Annurev Anchem 012809 102211

AC03CH10-Park ARI 11 May 2010 12:53
ANNUAL
REVIEWS Further Electrochemical Impedance
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Byoung-Yong Chang1 and Su-Moon Park2
• Our comprehensive search 1
Department of Chemistry, Pohang University of Science and Technology, Pohang 790-784,
Korea; email: [email protected]
2
School of Energy Engineering, Ulsan National Institute of Science and Technology,
Ulsan 689-805, Korea; email: [email protected]
Annu. Rev. Anal. Chem. 2010. 3:207–29 Key Words

First published online as a Review in Advance on electrochemical measurements, equivalent circuits, electrified interfaces,
February 25, 2010
electrode kinetics, biosensors
The Annual Review of Analytical Chemistry is online
at anchem.annualreviews.org Abstract
This article’s doi: This review describes recent advances in electrochemical impedance spec-
10.1146/annurev.anchem.012809.102211
troscopy (EIS) with an emphasis on its novel applications to various
Copyright c 2010 by Annual Reviews. electrochemistry-related problems. Section 1 discusses the development of
All rights reserved
new EIS techniques to reduce measurement time. For this purpose, various
1936-1327/10/0719-0207$20.00 forms of multisine EIS techniques were first developed via a noise signal syn-
thesized by mixing ac waves of various frequencies, followed by fast Fourier
transform of the signal and the resulting current. Subsequently, an entirely
new concept was introduced in which true white noise was used as an excita-
tion source, followed by Fourier transform of both excitation and response
signals. Section 2 describes novel applications of the newly developed tech-
niques to time-resolved impedance measurements as well as to impedance
imaging. Section 3 is devoted to recent applications of EIS techniques, specif-
ically traditional measurements in various fields with a special emphasis on
biosensor detections.
207
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1. INTRODUCTION
Electrochemical impedance spectroscopy (EIS) has been known to the electrochemistry commu-
nity for more than a century; Macdonald (1) recently published an excellent account of its history.
Whereas Macdonald wrote that electrical equivalent circuits (EECs) are merely analogs, rather
than models, we describe an electrochemical reaction that takes place at the electrode/electrolyte
interface, using an EEC as a model. We then examine whether an EEC can indeed be used as a
model for the reaction at the electrified interface.
The current flowing at an electrified interface due to an electrochemical reaction,
O + ne− → R, (1)
always contains nonfaradaic components, no matter how well the measurement is made. In this
equation, n is the number of electrons transferred, O is the oxidant, and R is its reduced product
(reductant). The electron is transferred across the electrified interface, as illustrated in Figure 1a.
The charge transfer leads to both faradaic and nonfaradaic components. The faradaic component
arises from the electron transfer via a reaction (1) across the interface by overcoming an appro-
priate activation barrier, namely the polarization resistance (Rp ), along with the uncompensated
a IHP OHP Diffusion layer b Cd
Rs Zw
Rp
Electrode
Cation
Electron
Solvent
Adsorbent
Cd
WE CE
Zw Rs
Rp
Figure 1
(a) At top is an electrified interface in which the electrode is negatively charged; countercations are aligned
along the electrified surface. At bottom are the electrical circuit elements corresponding to each interface
component. (b) An idealized Randles electrical equivalent circuit for the interface, shown with no specifically
adsorbed anions. The high-frequency components are shown on the left, and the low-frequency components
are shown on the right. Abbreviations: Cd , double-layer capacitor; CE, counterelectrode; IHP, inner
Helmholtz plane; OHP, outer Helmholtz plane; Rp , polarization resistance; Rs , solution resistance;
WE, working electrode; ZW , Warburg impedance.
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solution resistance (Rs ). The nonfaradaic current results from charging the double-layer capacitor
(Cd ). When the charge transfer takes place at the interface, the mass transports of the reactant
and product take on roles in determining the rate of electron transfer, which depends on the
consumption of the oxidants and the production of the reductant near the electrode surface. The
mass transport of the reactants and the products provides another class of impedance (ZW ), which
can be exploited by electroanalytical chemists because it shows up in the form of a peak current
in a voltammogram or a current plateau in a polarogram. The EEC in Figure 1a shows that
each circuit component corresponds to each interfacial component. The EEC first proposed by
Randles (2), shown in Figure 1b, displays both the high-frequency components (e.g., Rs ) and the
low-frequency components (e.g., ZW ). The left-to-right arrangement of the EECs is important
because the impedance data are normally displayed in this manner (Figure 2). Also, note that the
activation barrier at any potential is represented by the polarization resistance, Rp , but that the
barrier becomes the charge-transfer resistance, Rct , at the standard (or formal) electrode potential.
In efforts to eliminate or minimize the effects of capacitive currents during transient elec-
trochemical experiments, electrochemists have been developing techniques such as normal and
differential pulse voltammetry as well as other related methods (3). These techniques are necessary
because transient signals obtained from linear sweep or cyclic voltammetry, chronoamperometry,
and chronopotentiometry experiments are affected by double-layer charging currents to different
extents, depending on the experimental conditions. As shown in Figure 1, the environment in
which the charge-transfer reaction takes place dictates all the related parameters to be described
based solely on the full impedance data obtained during the reaction, given that the traditional
electrochemical measurements described above provide only limited information about the sys-
tem. For complete information about the interface, one must run either several separate traditional
transient experiments or an EIS experiment.
The frequency-dependent impedance, Z(ω), at the interface that has the circuit elements shown
in Figure 1b has a rather complex expression,
R p + σ ω−1/2
Z(ω) = Rs +
σ ω1/2 (Cd + 1)2 + ω2 Cd2 (R p + σ ω−1/2 )2
[ωCd (R p + σ ω−1/2 )2 + σ ω−1/2 (Cd σ ω1/2 + 1)]
+j . (2)
(Cd σ ω1/2 + 1)2 + ω2 Cd2 (R p + σ ω−1/2 )2
Here ω = 2π f, where f is frequency, j is (−1)1/2 , and

RT 1 1
σ = √ + 1/2 , (3)
2n2 F 2 A D1/2O C O (x, t) DR C R (x, t)
where A is the electrode area, Cs are concentrations of subscripted species at a distance x from the
electrode surface, and t is time. The other symbols either are defined above or have their usual
meanings. Equation 2 can be simplified to
Rp ω R2p Cd
Z(ω) = Rs + − j = Z (ω) − j Z (ω), (4)
1 + ω2 R2p Cd2 1 + ω2 R2p Cd2
at high frequencies (ω → ∞). At low frequencies (ω → 0), it becomes
Z(ω) = Rs + R p + σ ω−1/2 − j (σ ω−1/2 + 2σ 2 Cd ). (5)
The Warburg impedance is related to σ by the equation

1/2
2
ZW = σ. (6)
ω
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8,000
a
6,000
–Z'' (Ω)
4,000
2,000
0
0 4,000 8,000 12,000 16,000
Z' (Ω)
800
700
b
600
500
–Z'' (Ω)
400
300
200
100
200 Hz
0
–100
0 200 400 600 800 1,000
Z' (Ω)
1,800
1,600
c
1,400
1,200
1,000
–Z'' (Ω)
800
600
400
200
0 4 kHz
–200
0 500 1,000 1,500 2,000
Z' (Ω)
Figure 2
Nyquist plots obtained from Equation √ 7 with different kinetic parameters. The calculations were performed
between 50 kHz and 1 Hz. The k0 / D values (relative rates of electron transfer to that of mass transfer)
used for the calculation were (a) 1.0 × 10−3 s1/2 , (b) 1.0 s1/2 , and (c) 1.0 × 103 s1/2 . The high-frequency
component, Rs , is shown on the left, and the low-frequency component, ZW , is shown on the right. The
intermediate-frequency component (circles) arising from Rp and Cd is located in between. Data taken from
Reference 45.
Thus, Equation 4 shows that a semicircle with a radius of Rp /2, with a high-frequency intercept
of Rs and a low-frequency intercept of (Rs + Rp ) on the Z (ω) axis, is obtained when −Z (ω) is
plotted against Z (ω) (Figure 2) (4). In the low-frequency region, however, a straight line with a
slope of one and an intercept of (Rs + Rp – 2σ 2 Cd ) is obtained (Figure 2b,c). Thus, one can obtain
all the necessary circuit parameters from these plots. More detailed descriptions and derivations
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of equations can be found in recent textbooks and monographs (3, 5). Impedance responses under
various experimental conditions have been reviewed by Macdonald (1).
Many reviews of EIS have been published in recent years (1, 6–15); however, most of them
address applications of EIS as a detection tool for biosensors, biological cell analysis, or clinical
analysis (6–14). In this review, we focus on recent advances in EIS techniques and their applications
to various fields of studies. Because of space constraints, we cannot cover the topic exhaustively;
we apologize for any inadvertent omissions.
2. RECENT ADVANCES IN ELECTROCHEMICAL

IMPEDANCE SPECTROSCOPY MEASUREMENT
TECHNIQUES AND THEIR APPLICATIONS
2.1. New Forms of Electrochemical Impedance Spectroscopy Measurements

As stated by Macdonald (1), in the early twentieth century EIS experiments were conducted
primarily to measure the capacitance of an ideally polarizable electrode such as mercury. Mea-
surements of full impedance spectra were not made until approximately the 1970s, when the
use of reliable potentiostats had become widespread. Of the various methods of impedance mea-
surements, the frequency response analyzer (FRA) has become a de facto standard. FRA is a
single-sine method in which a small ac wave of 5 to 15 mV of a given frequency is overlaid on
a desired dc bias potential and applied to the working electrode; an ac current measurement is
then made. This process is repeated by scanning the frequency and computing the impedances
from the ac voltage and current data at desired frequencies, typically five to ten measurements
for a decade change in frequency. However, this method is viable only for a stable and reversible
system in equilibrium, as the system’s linearity, stability, and causality must be ensured. For this
reason, early investigators questioned the validity of impedance measurements (15–16) and hoped
to make instantaneous impedance measurements for nonstationary systems. Stoynov & Savova-
Stoynov (17–20) published mathematical expressions to extract instantaneous impedance values
for nonstationary systems. Problems with this approach arise primarily from the relatively long
data-acquisition time required for the single-sine FRA method.
In efforts to reduce the measurement time, investigators have proposed methods in which
no frequency scanning is employed. Smith (21) and others (22–24) used the fast Fourier trans-
form (FFT) method after obtaining the current signal upon application of a noise signal, which
was achieved by mixing the ac voltages of various frequencies, to an electrochemical cell. The
impedances were then computed from the deconvoluted ac voltages and currents; we term this
technique the first-generation Fourier transform EIS (1-FTEIS) method. Recently, Popkirov &
Schindler (25) simplified this technique and implemented it into an EIS spectrometer through use
of a noise signal obtained by mixing the ac waves of 42 appropriate frequencies. When the low-
frequency limit of the ac voltage is reasonably high at 10 Hz, for example, it takes approximately
0.1 s to obtain a full impedance spectrum, although the number of data points is limited.
A few other groups have adopted or further developed the simplified method (1 -FTEIS).
Baranski et al. (26) used the mixed multisine ac voltage signal with frequencies ranging from
5 kHz to 5 MHz to impedance measurements at a microelectrode and reported a data-acquisition
time of less than 5 ms. Rosvall & Sharp (27) developed a slightly more sophisticated form by
combining the multisine signal with staircase voltammetry, in which a wavelet consisting of mixed
sinusoidal waves of 20 frequencies between 150 Hz and 200 kHz was overlaid on the latter part
of the step during the staircase voltammetry experiment. A number of other studies, in which the
1 -FTEIS method was combined with cyclic voltammetry (28–41), soon followed.

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Darowicki et al. (28) validated the 1 -FTEIS method using a wavelet of seven ac frequencies
ranging from 60 to 997 Hz to record impedances of a nonstationary electrical system. This system
consisted of a capacitor and a diode connected in parallel and was polarized at a constant rate in the
conduction direction of the diode. After verifying that the method provided true impedance signals,
the authors coupled the method with cyclic voltammetry by overlaying the wavelet on a slow ramp
signal. They later termed this technique dynamic electrochemical impedance spectroscopy (DEIS)
(28–30). Darowicki et al. later used this method to study various electrochemical phenomena,
including corrosion of metals such as aluminum and stainless steel (31–33) and the appearance of
anodic excursion peaks from a lead-acid battery (34). They also developed a method with which to
monitor the local impedances of a 0.1-mm-thick polymer membrane [polyvinylchloride plasticized
with bis(2-ethylhexyl) sebacate and doped with tetradodecylammonium tetrakis(4-chlorophenyl)
borate] using a steel electrode with a tip diameter of 0.1 mm.
Several other groups have contributed to the development of FTEIS. For example, Roy and
colleagues (36) studied the underpotential deposition (UPD) of Bi3+ in the presence of ClO4 −
by employing 1-FTEIS (which they termed FFT-EIS). The authors claimed to have simultane-
ously probed both the steady-state and transient behaviors of the interface. They also reported
time-resolved impedance spectra for a gold electrode, describing considerations for running such
experiments as well as the hardware requirements for data acquisition (37). Later, the authors
conducted a more detailed analysis of the kinetic parameters for faradaic and nonfaradaic reac-
tions on thin films on gold (38). They used a scan rate of 5 mV s−1 and a multisine signal of 65
sinusoidal waves with a frequency range of 100 Hz to 10 kHz on the dc ramp signal. Ragoisha
& Bondarenko (39) conducted similar experiments, which they termed potentiodynamic electro-
chemical impedance spectroscopy (PDEIS), on a quasi-reversible redox system, Fe(CN)6 3−/4− .
They applied the technique to, for instance, identification of the capacitances of TiO2 films for
Mott-Schottky plots (40) and studies of the lead UPD on polycrystalline gold as well as on the
selenium atomic underlayer (41).
The Park group (42–51) developed an approach that was entirely different from those that had
been used thus far. In their experiments, a small step signal, instead of mixed sinusoidal waves, was
applied to a working electrode at a given dc bias voltage, and the resulting chronoamperometric
current was recorded. The step signal is an integrated form of the Dirac δ function, which is
obtained by summing the ac voltages of all frequencies. In this process, derivative signals obtained
from both the voltage step and the recorded current signals were deconvoluted into ac voltages, and
the currents were deconvoluted into the frequency domain by the FFT method. The impedance at a
desired frequency was first obtained by dividing an ac voltage at that frequency by the current at the
frequency. A full impedance spectrum was then constructed by repeating the calculation through
the frequency range. We term this technique second-generation Fourier transform EIS (2-FTEIS)
because true white noise (δ) containing ac waves of all frequencies is used as an excitation signal,
just as in Fourier transform infrared spectroscopy or nuclear magnetic resonance experiments.
There were several assumptions and requirements for this series of operations. The most
important and stringent requirements for hardware were (a) that the potentiostat be fast rising to
transmit the well-defined step signal to the cell and (b) that the data-acquisition system not only
be fast enough to ensure recording high-frequency data but also have a high bit resolution so that
low-frequency data could be recorded with high precision. Details of the other assumptions and
requirements for the system are given in Reference 42. The Park group took measurements at a
given dc bias potential by applying a small voltage step signal of 5 to 20 mV and recording the
resultant current for the step period of a few milliseconds to as long as a few seconds. The highest
frequency was 1/(2·t), and the lowest was 1/(n·t), where t is the signal-sampling interval, n
is the total number of samples, and n·t is the step period tp (52). Although the authors initially
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conducted the experiments at specified dc bias potentials, they later coupled the experiments
with staircase cyclic voltammetry to obtain both EIS data as a function of potential and staircase
cyclic voltammograms (SCVs). Thus, a series of ascending and/or descending voltage steps were
applied to the cell, and each step produced a full impedance spectrum (43) in a frequency region
ranging from 1/(2·t) to 1/tp . For example, for an experiment with a step period of 150 ms with
a 1-MHz sampling frequency, an impedance spectrum would be obtained in a frequency range
of 50 kHz to 6.7 Hz in 0.15 s. The authors validated the impedance data by conducting the
Kramers-Krönig transform operation (53). Thus, these SCV-FTEIS experiments allowed truly
time-resolved impedance spectra to be recorded as a function of time at every stepped potential
while SCVs were recorded. Note that an SCV recorded by connecting currents sampled at a
sampling time tp is equivalent to a cyclic voltammogram (CV) recorded at a scan rate of E/4tp ,
where E is the step height (54); the current sampling time does not need to be the same as tp . Thus,
scan rates as fast as a few hundred millivolts per second can be used while the impedance spectra
are obtained in real time. The scan rate can be much faster, provided that only high-frequency
data are acquired.
Another important conclusion reached from the above-described studies was that the EEC
is not merely an analog capable of simply fitting the impedance data, as had been described by
Macdonald (1); rather, it can serve as a true model for an electrochemical reaction. To demonstrate
this point, Chang & Park (45) derived the following expression for the current obtained upon
applying a potential step, E, across the EEC shown in Figure 1b,
⎡ √ 2 ⎤ √
−E 2σ 2σ √ −E · R p − (R p +Rs )
·t
i(t) = · exp ⎣ · t ⎦ · erfc · t + e R p Rs Cd , (7)
R p + Rs R p + Rs R p + Rs Rs (R p + Rs )
by using the impedance expression shown in Equation 2. In this equation, exp and erfc re-
fer to exponent and error-function complement, respectively. Surprisingly, the faradaic term of
Equation 7, which was obtained for the EEC, has exactly the same form as the current expression
that Delahay (55) obtained by solving diffusion equations for a potential step:
√
I f = nF A(k f · C O∗ − kb · C R∗ ) · exp(H 2 t) · erfc(H t). (8)
Here H is defined as
kf kb
H = √ +√ , (9)
DO DR
where kf and kb are the forward- and reverse-rate constants, respectively, for the electron-transfer
reaction (1) and D is the diffusion coefficient of the subscripted species. Thus, the current expres-
sion obtained for the EEC and the solution process for the same experiment have the same form
and produce identical currents when computed via two equations (45). Also, note that Equation 7
contains the nonfaradaic expression as its second term; the EEC indeed represents a real model
for the electron-transfer reaction.
After deriving the above expression, Chang & Park (45) computed impedances using Equation 7
for different H values and obtained the results shown in Figure 2. The Nyquist plot in Figure 2c
shows that the Warburg line dominates the impedance plot for a reversible electrochemical system
such as Ru(NH3 )6 3+/2+ and ferrocene/ferrocenium pairs. In such systems, the mass transport is
rate limiting due to the very fast charge-transfer rate; thus, use of frequencies higher than 1 kHz
is justified for recording a full impedance spectrum, including a Warburg line. This conclusion
suggests that the step period can be as short as 1 ms (1 kHz) to record a full spectrum. However,
only a semicircle is obtained, and no Warburg impedance is displayed, when the charge-transfer

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100
80
τ(Rs ||Rp)• Cd / τRs • Cd (%)

60
40
20
0.01 0.1 1 10 100

Rp /Rs
Figure 3
Ratio of the time constants plotted for the ratio of R values obtained from the parallel connection of Rp and
Rs (τ (Rs Rp)·Cd ) to the ratio calculated with Rs alone (τ Rs ·Cd ). Data taken from Reference 45. Abbreviations:
Cd , double-layer capacitor; Rp , polarization resistance; Rs , solution resistance.
rate is much smaller in comparison to the D1/2 value. In such cases, one may need to increase both
the overpotential and the E value in the SCV-FTEIS experiment.
Examination of the nonfaradaic term of Equation 7 also indicates that the system time constant
(τ ) acts as if the two circuit components, Rp and Rs , were connected in parallel rather than in series,
as electrochemists have so far assumed. As a result, the capacitive currents can be significantly
different depending on how large or small the Rp value is in comparison to Rs . Prior to the start
of the electron-transfer reaction, the time constant is determined only by Rs , but both Rs and Rp
values begin to play a role when the potential reaches a value at which Rp competes with Rs . At a
very large overpotential, the contribution from Rp dominates the time constant that would have
been obtained from a serial connection of Rs and Cd , namely an Rs Cd time constant. Figure 3 shows
how the system’s time constants behave, depending on the situation. Our present understanding
of the time constant of an electrochemical system is incorrect, although the difference may not be
significant for some cases.
Chang & Park (47) later demonstrated that it is possible to completely describe the electri-
fied interface through use of the impedance data acquired from a single pass of the SCV-FTEIS
experiment. To do so, one must obtain all the necessary reaction parameters such as (a) kinetic
parameters, including the exchange-rate constant (k◦ ) and the transfer coefficient (α); (b) thermo-
dynamic parameters, including E1/2 and n; and (c) the mass-transport parameter (D). The kinetic
parameters are obtained simply by plotting a series of Rp values as a function of the scanned
potential according to the Butler-Volmer or Tafel equation. To obtain the thermodynamic and
mass-transport parameters, the expression for σ can be expanded to

RT 1 nF nF
σ = √ exp − (E − E 1/2 ) + 2 + ξ exp (E − E 1/2 ) , (10)
2n2 F 2 ADO/ C O∗ ξ
1 2 RT RT
where ξ is (DO /DR )1/2 . Examination of the Warburg admittance obtained from Equation 6 reveals
that the admittance reaches a maximum at E1/2 , providing the E1/2 of the reaction. The n and D
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values are also obtained from the ac admittance voltammogram. This simple way of describing an
electrochemical system has been applied to studies of various reaction systems such as earlier phases
of electrochemical polymerization of aniline (48), resolution of multielectron-transfer steps during
sulfur reduction (49), UPD of lead on gold (50), and diffusional electrochemistry of cytochrome
c on a self-assembled monolayer (SAM)-covered electrode (51).
Several groups of investigators employed Laplace transform, instead of Fourier transform,
beginning as early as the 1970s (56–60). The general principle of this technique is similar to
that for the Fourier transform method. An appropriate perturbation signal—either the voltage or
the current step—is applied to the working electrode, and the impedance is obtained from the
response of the cell according to
∞
V (s ) v(t)e −s t d t
ZL = = 0∞ , (11)
I (s ) 0
i(t)e −s t d t
where ZL is the Laplace impedance function; v(t) and i(t) are the voltage and current functions
in the time domain, respectively; and s = α + jω, where α is a convergence parameter of the
real number. Note that either v(t) or i(t) can be a perturbation signal and that the other can be a
response, depending on the type of cell (58, 60). Although the corresponding Fourier transform
does not converge for a voltage step begun at t = 0, the Laplace integral shown in Equation 11
does converge when α is large enough. Details of experiments and evaluations of the impedances
in frequency domain have been described in the literature for studies of both battery electrodes
(58–60) and the corrosion of metals (57).
2.2. Applications of First- and Second-Generation Fourier Transform

Electrochemical Impedance Spectroscopy Techniques
Numerous interesting applications have evolved from the EIS experiments on various electro-
chemical problems that could not have been solved without the new methods described above.
Electrochemists have long desired to record impedance spectra fast enough to resolve the changes
that take place at the interface. In this section, we describe how FTEIS techniques are applied to
studies on biosensors, complex reaction mechanisms, UPDs, corrosion reactions, surface changes,
and semiconductor materials.
Park et al. (61, 62) demonstrated that their FTEIS technique can serve as a more sensitive
time-resolved detection tool than can its voltammetric counterpart for biosensors. Impedances
were monitored during a reaction whose product changed the charge-transfer rate for an electro-
chemical redox probe. The neurotransmitter serotonin was effectively captured by the host cavities
of a (R)-lipo-diaza-18-crown-6 SAM on gold electrodes through the formation of a host-guest
complex; the SAM provided molecular cavities of the correct size for the serotonin molecule by
housing it in the compound 18-crown-6. The captured serotonin molecules facilitated the charge-
transfer rate for the Fe(CN)6 3−/4− redox probe, the degree of which depends on the serotonin
concentration in solution. Figure 4 shows the sensing scheme, the potential program, and a series
of the simultaneously monitored signals for the reaction via CV and EIS measurements during
the reaction. The two experiments were conducted in series via the potential programmed, as
shown in Figure 4b. A 10-mV-potential step was used for the first 2.5 s, followed by a cyclic
ramp signal for the next 2.5 s. An impedance spectrum was recorded for the first 2.5 s (down
to 0.40 Hz), and a CV was obtained at a scan rate of 40 mV s−1 while the reaction proceeded.
The CVs show that only their reversibility improved and that there were almost no changes in
their peak currents (Figure 4d ), whereas the impedance spectra underwent significant changes
over time (Figure 4c). These results clearly indicate that the process of recording EIS spectra is a

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P P–
a b
P P–
Target 0.5
Potential (V)
Sensor
e– e– O.C.P.
10 mV
0
2.5 5
-Z''
-Z''
Time (s)
Z' Z'
20
c d
15
10
Current (μA)
6 5
5
–Zimg (kΩ)
0
4
3 –5
2 15
1 10 –10
0
0 5 Zre (kΩ) –15
100 200 300 400 0
500 0.0 0.1 0.2 0.3 0.4 0.5
Time (s)
Potential (V)
Figure 4
(a) General scheme for label-free detection via electrochemical impedance spectroscopy (EIS). The charge-transfer impedance for the
probe ions (P) is increased due to the target analyte bound to a proper sensing platform. (b) Potential program to sequentially acquire
both Fourier transform EIS (FTEIS) and cyclic voltammogram (CV) data. First, a potential step of 10 mV is applied on the dc bias of
0.245 V for 2.5 s. Second, a ramp signal, with upper and lower vertex voltages of 0 to 0.50 V and a scan rate of 400 mV s−1 , is applied.
(c) Series of FTEIS spectra. (d ) CVs obtained as a function of time upon injection of 400 μl of 1 mM serotonin to 4 ml of the probe
solution. Data taken from Reference 61.
much more sensitive detection tool than is the process of recording CVs for monitoring analyte
concentration. This is also true for the reaction of glycated hemoglobin (HbA1c ) with boronic acid
on the thiophene-3–boronic acid SAM-covered gold electrode (62).
Scientists are eager to apply their techniques to solving problems to demonstrate their utility,
and the investigators involved in developing 1-FTEIS are no exception. Darowicki & Slepski
(30) examined the well-known electrochemical reaction involving reduction of Cd2+ at a hanging
mercury electrode, and they characterized the reaction in terms of Rp and Cd , along with Warburg
coefficients, as a function of reduction potential. Both the Rp and the Warburg coefficient went
through a minimum at E1/2 , whereas the Cd value increased in the same manner as a polarogram
would. Similar observations were reported by other investigators, who provided additional inter-
pretable parameters by converting the circuit parameters into the electrode-reaction parameters
(36, 38, 46, 47). Furthermore, several researchers used this technique to probe more complex
reactions, including electrochemical oxidation of aromatic amines to produce conductive poly-
mers (43, 48, 63) such as polyaniline and poly(o-theoxyaniline). A series of potential-dependent
impedance spectra revealed that different EECs are needed in different potential regimes. This
is because the electrical environment of the interface changes during the potential scan as the
conductive polymer forms films on the electrode surface; this process may impart what is termed
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the autocatalysis for oxidation of the monomers. The authors made detailed kinetic analyses while
the potential was being scanned (48).
Problems related to the UPD of a few metal ions have also been addressed by a few groups
(41, 64–67), who concluded that the reason the FTEIS techniques may serve as a powerful tool
is because they allow one to monitor changes in capacitances during the potential scan. The
substrates studied included metal-chalcogen atomic multilayers as well as UPDs of Te, Se, Pb,
and Cu. The effects of an organic additive on copper deposition have also been addressed (66). A
real-time impedance study of a Pb UPD on polycrystalline gold, conducted while the potential
was scanned, indicated that the Pb2+ adsorption initially followed the Langmuir model and that it
was taken up by the Frumkin adsorption when the population of adsorbates became large enough
to allow the ions to interact with one another (50).
Another type of reaction that has received attention is metal corrosion (31–33, 67–72).
Darowicki et al. (31) used the DEIS technique to study the passive-layer cracking process of
aluminum alloys and the dissolution process of stainless-steel specimens (32, 33). The corrosion
of stainless-steel samples was studied by Nagarajan et al. (69) and Nagarajan & Rajendran (71)
under different solution environments. Roy and colleagues (68) reported on the effects of adsorb-
ing ions such as I− on Cu, on the chemical-mechanical planarization of copper with surfactants
present (67), and on tantalum in oxalic acid solutions (72).
This technique has also been applied to studies of semiconductor electrodes (40, 73–75).
Bondarenko & Ragoisha (40) used PDEIS to monitor the potential-dependent capacitances of
the space-charge layer of a cathodically treated TiO2 film. The capacitance data were used to
obtain Mott-Schottky plots, which allowed the characteristics of the film, such as doping levels
and flat-band potentials, to be determined. Phenomena such as oxide growth on silicon (73), pore
etching (74), and pore growth (75) have also been studied through use of these new impedance-
measurement techniques.
2.3. Impedance Imaging and Time-Resolved Measurements

Investigators first began recording and mapping local impedances as early as in 1992 (76), and
additional reports followed in the same decade (77, 78). Researchers measured local impedances
by arranging the tips of two parallel, microsized electrodes located vertically above the specimen
electrode and scanning across it after applying small ac waves between the large working electrode
and counterelectrode (76). The difference in ac voltage between the microelectrodes and the solu-
tion ac current, along with the distance between the tip electrodes and the solution conductivity,
led to the acquisition of the local impedance of the working electrode. By moving the two probe
electrodes and making impedance measurements at several frequencies, the authors (76) obtained
an impedance image of the working electrode. Other groups applied similar approaches to a mi-
crotip protruding below a small ring electrode encompassing it (77, 78). These approaches have
also been used to map pit growth (78) and the delaminated areas beneath organic coatings (79).
Later, Frateur et al. (80) addressed the experimental issues associated with the local impedance
by making measurements of the local interfacial impedances at two heights above the electrode
surface.
Another approach to impedance imaging involves scanning electrochemical microscopy
(SECM) (81–86). In a typical example (shown in Figure 5a), Ervin et al. (81) obtained an
impedance image by rastering a glass-sealed conical platinum tip with an approximately 1-μm
radius above the polycarbonate membrane surface containing conical shaped pores; they simul-
taneously measured the total impedance between the tip and a large platinum counterelectrode
located on the opposite side of the membrane. The image contrast was obtained due to the decrease

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a Scanning c Impedance
measurement
system
Rtip Rexit AFM

system
Membrane Rpore
Rentry
b d
Resistance
(MΩ)
7.1
6.8 10 μm
μ 1 μm
6.5 Resistance
6.2 4 MΩ
5.9
A
5.6
D
5.3 B
7 μm 5.0 E
C
2 kΩ
1,000
, Hz 1,000 Hz
Figure 5
Impedance imaging of two-dimensional surfaces via scanning probes. (a) Scheme for impedance imaging of a
cone-shaped pore in the polycarbonate membrane by scanning electrochemical microscopy. (b) An
impedance image for a conical pore. (c) Simultaneous atomic force microscopy (AFM) impedance and
topography-imaging experiments. (d ) Shown in the top row are the AFM topographic images of a
gold/silicon nitride pattern; shown in the bottom row are corresponding impedance images measured with
1000 Hz ac waves at 0 V dc bias. Panels a and b are reproduced from Reference 81; panels c and d are
reproduced from Reference 88.
in resistance between the tip and the membrane (Figure 5b). The sensitivity of the measurements
was enhanced through use of a low-impedance electrical shunt (i.e., a salt bridge) across the mem-
brane (82). Diakowski & Baranski (83) used SECM measurements to map the conductive and
insulating surfaces by analyzing positive and negative ac feedback currents, which depended on
experimental conditions. By combining atomic force microscopy (AFM) with alternating current
SECM (AC-SECM), Schuhmann and colleagues (84, 86) developed a method that maps the lo-
cal electrochemical properties at the electrode/electrolyte interface as well as the topography of
the substrate. They showed that AC-SECM approach curves toward the conducting substrate
can result in either positive or negative feedback responses, depending on the frequency and the
topography of the substrate. The AC-SECM technique has recently been reviewed (85).
In 2003, Layson et al. (87) made the first nanoscale impedance measurements on an ionic
conductive polymer [poly(ethylene) oxide] surface using a current-sensing AFM (CS-AFM). The
measurements were made at several spots on the polymer surface, with a nickel foil on the other
side of the film, in a frequency range of 10 kHz to 400 Hz after the topographic image was obtained.
Notably, the resistance measured vertically to the film increased by only two orders of magnitude
with a decrease in the contact area of the CS-AFM probe by approximately ten orders of magnitude.
Similar measurements on ZnO varistors and Nafion R
membranes (88) were reported; impedance
and topographical images were presented with a spatial resolution approaching approximately
10 nm (as shown in Figure 5c,d ). Building an image is time consuming, as one must scan both
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the frequency and the surface and record the impedance signals. For this reason, Darowicki et al.
(89) later combined the DEIS technique, in which 20 ac waves with frequencies ranging from 700
to 44,900 Hz are measured, with the CS-AFM technique in order to map the impedances of a
Prussian blue–covered gold surface.
Finally, we describe efforts to develop time-resolved EIS as the speed of recording EIS spectra
increases (also see Section 2.1) (33, 37, 43). Schiller et al. (90) demonstrated that enhanced mathe-
matical techniques are necessary for evaluation of EIS spectra that change with time. Quasi-causal
spectra were obtained due to the changing states of the polymer electrolyte fuel cell under con-
stant load during the electrolysis reaction. This report, as well as earlier publications describing
the stationarity requirements of EIS measurements (17–20), indicates that EIS spectra recorded
as a function of time from a system undergoing changes during electrolysis may not represent true
impedances unless the rate of measurement is faster than the rate of change.
As mentioned above, electrochemists have attempted to record time-resolved EIS spectra since
the early stages of FTEIS development (33, 37, 43, 90). To record time-resolved EIS spectra during
a cyclic voltammetric scan in DEIS or PDEIS experiments, one should use a potential scan slower
than 10 mV s−1 because of hardware constraints (38). In an SCV-FTEIS experiment, however,
Yoo et al. (43) demonstrated that the impedances recorded in real time during a voltage scan rate
of 240 mV s−1 met the Kramers-Krönig transform validity tests. Later studies revealed that scan
rates as fast as a few hundred millivolts per seconds could be used while the EIS spectra were
being recorded in real time (46–48). In their typical application as a detection tool for biosensors,
both CVs and EIS spectra were recorded back to back for the purpose of comparison (61, 62).
Whereas the EIS spectra were obtained every 2.5 s in the reports, the measurement time could
be decreased significantly, depending on the reversibility of the redox reaction.
3. ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY

AS A LABEL-FREE DETECTION TOOL FOR BIOSENSORS
During the past few years, impedance measurements have become increasingly popular as a
label-free detection tool for many different types of biosensors (6–10). In experiments employing
impedance measurements, the biosensor is prepared on an electrode such that the electron-transfer
rate is selectively modulated by the analyte. Although many different chemical reactions may be
used to modify the electrode surface, SAMs with appropriate functional groups that selectively
capture specific analytes are the most frequently employed technique because they are easy to
immobilize and have complete blocking capabilities and stabilities. A typical biosensor may be
prepared by dipping a gold electrode in a solution containing (a) an organic compound with a
thiol group on one side and (b) a functional group capable of selectively capturing a target analyte
on the other side. The SAM that forms on the gold electrode via covalent binding with the thiol
group modulates the electrical and electrochemical environments of the interface; changes in the
interfacial environments are detected in the form of changes in capacitances or in charge-transfer
rates. These properties are further modulated upon capture of the analyte by the functional group
facing the solution. The changes can be detected by voltammetric, amperometric, or impedomet-
ric measurements. The selectivity is provided via an appropriate functional group of the molecule
forming the SAM, and the analyte is detected by an electrochemical method and does not have
to be labeled. In a typical fluorometric method of detection, an efficiently fluorescing group or
compound must be labeled onto the analyte before it is analyzed so that the fluorescence intensity
of the labeled analyte is related to its concentration.
These types of biosensors detect the changes in electrochemical and/or electrical properties
that are caused by the blocking ability of SAMs and SAM-analyte adducts. Ganesh et al. (91)

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showed through impedance measurements that the charge transfer occurs to/from an electrode
covered by a SAM formed from thiophenol, o-aminothiophenol, or p-aminothiophenol from/to a
Fe(CN)6 3−/4− redox probe through the pinholes and defects of the monolayer, whereas tunneling
of electrons is responsible for the Ru(NH3 )3 3+/2+ pair. Thus, the extent to which the electrode
surface is blocked controls the pinholes as well as the tunneling ability, determining the charge-
transfer rate. Depending on what is on the surface, the charge-transfer rate may be enhanced by
the SAM instead (61, 92).
Berggren et al. (93) constructed capacitive biosensors for antibodies, antigens, proteins, DNA
fragments, and heavy metal ions with detection limits as low as 10−15 M by modifying electrode
surfaces with SAMs or SAM-analyte adducts, causing dielectric properties of the SAM layers to
change. A similar sensor was constructed for the detection of Escherichia coli and Salmonella ty-
phimurium on digitated gold electrodes, which were functionalized by anchoring biotinylated poly-
clonal anti–E. coli antibodies to a neutravidin-coated surface (94). The electrochemical impedance
and capacitance signals in the biosensor were shown to be significantly amplified through gold
nanoparticle conjugation for the model fluoroscein-antifluoroscein system (95). Capacitive sig-
nals were also shown to be modulated by changes in the thickness or the dielectric constant of the
total insulating layer (96). An impedance biosensor for Ara h 1, one of several allergenic proteins
found in peanuts, was also constructed on a gold electrode following immobilization of its anti-
bodies (97). The change in differential capacitance was then monitored, although the change in
charge-transfer resistance showed greater sensitivity.
Although in several cases changes in interfacial capacitances have been shown to be related to
analyte concentrations, changes in the charge-transfer rate generally show greater sensitivity. In
this case, an appropriate antibody molecule such as C-reactive protein (CRP) is anchored on a
SAM whose surface contains a good host molecule such as (R)-lipo-diaza-18-crown-6 (98). The
antibody-immobilized electrode is then exposed to the solution containing the analyte (CRP). As
the electrode surface is progressively modified by more than one step, the charge transfer across
the electrode-electrolyte interface to a redox probe present in the solution becomes increasingly
difficult due to the blocking effect of the SAM, antibodies, and antigens. Usually, a redox probe
such as Fe(CN)6 3−/4− , Ru(NH3 )6 3+/2+ , or a p-benzoquinone/hydroquinone redox pair is used to
monitor the modified electrode’s ability to transfer electrons. The selection of the redox probe
depends on various parameters; thus far, the Fe(CN)6 3−/4− pair has been the most frequently
used probe for a number of reasons. Usually, either the charge-transfer rate or the polarization

resistance Rp is obtained at equilibrium or formal potential (E0 ). This allows the charge-transfer

resistance Rct , measured at E0 , to be compared for different analytes and their concentrations;
these comparisons allowed the construction of an immunosensor for small proteins such as CRP
and ferritin (98). CRP immunosensors have also been constructed through covalent conjuga-
tion of CRP antibodies with 3–mercaptopropionic acid on a three-dimensionally ordered, macro-
porous, gold film–modified electrode (99). Similarly, a p53 protein sensor was constructed through
use of a (R)-lipo-diaza-18-crown-6 SAM (100). Sensors for other proteins, including myelin ba-
sic protein (101) and prostate-specific antigen (102), have been constructed in a similar manner,
except that the polyaniline film rather than the SAMs was used to immobilize respective anti-
bodies. Although in these cases antibodies were used as receptors for the corresponding antigens,
a so-called covalent virus layer obtained by the phage-display technique acts as a receptor for
a 148.2-kDa antibody (103). O’Grady & Parker (104) controlled protein-protein interactions
in the antibody-doped polypyrrole layer by changing the voltage applied to the polymer layer
and by monitoring impedances at different potentials. Physically large analytes such as bacteria
(105, 106), as well as cell deaths (107), have been counted via similar strategies. In fact, sensors
for small analyte molecules such as fluoroquinolone antibiotics (108, 109) and polyamines (110)
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have been constructed on the basis of these principles. Note, however, that the Rct values for the
Fe(CN)6 3−/4− probe did not increase but rather decreased, as was observed in earlier studies in
which the polyamine concentration was increased (111). This peculiar behavior arises from the
positive charges of protonated polyamines captured by calyx[4]crown-5, which facilitates the ap-
proach of probe ions by electrostatic forces for easier electron transfer. Park et al. (61) obtained
similar results for a serotonin sensor that used an (R)-lipo-diaza-18-crown-6 SAM in which the
serotonin molecule captured inside the cavity had a positive charge.
Note that, in addition to the label-free detections described above, analytes have also
been detected after being labeled with an electroactive group such as ferrocene. Mahmoud &
Luong (111) recently reported an assay format based on the immobilization of a thiol-terminated
ferrocene-pepstatin conjugate on a single-walled carbon nanotube/gold nanoparticle–modified
gold electrode. In this format, the alteration of the interfacial properties of the electrode upon
interaction between the HIV-1 protease and the Fc-pepstatin conjugate was monitored by EIS
measurements.
DNA hybridization, single-nucleotide mismatches, and DNA’s interactions with other
molecules remain popular subjects following Barton and colleagues’ (112) comprehensive re-
view on electrochemical DNA hybridization sensors. DNA analysis generally follows the same
protocol as do analyses for the other biosensors described above: DNA’s hybridization on the
electrode leads to a much more crowded surface than that covered by single-stranded DNA. Also,
highly populated negative charges that arise from phosphates linking DNA bases of hybridized
double-stranded DNA render the interface hostile to approaching anionic-probe ion pairs, namely
Fe(CN)6 3−/4− . Such ion pairs modulate the electrode’s capability to transfer electrons to the redox
probe, and Rct values increase significantly at double-stranded DNA–covered electrodes compared
to single-stranded DNA–covered electrodes. This is also true for DNA hybridization at exotic in-
terfaces, such as immiscible liquid-liquid (113) and gold-SiO2 -water (114) interfaces. Interestingly,
the DNA hybridized at the liquid-liquid interface significantly enhanced ion-transfer admittances
(113).
Through the use of appropriate strategies, a target DNA that has a single mismatch with
the probe DNA can be distinguished from its fully complementary target DNA. For example,
differences among the charge-transfer abilities of native B-DNA–covered electrodes and metal
ion–bound M-DNA–covered electrodes in the absence and presence, respectively, of Zn2+ at pH ≥
8.6 allowed unequivocal detection of all eight single-nucleotide mismatches within a 20-mer DNA
sequence (115, 116). A small molecular ligand, naphthyridine-azaquinolone, was also found to bind
to the G-A region of the mismatch. This binding caused significant changes in the structure of the
DNA, which in turn caused changes in the electrochemical properties of the DNA/naphthyridine-
azaquinolone films (117). An alternative approach is to secure just enough space for more efficient
DNA hybridization via a SAM made of cone-shaped dendron that generates mesospacing (average
3.2 nm) on the surface (118). In this case, the single mismatch at the middle of the target DNA chain
was distinguished from that at the end. The dendron-based SAM has an advantage over other thiol-
based SAMs in that the distance between each probe DNA is so well defined as to allow effective
hybridization with much fewer kinks, less nonspecific adsorption, and less crowdedness of probe
DNA molecules; the last problem is to be expected when the probe DNA is immobilized on the
thick forest of thin alkyl thiols. Finally, sensors for DNA-binding drugs have been constructed on
a gold electrode modified with gold nanoparticles (119), and physically adsorbed double-stranded
DNA molecules on polypyrrole nanofibers can act as a spermidine sensor (120).
Label-free aptamer-based sensors employ strategies similar to those of the biosensors described
above. In a label-free aptamer-based sensor, the electrode surface is modified by an aptamer
showing selective binding to a specified analyte; impedance measurements are made before and

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after the electrode is exposed to the solution containing an analyte. Several laboratories have used
this procedure to construct thrombin sensors (121–124). The subject has recently been reviewed
(125, 126).
4. OTHER APPLICATIONS
The electrochemistry community has long been interested in the use of EIS measurements to
solve various complex electrochemical problems. Because this review is intended primarily for
analytical chemists, in the section we compile a short list of recent reports on applications of EIS
measurements to areas other than biosensors. The primary purpose of EIS applications has been
to use impedance data to work out EECs under given experimental conditions, which in turn has
allowed the elucidation of the mechanisms of related reactions.
EIS has been applied to the dissolution of metals (127), corrosion inhibition (128–131), eval-
uation of corrosion rates (132), and corrosion protection by polymer coatings (133). Hardware
requirements (133) and acquisition of corrosion rates from polarization measurements (132) have
recently been reviewed in detail. Another area of interest is the study of complex electrochemical
reactions such as electrochemical synthesis of conducting polymers (134–136) and their product
characterization (137) and degradation (138). The EECs obtained for these reactions from the
impedance data acquired by single-sine or 1-FTEIS methods represent time-averaged results over
relatively long data-acquisition times (134–136); the EECs obtained earlier were recently found to
be significantly different from the those obtained by truly time-resolved 2-FTEIS methods (43, 48).
EIS measurements have also played an important roles in photoelectrochemistry; recent reports in
this area address the modeling of EECs for dye-sensitized solar cells (139–142), characterization of
electron-transport properties (142, 143), properties of semiconductor–conducting polymer inter-
faces (144), and correlations between solar cell performances and EIS results (145). Finally, we give
a few examples of the numerous EIS studies conducted on batteries and fuel cells. These EIS stud-
ies have provided solutions to difficult problems such as (a) the intercalation of Li+ into anode (146)
and cathode (147) materials of rechargeable lithium batteries and (b) the charge-transfer and mass-
transport behaviors of solid oxide (148) and polymer electrolyte membrane (149, 150) fuel cells.
5. CONCLUSIONS
In this review we have described recent progress in EIS measurement techniques, the science
related to the electrified interfaces according to results obtained with new techniques, and novel
interpretations and approaches to solving various electrochemical problems. The FTEIS tech-
niques, particularly 2-FTEIS, provide rich information about electrochemical systems at electri-
fied interfaces, allowing their complete descriptions to be made. The short measurement time
for the FTEIS method permits impedance measurements to be made in real time for many elec-
trochemical systems, which has allowed many complex electrochemical reactions and interfacial
phenomena to be solved. Also, the high data-acquisition rate for EIS spectra should lead to the
effective impedance mapping of electrically heterogeneous surfaces in the not-too-distant future.
Particularly important is the conclusion, obtained from the current expression derived from
the EEC, that the EEC represents a true model for an electrochemical interface and the reaction
taking place thereat. Further, new results on time constants for electrochemical systems, in which
polarization resistances take part in determining them (particularly at high overpotentials), are
significant.
Another important recent development in EIS is its use as a label-free detection tool for many
biosensors. Appropriate surface modification allows the electrode to selectively interact with target
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analytes or to form host-guest complexes; these analytes include large biological compounds such
as proteins, DNA, cells, and trace amounts of heavy metal ions, as well as biological cells and
bacteria. EIS sensitively analyzes the interactions of modified electrodes with analytes, producing
measurable electric signals. The fact that EIS is capable of more sensitive detection than either
voltammetric or amperometric methods is very significant (61, 62). Also, the measurement rate
of 2-FTEIS should enable use of this technique as a detection tool for an array of hundreds of
electrodes on, for example, DNA or other biochips in a short time as long as a reasonably reversible
redox probe is employed.
The new FTEIS techniques are expected to elucidate various unsolved problems in electro-
chemistry. Novel experiments that were thought to be difficult, if not impossible, to perform with-
out the new FTEIS techniques should be explored in order to solve complex problems encountered
during the studies on electrochemical energy conversion, biosensors, and other materials-related
areas.
DISCLOSURE STATEMENT
The authors are not aware of any affiliations, memberships, funding, or financial holdings that
might be perceived as affecting the objectivity of this review.
ACKNOWLEDGMENTS
Our work was supported by the World Class University program funded by the Korea Research
Foundation to the Ulsan National Institute of Science and Technology.
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Anal. Chem. 80:9233–39

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AC03CH10-Park ARI 11 May 2010 12:53

Annu. Rev. Anal. Chem. 2010. 3:207–29 Key Words

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a IHP OHP Diffusion layer b Cd

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Z(ω) = Rs + R p + σ ω−1/2 − j (σ ω−1/2 + 2σ 2 Cd ). (5)

The Warburg impedance is related to σ by the equation

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2. RECENT ADVANCES IN ELECTROCHEMICAL

2.1. New Forms of Electrochemical Impedance Spectroscopy Measurements

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τ(Rs ||Rp)• Cd / τRs • Cd (%)

0.01 0.1 1 10 100

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2.2. Applications of First- and Second-Generation Fourier Transform

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2.3. Impedance Imaging and Time-Resolved Measurements

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Rtip Rexit AFM

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3. ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY

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