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    seNsOpg ACTORS B ‘CHERICAL ELSEVIER Sensors and Actuators B 28 (1995) 95-102 Microfabricated conductimetric pH sensor Norman F. Sheppard, Jr.**, Matthew J. Lesho *, Philip McNally ®, A. Shaun Francomacaro ° “Department of Biomedical Engineering, The Jolt Hopkins University, Baltimore, MD 21218, USA “Applied Physics Laboratory, The Johns Hopkins Universi, Baltimore, MD 21218, USA Received 5 May 1994; in revised form 16 August 1994; accepted 19 August 1994 Abstract ‘A miniature conductimetric pH sensor has ivity of a pH-responsive hydrogel. The microfabricated sensor is constructed by coating planar interdigitated electrode arrays with a photolithographically patterned hydrogel membrane. The hydrogel sensing layer swells or shrinks to a hydration determined by the pH of the solution in which it is immersed. This leads to a corresponding increase or decrease in the mobility of the ions partitioned by the gel. The sensitivity of ion mobility to small changes in hydration leads to sensor resistance changes as large as 45% per pH unit at physiological pH. Since the sensor operation is based on changes in fon mobility, the sensor operates in high ionic strength solutions, whereas most conductimetric sensors to date have been limited to use in solutions with low mobile ion content. The sensor response time is approximately five minutes, and appears to be limited by the protonation/deprotonation of the polybasic hydrogel. Devices have operated for more than six weeks with a 50% loss of sensitivity over three weeks. ‘Kewords: Conductimetrie sensors; pH sensors; Hydrogel 1. Introduction Conductimetrie sensing is a promising modality for chemical sensors due to the relative simplicity of the measurement, and the ease with which miniature sensors can be fabricated, This type of sensor is most commonly constructed by coating a planar interdigitated electrode array with a thin film of a material designed to respond to the analyte of interest. The interaction of the analyte with this sensing layer leads to a change in the electrical impedance of the interdigitated electrode pair. Con- ductimetric gas sensors, often referred to as chemi- resistors [1], make use of inorganic or organic films, such as tin dioxide and lead phthalocyanine, whose electrical conductivity changes in the presence of organic vapors such as NO,. A considerable amount of effort has been expended towards the development of con- ductimettic biosensors. These devices typically use an enzyme immobilized in close proximity to the electrode surface in order to achieve specificity for a particu! biomolecule. The enzymatic reaction leads to the for- mation of ionic products, which increase the conductivity of the solution proximal to the electrodes [2]. Sensors developed to date include sensors for urea [3,4], pen- * Corresponding aut (0925-4005}95/809.50 © 1995 Elsevier Science $.A. All icillin [5], amino acids (6], creatinine, and glucose [7]. An alternative approach for constructing biosensors exploits the pH-dependent conductivity of electro- polymerized films of polypyrrole and polyaniline to construct conductimetric enzyme sensors for penicillin [5] and glucose {7} ‘An important factor in the design of a conductimetric sensor is the choice of the material or materials that act as a sensing layer. The sensing layer must respond selectively to the analyte of interest, and produce a measurable change in the electrical properties at the sensor's surface, The sensing-layer material chosen for the present application is a ‘responsive’ hydrogel [8]. Hydrogels are crosslinked hydrophilic polymers that swell by incorporating water to an extent that ranges from 10% to greater than 99% by weight [9]. The presence of weakly acidic or basic groups on the polymer leads to a hydration that depends on pH. The swelling of a hydrogel is governed by the free energy of interaction between the polymer, the solvent (water) and co- and counter-ions, Several applications have been proposed for pHL-tesponsive hydrogels, including drug-delivery systems [10] and separations (11). ‘The manufacture of miniature solid-state transducers is readily achieved using integrated circuit technology. However, most microfabricated chemical and biochem- 96 NF. Sheppard, Jr et al. | Sensors and Actuators B 28 (1995) 95-102 ical sensors require one or more membranes deposited over the electrodes to achieve the desired functionality Procedures for depositing the membrane must be com- patible with transducer packaging and lead attachment. ‘The most common procedureis to deposit the membrane after the sensor has been assembled [4], even though this approach can be cumbersome and the membrane uniformity and reproducibility can be poor. More re- cently, efforts have been made to pattern membranes on the silicon substrate of microfabricated transducers prior to separating and packaging the individual sensors, Work to date has focused primarily on coating ion- selective field-effect transistors (ISFETs) with mem- branes to make them specific for a given analyte. Patterned silicone rubber containing entrapped ion- ophore has been used to develop a Ca?* sensor [12]. Crosslinked albumin and polyvinyl alcohol membranes containing immobilized enzyme {13} have been used to construct glucose sensors. Hydrogel membranes [14] have been photolithographically patterned over ISFET gates to stabilize the interface needed for a reference device. This communication describes the construction and evaluation of a conductimetric pH sensor, based on a pH-responsive hydrogel, proposed in an earlier report [15]. Factors governing the sensitivity, response time, and lifetime are discussed. This sensor is unique in that it is completely microfabricated, operates in so- lutions with high electrical conductivity, and exhibits a response of up to 45% change in resistance per pH unit at physiological pH. The ease of construction of this sensor and the design flexibility afforded by con- trolling the chemistry of the polymer hydrogel sensing layer could make this approach useful for the con- struction of biosensors based on enzymes or antibodies. 2, Experimental 2. Electrode design The design of the conductimetric transducer used in this study is illustrated schematically in Fig. 1. The overall size of the ‘chip’ is 2.5 mmx5 mm. At one end of the 2.5 mmx5 mm die is a pair of platinum interdigitated electrode (IDE) arrays, each 750 mx 1000 ym. The width of the individual digits and the intervening spaces are both 10 ym. Conductor paths run from the IDEs to gold-plated bond pads located at the opposite end of the chip. A silver electrode, 250 umx1000 jam in size, is located between these leads, but was not used in the present work. 2.2. Electrode fabrication The devices were fabricated on oxidized silicon wafers using standard integrated circuit fabrication methods aid pets ah Pisinum itr steered (sox Fig. 1. Schematic illustration of conductimettc sensor chip, to deposit and pattern the platinum and silver electrodes, and to gold plate the bonding pads. The positive pho- toresist used in the photolithography steps described below was Shipley 1400-31, The photoresist exposure dose was nominally 100 mJ cm™? (measured at 365 nm), and development was for 45s in Shipley 352 developer. The platinum electrodes were patterned on the sub- strate using a ‘lift-off process. After cleaning the sub- strate, a 20 nm layer of chromium was sputtered over the wafer to improve the adhesion of the photoresist to the substrate. A reverse image of the electrodes was patterned in the photoresist by exposure and devel- opment. To provide an undercut profile needed for the lift-off step, the field chromium was etched away (KTI Cr etch) and the exposed oxide was then etched to a depth of approximately 200 nm with a buffered oxide etch. Next, a 30 nm thickness of chromium, followed by a 200 nm thickness of platinum, were deposited over the resist by electron-beam evaporation. The wafer was immersed in acetone with ultrasonic agitation to dissolve the resist and lift off the unwanted metal, leaving only the electrode patterns on the sub- strate. A ‘piranha’ etch (H,SO,iH,0,, 1:1) was used to remove any residual photoresist. In the next process step, the bond pads were plated with gold to form the ‘bumps’ needed for lead at- tachment, A layer of photoresist was deposited over the wafer, exposed through a mask and developed to provide openings over the bond pads, The photoresist, was then postbaked at 115 °C for 20 min. Sputtering was used to deposit a 400 nm thickness of gold over the photoresist, and a second layer of photoresist was patterned to expose the gold film over the bond pads. Gold was electroplated through the openings in the resist to a thickness of 2 jum. The topmost photoresist layer was dissolved in acetone to expose the sputtered gold layer. This configuration was etched with a gold etch consisting of one part Technistrip II, nine parts water, and 15 g I”? of potassium cyanide, for a period NE. Sheppard, Jr tal of time sufficient to remove the gold over the field of the device, yet retain the plated pads. Finally, the bottom layer of resist was removed with acetone, and a ‘piranha’ etch was used to clean the substrate Following patterning of the silver electrode using a lift-off procedure, a layer of photoresist was deposited as a passivation layer. This was exposed and developed to leave openings over the interdigitated electrode arrays, and the silver electrodes, and then hardbaked up to 250 °C to enhance its stability and chemical resistance. 2.3, Hydrogel synthesis and characterization Hydrogel copolymers were prepared from 2-hydrox- yethyl methacrylate (HEMA, Polysciences, ophthalmic grade, used as received) and N,N-dimethylaminoethyl methacrylate (DMAEMA, Polysciences, vacuum dis- tilled) by redox-initiated free-radical solution poly- merization, Tetraethylene diacrylate (TEDA, Aldrich, used as received) was used as the crosslinker, and water was used as the solvent. Gels were prepared with a HEMA:DMAEMA:TEDA mole ratio of (100~x):x:1.5 with x=0, 5, 10, and 20. The monomers were mixed together, and sparged with nitrogen to remove oxygen from the solution, Small aliquots of ammonium persulfate and sodium metabisulfite were then added to and mixed in the solution. The monomer, solution was injected into a mold prepared from glass plates and a 0.75 mm polyethylene spacer. Polymeri- zation was allowed to proceed overnight. The gels were conditioned in deionized water, which was changed daily, for a period of two weeks to leach out unreacted monomer. The gels were conditioned in buffered 0.5 M potassium chloride solutions, with pH ranging from 4 t0 10, using salts of citrate, phosphate, and borate at 0.1 M concentration [16]. The water content of the gels was determined gra- vimettically. After conditioning in dionized water and before exposure to the buffer solution, disks of the gel were punched out, dried in a vacuum oven at room temperature until a constant weight was achieved, and then weighed. The disks were then equilibrated in buffer solutions with different pH values, and reweighed. Gel conductivities were determined using 2 modified

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