Potentiostat3 PDF
Potentiostat3 PDF
Potentiostat3 PDF
3390/s110908593
OPEN ACCESS
sensors
ISSN 1424-8220
www.mdpi.com/journal/sensors
Article
Received: 8 August 2011; in revised form: 29 August 2011 / Accepted: 1 September 2011 /
Published: 2 September 2011
1. Introduction
Electrochemical sensors are widely utilized in many applications, such as disease diagnosis,
environmental monitoring, and food inspection, due to their fast analysis, high selectivity, high
sensitivity, and simplicity [1]. An electrochemical sensor acts as a transducer which converts the
chemical quantity of analytes within a given solution into electrical signals. In general, two forms of
output signal are generated, namely potential and current, each requiring its own readout circuit.
Amperometric electrochemical sensors, which generate a current signal, utilize a potentiostat as an
interface circuit during the gathering of signals [2]. Potentiometric electrochemical sensors, which
generate a potential signal, utilize an instrumentation amplifier (IA) as the readout circuit [3].
A back-end circuit system is necessary for acquiring sensor information and transmitting the
acquired data. Consequently, the development of an electrochemical sensing telemetry system that
targets clinical analytes such as nitrite and pH, both of which are essential tests for urinary tract
infection (UTI), is desirable. Some research has been conducted to develop a portable system using
discrete components for electrochemical sensor applications [4-6]. A telemetric potentiometric
electrochemical sensor was developed to sense pH and transmit the measured signals wirelessly [7].
Additional research has been devoted to the development of a readout chip for various electrochemical
sensor applications [8-10].
With the rapid development of the semiconductor industry, system-on-chip (SoC) technologies have
had a substantial impact on system integration. Portable application requirements include low power
consumption, compact size, and wireless communication. For portable applications and offering
freedom of mobility of users, this work presents a high-integration telemetry system with readout
circuits and a microcontroller unit for amperometric and potentiometric electrochemical sensor
applications. The readout circuits, which include a potentiostat and an instrumentation amplifier (IA),
were implemented in the TSMC 0.18-μm CMOS process. The microcontroller unit was implemented
using a field programmable gate array (FPGA). The system can display acquired data in real-time on a
graphical user interface (GUI) and is small enough to be portable. By integrating electrochemical
sensors with the proposed system, the detection of analytes can be conveniently performed.
Sensors 2011, 11 8595
A potentiometric pH sensor and an amperometric nitrite sensor were tested; the results verify the
feasibility of the proposed system.
The rest of this article is organized as follows. Section 2 describes the proposed real-time telemetry
system. In Section 3, the measurement results of the proposed system are shown. Finally, the
conclusions are given in Section 4.
The proposed telemetry system, illustrated in Figure 1, consists of front-end readout circuits, a
multiplexer (MUX), an analog-to-digital converter (ADC), a microcontroller unit (MCU), a radio
frequency (RF) transceiver module, a GUI, and a database. The chemical quantity of analytes is
converted into electrical signals by the electrochemical sensors. The electrical signals are amplified
and converted into digital form by the readout circuit and the ADC, respectively. The digital signals
are processed by the MCU and transmitted to a computer or a personal digital assistant (PDA) via RF
transmission for display on a GUI. The data are optionally uploaded to a database over the internet,
allowing remote access. The blocks of the system are described in detail below.
A potentiostat and an IA are adopted as the readout circuits for amperometric and potentiometric
electrochemical sensors, respectively. The cell potential (Vcell), which is the potential difference
between the working electrode (WE) and the reference electrode (RE) of an amperometric sensor,
varies with the sensor. The maximum supplied cell potential is determined by the supply voltage of the
potentiostat. The number of detectable analytes decreases with scaling down supply voltage. Therefore,
to maximize the number of detectable analytes in low-voltage processes, the rail-to-rail input
common-mode range (ICMR) and the rail-to-rail output swing are implemented in the readout circuits.
Sensors 2011, 11 8596
A DDA with rail-to-rail ICMR and rail-to-rail output swing is implemented to provide the
maximum dynamic range at the input and output, respectively, for various potentiometric sensor
applications. Figure 3 shows a schematic of the DDA and its bias circuit. The transistor dimensions for
the DDA of Figure 3 are listed in Table 1. The structure of the rail-to-rail input folded cascode
operational amplifier with a class-AB output stage is used to achieve the rail-to-rail input and output
Sensors 2011, 11 8597
range [14]. The input stage is modified to have two differential input ports. Vpp and Vpn are designated
as the non-inverting input ports and Vnp and Vnn are designated as the inverting input ports. The
rail-to-rail ICMR is realized by placing an NMOS and PMOS differential input pair in parallel
(MN1-MN4 and MP1-MP4). The floating class-AB control is formed by M18–M20. In practical
applications, the open-loop gain of the DDA has a finite value and the small-signal transconductances
of the non-inverting and inverting input ports are not equal. Thus, the output of the negative feedback
of a DDA is given by [15]:
Vout = g mp ro (VWE − VRE ) − g mn ro (Vnp − Vnn ) (2)
where Vnp − Vnn can be replaced by:
R1
Vnp − Vnn = (Vout − Vnn ) (3)
R1 + R2
Rearranging the above equations, the non-ideal closed-loop transfer function can be expressed as:
g mp ⎛ R ⎞
Vout ≅ ⎜⎜1 + 2 ⎟⎟(VWE − VRE ) + Vnn (4)
g mn ⎝ R1 ⎠
where gmp and gmn are the small-signal transconductances of the non-inverting and inverting input
ports, respectively, and ro is the small-signal output resistance of the DDA. The closed-loop gain of the
amplifier is directly affected by the ratio of gmp to gmn. However, the value of gm varies with the input
common-mode voltage of each input port. For this reason, a constant-gm technique is needed to
minimize the variation of the ratio of gm when the input ports have different common-mode voltages.
An electronic zener diode is inserted between the input pairs to obtain a constant gm [16]. The
electronic zener circuit is implemented by transistors M5–M9, M11, and M13. The zener voltage is
determined by two complementary diode-connected transistors, M5, M6. Descriptions of the electronic
zener topology can be found in [16]. This approach leads to fewer variations of the gm of the input
stage and is also power efficient because no additional current path is introduced between the
supply rails.
2.1.2. Potentiostat
Amperometric electrochemical sensor structures can be divided into two types: two-electrode and
three-electrode structures. The former comprises a WE and an RE. A lot of research has been devoted
to the development of potentiostats for two-electrode amperometric sensor applications [17,18]. The
latter comprises a WE, an RE, and a counter (or auxiliary) electrode (CE). This type is preferred over
the two-electrode type in precisely controlling of the cell potential because the CE supplies current
required for electrochemical reaction at the WE electrode to maintain the stability of the RE [19].
Thus, the proposed potentiostat is designed for three-electrode sensors.
A potentiostat typically consists of two main blocks: a control block and a current measurement
block. The control block maintains the desired cell potential, which depends on the electrochemical
sensor, between the WE and the RE. Normally, it can be realized using one of three approaches: a
grounded working electrode [20,21], a grounded counter electrode [22], or a virtually grounded
working electrode [23]. A grounded working electrode exhibits the best performance because it
enhances the suppression of interference and noise [24].
In the current measurement block, the sensor current can be acquired through either the WE or the
CE. For the former, a transimpedance amplifier is often adopted to transform the sensor current signal
into a voltage signal [8,23]. However, this architecture can pick up additional interference such as
environmental noise, which influences the output voltage of the measurement configuration due to the
topology of the virtually grounded working electrode. For the latter, one approach is to insert the active
components into the feedback loop of the control amplifier to measure the sensor current from the CE
via current mirroring [21,24,25]. However, linearity may suffer because the channel length modulation
effect of a MOSFET leads to a mismatched mirror current. Another approach is to insert a resistor into
the feedback loop to transform the current signal. In [26], a difference amplifier and two voltage
followers were used to amplify the voltage signal across the resistor to the desired amplitude; however,
the CMRR of this architecture is lower than that of the triple-opamp IA. Inserting a resistor has been
shown to be the most stable approach because there is no active component in the feedback loop.
In order to linearly convert the current signal into a voltage signal without decreasing the stability of
a potentiostat, a resistor is inserted into the feedback loop in the proposed architecture. The voltage
Sensors 2011, 11 8599
signal across the resistor is then amplified by an IA, which also enhances the CMRR of the proposed
potentiostat. Figure 4 shows the set-up of the proposed potentiostat circuit for three-electrode
amperometric sensors. The resistors R1, R2, and Rf were implemented off-chip to make the architecture
adjustable. A negative feedback loop is created around the control amplifier, which provides a virtual
short at the RE. The transfer function of the proposed potentiostat is expressed by:
R2
Vout = I F ⋅ R f ⋅ (1 + ) + Vcm (5)
R1
Figure 4. Set-up of the proposed potentiostat circuit for three-electrode amperometric sensors.
The control block consists of a control amplifier and resistor Rf. The control block supplies the
desired cell potential between the WE and the RE in order to maintain the function of the
amperometric sensor. The WE is connected to voltage VWE, taken from the supply voltage of the
potentiostat, to prevent it from picking up environmental noise and interference. In order to prevent
current from flowing into the RE, which affects the cell potential, the voltage of the RE is forced
through the virtual short of the control amplifier. Thus, the cell potential is given by:
Vcell = VWE − VRE = VWE − Vbias (6)
From Equation (6), the ICMR of the control amplifier restricts the voltage swing of Vcell. Therefore,
the control amplifier must have a rail-to-rail ICMR to provide the maximum swing of Vcell for various
sensor applications. The voltage gain of the control amplifier must also be considered because it
defines the accuracy of the virtual short voltage. It is usually suggested that the gain of the control
amplifier be larger than 80 dB [27]. Moreover, the number of stages of the architecture of the control
amplifier should be as few as possible to increase stability. From the above requirements, a rail-to-rail
input/output operational amplifier with a folded cascode input stage is adopted as the control amplifier
to obtain the minimum number of poles, sufficient gain, and rail-to-rail input and output. A schematic
of the control amplifier is shown in Figure 5. The transistor dimensions for the control amplifier of
Figure 5 are listed in Table 2. The bias circuit of this amplifier is the same as that of the DDA.
The amplifier block includes a negative feedback DDA which is used to linearly amplify the
converted voltage signal across Rf. The architecture of the DDA of the amplifier block is the same as
that in Figure 3.
Sensors 2011, 11 8600
A microcontroller unit is programmed to filter unwanted noise signals, control peripheral circuits to
reduce system power consumption, and transmit the data via a universal asynchronous receiver
transmitter (UART) interface. The proposed microcontroller unit is implemented on an Altera MAX II
EPM2210F324 FPGA device. This FPGA device is adopted due to its compact size and low cost;
however, the number of available logic elements is limited to 2,210. Figure 6 shows a block diagram
of the proposed MCU. The blocks of the proposed MCU are described in detail below.
In order to reduce hardware for multi-channel applications, a CMOS switch (4066BP, TOSHIBA),
is used to as a MUX. Four-channel control is provided by the proposed MCU, allowing four types of
analyte to be simultaneously detected. The sample frequency of each channel is set to 24 Hz due to the
long response time of the adopted electrochemical sensors (several tens of seconds). An ADC
with 8-bit resolution (ADC0804, National Semiconductor) is adopted. The clock frequency is set
to 192 kHz, which is supplied by the MCU.
In order to reduce interference and noise from the sensors and the power line, a low-pass filter (LPF)
is used. A moving average filter, which is a sample low-pass finite impulse response (FIR) filter, has
the properties of low hardware requirements and low computation time [28], and is thus adopted here
to satisfy the limitations of available hardware in the FPGA device. In order to conform to the response
times of various sensors, the architecture of adjustable points is utilized to provide three types
of 4-point, 8-point, and 16-point in the average. The types are switched by Filter_Type. The equation
of the moving average filter can be expressed by:
M −1
1
y[n] =
M
∑ x[n + j ]
j =0
(7)
where y[n] is the output signal, x[n + j] is the input signal, and M is the number of points in the average.
Figure 7 shows the structure of the moving average filter. In this work, two identical moving average
filters are cascaded to obtain faster roll-off. The simulated frequency response of the adjustable
cascade moving average filter is shown in Figure 8.
Figure 8. Simulated frequency response of the adjustable cascade moving average filter.
The UART interface is widely used for serial communication. The transport protocol of the UART
is simpler than that of USB. The relatively slow data transmission of UART is sufficient for this work
due to the long response time of the sensors. Thus, a UART interface, which is provided by the
adopted RF transceiver module, is adopted to convert parallel data into serial data for the transmitter.
The baud rate is set to 1,200 bps.
The signals of the electrochemical sensors need not be detected continuously due to the long
response time of the sensors. Thus, the function of mode control is implemented in the proposed MCU
to reduce the power consumption of the system. The modes can be changed by a trigger signal, which
is generated by the push-button switch on the FPGA board. Figure 9 shows the state diagram of the
mode control. After turning on the power, the hardware is properly configured and automatically
switched from Initial State to Wake Mode. In Wake Mode, the system is always enabled. In Time
Mode 1, the system alternates between wake (1 s) and sleep (1 s) modes. In Time Mode 2, the system
alternates between wake (1 s) and sleep (5 s) modes. In Time Mode 3, the system alternates between
wake (1 s) and sleep (10 s) modes.
The peripheral circuits and each function block of the MCU need a central control unit to manage
the proposed system and maintain correct operation. The state diagram of the control unit is shown in
Figure 10. Time_Enable is generated to wake up the system. When the system is disabled, it enters
sleep mode. The duration of sleep mode depends on the set operation mode.
3. Measurement Results
The proposed readout chip was implemented in the TSMC 0.18-μm CMOS technology.
A micrograph of the fabricated potentiostat is shown in Figure 11. The DDA part of the potentiostat is
used only to measure the open-circuit potential for potentiometric electrochemical sensors. The total
core area of the chip is 0.05 mm2. The total power consumption of the control amplifier and the DDA
is 82 μW at a 1.8 V supply voltage. Peripheral devices are supplied with 3.3 V. In order to use a single
Sensors 2011, 11 8604
power supply for the whole system, a low-dropout high-output-accuracy CMOS voltage regulator
(VRH1802LTX, Analog Semiconductor) is used to convert 3.3 V to 1.8 V to supply the implemented
readout chip.
To evaluate the performance of the proposed potentiostat, the equivalent model of the
electrochemical sensor, shown in Figure 12, was built to serve as a platform for data measurements.
CWE and CCE, chosen according to [24], are set to 1 uF and 1 nF, respectively. Rs is 10 Ω and RCE
is 1 kΩ. A varying voltage signal, Vin, was applied to the WE and the RE was biased at a constant
voltage, Vbias, by the virtual short of the input terminals of the control amplifier. The value of RWE
depends on the desired current. Therefore, the emulated sensor current, IF, is generated by:
Vin − Vbias
IF = (8)
RWE
An important specification of a readout circuit is its linearity. The coefficient of determination (R2)
for a linear regression was used to analyze the linearity of the proposed potentiostat. During linearity
measurement, a DC sweep voltage signal was applied to convert the equivalent current signal. For each
current range measurement, feedback resistor Rf was changed to maintain the voltage variation across
Rf of 10 mV to 100 mV. The closed-loop gain of the DDA was set to 15 V/V. Figure 13 shows the
experimental results of the relation between the equivalent sensor current and the absolute variation of
the voltage at the output terminal. The measurement results show that the R2 value is greater
than 0.99998 in each measured current range, indicating that the proposed potentiostat has high
linearity and a wide detectable current range. Additionally, the control amplifier and the DDA were
experimentally verified; both have a rail-to-rail ICMR and a rail-to-rail output swing, making them
Sensors 2011, 11 8605
suitable for multiple-sensor applications. The dynamic range of Vout is about 65 dB and the voltage
swing of the input common-mode voltage is 1.79 V. Moreover, the proposed potentiostat has a small
number of components, reducing component noise, and high values of CMRR and power supply
rejection ratio (PSRR) to suppress common-mode and power supply noise, respectively. It was verified
that the CMRR and the PSRR of the proposed DDA are both greater than 90 dB for frequencies
below 100 Hz. The input-referred voltage noise of the proposed DDA, integrated from 0.1 to 100 Hz,
was also measured to be 2.8 μVrms.
Figure 13. Equivalent sensor current versus Vout − Vcm of the proposed potentiostat. The
R2 value of each current range is greater than 0.99998.
The experimental results of the proposed potentiostat are summarized in Table 3. In this work, the
WE was connected to a bias voltage due to its insensitivity to environment noise and interference.
Compared to [29], the proposed potentiostat has a relatively simple architecture that can supply a
rail-to-rail value of Vcell for various sensor applications. Furthermore, the proposed potentiostat avoids
the mismatched current issue of [24] and [25]. The proposed architecture achieved excellent linearity
with an R2 value of 0.99998 and a wide detectable current range of 1 nA to 100 μA.
The proposed telemetry system for portable applications is shown in Figure 14. The PCBs are
integrated in a stacked manner for improved portability. The board size of the transmitter unit
is 5.6 cm × 8.7 cm and the height is 3 cm. In operation mode, the total power consumption of the
transmitter unit is 157.25 mW with a supply voltage of 3.3 V. In sleep mode, the transmitter unit
consumes 87.83 mW. Table 4 shows the overall power utilization for the proposed telemetry system.
Because USB is the most widely used computer interface, the receiver unit receives UART formatted
data transmitted via a USB port on a UART/USB interface IC (FT232RL, FTDI Chip).
Electrochemical analysis was conducted by integrating the proposed system with a nitrite
amperometric sensor [30] and a pH potentiometric sensor [31] in vitro. The nitrite sensor was
immersed into a 0.1 M phosphate-buffered-saline (PBS) solution (pH 6). The concentration of nitrite
was increased by 0.12 mM per step. A Vcell of 0.7 V vs. Ag/AgCl was applied. Figure 15 shows the
detected current signals versus nitrite concentration. Linearity with an R2 value of 0.9982 was achieved
in this electrochemical analysis. For the potentiometric sensor measurement, the pH sensor was
immersed into aqueous solution. The pH value of the aqueous solution was increased and the
potential vs. Ag/AgCl was measured. Figure 16 shows the detected signals for various pH values. An
R2 value of 0.9983 was obtained during the pH measurement. The measurement results are represented
by using mean ±S.D. with five observations and show that the proposed system has high linearity
because an R2 value greater than 0.99 was obtained in each experiment. The experimental results of the
proposed system are summarized in Table 5.
Sensors 2011, 11 8607
4. Conclusions
A real-time telemetry system with high-linearity readout circuits for electrochemical sensors and a
user-friendly GUI were developed for conveniently detecting analytes in real-time and uploading the
data to a database over the Internet. Remote users can easily obtain the detected data over the Internet
from the database. The proposed readout circuits were fabricated in the TSMC 0.18-μm CMOS
technology. An FPGA-based MCU was implemented to filter unwanted noise and to manage the
system power consumption. Electrochemical experiments were conducted to verify the feasibility of
integrating the proposed system with an amperometric nitrite sensor and a potentiometric pH sensor.
The proposed system has high linearity (an R2 value greater than 0.99), a small size of 5.6 cm × 8.7 cm,
and high integration.
Acknowledgments
The authors would like to thank the National Chip Implementation Center (CIC), Taiwan, for
supporting the chip fabrication service. Finally, this work was sponsored by the National Research
Council, Taiwan, under grant number NSC 99-2220-E-006-0013.
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