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A Compact Current Conveyor CMOS Potentiostat Circuit for Electrochemical Sensors Abstract— In this work, a new compact CMOS potentiostat circuit for electrochemical sensors is proposed. Integrated Potentiostats in CMOS technology are usually found in the literature designed with operational amplifiers performing both the electrochemical sensor bias and signal readout. In order to present alternative circuitry, a new potentiostat topology composed of a two-stage operational amplifier and a current conveyor circuit is proposed. The current conveyor is employed to perform the bias signal readout of an electrochemical cell with three electrodes. Simulations and experimental results of a discrete circuit version show that the proposed potentiostat topology yields results compliant with those of classical topologies presented in the literature. Keywords— Eletrochemical Sensor; Potentiostat; Current Conveyor; Amperometric Sensor. 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 microsystems used for monitoring and control of organic compounds, such as oxygen, glucose, and the cholesterol present in human blood [1, 2, 3, 7]. Portable devices require electronic systems with high integration and low power consumption for proper operation [1]. Electrochemical systems comprise an assembly formed of a sensor device, or electrochemical cell (ECC), that performs the detection of chemical species being sensitized due to reactions in chemical compounds, and an electronic circuit that performs the ECC bias and signal readout [1, 2, 4]. In this work, the sensor device of interest is a three-electrodes-ECC and the electronic circuit that performs the ECC bias and signal readout is a potentiostat. The scheme presented in Fig. 1 shows a basic electrochemical system diagram employing a three electrode ECC, a potentiostat circuit and their basic connections. Fig.1 - Basic Electrochemical System Carlos Augusto de Moraes Cruz Graduate Program in Electrical Engineering – Department of Electronics and Computation, Federal University of Amazonas Manaus, AM, Brazil agscruz@hotmail.com Greicy Costa Marques Department of Electronics and Computation Federal University of Amazonas Manaus, AM, Brazil greicymarques@gmail.com Alexandre Kennedy Pinto Souza Graduate Program in Electrical Engineering - Department of Electronics and Computation Federal University of Amazonas Manaus, AM, Brazil alexandre.akp7@gmail.com Thiago Brito Bezerra Graduate Program in Electrical Engineering -- Department of Electronics and Computation Federal University of Amazonas Manaus, AM, Brazil brito tb@gmail com Luís Smith Oliveira de Castro Graduate Program in Electrical Engineering - Department of Electronics and Computation Federal University of Amazonas Manaus, AM, Brazil luisfne@gmail.com 978-1-7281-2109-3/19/$31.00 © 2019 IEEE Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. Restrictions apply. Potentiostat circuits are usually implemented with three stage operational amplifiers in its composition [1, 7, 10], as shown in Fig. 2 and Fig. 3. The electrochemical systems presented in Fig. 2 and Fig. 3 are in the grounded WE, and grounded CE configurations, respectively[10]. The analyzes and electrochemical characterization using these types of electrochemical systems are performed by different voltammetric techniques applied to the potentiostat circuit, including: squarewave voltammetry, differential pulse voltammetry, and cyclic voltammetry [2]. With regard to circuit topology improvements, even the most recent developments in the field [2, 3, 7, 8] present few or none alternative circuitry. In this paper, a new compact potentiostat circuit topology is proposed, making use of an operational amplifier and a current readout circuit implemented with a circuit structure of first generation current conveyor. The proposed potentiostat circuit was designed to operate in the grounded WE configuration. The paper is organized as follows: Section II provides details of the proposed potentiostat topology. Section III presents the simulation and discrete circuit experimental results. Conclusions are summarized in Section IV. II. THE PROPOSED POTENTIOSTAT TOPOLOGY The three electrode electrochemical cell, in which the electrochemical analyzes are performed, is composed of a working electrode (WE), in which the redox reaction of the chemical analyte of interest takes place, a reference electrode (RE), which is used to perform the measurement of the electric potential of the chemical solution, or analyte, and the counter electrode (CE), which is an inert conductor material with the task of providing an electric current for the cell [6,12]. The dummy resistor-capacitor equivalent electric circuit model of the electrochemical cell [12] employed for the simulations, the results of which results are presented in this work, and its symbol indicating the electrodes that compose the ECC are shown in Fig. 4 (a) and (b) respectively. The proposed potentiostat topology, described in this section, connected to the electrochemical cell model shown in Fig. 4, and arranged in the grounded WE configuration, was evaluated using the cyclic voltammetry method. In order to compare its operation with the previous topologies presented in the literature, the cyclic voltammetry method was also applied to the potentiostat in Fig. 2. The potentiostat topology 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 Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. Restrictions apply. Fig. 5. The proposed circuit (EPproposed) have been designed and simulated in a standard 0.18 μm CMOS technology. In this technology, as the bias swing is from 0.0 V to 1.8 V, the reference voltage GND, in this case, is 0.9 V, VDD/2 that can be derived from VDD. The AOP is a two stage operational amplifier, designed with an output-stage that allows the control of the current flowing though itself, that is the same current flowing through the electrochemical cell. The MOS transistor dimensions employed in both the AOP and the CCI- circuitsare given in Table I. To perform the measurement of the current flowing through the electrochemical cell, the CCI- circuit was connected to the ECC working electrode, providing a low impedance level for this circuit node. The CCI- circuit also performed transport of the current flowing through the electrochemical cell to the Vout terminal, which is connected to the resistor Rout. In the Potentiostat topology shown in Fig. 2, the transimpedance amplifier forces a virtual ground to the WE terminal and at the same time generates an output voltage that is linearly proportional to the current flowing through the electrochemical cell, providing thus a way of measuring the ECC current. The proposed potentiostat circuit topology (EPproposed Fig.5) receives the Vin voltage signal on the non-inverting 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 0.18 um M1, M3, M4 NMOS 2.0 M2 NMOS 4.0 M5, M6 PMOS 4.0 M7, M9, M11 M14, M16, M17 NMOS 20.0 M8, M10, M12 M13, M15, M18 PMOS 40.0 The AOP is designed to satisfy two basic requirements involving electrochemical systems embedding potentiostats. The first is to control the electrical potential that arises between the ECC reference electrode and the ECC working electrode through the Vin input signal [10], and the second it to supply the ECC current through the AOP output terminal Vo that is connected to the ECC counter-electrode [10]. One of the main functions of the potentiostat circuit is the ability to measure the electrical current flowing between the ECC counter-electrode and its working electrode [10]. To implement such a functionality, a CMOS version of the first generation current conveyor circuit was employed. The operation of this circuit is such that applying an input voltage to the Y input terminal, a potential of the same level appears at input terminal X. Similarly an input current being forced through the X terminal results in a current of the same magnitude flowing through the terminal Y, and the CCI- circuit transports a current of the same level to its Z terminal [2]. Therefore, the CCI- circuit will work to impose a current to the output resistance Rout through its Z terminal of the same level of that flowing through the ECC. The voltage at the CCI- circuit Y terminal is set to its X terminal, regardless of the current level that is imposed through the X terminal [10]. In this case, the CCI- circuit Y terminal is connected to the ground, forcing therefore a virtual ground level at its X terminal that is connected to the ECC Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. Restrictions apply. 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 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 k . 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 k load resistance present in each circuit. These results show the effectiveness of the proposed compact potentiostat. Fig. 7: (a) Current flowing through ECC in EPproposed; (b) current flowing through RL of EPproposed; and (c) Current flowing through ECC in EPconventional. Figure 6: Input Triangular wave applied to EPproposed e EPconventional Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. Restrictions apply. 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 standard 6-metal 1-poly 0.18 μm CMOS technology. Fig. 9: Discrete EPproposed circuit implementation with CD4007: (a) circuit schematic; (b) PCB connections and assembled circuit; Vout_EPproposed Ideal_Vout_EPproposed Vout_EPconventional Ideal_Vout_EPconventional Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. Restrictions apply. Fig. 10: Setup Test of the EPproposed Circuit with Electrochemical Cell. Fig. 11: Oxidation-Reduction Reaction Cycle of the 5 mmol.L-1 Potassium Ferricyanide Solution by EPproposed Circuit. Fig. 12: Oxidation-Reduction Reaction Cycle of the 5 mmol.L-1 Potassium Ferricyanide Solution by PGSTAT302N Potentiostat. 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 6.008/2006, was funded by Samsung Electronics of Amazonia Ltda, under the terms of Federal Law nº 8.387/1991, through agreement nº 004, signed with CETELI/UFAM. REFERENCES [1] M. M. Ahmadi and G. A. Jullien, , K. Iniewski, Ed., “Circuits for amperometric electrochemical sensors,” in VLSI Circuit Design for Biomedical Applications. Norwood, MA: Artech House, 2008. [2] J. Kim, H.Kuo.“A 1.2V Low-Power CMOS Chopper-Stabilized Analog Front-End IC for Glucose Monitoring”. IEEE SENSORS JOURNAL, Sep. 2016. [3] A. Khandaker, A. Mamun, S. K. Islam, D.K. Hensley and N. McFarlane. “A Glucose Biosensor Using CMOS Potentiostat and Vertically Aligned Carbon Nanofibers”. IEEE TRANSACTIONS ON BIOMEDICAL CIRCUITS AND SYSTEMS. AUG. 2016. [4] M. Kimura , H. Fukushima, Y. Sagawa, K. Setsu, H. Hara, and S.Inoue Ed., “An integrated Potentiostat With an Eletrochemical Cell Using Thin-Film Transistors,” IEEE Transaction Electron Devices, vol. 56, No 9, 2009. [5] L. Zuo, S. K. Islam, I. Mahub and F. Quaiyum,“A Low-Power 1-V Potentiostat for Glucose Sensors”. IEEE TRANSACTIONS ON CIRCUITS AND SYTEMS-II, VOL. 62, NO. 2, FREBRUARY 2015. [6] M. M. Ahmadi, and G. A. Jullien, “ Current-Mirror-Based Potentiostats for Three-Electrode Amperometric Electrochemical Sensors”, IEEE Transactions on Circuits and Systems—i: regular papers, vol. 56, no. 7, july 2009. [7] Z. Xiao, X. Tan, X. Chen, S. Chen, Z. Zhang, H. Zhang, J. Wang, Y. Huang, P. Zhang, L, Zheng, and H. Min. “An implantable RFID Sensor Tag toward Continuos Glucose Monitoring”. IEEE JOURNAL OF BIOMEDICAL AND HEALTH INFORMATICS . MAY. 2015. [8] T. Luo, H. Wang, H. Song and J. B. Christen.“CMOS Potentiostat for Chemical Sensing Applications”. Sensors IEEE, Nov. 2013. [9] S. M. Martin, F. H. Geabra, B. J. Larive, and R. B. Brown, “A CMOS- Integrated Microinstrument for Trace Detection of Heavy Metals”, IEEE Journal of Solid-State Circuits, vol. 40, no. 12 , December 2005. [10] G. Eason, B. Noble, and I.N. Sneddon, “A comparison between potentiostatic circuits with grounded work or auxiliary electrode,” Rev. Sci. Instrument, vol.73, no.4, pp. 1921-1923, April.2002. [11] J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, 2nd ed. New York: Wiley, 2001. [12] C. N. Yarnitzky. “Part I. Design and construction of a potentiostat for a chemical metal-walled reactor 2000”. Journal of Electroanalytical Chemistry, vol. 91, pp. 154-159, Mar. 2000. [13] C. Toumazou, F. J. Lidgey, and D. G. Haigh, Analog IC design: the current-mode approach, Stevenage, U.K.: Peregrinus, 1990. Authorized licensed use limited to: UNIVERSIDADE DE SAO PAULO. Downloaded on March 25,2021 at 23:00:19 UTC from IEEE Xplore. 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