EP1904837A1 - Procede de detection simultanee de differentes pollutions de l'air par des transistors a effet de champ sensibles au gaz - Google Patents

Procede de detection simultanee de differentes pollutions de l'air par des transistors a effet de champ sensibles au gaz

Info

Publication number
EP1904837A1
EP1904837A1 EP06777780A EP06777780A EP1904837A1 EP 1904837 A1 EP1904837 A1 EP 1904837A1 EP 06777780 A EP06777780 A EP 06777780A EP 06777780 A EP06777780 A EP 06777780A EP 1904837 A1 EP1904837 A1 EP 1904837A1
Authority
EP
European Patent Office
Prior art keywords
gas
gas sensor
detection
sensitive
sensor arrangement
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.)
Withdrawn
Application number
EP06777780A
Other languages
German (de)
English (en)
Inventor
Peter Biber
Maximilian Fleischer
Stephan Heinrich
Uwe Lampe
Roland Pohle
Elfriede Simon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP1904837A1 publication Critical patent/EP1904837A1/fr
Withdrawn legal-status Critical Current

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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
    • G01N27/4141—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for gases
    • G01N27/4143—Air gap between gate and channel, i.e. suspended gate [SG] FETs

Definitions

  • the invention relates to a method for detecting different air loads, which are usually defined by gases or gas groups, in particular for the assessment of a passenger cabin of a motor vehicle air supplied.
  • Modern air conditioning systems in motor vehicles have features with which the air quality in the passenger cabin can be maintained on average better than the ambient air quality.
  • the quality of the fresh air sucked in for the ventilation of the passenger cabin is determined with a gas sensor.
  • measures are taken to prevent this bad air from loading the passenger cabin.
  • a ventilation possibly temporarily with circulating air, a throttling of the air supply to the required minimum or the cleaning of fresh air sucked temporarily by a filter conceivable before it is fed into the passenger cabin.
  • Previous sensors mainly determine the air quality by detecting the emission of preceding vehicles.
  • at least one predetermined guide gas can be detected.
  • the exhaust gases of gasoline engines are detected, for example, by the detection of the conductive gas carbon monoxide (CO) and in individual cases by the detection of hydrocarbons (HC) in the volume concentration range of 1 to 200 ppm.
  • the exhaust gases of diesel engines are detected by the detection of nitrogen oxide (NOx), which actually nitrogen dioxide (NO2) is measured, especially in the range of about 0.05-10 ppm by volume.
  • NOx nitrogen oxide
  • the pollution of the air quality by odor sources such as manure, Tar work, petrochemicals, sewage treatment plants etc. with accompanying strongly subjective odor impression more and more important.
  • EP 0448681 Bl shows a gas detection, based on the combination of a heated to several 100 0 C ceramic tin oxide conductivity sensor for
  • Another variant for the detection of air pollutants is to use a single heated ceramic tin oxide conductivity sensor either on ceramic or micromechanically produced substrates.
  • a signal generated at the sensor can not be clearly evaluated. It may be related to a reaction to one of the target gases or to a lessening of the reaction to the other target gas.
  • This problem was solved by an intelligent, time transient signal evaluation. It is assumed that the response is faster as the decline of a sensor reaction; see international patent application WO 95/29435.
  • Another system that can treat air quality in automotive systems consists of two heated oxide ceramic conductivity sensors.
  • the one conductivity sensor should react as selectively as possible to the one target gas, whereas the other one should react as selectively as possible to other target gases.
  • sensors used to date are, despite good sensitivity to the exhaust gases of other vehicles, in particular to the above-mentioned air polluting substances only weakly sensitive and record essentially only the burden of air quality by other vehicles. This weak reaction also occurs only as a superposition of the previous sensor signals and is therefore only weakly evaluated.
  • the additional, separate third and fourth sensor is uneconomical overall for cost and space reasons.
  • sensors which operate on the basis of semiconducting metal oxides require special control electronics which, on the one hand, consist of a heating control and, on the other hand, of readout electronics for the sensor signal. These sensors are also associated with significant operating costs.
  • the invention has for its object to provide an improved sensor for assessing the quality of fresh air sucked in the operation of motor vehicles.
  • the invention is based on the finding that an improvement of the conditions in the gas detection by the set of silicon microstructure technology in the manufacture of a gas sensor arrangement can be achieved.
  • This gas sensor arrangement of a plurality of sensors is in contact with the outside air and can be accommodated in an advantageous manner in a corrosion-resistant housing, which is particularly suitable for automobiles.
  • this housing must have a gas-permeable membrane, so that a measuring gas can reach the gas-sensitive field-effect transistors.
  • the comprehensive integration and miniaturization allows a variety of simultaneous detection capabilities, so that, for example, an air supply control for a passenger cabin, the u. U. additionally to be coupled with an air conditioner, is easy to control.
  • the gas sensors are kept at a constant, identical or different temperature with an electric heater.
  • field effect transistors for gas detection which are designed as so-called suspended gate field effect transistors (SGFETs), capacitively-coupled field effect transistors (CCFETs) or gateing gate field effect transistors (FGFETs) , These are characterized by an air gap between the gas-sensitive layer and the signal-receiving Si transducer.
  • SGFETs suspended gate field effect transistors
  • CFETs capacitively-coupled field effect transistors
  • FGFETs gateing gate field effect transistors
  • FGFETs gateing gate field effect transistors
  • Selected air pollutants are identified by appropriate target gases.
  • An occurrence of certain different target gases can trigger variable effects on the air supply to the passenger cabin.
  • FIG. 1 shows a sectional view of a gas sensor arrangement with different gas-sensitive elements
  • FIG. 2 shows a gas sensor arrangement according to FIG. 1 in a spatial representation, wherein only the common gate electrode with three different sensitive layers is shown,
  • FIG. 3 shows the basic structure of field-effect transistors combined with gas-sensitive layers.
  • FIG. 4 shows an embodiment of a gas sensor as
  • FIG. 5 shows an embodiment of a gas-sensitive field effect transistor as a floating gate field effect transistor
  • FIGS. 6, 7, 8 and 9 respectively show recorded gas loads as gas sensor signals as a function of time, partially indicating the influence of varying air humidity
  • FIG. 6 mainly shows a sensor signal in the detection of NO 2 with phthalocyanine as sensitive
  • FIG. 7 shows a result diagram for the carbon monoxide detection with a sensitive layer of Pd / SnO 2 .
  • FIG. 8 shows a result diagram for ammonia detection with a gas-sensitive layer of TiN.
  • FIG. 9 shows a result diagram in the case of ozone detection with a gas-sensitive layer of KI.
  • the miniaturization using silicon microstructure technology results in a gas sensor arrangement which, when in contact with the supply air to a passenger compartment, can determine target gases by means of a manifold gas measurement, each of which is representative of certain environmental impacts.
  • the field effect transistors used are preferably field-effect transistors with lifted gate electrode or field-effect transistors with additional floating or sliding potential, or field-effect transistors to which a porous gas-sensitive layer is applied without an air gap.
  • electronics integrated in the silicon-based sensor perform parts of the control of the sensors. These include in particular the control of the sensor heater with a corresponding
  • Control the reading and amplification of the sensor signal and the signal processing of the sensor signal with respect to, for example, a linearization, drift compensation, elimination of cross-sensitivities u. ⁇ .
  • a characteristic guide or target gas is usually assigned in each case, whereby the presence of the corresponding air pollution can be detected by detection of this one gas.
  • Vehicle exhaust gases are detected, for example, in connection with the target gas NOx or NC> 2.
  • this group of exhaust gases by the target gas carbon monoxide or hydrogen is detectable, whereby the sum of hydrocarbons (HC) is used.
  • odors such as liquid manure can be produced via organic conductive gases or via ammonia
  • NH3 smog load
  • target gas ozone 03
  • Tar odors as well as petrochemical or foul odors can also be detected.
  • H2S main gas hydrogen sulfide
  • a continuous low ventilation can be set, which reduces the load in the interior due to the natural ozone depletion or suitable ozone-decomposing filters be applied.
  • suitable ozone-decomposing filters be applied.
  • odors and odor filters are used.
  • gas-sensitive field-effect transistors with different gas-sensitive properties can be realized by selecting the sensitive layer.
  • An integration of the evaluation electronics or a part of this electronics in the gas sensor is possible without difficulty and can save costs of the overall system.
  • Due to the small size of the sensor arrangements can be realized with a variety of different individual sensors of different sensitivity without problems and integrated on a common sensor chip. As a result, cross sensitivities are eliminated, measurement accuracy is improved, and / or the measurement range is increased to improve overall sensor reliability.
  • the basic structure of gas sensitive field effect transistors is shown in FIG.
  • a gas-sensitive layer is applied to a conductive gate element, wherein the adsorption of the gas to be detected generates an electrical potential at the sensitive layer, which acts via an air gap directly on the region of a field-effect transistor for signal readout.
  • FIG. 4 shows an embodiment of a single gas sensor designed as SGFET. Shown are in particular the gate electrode on the air gap 2, 3, 4 side facing the sensitive layer 5,6,7 is applied. In the illustration of Figure 4 in addition a so-called guard ring (guard ring electrode) is provided to improve the signal evaluation.
  • the gas-sensitive layer 5,6,7 on the other side of the air gap 2, 3, 4 opposite element is a field effect transistor, which consists of a so-called gate insulation, wherein in the silicon base body 11, three essential areas of the semiconductor device are provided, source, channel and drain.
  • the field effect transistor is a signal readout element.
  • FIG. 5 shows an embodiment of a single gas sensor, shown as a so-called FGFET with different structure in relation to the gas sensor according to FIG. 4.
  • the read-out transistor 8, 9, 10 is not arranged directly at or below the air gap.
  • a sensor array is created by placing a plurality of individual gas sensitive field effect transistors on a chip.
  • the base is usually a silicon chip.
  • this silicon chip is in each case equipped with a separate gate, which is provided with the respective sensitive layer.
  • a very advantageous variant provides that a common gate, or a common gate electrode is used, wherein depressions are provided for receiving the sensitive layers. These recesses introduced in the common gate electrode are filled up with the materials of the sensitive layers, as shown in FIG.
  • These sensitive layers 5, 6, 7 are gas-sensitive in this case and generally have a uniform spacing from the top edge of the spacers 12, so that the air gap 2, 3, 4 to be represented assumes the same thickness for three regions shown in FIG.
  • the common gate 1 is then mounted on a readout chip, in which the readout elements are mounted at a distance from the sensitive layer.
  • the readout elements are, as described, the field effect transistors.
  • An improvement in the response time of the sensors can be achieved if in the gate one or more gas inlet holes are provided. These can be produced in the case of ceramic gate carriers, for example by means of mechanical processing or by means of laser material ablation.
  • FIG. 1 An arrangement of gas sensors equipped with a plurality of gas-sensitive field effect transistors, in which each field effect transistor is assigned a corresponding gas-sensitive layer, is shown in FIG.
  • the silicon chip 11 contains three read-out transistors 8, 9, 10, whereby signal transmission from the gas-sensitive layers 5, 6, 7 takes place via corresponding air gaps of generally equal size.
  • FIGS. 6 to 9 show diagrams with measurements on the basis of the sensor arrangements comprising the invention with the associated method with corresponding use. Directly above the respective abscissa in FIGS. 6 to 9, pulsed or staged target gas loads are shown.
  • a NO 2 concentration is specified
  • a carbon monoxide / CO concentration for FIG. 7
  • an ammonia / NH 3 concentration for FIG. 9 a stepwise increasing ozone / O 3 concentration.
  • FIG. 6 shows that, in accordance with the pulse-type nitrogen oxide concentration, the sensor in each case indicates a sensor function linked directly to the appearance of the target gas.
  • the evaluation according to FIG. 6 has been carried out on gas-sensitive layers of phthalocyanine for the detection of nitrogen oxide.
  • FIG. 7 shows the detection of carbon monoxide, wherein it is likewise recognizable that an increase of a target gas or a target gas concentration directly results in the rise of the sensor signal. Effect larger concentrations larger target gas amplitudes.
  • Pd / SnO2 has been used as a gas sensitive layer.
  • FIG. 8 shows the curves in the detection of ammonia on sensitive TiN layers. Here, too, follows
  • Figure 9 shows the detection of ozone using a gas-sensitive layer of potassium iodide (KI). Over time, a close correlation between the occurrence of a target gas and the corresponding sensor signal can be recognized.
  • KI potassium iodide
  • At least the representations corresponding to 6 and 8 apply to gas sensors, which are heated to about 95 and 6O 0 C.
  • metals, nitrides, organic layers, metal oxides or ionic salts are generally suitable.
  • organic layers, metal oxides or ionic salts are generally suitable.
  • porphyrin dyes or phthalocyanines or tin oxide layers with noble metal dispersion For the detection of nitrogen oxides porphyrin dyes or phthalocyanines or tin oxide layers with noble metal dispersion.
  • ammonia nitrides preferably titanium nitride TiN.
  • sensitive layers of Au or KI are to be used.
  • the detection of hydrogen sulfide or thiols is achieved with sensitive layers such as silver layers.
  • the gas-sensitive material can be placed in a matrix of a stable, inert body for stabilization.
  • Suitable materials are for example glass or polymer.
  • Typical operating temperatures of the layers are between 40 and 100 ° C., but preferably 85 ° C.
  • the gas sensor assembly is protected by gas-permeable filter from environmental influences such as dust and spray.
  • gas-permeable filter preferably from hydrophobic, so water-repellent, polymers such as Teflon with a typical pore diameter between 1 and 10 microns.
  • individual gas channels may still be provided with layers selectively filtering the interfering gases, e.g. be based on activated carbon. Strong changes in ambient humidity, which also cause spurious signals, can be detected with moisture stabilizing filters, e.g. on the basis of silicate gel.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

L'invention concerne un système détecteur de gaz destiné à la détection de la pollution de l'air, notamment de la pollution de l'arrivée d'air dans une cabine passager. Ce système comprend au moins une puce de silicium présentée dans la technique de microstructure et dotée de plusieurs transistors à effet de champ sensibles au gaz qui sélectionnent des réactions de gaz sur des couches sensibles en présence du gaz cible pour détecter au moins un gaz cible caractérisant respectivement une certaine pollution de l'air et représentant respectivement une pollution de l'air. Produits: capteurs de gaz robustes et économiques.
EP06777780A 2005-07-15 2006-07-14 Procede de detection simultanee de differentes pollutions de l'air par des transistors a effet de champ sensibles au gaz Withdrawn EP1904837A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510033226 DE102005033226A1 (de) 2005-07-15 2005-07-15 Verfahren zur gleichzeitigen Detektion mehrerer unterschiedlicher Luftbelastungen
PCT/EP2006/064260 WO2007009948A1 (fr) 2005-07-15 2006-07-14 Procede de detection simultanee de differentes pollutions de l'air par des transistors a effet de champ sensibles au gaz

Publications (1)

Publication Number Publication Date
EP1904837A1 true EP1904837A1 (fr) 2008-04-02

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EP06777780A Withdrawn EP1904837A1 (fr) 2005-07-15 2006-07-14 Procede de detection simultanee de differentes pollutions de l'air par des transistors a effet de champ sensibles au gaz

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Country Link
EP (1) EP1904837A1 (fr)
DE (1) DE102005033226A1 (fr)
WO (1) WO2007009948A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105229463A (zh) * 2013-05-30 2016-01-06 维萨拉公司 双气体传感器结构及测量方法

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DE102007039567A1 (de) * 2007-08-22 2009-02-26 Robert Bosch Gmbh Gassensor
EP2141491A1 (fr) * 2008-07-02 2010-01-06 Micronas GmbH Capteur de gaz
WO2010069853A1 (fr) * 2008-12-19 2010-06-24 Siemens Aktiengesellschaft Structure de capteur de gaz, contenant un capteur de gaz gasfet et un élément filtrant pour la dégradation de l'ozone
DE102009015121B4 (de) * 2009-03-31 2012-10-31 Siemens Aktiengesellschaft Selektiver Detektor für Kohlenmonoxid und Verfahren zum Betrieb des Detektors
DE102009045475B4 (de) 2009-10-08 2023-06-29 Robert Bosch Gmbh Gassensitive Halbleitervorrichtung sowie deren Verwendung
DE102016004338B4 (de) 2016-04-13 2019-03-21 Drägerwerk AG & Co. KGaA Verwendung eines Gassensor für Anästhesiegasse
DE112018004562A5 (de) 2017-09-27 2020-06-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Fluidsensor
RU2676860C1 (ru) * 2018-02-28 2019-01-11 Общество с ограниченной ответственностью "Технологии Печатной Электроники" (ООО "ПРИНТЭЛТЕХ") Газовый мультисенсор на основе органических полевых транзисторов (варианты) и устройство для анализа многокомпонентной газовой смеси типа "электронный нос" на его основе

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US7089780B2 (en) * 1999-03-03 2006-08-15 Smiths Detection Inc. Apparatus, systems and methods for detecting and transmitting sensory data over a computer network
JP2000323597A (ja) * 1999-05-14 2000-11-24 Toshiba Corp 半導体装置
SE524102C2 (sv) * 1999-06-04 2004-06-29 Appliedsensor Sweden Ab Mikro-hotplate-anordning med integrerad gaskänslig fälteffektsensor

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105229463A (zh) * 2013-05-30 2016-01-06 维萨拉公司 双气体传感器结构及测量方法

Also Published As

Publication number Publication date
WO2007009948A1 (fr) 2007-01-25
DE102005033226A1 (de) 2007-01-25

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