WO2012146453A1 - Capteur de gaz à effet de champ intégré, présentant des moyens de détermination d'une grandeur servant à la détermination du travail d'extraction et de la variation de masse d'un matériau capteur de gaz - Google Patents

Capteur de gaz à effet de champ intégré, présentant des moyens de détermination d'une grandeur servant à la détermination du travail d'extraction et de la variation de masse d'un matériau capteur de gaz Download PDF

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Publication number
WO2012146453A1
WO2012146453A1 PCT/EP2012/055468 EP2012055468W WO2012146453A1 WO 2012146453 A1 WO2012146453 A1 WO 2012146453A1 EP 2012055468 W EP2012055468 W EP 2012055468W WO 2012146453 A1 WO2012146453 A1 WO 2012146453A1
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WO
WIPO (PCT)
Prior art keywords
gas sensor
sensor
sensor material
gas
work function
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/EP2012/055468
Other languages
German (de)
English (en)
Inventor
Maximilian Fleischer
Stefan Stegmeier
Marcel THRÄNHARDT
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 WO2012146453A1 publication Critical patent/WO2012146453A1/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
    • 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
    • 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
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • G01N33/0032—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array using two or more different physical functioning modes

Definitions

  • the invention relates to a gas sensor assembly comprising a gas ⁇ sensitive layer whose work function is determined as streets ⁇ sorsignal.
  • the gas sensor assembly further comprises ⁇ towards means for determining and detecting changes in mass, which are also used as a gas sensor signal.
  • Senso ⁇ ren are those sensors that are based on chemical interactions with the to be measured gases. For example, sensors for mass attachment (QMBs, SAWs, CMUT), capacitance (IDKs), resistance (Metalloxidsen ⁇ sensors), the work function change (Kelvin probe, gas FET), the electrochemical work, the solid-Ionenleit- ability and thermal Conductivity.
  • Chemical sensors generally show problems with the domestic terpretier ashamed of measurements related. Cross-sensitivity to other gases than the to be measured gases, chemical Reaktio ⁇ NEN (conversion processes, such as the elimination of gases such as H 2 O), degradation effects (mass reduction of Sensiti ⁇ ven layer over time) as well as long-term stability (unge ⁇ wanted chemisorptions). These problems make their use very complicated.
  • a known solution paragraph for improving the sensor result is the formation of so-called arrays, ie the use of a plurality of sensors and the combination of signals measured by the individual sensors.
  • This combination allows an increase in the accuracy of the measurement and improved identification of those gases that contribute to the measurement result.
  • An improved identification of the measured gases is achieved especially when, for example, metal oxide sensors or gas FETs different sensor layers are used.
  • various sensor layers usually react differently to certain gases, can be calculated from the combination of the gas sensor signals the ratio in which the present ver ⁇ different measured gases.
  • Another possibility of the formation of an array is the combination of Senso ⁇ reindeer, which operate with a different sensor concept. From C. Hagleitner et al. , “Smart single-chip gas sensor microsystem", Nature 414, Nov.
  • a sensor system which includes one for mass changes in addition to a capacitive sensor and further comprises a sensor for catalytic effects.
  • This sensor system has the disadvantage that, despite a possibly before ⁇ taken integration with microsystems technology in very small space yet separate sensors are present. Local differences in the gas load and other effects can therefore lead to falsification of the measurement.
  • the sensor assembly comprises means to iden ⁇ lung of a size for the work function of a Gassensormate- rials. Further, the sensor assembly includes means for averaging a Determined ⁇ size for a mass change of the gas sensor material, or in the range of the gas sensor material.
  • the Gassensorma ⁇ TERIAL is applied to a membrane structure, and are further means are provided to encourage the membrane structure to vibrate.
  • the two measured variables namely the mass change and the work function of the gas sensor material essentially do not influence each other. Both sizes are largely independent from ⁇ forms of expression for reactions of the gas sensor material present in the ambient gases, so for example, a chemisorption of a gas.
  • This has the advantage that the two determined values for the mass change and for the initial work function are linearly independent and thus a grêttmög ⁇ Liche distinctiveness for identifying Einzelga ⁇ sen as well as the greatest possible accuracy of the result will he ⁇ ranges.
  • the sensor structure according to the invention also offers the advantage that both measuring principles manage with very little electrical power.
  • a metal is in particular no or only a very slight heating of the gas sensor material required for the measurement of the work function.
  • metal oxide sensors typically have to be operated permanently at temperatures of more than 200 ° C. in order to obtain a read-out of the electrical energy. trical resistance to have acceptable sufficient conductivity, which despite known micromechanical structures requires a heating power of about 100 mW.
  • a third advantage of the sensor structure according to the invention is that the determination of the work function by the field effect transistor structure is not bound to such gas sensor materials that are sufficiently conductive, as is required in the conductivity measurement of metal oxide materials.
  • the gas sensor material may be, for example, a metal oxide such as tin oxide, tungsten oxide or titanium oxide. Mixed oxides can also be used.
  • a polymeric material may also be used as the gas sensor material. For example, siloxanes come into question here.
  • the sensor ⁇ construction further comprises means for determining the electrical conductivity of the gas sensor material.
  • the sensor structure may have a device for heating the gas sensor material. If a conductivity measurement ⁇ performed, it may be advantageous to use this period ⁇ way to keep the gas sensor material on an elevated temperature level. It is advantageous but that Behei ⁇ limiting device, if any, to be used only in short heating cycles to effect, for example desorption previously adsorbed molecules and thus reset the sensor signal.
  • Figure 1 shows a combined gas sensor
  • FIG. 1 shows another combined gas sensor.
  • a first combined gas sensor 10 according to FIG. 1 comprises a lower substrate 11 and an upper substrate 12.
  • the lower and upper substrates 11, 12 are connected by means of a spacer 13.
  • the spacer 13 is realized for example as a ball of a polymer material.
  • the lower substrate 11 is based on a p-doped silicon substrate.
  • the ⁇ ses comprises a field effect transistor structure 14 having a source and a drain region.
  • the Feldef ⁇ Anlagentransistor für 16 of a floating gate is controlled
  • the upper substrate 12 is based on another silicon substrate.
  • the silicon substrate has a cavity 19.
  • the cavity is spanned by a membrane 20.
  • the membrane 20 is a silicon membrane. In alternative embodiments, however, there may also be a membrane of, for example, silicon nitride or silicon oxide.
  • a gas-sensitive layer 21 is applied on the membrane 20, a gas-sensitive layer 21 is applied.
  • Floating gate 16 and the gas-sensitive layer 21 as well as the membrane are DA provided at appropriate that they are each other repeatedlylie ⁇ gene and facing each other.
  • CMUT element is connected to a slightly modified bottom substrate 11 and implemented as a second sensor assembly 30th The measurement of the mass change takes place as in the first embodiment.
  • no field effect transistor structure 14 is provided in the lower substrate in the case ⁇ sem.
  • the floating gate 16 is connected to the gas-sensitive layer via a voltage source 31.
  • the electrical connection causes an equalization of the Fermi level of the gas-sensitive layer 21 and the floating gate 16.
  • the material with the higher Fermi level thus the lower work function gives up electrons to the material with the higher work function from ⁇ from.
  • the result is a Kunststoffpotentialdiffe ⁇ ence.
  • Due to the vibrational displacement of the CMUT the capacitance of the structure varies, resulting in a changing displacement ⁇ current.
  • the voltage source 31 is in this case controlled at ⁇ that it regulates the changing displacement current to zero.
  • the necessary for this voltage is the contact potential difference ⁇ and is used as a measured value.
  • a change of the contact potential difference is thus read as a size for the work and a change in mass of the sensitive layer simultaneously.
  • the first of the modes two different modes of operation can be used.
  • a sequential measurement is made.
  • the gas FET is alternately read in time, whereby no vibration is generated.
  • a vibration is excited and a mass change of the sensitive layer 21 is read out.
  • the measurements are carried out simultaneously.
  • a high-pass filter ⁇ or a lock-in amplifier is used either, which is attracted to the excitation frequency of the CMUT. This allows a significant improvement in the accuracy of the signals.

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

Abstract

L'invention concerne un capteur de gaz à effet de champ intégré, présentant une couche capteur de gaz sur une membrane. Des variations de masse sur la membrane sont déterminées, conjointement avec des variations du travail d'extraction, de manière à obtenir deux signaux de mesure indépendants d'une seule et même couche capteur de gaz.
PCT/EP2012/055468 2011-04-26 2012-03-28 Capteur de gaz à effet de champ intégré, présentant des moyens de détermination d'une grandeur servant à la détermination du travail d'extraction et de la variation de masse d'un matériau capteur de gaz Ceased WO2012146453A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011017501.6 2011-04-26
DE201110017501 DE102011017501A1 (de) 2011-04-26 2011-04-26 Integrierter Gassensor

Publications (1)

Publication Number Publication Date
WO2012146453A1 true WO2012146453A1 (fr) 2012-11-01

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PCT/EP2012/055468 Ceased WO2012146453A1 (fr) 2011-04-26 2012-03-28 Capteur de gaz à effet de champ intégré, présentant des moyens de détermination d'une grandeur servant à la détermination du travail d'extraction et de la variation de masse d'un matériau capteur de gaz

Country Status (2)

Country Link
DE (1) DE102011017501A1 (fr)
WO (1) WO2012146453A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1059528A2 (fr) * 1999-06-11 2000-12-13 Siemens Aktiengesellschaft Capteur de gaz sur le principe du potentiel d'extraction
EP1104884A2 (fr) * 1999-11-23 2001-06-06 Siemens Aktiengesellschaft Détecteur d'incendie
WO2005103668A1 (fr) * 2004-04-22 2005-11-03 Micronas Gmbh Procede pour mesurer des gaz et/ou minimiser des sensibilites transversales dans des capteurs de gaz a base de transistors a effet de champ (tec)
EP2105732A1 (fr) * 2008-03-26 2009-09-30 Micronas GMBH Procédé de mesure de la concentration d'un gaz
DE102009040052A1 (de) * 2009-09-03 2011-03-10 Siemens Aktiengesellschaft Kohlendioxid-Sensor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10019010B4 (de) * 2000-04-17 2007-11-29 Hans-Dieter Prof. Dr. Ließ Verwendung eines chemisch sensitiven Halbleitermaterials zum Nachweis von gas- und/oder dampfförmigen Analyten in Gasen
DE102004019639A1 (de) * 2004-04-22 2005-11-17 Siemens Ag FET-basierter Gassensor
US7171841B2 (en) * 2004-12-01 2007-02-06 Uchicago Argonne, Llc Ultrafast and ultrasensitive hydrogen sensors based on self-assembly monolayer promoted 2-dimensional palladium nanoclusters

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1059528A2 (fr) * 1999-06-11 2000-12-13 Siemens Aktiengesellschaft Capteur de gaz sur le principe du potentiel d'extraction
EP1104884A2 (fr) * 1999-11-23 2001-06-06 Siemens Aktiengesellschaft Détecteur d'incendie
WO2005103668A1 (fr) * 2004-04-22 2005-11-03 Micronas Gmbh Procede pour mesurer des gaz et/ou minimiser des sensibilites transversales dans des capteurs de gaz a base de transistors a effet de champ (tec)
EP2105732A1 (fr) * 2008-03-26 2009-09-30 Micronas GMBH Procédé de mesure de la concentration d'un gaz
DE102009040052A1 (de) * 2009-09-03 2011-03-10 Siemens Aktiengesellschaft Kohlendioxid-Sensor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. HAGLEITNER ET AL.: "Smart single-chip gas sensor microsystem", NATURE, vol. 414, 15 November 2001 (2001-11-15), pages 293 - 296
D. RICHTER ET AL.: "Integrated high temperature gas sensor system based on bulk acoustic wave Resonators", SENSORS AND ACTUATORS, vol. B118, 2006, pages 466 - 471, XP025112234, DOI: doi:10.1016/j.snb.2006.04.041

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