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WO2011026836A1 - Détecteur de dioxyde de carbone - Google Patents

Détecteur de dioxyde de carbone Download PDF

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Publication number
WO2011026836A1
WO2011026836A1 PCT/EP2010/062709 EP2010062709W WO2011026836A1 WO 2011026836 A1 WO2011026836 A1 WO 2011026836A1 EP 2010062709 W EP2010062709 W EP 2010062709W WO 2011026836 A1 WO2011026836 A1 WO 2011026836A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
sensor according
gas sensor
carbon dioxide
sensitive
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.)
Ceased
Application number
PCT/EP2010/062709
Other languages
German (de)
English (en)
Inventor
Stefan Stegmeier
Maximilian Fleischer
Angelika Tawil
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
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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, Siemens Corp filed Critical Siemens AG
Publication of WO2011026836A1 publication Critical patent/WO2011026836A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2
    • 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
    • G01N27/002—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the work function voltage

Definitions

  • Carbon dioxide sensor The invention relates to a gas sensor for detecting carbon dioxide (C0 2 )
  • the detection of carbon dioxide for a number of Appli ⁇ cations of high interest examples include the assessment of indoor air quality, energy-efficient control of air conditioning systems or the control of purified air.
  • the goal of detecting carbon dioxide can be an increase in comfort. But it is also possible to achieve significant energy savings under certain circumstances.
  • a sensor for carbon dioxide must starting from this Basiskonzent ⁇ ration to be able to detect increased concentrations of up to for example 4000 ppm.
  • the problem here is that the carbon dioxide molecule is a linear, symmetrical Mo ⁇ lekül and therefore no electrical dipole moment is present, which can cause a sensor signal at different transducer principles. Furthermore, the molecule is chemically very unreactive.
  • Solid state sensors such as semiconductor gas sensors avoid the disadvantages of the optical measuring systems. They are small in mass production compared to produce extremely cheap and require a less complex signal evaluation.
  • a disadvantage of solid state sensors is that they are integrally ⁇ showed some reactivity of the molecules to be measured and at the same time but detect all molecules that just have a certain reactivity. Otherwise formulated ⁇ profiled the solid-state sensors have a low selectivity. This makes it difficult, above all, to measure less reactive species such as carbon dioxide with such sensors, since they usually react very strongly to hydrocarbons or ozone.
  • the dependent claims relate to advantageous embodiments of the invention.
  • the gas sensor according to the invention has in its construction a gas-sensitive material which is linearly crosslinked and has primary amino groups emanating from the linear strand and is designed to generate a signal representing the concentration of carbon dioxide, the signal being influenced by the material.
  • amines are in three Categories classified: primary, secondary and tertiary amines. They differ by the number of hydrogen atoms which are bonded to the central nitrogen, while the other bonds are separated by groups other than hydrogen, such as. B. a carbon group are occupied.
  • Pri ⁇ mare amines have two bonded hydrogen atoms, one secondary and tertiary than a hydrogen atom.
  • a primary amino group is characterized in that the nitrogen atom N has two bonds to hydrogen atoms (H) and a bond to the remainder of the molecule.
  • the gas sensor is suitable for the detection of carbon dioxide. So it's a carbon dioxide sensor. It is designed to generate a signal representing the concentration of carbon dioxide.
  • the linear cross-linked material with amino groups used according to the invention forms with CO 2 reversibly charged species on the surface, which lead to a significant change in the work function.
  • the carbamate reaction is very efficient due to the adjacent amino groups and thus leads to a very rapid response of the sensor to carbon dioxide.
  • a field effect structure can be provided in the gas sensor structure, for example.
  • this expedient has a drain and a source electrode, which are connected via an influenceable line region.
  • the material is expediently provided in the region of the gate, that is to say the control electrode of the field effect transistor structure, or the material forms the gate of the field effect transistor structure.
  • the two electrodes as well as the field area in between are protected, for example via a passivation layer.
  • the conduction region or the current flow through the conduction region is influenced by the material. 100 mV, which acts as a gate voltage - the material by the gas-induced Su ⁇ alteration of the work function an additional potential on the order of usually 10 arises.
  • This influence can be measured, for example, by means of a variable current flow between source and drain.
  • the current flow or its change is used in this example as a measure of the concentration of carbon dioxide in the region of the material.
  • a Kelvin probe assembly To measure the contact potential difference and thus the work function change of a sensitive material is a Kelvin probe assembly.
  • an oscillating Re ⁇ reference electrode usually gold
  • an electrical conductor with an opposite electrode on which the sensitive material is located.
  • the consequence is a contact potential difference.
  • Due to the oscillation deflection of the reference electrode the capacitance changes, which results in an alternating displacement current.
  • a voltage source interposed in the electrical conductor controls the alternating displacement current to zero; the necessary voltage indicates the Kotaktpotentialdifferenz.
  • the material is located between two electrodes or in the region of two electrodes.
  • the material may be gas-permeable and arranged between two electrodes of a plate capacitor.
  • the material may be arranged as a layer on two electrodes designed as an interdigital capacitor or as a dielectric in a conventional capacitor structure, wherein in the second case expediently at least one of the electrodes is gas-permeable, for example porous, to allow gas access to the sensitive layer.
  • the carbamate reaction ultimately changes the capacitance between the electrodes, which can be used as an electrical measure of the concentration of carbon dioxide.
  • Another possibility is the mass-sensitive From ⁇ reading.
  • cantilever with a quartz oscillator, FBAR, CMUT or surface wave component.
  • Other possibilities include the use as an optically transparent layer on a surface plasmon resonance sensor or in the direct application of the material as a gate to form a field effect structure, wherein interface potentials are evaluated for channel isolation.
  • the material is suitably in the form of a layer.
  • the layer preferably has a thickness of less than 1 mm, in particular, it is in the range between 10 nm and 20 ym.
  • the lateral extent of the layer is preferably substantially greater than the thickness. It is for example at least 100 ym or at least 1 mm.
  • a starting material has two attachment sites for crosslinking. As a result, it can only form a linear strand.
  • An example of this is a siloxane with two alkoxy groups (oxygen atoms) for crosslinking.
  • a material with several attachment parts if it is ensured that a linear cross-linking is otherwise ensured.
  • a monolayer can be produced. In this case, the layer is automatically networked only 2-dimensional.
  • the signal is sufficiently strong be ⁇ based on expected concentrations and concentration changes of carbon dioxide.
  • the first material is a monomeric, primary amine having a second functional group on the carbon skeleton.
  • the second functional group may be a thiol, amino or carboxyl group. This funktionel ⁇ le group provides good chemical bonding of the
  • the senor has a second material which is hydrophobic.
  • the second material is suitably mixed with the first material and forms, for example, with the first Ma ⁇ TERIAL along the gas-sensitive layer. Due to the presence ⁇ unit of the second material, the material is less with Moisture and thus increase the sensitivity of the material to carbon dioxide. This makes it possible, for example, to detect smaller changes in concentration compared to the normal atmospheric background than would be possible only with the material.
  • the first and second material are mixed so fine that individual phases are smaller than 10 ym, in particular smaller than 100 nm. In this way, the reinforcing We ⁇ effect of the second material is brought to particularly good effect on the sensitivity.
  • the sensitive layer is overall water-repellent into ⁇ . As a result, excessive occupancy of the reactive primary amino groups and their partial deactivation are prevented.
  • the preparation of the mixture of both materials can be carried out, for example, by using monomers of the material having the primary amino groups as well as monomers of the hydrophobic second material in the polymerization. In the polymer strand thus follow parts with amino groups on hydrophobic parts.
  • the gas sensor is designed to bring or leave the gas-sensitive material in operation at a temperature of less than 70 ° C.
  • a heating for the material or the layer of the material can be provided, which ensures a temperature of less than 70 ° C in the material.
  • the temperature at which the material is left can also be the room temperature.
  • the gas sensor may be configured, for example, without possibility of heating. In this case, it is understood that in the absence of heating the material Tem ⁇ peraturschwankept is exposed from the outside and the tempera ture ⁇ can not be maintained. From an operation at less than 70 ° C or even at room temperature, there is advantageously a reduced or even significantly reduced energy consumption of the gas sensor.
  • the gas sensor can be operated with a power in the microwatt range the. This leads to a long service life when the gas sensor is operated out of an energy store, for example a battery.
  • an energy store for example a battery.
  • the first material is a polymer or monomer, both with primary amino groups.
  • the preparation of the material takes place beispielswei ⁇ se by screen printing, a CVD process, spin coating or a sol-gel process. It is also possible to produce very thin, in particular monolayer, layers by, for example, making use of a thiol-gold coupling or by way of activation via a spacer or a polymer which has both thiol, amino and carbonyl groups DCC / NHS or glutaric dialdehyde covalently binds a molecule with amino groups.
  • Step Example ⁇ le of this are the use of an intermediate layer of a polymer having both thiol, amino and carbonyl groups and the coupling of the monomeric amine by Akti ⁇ vation with DCC / NHS or glutaraldehyde.
  • the bond can be used here by means of functional groups such as thiol or carboxyl to anchor the layer.
  • the first material may be, for example, a polyaminosiloxane.
  • a heteropolysiloxane of aminoalkoxysilanes in combination with hydrophobic monomers may be used.
  • a concrete example of the first material is carbon ⁇ nitride with terminal amino group.
  • a material is used which is linearly crosslinked and has primary amino groups starting from the linear strand. The material generates a signal representing the concentration of carbon dioxide.
  • the material to a temperature of Weni ⁇ ger than 70 ° C is preferably used.
  • the material is used before ⁇ geous at room temperature; In negative terms, the material is not heated.
  • This example has the effect that battery-operated or otherwise energieau ⁇ Tarke systems have a significantly increased service life.
  • the power required for readout of the signal may be at ge ⁇ suitably interpreted in the microwatt range.
  • the measurement can also be carried out continuously and the presence of carbon dioxide can be detected with very fast response times.
  • the advantageous structure of the material with linear crosslinking and amino groups comes into play, since this combination allows operation at room temperature with sufficient signals.
  • the gas sensor according to the invention can, for. B. the formation of carbamates are used, which takes place at room temperature.
  • the carbon dioxide sensor is quickly by a rapid desorption of the carbon dioxide from its upper surface ⁇ also for another measurement cycle are available, and no reactivation processes required.
  • the signal stability of the signal at room temperature is high, without regeneration being required.
  • Figure 1 shows a structure for a carbon dioxide sensor as
  • FIG. 2 shows a measurement result of an A2EO layer
  • FIG. 3 shows a measurement result of an aged A2EO layer
  • FIG. 1 shows a highly schematic example of an exemplary structure for a sensor according to the invention.
  • a substrate 1 such as a silicon substrate carries a field effect this structure does not ge ⁇ more precisely shown in a drain and source electrode egg ner. Both are covered by a passivation layer 2.
  • the current flow through the field effect structure can be measured.
  • the effect of the outlet work can also be detected via a Kelvin probe assembly.
  • the further figures give measurement results of a philosophicalmög ⁇ probability for a carbon dioxide sensor according to the invention again.
  • the carbon dioxide sensor whose measurement result is shown in Figure 2, has a so-called.
  • A2EO layer as a sensor ⁇ layer on.
  • aminopropyl methyldiethoxysilane is dissolved in ethanol.
  • the solution is boiled in a glass flask with the addition of a small amount of water for 3 hours under reflux.
  • the resulting solution is applied after cooling by means of a spin-coating process on a Kelvin substrate and cured in the oven in a nitrogen atmosphere at 120 ° C for sixteen hours.
  • the layer may also gen at room temperature in several Ta or weeks are cured.
  • the base level Reset the base level.
  • the smallest produced increased con ⁇ concentration was approximately 600 ppm, or about 200 ppm above the ground level.
  • the highest concentration produced was about 4000 ppm.
  • the measurement signal CPD contact potential difference
  • CPD contact potential difference

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Pathology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

L'invention concerne un détecteur de dioxyde de carbone présentant une couche sensible aux gaz constituée de chaînes polymères linéaires qui portent des chaînes latérales pourvues d'un groupe amine primaire. Le groupe amine réagit avec le CO2 et forme des carbamates, ce qui provoque une variation du travail de sortie du matériau. Cette variation du travail de sortie peut être mesurée au moyen d'un transistor à effet de champ (TEC), d'une sonde de Kelvin ou par la mesure de la variation de capacité ou de la variation de masse. Les matériaux sont, à titre d'exemple, des siloxanes, par exemple le poly-aminopropylméthyldiéthoxysilane, le nitrure de carbone et la cystéamine. Le matériau sensible peut ainsi être mélangé avec un matériau hydrophobe ou bien copolymérisé avec des monomères hydrophobes (par exemple un alkylsilane).
PCT/EP2010/062709 2009-09-03 2010-08-31 Détecteur de dioxyde de carbone Ceased WO2011026836A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200910040052 DE102009040052A1 (de) 2009-09-03 2009-09-03 Kohlendioxid-Sensor
DE102009040052.4 2009-09-03

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WO2011026836A1 true WO2011026836A1 (fr) 2011-03-10

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WO (1) WO2011026836A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT6821B (lt) 2019-08-14 2021-05-25 Kauno technologijos universitetas Dujų jutiklis su talpinio mikromontuojamo ultragarso keitiklio struktūra ir funkciniu polimero sluoksniu

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011017501A1 (de) * 2011-04-26 2012-10-31 Siemens Aktiengesellschaft Integrierter Gassensor
EP2889612A1 (fr) 2013-12-24 2015-07-01 Honeywell International Inc. Capteur CO2 basé sur un transistor à effet de champ en diamant
CN110174450B (zh) * 2019-06-21 2024-03-12 贵州民族大学 一种高灵敏度人工等离激元传感器及使用方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005026694A2 (fr) * 2003-09-12 2005-03-24 Nanomix, Inc. Capteur nanoelectronique de dioxyde de carbone
US7913541B2 (en) * 2007-04-30 2011-03-29 Honeywell International Inc. Matrix nanocomposite containing aminocarbon nanotubes for carbon dioxide sensor detection

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ENDRES H-E ET AL: "A capacitive CO2 sensor system with suppression of the humidity interference", SENSORS AND ACTUATORS B, ELSEVIER SEQUOIA S.A., LAUSANNE, CH, vol. 57, no. 1-3, 7 September 1999 (1999-09-07), pages 83 - 87, XP004252989, ISSN: 0925-4005, DOI: DOI:10.1016/S0925-4005(99)00060-X *
STEGMEIER, S; FLEISCHER, M; TAWIL, A; HAUPTMANN, P; ENDRES, H-E: "Detection of CO2 with (Hetero-) Polysiloxanes sensing layers by the change of work function at room temperature", PROCEDIA CHEMISTRY, ELSEVIER, vol. 1, no. 1, 31 August 2009 (2009-08-31), pages 646 - 649, XP026799628, ISSN: 1876-6196, [retrieved on 20090901], DOI: 10.1016/j.proche.2009.07.161 *
ZHOU, R; VAIHINGER, S; GECKELER, K E; GÖPEL, W: "Reliable CO2 sensors with silicon-based polymers on quartz microbalance transducers", SENSORS AND ACTUATORS B, ELSEVIER SEQUOIA S.A., LAUSANNE, CH, vol. 19, no. 1-3, 1 April 1994 (1994-04-01), pages 415 - 420, XP026570850, ISSN: 0925-4005, [retrieved on 19940401], DOI: 10.1016/0925-4005(93)01018-Y *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT6821B (lt) 2019-08-14 2021-05-25 Kauno technologijos universitetas Dujų jutiklis su talpinio mikromontuojamo ultragarso keitiklio struktūra ir funkciniu polimero sluoksniu

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