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    • 专利摘要:
    A gas sensor contains a support structure with a cavity (6), a measuring element (1) which is sensitive to a gas and is arranged in the cavity (6), and a filter (3) which spans the cavity (6). The filter (3) is a size-selective filter that is permeable to the gas and the measuring element to be detected and not permeable to one or more other gases.
    公开号:CH714339B1
    申请号:CH00362/19
    申请日:2016-09-21
    公开日:2020-06-30
    发明作者:Andersson Pernilla；Pavelko Roman；Rotzetter Aline
    申请人:Sensirion Ag；
    IPC主号:
    专利说明:

    Technical field
    The invention relates generally to the field of gas sensors.
    background
    Known gas sensors detect gases based on a variety of methods. However, a measuring element of the gas sensor, which element is responsible for the conversion of a gaseous component into a representative electrical signal, can be adversely affected by the action of other gas as a component of the medium that is to be measured.
    Presentation of the invention
    Therefore, the general object of the invention is to provide a gas sensor which avoids such an effect.
    [0004] According to a first aspect of the present invention, a gas sensor is provided which has a carrier structure with a cavity. A measuring element is arranged in the cavity. The measuring element is at least sensitive to the gas which is to be measured or recognized as desired. A filter spans the cavity. The filter is a size-selective filter.
    The support structure of the gas sensor can be designed broadly, so that any element can contribute to the support structure that defines or co-defines the physical appearance of the gas sensor. In particular, the carrier structure used here can contain one or more of the following components: a die, a chip, a substrate, for example a glass substrate or a ceramic substrate, and in particular a semiconductor substrate containing, if required, electrical connection means, for example one or more wire connections, plated-through holes ( TSVs), etc. The carrier structure can additionally or alternatively have a leadframe or a printed circuit carrier or another type of circuit carrier on which the die, the chip or the substrate, etc. is arranged, for example in order to form a ball grid array, a land grid array, etc. In one embodiment, the carrier structure has a package, for example in the form of an encapsulation, a potting, a silicon cover, a silicon interposer, a metal cover, a plastic cover, etc., in particular for contributing to a chip package.
    One or more elements of the support structure can serve as mechanical support for the measuring element. In one embodiment, the measuring element is arranged on a die or chip or integrated therein. The same element or other elements of the support structure preferably define the cavity. The cavity is viewed as a volume that is in direct exchange with the measuring element. The volume should be filled with a gaseous medium, such as air. The presence and / or the concentration of a gaseous analyte in the medium, which analyte is also referred to as gas, should be recognized as desired. In this respect, at least elements of the support structure define the cavity, in particular together with the filter.
    In one embodiment, the carrier structure has a semiconductor chip that carries the measuring element, and an encapsulation that at least partially encapsulates the semiconductor chip. The encapsulation can preferably be designed as a potting which is formed on parts of the semiconductor chip and thereby defines a depression in the potting which ensures access to the measuring element arranged on or in the semiconductor chip. The encapsulation can therefore define the cavity together with the semiconductor chip and with the filter. In this embodiment, the surface of the encapsulation from which the access opening to the measuring element extends can be covered by the filter, so that the filter spans the access opening and the cavity is defined as the volume between the filter as a cover, the encapsulation as side walls and the semiconductor chip as the bottom of the cavity. The measuring element is at least exposed to the cavity, so that the measuring element has access to the gaseous medium in the cavity.
    In another development, the carrier structure contains a circuit carrier, such as a printed circuit carrier, on which the semiconductor chip is arranged with the measuring element and to which it is preferably electrically connected by surface mounting. A lid, preferably made of metal, is preferably attached to the printed circuit carrier in a sealing manner or is arranged in some other way in order to enclose the semiconductor chip together with the printed circuit carrier, thereby defining the cavity in which the semiconductor chip is arranged.
    So that the gaseous medium can be researched by means of the measuring element, the medium must penetrate into the cavity through the filter that covers the cavity. An opening in the support structure is preferably completely spanned by the filter in order to define the cavity and to deny access to the cavity to any gas molecules which have not passed the filter.
    The measuring element is sensitive to one or more gases which, as desired, should be detected with the gas sensor, and which are preferably detected in the gaseous medium which flows through the filter into the cavity. Therefore, the measuring element is preferably sensitive to the presence or concentration of one or more gases. In one embodiment, the measuring element can be a catalytic gas measuring element or a pellistor that detects the presence of combustion gases. In pellistors, a detector element provides an electrical resistance reading depending on the presence of a combustion gas. In particular, the resistance of the detector element changes due to changes in temperature caused by the catalytic oxidation of the combustion gas, if present. In order to facilitate the combustion of the gas, the sensors are operated at elevated temperatures, that is to say at temperatures typically greater than 300 ° C., for example between 450 ° C. and 750 ° C. In another embodiment, the measuring element is an electrochemical cell.
    In a further embodiment, the measuring element contains a chemo-resistor, which is a material whose electrical resistance changes in response to changes in the direct chemical environment. Chemo-resistors are sometimes also defined in that they are based on the direct chemical interaction between the measurement material and the gas. However, more general definitions of chemo-resistors include materials for which the electrical resistance changes in response to any interactions (chemical, hydrogen bonds, van der Waals, etc.) in their immediate vicinity.
    In any case, the material of the measuring element can comprise a metal oxide material (MOX), which can contain, for example, one or more of the following materials: tin oxide, zinc oxide, titanium oxide, tungsten oxide, indium oxide and gallium oxide. Metal oxides can be used to detect analytes such as volatile organic compounds (VOCs), carbon monoxide, nitrogen dioxide, methane, ammonia, hydrogen or hydrogen sulfide. In a preferred development, the measuring element contains SnO2, doped with 0.01-5.0 wt% platinum and / or palladium.
    [0013] In metal oxide gas sensors, gaseous analytes interact with the preferably heated metal oxide measuring element. As a result of this interaction, a conductivity of the measuring element can change. The change can be measured. Such gas sensors are also referred to as “high-temperature chemo-resistors” because a chemical property of the analyte is converted into an electrical resistance value at high temperatures of the measuring element. The material of such a measuring element may need to be heated during operation. In the case of a measuring element which is integrated in or on a semiconductor substrate, a heater is preferably arranged on a membrane above an opening in the semiconductor substrate. As a result, the thermal loss is reduced compared to arrangements in which the heater is arranged over the main part of the substrate material. Placing the heater on a membrane has several advantages: it reduces energy consumption and the time to switch on the arrangement is reduced.
    The filter, which grants or denies access to the cavity and consequently to the measuring element, is a size-selective filter. Therefore, the filter separates gas molecules that are allowed to pass through the filter and gas molecules that are excluded from passing through the filter, depending on the size of the gas molecules. The filter is preferably made of an inert material, which is a material that is not or not significantly reactive. Therefore, gas molecules do not react with the filter material, regardless of whether they pass through the filter or not, but are blocked due to their size. This has the advantage that the filter material does not degrade over time in comparison to filter materials that react chemically with undesired gas molecules.
    Therefore, the selection between gases that pass through the filter and gases that are blocked by the filter is based on the size of the gas molecules in question. The size-selective filter filters depending on the molecular size of the gas that hits the size-selective filter. The size-selective effect of the filter is preferably determined by a size of the pores in the filter material. In particular, the size of the pores in the filter material is dimensioned depending on the size of the gas molecules to be detected, which should therefore pass through the filter as desired. In particular, the size of a majority of the pores in the filter material is dimensioned to allow the passage of the molecule (s) of the gas to be detected and dimensioned to block one or more other gases which should not reach the cavity . The size of a majority of the pores in the filter material is preferably larger than the molecular size of the gas to be detected, and is smaller than the molecular size of a gas to which access by the filter is to be blocked. The filter material is preferably selected and / or designed for precisely this filter effect.
    Therefore, the filter is permeable to gas that is to be recognized by the measuring element and impermeable to one or more other gases. Such other gases can in particular include siloxane and variants thereof, which react well with the material of the measuring element and deteriorate its measuring properties over time. The size-selective filter therefore counteracts the access of one or more types of atmospheric gases to the measuring element, preferably made of MOX, whereas other types of gas molecules diffuse through the filter and reach the measuring element. The filter therefore enables the access of harmful or poisonous species to the measuring element to be counteracted, which property is achieved by size exclusion.
    In a very preferred embodiment, the size of a majority of the pores in the filter material is 1 nm or smaller. This dimension is particularly preferred for the inclusion of one or more of the following gases: CO, ethanol, H2, H2S. The gas molecules of the gas of interest are sufficiently small to pass through the filter, whereas many types of siloxane molecules are too large in size and are therefore blocked by the filter.
    Regarding the dimensioning of the pore size, it is preferred that all pores of the material in question meet the size requirements. However, due to the manufacturing process, not all but a smaller number of pores may meet the size requirements, preferably more than 99%. In the worst case, a majority of the pores in the filter material preferably meet the size requirements, so that at least a better selection can be achieved than with conventional procedures.
    In a preferred development, the average thickness of the filter is less than 20 microns, and more preferably between 0.5 microns and 5 microns. The filter can also be viewed as a filter layer that spans the access opening in the support structure. The thickness of the filter layer does not necessarily have to impair its filtering property. However, the thicker the filter layer, the longer it will take for gas molecules to pass through the filter layer and reach the measuring element. In this respect, a thick filter layer can increase the response time of the gas sensor in question. For this reason, the filter layer is designed to be rather thin, for example in the areas mentioned above, in order not only to ensure the size-selective separation of gas molecules by the filter, but also to ensure a quick response time of the filter. The filter can be designed as a single-layer filter or as a layered multi-layer filter.
    In view of the possibly very small thickness of the filter, the filter can preferably be attached to a carrier, so that a combination of carrier and filter spans the cavity. The filter is preferably attached to the carrier by means of coating or solution casting, or vice versa. The filter is preferably attached to the carrier in a laminar manner, or vice versa. In an advantageous development, the combination of the filter and the carrier spans the access opening in a common plane. They are also attached to each other. In an advantageous development, the filter and the carrier have the same areal extent. The carrier can either carry the filter or can at least support the mechanical stability of the filter. It may also prevent the filter from cracking.
    Preferably, the average thickness of the carrier is less than 1 mm to ensure mechanical stability during manufacture and / or later during operation, and preferably between 1 micron and 500 microns. The carrier and the filter are advantageously fastened to one another before the combination of the two is attached to the carrier structure.
    The carrier preferably has a size-selective filter property, which at most provides the same filter effect as the filter, in order not to block any gas molecules from entering the cavity, which should be detected as desired. Therefore, a size of the majority of the pores in the carrier material preferably exceeds the size of the majority of the pores in the filter, and in particular exceeds the size of the majority of the pores in the filter by a factor of at least 40. Such dimensioning ensures that the gas molecules to be detected pass through the combination and get into the cavity, whereas gas molecules with larger dimensions are at least blocked by the filter, even if they should have passed the carrier. The size of the majority of the pores in the carrier material is preferably 20 nm or more, and in particular between 50 nm and 200 nm. Preferably more than 99% of the pores in the carrier are dimensioned in this way.
    In another development, the carrier is permeable to all gas molecules, so that only the filter is responsible for the size-selective separation between gas molecules of different sizes.
    [0024] The combination of the filter and the carrier is preferably attached to the carrier structure by means of an adhesive. The material of the adhesive can contain polymers or filled polymers. In a preferred development, the combination is attached to the support structure such that the filter faces the cavity, whereas the support faces the surroundings of the gas sensor. The filter is preferably attached to a surface of the carrier structure by means of the adhesive. Theoretically, the cavity could interact with the environment through the filter, the adhesive or the support structure. Assuming that the carrier structure is not gas-permeable and in order to prevent the gas from passing through the adhesive, the adhesive is preferably gas-tight or at least has the same size-selective filter property as the filter. If the adhesive is gas-tight, gas molecules of the desired size can only enter the cavity through the filter.
    In another development, the carrier faces the cavity, whereas the filter faces the surroundings of the gas sensor. Again, gas molecules could still pass through the end faces of the carrier, provided the filter is attached to a surface of the carrier structure by means of an adhesive, even if the carrier would completely cover the filter. In this embodiment, the end face of the carrier, or generally any surface of the carrier that is not covered by the filter material, is preferably covered with the adhesive as a gas-tight or sufficiently gas-repellent material.
    [0026] The filter material preferably contains or consists of a fluoropolymer. The fluoropolymer is preferably a non-crystalline fluoropolymer with a free fraction per volume of at least 19%, and preferably with a free fraction per volume between 20% and 40%. For example, non-crystalline fluoropolymers such as Hyflon AD 80 or Hyflon AD 60 can be used, or the non-crystalline fluoroplastics Teflon AF, or for example Teflon AF 1600 or Teflon AF 2400, or a TTD homopolymer, or a Cytop homopolymer.
    [0027] The free volume fraction FFV is defined byFFV = (1-Vc / V) * 100%where V indicates the total volume and Vc the portion occupied by the polymer in the total volume V. That is why the FFV is a measure of the compression of the polymer, that is its density.
    In the embodiment with a homopolymer as the filter material, the filter material has perfluoro-butenyl vinyl ether. In another embodiment with a homopolymer as the filter material, the filter material has 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole.
    In an embodiment with a copolymer as filter material, a first component of the filter material contains 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole, whereas a second component of the filter material contains tetrafluoroethylene. In such an embodiment, it is preferred that the first component has a molar fraction between 20% and 99%, and the second component has a molar fraction between 1% and 80%. In particular, the 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole has a molar fraction of 80% and the tetrafluoroethylene has a molar fraction of 20%. In another development, however, the 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole has a molar fraction of 60% and the tetrafluoroethylene has a molar fraction of 40%.
    In an alternative development, the filter material contains 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole as a homopolymer. In another development, the filter material has a copolymer, a first component of the filter material containing 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole. A second component of the filter material preferably contains tetrafluoroethylene. In these versions, the first component preferably has a molar fraction between 20% and 99%, and the second component has a molar fraction between 1% and 80%. In a special development, the 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole has a molar fraction of 87% and the tetrafluoroethylene has a molar fraction of 13%. In another special development, the 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole has a molar fraction of 65% and the tetrafluoroethylene has a molar fraction of 35%.
    [0031] The carrier material, if present, likewise preferably has or consists of a fluoropolymer. This is advantageous because the two layers of the fluoropolymer, that is the filter and the carrier, can be easily attached to one another.
    The carrier material preferably contains polytetrafluoroethylene PTFE or polyethylene tetrafluoroethylene ETFE manufactured as bulk, woven or non-woven materials with the pore sizes specified above.
    Should the filter and the carrier both be fluoropolymers, the adhesion between the filter and the carrier is not only superior to other material combinations; A thermally induced expansion of the material is also uniform for materials from the same material classes.
    In a preferred embodiment, electrodes are electrically connected to the measuring element, and a heater is thermally connected to the measuring element. This is particularly advantageous in the event that the measuring element has to be heated before and / or during the measurement, for example if the measuring element contains metal oxide material. A distance between the measuring element and the combination of filter and carrier is preferably at least 100 µm. Therefore, the filter is not in direct contact with the measuring element, so that a direct heat flow from the measuring element to the filter is minimized. An indirect heat flow through the support structure or the gaseous medium in the cavity does not allow the filter to heat up to temperatures that exceed a critical temperature such as the glass transition temperature of the filter material during the operation of the heater, i.e. during the measurement operation. Therefore, any one, and especially this distance, is preferred so that the filter does not operate during heater operation, i.e. during the measuring operation, melts or is otherwise impaired. On the other hand, the glass transition temperatures of the filter and / or the carrier can be exceeded, for example, during the reflow soldering of the gas sensor, but this does not hurt, since the gas sensor is not operated at this point in time and a temporary change in the specific volume of the polymer material can be accepted.
    Thanks to the separation, the distance or the gap to the filter, the measuring element can be operated at elevated temperatures, for example at more than 350 ° C or even 400 ° C, without damaging the filter.
    In a preferred development of the present invention, a surface of the support structure is completely covered by the filter or the combination, and thereby spans the cavity. This is preferred together in the batch production of several gas sensors, since the filter or the carrier are jointly applied to several gas sensors without the filter or the carrier having to be cut to the individual gas sensor size beforehand. However, in order to separate the gas sensors from one another, for example by cutting, a cutting tool such as a saw must be placed on the surface of the gas sensors that are still connected to one another. This surface is formed by the filter or by the carrier. If the filter and / or the carrier has a fluoropolymer, it is therefore not easy to put this cutting tool on because of the smooth surface of fluoropolymers. In order to facilitate such a cutting operation, upper elements are preferably arranged on the surface of the gas sensor, that is to say at positions on the filter or on the carrier at which the cutting tool will start and / or cut. Such upper elements preferably have a surface roughness that exceeds the surface roughness of the filter or the carrier. The cutting tool can then rest on one or more of these upper elements and maintain its position. After cutting, remnants of the top elements can be found on the edges of the filter or carrier. An upper element can, for example, be made from one or more of the following materials: polymer, filled polymer, potting material, silicon, glass or metal.
    In a preferred development of the invention, the semiconductor chip not only contains the measuring element thereon or integrated therein, but also an integrated CMOS circuit, for example for controlling the recording of measured values, including the heating of an associated heater, and / or the evaluation of signals provided by the electrodes.
    [0038] According to a further embodiment of the present invention, the measuring element is designed as a “multipixel” resistance metal oxide gas sensor for the simultaneous recording of different types of gas molecules. To be sure, such a measuring element preferably has several spots of measuring material, each of the spots preferably containing a metal oxide material and being arranged on the support structure or partially surrounded by it. In addition, a set of electrodes is provided, each of the spots being electrically connected to a subset of the electrodes. One or more heaters are thermally connected to the spots of the measuring material. Ultimately, this gas sensor preferably contains a common size-selective filter that spans the cavity common to all spots of the measuring material.
    In a preferred development, the measuring element is designed to recognize one of the gases CO, ethanol, H2, H2S, so that the gas sensor is a sensor for detecting one or more of these gases.
    The present invention can be designed, for example, as an electronic device, in particular as a domestic technology device, as an electronic consumer goods device, as a mobile phone, as a tablet computer or as a watch, containing any of the resistive metal oxide gas sensors mentioned above.
    The present approaches prevent degradation of the gas sensor, and in particular its measuring element, by harmful gases. For example, siloxane or more generally volatile Si substances can damage measuring elements and in particular metal oxide measuring elements, which usually increases the response time of the measuring element and reduces the sensor signal. Exposure to such a harmful gas is preferably prevented or at least weakened by the provision of a filter which is objected to by the measuring element. The filter serves as a physical separator for gas molecules of different sizes. It has been found that, in particular, a fluoropolymer filter provides pores of the desired size for the passage of gas molecules of smaller size, while blocking various siloxane gas molecules, the size of which exceeds the size of the gas molecules typically to be measured. The fluorinated filter protects the measuring element against aggressive chemicals such as acids or bases and, due to its design, also prevents the accumulation of solids and liquids on the surface of the measuring element.
    Brief description of the drawings
    For a better understanding of developments of the invention, reference is made to the consideration of the following description. This description refers to the accompanying drawings, in which:<tb> <SEP> Figures 1 to 9 each show a schematic sectional view of a gas sensor according to an embodiment of the invention;<tb> <SEP> FIG. 10 shows a schematic section of a gas sensor structure which contributes to a gas sensor according to an embodiment of the invention.
    Way (s) of carrying out the invention
    Before presenting embodiments of the gas sensor, attention is paid to the materials used in or as a filter and carrier, if present.
    Preferably, the filter is made of a fluoropolymer, and is preferably made of a fluoropolymer. A fluoropolymer is a fluorocarbon-based polymer that has a variety of carbon-fluorine bonds. It is typically highly resistant to solvents, acids and bases, so that it can be used advantageously for the present purpose.
    Preferably, the same or similar material is used for the filter as the amorphous Teflon AF according to row 4 of Table I below, which contains preferred compositions for the filter material in each row. Row no. 4 denotes a collective term under which the other individual material compositions according to the preferred embodiments in rows 1 to 3 can be subsumed. Therefore, the filter fluoropolymer can be a homopolymer in one embodiment, see row # 3, whereas in other embodiments it is a copolymer, see row # 1 and row # 2.<tb> 1 <SEP> Teflon AF 2400 <SEP> 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole <SEP> tetrafluoroethylene<tb> 2 <SEP> Teflon AF 1600 <SEP> 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole <SEP> tetrafluoroethylene<tb> 3 <SEP> PDD homopolymer <SEP> 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole <SEP> n / a<tb> 4 <SEP> Teflon AF similar to <SEP> 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole <SEP> tetrafluoroethylene
    Table I
    In the following Table II properties of the respective material compositions of the above series Nos. 1 to 4 are shown, wherein<tb> - <SEP> Comp 1, mol% indicates the mole fraction of component 1;<tb> - <SEP> Comp 2, mol% indicates the mole fraction of component 2;<tb> - <SEP> FFV indicates the free share per volume;<tb> - <SEP> Tg ° C indicates the glass transition temperature of the resulting material in ° Celsius; and<tb> - <SEP> Tmax indicates a maximum temperature at which polymers show no significant degeneration (i.e. are thermally stable), in ° Celsius.<tb> 1 <SEP> Teflon AF 2400 <SEP> 87 <SEP> 13 <SEP> 33 <SEP> 240 <SEP> 360<tb> 2 <SEP> Teflon AF 1600 <SEP> 65 <SEP> 35 <SEP> 30 <SEP> 160 <SEP> 360<tb> 3 <SEP> PDD homopolymer <SEP> 100 <SEP> 0 <SEP>> 33 <SEP> 335 <SEP> 360<tb> 4 <SEP> Teflon AF similar to <SEP> 100-20 <SEP> 0-80 <SEP> <SEP> 80-250 <SEP> 360
    Table II
    Alternatively, a material according to one of the rows 5 to 9 of Table III below can also be used for the filter. Row no. 8 designates a collective term under which the other individual material compositions according to the preferred embodiments in row no. 5 to row no. 7 can be subsumed. Therefore, the filter fluoropolymer can be a homopolymer in one embodiment, see row No. 7, whereas in other embodiments it is a copolymer, see row No. 5 and row No. 6. Row No. 9 mentions another homopolymer, which is preferred as a filter material can be used.<tb> 5 <SEP> Hyflon AD 80 <SEP> 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole <SEP> tetrafluoroethylene<tb> 6 <SEP> Hyflon AD 60 <SEP> 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole <SEP> tetrafluoroethylene<tb> 7 <SEP> TTD homopolymer <SEP> 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole <SEP> n / a<tb> 8 <SEP> Hyflon AD alike <SEP> 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole <SEP> tetrafluoroethylene<tb> 9 <SEP> Cytop (homopolymer) <SEP> Perfluorobutyl vinyl ether <SEP> n / a
    Table III
    In the following Table IV properties of the individual material compositions of the above series Nos. 5 to 9 are shown, with the legend as for Table II.<tb> 5 <SEP> Hyflon AD 80 <SEP> 80 <SEP> 20 <SEP> 23 <SEP> 135 <SEP> approx. 400C<tb> 6 <SEP> Hyflon AD 60 <SEP> 60 <SEP> 40 <SEP> 23 <SEP> 129 <SEP> approx. 400C<tb> 7 <SEP> TTD homopolymer <SEP> 100 <SEP> 0 <SEP> <SEP> 170 <SEP> approx. 400C<tb> 8 <SEP> Hyflon AD alike <SEP> 100-20 <SEP> 0-80 <SEP> <SEP> 170 <SEP> approx. 400C<tb> 9 <SEP> Cytop (homopolymer) <SEP> 100 <SEP> 0 <SEP> 21 <SEP> 108 <SEP> 400
    Table IV
    The carrier, if present, is preferably made of a fluoropolymer, and is preferably made of a fluoropolymer, for example made of polytetrafluoroethylene (PTFE) or polyethylene tetrafluoroethylene (ETFE) as bulk, woven or non-woven material with the pore size as defined above.
    [0050] The measuring element is preferably a stain measuring material. In further developments, the present measuring element can be operated as a chemo-resistor. The metal oxide material from which the measuring element is made changes its electrical resistance in response to the passage of gas molecules through the filter, which leads to chemical interactions between the material of the measuring element and the gas / analytes. In further developments, one can rely on the calorimetric determination of the gas / analyte. In other developments, in turn, the stain measurement material can be used for two purposes, namely: (i) as a chemo-resistor, which changes its electrical conductivity when the analyte is present; and (ii) as a catalyst in a calorimetric determination of the analyte.
    In one embodiment, the latter contains a metal oxide material, or MOX. In addition to the above examples, preferred MOX materials include SnO2 and / or WO3, and also preferably contain dopants. The latter include one or more elements from the following list: Pd, Pt, Rh, Ir, Re, V, Ni, Au, and Co. The patch can be arranged on the support structure. For example, it may spread out on an exposed surface of the support structure, such as on a semiconductor substrate, for example flatly coated on its upper surface, or spread out on sub-structures thereof, such as on electrodes. Electrodes can be arranged in the gas sensor which are electrically connected to the patch of measuring material. They can be formed from a platinum or gold layer, which metals are well suited for forming durable electrodes. For example, electrodes can be arranged in an entangled configuration. Therefore, in one embodiment, the patch may have, for example, a convex shape that extends into a region that spans or covers the interdigitated fingers of the electrodes.
    In one embodiment, a heater is thermally connected to the patch to operate the measurement material at the required temperature. The heater can be a resistance heating element. For example, one can use a heater made of tungsten, which means a heater containing at least 50% and preferably at least 90% tungsten in order to withstand the highest possible temperatures. Several heaters can be provided to heat a plate, for example a membrane or a bridge, on which the spot is arranged. In variants, the heater can be designed as a hotplate, which is resistance-heated, without the need for additional resistance elements. The heater can be used to heat the stain and, if necessary, to further control its temperature. The semiconductor chip of the gas sensor preferably contains a circuit integrated thereon for heating the heater and for carrying out resistance measurements, that is to say for measuring an electrical conductivity and / or an electrical resistance of the spot.
    The same elements are denoted in the figures with the same reference numerals.
    Figure 1 shows a schematic sectional view of a gas sensor according to an embodiment of the invention. The gas sensor has a measuring element 1 which is arranged on a carrier structure or integrated therein. In this embodiment, the carrier structure has a semiconductor chip 2, for example a silicon substrate, and an adhesive 5, which in the present embodiment is sufficiently thick to form a cavity 6 together with a filter 3 and a carrier 4 for the filter 3.
    The gas to be measured can get into the cavity 6 and thereby reach the measuring element 1 through the carrier 4 and the filter 3. The combination of filter 3 and carrier 4 is attached to the semiconductor substrate 2 by means of the adhesive 5, so that the filter 3 faces the cavity 6 and the carrier 4 faces the surroundings of the gas sensor.
    FIG. 2 shows another embodiment of a gas sensor according to the present invention. In this embodiment, the semiconductor substrate 2, which can also be any other carrier, has a depression 21 which contributes to the cavity 6 and in which depression 21 the measuring element 1 is arranged. In this embodiment, not only the thickness of the adhesive 5 contributes to a sufficient distance d between the measuring element 1 and the filter 3 or, respectively, the carrier 4. The recessed part of the semiconductor substrate 2 contributes to this distance d.
    Figure 3 shows a further development of a gas sensor according to the present invention. In this development, the carrier structure of the gas sensor has a semiconductor substrate 2 and a spacer 22, for example on top of the semiconductor substrate 2. The spacer 22 can be made of a different material than the semiconductor substrate 2.
    FIG. 4 shows a further development of a gas sensor according to the present invention. This development is essentially similar to the development from FIG. 1 with the exception that upper elements 9 are added to the edges of the carrier 4.
    FIG. 5 shows another development of the gas sensor according to the present invention. In this development, the gas sensor in turn has a semiconductor chip 2 with a measuring element 1. The semiconductor chip 2 is partially covered by an encapsulation 22 in the form of an encapsulation. A lead frame 23 is used for contacting from the outside. The carrier structure for the measuring element 1 therefore has a semiconductor chip 2, the encapsulation 22, the adhesive 5 and the lead frame 23. A cavity 6 is formed by the support structure, which cavity 6 is closed by a combination of the filter 3 and the support 4 for the filter 3. The combination of filter 3 and support 4 extends over the entire surface of the support structure 2, on which the combination of filter 3 and carrier 4 is fixed by means of the adhesive 5.
    Figure 6 shows another embodiment of a gas sensor according to the present invention. In this embodiment, the gas sensor has a semiconductor chip 2 with the measuring element 1. The semiconductor chip 2 is partially covered by a silicon cover 24. A cavity 6 is formed by the semiconductor substrate 2, the silicon lid 24 and the adhesive 5, which elements therefore contribute to the carrier structure.
    [0061] FIG. 7 shows another embodiment of the gas sensor according to the present invention. Again, a measuring element 1 is arranged on / in a suspended part of a membrane of a semiconductor substrate 2, which suspended part of the membrane is prepared, for example, by etching substrate material from the rear of the semiconductor chip. This leads to the cavity 6. For this reason, the combination of filter 3 and carrier 4 is attached to the back of the semiconductor chip 2, again by means of an adhesive 5.
    Figure 8 shows a further embodiment of the gas sensor according to the present invention. This embodiment is similar to the embodiment from FIG. 5. In contrast to the embodiment in FIG. 5, the combination of filter 3 and carrier 4 is conversely attached to the surface of the carrier structure by means of the adhesive 5.
    The carrier 4 therefore faces the cavity, whereas the filter 3 faces the surroundings of the gas sensor. In this respect, it is desirable to seal a direct path from outside the gas sensor through the carrier 4 into the cavity 6. Such a path is sealed by covering any surface of the carrier 4 that is neither covered by the filter nor by the adhesive 5. For this purpose, the adhesive 5 also covers the end face of the carrier 4, and in one development is even pulled up the top of the carrier 4, so that it also serves as an upper element for one of the purposes listed above for upper elements.
    Figure 9 shows a further embodiment of the gas sensor according to the present invention. In this embodiment, a semiconductor chip 2, including the measuring element 1, is arranged on a circuit carrier 7, such as a printed circuit carrier, and is preferably electrically connected to the latter. In addition, one or more chips, such as an integrated circuit 71, can also be arranged on the circuit carrier 7. A cover 8, for example made of metal, can form together with the circuit carrier 7 a housing for the semiconductor chip 2, which encloses the cavity 6. The cover 8 has an opening 81 which is spanned by the combination of filter 3 and carrier 4. The combination is attached to the cover 8 by means of an adhesive 5 from the inside of the cover 8.
    Figure 10 shows a gas sensor structure that contributes to a gas sensor according to an embodiment of the present invention. The present structure still has to be finalized by attaching a filter or a combination of a filter and a support to the present structure. The present gas sensor structure contains a measuring element 1 on a semiconductor chip 2, which is etched from its rear, whereby a depression is formed. The measuring element 2 covers electrodes 10, so that an electrical signal can be supplied to an evaluation and control unit 11 in order to be evaluated there. The evaluation and control unit 11 is preferably integrated in the semiconductor chip 2. The evaluation and control unit 11 also preferably has a heater 12, which is integrated in the semiconductor substrate 2, for example in the membrane, which remains as a result of the etching of the recess 23.
    While the present advantageous developments of the invention have been shown and described, it is clearly expressed that the invention is not limited to this but can be designed and implemented differently in a variety of ways within the scope defined by the following claims.
    权利要求:
    Claims (31)
    [1]
    1. gas sensor, havingA carrier structure containing a cavity (6),A measuring element (1) which is sensitive to a gas and is arranged in the cavity (6) (6),A filter spanning the cavity (3),- The filter (3) is a size-selective filter (3),the size-selective filter (3) filters gas molecules depending on their size,the size-selective filter (3) being permeable to the gas to be detected with the measuring element (1) and not permeable to one or more other gases.
    [2]
    2. Gas sensor according to claim 1,the size-selective effect of the filter (3) being determined by a size of the pores in the filter material,in particular, the size of the pores in the filter material being dimensioned as a function of the size of a molecule of the gas which is to be detected,in particular wherein the size of a plurality of the pores in the filter material is dimensioned to allow molecules of the gas to be detected to pass through and to block molecules of one or more other gases,in particular where the size of the majority of the pores in the filter material is dimensioned larger than the size of a molecule of the gas that is to be detected and is dimensioned smaller than the size of a molecule of the one or more other gases that are to be blocked,in particular where the size of a plurality of the pores in the filter material is 1 nm or smaller.
    [3]
    3. Gas sensor according to one of the preceding claims,the filter material containing a fluoropolymer,preferably wherein the filter material consists of a fluoropolymer.
    [4]
    4. Gas sensor according to claim 3,wherein the filter material has an amorphous fluoropolymer with a free fraction per volume of at least 19%, andpreferably with a free proportion per volume between 20% and 40%.
    [5]
    5. Gas sensor according to claim 3 or claim 4,the filter material having a homopolymer,preferably wherein the filter material has perfluoro-butenyl vinyl ether.
    [6]
    6. Gas sensor according to claim 3 or claim 4,the filter material containing 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole.
    [7]
    7. Gas sensor according to claim 3 or claim 4,the filter material containing a copolymer,preferably wherein a first component of the filter material contains 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxol,preferably wherein a second component of the filter material contains tetrafluoroethylene.
    [8]
    8. Gas sensor according to claim 7,wherein the first component has a mole fraction between 20% and 99%, andwherein the second component has a mole fraction between 1% and 80%.
    [9]
    9. Gas sensor according to claim 7,the 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole has a molar fraction of 80%, andwherein the tetrafluoroethylene has a mole fraction of 20%.
    [10]
    10. Gas sensor according to claim 7,wherein the 2,2,4-trifluoro-5- (trifluoromethoxy) -1,3-dioxole has a molar fraction of 60%, andwherein the tetrafluoroethylene has a mole fraction of 40%.
    [11]
    11. Gas sensor according to claim 3 or claim 4,the filter material comprising 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole.preferably wherein the filter material is a homopolymer.
    [12]
    12. Gas sensor according to claim 3 or claim 4,the filter material comprising a copolymer,preferably wherein a first component of the filter material comprises 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole,preferably wherein a second component of the filter material has tetrafluoroethylene.
    [13]
    13. Gas sensor according to claim 12,wherein the first component has a mole fraction between 20% and 99%, andwherein the second component has a mole fraction between 1% and 80%.
    [14]
    14. Gas sensor according to claim 13,wherein the 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole has a molar fraction of 87%, andwherein the tetrafluoroethylene has a molar fraction of 13%.
    [15]
    15. Gas sensor according to claim 13,wherein the 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole has a molar fraction of 65%, andwherein the tetrafluoroethylene has a molar fraction of 35%.
    [16]
    16. Gas sensor according to one of the preceding claims,wherein an average thickness of the filter (3) is less than 20 µm, andis preferably between 0.5 µm and 5 µm.
    [17]
    17. Gas sensor according to one of the preceding claims, containinga carrier (4) for the filter (3), the carrier (4) and the filter (3) in combination (3, 4) spanning the cavity (6).
    [18]
    18. Gas sensor according to claim 17,the carrier (4) either being gas-permeable or having a size-selective filter property.
    [19]
    19. Gas sensor according to claim 17 or claim 18,wherein a size of the plurality of pores in the carrier material exceeds a size of the plurality of pores in the filter material, in particularwherein a size of the plurality of pores in the carrier material exceeds a size of the plurality of pores in the filter material by a factor of at least 20.
    [20]
    20. Gas sensor according to one of claims 17 to 19,wherein the size of the majority of the pores in the carrier material is 40 nm or larger, andis in particular between 50 nm and 200 nm.
    [21]
    21. Gas sensor according to one of claims 17 to 20,the carrier material comprising a fluoropolymer,preferably wherein the filter material consists of a fluoropolymer.
    [22]
    22. Gas sensor according to claim 21,the carrier material containing or consisting of polytetrafluoroethylene PTFE or polyethylene tetrafluoroethylene ETFE.
    [23]
    23. Gas sensor according to one of claims 17 to 22,wherein an average thickness of the carrier (4) is less than 1 mm, andis preferably between 1 μm and 500 μm.
    [24]
    24. Gas sensor according to one of claims 17 to 23,the combination (3, 4) of the filter (3) and the carrier (4) being fastened to the carrier structure by means of an adhesive (5),in particular where the adhesive (5) is either gas-tight or at least has the same size-selective filter effect as the filter (3).
    [25]
    25. Gas sensor according to one of claims 17 to 24,the filter (3) facing the cavity (6) and the carrier (4) facing an environment of the gas sensor,in particular wherein the filter (3) is attached to a surface of the support structure by means of an adhesive (5).
    [26]
    26. Gas sensor according to one of claims 17 to 24,the carrier (4) facing the cavity (6) and the filter (3) facing an environment of the gas sensor,in particular wherein the filter (3) is attached to a surface of the support structure by means of an adhesive (5).
    [27]
    27. Gas sensor according to one of claims 17 to 26,wherein a distance (d) between the measuring element (1) and the combination (3,4) of the filter (3) and the carrier (4) is at least 100 µm.
    [28]
    28. Gas sensor according to one of the preceding claims, containingElectrodes (10) which are electrically connected to the measuring element (1),a heater (12) which is thermally connected to the measuring element (1), andthe measuring element (1) containing metal oxide material,the measuring element (1) being designed to detect CO, ethanol, H2, or H2S.
    [29]
    29. Gas sensor according to one of the preceding claims,wherein the support structure hasA semiconductor chip (2) which carries the measuring element (1),An encapsulation (21) which at least partially encapsulates the semiconductor chip (2),the encapsulation (21) contributing to the formation of the cavity (6).
    [30]
    30. Gas sensor according to claims 17 and 29,one surface of the encapsulation (21) being completely covered by the combination (3, 4) and thereby spanning the cavity (6),one or more upper elements (9) being arranged on a surface and on edges of the combination (3, 4),wherein the one or more upper elements (9) have a surface roughness that exceeds the surface roughness of the surface of the combination (3, 4).
    [31]
    31. Gas sensor according to one of claims 1 to 28,wherein the support structure has- a circuit carrier (7),A semiconductor chip (2) which is arranged on the circuit carrier (7) and carries the measuring element (1),- a cap (8) for receiving the semiconductor chip (2),the cap (8) contributing to the formation of the cavity (6) and having an opening (81) which is spanned by the size-selective filter (3).
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    同族专利:
    公开号 | 公开日
    US20190250135A1|2019-08-15|
    WO2018053656A1|2018-03-29|
    US11204346B2|2021-12-21|
    CN109791117A|2019-05-21|
    GB201903913D0|2019-05-08|
    DE112016007246T5|2019-05-29|
    GB2568633A|2019-05-22|
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