• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Gravimetric detector comprising a nanoelectronic structure comprising: a fixed part (2), at least one suspended part (4) with respect to the fixed part (2), excitation means (8) so as to put in vibration the suspended part relative to the fixed part, - detection means (10) of the vibration variations of said suspended part, - a porous functionalization layer (6) covering at least part of the suspended part (4) the porosity of said functionalization layer (6) being between 3% and 50%.
    公开号:FR3016044A1
    申请号:FR1363628
    申请日:2013-12-27
    公开日:2015-07-03
    发明作者:Muriel Matheron；Regis Barattin；Vincent Jousseaume；Florence Ricoul
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD AND PRIOR ART The present invention relates to a gravimetric type gas sensor with a lowered detection limit. The gravimetric type gas sensors comprise gravimetric transducers coated with a chemically active layer whose role is to capture and concentrate the target gases, possibly reversibly and possibly selectively. The transducer converts the adsorbed mass into an electrical signal (frequency variation). The sensor performance in terms of resolution and detection limit depends not only on the design of the sensor, for example they depend on the geometrical parameters, the vibration modes ..., but also the affinity of the active layer towards the gases .
    [0002] The most common gravimetric sensors are quartz microbeads (or MCQs) coated with organic polymers. The active surface of the QCM is of the order of 0.2 cm2. There are also gas sensors based on microelectromechanical structure (MEMS) or nanoelectromechanical (NEMS) using resonant beams. Such a gas sensor may be disposed at the outlet of a gas chromatography column and ensure the detection of each constituent of the gas previously separated by the column. Compared to quartz microbalances, the nanoscale dimensions of NEMS significantly improve sensor performance. However, we are still trying to lower the detection limits of gravimetric sensors.
    [0003] SUMMARY OF THE INVENTION It is an object of the present invention to provide a NEMS type gravimetric detector with a lowered detection limit. The previously stated goal is achieved by a gravimetric detector comprising a nanoelectromechanical structure comprising at least one suspended part, said suspended part being covered at least in part by a layer made of a porous material having a porosity of between 3% and 50%, advantageously between 5% and 40%. Preferably, the thickness of the porous layer is between 10 nm and 200 nm. Preferably, the porous material is of SiOxCyHz or SiOw type. Advantageously, the layer of porous material is formed by chemical or physical vapor deposition, avoiding the risk of stiction between the suspended part and the substrate. Alternatively, the layer of porous material is formed by sputtering, which makes it possible to deposit materials such as graphite, SiOw, w varying between 0 and 2. In other words, the gas detector is formed by a device nanoelectromechanical system comprising a sensitive portion functionalized by means of a porous layer, which increases the amount of compound absorbed and lowers the limit of detection. The subject of the present invention is therefore a gravimetric detector comprising a nanoelectronic structure comprising a fixed part, at least a part suspended with respect to the fixed part, excitation means so as to vibrate the suspended part with respect to the part fixed, means for detecting the vibration variations of said suspended part, a porous functionalization layer covering at least part of the suspended part, the porosity of said functionalization layer being between 3% and 50%. Preferably, the porosity of the functionalization layer is between 5% and 40%.
    [0004] The functionalization layer is advantageously between 10 nm and 200 nm. The functionalization layer may be of SiOxCyHz type material, with x being between 1 and 2, preferably between 1.4 and 1.8, including between 0.8 and 3, preferably between 1 and 2.5. , z between 2.5 and 4.5, preferably between 3 and 4.1. By varying, the functionalization layer may be of a SiOw type material, with w between 0 and 2. The functionalization layer is for example present on at least a part of a face of the suspended part opposite to the fixed part. , advantageously over the entire face of the suspended part opposite the fixed part. The excitation means are, for example, electrostatic means, and the detection means are, for example, piezoelectric means. The present invention also relates to an analysis assembly comprising a gas chromatography column and at least one gravimetric detector according to the invention disposed at the outlet of said column.
    [0005] The subject of the present invention is also a method for producing a gravimetric detector according to the invention, comprising: the production of the nanoelectronic structure; the formation of the functionalization layer having a porosity of between 3% and 50%; on at least part of the suspended part of the nanoelectronic structure. The functionalization layer is obtained for example by chemical vapor deposition. During the chemical vapor deposition a porogenic agent can be used. The level of porosity can be set according to the pore flow rate. The pore-forming agent comprises, for example, organic molecules such as norbornadiene, norbornene, alpha terpinene, cyclohexene oxide, cyclopentene oxide, trivertal, etc.
    [0006] The formation of the functionalization layer can be obtained by introducing into a chamber a precursor and a pore-forming agent, by applying a plasma treatment and then by carrying out a heat treatment to oxidize the pore-forming agent. Formation of the functionalization layer can take place after liberation of the nanoelectronic structure. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be better understood with the aid of the following description and the appended drawings in which: FIG. 1A is a side view diagrammatically represented of an example of the NEMS that can be implemented in the detector according to the invention, FIG. 1B is a top view of the NEMS of FIG. 1A, FIG. 2 is a schematic representation of the analysis installation implementing at least one detector according to the invention; FIGS. 3A to 3D are graphical representations of the area of the peaks delivered by the detector according to the invention as a function of the area of the peaks delivered by an FID sensor for two porosities, for benzene, toluene, ethylbenzene and o-Xylene respectively, - Figures 4A to 4D are graphical representations of the area of the peaks delivered by the detector according to the invention as a function of the area of the peaks delivered by an FID sensor for different thicknesses, for benzene, toluene, ethylbenzene and o-xylene respectively, - Figures 5A to 5F are schematic representations of steps of producing a sensor according to an exemplary embodiment method. DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS For simplicity the nanoelectromechanical structure will be designated NEMS in the following description.
    [0007] FIG. 1 shows a schematic representation of an exemplary embodiment of a gravimetric detector D according to the invention comprising an NEMS comprising a fixed part 2 and a suspended part 4 intended to be vibrated with respect to the part fixed. In the example shown, the suspended part 4 is formed by a beam anchored by a longitudinal end 4.1 on the fixed part 2. The detector D also comprises a layer 6 of porous material covering at least partly the suspended portion 4. The layer porous 6 will be referred to hereinafter as "functional layer". As examples in Table T1 below are given two examples of NEMS1 and NEMS2 sizing in μm of the NEMS, the dimensions being indicated in FIGS. 1A and 18. fo is the resonance frequency of the NEMS. The sensor also includes excitation means for vibrating the sensor. the suspended part 4 and means for detecting the vibration frequency variation of the suspended part due to the adsorbed mass. In the example shown, the excitation means are of the electrostatic type comprising electrodes 8 carried by the fixed part 2 facing the lateral faces of the beam 4. In the example shown, the detection means are of the piezoresistive type, formed by two piezoresistive gauges 10 connecting the suspended part to the fixed part and deformed by the vibrations of the suspended part.
    [0008] Deformation of the gauges causes a variation in the electrical resistance measured within each gauge. It is then possible to correlate this variation of vibration frequency with a given compound. The use of two gauges advantageously provides a differential measurement, which makes it possible to overcome, for example, variations in external conditions such as temperature variations. Alternatively, a single gauge could be implemented. In another example, the detection means are of capacitive type and comprise for example an electrode on the fixed part facing the suspended part and forming with it a capacitor whose capacity varies with the vibration of the suspended part. Other detection means can be implemented. Alternatively, the NEMS could have several suspended parts. In addition, the suspended part could be a membrane connected to the fixed part 2 by suspension means. Furthermore, a detector comprising several NEMS is not outside the scope of the present invention. In the example shown and advantageously, the layer 6 covers the entire upper face of the suspended part 4.
    [0009] Layer 6 may also cover the entire or part of the bottom face and the flanks in whole or in part. In addition, the porous layer may cover all or part of the fixed part. The porous layer has a porosity of between 3% and 50%, preferably between 5% and 40%. The inventors have determined that the porosity range [3%; 50%] and preferably [5%; 40%] offered the best sensitivity. Preferably the pores have a radius of between 1 nm and 3 nm, or even between 1 nm and 5 nm. These dimensions were observed by ellipsoporosimetry, the probe molecule being Toluene, the measuring device being the EP12 model - Société SOPRA. This percentage represents the pore volume for a given volume of material. Preferably the thickness of the layer 6 is between 10 nm and 200 nm.
    [0010] The mass of a functionalization layer having a thickness of less than 200 nm has a negligible influence on the suspended part. A porous functionalization layer thickness greater than 10 nm allows the absorption of a more easily detectable amount of compound.
    [0011] According to a preferred example, the porous material is of SiOCH type. The term denotes a compound of formula SiOxCyHz with: x ranging between 1 and 2, preferably between 1.4 and 1.8, including between 0.8 and 3, preferably between 1 and 2.5, z between 2 , 5 and 4.5, preferably between 3 and 4.1.
    [0012] In another example, the porous material may be of Si ° type. The term denotes a compound of formula SiOw, with w between 0 and 2. It should be noted that such a compound can be obtained either by spraying or by applying an oxidizing plasma to a SiOxCyHz layer previously described, in order to eliminate the groups Methyl. The porous layer is intended to absorb the gas molecules to be detected. The porous material has an open porosity, the pores communicating with each other. Preferably, the porous layer, in particular SiOCH, is deposited by vapor deposition, in particular a chemical vapor deposition or CVD ("Chemical Vapor Deposition" in English terminology). The SiOxCyHz deposit then has a homogeneous thickness at least on the upper surface of the suspended part. Alternatively, porous materials, such as SiO, can be deposited by spraying. This is also the case for porous materials such as graphite or alumina. The production of the porous SiOCH or SiO layer by CVD very advantageously makes it possible to eliminate the risks of stiction which may appear between the suspended part and the fixed part when a layer is produced by deposition in the liquid phase. The capillarity effects due to the use of solvents can indeed lead to irreversible bonding of the nanostructures. Furthermore, thanks to the CVD deposit, it is possible to achieve porous layer thicknesses at least equal to 10 nm, which is not the case during a liquid phase deposition. In addition, thanks to the CVD deposit, it is possible to easily control the thickness of the deposited material with the deposition time. In addition, the layers of SiO and SiOCH by CVD deposition offer a very good thermal stability. This is particularly interesting in the case where the NEMS are placed at the outlet of a gas chromatography column, or even inside the gas chromatography column, they can then be exposed to a gas flow brought to a temperature above room temperature, for example at a temperature between 40 ° C and 300 ° C typically. The materials deposited by CVD deposition remain stable at these temperature levels, unlike some polymers, which at these temperatures are likely to degrade chemically or to see their mechanical properties evolve: for example, a melting or crystallization can occur, leading to a significant modification of the Young's modulus, which can disrupt the operation of NEMS, whose resonant frequency is a function not only of its effective mass but also of its rigidity and the stresses to which the resonator is subjected. An NEMS functionalized by means of a SiO or SiOCH layer then presents a purely gravimetric response, whereas in the case of a NEMS functionalized with certain organic polymers, the influence of the mechanical properties of the layers deposited on the NEMS response are not negligible. The porous SiOCH or porous SiO layers exhibit good chemical stability, avoiding drift from the sensor baseline. For example, it has been observed that a layer of SiOCH said "low k)" porous deposited by PECVD does not see its dielectric constant evolve over a period of several weeks, indicating a good stability over time, especially with respect to humidity. The term low K denotes materials of low dielectric permittivity, typically less than 2.5. Finally, the CVD deposition equipment being suitable for deposits on substrates in 200 mm diameter or 300 mm, it is possible to produce collective functionalization layer deposits of several sensors. According to an advantageous variant, the deposition can be carried out by filament-assisted chemical vapor deposition or FACVD (Filtered Assisted Enhanced Chemical Vapor Deposition), which makes it possible to further improve compliance. According to another variant, the deposition may be carried out by chemical vapor deposition of a first layer comprising SiOCH and the blowing agent, followed by chemical vapor deposition of a second layer so as to form a second, tight layer gas. A foaming step is then performed, which allows the formation of pores in the SiOCH layer. The second layer is then removed. Such a process is described in the patent application FR2918997. Deposition of the porous SiOCH layer can be carried out in a known type of PECVD equipment. The precursors for the matrix are, for example, organosilicon precursors such as DEMS (diethoxymethylsilane), tetramethylcyclotetrasiloxane, dimethyl-dioxiranyl-silane, diethoxy-methyloxiranyl-silane, etc. The precursor is subjected to a plasma and is vaporized in the enclosure of the PECVD equipment. It breaks up forming radicals that settle on at least the surface of the suspended element of NEMS, then these radicals react with each other to form a film. In order to produce a porous layer, a pore-forming agent may advantageously be used, for example NBD (Norbornadiene).
    [0013] Alternatively they may be organic molecules such as, for example, norbornene, alpha terpinene, cyclohexene oxide, cyclopentene oxide, triverta I, etc. The pore-forming agent also undergoes plasma treatment, it then forms inclusions in the layer formed by the precursor. Upon subsequent annealing, the pore-forming agent is removed forming the pores in the layer and the matrix is crosslinked. The duration of the deposit is adjusted to obtain the desired thickness. The deposit is followed by an annealing step which makes it possible to eliminate the porogenic agent and to crosslink the matrix. For example, the annealing lasts a few minutes under UV at 400 ° C. The duration of the annealing is adjusted according to the thickness of the material to be treated. The level of porosity is controlled by controlling the flow rate of precursors and pore-forming agent.
    [0014] The addition of a pore-forming agent during the vapor phase deposition makes it possible to control the porosity and to have a small dispersion in the pores of the functionalization layer. A porosity of at least 3% can be obtained by using or not a pore-forming agent, the use of a pore-forming agent can depend on the values of the various parameters of the formation of the porous layer. For example, in the case of a CVD deposit, the level of porosity may depend on the pressure prevailing in the CVD chamber, the substrate temperature, the plasma power and / or the flow rate of precursors and / or flow rates. gases such as oxygen or helium. The affinity of the layer for toluene will be calculated for SiOCH functionalization layers having different porosities. The greater the partition coefficient K of a material layer, the greater the affinity of this layer with toluene.
    [0015] The affinity of the layer for toluene is characterized by the partition coefficient K defined by: K = [toluene in the layer] / AC. It is shown that K = Af / (SeAC) with AC the concentration variation of the gas (in g / cm3). S the sensitivity of a quartz microbalance equal to 2.26 108 Hz cm2 / g and the thickness of the layer (in cm). The values of the partition coefficient K are collated in Table T2 below. Porosity K in the concentration range xx xx ppm SiOCH 27% 6400 SiOCH 3% 1900 SiOCH 0.6% 900 Table T2: values of the partition coefficient K for different porosity values of a SiOCH layer It can be seen that a porous layer according to the invention has a high partition coefficient compared to a very low porosity layer, 0.6% in the case considered. Therefore, thanks to the present invention, the sensor has a good or very good affinity with respect to toluene, that is to say that it has good or very good ability to capture toluene. It could be shown that for other gases such as benzene, ethylbenzene and o-xylene, the K coefficient would have similar values. Thus, it is considered that below 3%, the porosity is not sufficient to give the material a sufficient sensitivity. In order to show the efficiency of the gas detector comprising a NEMS having a suspended sensitive portion provided with a porous functionalization layer, according to the invention, measurements of detection of aromatic compounds have been carried out on a detector comprising a NEMS comprising a SiOCH layer deposited as described above. For this, was used an installation shown schematically in Figure 2, comprising an injector 10 for injecting a liquid mixture of aromatic compounds: the liquid compounds are vaporized in the chamber of the injector 10 and the vapors thus obtained are injected into the measurement chain, a gas chromatography column 12 for separating each component of the injected mixture, a functionalized NEMS D detector with an SiOCH layer at the outlet of the gas chromatography column 12. The NEMS detector D ensures the detection of each previously separated component in the chromatography column 12, and a reference detector 14, in this case a flame ionization detector (or FID) is provided downstream of the NEMS. The FID detector is used to control the quantity of material at the outlet of the column. The detector D and the reference detector 14 are connected to a recorder 16.
    [0016] In table T3 below, the detectable mass values in ng corresponding to the detection limit of the functionalized NEMS for two thicknesses 30 nm and 180 nm of SiOCH layer having a porosity of 27% are combined and for four compounds: the benzene, toluene, ethylbenzene and o-xylene. Detectable mass (ng) Benzene 5,541 3,149 2,357 2,695 Toluene Ethylbenzene o-Xylene Benzene Toluene Ethylbenzene o-Xylene NEMS unit SiOC-41 30nm 0.391 0.228 0.189 0.393 NEMS unit SiOC-41 180nm Table T3: mass detectable by a NEMS detector with a layer of Functionalization in SiOC having a porosity of 27%.
    [0017] The detection limit of the detectors according to the invention is lowered compared to gas detectors of the state of the art. On the curves 3A to 3D, we can see the area of the peaks obtained by the gravimetric measurement made by means of the NEMS detector in Hz.s as a function of the area of the peak obtained by FID in arbitrary units for SiOCH layers. 80 nm thick and having a porosity of 27% (curve I) and 3% (curve II). Curve 3A represents the detection of benzene, curve 3B represents the detection of toluene, curve 3C represents the detection of ethylbenzene, and the 3D curve represents the detection of o-Xylene. The area of the FID peak is proportional to the total mass of detected compound.
    [0018] The mass gain absorbed by a SiOCH layer with a porosity of 27% with respect to a SiOCH layer with a porosity of 3% is 2 for benzene, 1.8 for toluene, 1.6 for ethylbenzene and 1.4 for o-Xylene.
    [0019] In FIGS. 4A to 4B, the area of the peaks obtained by the gravimetric measurement carried out by means of the NEMS in Hz.s can be represented as a function of the area of the peak obtained by FID in pA.s (arbitrary units) for SiOCH layers of porosity 27% and increasing thickness, namely 10 nm (curve A), 30 nm (curve B), 80 nm (curve C) and 180 nm (curve D). Figure 4A shows the detection of benzene, Figure 4B shows the detection of toluene, Figure 4C shows the detection of ethylbenzene, and Figure 4D shows the detection of o-Xylene. Table T4 below shows the gains in mass absorbed in toluene calculated between different thicknesses. For example, the first column refers to the gain between a 30nm layer and a 10nm layer, this is 2. Gain S10C-41 Gain Si0C-41 Gain Si0C-41 30nm / 10nm 80nm / 30nm 180nm / 30nm Toluene x2 x1, 6 x5.9 Table T4: weight gain detected as a function of the thickness of the SiOCH layer 27% The material of the functionalization layer has a partition coefficient with respect to toluene of at least 1900 Advantageously, for a thickness of at least 10 nm, the product Kxe is at least equal to 1900 × 10 × 10 -7 cm = 19.1 cm for toluene.
    [0020] We will now describe an exemplary method for producing an NEMS detector according to the invention by means of FIGS. 5A to 5F.
    [0021] For example, an SOI (Silicon-On-Insulator) substrate is used. It comprises a silicon substrate 102, a dielectric layer 104, for example SiO 2 and a monocrystalline silicon layer 106. The layer 104 has for example a thickness of 400 nm and the layer 106 has for example a thickness of 160 nm. The layer 106 may be p-doped by implantation of boron ions at 1.5 × 10 19 cm -1. The SOI substrate is represented in FIG. 5. In a next step, the NEMS is produced, for which a lithography step and an etching step take place on the layer 106.
    [0022] Advantageously, the lithography is a hybrid lithography for example e-beam and DUV lithography which allows the structuring of large areas with structures whose dimensions may be less than 80 nm, or even 50 nm. Etching is for example an anisotropic etching.
    [0023] The element thus obtained is shown in FIG. 5B. In a next step, a layer of a dielectric 108, for example SiO 2, is formed on the structured layer 106. This layer is then structured by lithography and etching to access the layer 106 in zones 110.
    [0024] The element thus obtained is shown in FIG. 5C. In a next step, a layer 114 of conductive material, for example a metallic material, for example AlSi, is formed on the layer 110 in order to form contact pads, in particular in the zone 110 allowing access to the layer 106. The layer 112 has for example a thickness of 650 nm. This layer is then structured thus forming contact pads 114. The element thus obtained is shown in FIG. 5D. In a next step, the NEMS is released, in particular its suspended part, for example by hydrofluoric acid vapor.
    [0025] The element thus obtained is shown in FIG. 5E. In a subsequent step, a porous functionalization layer, for example SiOCH, is formed at least on the upper face of the suspended part of the NEMS preferably by CVD. This layer has a thickness of between 10 nm and 200 nm. The realization of this layer is done according to the mode described above. The functionalization layer is also deposited on the areas adjacent to the suspended portion, but only the sensitive area is useful to the sensor. The element thus obtained is shown in FIG. 5F.
    [0026] The invention therefore provides a NEMS type gravimetric sensor with lowered detection limit. In addition, an advantageous embodiment avoids the risks of stiction between the suspended part and the fixed part.
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. Gravimetric detector comprising a nanoelectronic structure comprising: a fixed part (2), at least one suspended part (4) with respect to the fixed part (2), - excitation means so as to vibrate the suspended part relative to at the fixed part, - means for detecting the vibration variations of said suspended part, - a porous functionalization layer (6) covering at least part of the suspended part (4), the porosity of said functionalization layer (6 ) being between 3% and 50%.
    [0002]
    2. gravimetric detector according to claim 1 wherein the porosity of the functionalization layer (6) is between 5% and 40%.
    [0003]
    Gravity sensor according to claim 1 or 2, wherein the thickness of the functionalization layer (6) is between 10 nm and 200 nm.
    [0004]
    4. gravimetric detector according to one of claims 1 to 3, wherein the functionalization layer (6) is of a SiOxCyHz type material, with x between 1 and 2, preferably between 1.4 and 1.8, between 0.8 and 3, preferably between 1 and 2.5, between 2.5 and 4.5, preferably between 3 and 4.1.
    [0005]
    5. gravimetric sensor according to one of claims there 3, wherein the functionalization layer (6) is a material of SiOw type, with w between 0 and 2.
    [0006]
    6. gravimetric sensor according to one of claims 1 to 5, wherein the functionalization layer is present on at least a portion of a face of the suspended portion (4) opposite the fixed portion (2), preferably on any the face of the suspended part (4) opposite to the fixed part (2).
    [0007]
    7. gravimetric sensor according to one of claims 1 to 6, wherein the excitation means are electrostatic means.
    [0008]
    8. gravimetric sensor according to one of claims there 7, wherein the detection means are piezoelectric means.
    [0009]
    9. Analysis set comprising a gas chromatography column and at least one gravimetric detector according to one of the preceding claims disposed at the outlet of said column.
    [0010]
    10. A method of producing a gravimetric detector according to one of claims 1 to 8, comprising: - the realization of the nanoelectronic structure, - the formation of the functionalization layer (6) having a porosity of between 3% and 50 %, on at least part of the suspended part of the nanoelectronic structure.
    [0011]
    11. Production method according to claim 10, wherein the formation of the functionalization layer is obtained by chemical vapor deposition.
    [0012]
    12. The production method according to claim 11, wherein during the chemical vapor deposition a pore-forming agent is used.
    [0013]
    13. The production method according to claim 12, wherein the porosity level is set as a function of the pore flow rate.
    [0014]
    14. The production method according to claim 12 or 13, wherein the pore-forming agent comprises organic molecules such as norbornadiene, norbornene, alpha terpinene, cyclohexene oxide, cyclopentene oxide, trivertal, etc.
    [0015]
    15. Production method according to one of claims 10 to 14, wherein the formation of the functionalization layer (6) is obtained by introducing into a chamber a precursor and a blowing agent, by applying a plasma treatment and then by performing a heat treatment to oxidize the blowing agent.
    [0016]
    16. The production method according to one of claims 10 to 15, wherein the formation of the functionalization layer occurs after release of the nanoelectronic structure.
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    法律状态:
    2015-12-31| PLFP| Fee payment|Year of fee payment: 3 |
    2016-01-01| TQ| Partial transmission of property|Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERG, FR Effective date: 20151202 Owner name: APIX ANALYTICS, FR Effective date: 20151202 |
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    申请号 | 申请日 | 专利标题
    FR1363628A|FR3016044B1|2013-12-27|2013-12-27|GRAVIMETRIC GAS SENSOR WITH LOWER DETECTION LIMIT|FR1363628A| FR3016044B1|2013-12-27|2013-12-27|GRAVIMETRIC GAS SENSOR WITH LOWER DETECTION LIMIT|
    US15/108,428| US9927401B2|2013-12-27|2014-12-24|Gravimetric gas sensor having a lowered detection limit|
    PCT/EP2014/079301| WO2015097282A1|2013-12-27|2014-12-24|Gravimetric gas sensor having a lowered detection limit|
    EP14819032.5A| EP3087386B1|2013-12-27|2014-12-24|Gravimetric gas sensor having a lowered detection limit|
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