thinner
films. However, since the conductivity goes lower as the film
gets thinner, a trade-off is needed to keep the resistance in
measurable range while designing the sensors. Since thicker
films have more robustness and higher potential for repeated
strain application, sensor designing will need consideration of
all these parameters depending on the strain requirements.
in an insulating matrix.
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87
Rubaiya Rahman received the B.Sc. and M.Sc.
degrees in electrical and electronic engineering
from the Bangladesh University of Engineering and
Technology, Dhaka, Bangladesh, in 2006 and 2008,
respectively. She received the Ph.D. degree in elec-
trical and computer engineering from the University
of British Columbia (UBC), Vancouver, BC, Canada,
in 2015. Her research interests include numerical
analysis of percolating network characteristics,
modeling of conductivity and sensitivity of carbon
nanotube/polymer composite films and fibers,
and applications of nanocomposites in conductive films, sensors, and flexible
devices.
Saeid Soltanian received the Ph.D. degree
from the University of Wollongong, Australia,
in 2003. Before joining The University of British
Columbia (UBC), Vancouver, Canada, in 2010,
he was an Associate Research Fellow with the
University of Wollongong (2004), an Assistant
Professor (2005–2008), and an Associate Professor
(2008–2010) with the University of Kurdistan,
Iran. He is currently a Research Associate with
the Department of Electrical and Computer
Engineering, UBC, where he works with the
Flexible Electronics and Energy Laboratory. His recent research interests
include fabrication and characterization of nanostructure materials and
devices for sensing and energy applications.
Peyman Servati (M’05) received the B.A.Sc. degree
from the University of Tehran, Tehran, Iran, in 1998,
and the M.A.Sc. and Ph.D. degrees from the Electri-
cal and Computer Engineering Department, Univer-
sity of Waterloo, Waterloo, ON, Canada, in 2000 and
2004, respectively. Before joining The University of
British Columbia (UBC), Vancouver, BC, Canada,
he was a Research Associate with the Centre for
Advanced Photonics and Electronics, University of
Cambridge, working on nanowire (NW) growth and
device engineering. Before joining the University of
Cambridge in 2005, he was a Senior Research Scientist with Ignis Innovation
Inc., a spin-off company of the University of Waterloo working on novel
glass and plastic displays. He is currently an Associate Professor with the
Department of Electrical and Computer Engineering, UBC. His research
interests include low-cost and flexible solar cells, flexible transistors and
electronics, growth and synthesis of semiconductor NWs and nanocomposites,
electronic device modeling and engineering, and novel device engineering for
medical and energy applications.