GAS SENSOR FOR ANESTHETIC GASES AND ITS USE

20170296771 · 2017-10-19

    Inventors

    Cpc classification

    International classification

    Abstract

    A gas sensor for the detection of gases and vapors in air is particularly for the detection of anesthetic gases. A method for the detection and for the monitoring of such gases is also provided including detecting anesthetic gases with the gas sensor.

    Claims

    1. A capacitively coupled field effect transistor gas sensor comprising: a receptor layer; an insulation layer; a substrate; a drain; a source; a channel area located between the drain and the source; a gate electrode; and a sensor electrode, wherein the channel area is spatially in connection with the gate electrode and at least the drain, the source and the channel area are arranged within the substrate; wherein the gate electrode is connected electrically conductively to the sensor electrode and an air gap is present between the sensor electrode and the receptor layer, and the sensor electrode and the receptor layer are otherwise separated by the insulation layer; and wherein an analyte gas flows through the air gap, the analyte gas is an anesthetic gas and the receptor layer contains positive charge centers.

    2. A gas sensor in accordance with claim 1, wherein the anesthetic gas is selected from among one or more members of the group comprising desflurane, sevoflurane, isoflurane, enflurane and halothane.

    3. A gas sensor in accordance with claim 1, wherein the receptor layer is configured as an electrically conductive layer and contains pure soft Lewis acids or mixtures of soft Lewis acids.

    4. A gas sensor in accordance with claim 3, wherein soft Lewis acids comprise Ti.sup.+, Ni.sup.2+, Pd.sup.2+, Pt.sup.2+, Cu.sup.+, Cu.sup.2+, Ag.sub.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, In.sup.3+, Ti.sup.3+, Ge.sup.2+, Sn.sup.2+ or Pb.sup.2+ or any combination of Ti.sup.+, Ni.sup.2+, Pd.sup.2+, Pt.sup.2+, Cu.sup.+, Cu.sup.2+, Ag.sub.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, In.sup.3+, Ti.sup.3+, Ge.sup.2+, Sn.sup.2+ and Pb.sup.2+.

    5. A gas sensor in accordance with claim 1, wherein the receptor layer contains or consists of titanium nitride and titanium+cations.

    6. A gas sensor in accordance with claim 1, wherein the receptor layer contains or consists of copper phthalocyanine

    7. A closed-circuit ventilation system comprising: a carrier gas source supplying a carrier gas; an anesthetic gas source supplying for an anesthetic gas; and a capacitively coupled field effect transistor sensor comprising a receptor layer, an insulation layer, a substrate, a drain, a source, a channel area located between the drain and the source, a gate electrode and a sensor electrode, wherein the channel area is spatially in connection with the gate electrode and at least the drain, the source and the channel area are arranged within the substrate; wherein the gate electrode is connected electrically conductively to the sensor electrode and an air gap is present between the sensor electrode and the receptor layer, and the sensor electrode and the receptor layer are otherwise separated by the insulation layer; and wherein the anesthetic gas, as an analyte gas, flows through the air gap and the receptor layer contains positive charge centers.

    8. A closed-circuit ventilation system in accordance with claim 7, further comprising a closed ventilation circuit with a patient feed connection wherein the gas sensor is arranged within the closed ventilation circuit of the closed-circuit ventilation system of an anesthesia device to quantitatively determine a concentration of the anesthetic gas as the anesthetic gas is being fed to the patient.

    9. A closed-circuit ventilation system in accordance with claim 7, wherein the closed ventilation circuit comprises an outlet for the discharge of at least one carrier gas and anesthetic gas and an anesthetic gas filter, wherein the anesthetic gas is sent at the outlet through the anesthetic gas filter and the gas sensor is arranged downstream of the anesthetic gas filter.

    10. A closed-circuit ventilation system in accordance with claim 8, wherein optical information or acoustic information or both optical information and acoustic information, which indicates that the anesthetic gas filter is to be replaced, is communicated when a defined threshold value is reached, and the information is transmitted to a receiver.

    11. A closed-circuit ventilation system in accordance with claim 9, wherein the closed ventilation circuit further comprises a nonreturn valve wherein the gas sensor is arranged between the anesthetic gas filter and the nonreturn valve.

    12. A closed-circuit ventilation system in accordance with claim 7, further comprising parallel circuit portions and at least another capacitively coupled field effect transistor sensor to provide a plurality of gas sensors with different receptor layers arranged such that anesthetic gas flows through the plurality of gas sensors in the parallel circuit portions.

    13. A closed-circuit ventilation system in accordance with claim 7, wherein the gas sensor further comprises a heating element or is surrounded by a heating element to heat the receptor layer or to heat the receptor layer and the sensor electrode prior to a measurement or to heat the receptor layer or to heat the receptor layer and the sensor electrode for regeneration between two measurements.

    14. A closed-circuit ventilation system in accordance with claim 13, wherein the heating element heats the receptor layer or heats the receptor layer and the sensor electrode for a time Δt.sub.H of 10 sec to 10 minutes to a temperature T of 60° C. to 120° C.

    15. A closed-circuit ventilation system in accordance with claim 7, wherein the receptor layer is configured as an electrically conductive layer and contains pure soft Lewis acids or mixtures of soft Lewis acids.

    16. A closed-circuit ventilation system in accordance with claim 15, wherein soft Lewis acids comprise Ti.sup.+, Ni.sup.2+, Pd.sup.2+, Pt.sup.2+, Cu.sup.+, Cu.sup.2+, Ag.sub.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, In.sup.3+, Ti.sup.3+, Ge.sup.2+, Sn.sup.2+ or Pb.sup.2+ or any combination of Ti.sup.+, Ni.sup.2+, Pd.sup.2+, Pt.sup.2+, Cu.sup.+, Cu.sup.2+, Ag.sub.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, In.sup.3+, Ti.sup.3+, Ge.sup.2+, Sn.sup.2+ and Pb.sup.2+.

    17. A closed-circuit ventilation system in accordance with claim 7, wherein the receptor layer contains or consists of titanium nitride and titanium+cations.

    18. A closed-circuit ventilation system in accordance with claim 7, wherein the receptor layer contains or consists of copper phthalocyanine

    19. A method for a quantitative determination of at least one anesthetic gas, the method comprising the steps of: providing a ventilation system comprising a carrier gas source supplying a carrier gas, an anesthetic gas source supplying for an anesthetic gas and a capacitively coupled field effect transistor sensor comprising a receptor layer, an insulation layer, a substrate, a drain, a source, a channel area located between the drain and the source, a gate electrode and a sensor electrode, wherein the channel area is spatially in connection with the gate electrode and at least the drain, the source and the channel area are arranged within the substrate; wherein the gate electrode is connected electrically conductively to the sensor electrode and an air gap is present between the sensor electrode and the receptor layer, and the sensor electrode and the receptor layer are otherwise separated by the insulation layer and wherein the receptor layer contains positive charge centers; providing a flow of an analyte gas, comprising the anesthetic gas, through the air gap; and determining quantitatively the anesthetic gas.

    20. A method according to claim 19, wherein the anesthetic gas is desflurane, sevoflurane, isoflurane, enflurane or halothane or any combination of desflurane, sevoflurane, isoflurane, enflurane and halothane.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0028] In the drawings:

    [0029] FIG. 1 is a schematic view showing the basic design of an anesthesia device in the form of a closed-circuit ventilation system;

    [0030] FIG. 2 is a schematic view showing the design of prior-art SG-FET sensors;

    [0031] FIG. 3 is a schematic view showing the design of the CCFET sensors according to the present invention;

    [0032] FIG. 4 is a schematic view showing the charge distribution of halothane;

    [0033] FIG. 5 is a view showing the formation of an electrical double layer by the adsorption of halothane, oriented in the same direction, in a CCFET sensor according to the present invention;

    [0034] FIG. 6 is a schematic view showing the interaction of sevoflurane with a surface having positive charge centers (with enlargement of the molecular structure);

    [0035] FIG. 7 is a graph showing the response time and the recovery time of a 0.5-vol. % isoflurane signal on a titanium nitride layer;

    [0036] FIG. 8 is a graph showing signals of different sevoflurane concentrations on a titanium nitride layer;

    [0037] FIG. 9 is a calibration curve of sevoflurane for a CCFET sensor with titanium nitride layer;

    [0038] FIG. 10 is a schematic view showing a configuration of a filter depletion indicator with CCFET sensor according to the present invention; and

    [0039] FIG. 11 is a graph showing a detection of a filter breakthrough with a CCFET sensor according to the invention.

    DESCRIPTION OF THE PREFERRED EMBODIMENTS

    [0040] Referring to the drawings, FIG. 1 shows the principle of a closed-circuit ventilation system with anesthesia device, in which the essential components are the directional valves (inhalation valve 25, exhalation valve 22 ), the CO.sub.2 absorber 26, the breathing bag 27, the outlet valve 21, which is configured as a pressure relief valve, folded tubes and the Y-piece 23. If no gas exhaust system is installed in the building, a gas outlet filter 20 is used, as a rule, which binds at least the anesthetic gas. In addition, there is an anesthetic evaporator 28. The carrier gases 30 (e.g., laughing gas, oxygen and/or compressed air) are made available via a gas cylinder-based high-pressure system. The respective carrier gas mixture is set by means of flow meters (29) as a function of the corresponding purpose of anesthesia to which the patient is subjected. The carrier gas mixture (30) is sent through the anesthetic evaporator (28) and thus mixed with the anesthetic gas. The evaporators are calibrated (e.g., compensated for temperature, flow and/or pressure) and coded for a certain anesthetic. The concentration that is relevant here for the anesthesia of a test subject is the so-called minimal alveolar concentration (MAC).

    [0041] In this case, 1 MAC is the alveolar concentration of an inhaled anesthetic gas in vol. %, which prevents, in the absence of other anesthetics and at equilibrium, 50% of the patients from responding to a normal surgical stimulus with motion (DIN EN ISO 21647). The adequate depth of anesthesia is at 1.2 to 1.4 MAC. This leads ultimately to anesthesia gas concentrations of 1 vol. % to 18 vol. %. The patient 24 inhales the respective carrier gas 30 plus anesthetic gas mixture 28 via the Y-piece 23 and the inhalation valve 25. During the subsequent exhalation, the exhaled air enters the closed circuit via the exhalation valve 22 and finally enters the CO.sub.2 adsorber. The carbon dioxide (CO.sub.2) reacts there with, e.g., calcium hydroxide to form calcium carbonate and water and is thus removed from the gas circulation. The anesthetic gas mixture present (carrier gas and anesthetic gas(es)) leaves the closed system via the pressure relief valve 21 and enters the operating room after flowing through the filter 20 and via an anesthetic gas discharge line into the exhaust air (not shown). Anesthetic gas sensors may be installed both within the closed-circuit ventilation system, e.g., in the Y-piece 23, but also outside, e.g., after the gas outlet filter. Excess breathing air and hence also the anesthetic gases are discharged to the outside and thus also the operating room via the outlet valve 21. For example, an activated carbon filter 20 is used for absorbing the anesthetic vapors to prevent this. The filter is a consumable part. If the filter is loaded, it must be replaced. The sensor, which shall indicate the breakthrough through the filter 20, is installed downstream directly after the filter 20.

    [0042] A Prior-art suspended-gate sensor (SG-FET) is shown in FIG. 2. The substrate 1 carries here a transistor trough with drain 2 and source 3 and a channel area 4. The cover 5 with the receptor layer 6 is separated from the transistor trough by an air gap 7. The surface of the receptor layer 6 and the channel area 4 are capacitively coupled with one another. The air to be tested reaches the receptor surface via the air gap 7. A reversible change occurs in the work function due to the gas adsorption/surface reaction of the analyte molecules at the receptor layer 6 as a function of the concentration of these molecules. This potential difference couples capacitively via the air gap to the channel surface and induces charges in the FET structure.

    [0043] The design of the CCFET (Capacitive-Coupled Field-Effect Transistor) sensors according to the present invention is explained schematically on the basis of FIG. 3. The channel area 4 is covered with a gate electrode 8 and is arranged within the substrate 1. The gate electrode 8 is connected to the sensor electrode 9 via an electrically conductive connection. The sensor electrode 9 and the receptor layer 6 are separated by the insulation layer 10. The air gap, through which analyte gas flows, is located between the sensor electrode 9 and the receptor layer 6. The substrate consists of pure, undoped silicon (intrinsic silicon) or slightly doped silicon. Embedded in it is a transistor comprising an electrically insulating n-doped trough (substrate 11), in which the drain 2 and source 3, which consist of p-doped silicon and are thus made conductive, are arranged. A channel area 4, which carries, in turn, a p-doped gate 8, is formed in the substrate 11 between the drain 2 and the source 3. This gate 8 is connected, in turn, electrically to a sensor electrode 9 made of noble metal (e.g., platinum or palladium), which is bound in an insulator layer 10. A carrier layer 5 is tightly connected to the insulator layer 10 above the sensor electrode 9. The carrier layer 5 carries a gas-sensitive receptor layer 6 such that an air gap 7 is formed between the receptor layer 6 and the sensor electrode 9. The distance between the receptor layer 6 and the sensor electrode 9 is less than 50 μm, preferably between 5 μm and 20 μm and especially preferably between 10 μm and 12 μm.

    [0044] If a negative voltage is present at the gate 8 compared to the source 3, the developing electrical field restricts the mobility of the electrons flowing between the drain 2 and the source 3: The channel 4 becomes narrower and the resistance thus becomes greater. This field-effect transistor can be used as a sensor if a variable to be measured—what is of interest here being the concentration of a substance in the air gap—influences a control parameter of the transistor. This control parameter is the potential between the sensor electrode 9 and the receptor layer 6.

    [0045] If molecules to be detected enter the air gap 7 due to diffusion, they interact with the surfaces 6 and 9. The receptor layer 6 shall ideally interact with the molecules of the substance much more strongly, so that an enrichment of the molecules of the substance will occur at the surface 6. This is achieved by utilizing especially Coulomb forces, i.e., forces acting between positive and negative partial charges.

    [0046] The charge distribution of halothane is shown in FIG. 4. The fluorine atoms carry the greatest part of the negative charge, while the C atom of the trifluoromethyl group carries the positive charge center. The CHBrCl group is neutral relative thereto.

    [0047] The analyte molecules present in the air gap 7 in FIG. 5 are distributed between the gas phase and the two surfaces 6 and 8. If it is possible to bind the analyte molecules to the surface through a correct configuration of the surface 6 such that they will be arranged oriented in the same direction, i.e., all trifluoromethyl groups in the example of halothane will point away from the sensor electrode 9, an electrical double layer (similar to the Helmholtz double layer in electrochemical sensors) will be formed. This situation can be considered to be a series connection of two capacitors C.sub.L and C.sub.DS. C.sub.L describes the capacitance over the air layer and C.sub.DS the capacitance of the analyte cover and of the receptor layer 6. A total capacitance C.sub.totcan be calculated according to


    C.sub.tot=C.sub.DS*C.sub.L/(C.sub.DS+C.sub.L).

    It is important for the sensor sensitivity that C.sub.tot be as low as possible. Since C.sub.L is relatively low due to the distance between the sensor electrode 9 and the analyte double layer, C.sub.DS must be selected to be as high as possible.

    [0048] C.sub.DS will become high if (according to C.sub.DS=ε.sub.0*ε.sub.r *A/d, where ε.sub.0 is the electrical field constant of vacuum, ε.sub.r is the relative permittivity and A is the electrode surface; all three parameters being constant here) the distance d between the analyte double layer and the receptor layer 6 becomes as low as possible. Maximum distances d are reached if analyte molecules are directly adsorbed on the receptor layer 6. Now, d is in the Angström range.

    [0049] In addition to the shortest possible distance d, especially the arrangement of the analyte molecules with identical orientation is important in order for the electrical double layer to be able to be formed. This can be ensured by suitable surfaces.

    [0050] The analyte-surface interactions that are relevant here are electrostatic interactions. The anesthetics being considered here act as Lewis bases based on their high electron density. This implies the presence of Lewis acids on the surface of the electrode (e.g., FIG. 6) for an effective interaction. A suitable Lewis acid is, for example, the Ti.sup.1 cation (formed, e.g., due to a defect in a titanium nitride layer) or also the Cu.sup.2+ cation in Cu-phthalocyanine surfaces.

    [0051] A sensor corresponding to FIG. 3, with titanium nitride as the receptor layer 6, reacts, for example, with sevoflurane with a response time of t.sub.90=7 sec as well as with a recovery time of t.sub.10=9 sec. The response and recovery times of the other anesthetics are on the same orders of magnitude.

    [0052] The sensor responses to different concentrations in a range from 0.05 vol. % to 8 vol. % of sevoflurane are shown in FIG. 8.

    [0053] The corresponding calibration curve is shown in FIG. 9. It follows the Langmuir function S=K*q.sub.max*c/(1+K*c). K is an analyte-specific constant and q.sub.max is an indicator of the complete coverage of the surface. All other anesthetic gases follow the Langmuir function as well, but they do so with differences in K and q.sub.max.

    [0054] FIG. 10 shows a conceptual design of a filter depletion indicator. The excess air in the closed circuit is sent through the filter. The anesthetic gases are absorbed in the process.

    [0055] At the beginning of the admission to the filter, the sensor detects only the highly volatile carrier gas components flowing through the filter, such as oxygen and possibly laughing gas as well as nitrogen and moisture present in the air. If the absorption capacity of the filter is depleted, the concentration of anesthetic gases rises directly behind the filter, there is a breakthrough through the filter and the anesthetic gas is identified based on the formation of a double layer. The reference number 31 represents the electronic detector, 32 designates the nonreturn valve, reference number 33 designates the outlet of the closed system, 34 designates the CCFET sensor, and the reference number 35 designates the filtered air.

    [0056] FIG. 11 shows a typical breakthrough curve of an anesthesia filter. Reference number 36 designates the filter breakthrough.

    [0057] While specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.