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A Compact Current Conveyor CMOS Potentiostat

Circuit for Electrochemical Sensors


Alexandre Kennedy Pinto Souza Carlos Augusto de Moraes Cruz Greicy Costa Marques
Graduate Program in Electrical Graduate Program in Electrical Department of Electronics and
Engineering - Department of Engineering – Department of Computation
Electronics and Computation Electronics and Computation, Federal University of Amazonas
Federal University of Amazonas Federal University of Amazonas Manaus, AM, Brazil
Manaus, AM, Brazil Manaus, AM, Brazil greicymarques@gmail.com
alexandre.akp7@gmail.com agscruz@hotmail.com

Luís Smith Oliveira de Castro Thiago Brito Bezerra


Graduate Program in Electrical Graduate Program in Electrical
Engineering - Department of Engineering -- Department of
Electronics and Computation Electronics and Computation
Federal University of Amazonas Federal University of Amazonas
Manaus, AM, Brazil Manaus, AM, Brazil
brito tb@gmail com
luisfne@gmail.com

Abstract— In this work, a new compact CMOS potentiostat microsystems used for monitoring and control of organic
circuit for electrochemical sensors is proposed. Integrated compounds, such as oxygen, glucose, and the cholesterol
Potentiostats in CMOS technology are usually found in the present in human blood [1, 2, 3, 7]. Portable devices require
literature designed with operational amplifiers performing both electronic systems with high integration and low power
the electrochemical sensor bias and signal readout. In order to consumption for proper operation [1].
present alternative circuitry, a new potentiostat topology
composed of a two-stage operational amplifier and a current Electrochemical systems comprise an assembly formed of
conveyor circuit is proposed. The current conveyor is employed a sensor device, or electrochemical cell (ECC), that performs
to perform the bias signal readout of an electrochemical cell with the detection of chemical species being sensitized due to
three electrodes. Simulations and experimental results of a reactions in chemical compounds, and an electronic circuit
discrete circuit version show that the proposed potentiostat that performs the ECC bias and signal readout [1, 2, 4]. In this
topology yields results compliant with those of classical topologies work, the sensor device of interest is a three-electrodes-ECC
presented in the literature. and the electronic circuit that performs the ECC bias and
signal readout is a potentiostat. The scheme presented in Fig. 1
Keywords— Eletrochemical Sensor; Potentiostat; Current shows a basic electrochemical system diagram employing a
Conveyor; Amperometric Sensor. three electrode ECC, a potentiostat circuit and their basic
connections.
I. INTRODUCTION
Electrochemical sensors have great potential for
applications in many areas requiring electrochemical analyzes
including the food industry, environmental monitoring, and
biotechnology [1, 2, 3], they are also employed to researches
related to the field of proteomics and genomics [2, 3, 4].
Electrochemical Sensors have good sensitivity and selectivity
in detection of many chemical species and organic
compounds, such as oxygen, glucose [2, 3, 5, 6, 7], and toxic
metals. These sensors essentially respond to a certain amount
of a chemical compound or analyte of interest, generating
electrical signals currents being proportional to concentration
of chemical species in analysis, characterized by a charge
transfer ion solution, through oxidation and reduction
reactions [2, 3, 8]. There are great interests in the
development of portable devices that include electrochemical
sensors and electronic systems in the same equipment [1].
Some examples of handheld devices, perform the detection of
heavy metals in natural waters [10] and implantable Fig.1 - Basic Electrochemical System

978-1-7281-2109-3/19/$31.00 © 2019 IEEE


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Potentiostat circuits are usually implemented with three II. THE PROPOSED POTENTIOSTAT TOPOLOGY
stage operational amplifiers in its composition [1, 7, 10], as
shown in Fig. 2 and Fig. 3. The electrochemical systems
The three electrode electrochemical cell, in which the
presented in Fig. 2 and Fig. 3 are in the grounded WE, and
electrochemical analyzes are performed, is composed of a
grounded CE configurations, respectively[10]. The analyzes
working electrode (WE), in which the redox reaction of the
and electrochemical characterization using these types of
chemical analyte of interest takes place, a reference electrode
electrochemical systems are performed by different
(RE), which is used to perform the measurement of the electric
voltammetric techniques applied to the potentiostat circuit,
potential of the chemical solution, or analyte, and the counter
including: squarewave voltammetry, differential pulse
electrode (CE), which is an inert conductor material with the
voltammetry, and cyclic voltammetry [2]. With regard to
task of providing an electric current for the cell [6,12]. The
circuit topology improvements, even the most recent
dummy resistor-capacitor equivalent electric circuit model of
developments in the field [2, 3, 7, 8] present few or none
the electrochemical cell [12] employed for the simulations, the
alternative circuitry.
results of which results are presented in this work, and its
In this paper, a new compact potentiostat circuit topology symbol indicating the electrodes that compose the ECC are
is proposed, making use of an operational amplifier and a shown in Fig. 4 (a) and (b) respectively.
current readout circuit implemented with a circuit structure of
The proposed potentiostat topology, described in this
first generation current conveyor. The proposed potentiostat
section, connected to the electrochemical cell model shown in
circuit was designed to operate in the grounded WE
Fig. 4, and arranged in the grounded WE configuration, was
configuration.
evaluated using the cyclic voltammetry method. In order to
The paper is organized as follows: Section II provides compare its operation with the previous topologies presented
details of the proposed potentiostat topology. Section III in the literature, the cyclic voltammetry method was also
presents the simulation and discrete circuit experimental applied to the potentiostat in Fig. 2. The potentiostat topology
results. Conclusions are summarized in Section IV. proposed in this paper, herein called electrochemical
potentiostat proposed (EPproposed), and its circuit components
are shown in Fig. 5.
The proposed potentiostat EPproposed is composed of an
operational amplifier (AOP), and a circuit which performs the
transport of current from the electrochemical cell to the output
of the potentiostat, called First-Generation Current Conveyor
(CCI), as shown in Fig. 5.

Fig 2 - Potentiostat Grounded (WE) configuration

(a) (b)
Fig. 4: Model of the Electrochemical Cell: (a) Schematic circuit of the dummy
resistor-capacitor cell and (b) Electrochemical Cell symbol

Fig. 3- Potentiostat grounded (CE) configuration

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AOP input, that is the gate terminal of the transistor M4. The
feedback signal is then being applied to the inverting input of
the AOP through the connection of the reference electrode of
the dummy cell capacitor-resistor to the gate terminal of
transistor M3. The difference between the Vin and RE signals
is then amplified by the first and second stages of the AOP
circuit. The second stage, that is the output stage of the AOP
circuit, is the one composed of the transistors M7 and M8. The
output signal of the second stage is applied to the ECC
counter-electrode terminal, CE of the resistor-capacitor
dummy cell, providing thus the necessary current through the
cell. Regarding the second stage, it was implemented
dimensioning the transistors M7 and M8 so that they could
provide the necessary current needed to meet the requirements
of the electrochemical cell.
TABLE I- DIMENSIONS OF THE POTENTIOSTAT TRANSISTORS
TRANSISTOR TYPE W [μm] L [μm]

MP PMOS 1.0
M1, M3, M4 NMOS 2.0
M2 NMOS 4.0
M5, M6 PMOS 4.0
0.18 um
M7, M9, M11
NMOS 20.0
M14, M16, M17
M8, M10, M12
PMOS 40.0
M13, M15, M18

The AOP is designed to satisfy two basic requirements


Fig. 5. The proposed circuit (EPproposed) have been involving electrochemical systems embedding potentiostats.
designed and simulated in a standard 0.18 μm CMOS The first is to control the electrical potential that arises
technology. In this technology, as the bias swing is from 0.0 V between the ECC reference electrode and the ECC working
to 1.8 V, the reference voltage GND, in this case, is 0.9 V, electrode through the Vin input signal [10], and the second it
VDD/2 that can be derived from VDD. to supply the ECC current through the AOP output terminal
The AOP is a two stage operational amplifier, designed Vo that is connected to the ECC counter-electrode [10].
with an output-stage that allows the control of the current One of the main functions of the potentiostat circuit is the
flowing though itself, that is the same current flowing through ability to measure the electrical current flowing between the
the electrochemical cell. The MOS transistor dimensions ECC counter-electrode and its working electrode [10]. To
employed in both the AOP and the CCI- circuits are given in implement such a functionality, a CMOS version of the first
Table I. generation current conveyor circuit was employed. The
To perform the measurement of the current flowing operation of this circuit is such that applying an input voltage
through the electrochemical cell, the CCI- circuit was to the Y input terminal, a potential of the same level appears at
connected to the ECC working electrode, providing a low input terminal X. Similarly an input current being forced
impedance level for this circuit node. The CCI- circuit also through the X terminal results in a current of the same
performed transport of the current flowing through the magnitude flowing through the terminal Y, and the CCI-
electrochemical cell to the Vout terminal, which is connected circuit transports a current of the same level to its Z terminal
to the resistor Rout. [2]. Therefore, the CCI- circuit will work to impose a current
to the output resistance Rout through its Z terminal of the
In the Potentiostat topology shown in Fig. 2, the same level of that flowing through the ECC.
transimpedance amplifier forces a virtual ground to the WE
terminal and at the same time generates an output voltage that The voltage at the CCI- circuit Y terminal is set to its X
is linearly proportional to the current flowing through the terminal, regardless of the current level that is imposed
electrochemical cell, providing thus a way of measuring the through the X terminal [10]. In this case, the CCI- circuit Y
ECC current. terminal is connected to the ground, forcing therefore a virtual
ground level at its X terminal that is connected to the ECC
The proposed potentiostat circuit topology (EPproposed
Fig.5) receives the Vin voltage signal on the non-inverting

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working electrode. Such a connection results in a low
impedance level at the ECC working electrode.
The current flowing through the X terminal is then
conveyed to the Z node, the output current is then converted
into the output voltage Vout, through the resistance Rout, that
is linearly proportional do the current flowing through the
ECC. Resulting thus in an indirect quantitative measure of the
current flowing through the ECC. Such a function,
implemented by the CCI- circuit, resembles the
transimpedance amplifier shown in Fig 3, connected to the
ECC working electrode performing the conversion current into
voltage. Therefore, the proposed potentiostat circuit topology Figure 6: Input Triangular wave applied to EPproposed e EPconventional
embeds all the requirements necessary for the proper operation
of an electrochemical system [1] [6].

III. SIMULATIONS AND EXPERIMENTAL RESULTS


In order to demonstrate the effectiveness of the proposed
EPproposed topology and to compare its performance with the
conventional topology shown in Fig. 2, hereinafter referred to
as EPconventional, simulations of both circuits using the cyclic
voltammetry method were performed. The dummy resistor-
capacitor cell shown in Fig. 4 (a) was employed in both
simulations, with EPproposed and EPconventional. The proposed
circuit design is the same as that presented in the previous
section. The load resistance RL of the EPconventional circuit, in
Fig. 2, has the same value as the load resistance Rout used
with the EPproposed circuit that is of 1.00 kȍ. The triangular
voltammetry wave called cyclic voltammetry (CV) was
applied to the two circuits according to the methodology
described in [1] and [11].
The triangular input signal employed in the simulations
with the EPproposed and EPconventional circuits is presented in Fig.
6. The triangular input signal has the following characteristics:
VPP = 1.6 V, f = 1 kHz, VLOW = -0.8 V, and VHIGH = 0.8 V.
The current generated in the electrochemical dummy
resistor-capacitor cell with both EPproposed and EPconventional
circuits for the described simulation configuration are
presented as Icell_ EPproposed in Fig. 7 (a), and
Icell_EPconventional in Fig. 7 (c). These results demonstrate that
the proposed potentiostat circuit yields results very similar to
those yielded by potentiostat topologies already well
established in the literature.
As expected, the output voltage is linearly proportional to
the current flowing through the dummy ECC in both circuits
EPproposed and EPconventional as presented in Fig. 8 (a) and (b),
Vout_EPproposed and Vout_ EPconventional, respectively. In order
to evaluate part of the distortions introduced by each circuit
topology when compared to their real delivered output
voltage, the ideal output voltage for both circuits are also
shown. The ideal output voltage is determined by multiplying
the current through each dummy ECC circuit, Icell_ EPproposed
and Icell_ EPconventional, by the 1.00 kŸ load resistance present Fig. 7: (a) Current flowing through ECC in EPproposed; (b) current flowing
in each circuit. These results show the effectiveness of the through RL of EPproposed; and (c) Current flowing through ECC in
proposed compact potentiostat. EPconventional.

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Vout_EPproposed Ideal_Vout_EPproposed

Vout_EPconventional Ideal_Vout_EPconventional

Fig. 8: Output voltage signal of: (a) EPproposed; and (b) EPconventional.

Although the dummy resistor-capacitor ECC circuit model


is very useful to evaluate some important characteristics of the
potentiostat circuits, as shown above. However, it has serious
limitations to emulate a real chemical oxidation-reduction
reaction cycle, and therefore it is not possible to represent a
true cyclic voltammetry plot with such a model. Therefore, in
order to overcome the limitations to further evaluate the new
potentiostat topology, while the integrated version is being
fabricated, a discrete version of the proposed circuit was
implemented.
The discrete version of the proposed potentiostat was
implemented in a printed circuit board (PCB), shown in Fig. 9
(a) and (b), with individual NMOS and PMOS transistors
found in the CI 4007. The implemented EPproposed PCB was
then connected to a standard electrochemical cell to measure
the oxidation-reduction reaction of a potassium ferricyanide
analyte solution with a concentration of 5 mmol.L-1 for
different scan rate, the setup of which is shown in Fig. 10.
The cyclic voltammetry plot for the employed analyte
solution for different scan rate delivered by the proposed
potentiostat circuit is presented in Fig. 11. The cyclic
voltammetry plot for the employed analyte solution for
different scan rate delivered by the commercial potentiostat
PGSTAT302N is presented in Fig. 12. These results are
compliant with those presented in the literature [1-8]. Despite
the limitations of such an approach with a discrete PCB
circuit, the yielded results were useful to confirm the
effectiveness of the proposed potentiostat topology.
In the near future, the preliminary experimental results will
be compared to those yielded by an integrated version of the
proposed potentiostat topology, implemented in the TSMC Fig. 9: Discrete EPproposed circuit implementation with CD4007: (a)
standard 6-metal 1-poly 0.18 μm CMOS technology. circuit schematic; (b) PCB connections and assembled circuit;

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IV. CONCLUSIONS
A new compact potentiostat circuit for electrochemical
sensors was proposed in this work. The EPproposed circuit
employs a single operational amplifier together with a current
conveyor circuit to both bias the electrochemical cell and
measure its current. The correct operation of the proposed
potentiostat was evaluated through simulations and
experimental results. The simulations were carried out with a
dummy resistor-capacitor model to emulate the behavior of a
real electrochemical cell. The experimental evaluation was
performed with a discrete version of the EPproposed circuit.
Comparisons of the simulation results with those yielded by
different potentiostat topologies found in the literature, as well
as, the experimental cyclic voltammetry plot results confirm
the effectiveness of proposed potentiostat topology.

ACKNOWLEDGMENT
This research, according for in Article 48 of Decree nº
Fig. 10: Setup Test of the EPproposed Circuit with Electrochemical
6.008/2006, was funded by Samsung Electronics of Amazonia
Cell.
Ltda, under the terms of Federal Law nº 8.387/1991, through
agreement nº 004, signed with CETELI/UFAM.
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