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Impedance spectroscopy analysis of the tunnelling conduction mechanism in piezoresistive

composites

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2014 J. Phys. D: Appl. Phys. 47 345306
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Journal of Physics D: Applied Physics

J. Phys. D: Appl. Phys. 47 (2014) 345306 (5pp)

doi:10.1088/0022-3727/47/34/345306

Impedance spectroscopy analysis of the

tunnelling conduction mechanism in
piezoresistive composites
Stefano Stassi1 , Adriano Sacco2 and Giancarlo Canavese2
1
Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli Abruzzi 24,
10129 Torino, Italy
2
Center for Space Human Robotics@PoliTo, Istituto Italiano di Tecnologia, Corso Trento 21, 10129
Torino, Italy

E-mail: stefano.stassi@polito.it
Received 31 March 2014, revised 18 June 2014
Accepted for publication 30 June 2014
Published 1 August 2014
Abstract

The piezoresistive behaviour based on the quantum tunnelling conduction of a

copperpolydimethylsiloxane composite was studied by means of impedance spectroscopy
and confirmed by the fitting with the tunnelling piezoresistance mathematical model. This
investigation paves the way to the implementation of the impedance spectroscopy technique in
the characterization of piezoresistive pressure sensors for robotic application.
Keywords: piezoresistive composite, impedance spectroscopy, quantum tunnelling,
polydimethylsiloxane, spiky particles
(Some figures may appear in colour only in the online journal)

Tactile sensing has been defined as a form of sensing that

can measure given properties of an object through physical
contact between the sensor and the object [1]. There are
several literature reviews describing touch sensing research
[13] and different available techniques for the transduction
of interface contact pressure or force between objects. Most
of these devices originate from biomedical applications such
as the evaluation of wheelchairs and prevention of pressure
ulcers in hospital beds [4]. Today, these technologies are
adopted in a wide range of fields such as computer peripherals,
automotive systems, consumer electronics, biomedical devices
and robotics [59]. In particular, tactile sensing technologies
have been dramatically broadened out by the increasing
development of humanoid robotics field [2, 10, 11].
Among different possible working principles, there are
few different promising technologies available for these
sensors. Currently the most commonly used methods are the
capacitive and resistive ones. The former is based on the
capacitance change between two conductive parallel plates
assembled on a non-conducting soft sheet, in response to
an applied force. The advantage of this technique is that
the output is generally less sensitive to temperature and
humidity variation, but this architecture suffers from parasitic
0022-3727/14/345306+05$33.00

capacitances. The latter method is based on the resistance

change in a piezoresistive layer when a deformation (induced
by a force or a pressure) is applied. In composite material,
this variation is induced by the creation of percolative network
paths or by the increase in probability of tunnelling conduction
with increasing applied pressure [12, 13].
The work of Maheshwari et al reviews several functional
materials based both on metal and organic fillers, highlighting
different potential improvements in sensor performances [2].
For example, the introduction of nanostructures such as carbon
nanotubes, nano-coils and nanowires into tactile/pressure
sensors based on conductive polymeric composites, replacing
conventional conductive particles, can significantly increase
the sensitivity and force range. Moreover, the enhancement
of sensor performance due to the presence of nanostructured
metal fillers has been previously demonstrated [1416].
In preceding experimental works, different piezoresistive
composites, based on nanostructured metal filler dispersed
in a silicone matrix as a functional material for tactile
devices, have been reported [1618]. In these materials
the achieved wide variation of resistance was ascribed to
the quantum tunnelling conduction induced by the spiky
particles covered by nanometric tips. In the aforementioned
1

2014 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 47 (2014) 345306

S Stassi et al

studies, the variation of electrical resistance as a function

of applied deformation embedding the functional materials
between planar electrodes has been evaluated. Since under
the undeformed condition the composite material shows an
insulating behaviour, and considering the simple design of a
dielectric embedded between two conductive electrodes, in
principle this structure could be suitable both for capacitive
and resistive transduction principles.
Normally the capacitive transduction technique reaches
lower output value with respect to the resistive one, since
capacitive sensors measure the average pressure over the
electrode sensing area, while resistive sensors measure the
peak pressure over the sensing area. So the possibility to
couple the two different transduction techniques could both
strengthen the pressure measurement and give complementary
information useful for the artificial sense of touch. For
example, in this way it could be possible to extract information
on the morphology and the shape of the object that interacts
with the sensitive surface of the device.
To design complex tactile sensing device able to
simultaneously couple capacitive and resistive transduction
mechanisms, as well as to properly design the matching readout electronic circuit, an exhaustive characterization of the
functional material is mandatory.
Impedance spectroscopy (IS) is a well-established
technique, widely used for the study of a great variety of
devices and systems, with applications in different fields of
research [1921]. A periodic voltage of variable frequency
superimposed to a constant bias voltage is applied to the device
under study and its electric response is analysed as a function
of the excitation frequency. Even if the transport and chargetransfer processes occurring in real systems are described by
nonlinear equations that connect the driving forces to the flux of
the particles, in the case of excitation voltages with amplitude
comparable to the thermal voltage (i.e. under small signal
condition), it is possible to depict all the processes by linear
equations in which the coefficient between the potential and
the current is the electric impedance [22]. With these premises,
the device behaviour can be studied by means of an appropriate
equivalent electrical circuit.
To the best of our knowledge, here for the first time, the
electrical conduction mechanism based on tunnelling effect
inside the prepared composite samples has been analysed by
means of IS.
The metalpolymer piezoresistive composite presented
in this work was prepared by carefully mixing copper
microparticles, presenting spiky tips on the surface (LT10,
Pometon), in a bi-component polydimethylsiloxane (PDMS)
matrix (Sylgard 184, Dow Corning). The fabrication process
of the piezoresistive material consisted in dispersing the
metallic filler in the elastomer base, adding the PDMS curing
agent, pouring the resulting paste in polymethylmethacrylate
moulds, prepared by the micro-milling technique, and then
outgassing in vacuum in order to remove all the air bubbles in
the final samples. Later the composites were baked in oven
at 70 C for 3 h to cure the polymer and then removed from
the moulds. The prepared samples were bonded between two
copper metalized polyimide foils with soldered metallic wires,

Figure 1. FESEM image of the nanostructured copperPDMS

composite. The scale bar corresponds to 10 m.

acting as electrodes. The composition of the piezoresistive

material was varied in order to evaluate the role of the metallic
filler content on the electrical response. The samples were
prepared with a quantity in weight of copper particles of 150,
200, 250 and 300 phr (per hundred resin by weight) with an
area of 10 10 mm and thicknesses of 0.5 and 1 mm. Instead
the weight ratio between PDMS base and curing agent was kept
constant at 10 : 1, because it represents the best compromise
between stiffness and mobility of the particles inside the
polymeric matrix in response to compressive pressure [23].
Field emission scanning electron microscope (FESEM)
analysis revealed that the particles result well dispersed
in the polymeric matrix, without touching each other
and creating percolation paths (figure 1). Moreover, the
gentle mixing process prevents the destruction and the
smoothing of the spiky tips on the copper particle surface,
which would result in a reduction in the piezoresistive
response [14]. Indeed the conduction mechanism inside the
composite material is the tunnelling conduction between closer
particles divided by a thin layer of insulating polymer that
constitutes the barrier. Applying a mechanical pressure to the
composite, the insulating barrier is reduced, thus increasing the
tunnelling probability and exponentially decreasing the sample
resistance. This behaviour is enhanced by the presence of the
nanostructured tips on the surface of the metallic particles that
work as charge accumulator, increasing the local electric field.
Variations up to seven orders of magnitude of the electrical
resistance were reached in 1 mm thick composite applying a
compressive pressure of 2 MPa with respect to the value in the
undeformed state [18]. The piezoresistive behaviour of the
composite can be modelled evaluating the resistance variation
of a single barrier constituted by two copper particles divided
by a thin layer of PDMS and then enlarging the computation to
the whole material, considering the effect of all the tunnelling
paths. As evaluated by Zhang et al [13, 16], the electrical
resistance Rp of a tunnelling composite sample under the effect
of a uniaxial pressure p results in





p
2m p
Rp = R0 1
exp 4
(1)
d0
G
h2
G
2

J. Phys. D: Appl. Phys. 47 (2014) 345306

S Stassi et al

Figure 2. Nyquist plot of the impedance spectra for the 300 phr
(1 mm thick) sample measured at various applied pressure values.
The points are experimental data, while the continuous lines are
fitting curves evaluated with CPE. The dashed line represents the
fitting of the 0 bar curve computed using an ideal capacitor instead
of CPE.

Figure 3. Tunnelling resistance and interparticle capacitance

dependence on the applied pressure for the 300 phr (1 mm thick)
sample. Rp and Q values were extracted from the fitting of
impedance spectra. The Rp points were fitted using equation (1)
(R 2 value equal to 0.997). Q values were fitted with a linear trend
(Q = A p + B with A = 2.74 1011 and B = 2.96 1010 ,
R 2 value equal to 0.981).

where R0 is the resistance of the sample in the undeformed

state, G is the composite compressive modulus, m is the
electron mass, h is Planks constant, and and d0 are the
height and the width (i.e. the distance between two adjacent
metal particles) of the potential barrier, respectively.
The impedance spectra were acquired by means of an
electrochemical workstation with an ac signal of 10 mV and a
bias voltage of 5 V, in the frequency range 10 Hz100 kHz.
Since in this kind of composite material only one chargetransfer process (namely the tunnelling effect) occurs, a
unique impedance arc has to be expected in the Nyquist plot.
In figure 2 an example of the results of IS measurements
performed at different applied pressures is shown, in particular
the one related to the 1 mm thick sample fabricated with
300 phr copper particles/PDMS weight ratio. A monotonic
decrease in the arc while increasing the external pressure can be
noted, meaning a decrease in the tunnelling resistance, similar
to what was observed by Loyola et al [24] for fibre-reinforced
polymer nanocomposites. Based on the knowledge of the
charge-transfer process inside the material and on the resulting
shape of the IS curves, the experimental data were fitted using
an equivalent circuit [25], where Rs stands for the series filler
resistance, and the interparticle gap is modelled through the
parallel of the tunnelling resistance Rp and the constant phase
element (CPE) Q. The constant phase element Q was used
in substitution to the capacitance C reported in [25]. In
fact, the CPEs are generalization of common capacitances
used to take into account some frequency dispersion observed
into impedance spectra [26] due to the roughness of the
particle/polymer interface [27], whose impedance is given by
the formula
1
,
(2)
ZCPE =
Q(j )

by two particles separated by the insulating polymer is far away

from the case of an ideal capacitor. With respect to the case
of infinite flat conductive plates, here the two electrodes of the
capacitor follow the particle surface protrusions generating a
non-uniform electric field. In the light of this heterogeneous
network of elementary capacitors with rough electrodes, the
use of CPE is preferable to ideal capacitor model. With
the substitution of the capacitance with a CPE, the equation
exploited for the fitting procedure was
Z = Rs +

Rp
.
1 + Rp Q(j )

(3)

The fitting results (also shown in figure 2 superimposed

to the measured curves) were in good agreement with the
experimental data, thus proving that the tunnelling effect is
the main conduction mechanism involved in the composite
material. In order to validate the use of a CPE instead of
an ideal capacitor for modelling the interparticle gap, the
experimental curves were fitted by fixing the CPE index to
1 (in this case equation (2) will represent the impedance
of a common capacitance). As an example, in figure 2
the fitting curve related to the spectrum acquired at 0 bar is
reported. A large mismatch between the experimental and the
computed data is clearly observable, evidencing the non-ideal
behaviour of the metal/polymer interface. In fact, the use of a
pure capacitance makes the Nyquist plot a perfect semicircle,
instead of the depressed arc that was found under real condition
(and fitted through a CPE). In figure 3 the dependence of the
tunnelling resistance and of the gap capacitance (evaluated
by the fitting process) on the applied pressure is shown. As
can be clearly seen, the Rp exhibits an exponential decrease
for increasing pressure values, witnessing an enhancement of
the tunnelling effect due to the reduction in the interparticle
gap caused by the applied pressure. At the same time, the
reduction in the gap is responsible for the linear increase in
the Q values, since capacitance is inversely proportional to the

where is the CPE index. In the case of this piezoresistive

composite the use of the CPE can be physically attributed
mainly to the interface between the metal particles and the
polymer and to the geometry of the system. In fact since
the metallic particles present spiky tips on their surface, as
evidenced in figure 1, the basic unit of the material constituted
3

J. Phys. D: Appl. Phys. 47 (2014) 345306

S Stassi et al

Figure 4. Nyquist plot of the impedance spectra of samples fabricated with different compositions measured at 2 bar of applied pressure.
The points are experimental data, while the continuous lines are fitting curves evaluated with CPE. In the inset a zoom of the area defined by
the dashed rectangle is reported.

distance between the metal particles. For all the experimental

curves fitted, the CPE indexes lie in the range 0.90.95,
with no dependence on the applied pressure. In fact, the
deviation from the ideal capacitance behaviour (consequence
of the roughness of the metal/polymer interface) is an intrinsic
characteristic of the material, thus it is not dependent on the
applied pressure. In order to further validate the proposed
model, the resistance exponential curve was fitted by means
of equation (1). By inserting the values of G and obtained
from a mechanical characterization and from the literature [28],
an average interparticle distance under no applied pressure
condition of around 15 nm was found, in agreement with the
results obtained in similar composite systems [13, 28]. The
data shown in figure 3 represent an average of ten different
measurements. In the 1 bar range, more interesting in tactile
applications, the error on the reproducibility for the resistive
measure is around 1015% of the resistance value, while the
capacitive one ranges around 12%. These error ranges affect
the pressure evaluation with an uncertainty of around 0.25 bar
for the resistive measurement and 0.1 bar for the capacitive one.
Thus, even if the resistive measurement has a higher sensitivity
with respect to the capacitive one, because of the exponential
dependence due to the tunnelling conduction, the capacitive
measurement guarantees a better pressure resolution. For
these reason, the simultaneous evaluation of the capacitive
and resistive variation of the sample (measured through the
impendence spectroscopy method) and their combination
represent an advantage with respect to the classic resistive
measurement method normally used for this composite family.
Similar results were also obtained by varying the material
composition and the device thickness. As an example, in
figure 4 the Nyquist plots of the impedance of the devices
fabricated with different compositions measured at the same
applied pressure are reported. As is clearly evident, a
monotonic decrease in the impedance arc while increasing the
filler loading can be observed: as in the case of the variation
with the applied pressure (see figure 2), this fact witnesses a
decrease in the tunnelling resistance. In figure 5 a comparison
of Rp and Q values obtained for the different devices at the

Figure 5. Tunnelling resistance and interparticle capacitance

dependence on the composition for 2 bar of applied pressure. Rp and
Q values were extracted from the fitting of impedance spectra.
Rp and Q points were fitted with an exponential
(Rp = A exp(comp/t) + B with A = 6.12 1010 , t = 19.55 and
B = 1.89 105 , R 2 value equal to 0.999) and a linear trend
(Q = C comp + D with C = 1.77 1012 and
D = 1.5 1010 , R 2 value equal to 0.975), respectively.

same applied pressure (2 bar) is reported. It can be seen that

the sample containing the lower concentration of particles
is characterized by the higher tunnelling resistance and the
lower capacitance. While increasing the filler concentration,
the mean distance between two filler particles experiences
a reduction that causes the already observed exponential
decrease in the tunnelling resistance and the linear increase
in the gap capacitance. Also in this case, no dependence of
on the composition was observed.
In summary, piezoresistive composite materials were
prepared by dispersing nanostructured copper particles in a
polydimethylsiloxane matrix, thus fabricating active devices
in which the electrical conduction mechanism is driven by
the quantum tunnelling effect. By applying an external
mechanical pressure, the interparticle insulating layer reduces
its thickness, thus enhancing the tunnelling probability.
This conduction mechanism was studied exploiting the IS
4

J. Phys. D: Appl. Phys. 47 (2014) 345306

S Stassi et al

technique, analysing the measured data through an equivalent

electrical circuit. This investigation revealed an exponential
decrease in the tunnelling resistance and a corresponding
linear increase in the interparticle capacitance for increasing
applied pressure values, thus confirming that the tunnelling
effect is the main conduction mechanism involved in the
proposed composite material. The obtained results were
further confirmed by fitting the extrapolated values with a wellknown mathematical model, thus validating the importance
of the impedance spectroscopy technique for the study of
piezoresistive composites. Moreover, this technique can be
directly implemented for the pressure monitoring in a tactile
sensor fabricated with the composite material. Indeed, the
possibility of employing electrical impedance measurement
to image the resistance distribution of a layer of conductive
fabric due to applied pressure [29] for robotic application has
recently been demonstrated. The application of this powerful
transduction tool to a continuous sheet of piezoresistive
composite would enhance the pressure spatial resolution
without increasing the number of electrodes, if compared with
the traditional matrix sensor designs affected by wire topology
problems, and would also increase the pressure resolution by
combining the measurement of both the induced resistance and
capacitance variations.

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Acknowledgments

The authors acknowledge the help of Dr Diego Manfredi

for FESEM characterization and Dr Valentina Cauda for the
fruitful discussion.
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