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51.3: ChemFET Arrays for Chemical Sensing Microsystems

Brian J. Polk

School of Chemishy and Biochemistry Georgia Institute of Technology. Atlanta, Georgia, USA

Abstract

Chemically sensitive field-effect transistors (ChemFETs). among the smallest chemical sensors available to-date, are attractivefor use in integrated systems. Favorable attrib- utes of the ChemFET array include inherent compatibility

with microfabricated electronics, small size of only 400 Fm by 500 pm, low noise, and simple support circuitry.

ChemFET structure is similar to other

insulated gatefield-

effect transistors except that the usual metal or polysilicon gate conductor is replaced with a semiconductingpolymer

or other chemically sensitive material. In this work, an array of eight ChemFETs utilizing dxerent partially selec- tive gate materials on each unit was constructed utilizing mainly standard microfabrication techniques. Although support electronics are currently housed off-chip, a proto- type array format designed to allow forflip-chip bonding of an ASIC service chip was alsofabricated. Selectivity of an individual sensor can be improved but, in practical terms, the ensemble response of an array of devices is needed to reliably identrfi a chemical vapor. In the case of ChemFETs, the detection transduction mechanism is a chemical modulation of the workfirnction (WF) of the gate material by the analyte gas. Selectivity may be enhanced by adjusting the initial WF of the conductingpolymer layer relative to the electronegativity of an analyte gas. It is shown in this work that solid-state WF adjustment ofpoly- aniline, a semiconducting polymer, may be achieved throughproton dopingfrom photogenerated acid.

Keywords

ChemFET, sensor array, work function, polyaniline, photo- .doping

INTRODUCTION

Janata defines a chemical sensor as “a device that provides continuous information about its [chemical] environ- ment”[4]. Its purpose is to transduce changes in a chemical environment into electrical signals. Sensor transduction principles fall into four main categories - thermal, mass, electrochemical, and optical[5]. Within each category, devices which fit the general definition of chemical sensor range widely in size and operational parameters. The phrase “chemical sensor microsystems” overtly implies a major goal of the technology is miniaturization. Size re- duction may take the form of smaller physical size, lower

power requirements, andor integration of system compo- nents. One chemical sensor that lends itself to all of these miniaturization considerations is the chemically sensitive field-effect transistor (ChemFET). The purpose of this paper is to describe ChemFETs and ChemFET arrays in relation to sensor microsystems and to discuss options for tuning devices within an array.

CHEMFET STRUCTURE

An idealized schematic cross section of a ChemFET is shown in Figure 1. The device is essentially a large feature size insulated gate field-effect transistor. The gate length is typically -20 microns. The large feature size is dictated by the need to have a minimum amount of chemically active material in order to obtain sufficient signal. The essential difference hetween a ChemFET and a typical FET for elec- tronic applications is that the gate conductor material is chosen such that its properties can be modulated by an ex- temal chemical stimulant. For example, an FET that can he

-c-- Current flow

I p-Tw SiliconSubstnte

I-

Figure 1. Idealized ChemFET cross section schematic

used for detection of hydronium ion (i.e. pH) is one with a bare insulator[5]. Ions will partition into the gate insulator and modulate current flow between source and drain. This configuration, however, requires an extemal refexence elec- trode. One of the first ChemFETs was the palladium gate design investigated by Lundstrom[lO]. This devices uses Pd metal as the gate conductor. Hydrogen is catalytically dissociated at the metal surface then diffuses to the metal / insulator interface where the H atom polarizes to induces

0-7803-7454-1/02/$17.0002002 IEEE

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modulations in the gate field effect. Many modem Chem- FET structures utilize conducting polymers such as polypyrrole or polyaniline as the gate conductors[2] and are used as vapor sensors.

ChemFET Transduction

The transduction principle for the modem ChemFET is a chemical modulation of the electron work function of the conducting polymer gate material[6]. The device threshold voltage, Vr, is dependant on the difference between the work function of the polymer, Opolyand that of silicon, Osi:

T‘

aSi - @Poly

The threshold voltage is determined from the drain current, IDSvs. gate voltage, V, relationship for non-degenerate, n- channel devices in saturation:

I,

= Const(v, - vT1’

where Const is a constant governed by the fabrication pa- rameters[l2]. Figure 2 gives an example of a measurement circuit for measuring changes in the threshold voltage of the gate conductor.

--

Figure 3. Measurement circuit for ChemFET work function

Design

The FET design used in this work is shown in a top down micrograph in Figure 3. The metallization layout is de-

signed to allow simultaneous detection of work function

Potentials are applied at a single

gold lead which contacts both the drain and the gate. Thus,

the device is hard-wired in the source-follower configura- tion The source and substrate are grounded. 10s is kept constant and gate voltage is monitored. A symmetrical lead on top of, but not connected to the source provides a contact point for monitoring the impedance of the chemi- cally active layer.

and impedance changes

Fabrication

Fabrication of ChemFETs requires slightly different proc- essing steps than a standard n-channel FET. One major difference is that noble metals must be used for contact

Gate (20 pn length

ImpedahceConlecl

$io, Surface Passivation

Figure 2. ChemFET top down view

leads to ensure chemical inertness. Another difference is that the gate requires a low stress silicon nitride insulator. This is deposited in a high temperature chemical vapor deposition process and reduces the chance for pin hole de- fects. One last difference is that the surfaces of the devices must be isolated from each other with a tall, inert polymeric material. These wells are filled with solution during gate conductor casting and electrochemical modification.

ADVANTAGES OF CHEMFETS FOR MICROSYSTEMS

The ChemFET for detection of chemical vapors may he compared with the competing technologies of surface acoustic wave (SAW) devices and chemiresistors, both of which and have utilized polymer active materials[l,l3,14]. SAW devices are mass sensor transducers that monitor the change in frequency and phase angle of an acoustic wave moving across the surface of a piezoelectric substrate. Ac- tive materials are coated over the device surface and the acoustic signature changes as the layer absorbs vapors an increases in mass. Chemiresistors are very simple devices in which active materials are coated onto interdigitated electrodes. The resistance between the digits is monitored. The resistance of the loaded polymer is modulated by the swelling of the polymer as it absorbs gases. Different sensor technologies may compared with a num- ber of parameters including size, sensitivity, noise, stabil- ity, and cost. Some factors are greatly influenced by the choice of chemically active material while others tend to be a function of the transducer.

A major objective of chemical sensor technology is to miniaturize the size of the entire system - transducer,

power supply, interface, etc.

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ChemFETs are among the

smallest chemical sensor transducers available. A conser- vative size estimate for a single device is 400 by 500 mi- crons. Further, ChemFETs typically draw milliwatts or less of power, reducing the need for a large power source.

ChemFETs are inherently compatible with silicon electron- ics. This suggests the possibility for greater system integration by fabricating both interfacing and support cir- cuits with the sensor on the same substrate. Such integra- tion could lead to further gains in size and power needs.

ChemFET sensitivity is a logarithmic function of vapor

concentration[6]. This means a much broader dynamic range than that of SAW devices or chemiresistors, both of

which have linear response curves[l,5,13].

its for some ChemFET systems in parts per billion @ph) range have been reported; well helow the limit of most chemical sensors[S]. A ChemFET designed to provide, both work function and impedance, offers another advantage for microsystems. Work function data gives information about the electron affinity of the active layer, while impedance data yields information on the charge carrier density and mobility. This multidimensional information moves the ChemFET into higher-order sensors with can provide several chemi- cally orthogonal signals. Chemiresistors, in contrast, has only impedance capability. SAW do have frequency and phase shift information which can also be used to obtain multidimensional data.

Detection lim-

ADVANTAGES OF AN ARRAY

There is no such thing as perfect selectivity for a single sensor/analyte system. Even if perfect selectivity were possible, then a single device could only provide infom- tion ahout a single analyte, and would not guarantee a broad dynamic range. Because real world samples are mix- tures, it is necessary to use an array of sensors to increase

Flip-chip bonde

electronicservica c

Figure 4. ChemFET array design. A) design for off-chip support electronics, B) design for in- tegrated support electronics

selectivity and dynamic range, and the number of simulta-

neous analytes. A simple illustration of array utility is the

pH test strip. Single component acid-base indicators mi-

cally can only response to pH changes over l or 2 pH units.

In contrast, the test strip, with many indicators on a single

sampling tool can resolve pH to within one unit or better. This is possible.by analyzing the panern of colors gener-

ated. In fact, much of the current development of sensor array technology comes from improving pattem recogni- tion algorithms[9].

Arrays can improve signal to noise by averaging response from many sensors. The optimum number of sensors has been investigated[9,14]. It was found to be between 6 and

10.

ARRAY LAYOUT

The ChemFET has been used in an array format. This was first done simply by using FETs on several different chips[2]. A step towards system miniaturization was taken when the array was fabricated on a single chip. In a simple application, the chip contained only FETs. A more inte- grated design allows for flip-chip bonding of support elec- tronics[ 111. Two integrated ChemFET array layouts are shown in Figure 4.

IMPROVING CHEMICAL ORTHOGONALITY IN A COMPACT ARRAY

The arrays shown in Figure 4 are just transduction plat- forms for chemical sensing. In order to make the device function as intended, each element must he made chemi- cally orthogonal to the others. The small overall dimen- sions of the array cause several engineering challenges to tuning the properties of each individual device. It is desir- able to fabricate ChemFETs at the wafer level for as many processing steps as possible. For this reason, it is hener to deposit the same gate conducting polymer on the whole wafer, rather than deposit several different materials after dicing. The material of choice for ChemFET gate conductor is polyaniline (PANI). The major property of interest for ChemFETs is initial work function of PANI. Several methods for adjusting the work function are known includ- ing electrochemical anion exchange[3] and exposure of dry film to dopant solution[7].

A novel approach recently demonstrated was the use of

photochemistry to dope PANI and change its work func- tion[l2]. In this method, polyaniline in the emeraldine base form is cast from a solution along with triphenylsulfo- nium salts. When the polymer film is dry, it is exposed to ultraviolet light, the Ph$ decomposes to release an acidic proton. The photogenerated acid then protonates the PANI into a different doping level and changes the work func- tion.

The photochemical tuning method offers the chance of depositing the same gate conductor material on all devices,

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then tuning the initial threshold voltage of the device with light. It is a much more precise method than others men- tioned above and could be adapted for use at the wafer level of fabrication.

SUMMARY

This paper described chemically sensitive field-effect tran- sistors and pointed out some advantages for their use in chemical sensing microsystems. Advantages include small size, low power requirements, large dynamic range, and compatibility with microfabricated electronics. The de- vices are best used in an array format. The array improves signal to noise, selectivity, and dynamic range. Photo- chemical tuning of the gate material on individual devices ensures chemical orthogonality

Acknowledgments

Funding was provided by National Science Foundation Grant No. CHE-9816017. The author wishes to thank Prof. Denise Wilson of the University of Washington, Seattle for providing the ChemFET measurement electronics.

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