Thermal conductivity detector comprising a resistive sensor incorporating adamantine carbon and corresponding method

Abstract

Thermal conductivity detector (1), in particular for the detection and, optionally, the quantification of a gaseous analyte within a gas, the detector comprising a resistive sensor (2) containing, or even consisting of, adamantine carbon.

Description

Title of the invention: Thermal conductivity detector comprising a resistive sensor incorporating adamantine carbon and corresponding method Technical field

[0001] The present invention relates to the detection and quantification of a gaseous analyte by means of a thermal conductivity detector. Such detection is for example implemented for gas chromatography, in particular to detect a leak of dihydrogen in a fuel cell. State of the art

[0002] A thermal conductivity detector, frequently referred to by the abbreviation TCD, an acronym for "Thermal Conductivity Detector", is commonly used to perform gas chromatography. It comprises a resistive sensor through which an electric current flows, which heats the resistive sensor by the Joule effect.

[0003] The resistive sensor of a thermal conductivity detector is characterized by the fact that it has an electrical resistance R which varies with the temperature T, for example linearly according to the following relationship

[0004] [Math.l] R-Rç^Y + aT)

[0005] where Ro is the resistance of the conductor at a temperature of 0 °C and a is the temperature coefficient, expressed in K '.

[0006] The resistive sensor is immersed in a gas, with which it exchanges a quantity of heat that it generates by the Joule effect. This quantity of heat being proportional to the thermal conductivity of the gas, the temperature of the resistive sensor therefore depends on the thermal conductivity of the gas. Thus, a variation in the composition of the gas induces a variation in the temperature of the resistive sensor. This results in a variation in the electrical resistance of the resistive sensor. By measuring this electrical resistance, it is thus possible to detect the presence of a gaseous analyte and possibly to determine its concentration.

[0007] [Fig. 1] illustrates an example of implementation of detection of a gaseous analyte with a thermal conductivity detector. The thermal conductivity detector 1 comprises a resistive sensor 2 of electrical resistance R arranged in a measuring chamber 3 in which the resistive sensor 2 is in contact with a gas to be analyzed 4. It further comprises a reference resistor Rref arranged in a reference chamber 5, hermetically separated from the measuring chamber 3. The resistance of reference is in contact with a reference gas 6 whose composition is known. The resistive sensor 2 and the reference resistance Rref are electrically integrated within a Wheatstone bridge 7. The value of the electrical resistance R of the resistive sensor 2 can thus be determined precisely, the reference resistance and the other resistances Ri and R2 of the Wheatstone bridge being known.

[0008] The materials used to form the resistive sensor of a thermal conductivity detector are chosen for their suitability for implementation over a wide temperature range, their stability and the linearity of the variation of their electrical resistance with a variation in temperature. In particular, platinum and nichrome (alloy of nickel and chromium) are commonly used to form the resistive sensor.

[0009] However, these metallic materials are expensive. Furthermore, in the context of manufacturing a small thermal conductivity microdetector, typically less than 1 cm, the implementation of techniques for depositing thin layers made of these metallic materials, for example such as those encountered in the field of layered components of CMOS (metal-oxide-semiconductor) technology, can induce pollution of the deposition devices and / or of the surface of the substrate on which the thin layers are deposited.

[0010] Now there is a growing interest in micro thermal conductivity detectors which have many advantages: a short response time to detect a gas, low energy consumption and use in applications where portability is required.

[0011] Furthermore, resistive sensors made of nichrome or platinum may have mechanical properties which deteriorate with use and which induce a drift in the long-term thermal conductivity measurement. Summary of the invention

[0012] The invention proposes a thermal conductivity detector, in particular for the detection and, optionally, the quantification of a gaseous analyte within a gas, the detector comprising a resistive sensor containing, or even consisting of, adamantine carbon.

[0013] The thermal conductivity detector can be easily manufactured, since carbon is abundant and can be easily produced in the form of adamantine carbon. Furthermore, the deposition of adamantine carbon by thin-film deposition processes, such as those of CMOS technology, advantageously does not cause pollution of the deposition devices. The manufacture of a micro thermal conductivity detector is thus facilitated. Furthermore, in the form of a thin film, adamantine carbon retains its properties at least up to 260°C, which allows gas detection at least up to this temperature, as is known from DR Tallant, JE Parmeter, MP Siegal, RL Simpson, Diamond and Related Materials. 4 (1995) 191-199, https: / / doi.org / 10.1016 / 0925-9635(94)00243-6.

[0014] Adamantine carbon is also referred to by the abbreviation DLC, an English acronym for “Diamond Like Carbon”.

[0015] Adamantine carbon consists of carbon whose structure lies between diamond, characterized by an eponymous crystallographic structure and sp3 hybridized bonds between the carbon atoms, and graphite, having a hexagonal crystallographic structure and sp2 hybridized bonds between the carbon atoms. Unlike diamond or graphite, which are crystalline forms of carbon, adamantine carbon is amorphous because it does not exhibit long-range order. However, it may contain sp2 or sp3 hybridized carbon nanocrystals, which are predominantly present in its composition.

[0016] The properties and examples of implementation of adamantine carbon are described for example in DR Tallant, JE Parmeter, MP Siegal, RL Simpson, Diamond and Related Materials. 4 (1995) 191-199, https: / / doi.org / 10.1016 / 0925-9635(94)00243-6, B. Li, Y. Zhao, X. Ma, C. Li, Q. Zhang, Y. Zhao. Proc. IEEE Sensors, 2017 (2017), pp. 1-3, https: / / doi.org / 10.1109 / ICSENS.2017.8234144 and K. Luo, YQ Fu, HR Le, JA Williams, SM Spearing, WI Milne, Journal of Micromechanics and Microengineering. 17 (2007) S147, https: / / doi.org / 10.1088 / 0960-1317 / 17 / 7 / S12.

[0017] Adamantine carbon is also chemically inert. It has a low coefficient of thermal expansion which reduces damage to layers deposited on a substrate, for example silica, silicon nitride, or silicon. It also has high thermal conductivity allowing accumulated heat to be dissipated quickly. A long service life of the thermal conductivity detector is thus ensured.

[0018] The thermal conductivity detector preferably comprises a Wheatstone bridge integrating the resistive sensor, in order to measure the electrical resistance of the resistive sensor.

[0019] The thermal conductivity detector preferably comprises a measuring chamber in which the resistive sensor is housed and a reference chamber in which at least one resistor, or even two resistors, of the Wheatstone bridge is arranged. In an exemplary embodiment, the Wheatstone bridge comprises four resistive sensors, two of said resistive sensors being housed in the measuring chamber and two other of said sensors being housed in the reference chamber.

[0020] Preferably, the thermal conductivity detector comprises a substrate, the resistive sensor being arranged on the substrate. The substrate is preferably made of silicon. It may have a thickness of between 300 μm and 1200 μm.

[0021] The thermal conductivity detector may comprise a cover superimposed on the substrate, the cover comprising a recess superimposed on the resistive sensor. The resistive sensor is thus arranged between the cover and the substrate, which define the measuring chamber in which the resistive sensor is housed.

[0022] The cover is preferably made of silicon. It may have a thickness of between 300 μm and 1200 μm.

[0023] Preferably, the resistive sensor is a thin layer, which may have a thickness of less than 1 μm, or even less than 250 nm.

[0024] The resistive sensor can be deposited, in particular at room temperature, by a vacuum deposition technique, for example by physical vapor deposition, in particular by cathodic sputtering, or by chemical vapor deposition.

[0025] The adamantine carbon can be doped, for example, by at least one element chosen from nitrogen, silicon, boron, oxygen, fluorine, and mixtures thereof.

[0026] Preferably the substrate comprises a cavity, at least a portion of the resistive sensor being superimposed on the cavity and at a distance from the cavity. Said portion is thus suspended above the cavity, which allows the resistive sensor to be immersed in a gas flow flowing into and above the cavity. In this way, thermal losses with the substrate are limited.

[0027] Preferably, at least the portion of the resistive sensor superimposed on the cavity has a serpentine shape. Such a shape makes it possible to increase the heat exchange surface between the resistive sensor and the gas flow.

[0028] Preferably, the coil extends parallel to the face of the substrate opposite the resistive sensor.

[0029] According to a variant, the part of the resistive sensor superimposed on the cavity is self-supporting. In other words, it does not deform substantially under the effect of its own weight and does not need to be carried by a supporting structure. Preferably, the part of the resistive sensor superimposed on the cavity is opposite the bottom of the cavity.

[0030] According to another variant, the thermal conductivity detector comprises at least one electrically insulating layer arranged between the substrate and the resistive sensor, the electrically insulating layer comprising a self-supporting part superimposed on the cavity, forming a membrane, on which the resistive sensor rests. The part of the resistive sensor superimposed on the cavity is thus suspended above the cavity while being supported by the membrane.

[0031] The membrane is preferably perforated, in order to facilitate gas flow between the cavity and opposite the cavity relative to the suspended part of the resistive sensor.

[0032] Furthermore, the resistive sensor may be partially in contact with the substrate. In particular, the resistive sensor may comprise parts, arranged on the substrate and not superimposed on the cavity, which extend the suspended part of the resistive sensor in order to electrically supply said suspended part of the resistive sensor.

[0033] The invention also relates to a method for detecting, and optionally quantifying, a gaseous analyte within a gas, the method comprising bringing the gas into contact with a thermal conductivity detector comprising a resistive sensor containing adamantine carbon and heating the resistive sensor by the Joule effect.

[0034] Joule heating of the resistive sensor results from the generation of an electric current in the resistive sensor. The thermal conductivity detector can be connected to an external power source, for example a battery or a land-based electrical transport network.

[0035] Preferably, the method comprises measuring the electrical resistance of the resistive sensor.

[0036] Furthermore, the method may comprise determining the concentration of the gaseous analyte in the gas from the measurement of the electrical resistance.

[0037] The method according to the invention can be applied to the detection of different gaseous analytes within different gases. In particular, the gaseous analyte can be dihydrogen, the gas further comprising dioxygen and / or water vapor. The thermal conductivity detector can be arranged in a fuel cell, in particular in order to detect a leak or an excessive concentration of dihydrogen. Alternatively, the gas can be a mixture of nitrogen and dioxygen, for example air, and the analyte can be chosen from carbon dioxide, water vapor and their mixtures.

[0038] According to a first embodiment of the method, the gas comprises a reference gas and the gaseous analyte, and the method may comprise a preliminary step of calibrating the detector comprising bringing the detector into contact with the reference gas. The method according to the first embodiment makes it possible to detect the gaseous analyte, within the detection limit of the resistive sensor.

[0039] Preferably, the gas consists of the reference gas and the analyte. The method according to this first embodiment then also makes it possible to measure the concentration of the gaseous analyte within the gas, with no interferent then disturbing the quantification of the analyte. By "interferent" is meant a chemical species present in the gas, generally as traces, and whose presence is not desired.

[0040] According to a second embodiment of the method, the gas comprises a carrier gas and at least one gaseous analyte, preferably several gaseous analytes, and / or at least one interferent and the method may comprise the detection and quantification of the gaseous analyte(s) with a chromatography column equipped with the detector according to the invention.

[0041] Preferably, the method according to the second embodiment comprises providing a sample containing the gaseous analytes and preconcentrating the sample, in order to reduce the detection limit of the analytes by the detector. Preferably, the method comprises, after the preconcentration, separating the analytes in the carrier gas.

[0042] In order to quantify each analyte, the method comprises a calibration step with a reference gas in order to determine the order of appearance of the detection peaks of each analyte.

[0043] The method according to the second mode of implementation makes it possible to detect and quantify separately each of the analytes, in particular distinguishing them from the interferents which may be contained in the gas to be analyzed.

[0044] The invention finally relates to a method of manufacturing a thermal conductivity detector according to the invention, the method comprising the following successive steps: (a) providing a substrate covered with an electrically insulating layer at least partially covering the substrate, b) depositing a layer of adamantine carbon at least in part on the electrically insulating layer, and c) selectively etching a portion of the assembly formed in step b) so as to form a cavity in the substrate with the portion of the electrically insulating layer superimposed on the cavity which is distant from the cavity.

[0045] The method may further comprise depositing the adamantine carbon layer in contact with the substrate and selectively etching the substrate at least under a portion of the adamantine carbon layer in contact with the substrate. Brief description of the figures

[0046] The invention may be better understood by reading the detailed description which follows and the non-limiting examples of the invention illustrated by the appended drawing, in which:

[0047] [Fig. 1] schematically represents an example of a thermal conductivity detector according to the prior art,

[0048] [Fig.2] is a photograph of an example of a thermal conductivity detector,

[0049] [Fig.3] is a schematic representation of an example of a conductivity detector thermal according to the invention,

[0050] [Fig.4] and [Fig.5] are schematic representations, in cross-section, of two other examples of thermal conductivity detector according to the invention, and

[0051] [Fig.6] and [Fig.7] are experimental curves illustrating the evolution of the electrical resistivity p, expressed in Qm of a layer of adamantine carbon and of a layer of platinum respectively, as a function of the temperature T, expressed in °C.

[0052] The proportions of the different elements constituting the detectors illustrated in the figures have not necessarily been represented to scale. Detailed description

[0053] [Fig. 2] is a top view of a thermal conductivity detector 1 according to the invention. The thermal conductivity detector 1 comprises a silicon substrate 8 in which a rectilinear groove is formed which defines a cavity 9. It further comprises an electrically insulating layer 10 comprising a membrane 11 suspended above the cavity 9 and which connects on either side of the cavity two parts 12 of the electrically insulating layer 10 which are in contact with the substrate 8. The membrane 11 comprises openings allowing the passage of a gas flow through it. The thermal conductivity detector 1 further comprises a resistive sensor 2 carried by and in contact with the electrically insulating layer 10. The resistive sensor 2 comprises a part 13 carried by the membrane which has a serpentine shape and which extends parallel to the face on which the electrically insulating layer is arranged.It further comprises portions 14 not superimposed on the cavity defining electrically conductive tracks and which are connected to the two opposite ends of the coil.

[0054] [Fig.3] is a schematic cross-sectional view illustrating a detector as photographed in [Fig.2].

[0055] The silicon substrate is covered with an electrically insulating multilayer 15 which supports the resistive sensor 2. The multilayer is formed of a silica layer 16 in contact with the substrate and a silicon nitride layer 17. The multilayer is further covered with an additional electrically insulating layer 18, for example silica. The additional electrically insulating layer may be abraded prior to the deposition of the resistive sensor. The detector further comprises a cover 20, for example made of silicon, superimposed on the substrate. The cover comprises a recess 21, superimposed on the cavity and the resistive sensor. The recess and the cavity thus define a measuring chamber in which a gas to be analyzed can flow. The thickness of the substrate es and / or the thickness of the cover ec are for example between 300 μm and 1200 μm.

[0056] Alternatively, the multilayer may be replaced by a single electrically insulating layer 10, for example of silicon nitride, as illustrated in [Fig.4]. The electrically insulating layer is optional, as illustrated in [Fig.5], the resistive sensor then being self-supporting on the cavity. In this configuration, the part 13 of the resistive sensor 2 superimposed on the cavity 9 is opposite the bottom 19 of the bottom of the cavity 9.

[0057] The cavity may be formed, after the deposition of the electrically insulating layer(s) and the deposition of the resistive sensor, for example by photolithography and chemical etching, as described for example in the article C. de Graff, A. Abarca Prouza, M. Ghaderi and RF Wolffenbuttel, Sensors and Acutators A249 (2016), 186-198, https: / / doi.Org / 10.1016 / j.sna.2016.08.019. Examples

[0058] A layer of nitrogen-doped adamantine carbon was deposited on a glass substrate with a surface area of ​​2x2 cm2, by a high pulse power magnetron sputtering HIPIMS process using the DPI 100 device marketed by the company Alliance Concept. A layer with a thickness of 120 nm, measured by ellipsometry, was obtained.

[0059] For comparison, a platinum layer with a thickness of 120 nm was deposited on a glass substrate.

[0060] The electrical resistivities of the adamantine carbon and platinum layers were each measured in a 4-tip configuration. An electrical voltage was generated between two tips, and the electrical current flowing between the other two was measured. Voltage generation and current measurement were performed using a Keithley 238 multimeter. Temperature was managed via a servo-controlled system. A hot plate was used to increase the temperature of a sample holder carrying the substrate, the temperature being measured via a thermocouple. Cooling was passive.

[0061] As observed in Figure 6, the electrical resistivity of the adamantine carbon layer decreases substantially linearly over a temperature range between 30°C and 100°C, according to a negative temperature coefficient α equal to -3.3x103 K '. On the contrary, the platinum layer is characterized by a resistivity that increases linearly with temperature between 50°C and 150°C according to a positive temperature coefficient α equal to 3.5x103 K '. Similar observations are known for nichrome, as is known for example from the work of DC Giancoli, Physics, 4th Edition, Prentice Hall, 1995.

[0062] Although the temperature coefficients of platinum and adamantine carbon are close in absolute value, the electrical resistivity of adamantine carbon is more than 1000 times higher for the same temperature. Advantageously, this improves the accuracy of the electrical resistance measurement of the resistive sensor during a 2-wire resistance measurement.

[0063] The low coefficient of thermal expansion of adamantine carbon and its high electrical resistivity therefore make this material particularly well suited to the formation of a thermal conductivity detector, in particular as illustrated in [Fig.5], the low thermal expansion guaranteeing good mechanical strength of the resistive sensor on the substrate in use, following the repetition of the heating by Joule effect of the sensor and its cooling.

[0064] Of course, the invention is not limited to the embodiments and applications described by way of non-limiting and illustrative purposes. For example, the deposition parameters of the adamantine carbon layer can be modified in order to vary its electrical resistivity by modifying the proportions of sp2 and sp3 hybridization states of the carbon. Furthermore, in addition to gas chromatography, the method according to the invention can be implemented to detect gas leaks or to measure air quality, for example in a building, an automobile, etc.

Claims

Claims

1. Thermal conductivity detector (1), in particular for the detection and, optionally, the quantification of a gaseous analyte within a gas, the detector comprising a resistive sensor (2) containing, or even consisting of, adamantine carbon, the detector comprising a substrate, the resistive sensor being arranged on the substrate, the substrate comprising a cavity, at least a portion of the resistive sensor being superimposed on the cavity and at a distance from the cavity.

2. Detector according to claim 1, comprising a Wheatstone bridge (7) integrating the resistive sensor (2).

3. Detector according to any one of claims 1 and 2, the resistive sensor being a thin layer.

4. Detector according to any one of the preceding claims, at least the part of the resistive sensor superimposed on the cavity having a serpentine shape, preferably extending parallel to the face of the substrate opposite the sensor.

5. Detector according to claim 4, the part of the resistive sensor superimposed on the cavity being self-supporting.

6. Detector according to claim 4, the detector comprising at least one electrically insulating layer (10) arranged between the substrate and the resistive sensor, the electrically insulating layer comprising a self-supporting part superimposed on the cavity, forming a membrane (11), on which the resistive sensor rests.

7. Detector according to the preceding claim, the membrane being perforated.

8. Detector according to any one of the preceding claims, the resistive sensor being partially in contact with the substrate.

9. A method of detecting and, optionally, quantifying a gaseous analyte within a gas, the method comprising contacting the gas with the thermal conductivity detector (1) according to any one of the preceding claims and heating the resistive sensor by Joule effect.

10. A method according to claim 9, comprising measuring the electrical resistance (R) of the resistive sensor.

11. The method of claim 10, comprising determining the concentration of the gaseous analyte in the gas from the measurement of the electrical resistance.

12. A method according to any one of claims 9 to 11, the gaseous analyte being dihydrogen, the gaseous mixture further comprising dioxygen and / or water vapor.

13. A method of manufacturing a thermal conductivity detector according to any one of claims 1 to 8, the method comprising the following successive steps: a) providing a substrate comprising a support and at least one electrically insulating layer arranged on the support, b) depositing an adamantine carbon layer on the electrically insulating layer, and c) selectively etching a portion of the assembly formed in step b) so as to form a cavity in the support with the portion of the electrically insulating layer superimposed on the cavity which is distant from the cavity.

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