WO2001036956A1 - Capteur de type film hybride - Google Patents

Capteur de type film hybride Download PDF

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Publication number
WO2001036956A1
WO2001036956A1 PCT/US2000/031660 US0031660W WO0136956A1 WO 2001036956 A1 WO2001036956 A1 WO 2001036956A1 US 0031660 W US0031660 W US 0031660W WO 0136956 A1 WO0136956 A1 WO 0136956A1
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WO
WIPO (PCT)
Prior art keywords
sensing
counter
electrode
substrate
reference electrodes
Prior art date
Application number
PCT/US2000/031660
Other languages
English (en)
Other versions
WO2001036956A9 (fr
Inventor
Otto J. Prohaska
Anthony B. Lacontio
Jose D. Giner
Mourad Manoukian
Original Assignee
Perkinelmer Instruments Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Perkinelmer Instruments Llc filed Critical Perkinelmer Instruments Llc
Priority to AU16204/01A priority Critical patent/AU1620401A/en
Priority to EP00978779A priority patent/EP1161678A4/fr
Priority to JP2001538793A priority patent/JP2003515131A/ja
Priority to CA002360595A priority patent/CA2360595C/fr
Publication of WO2001036956A1 publication Critical patent/WO2001036956A1/fr
Publication of WO2001036956A9 publication Critical patent/WO2001036956A9/fr

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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
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • 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

Definitions

  • the invention is directed toward a sensor with thick or thin film electrodes on a non-conductive substrate.
  • solid-state gas sensors While solid-state gas sensors have the advantage of being able to operate at elevated temperatures, they also have the disadvantages of slow response and recovery time and a high internal operating temperature as reported by Liu et al., 1993; and Narducci et al., 1993. More recent literature (Schwebel et al., 1997; Sheng et al., 1997; Micocci et al., 1997) details the substantial development work yet to be done before this type of sensor is applicable for use in battery-powered instruments.
  • Nafion ® -coated metal oxide pH sensor has been reported (Kinlen et al., 1994) with sputtered iridium oxide sensing and silver/silver chloride reference electrodes on alumina ceramic substrates. Nafion was used as a cation-selective ionomer coating in order to decrease the oxidation-reduction error generally affecting the performance of metal oxide pH electrodes.
  • the use of Nafion as polymer-electrolyte for a thin-film CO sensor is described (Yasuda et al., 1994) with macro-sized, sputtered Pt sensing and counter electrodes and a smaller, sputtered Au electrode as reference electrode.
  • a 5 wt% n-propyl alcohol solution of Nafion (DuPont, 1100 EW) is used to form the polymer electrolyte film over the electrodes by casting.
  • the polymer is washed and protonated in aqueous sulfuric acid prior to casting.
  • the reported lifetime of this sensor is reported to be less than one month.
  • the CO oxidation current decreases steadily down to a few percent of its original value without any period of stable measurement signal.
  • the lifetime of the device may be extended up to three years by laminating the polymer electrolyte layer with a cast perfluorocycloether-polymer film in order to keep the
  • One side of the electrolyte membrane is flooded with distilled water, making the sensor cell self-humidifying and independent of external humidity. Since no corrosive acids or bases are used in the sensor cell, a lifetime of over 10 years has been demonstrated for solid polymer ionomer sensor cells. Finally, the sensor cells are easy to maintain, and so are ideal for use in remote, unattended environments. Regular addition of water to the reservoir in the sensor housing every several months and monthly calibration checks are the only requirements.
  • a disadvantage of the state-of-the-art sensors described above is that the signal-to-noise ratio may not be conducive to detection of very low concentrations (parts per billion, ppb) of important environmental and biomedical gases and vapors. Also, response time may be relatively slow, and reproducibility between sensors and sensor cells may be difficult to achieve. Also, they are relatively costly.
  • the solid ionomer membrane acts as a conduit between the gas to be detected (sample gas) and the sensing electrode (Yasuda et al., 1994).
  • sample gas permeates through the membrane itself where a 3-phase contact area is established.
  • the solid ionomer membrane water content may control the gas permeation rate as well as proton conductivity. As the humidity increases, the membrane water content increases. This causes an increase in the gas diffusion rate as well as proton conductivity and sensor signal response.
  • the best method of controlling or fixing the water content of the membrane is to have a water reservoir on the back side of the membrane, directly opposite to where the film type electrodes and non-conductive supportive substrate are located.
  • the back side of the membrane is required to be free of liquid so that the sample gas can diffuse through the membrane to the sensing electrode.
  • the present invention overcomes the limitations of the state-of-the-art in miniaturized electrochemical sensors stated above by uniquely combining an advanced solid polymer ionomer membrane configuration with a film type electrode on a non-conductive supportive substrate.
  • the substrate has diffusion openings or holes having a known area which permit easy access of the sample gas to a sensing electrode contact area.
  • the sensor configuration provides a three phase contact area which serves as an interface for the membrane, the electrodes, and the gas being detected.
  • This design utilizes the precision of solid-state device fabrication techniques to yield inexpensive, low maintenance, highly sensitive, rapidly responsive, and reproducible sensor devices for environmental, industrial, and biomedical monitoring.
  • This invention is directed toward a controllable and reproducible gas sensor configuration having a three-phase contact area, whereby the sample gas diffuses to the sensing electrode and membrane through openings, holes or slits that extend through the non-conductive supportive substrate.
  • This invention is further directed toward a gas sensor where the gas diffusion process is decoupled from the proton conduction process.
  • the gas diffusion is controlled only by through openings of known area in the substrate or in the substrate and an additional rate limiting gas diffusion barrier film, eg: polyethlene, while proton conduction takes place only through an electrolyte layer, e.g., a Nafion ® membrane.
  • the invention is also directed toward utilizing a method of mass producing film type gas sensors by stacking a number of component layers to form a series of adjacent sensors which are subsequently separated into individual sensors.
  • the invention is still further directed toward a gas sensor utilized in conjunction with a gas sensor control circuit.
  • the invention is also directed toward a gas sensor utilized in a gas sensing instrument.
  • Figure 1 shows a schematic top view of the non-conductive supportive substrate.
  • Figure 2 shows a film type electrochemical sensor cell with Pt/Air (O 2 ) reference.
  • Figure 3 shows a film type electrochemical sensor cell with a polymeric gas-diffusion layer over the sensing electrode membrane.
  • Figure 4a shows a top view of a thick-film type electrochemical sensor cell.
  • Figure 4b shows a cross-section A-A'.
  • Figure 4c shows a cross-sectional view of sensor cell assembly.
  • Figure 5 shows a gas sensor control circuit
  • Figure 6 shows a gas sensor utilized in a gas sensing instrument.
  • Figure 1 shows the top view of a ceramic film type substrate (1) (e.g., alumina) having holes (2) uniformly distributed in parallel rows.
  • the distance between the holes in the parallel rows and the distance between the rows determine the dimensions of the sensor.
  • the holes are ideally punched in a single step, while the alumina plate is still soft, in the "green" stage of substrate fabrication, prior to high-temperature sintering.
  • Other techniques to create the holes include laser ablation or use of soluble fillers.
  • conducting leads (3) and thick- and thin-film electrodes are formed on the non-conductive substrate (1) for multiple electrodes.
  • a typical sensor design utilizing this method is shown in Figure 2, which has a single reference electrode (4) (e.g., Pt/Air (O 2 ) electrode) and a Pt counter electrode (5).
  • the contact for the sensing electrode (6) is a ring concentric to the hole. This ring can be made of smooth, rough or platinized platinum. Some platinization may provide better contact. Simultaneous platinization of electrodes can be performed by customized electrolytic plating on properly masked multi-sensor plates.
  • the sensing or working electrode (7) may be a disc of Teflon ® -bonded or Nafion-bonded platinum or other electrocatalyst.
  • a number of discs are deposited on an ionomer film, such as Nafion electrolyte membrane (8) at uniform distances from each other, for instance, by decal transfer, silk printing, spray painting, artist brush lettering, or by any approach which lends itself to uniform deposition of a design on a transfer substrate without waste.
  • the discs' distances from center to center are the same as for the holes of Figure 1.
  • the diameter of the sensing or working electrode disc is somewhat larger than the diameter of the hole in Figure 1 to allow for contact between the disc and the sensing electrode support ring of Figure 2.
  • a series of smaller openings may be used, with small enough diameters to control diffusion independently of the analyte flow.
  • the areas of the openings are chosen so as to control diffusion of the sample gas toward the sensor and to maintain a constant diffusion rate independent of any changes in the sample gas flow rate.
  • a gas-permeable diffusion film (9) is deposited in one configuration of the invention.
  • This film is made to conform to the sensor electrode over the holes (as shown in Figure 3), or hangs loose over the (sensor) sensing electrode (7).
  • the substrate with multiple arrays of printed conductors
  • the Nafion membrane with multiple sensing electrode discs
  • the gas-permeable film are arranged as shown in the schematic representation of Figure 3. After all the components are unitized, the resulting structure is cut in individual sensor units.
  • An additional advantage of this structure is that it allows for a water reservoir over the Nafion membrane on the opposite, or back side from where the sensing electrode is located as shown in Figure 4c.
  • FIG. 4 A schematic drawing of the sensor cell assembly of this invention is shown in Figure 4.
  • a hole of approximately 80 mils (0.080 in) is formed in a film type substrate and sensing electrode contacts (6), and Pt counter (5) and reference electrodes (4) are then deposited on the substrate (1) surface as shown in Figure 4a.
  • the hole (2) is drilled directly through the non-conductive substrate and integral sensing electrode contact structure.
  • the sample gas has direct contact through the substrate hole with the sensing electrode as shown in Figure 4b.
  • This film type substrate structure is mounted in a sensor housing (10) as shown in Figure 4c with a solid ionomer membrane (Nafion 117).
  • the Pt sensing electrode (with hole in center) and solid counter and reference electrodes are compressed tightly against the Nafion membrane.
  • the fixture as shown in Figure 4 has a water reservoir (11) on the opposite side of the membrane from where the electrodes are located.
  • the reservoir (11) is filled with distilled water and wets the membrane, thus fixing and controlling the water content of the membrane and electrode assemblies.
  • the reservoir (11) is sealed with a cap (20).
  • the film type sensor configuration from above is integrated with a potentiostat and a voltage of approximately +0.1 V is applied to the Pt sensing electrode with respect to a Pt/Air (O 2 ) reference. This corresponds to an applied potentiostatic voltage of approximately 1.16 V with respect to a normal hydrogen electrode (NHE).
  • NHE normal hydrogen electrode
  • Gas samples of air and 7.4 ppm SO 2 in air are introduced into the sampling port of the fixture described above.
  • the gas flow is approximately 60 cm 3 /min and temperature is approximately 25°C.
  • the sample gas diffuses through the 80-mil hole in the non-conductive substrate and electrochemically reactes at the exposed sensing electrode/solid ionomer electrolyte surface.
  • Humidification is provided by the liquid water in the reservoir which soaks the opposite, or back side of the membrane as to where the electrode structures are located.
  • the background response signal with air is 30 nanoamps (nA).
  • the response signal with 7.4 ppm SO 2 in air is 135 nA. This corresponds to a net response signal for 7.4 ppm SO 2 in air of 105 nA or 14.2 nA/ppm per 80-mil hole. It is possible to increase the magnitude of signal and signal-to-noise ratio by increasing the number of holes in the substrate above the integral sensing electrode structure. It is also possible, with this configuration, to detect other oxidizable or reducible gases such as CO, NO, NO 2 , H 2 S, ozone, CO 2 , hydrogen, hydrazine, ammonia, HCI, alcohols and acetone.
  • the sensor control circuit (13) is designed to: 1) control the potential of the sensing electrode (7) at a predetermined voltage (the "potentiostatic voltage", or “E pot "); 2) measure the temperature; 3) convert the gas concentration- related current to a temperature-compensated voltage signal; and 4) provide properly amplified voltage to the data acquisition/storage microprocessor (14).
  • An on-board micro power-regulated power supply (16) uses the microprocessor's (14) power supply to provide the required ⁇ 3.9 volts for the sensor circuitry.
  • the DC power can be supplied by a 6-V battery (16d) or an AC adaptor (16e).
  • the control amplifier portion (17b) of the sensor control circuit (13) consists of a micro power operational amplifier (e.g., MAX407 or LM6062).
  • the sensing (7), counter (5) and reference (4) electrode portions of the sensor assembly (1) are in the feedback loop of the control amplifier (17b) as shown in Figure 5, a standard configuration for potentiostat circuits.
  • An adjustable voltage divider (17a) allows the polarizing voltage (E pot ) to be set at a predetermined voltage range such as 0 to 50 mV. This signal is compared to the reference electrode (7) voltage (which appears with it at the summing junction) by the control amplifier ( 17b) of the sensor control circuit (13). The latter adjusts the current through the sensor cell (10) to minimize the difference between the E pot and the reference electrode (4) voltages.
  • the transformed current signal is directed to an A/D channel on the data acquisition board of the microprocessor (14).
  • Power for the sensor control circuit (13) is provided by a Duracell 6-V battery (16d) (PX 28A or 28L) through a micro power-regulated power supply (16).
  • the power supply (16) utilizes a voltage inverter (e.g., ICL 7660) (16a) to convert the positive battery voltage to a negative voltage of the same magnitude, and a positive voltage regulator (e.g., MAX663) (16c) and negative voltage regulator (e.g., MAX 664) (16b) to provide a stable ⁇ 3.9 volts.
  • the film type gas or vapor sensing instrument (12), as shown in Figure 6, includes the sensor cell assembly (19), potential-control circuitry (13), and the microprocessor (14) with the data acquisition-recording unit.
  • the sensing instrument (12) is preferably battery operated, and has the ability to sample the gas or vapor and temperature signals at intervals and store in the random access memory (RAM) on the data acquisition board days to weeks of data.
  • the data acquisition circuit microprocessor is programmed to sample and store the gas concentration signals at preset intervals. Data are off-loaded to a personal computer by accessing the microprocessor through an RS232 port.
  • the sensor cell assembly (19) and its potential-control circuit (13) are integrated with a battery-operated microprocessor (14) of 32K memory, which samples the sensor signal as well as temperature and other signals at 10-, 20-, or 30-second intervals and stores an average value at intervals of 2, 5, or 10 minutes according to a programmable protocol.
  • the data acquisition/storage unit in the microprocessor (14) can record 8 days of data, storing at 2-minute intervals, or up to 40 days storing at 10-minute intervals. In clinical testing to date, a 2-minute interval is suitable for one-day clinical studies and a 10-minute interval is appropriate for extended use.
  • the microprocessor (14) with data acquisition/logic circuit can be programmed to sample more than one analog signal from the control circuit (13), and to convert these to digital signals and store them (i.e., gas concentration and temperature) at preset intervals together with real-time data. Data are off-loaded to a personal computer by accessing the microprocessor (14) through an RS232 port. After downloading, the digital data are converted to engineering units of gas concentration and temperature, and can be graphed by a menu-driven Lotus ® 123 spreadsheet. Through a potentiometer in the gain amplifier circuit (15c), the device can be calibrated with calibrated gas samples, to indicate gas concentrations in the ambient.
  • the potential-control circuit (13) shown in Figure 5 is powered, in a preferred embodiment, by six VA volt AA-size batteries (16d).
  • a typical microprocessor (14) with data acquisition-recording capability that has been successfully used is sold by ONSET Computers, Falmouth, MA, under the product name of "Tattletale Lite ® .”
  • the sensor cell assembly (19) with its control circuit (13) is also designed to yield a current or voltage signal proportional to gas flux that could be used to continuously transmit the data to a remote receiving device or central monitoring station or unit.
  • the sensing electrodes can be organized in multiple arrays or sets containing a necessary number of counter or reference electrodes.
  • Reference electrodes such as Pt/air (O 2 ), PtO 2 , or dynamic hydrogen electrode as described by Giner (1964) may be employed.
  • Electrically driven 3- or 2-electrode film type configurations may be employed using potentiostatic, potentiodynamic or potential control.
  • Two-electrode configurations require a reversible or stable counter- reference electrode such as Pt/air (O 2 ), PtO 2 or Pt/H 2 which has a higher BET (Brunauer, Emmett, Teller) surface area (25 m 2 /g or larger) and/or larger geometric surface areas than the sensing lectrode.
  • BET Brunauer, Emmett, Teller
  • Electrochemically reversible electrodes may be used in 3 or 2 electrode configurations, but especially in a 2 electrode arrangement where the counter electrode also acts as a reference electrode. Electrochemically reversible electrodes are constructed of stable catalyst materials and usually have a relatively large electrochemical active surface area so that they remain stable and their potential is not perturbed by small current flow. Examples include PtO 2 and Ag/AgCI electrodes.

Abstract

La présente invention concerne un capteur de gaz miniaturisé qui comprend des électrodes de type film épais ou mince, placées sur un substrat (1) support non conducteur, et en contact avec un électrolyte (8) ionomère solide. Ce capteur est destiné à détecter les gaz toxiques, à savoir le monoxyde de carbone et d'autres gaz et vapeurs oxydables ou réductibles. Cette cellule capteur plane et complètement solide possède au moins deux électrodes (4, 5, 7) de type film agencées sur la surface plane non conductrice d'un substrat support. Ces électrodes sont distinctes et en contact étroit avec cette membrane ionomère de polymère solide. Cette cellule capteur contient un électrolyte non liquide et fonctionne à tension constante, dans un mode potentiostatique ou potentiodynamique. On obtient une haute sensibilité à un gaz ou à une vapeur choisie grâce à une nouvelle conception de zone de contact en trois phases destinée à une électrode de détection qui permet d'être en contact avec l'électrolyte ionomère solide, ainsi qu'avec l'échantillon de gaz via des ouverture ou des trous (2) de diffusion qui pénètrent à travers le substrat support.
PCT/US2000/031660 1999-11-19 2000-11-20 Capteur de type film hybride WO2001036956A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU16204/01A AU1620401A (en) 1999-11-19 2000-11-20 Hybrid film type sensor
EP00978779A EP1161678A4 (fr) 1999-11-19 2000-11-20 Capteur de type film hybride
JP2001538793A JP2003515131A (ja) 1999-11-19 2000-11-20 複合フィルム形センサー
CA002360595A CA2360595C (fr) 1999-11-19 2000-11-20 Capteur de type film hybride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44433499A 1999-11-19 1999-11-19
US09/444,334 1999-11-19

Publications (2)

Publication Number Publication Date
WO2001036956A1 true WO2001036956A1 (fr) 2001-05-25
WO2001036956A9 WO2001036956A9 (fr) 2002-05-23

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Application Number Title Priority Date Filing Date
PCT/US2000/031660 WO2001036956A1 (fr) 1999-11-19 2000-11-20 Capteur de type film hybride

Country Status (6)

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EP (1) EP1161678A4 (fr)
JP (1) JP2003515131A (fr)
CN (1) CN1195980C (fr)
AU (1) AU1620401A (fr)
CA (1) CA2360595C (fr)
WO (1) WO2001036956A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
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EP1304565A2 (fr) * 2001-10-22 2003-04-23 PerkinElmer Instruments LLC (a Delaware Corporation) Capteur de gaz électrochimique avec une membrane sèche ionomère
EP1326075A1 (fr) * 2002-01-03 2003-07-09 EnviteC-Wismar GmbH Appareil et méthode pour déterminer la concentration de vapeur d'alcool
EP1420247A1 (fr) * 2002-11-18 2004-05-19 PerkinElmer LAS, Inc. Capteur de type film hybride
WO2005059536A1 (fr) * 2003-12-17 2005-06-30 Perkinelmer Las, Inc. Capteur d'ionomere polymere solide de type film et cellule de capteurs
US8888979B2 (en) 2009-08-04 2014-11-18 Gentex Corporation Cathodic materials for use in electrochemical sensors and associated devices and methods of manufacturing the same
US8916037B1 (en) 2006-08-31 2014-12-23 Mocon, Inc. Instrument and method for measuring high concentrations of carbon monoxide in a gaseous sample

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US8075752B2 (en) * 2005-02-15 2011-12-13 Perkinelmer Health Sciences, Inc. Method and apparatus for providing an electrochemical sensor at an elevated temperature
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US11932080B2 (en) 2020-08-20 2024-03-19 Denso International America, Inc. Diagnostic and recirculation control systems and methods
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US11813926B2 (en) 2020-08-20 2023-11-14 Denso International America, Inc. Binding agent and olfaction sensor
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1304565A2 (fr) * 2001-10-22 2003-04-23 PerkinElmer Instruments LLC (a Delaware Corporation) Capteur de gaz électrochimique avec une membrane sèche ionomère
EP1304565A3 (fr) * 2001-10-22 2004-07-21 PerkinElmer Instruments LLC (a Delaware Corporation) Capteur de gaz électrochimique avec une membrane sèche ionomère
EP1326075A1 (fr) * 2002-01-03 2003-07-09 EnviteC-Wismar GmbH Appareil et méthode pour déterminer la concentration de vapeur d'alcool
EP1420247A1 (fr) * 2002-11-18 2004-05-19 PerkinElmer LAS, Inc. Capteur de type film hybride
EP2369332A1 (fr) * 2002-11-18 2011-09-28 PerkinElmer LAS, Inc. Capteur de type de film hybride
WO2005059536A1 (fr) * 2003-12-17 2005-06-30 Perkinelmer Las, Inc. Capteur d'ionomere polymere solide de type film et cellule de capteurs
US8916037B1 (en) 2006-08-31 2014-12-23 Mocon, Inc. Instrument and method for measuring high concentrations of carbon monoxide in a gaseous sample
US8888979B2 (en) 2009-08-04 2014-11-18 Gentex Corporation Cathodic materials for use in electrochemical sensors and associated devices and methods of manufacturing the same
US8951396B2 (en) 2009-08-04 2015-02-10 Gentex Corporation Cathodic materials for use in electrochemical sensors and associated devices and methods of manufacturing the same

Also Published As

Publication number Publication date
EP1161678A1 (fr) 2001-12-12
EP1161678A4 (fr) 2007-02-21
CN1347495A (zh) 2002-05-01
JP2003515131A (ja) 2003-04-22
CN1195980C (zh) 2005-04-06
CA2360595C (fr) 2006-02-07
CA2360595A1 (fr) 2001-05-25
WO2001036956A9 (fr) 2002-05-23
AU1620401A (en) 2001-05-30

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