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Current-Mirror-Based Potentiostats for Three-Electrode Amperometric Electrochemical Sensors

Current-Mirror-Based Potentiostats for Three-Electrode Amperometric Electrochemical Sensors

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We present a new circuit topology for potentiostats that interface with three-electrode amperometric electrochemical sensors. In this new topology, a current-copying circuit, e.g., a current mirror, is placed in the sensor current path to generate a mirrored image of the sensor current. The mirrored image is then measured and processed instead of the sensor current itself. The new potentiostat topology consumes very low power, occupies a very small die area, and has potentially very low noise. These characteristics make the new topology very suitable for portable or bioimplantable applications.
We present a new circuit topology for potentiostats that interface with three-electrode amperometric electrochemical sensors. In this new topology, a current-copying circuit, e.g., a current mirror, is placed in the sensor current path to generate a mirrored image of the sensor current. The mirrored image is then measured and processed instead of the sensor current itself. The new potentiostat topology consumes very low power, occupies a very small die area, and has potentially very low noise. These characteristics make the new topology very suitable for portable or bioimplantable applications.

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IEEE TRANSACTIONS ON CIRCUITS AND SYSTEMSI: REGULAR PAPERS, VOL. 56, NO. 7, JULY 2009 1339
Current-Mirror-Based Potentiostatsfor Three-Electrode AmperometricElectrochemical Sensors
Mohammad Mahdi Ahmadi
 , Member, IEEE 
, and Graham A. Jullien
 , Life Fellow, IEEE 
 Abstract—
We present a new circuit topology for potentiostatsthat interface with three-electrode amperometric electrochemicalsensors. In this new topology, a current-copying circuit, e.g., a cur-rent mirror, is placed in the sensor current path to generate a mir-roredimageofthesensorcurrent.Themirroredimageisthenmea-sured and processed instead of the sensor current itself. The newpotentiostat topology consumes very low power, occupies a verysmall die area, and has potentially verylow noise. Thesecharacter-istics make the new topology very suitable for portable or bioim-plantable applications. In order to demonstrate the feasibility of the new topology, we present the results of a potentiostat circuitimplemented in a 0.18- m CMOS process. The circuit convertsthe sensor current to a frequency-modulated pulse waveform, forwhich the time difference between two consecutive pulses is in-versely proportional to the sensor current. The potentiostat mea-sures the sensor current from 1 nA to 1 A with better than 0.1%of accuracy. It consumes only 70 W of power from a 1.8-V supplyvoltage and occupies an area of 0.02 mm
.
 Index Terms—
Amperometric sensor, current mirror, electro-chemical sensor, frequency compensation, potentiostat.
I. I
NTRODUCTION
A
THREE-ELECTRODE amperometric electrochemicalsensor, shown in Fig. 1, consists of a working electrode(WE), on which an electrochemical reaction takes place; areference electrode (RE), which is used to measure the solutionpotential; and a counter electrode (CE), which is an inertconductor supplying the current required for electrochemicalreaction at WE [1].As illustrated in Fig. 1, potentiostat is an electronic instru-ment that controls the potential difference between WEs andREs at a desired cell potentialby injecting the properamount of current into CE [1].In this paper, we present a new circuit topology to realize apotentiostat. The new topology is based on the use of a cur-rent-copying circuit (e.g., a current mirror), in the path of the
Manuscript received February 25, 2008; revised June 30, 2008. First pub-lished September 19, 2008; current version published July 01, 2009. This work was supported in part by the Alberta Informatics Circle of Research Excel-lence, by Micronet R&D, and by the Natural Sciences and Engineering Re-search Council of Canada. This paper was recommended by Associate EditorA. van Schaik.M. M. Ahmandi is with Sound Design Technologies Ltd., Burlington, ONL7L 5P5, Canada (e-mail: mmahmadi@ieee.org).G. Jullien is with the Department of Electrical and Computer Engineering,University of Calgary, Calgary, AB T2N 1N4, Canada.Color versions of one or more of the figures in this paper are available onlineat http://ieeexplore.ieee.org.Digital Object Identifier 10.1109/TCSI.2008.2005927Fig. 1. Conceptual drawing of a three-electrode amperometric electrochemicalsensor and a potentiostat.
sensor current, to generate a mirrored image of the sensor cur-rent and then to process the mirrored current instead of thesensor current. To better illustrate the advantages of the newtopology over existing topologies, in Section II, we review thebasicstructureofthepriorpublishedpotentiostattopologiesandbriefly explain their advantages and limitations. In Section III,we present the new topology with a few examples of its circuitrealization.InSectionIV,wediscusstheoperationofourimple-mented potentiostat circuit along with a detailed analysis of itsfrequencycompensation.InSectionV,weprovidethemeasure-ment results of our potentiostat circuit and conclude this paperin Section VI.II. R
EVIEW OF THE
E
XISTING
P
OTENTIOSTAT
T
OPOLOGIES
1
Basically, a potentiostat has two main functions: 1) control-ling the potential difference between WE and RE and 2) mea-suring the current flowing between WE and CE. Each of thesefunctions can be realized with a few different circuit configura-tions, as summarized in the following subsections.
 A. Potential-Control Configurations
The cell potential can be controlled in three configurations[3]: grounded WE; grounded RE; and grounded CE. The firsttwo configurations are electrically the same; thus, in fact, thereare really only two different configurations [3].The grounded-WE configuration is the most popular config-uration. Fig. 2 shows the basic implementation of this config-uration. As shown, WE is kept at the ground potential, and anoperational amplifier, called the control amplifier, controls the
1
Part of the introductory material presented in this section is taken from [2,Ch. 13]. It is included for completeness.1549-8328/$25.00 © 2009 IEEE
 
1340 IEEE TRANSACTIONS ON CIRCUITS AND SYSTEMSI: REGULAR PAPERS, VOL. 56, NO. 7, JULY 2009
Fig. 2. Potential control using the grounded-WE configuration.Fig. 3. Potential control using the grounded-CE configuration.
cell current such that the cell potential is kept at its de-sired preset potential .The grounded-CE configuration has recently been explored[3] as an alternative for potential control. The basic realizationof this configuration is shown in Fig. 3. Clearly, this configura-tion is more complex and requires more components; thus, it ismore vulnerable to component mismatches. However, in casesin which shielding and screening of the WE connection fromexternal electromagnetic interference (EMI) are difficult to im-plement, using a grounded-CE configuration may improve thecurrent measurement [3].
 B. Current Measurement Configurations
A few different configurations exist for measuring the cellcurrent . Here, the current measurement approaches are ex-plained for potentiostats that use a grounded-WE configurationfor potential control; however, many of these approaches can beadopted for potentiostats using the grounded-CE configuration.The use of a transimpedance amplifier is probably the mostpopular approach for current measurement. In this approach,as shown in Fig. 4, a transimpedance amplifier forces a vir-tual ground at WE, and at the same time, it generates an outputvoltage that is linearly proportional to .This approach has a few advantages [4], [5]. First, it is rel-atively simple to realize. Second, very small currents can bemeasured by switching the current measurement resistorto higher values. Third, both potential and current are measuredwith reference to ground.The circuit has three major drawbacks [3]–[5]. First, becauseWE is not connected to a true ground, if its connection to thepotentiostat is not carefully shielded, it can pick up environ-mentalnoiseandinterference,particularlyhigh-frequencyEMI.
Fig. 4. Current measurement using a transimpedance amplifier.Fig.5. Cellpotentialandcurrentdirectionin(a)O -basedand(b)H O -basedglucose sensors.
This induced noise passes through and produces signifi-cant noise levels at the output of the transimpedance amplifier.Second,theinputresistanceofthetransimpedanceamplifierbe-haves inductively [3]–[5]. In other words, at low frequencies,it exhibits a very small impedance; however, as frequency in-creases, the input impedance increases due to the roll-off in theopen-loop gain of the transimpedance amplifier. Since the inputimpedanceisinserieswiththeelectrochemicalcell,whichitself has very large capacitive components, the inductive behavior of the input impedance increases the possibility of instability andoscillation in the potential-control loop.The third drawback of the circuit appears while working withsingle supply voltages. This problem can be better explainedwith reference to two examples.The two most widely used electrochemical glucose biosen-sors are oxygen-electrode-based (O -based) and hydrogen-per-oxide-electrode-based (H O -based) sensors [6]. In O -basedglucosesensors,thecellpotential shouldbetypicallyabout600 mV (with reference to a standard Ag/AgCl RE), and theoutput current of the sensor is the result of the reduction of oxygen at the surface of WE [6]. In other words, as shown inFig. 5(a), RE (in this case, a Ag/AgCl electrode) is required tobemaintainedatapotentialofabout600mVabovethepotentialof WE, where the direction of the sensor current is from CE toWE. This means that the output of thetransimpedance amplifiermust move below the ground potential, which is not possible insingle-supply-voltage circuits.For the HO -based glucose sensor, the situation is reversed,but the circuit still suffers from the single-supply-voltage issue.In this case, the sensor current is the result of the oxidation of hydrogen peroxide at the surface of WE, and so, as shown inFig. 5(b), the current flows from WE to CE [6]. However, in this
 
AHMADI AND JULLIEN: CURRENT-MIRROR-BASED POTENTIOSTATS FOR SENSORS 1341
Fig. 6. Potentiostat, designed using a current conveyor, for a two-electrodeelectrochemical sensor.
case, the cell potential must be typically about 700 mV(assuming a Ag/AgCl RE), meaning that the potential of REmust be kept about 700 mV below the potential of WE, whichis again not possible with a single positive supply because WEis held at the lowest potential in the circuit, which is the groundpotential.As a result, with single-supply-voltage circuits, the potentialofthenoninvertinginputofthetransimpedanceamplifiershouldbe raised to an appropriate voltage, depending on the applica-tion.Thisagainpresentsanotherissuethatthemeasuredvoltageat the output of the transimpedance amplifier is no longer refer-enced to ground [2].Since very large resistors are difficult to realize in integrated-circuit form, the transimpedance amplifier is usually realizedwith switched-capacitor circuits [7]. In more complicated re-alizations, the sensor current can be injected directly to a cur-rent-input analog-to-digital converter [8] or to a current-inputdelta–sigma modulator [9], [10].Using a current conveyor is a similar approach for currentmeasurement, which is widely used for two-electrode sensors[11]–[14]. As shown in Fig. 6, in this approach, WE is held ata virtual ground potential (a low-impedance node), and, insteadof converting directly to voltage, it is conveyed from WE toa high-impedance node (X) and is then measured with any of the approaches explained earlier. It is also possible to convertthe sensor current to variables other than voltage, such as time[11] or frequency [15].Another approach for current measurement is to insert a re-sistor in the current path in WE and measure the voltage devel-oped across that resistor [4]. The voltage can also be amplifiedbefore the measurement. Two realizations of this approach areshown in Fig. 7. Clearly, WE is no longer at the ground poten-tial,butitspotentialchanges,dependingon .Thus,forproperpotential control, the potential is measured and fed back to thecontrol amplifier.This approach is more complex than using a transimpedanceamplifier and requires more active and passive components. Asa result, it is noisier and more vulnerable to mismatch betweenthe components. It also has noise and interference pickup issuesat WE. However, it is similarly capable of measuring very smallcurrents. Also, both current and voltage are measured with ref-erence to ground.Yet, another approach for current measurement is to insert aresistor in the current path in CE and measure the voltage gen-erated across that resistor [5]. Fig. 8 shows this approach. As
Fig. 7. Current measurement using an inserted resistor in the current path atWE.
shown, an instrumentation amplifier measures the voltage gen-erated across . Similar to the previous approach, this ap-proach suffers from mismatch in the components; however, itdoes have a few interesting advantages.First, because WE is connected to a true ground potential,it is very insensitive to noise and interference pickup. Second,since, excluding the control amplifier, there is no additional ac-tive component in the control feedback loop, this circuit hasbetter stability than the previous circuits. Third, both measuredvoltage and current are referenced to ground.The last two approaches do not have the problem that thefirst approach has when working with a single positive voltage.However, these approaches suffer from another issue: As thesensor current increases, the voltage drop across increases,which decreases the headroom for the voltage swing at CE.III. N
EW
P
OTENTIOSTAT
T
OPOLOGY
The idea behind the new topology is to interpose a circuit inthe path of the sensor current in order to generate a copy of thesensor current and then measure the copied current instead of the sensor current directly.Fig. 9 shows an implementation of this approach. The op-eration of the circuit can be explained as follows. The opera-tional amplifier and transistor generate a feedback loopthrough which the potential of RE is stabilized at the desired. Since the circuit is intended to be used in integrated cir-cuits, it is possible to very closely match and . Sinceboth transistors have the same gate-to-source voltage, the cur-rent of is copied in . An issue, however, is the currentmismatch in and due to channel-length modulation inthose transistors. However, we can minimize this effect by in-creasing the channel length of those transistors and/or using ad-vanced current-mirror topologies such as cascode or regulatedcascade (gain-boosted) circuits.This potentiostat circuit has important advantages. First, WEis connected to a true ground potential, making it insensitive tonoise and interference pickup.Second, the circuit potentially generates very low noise be-causeitusesfeweractiveandpassivecomponentsformeasuring

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