CA1282458C - Membrane anchor for ion-selective electrodes - Google Patents
Membrane anchor for ion-selective electrodesInfo
- Publication number
- CA1282458C CA1282458C CA000567152A CA567152A CA1282458C CA 1282458 C CA1282458 C CA 1282458C CA 000567152 A CA000567152 A CA 000567152A CA 567152 A CA567152 A CA 567152A CA 1282458 C CA1282458 C CA 1282458C
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- CA
- Canada
- Prior art keywords
- ion
- selective
- membrane
- insulating
- stratum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Abstract
ABSTRACT
A membrane anchor for an ion-selective elec-trode may be formed by intersolubilizing an ion-selec-tive membrane lying above a sensing pad with a region of thermoplastic material laterally disposed around the membrane. A first layer of electrically insulating thermoset material lies beneath the thermoplastic ma-terial and in intimate contact with an electrically insulating susbstrate. A second layer of exposed ther-moset material lies above the thermoplastic material and contacts the first layer of thermoset material around the entire lateral perimeter of the thermoset mater-ial.
The membrane anchor may be usefully employed with an ion-selective electrode having an electrically insulating substrate with a substantially planar surface and having non-metallic means for sensing a potential affixed to the surface beneath an ion-sensitive mem-brane.
A membrane anchor for an ion-selective elec-trode may be formed by intersolubilizing an ion-selec-tive membrane lying above a sensing pad with a region of thermoplastic material laterally disposed around the membrane. A first layer of electrically insulating thermoset material lies beneath the thermoplastic ma-terial and in intimate contact with an electrically insulating susbstrate. A second layer of exposed ther-moset material lies above the thermoplastic material and contacts the first layer of thermoset material around the entire lateral perimeter of the thermoset mater-ial.
The membrane anchor may be usefully employed with an ion-selective electrode having an electrically insulating substrate with a substantially planar surface and having non-metallic means for sensing a potential affixed to the surface beneath an ion-sensitive mem-brane.
Description
~28~458 MEMBRANE ANCHOR FOR ION-SELECTIVE ELECTRODES
Jill M. Geist and Thomas G. Schapira .
Background of the Invention The present invention pertains in general to ion-selective membranes and in particular to insulative layers associated with ion-selective membranes and con-ductive patterns suitable for fabrication of ion-selec-; tive electrodes.
When placed in contact with a solution, ion-selective electrodes provide an electrical output which15 is a func~ion of the concentration of a particular ion in the solution. In such electrodes an output potential ("Y") is measured between a "sensing element, responsive to the concentration of the particular ion, and a "re-ference element," held at a constant potential, Y may be20 plotted against the base 10 logarithm of the concentra-tion of the ion ("X") as a straight line having a slope ("M") and y-axis intercept ("B") as expressed in the Nernst equation:
Y = M (log10X) ~ B
Ion-selective elect}odes conventionally have an internal reference element of Ag/AgCl immersed in a solution or gel of chloride ion. The chloride ion solu-tion or gel holds the reference element at a constant potential, providing that the chloride concentration and thermodynamic functions, such as temperature and pres-sure, are held constant. An ion-selective glass or membrane sensing element is placed in contact with the solution or gel to form an interface between the test solution and this internal filling solution. However, ~ 35 this conventional design is complex to manufacture and -~ difficult to miniaturize.
~2~3245~3 .
In the fabrication of ion-selective electrodes a major problem is leakage at the interface of the ion-selective membrane and the insulative surface. This leakage causes corrosion and drift of the ion-selective ~- 5 electrode. Various attempts to ~revent leakage at the membrane interface are described in the literature.
U.S. Patent 4,180,771 describes placing the gate lead on the opposite face of ~ET device to isolate the ion-sens-ing area. U.S. Patent 4,449,011 t~ Kratachvil describes placing an insulating tape around the ion-sensing areas in an attempt to prevent moisture leakage.
U.S. Patent 4,393,130 to ~o et al. provides a dry film photoresist laminate which requires photo pro-cessing and etching to form a window around the ion-sensing areas for placement of the ion-selective mem-brane. A process for encapsulating ion-selective elec-trodes with thixotropic material having a window for an ion-selective membrane is also disclosed.
Jill M. Geist and Thomas G. Schapira .
Background of the Invention The present invention pertains in general to ion-selective membranes and in particular to insulative layers associated with ion-selective membranes and con-ductive patterns suitable for fabrication of ion-selec-; tive electrodes.
When placed in contact with a solution, ion-selective electrodes provide an electrical output which15 is a func~ion of the concentration of a particular ion in the solution. In such electrodes an output potential ("Y") is measured between a "sensing element, responsive to the concentration of the particular ion, and a "re-ference element," held at a constant potential, Y may be20 plotted against the base 10 logarithm of the concentra-tion of the ion ("X") as a straight line having a slope ("M") and y-axis intercept ("B") as expressed in the Nernst equation:
Y = M (log10X) ~ B
Ion-selective elect}odes conventionally have an internal reference element of Ag/AgCl immersed in a solution or gel of chloride ion. The chloride ion solu-tion or gel holds the reference element at a constant potential, providing that the chloride concentration and thermodynamic functions, such as temperature and pres-sure, are held constant. An ion-selective glass or membrane sensing element is placed in contact with the solution or gel to form an interface between the test solution and this internal filling solution. However, ~ 35 this conventional design is complex to manufacture and -~ difficult to miniaturize.
~2~3245~3 .
In the fabrication of ion-selective electrodes a major problem is leakage at the interface of the ion-selective membrane and the insulative surface. This leakage causes corrosion and drift of the ion-selective ~- 5 electrode. Various attempts to ~revent leakage at the membrane interface are described in the literature.
U.S. Patent 4,180,771 describes placing the gate lead on the opposite face of ~ET device to isolate the ion-sens-ing area. U.S. Patent 4,449,011 t~ Kratachvil describes placing an insulating tape around the ion-sensing areas in an attempt to prevent moisture leakage.
U.S. Patent 4,393,130 to ~o et al. provides a dry film photoresist laminate which requires photo pro-cessing and etching to form a window around the ion-sensing areas for placement of the ion-selective mem-brane. A process for encapsulating ion-selective elec-trodes with thixotropic material having a window for an ion-selective membrane is also disclosed.
2~ U.S. Patent 4,456,522 and U.S. Patent 4,486,292 to Blackburn describe a method for spinning a polyimide layer onto a conductor which is then chemical-ly etched to leave a floating polyimide mesh. The mesh provides a physical support for a polymeric ion-selec-tive membrane.
U.S. Patent 4,454,007 to Pace describes a system whereby the ion-selective membrane is anchored to a conductor by intersolubilization. However, moisture may penetrate between the membrane and insulating layers to corrode the contacts.
In all these cases effective anchoring of the ion-selective membrane and insulation of the conductors are not achieved. Therefore, new systems for anchoring ion-selective membranes are desirable. The present invention describes a system comprising a plurality of insulative layers deposited over the substrate where at 8Z~58 least a portion of one of the layers is intersolubilized with ion-selective membrane. This system is effective for preventing leakage between the membrane and the insulating layers.
Sum~ary of the Inventio~
The present invention provides an ion-selective electrode comprising:
an electrically insulating substrate having a substantially planar surface;
a conductor on said surface;
an ion-selective membrane affixed to said conductor, for sensing a potential, and an electrically insulating layer comprising a first insulating stratum affixed to said surface and surrounding said ion-selective membrane, and a second insulating stratum surrounding and intersolubilized with said ion-selective membrane.
The present invention also relates to an ion-selective membrane anchor for containment of ion-selective membranes in substantially planar ion-selective electrodes having a conductive sensing area contacteclby an ion-selective membrane and having a substantially planar surface surrounding said sensing area comprising:
a first insulating stratum affixed to said planar surface surrounding said conductive sensing area of said ion-selective electrode; and il24~
- 3a -a second insulating stratum affixed to said first stratum and intersolubilized with said ion-selective membrane of said sensing area.
Preferably, a third insulatiny stratum covers the first insulating stratum and the second insulating stratum.
The ion-selective electrode having an anchored membrane according to the pre~ent invention may have means for sensiny including a field effect transistor and a conductive termination, preferably non-metalic, coupled to an electrode of the field effect transistor.
~he ion-sensitive electrode having an anchored membrane according to the present invention may have means for sensing which includes a non-metallic, offset gate conn,scted to a bulk electrode of a ChemFET and an exposed ion-selective membrane layer covering the offset gate.
In a preferred embodiment of the present invention, metalization is not used on the surface of the device which contacts an analyte. Rather, a non-~X~324~3 metallic, conductive material forms the conductive por-tions of the sensing element contacting the anchored membrane and also forms the leads between the anchored membrane and a conductor passing through the insulating substrate to a surface of the device, which surface is shielded from the analyte. The non-metallic conductive material may include graphite in a suita~le supportive and binding matrix or may include a conductive polymer, such as polyacetylene, and polypyrrole among others.
~rie ~escription of the Drawin~s FIG. 1 is a cross-sectional view of a ~ET
de~ice according to the present invention FIG. 2 is a schematic view of a preferred embodime~nt of a ~ET device according to the present invention; and FIG. 3 is an exploded ion-selective electrode view of an ISE with no electronics on the substrate.
Detailed Description The present invention provides a screen-print-able chemical anchor and well for containing a polymericmembrane which is specially formulate~ for application on a semiconductor chip or on a thin- or thick-film sub-strate in order to detect specific chemistries such as ions, electrolytes, metabotites, enzymes, proteins, and blood gasses.
Screen printing is used in the fabrication of thick film microelectronics such as hybrids, and is an established technique for the laydown of thixotropic electronic materials. Construction of a membrane anchor/well by screen printing simplifies physical ap-plication of the membrane, controls the geometry of the membrane, control~ the ~hickness o~ membrane, and pro-vide~ phy~ical support fo~ the membrane. Scree~ print-ing o~ a membrane anchor and well permits unlimited variation in p1anar geometry of sensing areas without a threat to the membrane, and al~o permit~ a virtually unlimited number o~ sensor~ per device. Moreover, en-capsulation and definition of sensor areas are accom-plished sîmultaneously and cro~s co~tamina~ion of vari-ous membranes on one device is prevented.
~n addition, spesific polymeri~ materials may be selected to provide for: chemical adherence between membrane and encapsulan~ or anchor; physica~ protection of sensing surface; and electrical in~egrity of sub-( strate, chip circuitry and external electrical connec-tions ~om adverse env$ronments.
The present ~nvention employs a solvent sensi-tive material (which may ~e a therm~plastic polymer) to encapsulate part of overcoat material in a zone around the sen~inq areas. Nhen implemented by screen printing, a ~creening pass is made af~er or between undercoat and overcoat passes. A sol~ent in the membrane formulation partially dissolves the thermoplastic material and thus provides an ''anchor" for i~proved adhe~ion of the mem-brane. Thi~ adhesion also improves moisture resistance and eliminate~ leakage current failure of the coating.
- There is a c~emical adherence between the membrane and the material encapsulating conductive areas.
A deep membrane well prevents cross contamina-tion of the membranes and provides physical support for the membranes.
In a preferred embodiment, an insulating sub-strate is cleaned ultrasonically and by vapor degrea~ing using an appropriate solvent (such as Frëon TA (trademark)~.
The substrate is annealed at 160c for 90 minutes and slow cooled to room temperature. The substrate is used as a ~2~32~ ;8 base for a screen printing pattern~ The screens used consist of standard mesh materials with emulsions as known in the art. Inks for various layers are formu-lated to meet ~equirements for thick film printing.
Standard screen printing apparatus are adjusted to meet the print requirements of th2 various inks and patterns employed.
In a preferred embodiment, graphite particles are dispersed in a suitable matrix for printing straight line patterns on a substrate. ~hree insulating layers are then spread or printed over the graphite and sub-strate in a pattern which ~orms a window or o~ening aver an area of the graphite. In this embodiment the inter-mediate layer is choosen such that it intersolubilizes15 with the ion-selective membrane to effectively anchor the membrane to the insulating layers. The insulating layers are printed to a total thickness, varying from 15 to 500 microns, to define a well over the opening. The substrate and/or insulating design also permits electri-cal contact of an analyte with the graphite pattern directly below the well or at some offset.
To remove potential contamination (particu-late, organic, etc.), the opening above the conductor is rinsed with an appropeiate s~lvent (such as acetone, MEK
or TEF). After rinsing, a membrane formulated as known in the art, is applied in liquid form over the conductor surface in the well area. Approximately 0.1 microliters of the membrane formula may be applied in the well. De-pending on membrane formula, multiple applications of amembrane may be used in the same well to provide the proper integrity.
As examples, some useful membrane formulas are: for Na+, 140 mg dibutyl sebacate, 60 mg PCV, 1 ml THF, and 2 mg of a Na+ ionophore; for pH, 20 mg tri-dodecylamine, 132 mg dibutyl sebacate, 1 ml THF, 51 mg ~2~3X~
P~C and 1.4 mg tetraphenylborate; for K~, 140 mg di-2-ethylhexyladipate, 1 ml THF, 60 mg PVC and 2.0 mg vali nomycin; and for Ca++, 41.8 mg nitrophenyloctylether, 6.6 mg PVC, 0.2 m/THF, 4.7 mg Ca++ ionophore, and 0.47 mg sodium tetraphenylborate~ After applying the mem-brane, the solvent is allowed to evaporate out of the membrane. After evaporating the solvent, membranes may be conditioned in appropriate solutions as known in the art.
FIG. l depicts an embodiment o~ a sensing element according to the present invention. In F~G. 1, a portion of an electrically insulating substrate lO is shown to have a first planar surface lOa and a second planar surface lOb. As indicated in FIG. 1, surfaces lOa and lOb may respectively be an obverse and a reverse surface of a planar substrate 10. Into a depression 15 in surface lOa, a field effect transistor (FET) 20, surrounded by a screen printed insulating underring 25, is inserted s~bstantially flush with surface lOa. A
conductive finger 30 (preferably formed by a graphite ink) passes along surface lOa between a gate contact of FET 20 and an offset gate 35. Upon this construction, the rest of the sensing element is formed by layers or deposits of materials having the appropriate properties.
An electrically insulating undercoat 40 covers all portio~s of semiconductor 20 which are exposed at surface ~Oa except for an aperture 20a around an offset gate 35 and for an aperture 20b around a source contact of FET 20 and an region 20c (not shown) around a drain contact (not shown) of FET 20 and similarly for a region 20d (not shown) around a bulk con~act (not shown) of FET
20. A lead 45 provides an external electrical connec-tion for the source (not shown) of FET 20. A similar lead (not shown) provides an external electrical connection for the drain (not shown) of FET 20. A
24~58 conductive, screen-printed contact 30 (preferably formed of graphite ink) connects a gate contact to a sensing layer 35 offset from the gate contact.
A layer 50 of an electrically insulatlng mem-brane anchor surrounds and dips down into aperture 20ato contact gate 35 while maintaining an aperture 20a.
An electrically-insulating overcoat 60 covers the entire surface o~ substrate lO except for aperture 20a. An ion-selective membrane 90 fills aperture 20a and is surrounded by a membrane we1l lO0.
membrane anchor 50 according to the present invention may be composed of homopolymers or copolymers of polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, cellulosics, polyurethanes, polyesters, vinyls, styxenas or polycarbonates.
Commercially available materials of this format are:
product number P7138, available from EMCA, Mamaroneck, New York; product number 432SS, available from Acheson, Port Huron, Michigan, and product number M7400, available from Minico, Congers, New York.
The device of FIG. l may be constructed as follows. First, the substrate is annealed to remove all stress by placing it in an oven at highest expected process temperature for 2 hours and then turn oven off allowing the substrate to cool to rGom temperature slow-ly. The substrate is cleaned by sonication in the pre-sence of isopropyl alcohol and vapor degreasing with trichlorotrifluorethane. FET 20 is mounted by dispens-ing adhesive into substrate recess 15, and then using avacuum tool to pick up the chip and locate it in the recess. Then the adhesive is cured according to the manufacturer's recommendations. Standard precautions are taken to avoid static shock.
~n underring is screen-printed around the chip as an insulative ~ridge, using a screen with a mesh, 12~ 458 angle, and emulsion as is known in the industry. An insulating ink suitable for screen printing is used and the insulating ink cured according to manufacturers re-commen~ations. Graphite is screen-printed as the sens-ing media over the metallized sensing pads of the gatecontact on FET 20, curing the ink according to manu-facturers recommendations. Insulating material 60 is next screen printed onto chip 20 and overlapping sub-strate 10, leaving sensor areas and contact pads un-covered. This insulating layer protects sensitive elec-tronics of the sPmiconductor from adverse environ-ments. Silver conductive runs connecting to the source and drain of FET 20 are screen-printed. Insulative overcoat material 60 is screen-printed and cured after screen printing and curing layer 50 of the membrane anchor to protect circuitry while also defining the sensing areas.
The substrate is theQ prepared for membrane application by rinsiQg sensing areas with a solvent such as trichlorotrifluoroethane, methyl ethyl ketone (MEK), or tetrahydrofuran (THF) to remove particulate matter from surface and allowing all remaining solvent to eva-porate. The surface of the substrate i5 visualized with a microscope at approximately 50X magnification. An appropriate membrane formulation is applied to well 100 using a microliter syringel onto sensing area within well 20a. The drop size is approximately 0.1 micro-liter. One to several drops may be applied, to obtain desired thickness of membrane 90. If multiple drops are used, each application is allowed to partially dry before the next one is applied. The membrane is cured for a period appropriate to membrane 90.
In order to test the sensing element, membrane 90 is conditioned by soaking in the appropriate ionic solution, for a period of time. The sensor is immersed :
~282~58;
in alternating sQlutions containing varying amounts of the appropriate analyte and an ionic strength adjuster to maintain constant solution ionic strength. The solu-tions are maintained at 25 degrees centrigrade with a water bath and jacketed beakers. U~ing a pH meter in the "millivolt" mode, the potentials generated by the sensing elements are monitored. A saturated calomel electrode is employed as the reference element. Re-sponse time, drift, slope and c~rrelation are observed.
Although this embodiment retains some metalli-zation at the surface of substrate 20 in pro~imity of the analyte, the membrane anchor formed by layer 50 and the minimization of metalization on surface lOa permits a longer use~ul life than is exhibited by devices lack-ing these features.
In FIG. 2, a preferred embodiment of a FET
device according to the présent invention is schemati-cally depicted. In this device a graphite pad 110 con-nects a sensing area to gate 115 of FET 200. FET 200 may thus be placed away from the well in which the analyte is placed or even on the reverse surface of the substrate by connecting a ~ET test box to source lead 201, drain lead 202 and bulk lead 203 of FET 200 and to 2~ a standard calomel electrode 300, the device may be used as an i~n-selecti~e electrode ~ The Vds of a FET test box 250 i5 set at a - constant value of approximately 2 volts. The ~d is fixed at a value of -50 microamps. The frit of elec-trode 300 and the membrane area over the graphite are completely immersed into a test solution. The gate voltage is read in millivolts. As the concentration of an ion changes, the potential of the membrane changes according to the Nernst equation. The FET box is confi-gured to adjust the Vg (gate voltage) proportionally to the membrane potential change, such that a constant Id ~LX8~
is maintained. This Vg adjustment is used in the Nernst equation as the negative equivalent of membrane pote~tial.
The membranes useful in sensing element and FET embodiments of the present invention may be prepared as follows:
For the sensing element embodiments (i.e.
those not having an active device mounted on the first surface) a pH membrane may be prepared by dissolving:
20 mg tridodecylamine (ionophore), 132 mg dibutyl seba-cate (plasticizer), 51 my polyvinyl (PVC) and 1.4 mg sodium tetraphenylboron in 1 ml tetraphydrofuran (TH~).
A potassium membrane may be prepared by dis-solving 2.0 mg valinomylin ~ionophore), 140 mg di-2-ethylhexyl adipate ~plasticizer) and 60 mg PVC in 1 ml THF.
A sodium memhrane may be prepared by preparing a stock PVC/THF solution of 33.0 mg PVC in 1 ml THF and ~20 dissolving 41.8 mg o-nitrophenyl octylether (plastic-;izer), 1.0 mg sodium tetraphenylboron, and 4.7 mg monen-sin methylester (ionophore) in 0.2 ml of the stock PVC/-THF sslution.
For both sensing element embodiments and for FET embodiments (i.e. those having an active device mounted on the first surface), a calcium membrane may be prepared using a stock PVC/THF solution of 13.2 mg PVC
in 0.4 ml THF and dissolving 41.8 mg o-nitrophenyl octylether, 0.47 mg sodium tetraphenylboron and 4.7 mg 3Q Fluka. #21192 calcium ionophore in 0.2 m~ of the stock PVC/THF solution.
For F~T embodiments, a potassium membrane may be prepared by dissolving 41.8 mg o-nltrophenyl octyl-ether, 0.47 mg sodium tetraphenylboron and 4.7 mg vali-nomycin in 0.2 ml of the same stock PVC/THF solution ~282~L~8 - 12 ~
described for the calcium membrane.
Materials useful in the construction of ion-selective electrodes as described herein may be obtained from the following sources. PVC from Polysciences In-corporated, Warrington, Pennsylvania; THF from Aldrich Chemical Company, Milwaukee, Wisconsin,, sodium tetra-phenylboron from Aldrich Chemical Compan~, Milwaukee, Wisconsin; dibutyl sebacate from Kodak Chemicals, Rochester, New York; tridodecylamine from Kodak Chemicals, Rochester, New York; valinomycin from Sigma Chemical Company, St. Louis, Missouri; di-2-ethylhexyla-dipate ~rom Polysciences, $nc., Warrington, Pennsylvania; o-nitrophenyloctylether fr~m Fluka Chemical Corporation, Ronkonkona, New York; monensin methyl ester from Calbiochem Biochemicals, San Diego, California and Calcium Ionophore #21192, Fluka Chemical Corp., E~onkonkona, New York.
A useful substrate material for embodiments of the present invention is a thermoplastic polyester resin for injection molding available from General Electric Corporation, Albany, New York, as the product Valox~
865. Screens for screen printing according to the pre-sent inventor may be obtained from Microcircuit En-gineering Corporation Mount Ho~ly, ~ew Jersey as 200MES~W/1.655 wire @ 30 degree an~le using type ES emulsion.
A graphite ink use~ul according to the present invention is available from Acheson Colloids Company, Port Huron, Michigan as product #423SS.
30In one embodiment of the present invention the ion~selective electrode, as illustrated in FIG. 3, a plastic substrate 700 holds five electrical pins (701, 702, 703, 704 and 705), a reference electrode 710, five ion-selective-electrode membranes (751, 752, 753, 754 35and 755), a first insulating layer 730 have apertures defining respective spaces 740 for reference electrode 4~3 710 and 741 745 respectively for sensing electrodes 721-725, cylindrical apertures 731-736 pass through sub-strate 700, and conductors (7?1-726) between the pins (701-706) and the reference electrode and the membranes. Reference electrode 710 is a small silver/-silver chloride square. It is inse~ted in the bottom of substrate 700 with a potassium chloride gel above it.
The gel is exposed to the test solutions via a small 0.005 inch diameter hole in the top surface of substrate Deposited above layer 730, overlapping the respective perimeters oE spaces 741-745 are square membrane anchors 761, 762, 763, 764 and 765, each of - which has a central, square aperture respectively beneath membranes 751-75~. A second insulating layer 760 is approximately identical to layer 730 in configuration, including the location and size of apertures 741-745, but lies above membrane anchors 761-765.
; 20 The top side of substrate 700 is covered with conductive car~on traces from the pins to the area where the ion-selective-electrode membranes are placed. An insulating pattern is formed over the conductive traces to protect them. The ion-selective electrode membranes 721-723 are placed above the insulating and conductive traces.
Moreover, although a single membrane anchor layer has been described herein, it is contemplated that a plurality of membrane anchor layers may be intersolu-bilized with the ion-sensitive membrane and interleaved with insulating layers to provide as circuitous a path for moisture to reach any metallization as may be prac-tical or desired.
Furthermore, in addition to those materials listed herein, thermoset materials suitable for tight ~1.2~32~iia adherence to a substrate and for insulating layers in-clude, for example, epoxies, urethanes, phenolics, ~nd silicones-. In addition to the thermoplastic material employed herein, the following thermoplastic materials, for example, may be useful for intersolubilization with ion~sensitive membranes, e.g., P~C, PVAc, PVAl, cellu-losics, acrylics, urethanes, PVDF, and polyesters. In general, anchor materials which are soluble in the same solvent or the membrane may be.intersolubilized with the membrane. Exceptions to this general rule involve ma-terials which may not be intersolubilized because of mismatch in crystallinity, packing, or interaction para-meters as defined by, for example: ~lory, "Principles of Polymer Chemistry," Cornell ~niversity Press, Ithaca, 15 ~ew York, (1953) ~u~gLns, Polym. J. ~ 4, 51l ~19733 Hildebrand, Ind. Eng. Chem. Fund., 17, 365 (1978); and Hansen, J. Paint Technol., 39, 511 (1967).
Therefore, it is intended that the present - invention include all such variations and improvements which come within the scope oE the invention as claimed.
~ ~ 30 :~
,
U.S. Patent 4,454,007 to Pace describes a system whereby the ion-selective membrane is anchored to a conductor by intersolubilization. However, moisture may penetrate between the membrane and insulating layers to corrode the contacts.
In all these cases effective anchoring of the ion-selective membrane and insulation of the conductors are not achieved. Therefore, new systems for anchoring ion-selective membranes are desirable. The present invention describes a system comprising a plurality of insulative layers deposited over the substrate where at 8Z~58 least a portion of one of the layers is intersolubilized with ion-selective membrane. This system is effective for preventing leakage between the membrane and the insulating layers.
Sum~ary of the Inventio~
The present invention provides an ion-selective electrode comprising:
an electrically insulating substrate having a substantially planar surface;
a conductor on said surface;
an ion-selective membrane affixed to said conductor, for sensing a potential, and an electrically insulating layer comprising a first insulating stratum affixed to said surface and surrounding said ion-selective membrane, and a second insulating stratum surrounding and intersolubilized with said ion-selective membrane.
The present invention also relates to an ion-selective membrane anchor for containment of ion-selective membranes in substantially planar ion-selective electrodes having a conductive sensing area contacteclby an ion-selective membrane and having a substantially planar surface surrounding said sensing area comprising:
a first insulating stratum affixed to said planar surface surrounding said conductive sensing area of said ion-selective electrode; and il24~
- 3a -a second insulating stratum affixed to said first stratum and intersolubilized with said ion-selective membrane of said sensing area.
Preferably, a third insulatiny stratum covers the first insulating stratum and the second insulating stratum.
The ion-selective electrode having an anchored membrane according to the pre~ent invention may have means for sensiny including a field effect transistor and a conductive termination, preferably non-metalic, coupled to an electrode of the field effect transistor.
~he ion-sensitive electrode having an anchored membrane according to the present invention may have means for sensing which includes a non-metallic, offset gate conn,scted to a bulk electrode of a ChemFET and an exposed ion-selective membrane layer covering the offset gate.
In a preferred embodiment of the present invention, metalization is not used on the surface of the device which contacts an analyte. Rather, a non-~X~324~3 metallic, conductive material forms the conductive por-tions of the sensing element contacting the anchored membrane and also forms the leads between the anchored membrane and a conductor passing through the insulating substrate to a surface of the device, which surface is shielded from the analyte. The non-metallic conductive material may include graphite in a suita~le supportive and binding matrix or may include a conductive polymer, such as polyacetylene, and polypyrrole among others.
~rie ~escription of the Drawin~s FIG. 1 is a cross-sectional view of a ~ET
de~ice according to the present invention FIG. 2 is a schematic view of a preferred embodime~nt of a ~ET device according to the present invention; and FIG. 3 is an exploded ion-selective electrode view of an ISE with no electronics on the substrate.
Detailed Description The present invention provides a screen-print-able chemical anchor and well for containing a polymericmembrane which is specially formulate~ for application on a semiconductor chip or on a thin- or thick-film sub-strate in order to detect specific chemistries such as ions, electrolytes, metabotites, enzymes, proteins, and blood gasses.
Screen printing is used in the fabrication of thick film microelectronics such as hybrids, and is an established technique for the laydown of thixotropic electronic materials. Construction of a membrane anchor/well by screen printing simplifies physical ap-plication of the membrane, controls the geometry of the membrane, control~ the ~hickness o~ membrane, and pro-vide~ phy~ical support fo~ the membrane. Scree~ print-ing o~ a membrane anchor and well permits unlimited variation in p1anar geometry of sensing areas without a threat to the membrane, and al~o permit~ a virtually unlimited number o~ sensor~ per device. Moreover, en-capsulation and definition of sensor areas are accom-plished sîmultaneously and cro~s co~tamina~ion of vari-ous membranes on one device is prevented.
~n addition, spesific polymeri~ materials may be selected to provide for: chemical adherence between membrane and encapsulan~ or anchor; physica~ protection of sensing surface; and electrical in~egrity of sub-( strate, chip circuitry and external electrical connec-tions ~om adverse env$ronments.
The present ~nvention employs a solvent sensi-tive material (which may ~e a therm~plastic polymer) to encapsulate part of overcoat material in a zone around the sen~inq areas. Nhen implemented by screen printing, a ~creening pass is made af~er or between undercoat and overcoat passes. A sol~ent in the membrane formulation partially dissolves the thermoplastic material and thus provides an ''anchor" for i~proved adhe~ion of the mem-brane. Thi~ adhesion also improves moisture resistance and eliminate~ leakage current failure of the coating.
- There is a c~emical adherence between the membrane and the material encapsulating conductive areas.
A deep membrane well prevents cross contamina-tion of the membranes and provides physical support for the membranes.
In a preferred embodiment, an insulating sub-strate is cleaned ultrasonically and by vapor degrea~ing using an appropriate solvent (such as Frëon TA (trademark)~.
The substrate is annealed at 160c for 90 minutes and slow cooled to room temperature. The substrate is used as a ~2~32~ ;8 base for a screen printing pattern~ The screens used consist of standard mesh materials with emulsions as known in the art. Inks for various layers are formu-lated to meet ~equirements for thick film printing.
Standard screen printing apparatus are adjusted to meet the print requirements of th2 various inks and patterns employed.
In a preferred embodiment, graphite particles are dispersed in a suitable matrix for printing straight line patterns on a substrate. ~hree insulating layers are then spread or printed over the graphite and sub-strate in a pattern which ~orms a window or o~ening aver an area of the graphite. In this embodiment the inter-mediate layer is choosen such that it intersolubilizes15 with the ion-selective membrane to effectively anchor the membrane to the insulating layers. The insulating layers are printed to a total thickness, varying from 15 to 500 microns, to define a well over the opening. The substrate and/or insulating design also permits electri-cal contact of an analyte with the graphite pattern directly below the well or at some offset.
To remove potential contamination (particu-late, organic, etc.), the opening above the conductor is rinsed with an appropeiate s~lvent (such as acetone, MEK
or TEF). After rinsing, a membrane formulated as known in the art, is applied in liquid form over the conductor surface in the well area. Approximately 0.1 microliters of the membrane formula may be applied in the well. De-pending on membrane formula, multiple applications of amembrane may be used in the same well to provide the proper integrity.
As examples, some useful membrane formulas are: for Na+, 140 mg dibutyl sebacate, 60 mg PCV, 1 ml THF, and 2 mg of a Na+ ionophore; for pH, 20 mg tri-dodecylamine, 132 mg dibutyl sebacate, 1 ml THF, 51 mg ~2~3X~
P~C and 1.4 mg tetraphenylborate; for K~, 140 mg di-2-ethylhexyladipate, 1 ml THF, 60 mg PVC and 2.0 mg vali nomycin; and for Ca++, 41.8 mg nitrophenyloctylether, 6.6 mg PVC, 0.2 m/THF, 4.7 mg Ca++ ionophore, and 0.47 mg sodium tetraphenylborate~ After applying the mem-brane, the solvent is allowed to evaporate out of the membrane. After evaporating the solvent, membranes may be conditioned in appropriate solutions as known in the art.
FIG. l depicts an embodiment o~ a sensing element according to the present invention. In F~G. 1, a portion of an electrically insulating substrate lO is shown to have a first planar surface lOa and a second planar surface lOb. As indicated in FIG. 1, surfaces lOa and lOb may respectively be an obverse and a reverse surface of a planar substrate 10. Into a depression 15 in surface lOa, a field effect transistor (FET) 20, surrounded by a screen printed insulating underring 25, is inserted s~bstantially flush with surface lOa. A
conductive finger 30 (preferably formed by a graphite ink) passes along surface lOa between a gate contact of FET 20 and an offset gate 35. Upon this construction, the rest of the sensing element is formed by layers or deposits of materials having the appropriate properties.
An electrically insulating undercoat 40 covers all portio~s of semiconductor 20 which are exposed at surface ~Oa except for an aperture 20a around an offset gate 35 and for an aperture 20b around a source contact of FET 20 and an region 20c (not shown) around a drain contact (not shown) of FET 20 and similarly for a region 20d (not shown) around a bulk con~act (not shown) of FET
20. A lead 45 provides an external electrical connec-tion for the source (not shown) of FET 20. A similar lead (not shown) provides an external electrical connection for the drain (not shown) of FET 20. A
24~58 conductive, screen-printed contact 30 (preferably formed of graphite ink) connects a gate contact to a sensing layer 35 offset from the gate contact.
A layer 50 of an electrically insulatlng mem-brane anchor surrounds and dips down into aperture 20ato contact gate 35 while maintaining an aperture 20a.
An electrically-insulating overcoat 60 covers the entire surface o~ substrate lO except for aperture 20a. An ion-selective membrane 90 fills aperture 20a and is surrounded by a membrane we1l lO0.
membrane anchor 50 according to the present invention may be composed of homopolymers or copolymers of polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, cellulosics, polyurethanes, polyesters, vinyls, styxenas or polycarbonates.
Commercially available materials of this format are:
product number P7138, available from EMCA, Mamaroneck, New York; product number 432SS, available from Acheson, Port Huron, Michigan, and product number M7400, available from Minico, Congers, New York.
The device of FIG. l may be constructed as follows. First, the substrate is annealed to remove all stress by placing it in an oven at highest expected process temperature for 2 hours and then turn oven off allowing the substrate to cool to rGom temperature slow-ly. The substrate is cleaned by sonication in the pre-sence of isopropyl alcohol and vapor degreasing with trichlorotrifluorethane. FET 20 is mounted by dispens-ing adhesive into substrate recess 15, and then using avacuum tool to pick up the chip and locate it in the recess. Then the adhesive is cured according to the manufacturer's recommendations. Standard precautions are taken to avoid static shock.
~n underring is screen-printed around the chip as an insulative ~ridge, using a screen with a mesh, 12~ 458 angle, and emulsion as is known in the industry. An insulating ink suitable for screen printing is used and the insulating ink cured according to manufacturers re-commen~ations. Graphite is screen-printed as the sens-ing media over the metallized sensing pads of the gatecontact on FET 20, curing the ink according to manu-facturers recommendations. Insulating material 60 is next screen printed onto chip 20 and overlapping sub-strate 10, leaving sensor areas and contact pads un-covered. This insulating layer protects sensitive elec-tronics of the sPmiconductor from adverse environ-ments. Silver conductive runs connecting to the source and drain of FET 20 are screen-printed. Insulative overcoat material 60 is screen-printed and cured after screen printing and curing layer 50 of the membrane anchor to protect circuitry while also defining the sensing areas.
The substrate is theQ prepared for membrane application by rinsiQg sensing areas with a solvent such as trichlorotrifluoroethane, methyl ethyl ketone (MEK), or tetrahydrofuran (THF) to remove particulate matter from surface and allowing all remaining solvent to eva-porate. The surface of the substrate i5 visualized with a microscope at approximately 50X magnification. An appropriate membrane formulation is applied to well 100 using a microliter syringel onto sensing area within well 20a. The drop size is approximately 0.1 micro-liter. One to several drops may be applied, to obtain desired thickness of membrane 90. If multiple drops are used, each application is allowed to partially dry before the next one is applied. The membrane is cured for a period appropriate to membrane 90.
In order to test the sensing element, membrane 90 is conditioned by soaking in the appropriate ionic solution, for a period of time. The sensor is immersed :
~282~58;
in alternating sQlutions containing varying amounts of the appropriate analyte and an ionic strength adjuster to maintain constant solution ionic strength. The solu-tions are maintained at 25 degrees centrigrade with a water bath and jacketed beakers. U~ing a pH meter in the "millivolt" mode, the potentials generated by the sensing elements are monitored. A saturated calomel electrode is employed as the reference element. Re-sponse time, drift, slope and c~rrelation are observed.
Although this embodiment retains some metalli-zation at the surface of substrate 20 in pro~imity of the analyte, the membrane anchor formed by layer 50 and the minimization of metalization on surface lOa permits a longer use~ul life than is exhibited by devices lack-ing these features.
In FIG. 2, a preferred embodiment of a FET
device according to the présent invention is schemati-cally depicted. In this device a graphite pad 110 con-nects a sensing area to gate 115 of FET 200. FET 200 may thus be placed away from the well in which the analyte is placed or even on the reverse surface of the substrate by connecting a ~ET test box to source lead 201, drain lead 202 and bulk lead 203 of FET 200 and to 2~ a standard calomel electrode 300, the device may be used as an i~n-selecti~e electrode ~ The Vds of a FET test box 250 i5 set at a - constant value of approximately 2 volts. The ~d is fixed at a value of -50 microamps. The frit of elec-trode 300 and the membrane area over the graphite are completely immersed into a test solution. The gate voltage is read in millivolts. As the concentration of an ion changes, the potential of the membrane changes according to the Nernst equation. The FET box is confi-gured to adjust the Vg (gate voltage) proportionally to the membrane potential change, such that a constant Id ~LX8~
is maintained. This Vg adjustment is used in the Nernst equation as the negative equivalent of membrane pote~tial.
The membranes useful in sensing element and FET embodiments of the present invention may be prepared as follows:
For the sensing element embodiments (i.e.
those not having an active device mounted on the first surface) a pH membrane may be prepared by dissolving:
20 mg tridodecylamine (ionophore), 132 mg dibutyl seba-cate (plasticizer), 51 my polyvinyl (PVC) and 1.4 mg sodium tetraphenylboron in 1 ml tetraphydrofuran (TH~).
A potassium membrane may be prepared by dis-solving 2.0 mg valinomylin ~ionophore), 140 mg di-2-ethylhexyl adipate ~plasticizer) and 60 mg PVC in 1 ml THF.
A sodium memhrane may be prepared by preparing a stock PVC/THF solution of 33.0 mg PVC in 1 ml THF and ~20 dissolving 41.8 mg o-nitrophenyl octylether (plastic-;izer), 1.0 mg sodium tetraphenylboron, and 4.7 mg monen-sin methylester (ionophore) in 0.2 ml of the stock PVC/-THF sslution.
For both sensing element embodiments and for FET embodiments (i.e. those having an active device mounted on the first surface), a calcium membrane may be prepared using a stock PVC/THF solution of 13.2 mg PVC
in 0.4 ml THF and dissolving 41.8 mg o-nitrophenyl octylether, 0.47 mg sodium tetraphenylboron and 4.7 mg 3Q Fluka. #21192 calcium ionophore in 0.2 m~ of the stock PVC/THF solution.
For F~T embodiments, a potassium membrane may be prepared by dissolving 41.8 mg o-nltrophenyl octyl-ether, 0.47 mg sodium tetraphenylboron and 4.7 mg vali-nomycin in 0.2 ml of the same stock PVC/THF solution ~282~L~8 - 12 ~
described for the calcium membrane.
Materials useful in the construction of ion-selective electrodes as described herein may be obtained from the following sources. PVC from Polysciences In-corporated, Warrington, Pennsylvania; THF from Aldrich Chemical Company, Milwaukee, Wisconsin,, sodium tetra-phenylboron from Aldrich Chemical Compan~, Milwaukee, Wisconsin; dibutyl sebacate from Kodak Chemicals, Rochester, New York; tridodecylamine from Kodak Chemicals, Rochester, New York; valinomycin from Sigma Chemical Company, St. Louis, Missouri; di-2-ethylhexyla-dipate ~rom Polysciences, $nc., Warrington, Pennsylvania; o-nitrophenyloctylether fr~m Fluka Chemical Corporation, Ronkonkona, New York; monensin methyl ester from Calbiochem Biochemicals, San Diego, California and Calcium Ionophore #21192, Fluka Chemical Corp., E~onkonkona, New York.
A useful substrate material for embodiments of the present invention is a thermoplastic polyester resin for injection molding available from General Electric Corporation, Albany, New York, as the product Valox~
865. Screens for screen printing according to the pre-sent inventor may be obtained from Microcircuit En-gineering Corporation Mount Ho~ly, ~ew Jersey as 200MES~W/1.655 wire @ 30 degree an~le using type ES emulsion.
A graphite ink use~ul according to the present invention is available from Acheson Colloids Company, Port Huron, Michigan as product #423SS.
30In one embodiment of the present invention the ion~selective electrode, as illustrated in FIG. 3, a plastic substrate 700 holds five electrical pins (701, 702, 703, 704 and 705), a reference electrode 710, five ion-selective-electrode membranes (751, 752, 753, 754 35and 755), a first insulating layer 730 have apertures defining respective spaces 740 for reference electrode 4~3 710 and 741 745 respectively for sensing electrodes 721-725, cylindrical apertures 731-736 pass through sub-strate 700, and conductors (7?1-726) between the pins (701-706) and the reference electrode and the membranes. Reference electrode 710 is a small silver/-silver chloride square. It is inse~ted in the bottom of substrate 700 with a potassium chloride gel above it.
The gel is exposed to the test solutions via a small 0.005 inch diameter hole in the top surface of substrate Deposited above layer 730, overlapping the respective perimeters oE spaces 741-745 are square membrane anchors 761, 762, 763, 764 and 765, each of - which has a central, square aperture respectively beneath membranes 751-75~. A second insulating layer 760 is approximately identical to layer 730 in configuration, including the location and size of apertures 741-745, but lies above membrane anchors 761-765.
; 20 The top side of substrate 700 is covered with conductive car~on traces from the pins to the area where the ion-selective-electrode membranes are placed. An insulating pattern is formed over the conductive traces to protect them. The ion-selective electrode membranes 721-723 are placed above the insulating and conductive traces.
Moreover, although a single membrane anchor layer has been described herein, it is contemplated that a plurality of membrane anchor layers may be intersolu-bilized with the ion-sensitive membrane and interleaved with insulating layers to provide as circuitous a path for moisture to reach any metallization as may be prac-tical or desired.
Furthermore, in addition to those materials listed herein, thermoset materials suitable for tight ~1.2~32~iia adherence to a substrate and for insulating layers in-clude, for example, epoxies, urethanes, phenolics, ~nd silicones-. In addition to the thermoplastic material employed herein, the following thermoplastic materials, for example, may be useful for intersolubilization with ion~sensitive membranes, e.g., P~C, PVAc, PVAl, cellu-losics, acrylics, urethanes, PVDF, and polyesters. In general, anchor materials which are soluble in the same solvent or the membrane may be.intersolubilized with the membrane. Exceptions to this general rule involve ma-terials which may not be intersolubilized because of mismatch in crystallinity, packing, or interaction para-meters as defined by, for example: ~lory, "Principles of Polymer Chemistry," Cornell ~niversity Press, Ithaca, 15 ~ew York, (1953) ~u~gLns, Polym. J. ~ 4, 51l ~19733 Hildebrand, Ind. Eng. Chem. Fund., 17, 365 (1978); and Hansen, J. Paint Technol., 39, 511 (1967).
Therefore, it is intended that the present - invention include all such variations and improvements which come within the scope oE the invention as claimed.
~ ~ 30 :~
,
Claims (9)
1. An ion-selective electrode comprising:
an electrically insulating substrate having a substantially planar surface;
a conductor on said surface;
an ion-selective membrane affixed to said conductor, for sensing a potential, and an electrically insulating layer comprising a first insulating stratum affixed to said surface and surrounding said ion-selective membrane, and a second insulating stratum surrounding and intersolubilized with said ion-selective membrane.
an electrically insulating substrate having a substantially planar surface;
a conductor on said surface;
an ion-selective membrane affixed to said conductor, for sensing a potential, and an electrically insulating layer comprising a first insulating stratum affixed to said surface and surrounding said ion-selective membrane, and a second insulating stratum surrounding and intersolubilized with said ion-selective membrane.
2. The ion-selective electrode as recited in claim 1, comprising sensing means including a field effect transistor and a conductive termination coupled to a gate of said field effect transistor.
3. The ion-selective electrode of claim 1, wherein said second insulating stratum comprises a solvent sensitive material whereby solvent in said ion-selective membrane partially dissolves said material.
4. The ion-selective electrode of claim 3, wherein said second insulating stratum is a thermoplastic polymer.
5. The ion-selective electrode of claim 1, wherein said electrically insulating layer further comprises a third insulating stratum covering said first and second stratums.
6. An ion-selective membrane anchor for containment of ion-selective membranes in substantially planar ion-selective electrodes having a conductive sensing area contacted by an ion-selective membrane and having a substantially planar surface surrounding said sensing area comprising:
a first insulating stratum affixed to said planar surface surrounding said conductive sensing area of said ion-selective electrode; and a second insulating stratum affixed to said first stratum and intersolubilized with said ion-selective membrane of said sensing area.
a first insulating stratum affixed to said planar surface surrounding said conductive sensing area of said ion-selective electrode; and a second insulating stratum affixed to said first stratum and intersolubilized with said ion-selective membrane of said sensing area.
7. The ion-selective membrane anchor of claim 6, wherein said second insulating stratum comprises a solvent sensitive material whereby solvent in said ion selective membrane partially dissolves said material.
8. The ion-selective membrane anchor of claim 7, wherein said second insulating stratum is a thermoplastic polymer.
9. The ion-selective membrane anchor of claim 6, which further comprises a third insulating stratum covering said first and second insulating stratums.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/053,454 US4772377A (en) | 1987-05-22 | 1987-05-22 | Membrane anchor for ion-selective electrodes |
| US053,454 | 1987-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1282458C true CA1282458C (en) | 1991-04-02 |
Family
ID=21984352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000567152A Expired - Fee Related CA1282458C (en) | 1987-05-22 | 1988-05-18 | Membrane anchor for ion-selective electrodes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4772377A (en) |
| EP (1) | EP0291903A3 (en) |
| JP (1) | JPS6453150A (en) |
| AU (1) | AU600360B2 (en) |
| CA (1) | CA1282458C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2516450B2 (en) * | 1990-04-02 | 1996-07-24 | 株式会社堀場製作所 | Sheet type electrode for ion measurement |
| CA2040610A1 (en) * | 1990-05-21 | 1991-11-22 | John E. Bennett | Apparatus for the removal of chloride from reinforced concrete structures |
| US5565143A (en) * | 1995-05-05 | 1996-10-15 | E. I. Du Pont De Nemours And Company | Water-based silver-silver chloride compositions |
| KR100474880B1 (en) * | 1997-01-24 | 2005-08-10 | 엘지전자 주식회사 | Solid ion sensor manufacturing method |
| TW555651B (en) * | 1998-04-14 | 2003-10-01 | Fuji Photo Film Co Ltd | Paper feeding cassette printer for use with paper feeding cassette and paper feeding method |
| AU7138200A (en) | 1999-07-22 | 2001-02-13 | Infrastructure Repair Technologies, Inc. | Method of treating corrosion in reinforced concrete structures by providing a uniform surface potential |
| US7101472B2 (en) * | 2002-03-13 | 2006-09-05 | The Charles Stark Draper Laboratory, Inc. | Microfluidic ion-selective electrode sensor system |
| US7407570B2 (en) * | 2002-03-13 | 2008-08-05 | The Charles Stark Draper Laboratory, Inc. | Disposable, self-administered electrolyte test |
| CN1267780C (en) * | 2002-11-11 | 2006-08-02 | Lg.飞利浦Lcd有限公司 | Array substrate for LCD device and its mfg. method |
| WO2004093145A2 (en) * | 2003-04-11 | 2004-10-28 | Paratek Microwave, Inc. | Voltage tunable photodefinable dielectric and method of manufacture therefore |
| JP2008094510A (en) * | 2006-10-06 | 2008-04-24 | Seiko Epson Corp | Feeding device, recording device, liquid injection device, and feeding method |
| JP5531886B2 (en) * | 2010-09-29 | 2014-06-25 | 大日本印刷株式会社 | Biosensor system |
| DE102011103195A1 (en) | 2011-05-31 | 2012-08-02 | NMI Naturwissenschaftliches und Medizinisches Institut an der Universität Tübingen | Micro system e.g. micro electromechanical system, for use in e.g. electrical engineering, has anchor structure provided at carrier substrate and/or at electrical component, where membrane is fixed to anchor structure in form-fit manner |
| WO2015042181A2 (en) | 2013-09-18 | 2015-03-26 | Suprasensor Technologies, Llc | Molecular receptor-based chemical field-effect transistor (chemfet) devices, systems, and methods for in-situ nitrate monitoring in field soils |
| CA3113665A1 (en) | 2018-09-21 | 2020-03-26 | Teralytic Inc. | Extensible, multimodal sensor fusion platform for remote, proximal terrain sensing |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180771A (en) * | 1977-12-02 | 1979-12-25 | Airco, Inc. | Chemical-sensitive field-effect transistor |
| US4456522A (en) * | 1981-09-23 | 1984-06-26 | Critikon, Inc. | Support and anchoring mechanism for membranes in selectively responsive field effect devices |
| US4486292A (en) * | 1981-09-23 | 1984-12-04 | Critikon, Inc. | Support and anchoring mechanism for membranes in selectively responsive field effect devices |
| US4449011A (en) * | 1982-01-08 | 1984-05-15 | Critikon, Inc. | Method and apparatus for encapsulation of chemically sensitive field effect device |
| US4393130A (en) * | 1982-01-11 | 1983-07-12 | Critikon, Inc. | System for encapsulation of semiconductor chips |
| JPS5938647A (en) * | 1982-08-28 | 1984-03-02 | Toshiba Corp | Ion selective electrode apparatus and flowing type ion analytical apparatus |
| US4454007A (en) * | 1983-01-27 | 1984-06-12 | E. I. Du Pont De Nemours And Company | Ion-selective layered sensor and methods of making and using the same |
| JPS60243555A (en) * | 1984-05-18 | 1985-12-03 | Fuji Photo Film Co Ltd | Ion-selecting electrode and manufacture thereof |
-
1987
- 1987-05-22 US US07/053,454 patent/US4772377A/en not_active Expired - Fee Related
-
1988
- 1988-05-16 EP EP19880107816 patent/EP0291903A3/en not_active Withdrawn
- 1988-05-18 CA CA000567152A patent/CA1282458C/en not_active Expired - Fee Related
- 1988-05-20 AU AU16481/88A patent/AU600360B2/en not_active Ceased
- 1988-05-23 JP JP63125596A patent/JPS6453150A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU600360B2 (en) | 1990-08-09 |
| US4772377A (en) | 1988-09-20 |
| JPS6453150A (en) | 1989-03-01 |
| EP0291903A2 (en) | 1988-11-23 |
| AU1648188A (en) | 1988-11-24 |
| EP0291903A3 (en) | 1990-09-19 |
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