WO2020109008A1 - Gas sensor device, and methods for the production and operation of said device - Google Patents

Gas sensor device, and methods for the production and operation of said device Download PDF

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Publication number
WO2020109008A1
WO2020109008A1 PCT/EP2019/081258 EP2019081258W WO2020109008A1 WO 2020109008 A1 WO2020109008 A1 WO 2020109008A1 EP 2019081258 W EP2019081258 W EP 2019081258W WO 2020109008 A1 WO2020109008 A1 WO 2020109008A1
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WIPO (PCT)
Prior art keywords
transducer
receptor
sensor device
gas sensor
pixels
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PCT/EP2019/081258
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German (de)
French (fr)
Inventor
Philipp NOLTE
Maria Martinez Prada
Bernd Schumann
Original Assignee
Robert Bosch Gmbh
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Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Priority to EP19808711.6A priority Critical patent/EP3887805A1/en
Publication of WO2020109008A1 publication Critical patent/WO2020109008A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/128Microapparatus
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G01N27/227Sensors changing capacitance upon adsorption or absorption of fluid components, e.g. electrolyte-insulator-semiconductor sensors, MOS capacitors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0031General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7793Sensor comprising plural indicators

Definitions

  • Gas sensor device and method for its manufacture and its operation
  • the present invention relates to a gas sensor device.
  • the present invention also relates to a method for producing the
  • Gas sensor device and a method for operating the gas sensor device.
  • Gas sensors for odor detection are considered electronic
  • Substrate are provided. If different receptor materials are used for this purpose, the manufacturing effort increases with each type of material in thin-film processes, since it must be ensured that each material is applied and structured in the desired position.
  • the gas sensor device has a multi-transducer matrix
  • CCD camera chip charge-coupled device
  • Transducer pixels are read out individually, particularly in analog, amplified or digitized form.
  • the gas sensor device has receptor particles of different ones
  • Receptor types are understood to mean particles which are able to absorb or adsorb gas components.
  • Different types of receptors are understood to mean types of receptor particles which have a different absorption or adsorption behavior than the gas components, or whose physical properties are influenced differently by the same gas component. There are therefore several types of receptor particles, each of which can have different selectivities and sensitivities. These receptor particles can be applied to the transducer pixels in a different mixture.
  • the transducer pixels can be differentiated into first transducer pixels and second transducer pixels.
  • the first transducer pixels each have one or more receptor particles.
  • the second transducer pixels have no receptor particles. There are several in the multi-transducer matrix
  • Receptor particles arranged from each type of receptor are arranged from each type of receptor.
  • the gas sensor device is an integrated solution. It is therefore not necessary to combine many individual sensors with one another, which allows a small space requirement. By covering several transducer pixels with receptor particles of the same receptor type or the same mixture of different receptor types, redundancies result which can be used to increase the quality. If individual transducer pixels cannot be read or do not work, the Gas sensor device still have the desired function. Measured signals can also be averaged via the redundant receptor particle arrangements in order to increase the measurement quality.
  • the receptor particles are randomly distributed across the transducer pixels.
  • a random distribution enables a particularly simple production of the gas sensor device. This is especially true before
  • the gas sensor device preferably has more than 50 transducer pixels, particularly preferably more than 100 transducer pixels. Especially with such a high number of transducer pixels, there is a clear advantage of this integrated solution over an equal number of individual pixels.
  • the number of transducer pixels is at least ten times as large as the number of receptor types. It is particularly preferably at least twenty times as large. In this way it can be produced in such a way that it is highly likely that all types of receptors in the
  • receptor particles can be produced in one, two, three, four or even up to ten or more types of receptors if the number of transducer pixels is large enough to provide redundancies.
  • the multi-transducer matrix is arranged on an array that is set up around each
  • the array is an array, which uses the measurement of electrical, optical or thermal properties as an active principle of sensitivity and selectivity for the detection of one or more variables, in particular an electrical, an optical or a thermal array.
  • An electric one Array can determine the presence of a gas adsorbed on the receptor particles in particular via a resistance measurement, for example via
  • the receptor particles are preferably selected from metal oxide semiconductor particles, graphene and phthalocyanines.
  • Metal oxide semiconductors are preferably selected from the group consisting of tin (IV) oxide, tungsten (VI) oxide, zinc (II) oxide, tin (IV) oxide, copper (II) oxide or mixtures of these materials.
  • An optical array measures the change in the color and / or the brightness of the receptor particles when gas components are absorbed or adsorbed.
  • it can have diodes or a camera chip. If the array is an optical array, then the receptor particles are
  • chemochromic materials preferably selected from chemochromic materials, organometallic networks, quantum dots and materials which are gas-dependent
  • a thermal array can preferably be implemented by bimetallic contacts and the measurement of the thermal voltage.
  • Thermal voltage can be caused by the heat of reaction of a chemical reaction taking place on receptor particles. Therefore, if the array is a thermal array, then the receptor particles are
  • catalytically active particles in particular around metal particles which have at least one of the metals nickel, palladium, platinum, silver or gold.
  • the transducer pixels are designed as troughs. Due to the presence and size of the troughs, the arrangement of the
  • Receptor particles in terms of their position to match the location of the
  • Transducer pixels are aligned. For example, a
  • Access receptor particles if this lies exactly in the middle between two metal fingers of an interdigital electrode.
  • each well is so large that it can receive a receptor particle. This ensures that each transducer pixel has only one type of receptor and that the receptor particle of this type of receptor is precisely positioned.
  • each well is so large that it can accommodate several receptor particles.
  • Receptor particles In this way, different types of receptor particles can also be located in one well, so that different gas selectivities can be realized on a single transducer pixel or one transducer pixel is then sensitive to several gases to be detected.
  • the troughs can also have different sizes.
  • the transducer pixels each have a plurality of depressions, which are then together from the transducer element of the
  • Transducerpixels can be measured. If its array is designed, for example, as an electrical array, then several troughs can be located between the electrode fingers of an interdigital electrode, so that the electrical resistance between the electrode fingers is created by applying several
  • Receptor particles can be reduced.
  • the troughs can be realized by depressions. However, structuring should also be understood as wells that are caused by chemical
  • auxiliary materials such as a structured intermediate layer locally improve the adhesion of receptor particles on the substrate of the transducer pixels.
  • the method for manufacturing the gas sensor device comprises a
  • a multi-transducer matrix with transducer pixels Provide a multi-transducer matrix with transducer pixels.
  • a mixture is applied to these, which contains receptor particles from different receptor types and / or precursors of these receptor particles. These are then converted to sensitive receptor particles on the sensor by heating or another treatment.
  • the mixture is a suspension such as an ink or a paste, which is dropped onto the multitransducer matrix and then dried. This allows a random distribution of the
  • Receptor particles can be reached on the transducer pixels.
  • the method for operating the gas sensor device comprises a calibration step in which the
  • Gas sensor device is exposed to a reference atmosphere.
  • Reference atmosphere contains gas components that are known to interact with the receptor particles of the gas sensor device. If transducer pixels behave in the same way in the reference atmosphere, it is concluded that they are coated with receptor particles of the same receptor type.
  • the calibration step is preferably used to:
  • transducer pixels that are not occupied by at least one receptor particle. These second transducer pixels are then determined to be invalid and are no longer activated or read out in later measuring steps carried out by means of the gas device.
  • transducer pixels can also be determined in the calibration step which do not function properly because, for example, several receptor particles undesirably touch and occupy the same transducer pixel or because a receptor particle does not lie optimally on a transducer pixel. If, however, for the
  • the gas sensor device provides that touching receptor particles of different compositions may be arranged in a group of receptors on a transducer pixel
  • the composition of the receptor particle group is stored on the transducer pixel. This can be done, for example, in a computer with a data memory, the composition then being processed in a computer program.
  • the assignment between transducer pixels and receptor type is also saved for all other transducer pixels.
  • the calibration step can in particular provide for the transducer pixels to be subdivided into a group of selective or sensitive transducer pixels and into a group of nonsensitive or non-selective transducer pixels.
  • the group of selective or sensitive transducer pixels is then preferably used in measurement steps for the analysis of a gas mixture, while the non-sensitive or non-selective ones
  • Transducer pixels can be used for self-diagnosis of the measurement process.
  • the gas sensor device can be trained in a manner that is also used for known nasal devices.
  • the concentration of gas components in reference gases is compared with the sensor response and the sensor response for gas mixtures that correspond to certain human perceptions, such as a good or bad smell, is recorded.
  • the result of the training can be stored in a computer unit using characteristic maps and used to output the measurement result in an HMI (Human Machine Interface) such as a display.
  • HMI Human Machine Interface
  • the gas sensor device is exposed to a measuring atmosphere and the transducer pixels that are not found to be invalid are read out electrically, optically or thermally.
  • the type of reading depends on the array of the multi-transducer matrix. It is further preferred that the transducer pixels are optically and / or thermally modulated in the measuring step.
  • the gas sensor device can be excited in particular by light in a suitable wavelength range in order to achieve a predetermined balance between adsorption and
  • regeneration can take place in a regeneration step in which the gas components are also excited optically or thermally.
  • the wavelength range or temperature are selected so that the gas components are desorbed or oxidized.
  • Figure 1 shows a multi-transducer matrix of a gas sensor device according to an embodiment of the invention.
  • FIG. 2 shows a multi-transducer matrix of a gas sensor device according to another exemplary embodiment of the invention.
  • Figure 3 shows a plan view of a trough of a gas sensor device according to an embodiment of the invention.
  • Figure 4 shows a sectional view of the trough according to Figure 3 along the line IV-IV.
  • Figure 5 shows a plan view of a trough of a gas sensor device according to another embodiment of the invention.
  • a multi-transducer matrix 10a with 16x16 transducer pixels in 20 is shown in FIG. In the present case, these have an electrical array
  • a suspension of receptor particles 30 is dropped onto the transducer matrix 10a consist of five different types of receptors 1 to 5.
  • the receptor types are tin (IV) oxide (receptor type 1), tungsten (VI) oxide (receptor type 2), zinc (II) oxide (receptor type 3), tin (II) oxide (receptor type 4) ) and copper (II) oxide (receptor type 5).
  • the receptor particles 30 are suspended in a volatile organic solvent. After its evaporation, the random arrangement of the receptor particles 30 results, which is shown in FIG. 1.
  • the suspension contains the same types of receptors 1 to 5. Their concentration in the suspension was chosen such that it was to be expected that after evaporation of the solvent every second transducer pixel 20 would be coated with a receptor particle 30. This results in the expected values listed in Table 1 for the assignment of the 256 transducer pixels 20. Furthermore, the random distribution actually achieved is on the
  • the arrangement of the receptor particles 30 in the transducer pixels 20 is shown in Figures 3 and 4.
  • the transducer pixels 20 are designed such that the electrode fingers 41, 42 of the interdigital electrode of each transducer pixel 20 each form a trough 51 which can receive exactly one receptor particle.
  • the receptor particles 30 of all receptor types 1 to 5 have an essentially identical number-average particle size. This design of the wells 51 ensures that each transducer pixel 20 has only one
  • Receptor particles 30 can accommodate a type of receptor.
  • Figure 5 shows the execution of a trough 52 in a second
  • Embodiment of the gas sensor device This well is so large that it can hold several receptor particles 30 of the different receptor types 1 to 5. This means that one transducer pixel 20 can have several
  • the gas sensor device After the gas sensor device has been manufactured, it is first calibrated. For this purpose, it is exposed to a reference atmosphere, the gas components of which are adsorbed on the receptor particles 30 and thus change their electrical resistance. This change in resistance can be measured for each transducer pixel 20 by means of the interdigital electrodes 41, 42. Transducer pixels 20 which have no change in resistance in the reference atmosphere are not covered with receptor particles 30 and are found to be invalid. If an unfavorable positioning of a receptor particle 30 on the
  • Interdigital electrodes 41, 42 gives a measured value that is outside of a
  • the respective transducer pixel 20 is also determined to be invalid. All other transducer pixels 20 are divided into five groups, each with the same change in resistance, which is the five
  • the gas sensor device is then trained using the transducer pixels 20 which are not found to be invalid
  • Transducer pixels 20 of the same group each form the basis for the generation of a redundant measurement signal.
  • the gas sensor device If the gas sensor device has been trained, it is exposed to a measuring atmosphere in a measuring operation and, based on the electrical response of the transducer pixels 20, it is concluded which gas components in the each sample gas are included.
  • the temperature of the transducer pixels 20 can be modulated in each case in order to obtain a plurality of measuring points for the measuring gas at each transducer pixel 20. This takes advantage of the fact that different gases desorb from the receptor particles 30 at different temperatures, which can be measured as an electrical resistance change.
  • the multi-transducer matrix 10a, 10b is then heated to such an extent that any eventual adsorb on the receptor particles 30

Abstract

The invention relates to a gas sensor device. The device has a multi-transducer matrix (10a) comprising transducer pixels (20), which has receptor particles (30) of different receptor types (1-5), wherein first transducer pixels (20) each have one or more receptor particles (30) and second transducer pixels (20) do not have any receptor particles (30). The multi-transducer matrix (10a) has multiple receptor particles (30) of each receptor type. A method for producing the gas sensor device comprises providing a multi-transducer matrix (10a) with transducer pixels (20) and applying a mixture to the multi-transducer matrix (10a), which mixture contains receptor particles (30) of different receptor types (1-5) and/or their precursors. A method for operating the gas sensor device comprises a calibration step in which the gas sensor device is exposed to a reference atmosphere, and conclusions are drawn that transducer pixels (20) which behave the same are coated with receptor particles (30) of the same receptor type (1-5).

Description

Beschreibung description
Titel title
Gassensorvorrichtung, sowie Verfahren zu ihrer Herstellung und zu ihrem Betrieb Gas sensor device, and method for its manufacture and its operation
Die vorliegende Erfindung betrifft eine Gassensorvorrichtung. Außerdem betrifft die vorliegende Erfindung ein Verfahren zur Herstellung der The present invention relates to a gas sensor device. The present invention also relates to a method for producing the
Gassensorvorrichtung und ein Verfahren zum Betrieb der Gassensorvorrichtung. Gas sensor device and a method for operating the gas sensor device.
Stand der Technik State of the art
Gassensoren zur Geruchserkennung werden als elektronische Gas sensors for odor detection are considered electronic
Nasenvorrichtungen bezeichnet. Hierzu werden Kombinationen mehrerer Sensoren verwendet. Um gleichzeitig eine Miniaturisierung eines Called nasal devices. Combinations of several sensors are used for this. To simultaneously miniaturize a
Multisensorsystems zu erreichen, können integrierte Lösungen auf einem Achieving multi-sensor systems can be integrated solutions on one
Substrat vorgesehen werden. Wenn hierzu verschiedene Rezeptormaterialien verwendet werden, so steigt bei Dünnschichtprozessen mit jedem Materialtyp der Herstellungsaufwand, da bei jedem Material dafür gesorgt werden muss, dass es an die gewünschte Position aufgetragen und strukturiert wird. Substrate are provided. If different receptor materials are used for this purpose, the manufacturing effort increases with each type of material in thin-film processes, since it must be ensured that each material is applied and structured in the desired position.
Die DE 20 2013 005 433 Ul beschreibt eine Gassensorvorrichtung mit einem Sensorarray, das ein Substrat mit mehreren verschiedenen Sensormedien aufweist. Diese können in einem ringförmigen oder in einem quadratischen Muster auf dem Substrat angeordnet sein. Bei den Sensormedien handelt es sich jeweils um unterschiedliche Substanzen, die chemisch-sensitive Widerstände aufweisen. DE 20 2013 005 433 U1 describes a gas sensor device with a sensor array that has a substrate with several different sensor media. These can be arranged in an annular or in a square pattern on the substrate. The sensor media are each different substances that have chemically sensitive resistances.
Offenbarung der Erfindung Disclosure of the invention
Die Gassensorvorrichtung weist eine Multi-Transducer-Matrix mit The gas sensor device has a multi-transducer matrix
Transducerpixein auf. Hierbei handelt es sich insbesondere um einzeln auslesbare Interdigitalelektrodenstrukturen oder es handelt sich bei der Multi- Transducer- Matrix um eine Vorrichtung, bei der schon neben jedem oder einer Gruppe von sensitiven Transucerpixeln eine elektronische Auswertevorrichtung angebracht ist, um die Signale der Transducerpixel auf eine oder mehrere Leitungen zu geben wo diese in digitaler oder analoger Form, parallel oder sequentieller Form ausgelesen werden können, ähnlich wie bei einem CCD- Kamerachip (charge-coupled device). Dabei können bevorzugt die Transducerpixein on. These are particularly individual Readable interdigital electrode structures or the multi-transducer matrix is a device in which an electronic evaluation device is already installed next to each or a group of sensitive transducer pixels in order to transmit the signals of the transducer pixels to one or more lines where they are digital or analog form, parallel or sequential form, similar to a CCD camera chip (charge-coupled device). In this case, the
Transducerpixel individuell ausgelesen werden insbesondere in analoger, in verstärkter oder in digitalisierter Form. Transducer pixels are read out individually, particularly in analog, amplified or digitized form.
Die Gassensorvorrichtung weist Rezeptorpartikel von unterschiedlichen The gas sensor device has receptor particles of different ones
Rezeptorsorten auf. Unter Rezeptorpartikeln werden dabei Partikel verstanden, welche in der Lage sind, Gaskomponenten zu absorbieren oder zu adsorbieren. Unter unterschiedlichen Rezeptorsorten werden Sorten von Rezeptorpartikeln verstanden, welche gegenüber den Gaskomponenten ein unterschiedliches Absorptions- oder Adsorbtionsverhalten aufweisen, oder deren physikalische Eigenschaften durch dieselbe Gaskomponente unterschiedlich beeinflusst werden. Es gibt also mehrere Sorten von Rezeptorpartikeln, die jeweils unterschiedliche Selektivitäten und Sensitivitäten aufweisen können. Diese Rezeptorpartikel können in unterschiedlicher Mischung auf den Transducerpixein aufgebracht sein. Receptor types. Receptor particles are understood to mean particles which are able to absorb or adsorb gas components. Different types of receptors are understood to mean types of receptor particles which have a different absorption or adsorption behavior than the gas components, or whose physical properties are influenced differently by the same gas component. There are therefore several types of receptor particles, each of which can have different selectivities and sensitivities. These receptor particles can be applied to the transducer pixels in a different mixture.
Die Transducerpixel können in erste Transducerpixel und zweite Transducerpixel unterschieden werden. Dabei weisen die ersten Transducerpixel jeweils einen oder mehrere Rezeptorpartikel auf. Die zweiten Transducerpixel weisen keine Rezeptorpartikel auf. In der Multi-Transducer-Matrix sind jeweils mehrere The transducer pixels can be differentiated into first transducer pixels and second transducer pixels. The first transducer pixels each have one or more receptor particles. The second transducer pixels have no receptor particles. There are several in the multi-transducer matrix
Rezeptorpartikel von jeder Rezeptorsorte angeordnet. Receptor particles arranged from each type of receptor.
Bei der Gassensorvorrichtung handelt es sich um eine integrierte Lösung. Es müssen also nicht viele einzelne Sensoren miteinander kombiniert werden, was einen geringen Platzbedarf ermöglicht. Indem jeweils mehrere Transducerpixel mit Rezeptorpartikeln der gleichen Rezeptorsorte oder der gleichen Mischung unterschiedlicher Rezeptorsorten belegt sind, ergeben sich Redundanzen, die zur Qualitätssteigerung genutzt werden können. Wenn einzelne Transducerpixel nicht auslesbar sein sollten oder nicht funktionieren, wird die Gassensorvorrichtung immer noch die gewünschte Funktion haben. Über die redundanten Rezeptorpartikelanordnungen können gemessene Signale außerdem gemittelt werden, um die Messqualität zu steigern. The gas sensor device is an integrated solution. It is therefore not necessary to combine many individual sensors with one another, which allows a small space requirement. By covering several transducer pixels with receptor particles of the same receptor type or the same mixture of different receptor types, redundancies result which can be used to increase the quality. If individual transducer pixels cannot be read or do not work, the Gas sensor device still have the desired function. Measured signals can also be averaged via the redundant receptor particle arrangements in order to increase the measurement quality.
Vorzugsweise sind die Rezeptorpartikel zufällig auf den Transducerpixein verteilt. Eine Verteilung nach dem Zufallsprinzip ermöglicht eine besonders einfache Herstellung der Gassensorvorrichtung. Dies gilt insbesondere vor dem Preferably, the receptor particles are randomly distributed across the transducer pixels. A random distribution enables a particularly simple production of the gas sensor device. This is especially true before
Hintergrund, dass bei der Herstellung keine Belegung aller Transducerpixel mit Rezeptorpartikeln erreicht werden muss, sondern dass stattdessen die zweiten Transducerpixel frei bleiben dürfen. Background that during the manufacturing process it is not necessary to cover all transducer pixels with receptor particles, but instead that the second transducer pixels may remain free.
Die Gassensorvorrichtung weist bevorzugt mehr als 50 Transducerpixel, besonders bevorzugt mehr als 100 Transducerpixel, auf. Insbesondere bei einer so hohen Anzahl von Transducerpixein ergibt sich ein deutlicher Vorteil dieser integrierten Lösung gegenüber einer gleichen Anzahl von Einzelpixeln. The gas sensor device preferably has more than 50 transducer pixels, particularly preferably more than 100 transducer pixels. Especially with such a high number of transducer pixels, there is a clear advantage of this integrated solution over an equal number of individual pixels.
Weiterhin ist bevorzugt, dass die Anzahl der Transducerpixel mindestens zehnmal so groß ist wie die Anzahl der Rezeptorsorten. Besonders bevorzugt ist sie mindestens zwanzigmal so groß. Auf diese Weise kann sie so hergestellt werden, dass mit hoher Wahrscheinlichkeit alle Rezeptorsorten in der It is further preferred that the number of transducer pixels is at least ten times as large as the number of receptor types. It is particularly preferably at least twenty times as large. In this way it can be produced in such a way that it is highly likely that all types of receptors in the
Gassensorvorrichtung mit einer so großen Häufigkeit Vorkommen, dass diese messqualitätssteigernde Redundanzen aufweist. So können zur Steigerung der Sensitivität Rezeptorpartikel in eins, zwei, drei, vier oder auch bis zu zehn und mehr Rezeptorsorten hergestellt werden, wenn die Anzahl der Transducerpixel groß genug ist, um Redundanzen zu ergeben. Gas sensor device with such a high frequency that it has redundancies that increase measurement quality. To increase sensitivity, receptor particles can be produced in one, two, three, four or even up to ten or more types of receptors if the number of transducer pixels is large enough to provide redundancies.
Zum Auslesen der Transducerpixel ist es bevorzugt, dass die Multi-Transducer- Matrix auf einem Array angeordnet ist, das eingerichtet ist, um jeden For reading the transducer pixels, it is preferred that the multi-transducer matrix is arranged on an array that is set up around each
Transducerpixel individuell elektronisch auszulesen. Je nachdem, welche Gase mittels der Gassensorvorrichtung detektiert werden sollen, kann ein solches Array unterschiedliche physikalische Messprinzipien ausnutzen. Dabei ist es bevorzugt, dass das Array ein Array ist, welches die Messung elektrischer, optischer oder thermischer Eigenschaften als Wirkprinzip der Sensitivität und Selektivität zum Nachweis einer oder mehrerer Größen verwendet, insbesondere ein elektrisches, ein optisches oder ein thermisches Array ist. Ein elektrisches Array kann die Anwesenheit eines an den Rezeptorpartikeln adsorbierten Gases insbesondere über eine Widerstandsmessung, beispielsweise über Read out transducer pixels individually electronically. Depending on which gases are to be detected by the gas sensor device, such an array can use different physical measurement principles. It is preferred that the array is an array, which uses the measurement of electrical, optical or thermal properties as an active principle of sensitivity and selectivity for the detection of one or more variables, in particular an electrical, an optical or a thermal array. An electric one Array can determine the presence of a gas adsorbed on the receptor particles in particular via a resistance measurement, for example via
Interdigitalelektrodenstrukturen, oder kapazitiv ermitteln. Wenn das Array ein elektrisches Array ist, dann sind die Rezeptorpartikel vorzugsweise ausgewählt aus Metalloxidhalbleiterpartikeln, Graphen und Phthalocyaninen. Die Interdigital electrode structures, or determine capacitively. If the array is an electrical array, then the receptor particles are preferably selected from metal oxide semiconductor particles, graphene and phthalocyanines. The
Metalloxidhalbleiter sind bevorzugt ausgewählt aus der Gruppe bestehend aus Zinn(IV)-oxid, Wolfram(VI)-oxid, Zink(ll)-oxid, Zinn(IV)-oxid, Kupfer(ll)-oxid oder Mischungen dieser Materialien. Metal oxide semiconductors are preferably selected from the group consisting of tin (IV) oxide, tungsten (VI) oxide, zinc (II) oxide, tin (IV) oxide, copper (II) oxide or mixtures of these materials.
Ein optisches Array misst die Änderung der Farbe und/oder der Helligkeit der Rezeptorpartikel bei Absorption oder Adsorption von Gaskomponenten. Es kann insbesondere Dioden oder einen Kamerachip aufweisen. Wenn es sich bei dem Array um ein optisches Array handelt, dann sind die Rezeptorpartikel An optical array measures the change in the color and / or the brightness of the receptor particles when gas components are absorbed or adsorbed. In particular, it can have diodes or a camera chip. If the array is an optical array, then the receptor particles are
vorzugsweise ausgewählt aus chemochromen Materialien, metallorganischen Netzwerken, Quantendots und Materialien, welche gasabhängige preferably selected from chemochromic materials, organometallic networks, quantum dots and materials which are gas-dependent
Konformitätsänderungen durchführen wie insbesondere Rodopsin. Carry out conformity changes, in particular rodopsin.
Ein thermisches Array kann vorzugsweise durch Bimetallkontakte und die Messung der Thermospannung realisiert werden. Eine Thermospannung kann durch die Reaktionswärme einer an Rezeptorpartikeln ablaufenden chemischen Reaktion hervorgerufen werden. Wenn es sich bei dem Array um ein thermisches Array handelt, so handelt es sich bei den Rezeptorpartikeln deshalb A thermal array can preferably be implemented by bimetallic contacts and the measurement of the thermal voltage. Thermal voltage can be caused by the heat of reaction of a chemical reaction taking place on receptor particles. Therefore, if the array is a thermal array, then the receptor particles are
vorzugsweise um katalytisch aktive Partikel, insbesondere um Metallpartikel, die mindestens eines der Metalle Nickel, Palladium, Platin, Silber oder Gold aufweisen. preferably around catalytically active particles, in particular around metal particles which have at least one of the metals nickel, palladium, platinum, silver or gold.
Weiterhin ist es bevorzugt, dass die Transducerpixel als Mulden ausgeführt sind. Durch die Anwesenheit und Größe der Mulden kann die Anordnung der It is further preferred that the transducer pixels are designed as troughs. Due to the presence and size of the troughs, the arrangement of the
Rezeptorpartikel hinsichtlich ihrer Position passend auf den Ort der Receptor particles in terms of their position to match the location of the
Transducerpixel ausgerichtet werden. So kann beispielsweise eine Transducer pixels are aligned. For example, a
leitfähigkeitsmessende Struktur im Transducer besonders gut auf einen Conductivity measuring structure in the transducer particularly well on one
Rezeptorpartikel zugreifen, wenn dieser genau mittig zwischen zwei Metallfingern einer Interdigitalelektrode liegt. In einer bevorzugten Ausführungsform der Gassensorvorrichtung ist jede Mulde so groß, dass sie einen Rezeptorpartikel aufnehmen kann. Die stellt sicher, dass jedes Transducerpixel jeweils nur eine Rezeptorsorte aufweist und dass der Rezeptorpartikel dieser Rezeptorsorte genau positioniert wird. Access receptor particles if this lies exactly in the middle between two metal fingers of an interdigital electrode. In a preferred embodiment of the gas sensor device, each well is so large that it can receive a receptor particle. This ensures that each transducer pixel has only one type of receptor and that the receptor particle of this type of receptor is precisely positioned.
In einer anderen bevorzugten Ausführungsform der Gassensorvorrichtung ist jede Mulde so groß, dass sie mehrere Rezeptorpartikel aufnehmen kann. In another preferred embodiment of the gas sensor device, each well is so large that it can accommodate several receptor particles.
Dadurch ergibt sich eine höhere Variantenvielfalt von gruppierten This results in a higher variety of grouped
Rezeptorpartikeln. So können auch verschiedenartige Rezeptorpartikeln in einer Mulde liegen, so dass verschiedene Gasselektivitäten auf einem einzigen Transducerpixel realisiert werden können oder ein Transducerpixel dann auf mehrere nachzuweisende Gase sensitiv ist. Receptor particles. In this way, different types of receptor particles can also be located in one well, so that different gas selectivities can be realized on a single transducer pixel or one transducer pixel is then sensitive to several gases to be detected.
Die Mulden können auch verschiedene Größen haben. The troughs can also have different sizes.
Es kann auch vorgesehen sein, dass die Transducerpixel jeweils mehrere Mulden aufweisen, die dann zusammen vom Transducerelement des It can also be provided that the transducer pixels each have a plurality of depressions, which are then together from the transducer element of the
Transducerpixels gemessen werden können. Wenn dessen Array beispielsweise als elektrisches Array ausgeführt ist, so können mehrere Mulden zwischen den Elektrodenfingern einer Interdigitalelektrode liegen, sodass der elektrische Widerstand zwischen den Elektrodenfingern durch Anlage mehrerer Transducerpixels can be measured. If its array is designed, for example, as an electrical array, then several troughs can be located between the electrode fingers of an interdigital electrode, so that the electrical resistance between the electrode fingers is created by applying several
Rezeptorpartikel verringert werden kann. Receptor particles can be reduced.
Die Mulden können durch Vertiefungen realisiert werden. Es sollen jedoch auch Strukturierungen als Mulden verstanden werden, die durch chemische The troughs can be realized by depressions. However, structuring should also be understood as wells that are caused by chemical
Funktionalisierung oder durch Hilfsmaterialien wie beispielsweise eine strukturierte Zwischenschicht lokal die Haftung von Rezeptorpartikeln auf dem Substrat der Transducerpixel verbessern. Functionalization or by means of auxiliary materials such as a structured intermediate layer locally improve the adhesion of receptor particles on the substrate of the transducer pixels.
Das Verfahren zum Herstellen der Gassensorvorrichtung umfasst ein The method for manufacturing the gas sensor device comprises a
Bereitstellen einer Multi-Transducer-Matrix mit Transducerpixein. Auf diese wird ein Gemisch aufgebracht, welches Rezeptorpartikel von unterschiedlichen Rezeptorsorten und/oder Prekursoren dieser Rezeptorpartikel enthält. Diese werden dann auf dem Sensor durch Erhitzen oder einer anderen Behandlung in sensitive Rezeptorpartikel umgewandelt. Insbesondere kann es sich bei dem Gemisch um eine Suspension wie beispielsweise eine Tinte oder eine Paste handeln, die auf die Multitransducer-Matrix getropft und anschließend getrocknet wird. Hierdurch kann in einfacher Weise eine zufällige Verteilung der Provide a multi-transducer matrix with transducer pixels. A mixture is applied to these, which contains receptor particles from different receptor types and / or precursors of these receptor particles. These are then converted to sensitive receptor particles on the sensor by heating or another treatment. In particular, it can The mixture is a suspension such as an ink or a paste, which is dropped onto the multitransducer matrix and then dried. This allows a random distribution of the
Rezeptorpartikel auf den Transducerpixein erreicht werden. Receptor particles can be reached on the transducer pixels.
Nach einer Herstellung der Gassensorvorrichtung unter zufälliger Verteilung der Rezeptorpartikel ist zunächst nicht bekannt, auf welchen Transducerpixein sich Rezeptorpartikel welcher Rezeptorsorte befinden und welche Transducerpixel vollständig frei von Rezeptorpartikeln sind. Deshalb umfasst das Verfahren zum Betreiben der Gassensorvorrichtung einen Kalibrierschritt, in dem die After the gas sensor device has been manufactured with a random distribution of the receptor particles, it is initially not known which transducer pixels are in which receptor particles and which type of receptor are located and which transducer pixels are completely free of receptor particles. Therefore, the method for operating the gas sensor device comprises a calibration step in which the
Gassensorvorrichtung einer Referenzatmosphäre ausgesetzt wird. Die Gas sensor device is exposed to a reference atmosphere. The
Referenzatmosphäre enthält Gaskomponenten, von denen bekannt ist, dass sie mit den Rezeptorpartikeln der Gassensorvorrichtung wechselwirken. Wenn Transducerpixel sich in der Referenzatmosphäre gleich verhalten, dann wird darauf geschlossen, dass sie mit Rezeptorpartikeln der gleichen Rezeptorsorte belegt sind. Reference atmosphere contains gas components that are known to interact with the receptor particles of the gas sensor device. If transducer pixels behave in the same way in the reference atmosphere, it is concluded that they are coated with receptor particles of the same receptor type.
Weiterhin wird der Kalibrierschritt vorzugsweise dazu genutzt, um Furthermore, the calibration step is preferably used to:
Transducerpixel zu ermitteln, die nicht mit mindestens einem Rezeptorpartikel belegt sind. Diese zweiten Transducerpixel werden dann als ungültig festgestellt und in späteren mittels der Gasvorrichtung durchgeführten Messschritten nicht mehr angesteuert oder ausgelesen. In gleicher Weise können im Kalibrierschritt auch Transducerpixel ermittelt werden, welche nicht richtig funktionieren, weil sich beispielsweise mehrere Rezeptorpartikel unerwünschter Weise berühren und dasselbe Transducerpixel besetzen oder weil ein Rezeptorpartikel nicht optimal auf einem Transducerpixel liegt. Wenn hingegen für die To determine transducer pixels that are not occupied by at least one receptor particle. These second transducer pixels are then determined to be invalid and are no longer activated or read out in later measuring steps carried out by means of the gas device. In the same way, transducer pixels can also be determined in the calibration step which do not function properly because, for example, several receptor particles undesirably touch and occupy the same transducer pixel or because a receptor particle does not lie optimally on a transducer pixel. If, however, for the
Gassensorvorrichtung vorgesehen ist, dass sich berührende Rezeptorpartikel unterschiedlicher Zusammensetzung zu einer Gruppe von Rezeptoren auf einem Transducerpixel angeordnet werden dürfen, so wird die Zusammensetzung der Rezeptorpartikelgruppe auf dem Transducerpixel gespeichert. Dies kann beispielsweise in einem Computer mit Datenspeicher erfolgen, wobei die Zusammensetzung dann in einem Computerprogramm verarbeitet wird. Auch für alle weiteren Transducerpixel wird die Zuordnung zwischen Transducerpixel und Rezeptorsorte gespeichert. Weiterhin kann in dem Kalibrierschritt insbesondere vorgesehen sein, dass die Transducerpixel in eine Gruppe von selektiven oder sensitiven Transducerpixein und in eine Gruppe von nicht sensitiven oder nicht selektiven Transducerpixein unterteilt wird. Die Gruppe der selektiven oder sensitiven Transducerpixel wird dann in Messschritten vorzugsweise zur Analyse eines Gasgemisches herangezogen, während die nicht sensitiven oder nicht selektiven If the gas sensor device provides that touching receptor particles of different compositions may be arranged in a group of receptors on a transducer pixel, the composition of the receptor particle group is stored on the transducer pixel. This can be done, for example, in a computer with a data memory, the composition then being processed in a computer program. The assignment between transducer pixels and receptor type is also saved for all other transducer pixels. Furthermore, the calibration step can in particular provide for the transducer pixels to be subdivided into a group of selective or sensitive transducer pixels and into a group of nonsensitive or non-selective transducer pixels. The group of selective or sensitive transducer pixels is then preferably used in measurement steps for the analysis of a gas mixture, while the non-sensitive or non-selective ones
Transducerpixel für eine Eigendiagnose des Messverfahrens verwendet werden können. Transducer pixels can be used for self-diagnosis of the measurement process.
Ein Training der Gassensorvorrichtung kann in einer Weise erfolgen, wie sie auch für bekannte Nasenvorrichtungen verwendet wird. Die Konzentration von Gaskomponenten in Referenzgasen wird dabei mit der Sensorantwort verglichen und es wird die Sensorantwort für Gasgemische erfasst, die bestimmten menschlichen Wahrnehmungen wie beispielsweise einem guten oder einem schlechten Geruch entsprechen. Das Ergebnis des Trainings kann durch Kennfelder in einer Recheneinheit hinterlegt werden und zur Ausgabe des Messresultats in einem HMI (Human Machine Interface) wie beispielsweise einem Display verwendet werden. The gas sensor device can be trained in a manner that is also used for known nasal devices. The concentration of gas components in reference gases is compared with the sensor response and the sensor response for gas mixtures that correspond to certain human perceptions, such as a good or bad smell, is recorded. The result of the training can be stored in a computer unit using characteristic maps and used to output the measurement result in an HMI (Human Machine Interface) such as a display.
In einem Messschritt wird die Gassensorvorrichtung einer Messatmosphäre ausgesetzt und die nicht als ungültig festgestellten Transducerpixel werden elektrisch, optisch oder thermisch ausgelesen. Die Art des Auslesens hängt dabei vom Array der Multi-Transducer- Matrix ab. Es ist weiterhin bevorzugt, dass die Transducerpixel in den Messschritt optisch und/oder thermisch moduliert werden. Für eine optische Modulation kann die Gassensorvorrichtung insbesondere durch Licht in einem geeigneten Wellenlängenbereich angeregt werden, um ein vorgegebenes Gleichgewicht zwischen Adsorption und In one measuring step, the gas sensor device is exposed to a measuring atmosphere and the transducer pixels that are not found to be invalid are read out electrically, optically or thermally. The type of reading depends on the array of the multi-transducer matrix. It is further preferred that the transducer pixels are optically and / or thermally modulated in the measuring step. For optical modulation, the gas sensor device can be excited in particular by light in a suitable wavelength range in order to achieve a predetermined balance between adsorption and
Desorption zu erzeugen. Weiterhin können aufgrund optischer Anregungen elektrisch messbare Gassensitivitäten induziert werden. Eine thermische Modulierung ist insbesondere dann möglich, wenn die Gassensorvorrichtung Heizerstrukturen beinhaltet, die es erlauben, verschiedene Temperaturen der Transducerpixel dynamisch oder statisch einzustellen. Ebenso kann ein kühlendes Element wie beispielsweise ein Peltier-Element vorgesehen sein. Durch die optische und/oder thermische Modulation werden in einem Messzyklus nicht nur so viele Datenmesspunkte erzeugt wie der Anzahl der Rezeptorsorten entsprechen, sondern eine höhere Anzahl unabhängiger Datenmesspunkte. To produce desorption. Electrically measurable gas sensitivities can also be induced on the basis of optical excitations. Thermal modulation is possible in particular if the gas sensor device contains heater structures which allow different temperatures of the transducer pixels to be set dynamically or statically. A cooling element such as a Peltier element can also be provided. Due to the optical and / or thermal modulation in one measurement cycle not only generates as many data measurement points as the number of receptor types, but a higher number of independent data measurement points.
Um die Gassensorvorrichtung von adsorbierten Gaskomponenten zu befreien, kann eine Regeneration in einem Regenerationsschritt erfolgen, in dem die Gaskomponenten ebenfalls optisch oder thermisch angeregt werden. Hierbei werden Wellenlängenbereich oder Temperatur jedoch so gewählt, dass es zu einer Desorption oder Oxidation der Gaskomponenten kommt. In order to free the gas sensor device from adsorbed gas components, regeneration can take place in a regeneration step in which the gas components are also excited optically or thermally. Here, however, the wavelength range or temperature are selected so that the gas components are desorbed or oxidized.
Kurze Beschreibung der Zeichnungen Brief description of the drawings
Ausführungsbeispiele der Erfindung sind in den Zeichnungen dargestellt und werden in der nachfolgenden Beschreibung näher erläutert. Exemplary embodiments of the invention are shown in the drawings and are explained in more detail in the description below.
Figur 1 zeigt eine Multi-Transducer-Matrix einer Gassensorvorrichtung gemäß einem Ausführungsbeispiel der Erfindung. Figure 1 shows a multi-transducer matrix of a gas sensor device according to an embodiment of the invention.
Figur 2 zeigt eine Multi-Transducer-Matrix einer Gassensorvorrichtung gemäß einem anderen Ausführungsbeispiel der Erfindung. FIG. 2 shows a multi-transducer matrix of a gas sensor device according to another exemplary embodiment of the invention.
Figur 3 zeigt eine Aufsicht auf eine Mulde einer Gassensorvorrichtung gemäß einem Ausführungsbeispiel der Erfindung. Figure 3 shows a plan view of a trough of a gas sensor device according to an embodiment of the invention.
Figur 4 zeigt eine Schnittdarstellung der Mulde gemäß Figur 3 entlang der Linie IV-IV. Figure 4 shows a sectional view of the trough according to Figure 3 along the line IV-IV.
Figur 5 zeigt eine Aufsicht auf eine Mulde einer Gassensorvorrichtung gemäß einem anderen Ausführungsbeispiel der Erfindung. Figure 5 shows a plan view of a trough of a gas sensor device according to another embodiment of the invention.
Ausführungsbeispiele der Erfindung Embodiments of the invention
In Figur 1 ist eine Multi-Transducer-Matrix 10a mit 16x16 Transducerpixein 20 dargestellt. Diese weisen vorliegend ein elektrisches Array zur A multi-transducer matrix 10a with 16x16 transducer pixels in 20 is shown in FIG. In the present case, these have an electrical array
Widerstandsmessung mittels Interdigitalelektroden auf. Auf die Transducer- Matrix 10a wird eine Suspension von Rezeptorpartikeln 30 aufgetropft, welche aus fünf unterschiedlichen Rezeptorsorten 1 bis 5 bestehen. Beispielsweise handelt es sich bei den Rezeptorsorten um Zinn(IV)-oxid (Rezeptorsorte 1), Wolfram(VI)-oxid (Rezeptorsorte 2), Zink(ll)-oxid (Rezeptorsorte 3), Zinn(ll)-oxid (Rezeptorsorte 4) und Kupfer(ll)-oxid (Rezeptorsorte 5). Die Rezeptorpartikel 30 sind in einem flüchtigen organischen Lösungsmittel suspendiert. Nach dessen Verdampfen ergibt sich die zufällige Anordnung der Rezeptorpartikel 30, die in Figur 1 dargestellt ist. Resistance measurement using interdigital electrodes. A suspension of receptor particles 30 is dropped onto the transducer matrix 10a consist of five different types of receptors 1 to 5. For example, the receptor types are tin (IV) oxide (receptor type 1), tungsten (VI) oxide (receptor type 2), zinc (II) oxide (receptor type 3), tin (II) oxide (receptor type 4) ) and copper (II) oxide (receptor type 5). The receptor particles 30 are suspended in a volatile organic solvent. After its evaporation, the random arrangement of the receptor particles 30 results, which is shown in FIG. 1.
Diese Anordnung ist weder vorherbestimmbar noch reproduzierbar. Wird eine weitere identische Multi-Transducer-Matrix 10b mit derselben Suspension betropft, so ergibt sich nach deren Trocknen beispielsweise die Anordnung, die in Figur 2 dargestellt ist. This arrangement is neither predictable nor reproducible. If another identical multi-transducer matrix 10b is dripped with the same suspension, the arrangement shown in FIG. 2 results, for example, after it has dried.
Die Rezeptorsorten 1 bis 5 sind in gleichem Anteil in der Suspension enthalten. Ihre Konzentration in der Suspension wurde so gewählt, dass zu erwarten war, dass nach Verdampfen des Lösungsmittels jedes zweite Transducerpixel 20 mit einem Rezeptorpartikel 30 belegt ist. Daraus ergeben sich die in Tabelle 1 aufgeführten Erwartungswerte für die Belegung der 256 Transducerpixel 20. Weiterhin ist die jeweils tatsächlich erreichte zufällige Verteilung auf der The suspension contains the same types of receptors 1 to 5. Their concentration in the suspension was chosen such that it was to be expected that after evaporation of the solvent every second transducer pixel 20 would be coated with a receptor particle 30. This results in the expected values listed in Table 1 for the assignment of the 256 transducer pixels 20. Furthermore, the random distribution actually achieved is on the
Transducer- Matrix 10a und der Transducer- Matrix 10b dargestellt. Transducer matrix 10a and the transducer matrix 10b shown.
Tabelle 1 Table 1
Figure imgf000011_0001
Figure imgf000011_0001
Die Anordnung der Rezeptorpartikel 30 in den Transducerpixein 20 ist in den Figuren 3 und 4 dargestellt. Die Transducerpixel 20 sind dabei so ausgeführt, dass die Elektrodenfinger 41, 42 der Interdigitalelektrode jedes Transducerpixels 20 jeweils eine Mulde 51 bilden, die genau einen Rezeptorpartikel aufnehmen kann. Hierzu weisen die Rezeptorpartikel 30 aller Rezeptorsorten 1 bis 5 eine im Wesentlichen gleiche zahlenmittlere Partikelgröße auf. Diese Ausführung der Mulden 51 stellt sicher, dass jedes Transducerpixel 20 nur einen The arrangement of the receptor particles 30 in the transducer pixels 20 is shown in Figures 3 and 4. The transducer pixels 20 are designed such that the electrode fingers 41, 42 of the interdigital electrode of each transducer pixel 20 each form a trough 51 which can receive exactly one receptor particle. For this purpose, the receptor particles 30 of all receptor types 1 to 5 have an essentially identical number-average particle size. This design of the wells 51 ensures that each transducer pixel 20 has only one
Rezeptorpartikel 30 einer Rezeptorsorte aufnehmen kann. Receptor particles 30 can accommodate a type of receptor.
Figur 5 zeigt die Ausführung einer Mulde 52 in einem zweiten Figure 5 shows the execution of a trough 52 in a second
Ausführungsbeispiel der Gassensorvorrichtung. Diese Mulde ist so groß, dass sie mehrere Rezeptorpartikel 30 der unterschiedlichen Rezeptorsorten 1 bis 5 aufnehmen kann. Dadurch kann ein Transducerpixel 20 mehrere Embodiment of the gas sensor device. This well is so large that it can hold several receptor particles 30 of the different receptor types 1 to 5. This means that one transducer pixel 20 can have several
Rezeptorpartikel 30 aufweisen. Es ergibt sich dann eine von den Darstellungen in den Figuren 1 und 2 abweichende Verteilung der Rezeptorsorten. Have receptor particles 30. This then results in a distribution of the receptor types that deviates from the representations in FIGS. 1 and 2.
Nach Herstellung der Gassensorvorrichtung wird diese zunächst kalibriert. Hierzu wird sie einer Referenzatmosphäre ausgesetzt, deren Gasbestandteile an den Rezeptorpartikeln 30 adsorbiert werden und damit ihren elektrischen Widerstand ändern. Diese Widerstandsänderung kann für jedes Transducerpixel 20 mittels der Interdigitalelektroden 41, 42 gemessen werden. Transducerpixel 20, die in der Referenzatmosphäre keine Widerstandsänderung aufweisen, sind nicht mit Rezeptorpartikeln 30 belegt und werden als ungültig festgestellt. Wenn sich durch eine ungünstige Positionierung eines Rezeptorpartikels 30 auf den After the gas sensor device has been manufactured, it is first calibrated. For this purpose, it is exposed to a reference atmosphere, the gas components of which are adsorbed on the receptor particles 30 and thus change their electrical resistance. This change in resistance can be measured for each transducer pixel 20 by means of the interdigital electrodes 41, 42. Transducer pixels 20 which have no change in resistance in the reference atmosphere are not covered with receptor particles 30 and are found to be invalid. If an unfavorable positioning of a receptor particle 30 on the
Interdigitalelektroden 41, 42 ein Messwert ergibt, der außerhalb eines Interdigital electrodes 41, 42 gives a measured value that is outside of a
Erwartungsbereiches liegt, so wird der jeweilige Transducerpixel 20 ebenfalls als ungültig festgestellt. Alle weiteren Transducerpixel 20 werden in fünf Gruppen mit jeweils gleicher Widerstandsänderung unterteilt, welche den fünf Expected range, the respective transducer pixel 20 is also determined to be invalid. All other transducer pixels 20 are divided into five groups, each with the same change in resistance, which is the five
unterschiedlichen daran angeordneten Rezeptorsorten 1 - 5 entsprechen. correspond to different receptor types 1 - 5 arranged thereon.
Anschließend erfolgt ein Trainieren der Gassensorvorrichtung unter Verwendung der nicht als ungültig festgestellten Transducerpixel 20. Dabei bilden alle The gas sensor device is then trained using the transducer pixels 20 which are not found to be invalid
Transducerpixel 20 derselben Gruppe jeweils die Grundlage für die Erzeugung eines redundanten Messsignals. Transducer pixels 20 of the same group each form the basis for the generation of a redundant measurement signal.
Wenn die Gassensorvorrichtung trainiert wurde, wird sie in einem Messbetrieb einer Messatmosphäre ausgesetzt und aufgrund der elektrischen Antwort der Transducerpixel 20 wird darauf geschlossen, welche Gaskomponenten in dem jeweiligen Messgas enthalten sind. Mittels nicht dargestellter Heizerstrukturen kann jeweils während eines Messzyklus die Temperatur der Transducerpixel 20 moduliert werden, um so an jeden Transducerpixel 20 mehrere Messpunkte für das Messgas zu erhalten. Hierbei wird ausgenutzt, dass unterschiedliche Gase bei unterschiedlichen Temperaturen von den Rezeptorpartikeln 30 desorbieren, was als elektrische Widerstandsänderung messbar ist. Nach Abschluss der Messung wird die Multi-Transducer-Matrix 10a, 10b dann so stark erhitzt, dass alle eventuellen noch an den Rezeptorpartikeln 30 adsorbierten If the gas sensor device has been trained, it is exposed to a measuring atmosphere in a measuring operation and, based on the electrical response of the transducer pixels 20, it is concluded which gas components in the each sample gas are included. By means of heater structures (not shown), the temperature of the transducer pixels 20 can be modulated in each case in order to obtain a plurality of measuring points for the measuring gas at each transducer pixel 20. This takes advantage of the fact that different gases desorb from the receptor particles 30 at different temperatures, which can be measured as an electrical resistance change. After the measurement has been completed, the multi-transducer matrix 10a, 10b is then heated to such an extent that any eventual adsorb on the receptor particles 30
Gaskomponenten desorbiert werden. Gas components are desorbed.

Claims

Ansprüche Expectations
1. Gassensorvorrichtung, aufweisend eine Multi-Transducer-Matrix (10a, 10b) mit Transducerpixein (20), welche Rezeptorpartikel (30) von 1. Gas sensor device, comprising a multi-transducer matrix (10a, 10b) with transducer pixels (20), which receptor particles (30) from
unterschiedlichen Rezeptorsorten (1 - 5) aufweist, wobei erste different types of receptors (1-5), the first
Transducerpixel (20) jeweils einen oder mehrere Rezeptorpartikel (30) aufweisen und zweite Transducerpixel (20) jeweils keine Rezeptorpartikel (30) aufweisen und wobei die Multi-Transducer-Matrix (10a, 10b) mehrere Rezeptorpartikel (30) von jeder Rezeptorsorte aufweist. Transducer pixels (20) each have one or more receptor particles (30) and second transducer pixels (20) each have no receptor particles (30), and the multi-transducer matrix (10a, 10b) has several receptor particles (30) from each receptor type.
2. Gassensorvorrichtung nach Anspruch 1, dadurch gekennzeichnet, dass die Rezeptorpartikel (30) zufällig auf den Transducerpixein (20) verteilt sind. 2. Gas sensor device according to claim 1, characterized in that the receptor particles (30) are randomly distributed on the transducer pixels (20).
3. Gassensorvorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie mehr als 50 Transducerpixel (20) aufweist. 3. Gas sensor device according to claim 1 or 2, characterized in that it has more than 50 transducer pixels (20).
4. Gassensorvorrichtung nach einem der Ansprüche 1 bis 3, dadurch 4. Gas sensor device according to one of claims 1 to 3, characterized
gekennzeichnet, dass die Anzahl der Transducerpixel (20) mindestens zehnmal so groß ist wie die Anzahl der Rezeptorsorten (1 - 5). characterized in that the number of transducer pixels (20) is at least ten times as large as the number of receptor types (1-5).
5. Gassensorvorrichtung nach einem der Ansprüche 1 bis 4, dadurch 5. Gas sensor device according to one of claims 1 to 4, characterized
gekennzeichnet, dass die Multi-Transducer-Matrix (10a, 10b) auf einem Array angeordnet ist, dass eingerichtet ist, um jeden Transducerpixel (20) individuell elektronisch auszulesen. characterized in that the multi-transducer matrix (10a, 10b) is arranged on an array that is set up to individually read each transducer pixel (20) electronically.
6. Gassensorvorrichtung nach Anspruch 5, dadurch gekennzeichnet, dass das Array ein Array ist, welches die Messung elektrischer, optischer oder thermischer Eigenschaften als Wirkprinzip der Sensitivität und Selektivität zum Nachweis einer oder mehrerer Größen verwendet. 6. Gas sensor device according to claim 5, characterized in that the array is an array which uses the measurement of electrical, optical or thermal properties as an active principle of sensitivity and selectivity to detect one or more quantities.
7. Gassensorvorrichtung nach einem der Ansprüche 1 bis 8, dadurch 7. Gas sensor device according to one of claims 1 to 8, characterized
gekennzeichnet, dass die die Transducerpixel (20) als Mulden (51, 52) ausgeführt sind. characterized in that the transducer pixels (20) are designed as depressions (51, 52).
8. Gassensorvorrichtung nach Anspruch 7, dadurch gekennzeichnet, dass jede Mulde (51) so groß ist, dass sie einen Rezeptorpartikel (30) aufnehmen kann. 8. Gas sensor device according to claim 7, characterized in that each well (51) is so large that it can receive a receptor particle (30).
9. Gassensorvorrichtung nach Anspruch 7, dadurch gekennzeichnet, dass jede Mulde (52) so groß ist, dass sie mehrere Rezeptorpartikel (30) aufnehmen kann. 9. Gas sensor device according to claim 7, characterized in that each well (52) is so large that it can accommodate several receptor particles (30).
10. Verfahren zum Herstellen einer Gassensorvorrichtung nach einem der 10. A method for producing a gas sensor device according to one of the
Ansprüche 1 bis 9, umfassend ein Bereitstellen einer Multi-Transducer-Matrix (10a, 10b) mit Transducerpixein (20) und ein Aufbringen eines Gemisches auf die Multi-Transducer-Matrix (10a, 10b) welches Rezeptorpartikel (30) von unterschiedlichen Rezeptorsorten (1 - 5) und/oder deren Prekursoren enthält. Claims 1 to 9, comprising providing a multi-transducer matrix (10a, 10b) with transducer pixels (20) and applying a mixture to the multi-transducer matrix (10a, 10b) which receptor particles (30) from different receptor types ( 1 - 5) and / or their precursors.
11. Verfahren zum Betreiben einer Gassensorvorrichtung nach einem der 11. Method for operating a gas sensor device according to one of the
Ansprüche 1 bis 9, umfassend einen Kalibrierschritt in dem die Claims 1 to 9, comprising a calibration step in which the
Gassensorvorrichtung einer Referenzatmosphäre ausgesetzt wird und darauf geschlossen wird, dass Transducerpixel (20), die sich gleich verhalten mit Rezeptorpartikeln (30) der gleichen Rezeptorsorte (1 - 5) belegt sind. Gas sensor device is exposed to a reference atmosphere and it is concluded that transducer pixels (20) which behave in the same way are occupied by receptor particles (30) of the same receptor type (1-5).
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass in dem 12. The method according to claim 11, characterized in that in the
Kalibrierschritt Transducerpixel (20) ermittelt werden, die nicht mit Calibration step transducer pixels (20) are determined that are not with
mindestens einem Rezeptorpartikel (30) belegt sind und als ungültig festgestellt werden. at least one receptor particle (30) is occupied and is found to be invalid.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass in einem 13. The method according to claim 12, characterized in that in one
Messschritt die Gassensorvorrichtung einer Messatmosphäre ausgesetzt wird und die nicht als ungültig festgestellten Transducerpixel (20) elektrisch, optisch oder thermisch ausgelesen werden. Measuring step, the gas sensor device is exposed to a measuring atmosphere and the transducer pixels (20) which are not found to be invalid are read out electrically, optically or thermally.
14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die 14. The method according to claim 13, characterized in that the
Transducerpixel (20) in dem Messschritt optisch oder thermisch moduliert werden. Transducer pixels (20) are optically or thermally modulated in the measuring step.
PCT/EP2019/081258 2018-11-29 2019-11-14 Gas sensor device, and methods for the production and operation of said device WO2020109008A1 (en)

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