EP4337953A1 - Procédé de production d'un capteur et capteur - Google Patents

Procédé de production d'un capteur et capteur

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Publication number
EP4337953A1
EP4337953A1 EP22723971.2A EP22723971A EP4337953A1 EP 4337953 A1 EP4337953 A1 EP 4337953A1 EP 22723971 A EP22723971 A EP 22723971A EP 4337953 A1 EP4337953 A1 EP 4337953A1
Authority
EP
European Patent Office
Prior art keywords
sensor
substances
determined
substance
circuit
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.)
Pending
Application number
EP22723971.2A
Other languages
German (de)
English (en)
Inventor
Johannes BINTINGER
Patrik ASPERMAIR
Ciril REINER-ROZMAN
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.)
AIT Austrian Institute of Technology GmbH
Original Assignee
AIT Austrian Institute of Technology GmbH
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 AIT Austrian Institute of Technology GmbH filed Critical AIT Austrian Institute of Technology GmbH
Publication of EP4337953A1 publication Critical patent/EP4337953A1/fr
Pending 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
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating 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
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating 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
    • G01N27/122—Circuits particularly adapted therefor, e.g. linearising circuits
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating 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
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating 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
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/10—Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing

Definitions

  • the invention relates to a method for producing a sensor having a circuit with a plurality of sensor substances.
  • the invention further relates to a sensor for detecting gas components in ambient air, which has an electrical circuit.
  • the object of the invention is to specify a method of the type mentioned at the outset, with which a particularly cost-effective sensor for detecting gas components in ambient air can be produced.
  • Such a sensor is also to be specified.
  • a method for determining gas components in an environment with a sensor system is to be specified, which can be implemented particularly cost-effectively.
  • the first object is achieved according to the invention by a method of the type mentioned at the outset, wherein electrical conductivities of sensor substances in a sensor substance list, which sensor substances each have an electrical conductivity that is dependent on a concentration of one or more gases in an environment of the sensor substance, in environments with different Concentrations of different gases and optionally different degrees of humidity and / or different temperatures are measured in order to determine sensitivities of the conductivities of the individual sensor substances for the different gases, the measured conductivities and determined sensitivities of the sensor substances 2
  • Sensor substance list are stored in a database, after which, depending on requirements for the sensor in relation to the gas concentrations to be determined with the sensor in an environment and predefined conditions of use, in particular in relation to a degree of humidity and / or temperature, based on the sensitivity stored in the database of the respective sensor substances for the gas concentrations to be determined, at least two sensor substances from the sensor substance list are selected, which are placed in an electrical circuit in such a way that a conductivity of the sensor substances can be measured, so that by measuring the conductivity of the sensor substances in the circuit and/or by measuring changes in the Conductance values of the sensor substances in the circuit, the concentration of the gas component to be determined and/or a change in the concentration of the gas component to be determined in the vicinity of the circuit can be determined.
  • a correlation between a change in a conductance of one sensor substance and a change in conductance of another sensor substance may also be dependent on gas components in an environment, so that gas components can be inferred from changes in conductance of individual sensor substances relative to one another.
  • a sensor formed in a method according to the invention is therefore usually only for the detection of certain gas components in a specific environment 3
  • sensors produced according to the invention are also suitable for low-cost applications, for example to detect the composition of waste in a dustbin.
  • sensors can be produced at a cost of less than one euro.
  • sensors produced according to the invention can also be miniaturized and operated in a very wide range of applied voltages, for example even with a voltage of only 1 mV, and can therefore also be operated mobile using an energy store, in particular using an electric battery or a rechargeable battery.
  • sensor substances that are suitable for a corresponding sensor are analyzed in preliminary tests with regard to whether and, if so, how the individual sensor substances have an electrical conductance dependent on a concentration of a wide variety of gas components in an environment. After the sensitivity of the conductance is examined in relation to a wide variety of gas components in an environment, this also results in a specificity of a change in the conductance of the individual sensor substances for one or more gas components in an environment.
  • the tests can be carried out with different degrees of humidity in an environment and different temperatures as well as different exposure times. Furthermore, the tests can also be carried out with different states of the respective sensor material, for example with different states of the sensor material which result from different speeds at which the sensor materials were applied to a substrate.
  • experiments can also be carried out at different points in time after a volume exchange of a gas in an area surrounding the sensor.
  • a behavior of the sensor substances can also depend on a previous treatment of the sensor substances. For example, the behavior or the sensitivity and / or specificity for individual gas components by a previous exposure to a particularly high or low temperature, a 4 electromagnetic field or other environmental parameters can be influenced. This change in behavior can also be analyzed by experiments and the sensor substances can be treated accordingly depending on the requirements placed on the sensor. Furthermore, when evaluating sensor signals, it can be taken into account which environmental parameters these sensor substances have been exposed to up to that point, possibly also during use in the sensor, so that measurement results can be corrected accordingly.
  • Aerosols are also understood to be gases in the sense of this application.
  • the database can, for example, be stored and evaluated directly on the sensor, in a centralized cloud solution or in a data storage device connected via a data connection, or in a decentralized manner using blockchain methods.
  • Interpolation can be used to deduce intermediate values between the measurement results determined by tests. 5
  • the results of these investigations are stored in a database, after which, depending on the requirements for a sensor to be produced, those sensor substances are selected based on the data stored in the database, which have a favorable selectivity and, if necessary, a have favorable specificity, after which the sensor materials are introduced accordingly in a circuit, so that conductances of the sensor materials and changes in the conductances of the sensor materials can be measured by means of the circuit in order to determine gas components in an environment with the sensor based on the conductances of the sensor materials.
  • sensor materials are selected which have complementary sensitivities and selectivities in relation to the gas components to be analyzed.
  • the conductivities of the sensor substances can be determined at different concentrations of one or more volatile organic gases in the atmosphere or an environment around the sensor.
  • the conductivities can be determined at different concentrations of one or more of the following substances: 1,5-diaminopentane (C5H14N2), butane-1,4-diamine (C4H12N2), ethene (C2H4), triethylamine (C 6 H15N), 6
  • Methylsulfonylmethane (CHS), 1-methyl-4-(1-methylethenyl)-cyclohexene (CioHie), methyl acetate (C 3 H 6 O 2 ), acetic acid (C 2 H 4 O 2 ), ethanol (C 2 H 6 O) , 2-propanol (C ß lHsO), acetone (CHO).
  • a dopant in particular F4TCNQ (2,3,5,6-tetrafluor - 7,7,8,8-tetracyanoquinodimethane) is formed.
  • F4TCNQ 2,3,5,6-tetrafluor - 7,7,8,8-tetracyanoquinodimethane
  • 4-dodecylbenzenesulfonic acid and/or iron(III) p-toluenesulfonate can also be used as dopants.
  • the doping states of sensor substances have a significant influence on the behavior of the sensor substance and that different behaviors of the same sensor substance can therefore be achieved simply by doping.
  • a conductance of the sensor substance PANI in an undoped state exposed to 2,3-butanedione differs greatly from an achievable conductance of the same sensor substance in a doped state, which is achieved by mixing with 4.25% by weight F4TCNQ.
  • the behavior towards ethanol changes greatly depending on whether PANI is used in a doped or undoped state.
  • sensors with different behaviors can also be formed with the same sensor substances but with different doping states. Accordingly, it is favorable if not only the sensor substances themselves but also the doping states or doping states are stored in the database in order to be able to select doped or doped or undoped or undoped sensor substances for the sensor as required.
  • Volatile substances in any state of aggregation e.g. gases or primary or secondary aerosols
  • organic gases VOC for short for Volatile Organic Compounds
  • these include, in particular, hydrocarbons with up to 20, in particular with up to about ten, carbon atoms, where the carbon atoms can form branched or unbranched chains and/or be present in ring form. 7
  • Compounds with one carbon atom such as methane, ChU, are also subsumed here within the scope of the invention.
  • This also includes ring-shaped carbon compounds with up to 20, preferably up to ten, carbon atoms, for example aromatic compounds such as benzene, toluene or saturated compounds such as cyclohexane.
  • One or more carbon atoms can be substituted, for example, by nitrogen (N) and/or oxygen (O) and/or sulfur (S), both for chain-like molecules and for ring-shaped molecules, so that the invention also includes volatile heterocycles, for example pyridine.
  • the volatile organic compounds also include hydrocarbons substituted, for example with halogens such as fluorine (F), chlorine (Cl) and/or bromine (Br), thiols (-SH), hydroxyls (-OH), carboxylic acids (-COOH) and their derivatives or the like. Also included are hydrocarbons with double bonds and alkenes such as ethene or triple bonds, thus alkynes such as ethyne.
  • halogens such as fluorine (F), chlorine (Cl) and/or bromine (Br), thiols (-SH), hydroxyls (-OH), carboxylic acids (-COOH) and their derivatives or the like.
  • hydrocarbons with double bonds and alkenes such as ethene or triple bonds, thus alkynes such as ethyne.
  • gas compositions can also be analyzed with regard to components and their concentrations that do not belong to this category, such as carbon dioxide (CO 2 ), ammonia (NH 3 ), hydrogen (H 2 ), nitrogen ( N 2 ), oxygen (O 2 ) and/or hydrogen sulfide (H 2 S).
  • CO 2 carbon dioxide
  • NH 3 ammonia
  • H 2 hydrogen
  • N 2 nitrogen
  • O 2 oxygen
  • H 2 S hydrogen sulfide
  • a multi-component gas mixture with volatile organic gases and inorganic gases such as carbon dioxide can optionally be determined quasi-continuously or optionally also in real time or at least close to real time.
  • the sensor substances are applied in the liquid state to a substrate, in particular to a printed circuit board, which is an electrical conductor 8, after which the sensor substances harden on the substrate, the sensor substances connecting electrical conductors so that an electrical conductance of the sensor substances can be determined via the electrical conductors of the substrate.
  • the substrate itself is usually not electrically conductive or insulating, but can have electrical conductors, as is usual with printed circuit boards, by means of which a conductivity of the sensor substances can be measured.
  • a particularly simple, cost-effective sensor can be formed in a simple manner.
  • the individual sensor substances can be brought into a liquid state in a wide variety of ways known from the prior art, for example by heating, by adding a solvent which remains in the sensor substance during hardening or is removed from it, in particular evaporated or evaporated.
  • individual sensor substances can also be brought into a liquid state by the action of mechanical force.
  • the substrate can be surface modified to achieve favorable surface energy and wettability.
  • the sensor substances can be applied in any manner, for example by pipetting or another type of application, in particular an automatic application. Provision is preferably made for the sensor substances to be printed onto the printed circuit board using a printer.
  • a layer thickness of the sensor substances on the printed circuit board can also be defined particularly precisely, which layer thickness in turn can be relevant for the conductance of the sensor substance on the printed circuit board or a sensitivity and specificity of the sensor substance for different gas components.
  • polymerization can only take place on the substrate or on electrodes of the circuit.
  • the sensor substances are dissolved in a solvent in order to bring the sensor substances into a liquid state.
  • a precisely definable liquid state can be achieved in order to place the sensor substance precisely on a printed circuit board or the like in a repeatable method step 9 to be able to apply, so that the sensor substance can be introduced into the circuit in a precisely reproducible manner.
  • nucleation agents and/or thickeners can also be used, for example to accelerate crystallization in a polymer.
  • Thickening agents can also be used in order to increase the viscosity in order to improve targeted application to the sensor surface or the substrate.
  • sensitivities of the conductance values of the sensor substances for different gases in an environment are determined as a function of one or more parameters, in particular pressure parameters, with which the sensor substances are applied to a substrate, after which these dependencies are stored in the database, after which parameters for the application of the individual sensor substances based on data stored in the database and depending on requirements for the sensor in relation to the gas concentrations in an environment that are determined by the sensor and predefined operating conditions, in particular in relation to a degree of humidity and/or a temperature the substrate can be selected, after which the sensor substances are applied to the substrate with appropriate parameters.
  • a sensor can be formed in a simple manner, which is optimally designed for predefined operating conditions and gas components to be determined.
  • sensitivities of the conductance values of the sensor substances for different gases in an environment are determined as a function of a speed at which the sensor substances are applied to a substrate, after which these dependencies are stored in the database, after which they are based on data stored in the database as well as depending on the requirements of the sensor in relation to the gas concentrations in an environment to be determined with the sensor and predefined operating conditions, in particular in relation to a degree of humidity and/or a temperature, speeds for the application of the individual sensor substances to the substrate are selected, after which the Sensor substances with 10 corresponding speeds are applied to the substrate, in particular at speeds of 0.2 mI / s to 30 mI / s.
  • different sensor substances are applied at different speeds, in principle the same speeds can of course also be selected for two or more different sensor substances, depending on which speed of application leads to favorable behavior of the respective sensor substance, in particular to high sensitivity and/or specificity in relation to certain gas components.
  • the pressure parameters temperature of the sensor substance, temperature of the substrate, pressure and the like can be varied and the effects on the conductance can be assessed in order to achieve correspondingly favorable properties of the sensor substances by using corresponding pressure parameters when applying the sensor substances .
  • pressure parameters have an influence on sensor behavior, which is why the sensor substance or the sensor substances are usually applied at one or more speeds, which are selected depending on which behavior of the individual sensor substances is desired or which gas components with the sensor should be determinable. It has been shown that different printing speeds, for example 1 mm/s, 0.4 mm/s and 0.1 mm/s, result in different material structures, possibly crystal structures, of the cured sensor substances, in particular polymers and low-molecular compounds , which lead to different conductivity values of the sensor substances under identical environmental conditions or to increased and/or reduced sensitivities and/or specificities in relation to individual gas components. In other words, a sensor behavior with the same sensor substances can be influenced by different pressure parameters.
  • the sensor substances are thus arranged in the circuit by a corresponding application of the sensor substances to the substrate, which generally has electrical conductors according to a circuit.
  • the substrate which generally has electrical conductors according to a circuit.
  • the circuit can be formed by two electrical conductors, which are connected by one or more sensor substances, so that conductance values and changes in the conductance values of the sensor substances can be measured via the electrical conductors.
  • the liquid sensor substances are applied to the substrate with a nozzle that is moved relative to the substrate, the nozzle preferably having a nozzle diameter of less than 1 mm , in particular 100 ⁇ m to 500 ⁇ m.
  • the sensor substances are applied to the substrate at a speed of 0.1 mm/s to 10 mm/s, in particular 0.2 mm/s to 4 mm/s, in particular with a nozzle as stated above.
  • a layer of the sensor material on the substrate with a particularly precisely reproducible behavior is achieved.
  • the substrate is kept at a predefined temperature during the application of the sensor substances, especially at a temperature of 25°C to 120°C. Reliable evaporation of the solvent can then be ensured, in particular, as a result of which microscopic cavities can be produced in particular, which enlarge an active surface and can improve sensitivity and/or specificity.
  • a predefined temperature of the substrate when applying the sensor substances is also favorable in order to be able to produce reproducible sensors with essentially identical behavior.
  • the substrate is positioned on a heating device, in particular a heating plate, which is kept at a constant temperature, in particular a temperature at which a solvent, with which the sensor substance is brought into a liquid state, evaporates.
  • a temperature of the substrate can be set particularly precisely by means of a corresponding heating device, so that conditions under which the sensor substances are applied to the substrate or introduced into the circuit can be specified particularly precisely. This makes it possible to obtain sensors with predictable behavior in a particularly simple manner.
  • the substrate usually has a temperature of 15.degree. C. to 150.degree. C., preferably 30.degree. C. to 100.degree. C., in particular 40.degree. C. to 80.degree. C., when the sensor substances are applied.
  • any sensor substances can be used for a sensor produced in a method according to the invention, which have an electrical conductance dependent on a gas in an environment. It has proven particularly useful if at least one of the sensor substances that are attached to the circuit has a polymer. On the one hand, polymers can be produced cheaply and, on the other hand, they have advantageous chemical properties which predestine them for use in a corresponding sensor. This applies in particular to organic polymers and preferably, for the purposes of the invention, to electrically conductive organic polymers.
  • the polymers can also be in the form of doped or doped polymers, for example mixtures of polymers with molecular dopants or dopants, in particular F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), where, for example, 4-dodecylbenzenesulfonic acid and/or iron(III) p-toluenesulfonate can be used as dopants. 13
  • the sensor substances have or consist of metal oxides, in particular copper oxide or zinc oxide, metal particles, in particular gold particles, and/or polymers, in particular organic, preferably electrically conductive polymers, preferably electrically conductive, in particular organic electrically conductive polymers, especially since these substances also have a conductance dependent on gas concentrations in an environment.
  • metal oxides are particularly well suited as sensor substances for operating temperatures of 250° C. to 450° C.
  • polymers are particularly well suited as sensor substances, in particular for sensors which are operated at room temperature.
  • a heating and/or cooling device can also be provided, with which a favorable temperature of the sensor substance is achieved. Accordingly, the entire sensor or just one or more sensor substances can be brought to a predefined temperature in a targeted manner.
  • those sensor substances are preferably used which can be operated well in the corresponding temperature range.
  • polymers are preferably used as sensor substances.
  • the sensor substances contain Mn 3 Ü 4 , ZrÜ 2 , T1O 2 , CeO 2 , ZrÜ 2 , ZnO, T1O 2 , C ⁇ O ß , CO 3 O 4 and/or SnÜ 2 or one or more of these metal oxides exist.
  • any substance that has sufficient selectivity and sensitivity for the gas to be determined, taking into account the desired detection limits, can be considered as sensor substances. It cannot be ruled out that two or more sensor substances will be used with regard to a single gas component to be determined, for example a specific volatile organic gas, for example in order to be able to cover different concentration ranges and/or to statistically secure the measurement result better.
  • the list of sensor substances contains polymers, preferably conductive, in particular organic, electrically conductive polymers and/or metal oxides. 14, in particular copper oxide or zinc oxide, and/or metal particles, in particular gold particles, contains or consists of such substances.
  • the sensor substance can also contain nanoparticles, as these are already known from the prior art.
  • they can be nanoparticles made of gold or platinum that respond to certain gases.
  • metal oxides such as copper oxide or zinc oxide.
  • Metal oxides can also be used in particular, as can metal particles if they have a certain resistance to oxidation, such as gold particles, for example.
  • the metal oxides can be present as a bulk material or, like the nanoparticles mentioned, as nanomaterials, for example as metal oxide nanowires with a length of, for example, up to a maximum of 500 nanometers and a width of, for example, no more than 50 nanometers.
  • Polymers in particular organic polymers, are particularly preferably used as sensor substances, since these can be printed relatively easily and can therefore be applied from a printable mass to almost any substrate.
  • electrically conductive polymers in particular have proven to be particularly well suited sensor substances.
  • the electrically conductive polymers usually organic polymers, can, like polymers, also be present as nanowires, although this is not mandatory.
  • the polymers can also be applied to a substrate as a sheetlike substance.
  • the electrically conductive polymers can be connected to other sensor substances on a sensor. However, if electrically conductive polymers are used, they are preferably used as exclusive sensor substances, since in this case all sensor substances can be printed under largely the same conditions, for example by printing, in particular inkjet printing, or in another way such as spraying, spin coating, dip coating or other flat coating process as 15 flat coating layer with a thickness of less than one millimeter, preferably less than 0.5 millimeters, can be applied.
  • Suitable additives can also be added, for example carbon black or soot, in order to adapt the conductivity.
  • carbon black for example carbon black or soot
  • Exclusive sensor substances thus also includes suitable excipients, but preferably not more than 20 percent by weight (% by weight), preferably not more than 10% by weight, in particular not more than 5% by weight, based on the total mass (polymer and auxiliary materials).
  • polyurethanes polyaniline (PANI) and its derivatives, optionally also in mixtures with carbon black, poly(3-hexylthiophene-2,5-diyl) [P3HT] and its derivatives, poly(3,4- ethylenedioxythiophene): polystyrene sulfonate(PEDOT:PSS), poly(2,2'-[(2,5-bis(2-hexyldecyl)-3,6dioxo-2,3,5,6-tetrahydropyrolo[3,4-c] pyrol-1,4-diyl)dithiophene]-5,5'-diyl-alt-tthiophene-2,5-diyl) ⁇ [PDPP3T], polyepichlorohydrin (PECH) or poly[(chloromethyl)ethylene oxide, poly[2- (3-thienyl)-ethoxy-4-butylsulfonates] as well as
  • Substances for which no CAS number is specified can be obtained on the filing date by specifying the chemical name, for example via one of the websites riekemetals.com or brilliantmatters.com.
  • the senor substances it is possible for the sensor substances to be purposefully matched to the application.
  • the 21 it is possible for the sensor substances to be purposefully matched to the application.
  • electrically conductive polymers as sensor substances, provision can be made for the electrically conductive polymers to be modified.
  • the peptide side chains used can be based on biopeptides that are sensitive to certain molecules, similar to the human sense of smell. In this way, sensitivity can be specifically controlled or adjusted on the basis of various analyte-polymer interactions based on aromatic and dipole-dipole interactions and hydrogen bridge bonds via amino acids.
  • 1,4-di-2-dienyl-1,4-butanedione can be reacted in a Paal-Knorr condensation reaction with an amino group of the chosen amino acid sequence to give the corresponding substituted 2,5-di(2-dienyl)pyrrole, which can then be electrochemically polymerized to form poly(2,5-dienylpyrol).
  • Graphene and, in particular, graphene compounds are also suitable as a sensor substance.
  • graphene can be combined by addition reactions with molecules that have a specificity for certain molecules.
  • 1-pyrenebutyric acid or 1-pyrenebutyric acid N-hydroxysuccinimide ester can be used as a linker.
  • TT-tt interactions a pyrene group attaches to other conjugated double bonds (graphene, reduced 24
  • the sensor substances are selected based on the substances in the following list:
  • the sensor substances can have one or more of the substances mentioned or be formed from one or more of the substances mentioned.
  • substances specified on the basis of the list are to be understood as meaning that suitable derivatives of the substances specified in the list can also be selected.
  • a behavior of the sensor can thus be determined based on the actual concentrations of certain gas components in the environment in order to use the conductance values of the individual sensors for later use 25
  • the sensor can then be calibrated based on the conductivities of the individual sensor substances depending on the gas mixtures in an environment around the sensor, with data being recorded during operation of the sensor within the framework of methods known from the prior art for pattern recognition (pattern recognition and/or artificial neural networks) can be used to draw conclusions about the gases in the environment based on conductance values of the individual sensor substances.
  • pattern recognition pattern recognition and/or artificial neural networks
  • the conductance values of the individual sensor substances are measured at different ambient pressures, in particular at a pressure range of 0.3 bar to 4 bar, in order to also take into account this parameter or the ambient pressure to which the sensor is to be exposed during operation Production of the sensor and in particular to be able to take into account the choice of appropriate sensor substances.
  • the further object of the invention is achieved according to the invention by a sensor of the type mentioned at the outset, which has at least two sensor substances from a sensor substance list, with the conductivities of the sensor substances being able to be determined by means of the circuit.
  • the sensor is preferably produced in a method according to the invention.
  • a corresponding sensor can be produced with little effort and thus at low cost and is nevertheless suitable for determining the presence, concentration and/or change in concentration of a gas component in an environment around the sensor.
  • a corresponding sensor can therefore be used in particular to be used in a smart waste bin to determine a component of waste.
  • those sensor substances are preferably combined and arranged on the circuit which have a particularly high sensitivity, selectivity and/or a particularly high specificity for the gas component or components to be determined in order to use a combination of the respective measured values in relation to the conductivity of the individual sensor substances to determine the to be able to precisely determine the gases to be determined.
  • One or more sensor substances can also be used which show no reaction to a gas component to be determined, in order to rule out the presence of other gases to which this sensor substance is sensitive and thus specifically verify the reactions of the other sensor substances attached to the circuit. Such sensor substances are therefore used for the negative control of certain gas components.
  • At least one of the sensor substances has a polymer or consists of a polymer.
  • one or more of the sensor substances arranged in the circuit have and/or consist of metal oxides, in particular copper oxide or zinc oxide, metal particles, in particular gold particles, and/or polymers, in particular organic, preferably electrically conductive polymers.
  • the sensor substance list is formed based on the substances specified below, the substances specified in Table 1 and/or the substances specified in Table 2 and/or consists of these substances:
  • the sensor substance list can of course also contain suitable derivatives of the substances mentioned. Suitable derivatives are those which still have sufficient sensitivity for the purpose of the invention.
  • the sensor substances can be attached in the circuit in a wide variety of ways, so that a conductivity of the sensor substance can be determined by means of the circuit. Provision is particularly preferably made for the sensor substances to be printed onto the circuit.
  • Electrodes which are connected by the sensor substances, are usually arranged on the circuit. As a result, a conductance value of the sensor substance can be directly inferred from an electrical conductance value between the electrodes or an electrical resistance between the electrodes.
  • an identical sensor substance is used in parallel and/or in series with each sensor substance that connects two electrodes of the circuit and is connected to an environment is arranged in the circuit, which is hermetically or substantially hermetically separated from the environment. It can then be used to determine a 28
  • Gas component in an environment for example with a bridge circuit, a voltage divider or the like, a difference between the conductance of the associated with the environment sensor substance and the identical, hermetically separated from the environment sensor substance can be determined.
  • effects of aging processes in the sensor substances and influences of temperature changes on the conductivity of the respective sensor substance when measuring gas components are equalized.
  • a differential measurement can be implemented in particular, by means of which only differences between the conductance values of the individual sensor substances are detected, but aging effects that occur synchronously with a number of sensor substances are not taken into account.
  • a voltage is preferably measured at a voltage divider formed by appropriately arranged sensor substances by means of an analog/digital converter, and a measured value thus digitized is further processed in a data processing device.
  • a difference between the conductances of the sensor substances and a change in a conductance of a sensor substance relative to the conductance of a second sensor substance of the voltage divider can thus be easily measured with the voltage divider.
  • a sensor according to the invention is usually used in connection with a data processing system in order to be able to draw conclusions about gas components in an environment based on measured conductance values of the individual sensor substances, for example by determined correlations and/or targeted utilization of multivariate aspects of the individual sensor substances.
  • the individual sensor substances can have different functional groups in order to be able to cover the widest possible range of analytes with the resulting overlapping specificities.
  • sensor substances that have a polymer can be combined on a sensor with sensor substances that have a metal oxide.
  • Machine learning methods for pattern recognition such as, in particular, support vector machines and artificial neural networks, monitored and unsupervised machine learning, and methods from probability calculation such as Gaussian mixed models can also be used for an evaluation to be 29
  • the sensor is therefore usually used within the framework of a sensor system which, in addition to the sensor, also has a data processing device.
  • the senor is designed according to the invention.
  • the data processing device can be used for a wide variety of application areas, while the sensor can have different sensor substances depending on the application area. It is therefore favorable if the sensor can be releasably connected to the data processing device.
  • a mechanical and electrical connection of the sensor to the data processing device can, for example, take place in a non-positive and/or positive manner.
  • the senor is particularly preferably made for the sensor to be in the form of a plug-in card and to be connected to the data processing device via a receptacle, so that the sensor can be plugged into the receptacle, with an electrical connection being established between the sensor and the data processing device by plugging the sensor into the receptacle is.
  • this enables sensors to be easily exchanged, so that the sensor system can easily be adapted to different areas of application.
  • the sensor can be replaced by a detachable connection such as a plug-in connection, a possibly short service life of individual sensor substances can be compensated for in a cost-effective manner without replacing the entire sensor system.
  • the data processing device is suitable for carrying out a method whereby concentrations of one or more gases in the vicinity of the sensor are determined using measured conductivity values of the sensor substances and sensitivities of the individual sensor substances stored in a database. A comparatively precise determination of gas components in an environment around the sensor can then be carried out on the basis of the determined sensitivities, despite the inexpensive sensor construction.
  • the database can be stored centrally or decentrally, for example distributed to different data storage devices which are connected via an Internet of Things network.
  • the data processing device can also be used to carry out methods for pattern recognition and methods which are known from the field of machine learning, in order to use measured conductance values of the individual sensor substances to infer gas components in the environment.
  • the sensor system has an acoustic sensor and/or an optical sensor, in particular a light sensor or a brightness sensor, in order to carry out a measurement by means of the sensor, triggered in particular by acoustic and/or optical changes in the surroundings of the sensor system.
  • a measurement can then be carried out triggered by an opening noise and/or a sudden change in the incidence of light. This makes it possible to determine the composition of the contents of waste bins in a particularly efficient manner.
  • a measurement does not have to be carried out continuously, but it is often sufficient to carry out a measurement after a trigger event such as opening the garbage can.
  • Data from the trigger event can also be used to calculate probabilities of gas components to be determined, in particular by software in the data processing device. For example, when using the sensor in a garbage can, a specific noise can indicate that a beverage can has been thrown into the garbage can, so that there is an increased probability of an increase in the concentration of gas components in the garbage can, which gas components are associated with a beverage can. This increased probability can when evaluating the sensor signals or an automated 31
  • Interpretation of conductance changes of the sensor substances can be used in order to achieve a particularly high measurement accuracy by combining the data of the trigger event with the measured conductance values of the sensor substances or by measuring changes in the conductance values.
  • sensors can of course also be provided on the sensor system, for example distance and/or movement or acceleration sensors.
  • a transport device is provided with which a gas to be analyzed can be actively transported to the sensor substances of the sensor, in particular a pump, a compressor, a fan or the like.
  • a transport device can be activated, for example, triggered by a trigger event, which trigger event can in turn be automatically detected, for example by means of a distance sensor, a motion sensor, an acoustic sensor and/or an optical sensor, such as a camera.
  • the analysis can also include a headspace sampling method.
  • the senor is preceded by a volume, in particular a closed space, which is charged with a gas to be analyzed by a transport device and in which a concentration of an analyte takes place.
  • An algorithm which can be stored in a program in the data processing device, can then, for example, be designed in such a way that an evaluation is only carried out for a predefined time after the trigger event, for example opening a door or a lid. This can be expedient in particular when changes in a gas composition are essentially only expected when this trigger event occurs.
  • the further object is achieved by a method for determining gas components in an environment with a sensor system in which a 32 sensor system according to the invention is used.
  • the sensor system can thus be produced in a particularly cost-effective manner, which is why the method can also be implemented in a simple and cost-effective manner.
  • the method can be used for a wide variety of purposes, for example to automatically monitor an odor in a sanitary facility, to detect anomalies, in particular leaks. It can further be provided that the method is used to determine the contents of a rubbish bin. Supplementary data, which can be recorded with additional sensors, for example a camera, can then also flow into the method in order to achieve a continuous improvement of the results of the method, for example through machine learning and/or with methods of pattern recognition.
  • a trigger event is detected and an analysis of gas components is carried out beginning with the trigger event.
  • an analysis can always be carried out when an opening and/or closing of a lid of the rubbish bin has been detected, especially since the composition of the waste in the rubbish bin usually only changes after such an event.
  • sensors are determined. It has been shown that different sensor substances respond differently to different gas components in an environment. Consequently, conclusions can be drawn not only about a conductivity and/or a change in concentration of a gas component in an environment, but also about a change in the conductivity over time, in particular after the trigger event.
  • an analysis can also be time-dependent, for example a composition of a gas can be carried out according to fixed time intervals. It can also be provided that the time intervals are adjustable. Thus, even with a continuous measurement, data points can be recorded, for example, at a time interval of only a few milliseconds or at an interval of several minutes. This optimizes energy efficiency depending on the respective requirements or a question to be answered.
  • two different gas components can cause the same conductance in a sensor substance, but the change in conductance can occur at different speeds.
  • the change in conductance can occur at different speeds.
  • FIG. 1 shows a flowchart of a method for producing a sensor according to the invention
  • Figure 10j Effects of doping level on sensor resistance
  • Figures 10k and 101 Effects of doping level on distinguishability of different analytes.
  • a large number of possible sensor substances 16 are analyzed to determine whether and, if so, how an electrical conductivity of the respective sensor substance 16 changes when the concentrations of different gases in an area surrounding the sensor substance 16 change. Tests are preferably also carried out with different degrees of humidity in the ambient air and different speeds at which the sensor substances 16 are applied to a substrate 7 in the liquid state.
  • Results of these tests are stored in a database 6, so that in the database 6 data relating to a conductance of individual sensor substances 16 in the presence of different concentrations of different gases at different degrees of humidity in the air and different
  • sensors with the respective sensor substances 16 can thus be produced, with which corresponding odors can be determined at low cost or with which concentrations of the gases which trigger corresponding odor perceptions in humans can be determined.
  • a second step 2 the requirements for the sensor in relation to the gases to be determined and the conditions of use are defined.
  • a third step 3 based on the requirements and in the
  • At least two sensor substances 16 are selected from the data stored in database 6, which are subsequently attached to a circuit in a fourth step 4, so that conductance values of the individual sensor substances 16 can be determined by means of the circuit, in order to use the conductance values to determine concentrations of gases in the environment shut down.
  • the sensor is then calibrated by subjecting the sensor to defined boundary conditions, in particular with regard to concentrations of certain gas components in an environment, after which conductivity values of the individual sensor substances 16 are measured via the circuit.
  • the sensor has a circuit with electrodes or 36 electrical conductors 8, which can be made of copper or gold, for example, the electrodes being connected by sensor substances 16 in order to determine conductance values of the individual sensor substances 16 via the electrodes.
  • the sensor substances 16 are printed on the substrate 7, usually with a thickness of less than one millimeter and at a predefined speed, since the speed at which the sensor substance 16 is printed on the substrate 7 often also has an influence on the behavior of the sensor substance 16 Has.
  • the sensor shown has two different sensor substances 16, with a first contacting element 10 formed by a sensor substance 16, which can be formed, for example, by one of the substances specified in Table 1 or one of the substances specified in Table 2, between a voltage electrode 14 and an electrical conductor 8, to which a voltage of, for example, +1.5 V or +5 volts relative to a reference potential is applied during operation of the sensor, and a measuring electrode 15 can be arranged so that the measuring electrode 15 is electrically connected essentially only through the first contacting element 10 to the voltage electrode 14 is connected.
  • the measuring electrode 15 is also connected by a second contacting element 11 to a ground electrode 9 to which the reference potential is applied, with the second contacting element 11 also being formed by the sensor substance 16 which also forms the first contacting element 10 .
  • the first contacting element 10 and the second contacting element 11 thus form a voltage divider in connection with the measuring electrode 15, the voltage electrode 14 and the ground electrode 9, so that basically a voltage corresponding to half the voltage of the voltage electrode 14 is present at the measuring electrode 15 when the conductances or The resistances of the first contacting element 10 and the second contacting element 11 are identical.
  • the first contacting element 10 or the second contacting element 11 is hermetically separated from an environment, for example by applying a coating to the first contacting element 10.
  • This ensures that a change in the composition of ambient air only changes a conductance of the second Contacting element 11 leads while 37 the first contacting element 10 remains as a reference in the circuit.
  • measurement errors that are based on changes in the conductivity of the corresponding sensor substance 16, which are independent of the composition of ambient air, in particular aging effects and temperature influences, can easily be avoided.
  • a measured value corresponding to a sensitivity of the first sensor substance 16 is thus obtained with the first contacting element 10 and the second contacting element 11 .
  • a further measured value can be obtained based on a third contacting element 12 and a fourth contacting element 13, each of which consists of a second sensor substance 16 that is different from the sensor substance used in the first contacting element 10 and second contacting element 11 and also from the table 1 or Table 2 can be taken.
  • either the third contacting element 12 or the fourth contacting element 13 is hermetically separated from the environment.
  • sensor substance 16 which forms first contacting element 10 and second contacting element 11, has a high sensitivity for a first gas component to be determined
  • sensor substance 16, which forms third contacting element 12 and fourth contacting element 13 has high sensitivity or selectivity for a second have the gas component to be determined, so that the sensor can be used to determine the presence and, if appropriate, the concentration of two different gas components in the vicinity of the sensor.
  • a sensor according to the invention can have twelve different sensor substances 16 in 24 contacting elements, which are connected in a circuit similar to that in Fig. 2 38 are arranged on the sensor in order to be able to measure 16 changes in the conductance with twelve sensor substances.
  • a change in the conductivity has the effect of a potential shift at the measuring electrode 15 .
  • This voltage can be detected, for example, with an analog-to-digital converter which, given identical conductance values of the first contacting element 10 and the second contacting element 11, receives 50% of the voltage present at the voltage electrode 14 as an analog input signal and digitizes this value in order to forward it to the data processing device to direct. If the conductance of the first contacting element 10 changes relative to the conductance of the second contacting element 11, this voltage also changes and the voltage change can be detected with the analog-to-digital converter and automatically processed further.
  • sensor substances 16 are also possible.
  • 96 different sensor substances can also be provided in a sensor according to the invention.
  • a sensor substance 16 can also only be suitable for determining a concentration of a gas component within a specific range and, for example, saturate when this concentration range is exceeded, so that several different sensor substances 16 can be required to determine a concentration of a gas over a large range.
  • specific gas mixtures can only be determined with acceptable accuracy by a combination of specific sensor substances 16 .
  • the conductance of a sensor substance can increase as the concentration of two different gas components in the environment increases, while the conductance of another sensor substance can decrease, inter alia, as the concentration of one of these two gas components in an environment increases.
  • a method according to an algorithm can be carried out in a data processing device to which the sensor is connected as part of a sensor system and with which the conductance values of the sensor substances are measured and evaluated, which algorithm contains a corresponding correlation.
  • the correlation of the conductance values of the individual sensor substances to the concentrations of the respective gas components can, for example, be determined empirically in advance and stored in a data memory in the sensor system.
  • the sensor system can of course also be connected to a central database via a possibly wireless data connection, so that corresponding correlations can also be changed after commissioning without having to make changes to the sensor system itself.
  • the senor is usually integrated into a sensor system that has a data processing device and a data memory, so that certain gas components can be inferred, for example, based on determined correlations that are determined in advance and stored in the data memory, and measured conductance values. In particular, a regression analysis can also be used for this purpose.
  • the senor can be releasably connected to the data processing device, in particular by a plug-in connection.
  • a wide variety of sensors which have different sensor substances 16 depending on the application, can be combined with the same data processing device or the same type of data processing device, so that a high level of equality can be achieved with regard to the data processing device, even if the individual sensor systems are used for a wide variety of applications.
  • FIG. 3 shows a method step of printing a sensor substance 16 onto a substrate 7 in a method according to the invention.
  • the sensor substance 16 brought into a liquid state is applied to an electrically non-conductive substrate 7 by means of a pneumatic nozzle, the needle usually having a diameter of less than one millimeter.
  • the sensor substance 16 can be under negative pressure or a vacuum inside the needle and can be ejected from the needle only by a short pressure pulse or by continuous pressure and brought into connection with the substrate 7, after which the needle can be pushed over the substrate 7 is moved in order to apply the sensor substance 16 to the substrate 7 .
  • the needle is generally moved at a speed of 0.2 mm/s to 10 mm/s along a feed direction 18 over the substrate 7, so that the sensor substance 16 has a layer thickness of 0.5 mm, for example, in a hardened state the substrate 7 remains.
  • the speed can also be 0 mm/s.
  • the application is then equivalent to pipetting, but can also be controlled via the pressure with which the sensor substance 16 is applied to the substrate 7 .
  • pipetting can also be carried out directly, in which case application of the sensor substance 16 to the substrate 7 can be controlled via a volume which is applied in each case.
  • the sensor substance 16 is usually brought into a liquid state by a solvent.
  • the sensor substance 16 is preferably applied to the substrate 7 when the substrate 7 is kept at a predefined temperature.
  • the substrate 7 can be arranged on a heating plate (not shown in FIG. 3) for this purpose, with a temperature usually being higher than a temperature at which the solvent with which the sensor substance 16 was brought into a liquid state evaporates.
  • a corresponding sensor can in particular have the substances specified in Table 2 in order to be able to determine the gases in an environment which trigger the olfactory sensations specified in Table 2 in the last column in a person.
  • such a sensor can also be used to determine the contents of a garbage can based on a gas composition, especially since these sensor substances 16 can be used to determine particularly precisely volatile organic gases, such as those that occur during the decomposition of waste materials in a garbage can .
  • 4a to 4c show a relationship between a speed of application of a sensor substance formed by a polymer and an electrical resistance of this sensor substance on the finished sensor for four different sensor substances, for example one of the sensor substances mentioned in Table 1 or Table 2, which are made with polymer material 1 , Polymer Material 2 and Polymer Material 3 are denoted.
  • the diagrams were created by measurements, so that statistically relevant data such as a scatter and a median can also be seen using several measuring points. Other parameters relevant to printing are at 42
  • series of measurements can also be carried out in which initially only one parameter such as the printing speed is varied and this series of measurements is carried out for different temperatures in order to be able to assess any interactions.
  • the speed of application shown on the horizontal axis which can also be referred to as printing speed, deposition rate or printing speed, has an influence on the resistance of the sensor substance on the sensor shown on the vertical axis.
  • a lower resistance is usually more favorable, so that a pressure speed of 3.8 mI/s is favorable for the relationship between the electrical resistance and the pressure speed in the case of a first sensor substance or a polymer material 1, as shown in FIG. 4a.
  • the scatter and median of the resistance increase sharply at higher printing speeds, so that a printing speed of less than 3.8 mI/s is favorable here in order to achieve a low resistance, for example a speed of 0.76 mI/s to 1.9 mI/s.
  • the sensor performance is characterized by a change in the sensor signal due to the effect of the respective gas component 43 shows which change is indicated relatively, namely via the value of the signal after an exposure time of 300 seconds based on the value of the signal before the sensor substance was exposed to the respective gas component. Higher values thus indicate better sensor performance in relation to the respective gas component, since the sensor substance then has a higher sensitivity for the respective gas component, i.e. the signal changes more strongly when the sensor substance is acted upon.
  • FIG. 5a to 5c show this relationship in relation to a sensor substance referred to as polymer material 1, which can correspond to one of the sensor substances listed in Table 1 or Table 2, for example.
  • polymer material 1 can correspond to one of the sensor substances listed in Table 1 or Table 2, for example.
  • lower printing speeds lead to larger changes in the sensor signal, for example a resistance of the sensor substance or a voltage drop across the sensor substance, with respect to acetone, acetonitrile and isopropanol. Consequently, a low printing speed of 1 mI/s, for example, is favorable here for the sensor performance of the polymer material 1 with regard to acetone, acetonitrile and isopropanol.
  • 5b shows the behavior in relation to ammonia water and deionized water.
  • 6a to 6d show corresponding diagrams of another sensor substance, which is referred to here as polymer material 2 and can also be formed by one of the substances mentioned in Tables 1 and 2, for example.
  • polymer material 2 can also be formed by one of the substances mentioned in Tables 1 and 2, for example.
  • a higher pressure speed or deposition rate of, for example, 7 mI/s is favorable for a strong reaction of the sensor substance with regard to acetone, acetonitrile and ethanol, while a higher speed is favorable for the detection of ammonia.
  • a sensor can be produced with several of the same sensor substances, which, however, are applied at different printing speeds, so that, for example, the one with the lower 44
  • Pressure speed applied sensor substance polymer material 2 acetone, acetonitrile and ethanol can be easily recognized, while the same sensor substance applied with high pressure speed is favorable for the determination of ammonia.
  • FIG. 7a to 7c show the effects of temperature on the resistance of the sensor substance for three different polymers.
  • the resistance of polymer material 1 increases with increasing temperature
  • the resistance of polymer material 2 increases up to a temperature of 75° C. and then decreases again with increasing temperature, as shown in FIG. 7b is.
  • FIG. 7c shows a relationship that runs counter to the relationship shown in FIG. 7a, with the resistance decreasing as the printing speed increases.
  • a correspondingly strong effect on the behavior of the sensor substance can of course be achieved, for example to achieve a sensor with a particularly low resistance that is suitable for a or several specific gas components is particularly sensitive.
  • a sensor behavior for example a nozzle cross section of a nozzle from which the liquid sensor substance is applied during printing.
  • the temperature is shown on the horizontal axis and the change in a signal of the sensor substance is shown on the vertical axis, e.g. again a resistance of the sensor substance after an exposure time of 300 seconds relative to the same signal before the start of exposure to the gas component.
  • High scores 45 thus indicate a relatively strong change in the signal or the conductance of the sensor substance in the presence of the respective gas component.
  • FIGS. 8a to 8d show a change in the behavior of a first polymer, which is referred to as polymer material 1 and can be formed, for example, by one of the substances listed in Tables 1 and 2.
  • polymer material 1 which is referred to as polymer material 1 and can be formed, for example, by one of the substances listed in Tables 1 and 2.
  • high temperatures of around 80° C. during pressing or during drying of the sensor substance are favorable in order to ensure a strong response from the sensor material, i.e. a strong signal change, in the presence of ammonia, hexanes , water, and isopropanol, while temperature during pressing has little effect on sensor performance in terms of acetone, acetonitrile, and diacetyl.
  • Fig. 10a to 10h show differences in the behavior of the sensor substance PANI and
  • the resistance of the polyaniline doped with 4.25 percent by weight changed by minus 2.5 percent in twelve samples when exposed to acetonitrile, while a change of 2.5 percent resulted in only one sample in the case of undoped polyaniline.
  • the resistance of doped polyaniline changes by minus 2.3 percent when acetonitrile is applied, while the resistance of undoped polyaniline changes by only minus 1.57 percent on average.
  • the different doping state affects behavior towards 2,3-butanedione and ethanol more than towards hexane.
  • a behavior can thus also be targeted by simply doping sensor substances 46 are influenced, which is why it is favorable to also record the doping state when creating a database which contains the behavior of different sensor substances in relation to different gas components. In this way, a correspondingly doped or doped sensor substance can be specifically selected during production of the sensor.
  • two sensors were produced, each containing several sensor substances, whose conductance values were measured, with a first sensor containing undoped sensor substances and a second sensor containing 4.25% F4TCNQ-doped sensor substances and these sensors having identical environmental conditions with regard to exposed to the gas components indicated in the illustrations for 300 seconds each.
  • the undoped sensor substances, here undoped polyaniline in each case are shown by white bars and the doped polyaniline, here each doped with 4.25% F4TCNQ, by black bars in the figures.
  • the measured values also scatter within the undoped and within the doped sensor substances, but with regard to some gas components, the mean value of the individual measured values changes as a result of the doping, so that the sensor behavior of individual sensor substances with regard to certain gas components can be specifically influenced by doping.
  • Figure 10i shows effects of doping level on sensor resistance.
  • the doping level of F4TCNQ is shown on the abscissa in percent by weight and the measurement results of a resistance of the sensor substance, for example polyaniline, are shown in ohms on the ordinate, so that it is also clear how strongly the results scatter.
  • a doping content of 4.25% by weight F4TCNQ leads to a favorable ratio of reproducibility and conductivity.
  • 10j shows effects of the doping level on the sensor resistance or sensitivity at different concentrations of ammonia.
  • An exposure time in hours is shown on the abscissa axis, while a resistance of the sensor substance, for example polyaniline, is shown in megaohms on the ordinate axis.
  • the measurement started with ambient air, after which the concentration of ammonia was increased first to 0.1 ppm and finally to 50 ppm at 25 hours, after which the sensor substances were again exposed to the ambient air without ammonia.
  • the resistance of the sensor substance generally decreases with increasing 47
  • a good compromise between low resistance and good sensitivity is a doping level of 4.25 percent by weight F4TCNQ.
  • Figures 10k and 10l show effects of polyaniline doping level on discriminability of different analytes.
  • the illustrations show main components, which were determined as part of a main component analysis
  • the main components result after extraction of information from sensor responses for all polymers in the integrated circuit with n sensor elements.
  • the information extracted in this case the sensor response after 600 seconds, an exponential fit and the slope of the curve, is then plotted in an n-dimensional vector space and the normal vector on a plane, i.e. a viewing angle, is sought using principal component analysis the best distinguishability of the data points can be seen.
  • This is also known as the principal axis transformation.
  • the two axes of the plane found in this way are called principal components and are also shown in Figs. 10k and 10l in the abscissa axis and the ordinate axis.
  • These main components can also be referred to as principal components, which is why the axes in the diagrams are labeled C1 and C2.
  • FIG. 10k shows the behavior of polyaniline doped with 4.25 weight percent F4TCNQ and FIG. 10j shows the behavior of undoped polyaniline when exposed to various analytes.
  • the doping improves the distinguishability.
  • the main component analysis when exposed to ethanol, hexane and propan-2-ol gives similar values for undoped polyaniline, while polyaniline doped with 4.25 percent by weight F4TCNQ has main components that are easier to distinguish, which are dependent on the three analytes mentioned.
  • a sensor according to the invention can be produced at very low cost, so that such a sensor can be used for a wide variety of applications, for example to continuously a composition of in the garbage cans 48
  • Garbage can located waste to determine which composition in turn can be transmitted, for example via a modem to a waste disposal company, so that when the garbage can is full, the collection vehicle corresponding to the respective waste can be sent to the garbage can.

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Abstract

L'invention concerne un procédé de production d'un capteur comportant un circuit avec une pluralité de substances de capteur. Selon l'invention, des conductivités électriques de substances de capteur d'une liste de substances de capteur, lesdites substances de capteur ayant chacune une conductivité électrique dépendant de la concentration d'un ou de plusieurs gaz dans un environnement de la substance de capteur, sont mesurées dans des environnements ayant différentes concentrations de différents gaz et éventuellement différents rapports de mélange d'humidité et/ou différentes températures afin de déterminer les sensibilités des conductivités des substances de capteur individuelles pour les différents gaz ; les conductivités mesurées et les sensibilités déterminées des substances de capteur de la liste de substances de capteur sont stockées dans une base de données, puis, en fonction des exigences du capteur par rapport aux concentrations de gaz dans un environnement à déterminer au moyen du capteur et des conditions d'utilisation prédéfinies, plus particulièrement par rapport à un rapport de mélange d'humidité et/ou à une température, au moins deux substances de capteur de la liste de substances de capteur sont sélectionnées pour les concentrations de gaz à déterminer, sur la base de la sensibilité stockée dans la base de données de chaque substance de capteur, et sont intégrées dans un circuit électrique de sorte qu'une conductivité des substances de capteur puisse être mesurée, de sorte que, pour le constituant gazeux à déterminer, la concentration dudit constituant gazeux et/ou une modification de la concentration dudit constituant gazeux dans l'environnement du circuit peuvent être déterminées par mesure des conductances des substances de capteur dans le circuit et/ou par mesure des changements des conductances des substances de capteur dans le circuit. L'invention concerne également un capteur pour mesurer des constituants gazeux dans l'air d'un environnement, comprenant un circuit électrique qui présente au moins deux substances de capteur d'une liste de substances de capteur, les conductivités des substances de capteur pouvant être déterminées au moyen du circuit. En outre, l'invention concerne un procédé de détermination de constituants gazeux dans un environnement.
EP22723971.2A 2021-05-12 2022-05-10 Procédé de production d'un capteur et capteur Pending EP4337953A1 (fr)

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ATA50363/2021A AT524446B1 (de) 2021-05-12 2021-05-12 Verfahren zur Herstellung eines Sensors sowie Sensor
PCT/AT2022/060164 WO2022236354A1 (fr) 2021-05-12 2022-05-10 Procédé de production d'un capteur et capteur

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