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 Copyright © 2016 by American Scientific Publishers
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Reviews in Advanced Sciences and Engineering
Vol. 5, pp. 86–105, 2016
(www.aspbs.com/rase)

Electrical Characterization of Semiconductor

Oxide-Based Gas Sensors Using Impedance
Spectroscopy: A Review
F. Schipani1, 2 , D. R. Miller1 , M. A. Ponce2 , C. M. Aldao2 , S. A. Akbar1, ∗ , and P. A. Morris1
1
Department of Materials Science and Engineering, The Ohio State University, Columbus, OH 43210, United States
2
Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and
National Research Council (CONICET), B7608FDQ Mar del Plata, Argentina

ABSTRACT
Impedance spectroscopy is essential in understanding the physical and chemical processes that affect the
electronic behavior of semiconducting metal oxide-based gas sensor materials, but is often overlooked or
avoided by researchers because of the complexity of proper data interpretation. These metal oxide nanomate-
rials are promising as resistive-type gas sensors because they have the potential to meet the critical need that
has developed for low-power, low-cost, portable gas sensors. However, the mechanisms that determine these
materials’ gas-sensing performance is still not understood well enough to advance the field toward bottom-up
design for specific applications. Direct current (DC) measurements give information on the device performance
such as sensitivity, selectivity and response time. Alternating current (AC) measurements are a lesser-used
approach that can give the same information, but also allow the varying contributions from the bulk, surfaces
and interfaces, grain boundaries, electrode contacts and even substrate to be quantified, whether we work with
polycrystalline materials or single-crystal structures such as nanowires and nanorods. With this technique it is
possible to extract fundamental information about intergranular potential energy barrier height, width and donor
concentration changes in different atmospheres and temperatures. The equivalent circuit method is the most
common method of relating the impedance data to the physical system. However, the main weakness of this
method is that the ideal circuit elements used in the fitting can be connected in many different ways to fit the
same signal. To properly apply this technique, the model development should consider both the impedance
measurement and the physical and chemical characteristics of the system being studied. This review presents
a detailed description of impedance spectroscopy techniques for fundamental analysis of materials behavior in
gas sensing applications, including proper data interpretation and types of fitting models commonly used, to
enable researchers to better apply these techniques toward understanding of their materials systems.
KEYWORDS: Oxide-Based Gas Sensors, Impedance Spectroscopy, Conduction Mechanisms.

CONTENTS 3.1. One-Dimensional Model of Conduction for

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 Spherical Grains . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2. Fundamentals of Impedance Spectroscopy (IS) . . . . . . . . . . . 89 3.2. Electron Traps and CPE Fitting . . . . . . . . . . . . . . . . . 96
2.1. Definitions and Impedance of Ideal Elements . . . . . . . . 90 3.3. Review of Relevant Literature . . . . . . . . . . . . . . . . . . 97
2.2. The RC Parallel Circuit . . . . . . . . . . . . . . . . . . . . . . 92 3.4. Nanowire-Based Sensors . . . . . . . . . . . . . . . . . . . . . . 101
2.3. The Triple RC Circuit . . . . . . . . . . . . . . . . . . . . . . . 93 4. Conclusions and Future Directions . . . . . . . . . . . . . . . . . . 103
2.4. Distributed Circuit Elements, the Constant Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Phase Element (CPE) . . . . . . . . . . . . . . . . . . . . . . . . 93 References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.5. Frequency Dependence and Graphical Representation . . . 94
2.6. Ambiguous Circuits and Element Response . . . . . . . . . . 95
2.7. Experimental Considerations . . . . . . . . . . . . . . . . . . . 95 1. INTRODUCTION
3. Applications to Metal Oxide Gas Sensors . . . . . . . . . . . . . . 95 The demand for metal oxide-based gas sensors has been
increasing since the first commercial sensors were devel-
∗
oped in the 1970’s by Taguchi to the point that they have
Author to whom correspondence should be addressed.
Email: akbar.1@osu.edu
become indispensable in several aspects of life. These
Received: 2 March 2016 type of sensors are among the most studied since they
Accepted: 21 April 2016 are attractive to industry due to low cost of production

86 Rev. Adv. Sci. Eng. 2016, Vol. 5, No. 1 2157-9121/2016/5/086/020 doi:10.1166/rase.2016.1109

Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review

F. Schipani obtained his B.Sc. in Physics in 2012 in the University of Mar del Plata. He is a
Ph.D. student in the same university. At the moment he is at the Ohio State University for a
research stay. His main interests cover the gas sensing properties and conduction mechanism
in grain-based and nanowire-based sensors.

D. R. Miller is a Ph.D. candidate at The Ohio State University. He began his graduate
career in 2011 on an NSF GRFP Fellowship and in 2013 was awarded a NASA NSTRF
Fellowship. His research focuses on growing and synthesizing new oxide nanostructures for
applications in gas sensing, photovoltaics, and biocompatible surfaces. His recent focus is
on fabrication and characterization of oxide nano-heterostructures to enhance performance
in these applications. Derek was also the 2013 Chair of the ACerS’ PCSA, a national
ceramics-focused student organization.

M. A. Ponce obtained his B.Sc. in Chemistry in 1999 and Ph.D. in Material Science in 2005
from Mar del Plata National University, Argentina. Since April 2007 he is a member of
the research staff of the National Research Council (CONICET). His current research inter-
est includes the development of electronic conduction mechanism of functional inorganic
materials.

C. M. Aldao completed his Ph.D. at the Department of Chemical Engineering and Materials
Science of the University of Minnesota in 1989. He was appointed as Professor in 1990
at the University of Mar del Plata. Since 1992 he is a member of the research staff of the
National Research Council (CONICET). His research activities focus on the physics and
chemistry of surfaces and interfaces, with special emphasis on semiconductors.

S. A. Akbar is a Professor in Materials Science and Engineering at The Ohio State Univer-
sity. He received his Ph.D. in 1985 from Purdue University. He teaches courses on Sensor
Materials, Electronic Ceramics, and Thermodynamics. He is the founding director of the
NSF Center for Industrial Sensors and Measurements (CISM) and his main research interests
include thin film sensors, metal oxide sensors, and nano-textured biomedical coatings.

Rev. Adv. Sci. Eng., 5, 86–105, 2016 87

Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review Schipani et al.

P. A. Morris is an Associate Professor in Materials Science and Engineering at The Ohio

State University. She received her B.S. from The Ohio State University in 1980 and Ph.D. in
1986 from MIT. Dr. Morris was a Technical Leader working on chemical sensors at Dupont
from 1999–2005. Her current research interests focus on oxide nanoparticles deposited on
miniaturized sensors using ink-jet printing.

and simplicity of their use.1–4 They have a wide range
of applications such as health and safety (medical diag-
nosis, food processing, and detection of flammable, toxic
or explosive gases), energy efficiency and emission con-
trol in combustion and industrial processes.5 There are
several types of nanostructures for gas sensing applica-
tions such as spherical nanoparticles, nanowires, nanorods,
hollow spheres and nano-flowers, among others,6 that
exhibit enhanced surface-to-volume ratios and porosities
that allow gases to interact in different ways with the
structures. These structures also can be composed of multi-
ple oxides to form hierarchical nanocomposite heterostruc-
tures that often show enhanced sensing properties.7–9
Several routes have been developed for the fabrication
of these structures such as hydrothermal, electrospinning,
sol–gel, anodization, and solid-state chemical reactions
among others.6 There is a rich diversity of mechanisms of
interaction between the oxides and analyte gases that is
only beginning to be unraveled.9
The resistive-type gas sensing mechanism is based
on the change of electrical resistance of the oxide fol-
lowing a change in the gas atmosphere, induced by
gas-solid interactions on the surface. The properties of
thin-film nanoparticle and nanowire sensors are mainly
influenced by the microstructural features such as the
size of particles and the contact between them.10 It is
widely accepted that potential energy barriers formed
atinter-particle junctions have a Schottky-type nature.
Thus, understanding the Schottky barrier formation mech-
anism is crucial to the development of better gas sensor
devices.11 12
The last decade has shown that sensors based on well-
defined structures like nanowires can be highly engineered
toward a specific application given the high crystallinity
and well-defined facets that lead to a more stable and
predictable response. This makes single-crystal nanowires
a useful basis on which to develop a new class of gas
sensors engineered from the bottom up.6 13–15 However,
it has become paramount that researchers understand the
relative contributions of competing mechanisms governing
the resistance modulation in these sensors. Careful mea-
surements using single nanowires and randomly-oriented
nanowire films have shown promise, but further research
is needed in order to reach a better understanding and
control of these structures and their electrical and sensing
properties.7 16–25
Impedance spectroscopy (IS) is a very promising
alternating-current (AC) technique for measuring fun-
damental electronic properties of thick, thin films and
single nanowires but unfortunately is rarely used in
the gas sensor field in favor of much simpler direct-
current (DC) measurements. Impedance spectroscopy is
not a new technique. It was initially used as early as
the 1940’s to characterize electrochemical systems.26 27
Although many electrochemical gas sensors have ben-
efitted from impedance spectroscopy, this review will
focus on using the technique on semiconducting oxides.
Nanowires entered into the sensor field relatively recently
so impedance spectroscopy techniques are not fully devel-
oped on these devices. One of the main problems of using
DC measurements in nanowire sensors is the heat genera-
tion and dissipation. From simple geometrical calculations,
an applied current of 100 nA to a single ideal nanowire
with 150 nm diameter generates a current density of about
566 A/cm2 . So, poor heat dissipation could lead to high
local temperatures in the nanowire that can cause diffu-
sion of charged species, quick degradation, or a complete
failure. High temperatures and high DC current can cause
interstitial or vacancy migration and build up at the elec-
trode contact, changing the electrical character of the con-
tact. Studies have also shown that the degree of Ohmic
or Schottky behavior at a metal oxide-electrode contact
can change with temperature and fabrication parameters,
especially for single-nanowire devices.28 Alternating cur-
rent measurements can eliminate these electrode effects.
The most powerful use of impedance spectroscopy is in
tracing approximations of donor concentration and deple-
tion region width, as well as relative contributions of inter-
facial and bulk mechanisms to conductivity as a function
of operating temperature and gas environment.
In this article, we present a theoretical explanation and
show experimental implementation of IS measurements
summarizing a complex technique to enable and convince
the reader to utilize these methods in better understand-
ing their own sensor materials. Proper implementation of
these methods will yield simple electrical circuit models
that lead to the understanding of conduction mechanisms
and the contribution of each part of the device toward the

88 Rev. Adv. Sci. Eng., 5, 86–105, 2016

Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review

sensing characteristics of metal oxide-based sensors. Also,

summarized are different models and approaches used by
researchers in order to explain their experimental data in
relation to the best practices we propose here.

2. FUNDAMENTALS OF IMPEDANCE
SPECTROSCOPY (IS)
Impedance methods are quite powerful in that they are
capable of characterizing physicochemical processes of
widely differing time constants and can be used as a tool
to understand the conduction mechanisms in materials.
Figure 1 shows an ideal behavior of a polycrystalline mate-
rial that contain intra-grain (bulk), inter-grain (junction)
and electrode effects. In order to understand the electrical
properties of a given sample, the contributions from each
of these effects must be separated, which can be done and
analyzed in detail using IS.29–31 The output response of a
frequency sweep from 10−3 –107 Hz, typically plotted in
a complex plane plot (Nyquist plot), takes the form of a
series of semicircles (ideally) representing electrical phe-
nomena due to bulk material, grain boundary/inter-grain
effects and electrode phenomena, if any. Each semicircular
arc in the impedance spectrum has a characteristic max-
imum occurring at a unique relaxation frequency (max )
attributed to electrical phenomena from different compo-
nents of the sample. Impedance data can be represented
in several forms (plotting its imaginary and real compo-
nents, or its modulus and phase), but is commonly ana-
lyzed by fitting it to an equivalent electrical circuit model,
as shown at the top of Figure 1. This simple equivalent cir-
cuit consists of three resistance-capacitance (RC) elements
in series, each representing a physical part of the device
Fig. 1. Schematic representation of, from top to bottom: (1) an ideal cir-
that has a resistance and an alternating-current capaci- cuit model with bulk, junction and electrode elements, each represented
tance. In practice, the bulk capacitance is usually small as a parallel RC circuit. (2) Band structure of an n-type SnO2 junc-
compared to that of the various interfaces. The capacitive tion and its contact with the electrode. Junction capacitance is associated
elements usually encountered are, in order of descend- with the net charge of the depletion zone of the particle (of width w1 ).
ing typical characteristic relaxation frequency: bulk, grain The trapping mechanism contributes to capacitance at low frequencies.
Here, the resistance is primarily due to electrons overcoming the bar-
boundaries, electrodes, and electron traps. Relaxation fre-
rier (of height 1 ) from particle to particle. (3) Physical representation
quencies depend only on the intrinsic properties of the of two partially-depleted SnO2 nanoparticles. Electrons are pulled to the
material and not on the sample geometrical factors. When surface for oxygen chemisorption which creates a region depleted of free
a substrate is present, it is desirable to separate its capaci- carriers and a surface with net negative charge. Temperature and/or atmo-
tance from the measurements to focus on the oxide parti- sphere changes alter this equilibrium. The darker center of the particles
are not depleted by surface processes and have a higher conductivity.
cles’ response. This is especially important when dealing
(4) Ideal Nyquist plot where the Z axis represents the real component
with thin films and nanowire devices whose capacitance of impedance and Z represents the imaginary component of impedance.
can be very small compared to the substrate.32 This can All three contributions from the circuit in (1) are represented. Each RC
be achieved by the proper electrical model where usually element (or associated arc) has a characteristic relaxation frequency, max ,
non-ideal elements, as introduced later, are needed to sim- equal to  −1 , where  is the relaxation time of the mechanism. The full
electrode semicircle is not usually measured in polycrystalline materials
ulate this behavior.
because of frequency limitation.
Usually, simple electrical circuits are used to generate
simulated impedance plots that represent the experimen-
tal data. The elements of the circuits can be resistors, can be made as a first approximation, resulting in an ini-
capacitors, inductances or non-ideal elements such as con- tial fitting with the experimentally measured impedance.
stant phase elements (CPE). Initially, a system is measured One has to be careful to not naively fall into the conve-
and impedance data is produced and plotted. A compari- nience of using the equivalent circuit modeling as a “black
son with usual or well-known equivalent electrical circuits box.” Some knowledge of the physicochemical process

Rev. Adv. Sci. Eng., 5, 86–105, 2016 89

Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
involved and simplification of the representation as much
as possible are fundamental requirements to correctly use
circuit modeling. The interpretations can be supported with
information from techniques such as Raman spectroscopy
to determine surface bonding and chemistry, X-ray photo-
electron spectroscopy to determine surface properties such
as barrier height and positron annihilation spectroscopy
which gives the type and concentration of vacancy-like
defects. Microscopy should also be used to evaluate the
microstructure and dispersion of sensor particles on the
electrodes to construct the most physically representa-
tive circuit models since particle size and distribution can
directly affect the impedance measurements.
The circuit elements can be chosen and full circuits built
based on
(i) support from other experimental techniques,
(ii) examination of the experimental data to see whether
the proposed circuit is consistent with the response and
(iii) inspection of the resistance and capacitance values
that are obtained in order to check that if they are realis-
tic and that their response changes to gas atmosphere are
reasonable.33–38
As MacDonald states,39 the condition of “the best fit”
between the model and the experimental data still applies,
but producing the best fit does not necessarily mean
that the developed equivalent circuit model has the cor-
rect physical meaning. See, for example in Section 3.2
where fitting with a non-appropriate circuit often used by
researchers leads to a capacitance value for the electrode
that is unphysically high.
In practice it is usually possible to find more than
one equivalent circuit that numerically fits a given data
set, but only one of these is likely to provide a realis-
tic representation of the electrical behavior of the sample.
In the polycrystalline materials, inter- and intra-granular
impedances are typically present so the electrical prop-
erties are determined in general by a series combina-
tion of such impedances. These two components may be
represented by a parallel RC (resistance-capacitance) ele-
ment. This circuit configuration was proposed by Bauerle40
and is frequently used to represent bulk, grain-boundary
and electrode phenomena in polycrystalline materials.40
There are other circuits that have some modifications to
∗ C and inductive
include deep trap behavior that was not initially included
∗L usually yield very complex
in Bauerle’s circuit.
The most powerful implementation of this technique, in
the author’s opinion, is in the traceability of the changes in
depletion zone width at changing temperatures and atmo-
spheres. This is critical since the Schottky barrier formed
between two particles in physical contact dominates the
electrical conduction behavior of most metal-oxide based
devices. Once the experimental data are fitted with the
proper equivalent circuit, the resistance and capacitance
values of grain boundaries can be related to the deple-
tion zone of the particles. Using the depletion approxima-
tion, which considers the charge density to be constant in
90
Schipani et al.
the depletion region, a direct relation between the barrier
height and the donor concentration (mostly from oxygen
vacancies) can be found. Exact magnitudes of these values,
however, cannot be found with this technique alone. It is
still useful to point out that changes in the grain bound-
ary capacitance and resistance can be linked to barrier
height and donor concentration in situ. If a thermionic con-
duction mechanism (thermal energy assists electrons over
the energy barrier) is considered primarily responsible for
the conduction between grains, an Arrhenius-type graphic
(log RDC vs. log T −1 ) can be generated and the potential
energy barrier height can generally be found from its slope.
There are some special cases where this is not valid that
will be discussed later.
2.1. Definitions and Impedance of Ideal Elements
It is important to have some basic knowledge of the behav-
ior of the simplest ideal circuit components. The three
basic components are resistance, capacitance and induc-
tance. In this context, the resistance element represents
electron movement through the lattice. The impedance of
a resistor is always a real number and because of that,
its current and voltage are in phase. The impedance of a
capacitor is purely imaginary. The impedance of a capac-
itor has an inverse dependence with frequency because
at high frequencies a fast alternating current most effi-
ciently displaces charges where at low frequencies a net
migration of charge carriers is blocked due to the physi-
cal interface or energy barrier. The waveform of the volt-
age through a capacitor lags current by 90 . The inductor
has the opposite behavior—the impedance increases with
frequency and the waveform of the voltage leads current
by 90 . Table I lists these three elements and also the con-
stant phase element (CPE) that is a non-ideal component
with a variable phase 0 to 90 and will be treated in detail
later.
A signal of type V t = V0 sint, where  is the fre-
quency of the sinusoidal wave, is applied to the sample
and the resulting current I t = I0 sint +  is then mea-
sured, where  is the phase difference between the voltage
and the current. This is a very complex problem to treat
in the time domain as periodic excitations mixed with the
response of capacitive I t = dV t/dt
elements V t = dI t/dt
Table I. Basic circuit elements used to model the physicochemical
processes in metal oxide-based gas sensors. Frequency dependence and
phase shifting with
√ respect to the voltage is included. “j” is the imaginary
component, j = −1.
Impedance Contribution
element to impedance Phase angle Frequency dependence

R Z=R 0 Constant
L Z = jL −90 Directly proportional
C Z = 1/jC 90 Inversely proportional
CPE Z = 1/Aj 0 –90 Inversely proportional
Rev. Adv. Sci. Eng., 5, 86–105, 2016
Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
differential equations.41 In addition to the applied alter-
nating voltage bias, impedance techniques can also apply
a constant applied DC voltage, known as bias or offset
voltage.
We can use the Fourier transform to treat the problem
in a simpler way in the frequency domain; the differential
equations can be transformed and rearranged to form a
similar Ohm’s law. The relation between the voltage and
the current is represented in Figure 2.
V 
The ideal switching rate of each charge storage mech-
anism is called the relaxation frequency. This frequency
maximizes the efficiency of energy transfer from the
applied field to the charge storage mechanism. Usually
dielectric relaxation processes as a whole occur in a fre-
quency range from 102 –1010 Hz. The time required for
each relaxation process to take place is the relaxation time
 and is related to the relaxation frequency, fc :
1
= (9)
Z = (1) 2fc
I 
Depending on the material, different kinds of relaxation
Here, Zj is defined as complex impedance. processes can be measured. These can be electronic or
The magnitude and direction of a vector can be ionic, depending on the frequency of the applied field
expressed as the sum of its components used to measure. In the frequency range usually used in
Z = Z   + jZ   (2) impedance measurements (10−3 –107 Hz) the various pro-
cesses of charge storage are each affected differently by
Where Z  is the real part of the impedance and Z  is the the frequency of the applied field, which affects the over-
imaginary part. We can express all conductivity. In the low-frequency range, charged point
defects may migrate back and forth following the applied
ReZ ≡ Z  = Z cos  (3a) field. At higher frequencies, these species can no longer
 move an appreciable distance before the direction of the
ImZ ≡ Z = Z sin  (3b)
field reverses. Once this happens they can no longer store
With the phase angle  and the modulus Z: energy or contribute to conduction.26 39 41
The delocalized or “conduction” electrons in a semicon-
 = tan−1 Z  /Z   (4) ductor can be thought of as free to move in the lattice.

Z = Z  2 + Z  2 (5) When an electron reaches the end of a grain it can move
to the neighboring grain by a phenomenon called electron
It is important to note that, in the frequency domain, the hopping. This can be conceptualized as a two-step pro-
impedance is time-invariant so the calculation becomes cess which can only occur at very low frequencies. At the
easier without the sinusoidal functions and exponentials of surface of a grain there are defects which can trap and
the time domain.41 emit electrons. At low enough frequency these traps can
There are other quantities derived from impedance, capture some incident electrons and re-emit some others
called admittance, where out of the traps to the neighboring grain. Eventually the
frequency of the applied bias can become too high for
Y = Z −1 = Y  + jY  (6) this process of charge–discharge to keep up and it will
We can express both impedance and admittance in terms no longer play a role in the charge transport through the
of their resistive and capacitive components grains. This phenomenon is distinguishable at low frequen-
cies (<101 Hz) where capacitance can be several orders of
Z = R + jX (7) magnitude higher than at high frequencies.42
At the grain boundary or particle junction the capaci-
Y  = G + jB (8)
tance and the resistance are larger than the inside of the
Where X is the reactance, B the susceptance and G is the grain because this region is depleted of free carriers that
conductance. have been pulled to the surface, typically for bonding with
adsorbed oxygen. This depletion region has a net positive
V charge (in n-type materials) and the electrons pinned at the
Im(Z)

surface have a net negative charge, which can be treated as

t a parallel plate capacitor with the permittivity of the mate-
rial being studied. This is shown schematically in Figure 1.
I Then in a single grain, two different semicircles can be
distinguished in the Nyquist plot, corresponding to bulk
α
t and grain boundary mechanisms. The difference in capac-
Re(Z) itance and resistance between these two regions leads to
Fig. 2. Relation between sinusoidal input voltage at a single frequency very different relaxation frequencies. The product RC is
and output current in the time domain delayed by phase shift, . much larger in the depleted zone leading to a semicircle at

Rev. Adv. Sci. Eng., 5, 86–105, 2016 91

Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review Schipani et al.

lower frequencies (on the right in a Nyquist plot) than for

the interior of the grains (on the left in a Nyquist plot).43–46
If only one semicircle is observed in the plots, three things
can be happening:
(i) the relaxation frequency for one of the processes
(max ) is beyond our measurement frequency range (usu-
ally the one that represents the interior of the grains). This
can happen if the constant RC of this process is small,
yielding a large relaxation frequency.
(ii) The constants of the bulk process and the grain bound-
ary process can be similar to each other, so both arcs are
overlapping, resulting in an arc depressed in the middle.
In this case, changing the temperature and/or atmosphere
of the measurements can help discriminate between these
two semicircles.
(iii) One semicircle is much larger than the other and
cannot be distinguished in the plot. Here, as before,
raising temperature will usually help decrease the grain
boundary resistance with a smaller change in the bulk
resistance.

2.2. The RC Parallel Circuit

In a system with an applied potential, the current chooses
a preferred path (or paths) to travel from one electrode to
the other, the path of least impedance. This can be illus-
trated with a simple example of an ideal RC parallel circuit
(see Fig. 3). At high frequencies the impedance to current
is lower in the capacitor due to its inverse dependence on
frequency and therefore smaller than the impedance of a
resistor (which is constant at all frequencies). At lower
frequencies, the impedance of the capacitor increases and
the current begins to flow through the resistor (see Fig. 3).
The characteristics of this system can be determined by
Fig. 3. Simulated data from an RC parallel circuit. Different time con-
the capacitive response at high frequencies and the resis-
stants ( = RC) were chosen to show frequency dependence. With the
tive response at low frequencies. The relaxation frequency product RC and using the Eq. (17) the relaxation frequency can be found.
of the circuit is the value where the currents switch from This is the frequency of the maximum height (in the Z axis) in the
one element to the other. As will be later discussed, charge impedance arc and the inflexion points on the modulus, capacitance and
carriers traveling through a sample have to overcome suc- resistance graphs.
cessive impedances of two different regions. One of them
is the center of the sample (usually called bulk), and the Where Z is the total impedance of the circuit, and R = Rp
other is at the grain boundary or particle–particle interface and C = Cp because they originate from a parallel circuit,
where the sample has different dielectric properties. as will be used in the later notation. Then, we can separate
The sum of impedances follows the same rule as the its real and imaginary parts
sum of resistances. The impedance of an RC parallel cir- R
ReZ = x = = Rs (13a)
cuit is
1 1 1 1 + 2 R2 C 2
= + (10) R2 C 1
Z ZR Zc ImZ = y = =− (13a)
Then, 1 + 2R2 C 2 Cs
ZR ZC where Rs and Cs are the expressions for the series resis-
Z= (11) tance and capacitance of a parallel circuit.47 Interestingly,
ZR + Zc
although R is frequency independent, ReZ is frequency
R1/jC R 1 − jRC dependent.
Z= =
R + 1/jC 1 + jRC 1 − jRC By taking both terms of the impedance
R − jR2 C R2 + 2 R4 C 2 R2
= (12) x2 + y2 = = (14)
1 + 2R2 C 2 1 + 2 R2 C 2 2 1 + 2 R2 C 2
92 Rev. Adv. Sci. Eng., 5, 86–105, 2016
Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
Then, using the equation of a circle and completing the
square, we have a circle with radius R/2 centered at R/2.
 2  2
R R
x− +y =
2
(15)
2 2
The highest value for ImZ can be found with the cir-
cle equation given in Eq. (15):
max  = max RC = 1
 = RC
Once an impedance measurement is done, the out-
come regularly consists of two sets of values: a real one
and an imaginary one (Z  and Z  ) as a function of fre-
quency. We can assign to these values the resistive and
capacitive behavior of the measured sample (Rs = Z  and
Cs = −1/Z  ) which will both most likely be frequency
dependent. If we wanted to transform these experimental
impedance values that can be represented as an RC series
circuit with Eq. (13) into an RC parallel circuit we can
use Eq. (18). The main point on going from a series rep-
resentation to a parallel representation of the RC circuit
and vice versa is mainly based on the information that can
be extracted from the experimental data. To plot the total
capacitance as a function of frequency, one must convert
this experimental information represented as a series cir-
cuit into a parallel representation and then information of
the depleted zone of particles at high frequency and traps
at low frequency can be extracted. From here and using
Eq. (25) donor concentration and depletion zone width can
be calculated using the high frequency value of the total
parallel capacitance and is discussed later in Section 3.1.
This information is not visible using the regular impedance
Nyquist plots.
1 + 2 R2s Cs2 Cs
Rp = Rs Cp =
2 R2s Cs2 1 + 2R2s Cs2
If we want to express the impedance of an RC parallel
circuit taking into account the frequency dependence, we
can use the expressions in Eq. (18). To get to the Eq. (19),
that is a series representation of an RC parallel circuit
one must follow the steps in Eqs. (10)–(14) but using the
appropriate impedance expression in Eq. (10) for the series
circuit.
Rp 1 + 2 R2p Cp2
Rs = C = Cp
1 + 2 R2p Cp2 s
2 R2p Cp2
This is useful if treating the circuits manually (without
software). Following the high and low frequency limits in
Figure 3, we can see that the behavior of the equivalent
capacitance is constant for high frequencies and has a 1/2
dependence for low frequencies. The opposite stands for
the resistance, where a constant behavior for low frequen-
cies is observed but is 1/2 for high frequencies. It is
Rev. Adv. Sci. Eng., 5, 86–105, 2016
worth noticing that now Eq. (19) takes the same gen-
eral form as Eq. (18), but with the capacitance function
of Eq. (19) taking the form of the resistance function in
Eq. (18).
Figure 3 shows the simulation of a single RC paral-
lel element response to frequency. For the modeling of
the different examples the resistance was fixed and the
capacitance values were changed. To plot the equivalent
(16) series capacitance and resistance from the parallel element,
Eq. (19) was used. The complete analytical expression for
(17) the frequency dependence can be very complicated for
more complex circuits and will not be presented here.
2.3. The Triple RC Circuit
The electrical properties of polycrystalline materials can
be simulated, to a first approximation, by a series array of
parallel RC elements. A method of treating experimental
data is required that can be capable of resolving a series
of RC elements into one equivalent RC parallelelement.47
The triple RC circuit (or a small variation) is the funda-
mental circuit for modeling grain-based metal oxide sys-
tems due to its ability to reproduce the basic contributions
to impedance. This, as said earlier for an ideal case, will
be represented as three semicircles in the impedance plane
plot. In principle, this can be fit by choosing the proper
contributions from each of the circuit elements. The cor-
responding complex impedance plane plot will show sepa-
rate semicircles only if the relaxation times of the elements
differ from each other.47
The triple RC circuit model should be converted into
a single total (equivalent) RC parallel circuit element for
further analysis. The reason for this is that the experimen-
tal data we obtain can be associated with a series array of
RC elements and converting it into a single RC element
is highly convenient. Returning to the previous point, if a
series array of RC parallel circuits is used to fit the data
(18)
(see Fig. 4, for example) each RC element has to be con-
verted into a series RC element with the purpose of using
circuit rules to add the series capacitances and resistances
to finally obtain a total series contribution for both resis-
tance and capacitance (for details, see Refs. [26, 48, 49]).
Then it can be “easily” transformed into a parallel RC
circuit to use for fitting or comparison purposes. This pro-
cess is often complicated and usually done by software
but for simple circuits it can be done analytically. Even
though this circuit is regularly used, it cannot reproduce
(19) the total capacitance at low frequencies. This behavior is
attributed to the electron traps. This will be explained in
Section 3.2.50
2.4. Distributed Circuit Elements, the Constant
Phase Element (CPE)
The deviation from the ideal semicircle in our measure-
ments, often with the center of the circle depressed below
the X-axis, can be attributed to electron traps in the metal
93
Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
Fig. 4. Simulated data from a triple RC circuit. The simulation of
impedance arcs, from right to left (low to high frequency) show-
semicircles are attributed to electrode, grain boundary and bulk. Total
parallel capacitance and resistance from using Eq. (18) are plotted in the
same frequency range as the corresponding phase angle and modulus.
Table of values used in simulation is in the inset.
oxide, microstructural features such as inhomogeneities in
grain size51 or a distribution of relaxation times.52 The con-
stant phase element (CPE) is used to model this behavior.
Actual behavior of samples can only be approximated over
a limited frequency range. Electron traps can be distributed
over a wide band of activation energies (shallow to deep),
which causes the ideal resistor and capacitor in parallel or
series to behave as a non-ideal distributed impedance ele-
ment. A constant phase element is a simple distributed ele-
ment that produces an impedance having a constant phase
angle in the complex plane.
A CPE is an empirical impedance function of the fol-
lowing form:
Schipani et al.
resistor. When a single CPE is represented in a Nyquist
plot, a straight line with an angle of 90 ∗  relative to the
real impedance axis is shown. When this element is repre-
sented together with a parallel resistance R, the outcome is
a semicircle with reduced height, depending on the phase
angle, as seen in Figure 5.
2.5. Frequency Dependence and Graphical
Representation
There are two main types of graphic representation of
impedance data:
1. Nyquist plots—shows the imaginary part of the
impedance Z  versus the real part, Z  . Usually, the imagi-
nary values of the impedance are negatives, so –Z  versus
Z  is actually plotted. Figure 3 shows an ideal Nyquist
plot of an RC circuit. An extension of the Nyquist plot
is plotting the imaginary part of impedance against fre-
quency. This shows a succession of peaks for each semi-
circle where the maximum value of each peak shows the
relaxation frequency.
2. Bode plots—shows the phase angle  and the Z mod-
ulus, Z, plotted against the frequency. Figure 3 shows
Bode plots of an ideal RC circuit.
Both types of plots are needed in order to extract all
information to fit with the appropriate circuit model. How-
ever, for more complicated circuits than an RC, both Bode
plots and Nyquist plots can be insufficient to show the
processes at all frequencies, especially if the relaxation
frequencies of the involved processes are of similar value.
To help improve our understanding, it is also helpful to
plot the parallel resistance and capacitance as a function
of frequency (see Figs. 3 and 4). These plots can be made
using Eq. (18), and they can assist in observing electron
trap behavior, among other things (see Section 3.2).
The high frequency component usually corresponds to
the bulk properties but sometimes the frequencies that
would show this behavior cannot be reached due to lim-
ited frequency range in the equipment. If the relaxation
1 cos /2 sin /2
ZCPE = = −j (20)
Aj A A
The constant A determines the impedance modulus and the
exponent  determines the impedance angle which goes
Fig. 5. Simulated behavior of a CPE in parallel with a resistance. For
from 0 to 90. In the specials cases of  = 1 (90 ), the the model of the different cases, the resistance and the modulus of the
CPE acts as an ideal capacitor with the capacitance equal CPE was taken constant. Only the phase was varied. The frequency used
to A while at  = 0 (0 ) the element behaves as an ideal for the simulation of the curves was 10−2 –106 Hz.

94 Rev. Adv. Sci. Eng., 5, 86–105, 2016

Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
frequencies of any of the processes occurring in the mate-
rial have very different relaxation times the Nyquist plots
should show separate semicircles for the bulk, junction,
and electrode terms, although this condition is rarely seen.
The junction arc may interfere with the bulk arc when
the bulk and junction relaxation frequencies are similar
to within 1–2 orders of magnitude. The electrode pro-
cesses are less likely to affect the bulk contribution. The
experimentally available frequencies are used to deter-
mine whether a complete, partial or no semicircle at all is
observed.53
0
r A
2.6. Ambiguous Circuits and Element Response
All the circuits of Figure 6 can have the same overall
response to all frequencies if their elements are properly
related (this exceeds the purpose of this review and will
0
r is the permittivity of the material and A is the area of
not be shown). The circuit b for example is regularly used
to model grain boundary and bulk behavior in polycrys-
talline metal oxides and the circuit d can be thought of as
a grain boundary that includes the contributions of elec-
tron traps at one particular energy level, but they cannot
be interchanged. Circuits a and c do not have any physi-
cal explanation but they still can reproduce the same data
modeled with the circuits b or d. Excessively large or
small values of the circuit elements are the first clue to
know in determining if the right circuit is being used to fit
the data.
Another possible problem appears when trying to
fit experimental data, which impedance-related function
should be fit? MacDonald55 states that it is better from a
statistical point of view to fit the data the same way as
obtained, rather than in a transformed form. For example,
large errors can occur when transforming Z = Y −1 and this
can lead to a different parameter estimation than using the
original function.
2.7. Experimental Considerations
It is a good recommendation when measuring any kind
of sensor to first measure the substrate alone, without any
particles or nanowires deposited. An impedance arc would
Fig. 6. The circuits presented here can have the same impedance at
all frequencies if their elements are properly related.54 Not all of these
circuits represent physical phenomena due to the unphysical values of
their elements to fit the experimental data.
Rev. Adv. Sci. Eng., 5, 86–105, 2016
not be possible to obtain due to the lack of a low-resistivity
path or paths through which current could travel. How-
ever, the measurement at high frequency will give us an
idea of the capacitance of the substrate. Once the sensor
is made, it can be measured again in the same frequency
range to see if the deposited particles have increased the
capacitance.56 A simple calculation can be made to see if
the deposited grains are fully depleted. One can think of
the material as a continuum and calculate capacitance as if
it were a parallel plate capacitor. This assumption is most
valid when the material is fully depleted. So, we use
Ctotal − Csubstrate = (21)
d
where d is the thickness of the deposited film on top (or in
between, depending on the configuration) of the substrate,
this “capacitor.” Only depleted zones of grains contribute
to the capacitance, so if the calculated right hand side of
Eq. (21) is substantially different from the measured film
capacitance, it probably means that there are zones in the
material that are bulk and do not contribute to capacitance.
The geometrical capacitance of the substrate, usually with
coplanar electrodes, can also be calculated.57
3. APPLICATIONS TO METAL OXIDE
GAS SENSORS
3.1. One-Dimensional Model of Conduction for
Spherical Grains
Gas sensors based on semiconducting metal oxides are
devices that show a change in the electrical conductiv-
ity with a change in the gas atmosphere.58 The sens-
ing mechanism is based on surface gas adsorption which
requires conduction electrons for adsorption, resulting in
a net change in charge carrier concentration and thus an
electrical conductance change. It is widely recognized that
wide bandgap semiconducting oxides such as SnO2 exhibit
surface states that behave as electron donors and/or elec-
tron acceptors. Electron donors or acceptors at the surface
cause an exchange of electrons with the interior of the
semiconductor, thus forming a space charge layer close to
the surface. Gas adsorption then alters surface states mod-
ifying the space charge layer and the film conductivity is
thus modulated.
As a first approach, it is regularly considered that
a thermionic mechanism is responsible for the sample
conductivity at the particle or grain interface and is
described by
Jthermionic = AT 2 e−b /kT (22)
where, b is the barrier height, which is the difference
between the Fermi level and the conduction band energy
at the surface.59 J , T , k and A are current density, the
absolute temperature, the Boltzmann constant and the
Richardson constant,60 respectively. This equation reflects
a thermally activated process due to intergranular barriers.
95
Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
It has also been pointed out.56 61–65 that a thermionic field
emission, also known as electron tunneling, is unavoidable
for the usual barrier characteristics and can be calculated as
AT  Vs
Jtunneling = F E ∗ P E dE (23)
k o
where, F E is the Fermi-Dirac distribution function and
P E is the transmission probability (T ) determined by the
one-dimensional and time-independent Wentzel-Kramers-
Brillouin (WKB) approximation. After integration and for
a parabolic barrier, P E can be calculated, as expressed
in Eq. (23).64 The total conduction in the sample can be
calculated as the sum of both contributions, thermionic
and tunneling. Thermionic conduction only depends on the
barrier height and tunneling depends both on barrier height
and width. Usually, for metal-oxides, both contributions
can be relevant. Tunneling becomes the dominant con-
duction mechanism as temperature decreases and/or donor
concentration increases.64 66
The relationship between capacitance C and barrier
height  can be derived from Poisson’s equation. Accord-
ing to the depletion approximation, the barrier height is
given by67
eNd w 2
= (24)
2
0
r
And the capacitance per unit area by
 material based on the presence of defects at the grain
e
0
r Nd
boundaries.
C= = 0 r (25)
2 w
Where, e is the electron charge,
the permittivity, Nd the electron traps. The experimental impedance measurements
donor concentration, e (given in eV) the barrier height
and w is the width of the depletion region. Equation (25)
shows that the capacitance corresponds to that of a parallel
plate capacitor67 with a dielectric permittivity
and can the total parallel capacitance and resistance of the sam-
be associated with the capacitance of a surface depleted
of charge carriers. A Nyquist plot and its derivative plots
along with the appropriate circuit model can extract these
junction contributions from total contributions and allow a
calculation of the width of the depleted region. From here,
the donor concentration can be calculated in a first approx-
imation. This information is not possible to obtain with
DC measurements. Before performing this calculation, one
has to be sure to have a junction capacitance properly fit-
ted and to include a barrier height that can be based either
on literature or measured, for example, by calculating the
slope of an inverse resistance versus inverse temperature
plot, known as an Arrhenius plot. If tunneling contribu-
tion to the total current is considered, then the width of
the depletion region is crucial because tunneling through a
barrier strongly depends on the barrier width. For a detail
analysis on this, these references are useful.56 61 63
3.2. Electron Traps and CPE Fitting
There are two types of defects: extrinsic defects due to
doping additives, and intrinsic defects, such as intersti-
tials and oxygen vacancies, due to non-stoichiometry of
96
Schipani et al.
the material. These defects lead to electron traps that influ-
ence the electrical properties of the semiconductor. These
traps can be present in the bulk but are usually more
highly-concentrated at the surface. A flow of charge car-
riers moving from the center of the grain toward a grain
boundary will encounter a potential energy barrier near the
surface. There are charge carriers trapped in the defects at
thin interfaces between adjacent grains that are balanced
by the space charge (depletion) region in the grain, as
shown in Figure 1. At low frequencies (<1 Hz) some of
the incident electrons can get trapped at this thin inter-
face and others can be re-emitted into the next grain. This
charge–discharge mechanism can be the cause of the high
increase in capacitance at the lowest frequencies.50 68 69
Therefore, evaluation of the capacitance of a sensor mate-
rial should be done at high frequency where traps are not
active and do not modify the capacitance of the depleted
region. This depleted region can be thought of as a dielec-
tric that has the permittivity of the material being stud-
ied. At high frequencies, this process becomes a one-step
thermionic mechanism because the applied bias switching
is too fast for the two-step mechanism to occur. The elec-
trons simply must overcome the double Schottky barrier
to move into the neighboring grain. Thus these frequency-
dependent mechanisms can affect the conduction of the
Here, experimental results will be analyzed in order to
elucidate the proper model to characterize the effects of
were carried out on SnO2 thick films with a grain diameter
of approximately 150 nm. The explanation here is a sum-
mary of the work done by Ponce et al.50 Figure 9 shows
ple in a wide frequency range. This transformation from
impedance to parallel capacitance and resistance was done
using Eq. (18). As can be seen in Figure 9(a), the resis-
tance can be properly simulated in the whole frequency
range, but the capacitance cannot. The chosen circuit to
model the behavior was the triple RC parallel circuit of
Figure 4.70 71 A closer look in the capacitance plot will
show that only two corner frequencies (frequency where
an inflexion point in the plotted function is observed) can
be observed with this fitting. This is a consequence of the
low values of capacitance and resistance used to model the
experimental data. It is important to point out that the cir-
cuit used to model this behavior fits well to the impedance
arc. We can see that capacitance cannot be reproduced
even assuming a quite high value for the electrode capac-
itance (10−5 F).29 30 It is found that the electrode con-
tact can only be responsible for a rapid quadratic decrease
in the 10–100 Hz range. Figure 9(b) shows in the fit-
ting with the triple RC circuit that for frequencies lower
than 1 Hz, the Cp fitting remains constant. A 1/2 depen-
dence of the fitting is observed, while the experimental
data shows a 1/ dependence with frequency. Therefore,
Rev. Adv. Sci. Eng., 5, 86–105, 2016
Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review

the electrode cannot be responsible for the measured comparison with the circuit of Fig. 7) is not appropriate to
behavior. describe the experimental data.
We will focus now in the low frequency range The circuit of Figure 8 is a modification of Baurele’s
(<100 Hz) to study the contribution of electron traps.72 circuit.40 The total parallel capacitance can now be repro-
The proposed circuit consists of a resistor in parallel with duced in the complete frequency range and includes the
a capacitor and also parallel with an RC series circuit (see contribution of traps.
Fig. 7). There are two contributions here: the R1 C1 par- In Figure 9 it can be seen that the simulation includ-
allel circuit would represent the contribution due to grain ing traps with a single activation energy goes in the right
boundaries and the R2 C2 series would represent the con- direction to fit the experimental data. A second activation
tribution from traps (represented for now with a single energy can be added to the circuit of Figure 7 in the form
activation energy). of a resistance and a capacitance in parallel with C2 R2 .
The circuit can be divided into two parts: The admit- The blue line corresponds to the fitting made with two
tance of the parallel R1 C1 circuit can be expressed as traps. A better fitting can be obtained including a larger
number of RC series circuits. This can be extended to a
1
Y1 = + jC1 (26) multi-trap system, where “n” traps are in parallel with the
R1 original RC circuit representing the grain boundary. This
And the admittance of the R2 C2 circuit is none other than a discrete representation of a constant
phase element.
1
Y2 = (27)
R2 + 1/jC2  3.3. Review of Relevant Literature
Separating the real and imaginary parts of Y2 we can write Table II is a compilation of the most common circuits
the conductance and the capacitance as used to model impedance measurements in particle-based
and nanowire-based metal-oxide gas sensors. For particle-
2 C22 R2 based sensors all authors listed here model the bound-
G2 = (28)
1 + 2 C22 R22 ary behavior with an RC parallel circuit. Circuit modeling
jC2 from impedance data can be an ambiguous procedure if
jCeq = (29) it is not complemented with other techniques or one does
1 + 2  2
not have information on the system being studied. Some-
Where, the time constant of the circuit is = R2 C2 . times, circuits are just a simplification of a general one.
Finally, the total conductance and capacitance of the cir- For example, B and D are a simplification of circuit A.
cuit can be calculated as A simplified circuit may be used when it is not possible
 
1  to find or separate all contributions (for example electrode
Gtotal = + C2 2 (30) and bulk from grain boundary) or simply discard them for
R1 1 + 2  2
  being negligible. It is typical to make the assumption that
1 the main contribution comes from the particle junctions
Ctotal = C1 + C2 (31)
1 + 2  2 and to discard all others previous to the measurements;
A double RC parallel circuit can be used to compare that can lead to miscalculations. On the other hand, not
with Figure 7. This circuit can have the same impedance all authors found the same kind of behavior, even for the
at all frequencies and with some calculations,50 an equiva- same material, when inhomogeneities, porosity, or even
lence between both circuits can be done to finally find that substrate contributions are observed, so the modeling may
the capacitance of the electrode (Ce ) is ≈10−2 F, which is a or may not include non-ideal elements. For example, a
non-physical value for an electrode capacitance. This indi- SnO2 thick film composed of spherical particles can have
cates that the circuit of Figure 4 (or in this case, the sim-
plified double RC circuit for the purpose of an analytical

Fig. 7. Circuit model where the traps contribution is introduced as a Fig. 8. Proposed model to fit experimental data with the contribution of
resistance R2 in series with a capacitance C2 . A single activation energy the bulk of the grains, the grain boundaries, and deep traps represented
for the traps is considered here. with a CPE and the electrode contribution.

Rev. Adv. Sci. Eng., 5, 86–105, 2016 97

Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
Fig. 9. Equivalent parallel resistance and capacitance as a function of
frequency. Filled black diamonds correspond to the experimental values
of SnO2 thick film 150 nm particle-based sensor measured in oxygen
at 425  C. Dark blue dots corresponds to the simulation made with the
triple RC circuit of Figure 4. Here, Cgb = 7 × 10−12 F, Rgb = 14 × 105 ,
Cb = 5 × 10−14 F, Rb = 15 × 104 , Re = 1 × 104  and even assuming
a high value for the electrode Ce = 1 × 10−5 F the experimental capaci-
tance results cannot be reproduced in the low frequency range. Resistance
can be simulated with this circuit. Open darkblue symbols correspond
to the simulation made with the circuit of Figure 7, where traps with a
single energy are considered. Here, C1 ≡ Cgb = 7 × 10−12 F, R2 ≡ Rgb =
14 × 105 , C2 ≡ Ctrap1 = 45 × 10−9 F and R2 ≡ Rtrap1 = 22 × 107 .
The blue line corresponds to the same circuit modelling but now with
another capacitance and resistance representing a different trap level, in
addition to the first one. Ctrap2 = 9 × 10−7 F and Rtrap2 = 4 × 107  and
the other values are the same as the circuit with one trap. Finally, the red
line represents the fitting with the complete circuit of Figure 8, which
corresponds to “n” parallel traps. The fitting values are Cgb 7 × 10−12 F,
Rgb = 14 × 105 , CPE = 02 CPE = 5 × 10−8 F, Rt = 4 × 106 , Ce =
1 × 10−5 F, Re = 1 × 104 , Cb = 5 × 10−14 F and Rb = 15 × 104 . Now
the capacitance is properly fitted in the entire frequency range. This is
a replotted figure from [50], M. A. Ponce, et al., J. Mater. Sci. Mater.
Electron. 20, 25 (2008). © 2008, Springer.
different AC behavior depending on porosity of the film,
substrate characteristics and grain size heterogeneity.
Not all particles and nanowires have a conductive bulk
region in their center that is unaffected by the surface
depletion phenomenon. Materials with a low dopant con-
centration have wide depletion zones and if the particle is
not big enough this depleted zone can occupy the entire
volume. When grain size approachestens of nanometers in
diameter or less, they are more likely to be completely
depleted of carriers. This critical radius for complete
depletion can be approximately calculated.73 Some of the
studies cited in Table II did not take this into consideration.
98
Schipani et al.
Electrode contributions are rarely seen in Nyquist plots
due to low resistance that would make a very small arc
compared with other measured points. Experimental noise
is also a factor to mask electrode contributions. For that
reason, it is recommended first to measure impedance
to the lowest possible frequency and then to plot the
total capacitance versus frequency, following Sections 2.2
and 2.3. As can be noticed in Figure 9(b), there is a small
contribution in the 101 –102 Hz range that was attributed to
the electrode. Usually, omission or inclusion of electrode
contributions in the grain-based sensors does not change
the fitted values of the other elements. Also, one has to
have values free of experimental noise to try to fit electrode
contributions. There is also a capacitance contribution due
to the substrate that should be constant in frequency but
adds an offset to the measurements (see Section 2.7). This
is particularly important in single nanowire-based sen-
sors due to the small capacitance of that one nanowire
compared to the substrate contributions. In this case it is
difficult to isolate contributions in capacitance from the
nanowire.32
Among all the studies presented here there is a con-
sensus that depressed semicircles should be modeled
with a constant phase element as done by Ponce,50 74
Al-Hardan,75 Weimar76 and Hernandez-Ramirez,32 when
fitting their experimental data. This is substantiated by
the following Ponce50 attributed the low frequency capac-
itance response to electron traps in the bulk and surface
of the particles and successfully modeled it with a CPE.
Al-Hardan75 used an RC circuit to model interface con-
tributions, but with doping, the ideal capacitor had to be
replaced by a non-ideal one. On the other hand, there
are also reasons not to use CPEs. Hulser77 and Lee78
stated that due to the homogeneity of the particle size that
was reflected in non-depressed impedance arc, their use
was not necessary. Nan79 found depressed arcs that were
attributed to the porosity of the sample47 but still mod-
eled them with an ideal capacitor. However, the data points
might have been better fitted with a non-ideal element. For
nanowire-based sensors the capacitance of the substrate
can be large relative to the contribution of the nanowires if
their number density on the substrate is small. ACPE can
be used to model the contribution of the substrate (typ-
ically a Si wafer) based on the author’s experience and
other studies.32
There is also an overwhelming consensus on modeling
particle boundary contributions with RC elements. Most
researchers agree that large particles have a highly con-
ductive bulk and highly resistive boundary and these are
usually modeled with circuit A, B or D. In this case,
two arcs should ideally be present, showing contributions
of the depleted particle boundary zone (larger arc) and
the conductive centers (smaller arc), as seen by Akbar.80
If these two arcs cannot be distinguished, that does not
mean that the contribution is not there. It can be too small
to be noticed or it can show up at higher frequencies not
Rev. Adv. Sci. Eng., 5, 86–105, 2016
Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review

Table II. Compilation of circuits used to fit impedance measurements. Circuits C, H and I are the ones used by the authors of this paper. Sometimes,
circuits A and B can be used as a simplification, for example when low frequency capacitance measurements do not show the presence of traps (see
Fig. 9(b)). Other authors used several variations of the original circuit A proposed by Bauerle for electrochemical systems, where bulk and electrode
contributions were mostly not reported due to small values that were neglected. Sometimes, over-simplified models like circuit D are useful to briefly
describe or characterize a system, but often will not reflect the nature of the involved processes. A depression in one of the impedance arcs can be
usually attributed to a non-homogeneous microstructure of the sample (grain size distribution), the presence of traps in the bulk or interface between
two particles or the substrate used to deposit the sensing material (circuit H and I). These characteristics were simulated using a constant phase
element (CPE). The reference [up] stands for recent unpublished work from the authors of this review.

in the range of the equipment. Lee78 and Ponce,50 only
saw one contribution which was attributed to the particle
boundary. If some parameters are approximately known,
like donor concentration or potential barrier height, one
can estimate the width of the depletion zone (Eq. (24)) and
compare it with the particle diameter. If that shows that
the particle should not be completely depleted, then further
measurements should be done such as changing gases and
temperature that mainly affects boundary response and not
the interior. In these cases one should start modelling the
data with a simple circuit like B and then move to a more
complete expression (circuit C) once it is determined that
there are two contributions. Another problem arises when
the decreasing size of particles increases the probability of
complete depletion and the experimental data show again
only one impedance arc. Some studies77 with grain sizes
less than a few tens of nanometers have considered the
center of the particle to be non-depleted, though this dis-
agrees with many of the previous studies mentioned.
Malagu et al.81 modeled the impedance behavior to find
a value of the depletion width of the particles that came
from solving the Poisson equation for spherical grains
where they treated the WO3 thick films as “l” parallel
planes each containing “n” parallel rows of “n” spherical
capacitors in series. Pokhrel et al.82 modeled the behav-
ior of Cr2 O3 , a p-type semiconducting oxide, using an RC
parallel circuit in series with a resistance. They state that
the parallel RC circuit represents the contact between the
grains and the electrode. This parallel circuit is indepen-
dent of the gas concentration, meaning that the interface
is gas-insensitive. On the other hand, the series resistance
is found to be highly dependent on gas concentrations
and is related to the conductivity of the thin accumulation
region formed at the surface of the grains. This mech-
anism is explained by saying that current preferentially
flows along the surface accumulation layer and around the
high-resistivity bulk. The capacitance associated with this
low-resistance accumulation layer is too small to be mea-
sured. This is an important result because it seems to have
differentiated between a gas-insensitive component (the
electrode-oxide interface) and a highly gas-sensitive com-
ponent (the oxide surface accumulation layer). This type of

Rev. Adv. Sci. Eng., 5, 86–105, 2016 99

Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review Schipani et al.

analysis can help to engineer sensor architecture to max-

imize the contribution of the most sensitive components.
Weimar and Gopel76 describe the sensor response using
a series resistance to describe bulk properties and an RC
element to represent the depleted zone in the semiconduc-
tor. The measured experimental data showed a small semi-
circle in the low frequency range. They attribute this to
migration effects of charged particles such as adsorbed O− 2
O− , O2− or lattice species such as V2+
O (oxygen vacancies),
which they modeled with a constant phase element in par-
allel with a resistance. Hernandez-Ramirez et al.32 charac-
terized a single SnO2 nanowire where at low temperatures
Fig. 10. Single SnO2 nanowire response to CO measured at 295  C. At
the behavior of the sensor was dominated by a Schot- this temperature, the contribution of the Pt contact was neglected and
tky contact between the nanowire and the Pt deposited the circuit model H of the Table II was used to fit the data. Capacitance
electrode, characterized by an RC parallel circuit. At high contribution was attributed to the substrate. This is a replotted figure from
temperatures the bulk resistance of the single nanowire [32], F. Hernández-Ramírez, et al., Sensors Actuators B Chem. 121, 3
dominated. Recent data from the author’s laboratory (will (2007).© 2007, Elsevier.
be published in a future paper) show that the behavior of a
single nanowire of the same material at high temperatures and parallel should produce a larger capacitance than a
is also dominated by the nanowire behavior. Unfortunately single nanowire, this has yet been too small to measure
the capacitance of a single nanowire cannot be measured and model compared to the substrate capacitance.
due to the relatively large contributions of the substrate Published data on thick- and thin-film oxide sensors
capacitance at all frequencies. A few additional studies are vary widely. Most of the authors that did successfully find
also listed in Table II.83–85 and isolate a particle boundary contribution did not attempt
Although impedance spectroscopy is a well-established to extract useful physical values such as depletion width
technique, it is not often used to characterize nanowire- and donor concentration as could be approximated by the
based sensors. Usually, single-nanowire impedance mea- equations presented in Section 3.1.
surements show a single arc, depressed in the middle, Many impedance measurements do not show a clear
where the nanowire is the dominant resistive element distinction between bulk and junction contributions in the
and the substrate is the dominant capacitive element. At Nyquist plot. In these cases, higher temperature measure-
high temperatures (>200  C, approximately) and for thin ments can be taken to enhance the change injunction con-
nanowires (<100 nm, approximately),28 86 87 the experi- tribution with respect to the bulk contribution. The real and
mental data can be modeled with a simple resistance in imaginary parts of the impedance can be plotted separately
parallel with a CPE representing the substrate. At lower against frequency to help separate these regimes.
temperatures, the contribution to resistivity of the contact The electrical behavior of a gas sensor can depend
between the nanowire and the electrode becomes impor- strongly on previous test conditions. When characterizing
tant and cannot be neglected. This is explained well in two a sensor’s electrical response, one must be careful with the
studies23 32 and agrees with recent unpublished data by the order in which measurements are done. Each time a sensor
authors of this review. Figure 10 shows AC measurements is exposed to a different test condition (temperature and/or
on a SnO2 single nanowire sensor exposed to different atmosphere change) the physicochemical processes occur-
concentrations of CO, as re-plotted from Ref. [32]. ring in the material can manifest as a resistance and/or
For a randomly-oriented multiple-nanowire sensor, capacitance change. For n-type materials it is expected
impedance spectroscopy can be useful to distinguish
between the contributions from the nanowire–nanowire
(junction) resistance and the nanowire resistance modula-
tion as a consequence of changing temperature and atmo-
sphere. Figure 11 shows the modulation of the impedance
arcs with change in oxygen content of the atmosphere
at 300  C. Although only one arc can be seen visu-
ally, it is actually a summation of three contributions
representing the nanowires (RC parallel element), junc-
tions (resistor), and substrate (CPE) as shown in cir-
cuit I in Table II. Although the simulated arc does not
Fig. 11. Multiple nanowire response to air and nitrogen measured at
perfectly match the data, it is the closest fit possible 300  C. The circuit model I of the Table II was used to fit the data.
using physically representative values and circuit elements. Capacitance contribution was attributed to the substrate. Unpublished
Although many nanowires connected randomly in series data recently measured by the authors.

100 Rev. Adv. Sci. Eng., 5, 86–105, 2016

Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
that increasing temperature and/or exposure to a reduc-
ing gas would decrease the size of the arcs. Surface
processes are generally immediately reversible but bulk
processes including diffusion of oxygen causing overall
stoichiometry changes can cause more permanent changes
in behavior.
Figure 12 is a clear example of how previous treatments
can modify the conclusions drawn from a measurement.37
All data sets were measured at 419  C where the sam-
ple is a SnO2 thick film with a grain size of 250 nm in
diameter. The initial and final measurements were done in
a vacuum atmosphere. Here, the sensors were exposed to
atmospheres that substantially changed their response in an
otherwise identical follow-up measurement. All data were
fitted with a double RC circuit (see Table II, circuit B) and
trapping mechanisms were not considered.
a. An initial vacuum measurement was done at 419  C.
b. Exposure to airat 419  C increased the resistance. This
large increase can be explained by stating that the both
barrier height and width increase due to the oxidizing
atmosphere present during the measurement. Capacitance
decrease in air was attributed to a depletion width increase.
It is important to point out that the increase in the deple-
tion width was not only due to the increase in the amount
of negative charge trapped in the interface but also to
oxygen in-diffusion that decreased the concentration of
oxygen vacancies in the bulk (see Eqs. (24) and (25)).
c. Exposure to CO at 419  C caused a large decrease in
resistance attributed to desorption of oxygen and reduction
of barrier height. Capacitance was increased not only due
to a surface effect, but also to the out-diffusion of oxygen
promoted by the high temperature reducing atmosphere.
This process reduces the width of the depletion layer. Now
Fig. 12. Impedance measurements on particle-based SnO2 sensor in sev-
eral atmospheres at 419  C. The circuit B of Table II was used to model the
data. No traps were considered here. This is a replotted figure from [37],
M. A. Ponce, et al., J. Appl. Phys. 104, 054907 (2008). © 2008, American
Institute of Physics (AIP).
Rev. Adv. Sci. Eng., 5, 86–105, 2016
electrons see a thinner and lower barrier, increasing con-
ductivity (see Eqs. (24) and (25)).
d. A second vacuum measurement was performed under
the same condition as the first measurement, but showed
a significantly lower resistance. The fact that the initial
impedance values were not recovered can be attributed
to the oxygen in/out diffusion that altered the vacancy
concentration.56 63 73 At lower temperatures these pro-
cesses are much slower and would have a smaller or neg-
ligible effect on the measurements. It should be noted that
capacitance did not change much from the CO measure-
ment to the second vacuum measurement. This should be
expected as capacitance changes rely mostly on changes
in surface adsorption and vacancy concentration.
In order to recover the values of the first measurement
in vacuum, an oxygen treatment needs to be done at a
high temperature. It is important to point out that if the
particle is small enough for an oxidizing gas to entirely
deplete it of carriers, depending on the donor concentration
and barrier height, the conduction mechanism is different.
On the one hand, the amount of electrons available for
conduction is much smaller because the conduction (and
valence) bands have been pushed higher relative to the
Fermi energy. On the other hand, electrons see a much
smaller barrier, making it is easier for them to cross into
the next particle. This could make sensors with small
grains more sensitive to gases. See further studies63 73 88
for a detailed discussion.
As seen in Figure 12 above, both measurements were
done in the same vacuum atmosphere, but the test history
modified the resistance by an order of magnitude. If any
parameter is going to be calculated or estimated from these
values, one should be careful with the order in which tests
are carried out.
3.4. Nanowire-Based Sensors
3.4.1. Fabrication of Single-Nanowire Sensors
Single-nanowire sensors are important in the sensor field
for studying intrinsic material properties while minimiz-
ing the unknown variables present in the test device.
This architecture removes any nanowire–nanowire inter-
faces and a simple SEM measurement of the diameter
gives a good estimate of the cross-sectional area and thus
resistivity of this single-crystal nanowire can in principle
be calculated. Single-nanowiresensors are typically single-
crystal and can be fabricated in a variety of methods.6 89–91
After nanowires are grown on a substrate, they are usually
scraped or sonicated off of the substrate in a dispersion
of solvent such as methanol or isopropanol. Then, a few
very small drops of the nanowire dispersion are applied
to the substrate and dried at elevated temperature. Iso-
lated nanowires are then located on the substrate with a
good optical microscope or SEM and electrical contacts
are fabricated using a focused ion beam (FIB) to deposit
or “draw” the electrodes (usually Pt) from each end of the
101
Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review Schipani et al.

nanowire to pre-patterned electrodes. The substrate with
the nanowire is then annealed for better adherence and to
eliminate any organics left by the solvent.92 An alternative
method used almost as frequently is to disperse nanowires
onto a blank substrate and then use lithography to deposit
an intricate electrode pattern.93 An SEM is then used to
search the electrode gaps for nanowires that, by chance,
with an unaffected or “bulk” concentration of conduction
electrons, for an n-type material. When the cross-sectional
area of this zone is decreased due to oxidation at the sur-
face, the resistance of the device is increased. According
to this, we can write91
L
RN W = (32)
end up bridging the gap. This technique generates better-
quality electrodes but does not allow as good of choice of
nanowire(s) to measure and the chemicals used in lithog-
raphy could affect the nanowire’s surface properties.
3.4.2. The Importance of the Electrode-
Nanowire Junction
There are many authors working on single nanowires
as gas sensing devices. Among these, SnO2 nanowires
and Pt-FIB deposited contacts are very common
among researchers to build single-nanowire circuits and
sensors.28 32 86 89 94 The literature mentions several fac-
tors affecting the nature of this junction, i.e., if it has
Ohmic or Schottky behavior, depending on atmosphere,
temperature28 and contact area.28 86 To complicate it fur-
ther, it has been shown that there is sheer randomness in
the quality of the contact formation via these methods that
can affect the electronic behavior.95 The theoretical dif-
ference between the work function of Pt and the electron
affinity of SnO2 intrinsically causes a Schottky barrier of
about 0.75 eV to form at this interface, neglecting surface
defects.32 This value will vary based on the materials cho-
sen and should be a primary consideration when choosing
electrode materials for single-nanowire devices.
Hernandez-Ramirez et al.32 and Lin et al.96 state that
only at high temperatures (>200  C) is the behavior of
the sensor dominated by the bulk nanowire resistance. At
low temperatures, such as room temperature, there is a
high contribution to the overall resistance from the Schot-
tky contacts with the deposited electrode. It is difficult to
know the role of the electrodes on sensing behavior in
simple two-wire DC measurements. To measure the con-
tact resistance of the electrode-nanowire junction, four-
wire DC electrical measurements can be used, where all
the four leads directly contact the single nanowire.97 One
of the primary advantages of impedance measurements is
that the contribution of the electrode can be avoided at
higher frequencies using only two leads connected directly
to the nanowire.
3.4.3. Conduction Through the Length of the Nanowire
Depending on the type of material and target gas, the
surface interaction is based on the exchange of electrons
between the adsorbed gas and the nanowire. The adsorp-
tion of gas molecules on the surface of the nanowire mod-
ulates the width of the depleted region near the surface of
the nanowire. The non-depleted zone in the center of the
nanowire, often called the conduction channel, is a region
102
r − W 2
Where,  is the nanowire resistivity, L its length, r the
radius, and w the width of the depletion zone. This equa-
tion is only valid in “large” nanowires that cannot be fully
depleted. Most studies13 86 show that diameters greater
than approximately 100 nm can have a “bulk” conduc-
tion channel, although this varies greatly depending on the
materials used and the operating conditions. If these condi-
tions are met, impedance spectroscopy can allow the varia-
tion in depletion region width to be tracked under changing
atmospheres, following the approximations in Eq. (24).
Most oxide nanowires grown via vapor–liquid–solid or
thermal oxidation mechanisms tend to be single crystals.9
This means that the only interfaces in single-nanowire sen-
sors will occur at the contacts. However, through a tech-
nique called electrospinning98 99 it is possible to create
fibers composed of many small oxide particles. In theory
it is possible to distinguish between these polycrystalline
strings and crystalline fibers or nanowires with the AC
technique that would allow us to quantify the contribution
of the particle junctions, but it is most likely not possi-
ble due to the small dimensions of the particles that will
likely be completely depleted of carriers. To this author’s
knowledge this has not yet been studied by AC methods
so only speculations can be made.
3.4.4. Role of Substrate Capacitance in
Single-Nanowire Measurements
Usually, p-doped silicon with a thermally oxidized SiO2
insulating layer is used as a substrate for the nanowires.
The metallic electrodes are deposited via lithography on
top of the SiO2 layer and a nanowire or nanowires can
later be used to complete the electrical path between
electrodes.32 100 101 Nanowires can have a very small cross-
sectional area. Their size is generally 10–200 nm in diame-
ter and 1–50 m in length, so their associated capacitance
can be well below 1 pF (10−12 F).23 Although this is a mea-
surable capacitance for modern impedance equipment, it is
usually hidden between experimental noise and substrate
capacitance. Depending on the frequency, the noise can be
of several pF, while the substrate capacitance, depending
on thickness of the substrate and inter-electrode distance,
can be in the hundreds of pF.23 Substrate capacitance and
nanowire capacitance sum in parallel, making it difficult
to isolate and properly model the nanowire capacitance.
A constant phase element is regularly used to model the
capacitance behavior of the sensor response to impedance,
attributing the capacitance to the substrate and not to the
nanowire(s).
Rev. Adv. Sci. Eng., 5, 86–105, 2016
Schipani et al. Electrical Characterization of Semiconductor Oxide-Based Gas Sensors Using Impedance Spectroscopy: A Review
3.4.5. Multiple-Nanowire Sensors
Multiple-nanowire sensors can be fabricated easily by dis-
persing a suspension of highly concentrated nanowires
onto a substrate electrodes. This architecture is randomly
oriented with many nanowire–nanowire and nanowire-
electrode interfaces. This kind of sensor can have hundreds
to many thousands of nanowires. Some methods such as
directional sliding or dielectrophoresis can assist in align-
ing the nanowires into a preferential orientation.102 103 An
annealing process typically follows to eliminate organics
and improve interfacial contact.
This architecture includes many nanowire–nanowire
junctions which are not present in the single-nanowire
devices. When exposed to an oxidizing gas, these junctions
form a depletion layer around the contact point block-
ing the electron transport in a way which is typically
more direct and efficient than only reducing the conduc-
tion channel volume as in single-nanowire sensors. Thus,
there are two primary mechanisms affecting the measured
resistance, and the interfacial barrier modulation is gener-
ally considered as being the most sensitive.21 Impedance
spectroscopy is a powerful tool for studying the rela-
tive contributions of these two mechanisms in this type
of sensor, which can guide development of future sensor
architectures.
4. CONCLUSIONS AND FUTURE
DIRECTIONS
Impedance spectroscopy has been presented as a useful
technique for electrical characterization of metal oxide
gas sensors based on nanoparticles and nanowires. Careful
measurements can lead to estimation of important param-
eters such as donor concentration, depletion region width,
and interface barrier heights as a function of their environ-
ment. It can also extract values of relative contributions
to conductivity from different components of the sensor
device. However, one has to be careful with the chosen
equivalent circuit model used to fit the data. The “best
fit” condition is not sufficient to properly fit the experi-
mental measurements. It must physically make sense given
what is already known of the material. Other experiments
such as X-ray photoelectron spectroscopy, positron anni-
hilation spectroscopy, Raman spectroscopy and electron
microscopy should be used alongside IS to paint a full
picture of the processes occurring in the material.
Impedance measurements are most commonly done on
thick and thin films of metal oxide powders, but have the
potential to provide valuable information in systems based
on nanowires. To date, the nanowire contribution to capac-
itance in single-nanowire sensors has not been isolated due
to large substrate contributions. However, careful electrode
design and substrate choice may allow tracing of single-
nanowire capacitance changes during sensor tests and lead
to better fundamental understanding of this new class of
gas sensors.
Rev. Adv. Sci. Eng., 5, 86–105, 2016
Many new and unique types of metal oxide gas sen-
sors are being constructed from nano-heterostructures.
These combine two or more materials, typically oxides,
in a well-defined hierarchical form. Typical heterostruc-
tures are core–shell nanowires and nanoparticles, discrete
nanoparticle-decorated nanowires, branching 1D-1D struc-
tures, and layered thin films.9 The electron interactions
and charge transport between the component materials are
of utmost importance for understanding sensor behavior.
Careful impedance spectroscopy measurements on well-
defined heterostructures may in the future be able to show
varying relaxation times across the heterostructure inter-
face due to defect states present and relative contributions
to sensor response from each material component. Under-
standing at these levels is anticipated to help design hetero-
nanostructure sensors with better performances.
Acknowledgments: The current work was partially
supported by a Fulbright/BEC.AR Fellowship and by a
NASA Space Technology Research Fellowship.
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