CN113155904B - High-sensitivity hydrogen sensor used in air environment and preparation method thereof - Google Patents
High-sensitivity hydrogen sensor used in air environment and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-sensitivity hydrogen sensor used in an air environment and a preparation method thereof, wherein the high-sensitivity hydrogen sensor comprises a drying unit, a sensing unit and an external circuit; the sensing unit comprises a sealed cavity and a sensing assembly arranged in the sealed cavity, wherein the sensing assembly comprises an insulating substrate arranged at the bottom of the sealed cavity, a palladium cluster film arranged on the upper surface of the insulating substrate and two conductive microelectrodes arranged at two ends of the palladium cluster film, two wiring terminals are arranged on the sealed cavity, one end of each wiring terminal, which is positioned in the sealed cavity, is connected with the corresponding conductive microelectrode through a wire, and one end, which is positioned outside the sealed cavity, is connected with an external circuit through a wire; the sealed cavity is communicated with a drying unit, and an air inlet is arranged on the drying unit. The invention adopts the seepage conductive film formed by palladium clusters, can sense and monitor the change of the hydrogen concentration in the air in real time, has the advantages of high sensitivity and short response time, does not need heating in the operation process, and does not need to separate the hydrogen in advance.
Description
Technical Field
The invention relates to the field of sensors, in particular to a high-sensitivity hydrogen sensor used in an air environment and a preparation method thereof.
Background
The hydrogen has the advantages of high heat value, no pollution, convenient production and the like, is concerned by people as a novel energy source, and has wide application in the fields of industrial and agricultural production, medical treatment, scientific research and the like. However, because hydrogen is colorless and odorless, and flammable and explosive, the human perception system cannot sense the presence of hydrogen in the environment at all. Therefore, the hydrogen is safely used, and the final elbow stopper for large-scale popularization and use of hydrogen energy is realized. The reliable hydrogen sensing and alarming device is developed, effective safety guarantee is provided for the industries using hydrogen and involving hydrogen, and the method is the most effective way for solving the problem of the elbow pulling.
Materials that are responsive to hydrogen, such as metallic palladium and oxides of some metals, are not lacking in nature. Based on the hydrogen sensitive materials, people design different sensing structures, and develop various hydrogen sensing alarm devices through measurement means such as electricity, electrochemistry, catalytic combustion, optics and the like. Among them, the hydrogen sensor using a palladium thin film as a sensing device is most commonly used. For example, in the "a hydrogen sensor based on a carbon nanotube and palladium composite film" disclosed in the chinese patent literature, the publication number CN105510400B sequentially includes, from inside to outside, a P-type silicon substrate, a carbon nanotube, a metal palladium film, and two metal electrodes, where the carbon nanotube is arranged uniformly in a longitudinal direction and a transverse direction, and the two metal electrodes are both bar-shaped and are symmetrically disposed on the upper surface of the metal palladium film. But such sensors have long response times and lower resolution; while the electrochemical sensor for measuring the electrochemical reaction signal of the hydrogen through the reference electrode can effectively shorten the response time, but can only maintain a very narrow measurement range; in addition, when part of metal oxide is used as hydrogen sensitive material, hydrogen reacts with oxygen element on the surface of the material to change the impedance property of the material, however, the reaction needs external heating; similarly, the hydrogen sensors measured by the catalytic combustion method also need to work in a high-temperature environment of 200-300 ℃, have a certain risk in the use process, and have the defect of poor selectivity; in addition, the hydrogen sensors of various other types only have response capability to pure hydrogen, and when the sensors are in an air environment, the interference of other gases in the air cannot be eliminated, and the hydrogen needs to be separated from the air in advance for subsequent quantitative measurement of the sensors.
In general, the existing hydrogen sensing technology often has the defects of long response time, narrow measurement range, poor selectivity, poor interference resistance and the like, and is difficult to meet the sensing alarm requirements of various hydrogen-using, hydrogen-related and hydrogen-monitoring occasions.
Disclosure of Invention
The invention provides a high-sensitivity hydrogen sensor for air environment and a preparation method thereof, which aims to overcome the defects of long response time, narrow measurement range, poor selectivity, poor interference resistance and the like existing in the hydrogen sensing technology in the prior art, and hardly meets the sensing alarm requirements of various hydrogen-using, hydrogen-related and hydrogen-monitoring occasions.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high-sensitivity hydrogen sensor used in an air environment comprises a drying unit, a sensing unit and an external circuit; the sensing unit comprises a sealing cavity and a sensing assembly arranged in the sealing cavity, wherein the sensing assembly comprises an insulating substrate arranged at the bottom of the sealing cavity, a palladium cluster film arranged on the upper surface of the insulating substrate and two conductive microelectrodes arranged at two ends of the palladium cluster film, two wiring terminals are arranged on the sealing cavity, one end of each wiring terminal is positioned outside the sealing cavity, one end of each wiring terminal is positioned inside the sealing cavity and connected with the conductive microelectrode through a wire, and one end of each wiring terminal is positioned outside the sealing cavity and connected with an external circuit through a wire; the sealed cavity is communicated with the drying unit, and the drying unit is provided with an air inlet.
Preferably, the material of the insulating substrate is selected from flexible or rigid insulating materials, and the stable resistivity of the insulating substrate is more than or equal to 10 9 Omega.m; the flexible insulating material is selected from polyimide, polydimethylsiloxane and polyethylene terephthalateIs one of (a); the rigid insulating material is selected from one of quartz, glass, ruby, sapphire, resin and monocrystalline silicon piece with silicon oxide insulating layer.
Preferably, the shape of the conductive microelectrode is an interdigital electrode or a spiral electrode, the thickness of the conductive microelectrode is 50 nm-10 μm, and the distance between the two conductive microelectrodes is 2-100 μm.
Preferably, the material of the conductive microelectrode is one selected from gold, silver, copper, iron, aluminum and indium tin oxide.
Preferably, the diameter distribution of palladium clusters in the palladium cluster film is 1-10 nm, and the average nearest neighbor distance between the palladium clusters is 0.5-5 nm.
Preferably, the coverage rate of the palladium cluster film is 30-95%, and the resistance of the palladium cluster film is 50kΩ -1 gΩ.
Preferably, the external circuit comprises a power supply, an electric signal measuring device and a programmable and visual output device, wherein the power supply and the electric signal measuring device are connected through wires, and the programmable and visual output device can convert the measured electric signal into a hydrogen concentration signal and visually output and display the hydrogen concentration signal.
Preferably, the drying unit comprises a drying tank body and a drying agent arranged in the drying tank body, wherein a plurality of air inlets are formed in the drying tank body, and the drying tank body is communicated with the sealing cavity.
The invention also provides a preparation method of the hydrogen sensor, which comprises the following steps:
(1) Preparing an insulating substrate;
(2) Printing a conductive microelectrode on the surface of an insulating substrate;
(3) Depositing a palladium cluster film between the conductive microelectrodes;
(4) Placing the insulating substrate with the deposited palladium cluster film in a sealed cavity, respectively connecting the conductive microelectrode with one end of the wiring terminal, which is positioned in the sealed cavity, by using a wire, and connecting one end of the wiring terminal, which is positioned outside the sealed cavity, with an external circuit by using the wire;
(5) Assembling a drying unit, and communicating the drying unit with the sealed cavity to obtain the assembled hydrogen sensor;
(6) Placing the assembled hydrogen sensor in hydrogen environments with different concentrations, recording macroscopic resistance changes of the palladium cluster film in the hydrogen environments with different concentrations through an external circuit, fitting a response relation, and inputting the response relation into the external circuit to finish the calibration of the hydrogen sensor;
(7) And placing the calibrated hydrogen sensor in an air environment to be measured, and measuring the hydrogen concentration through an external circuit.
Preferably, the palladium cluster film in the step (3) is deposited by adopting a nano printing method, a physical vapor deposition method, a chemical vapor deposition method or a block self-assembly method.
In the hydrogen sensor, a seepage conductive film formed by small-size palladium clusters is adopted, the transmission mode of electrons among the palladium clusters is quantized tunneling jump, the tunneling probability of the seepage conductive film and the intrinsic property of a tunnel junction among the clusters show an exponential decay relation, and the intrinsic property of the tunnel junction is directly determined by parameters such as barrier filling materials, barrier dielectric constants, barrier geometric dimensions and the like, so that the macroscopic resistance of the cluster film is very sensitive to weak changes of filling material types and components among the clusters. For example, filling a certain insulating substance (such as purified water) between clusters can greatly change the resistance of the cluster film. Therefore, the hydrogen sensor manufactured by taking the palladium cluster film as the sensitive element is placed in an air environment mixed with hydrogen, mixed gas is diffused into the sealed cavity of the sensing unit through the drying unit, and the drying unit can absorb the original vapor in the mixed gas, so that the interference to the subsequent detection is avoided. As shown in fig. 2, after the mixed gas is diffused into the sealed cavity, hydrogen molecules and oxygen molecules are adsorbed on the surfaces of palladium clusters, at the moment, bias voltage is applied to two sides of the conductive microelectrode through a power supply in an external circuit, electrons of the palladium clusters d in the film are excited to a higher energy level under the action of the bias voltage, the hydrogen molecules and the oxygen molecules are easily dissociated into active hydrogen atoms and active oxygen atoms respectively, then water molecules are catalytically synthesized, the generated water molecules belong to purified water and are enriched on the surfaces of the palladium clusters and are stuffed between the clusters, so that tunneling resistance of electron transmission is enhanced, and macroscopic resistance of the palladium cluster film is increased. Therefore, the resistance change of the palladium cluster film is monitored in real time through an electric signal measuring device in an external circuit, and the change of the hydrogen concentration in the air environment can be perceived.
The hydrogen sensor can sense and monitor the change of the concentration of hydrogen in the air in real time, has the advantages of high sensitivity and short response time, does not need to be heated in the operation process, does not need to separate the hydrogen in advance, can be directly applied to the air environment, and is suitable for various occasions of hydrogen utilization, hydrogen involvement and hydrogen monitoring.
Therefore, the invention has the following beneficial effects:
(1) The method can sense and monitor the change of the concentration of the hydrogen in the air in real time, has the advantages of high sensitivity and short response time, and provides safe and reliable guarantee for the industries and places of hydrogen utilization, hydrogen involvement and hydrogen monitoring;
(2) The sensor core device adopts a palladium cluster film with high impedance, the power consumption of the device is low, and the device is in micro-nano watt level;
(3) The palladium cluster film does not generate a large amount of Joule heat when conducting electricity, and the sensor does not need to be heated when working, so that potential safety hazards caused by high temperature are avoided;
(4) Can directly work in an air environment without operation procedures such as gas pre-separation and the like.
Drawings
FIG. 1 is a schematic view of a hydrogen sensor according to the present invention;
in the figure: 1 a sealing cavity, 2 an insulating substrate, 3 a palladium cluster film, 4 a conductive microelectrode, 5 a wiring terminal, 6 an external circuit and 7 a drying unit;
FIG. 2 is a basic operation schematic of the hydrogen sensor of the present invention;
FIG. 3 is a graph showing the real-time change in resistance of the palladium cluster film of example 1 as it is deposited;
FIG. 4 is a transmission electron micrograph of the palladium cluster film of example 1;
FIG. 5 is a graph showing the real-time change in resistance of the hydrogen sensor of example 1 in response to hydrogen at different concentrations;
FIG. 6 is a calibration curve of the hydrogen sensor in example 1;
FIG. 7 is a graph showing the resistance change of the hydrogen sensor of example 1 in response to hydrogen gas of unknown concentration;
FIG. 8 is a hydrogen sensor calibration curve in example 2;
FIG. 9 is a calibration curve of the hydrogen sensor in example 3.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
In the present invention, unless otherwise specified, all equipment and materials are commercially available or are commonly used in the industry, and the methods used in the present invention are conventional in the art unless otherwise specified.
As shown in fig. 1, a high-sensitivity hydrogen sensor for use in an air environment includes a drying unit 7, a sensing unit, and an external circuit 6.
The sensing unit comprises a sealed cavity 1 and a sensing assembly arranged in the sealed cavity, wherein the sensing assembly comprises an insulating substrate 2 arranged at the bottom of the sealed cavity, a palladium cluster film 3 arranged on the upper surface of the insulating substrate and two conductive microelectrodes 4 arranged at two ends of the palladium cluster film. The left side wall of the sealing cavity is provided with two wiring terminals 5, one end of each wiring terminal is positioned outside the sealing cavity, one end of each wiring terminal is positioned inside the sealing cavity and connected with the conductive microelectrode through a wire, one end of each wiring terminal is positioned outside the sealing cavity and connected with an external circuit through a wire, and the external circuit comprises a power supply connected through a wire, an electric signal measuring device and a programmable and visual output device which can convert measured electric signals into hydrogen concentration signals and visually output and display.
The right side wall of the sealing cavity is provided with a connecting through hole, the drying unit comprises a drying tank body made of stainless steel and a silica gel drying agent arranged in the drying tank body, the drying tank body is provided with a mounting part matched with the connecting through hole on the sealing cavity, the mounting part is clamped in the connecting through hole, the drying tank body is positioned on the side wall outside the sealing cavity and the surface of the mounting part in the sealing cavity is provided with a plurality of air inlet holes with the diameter of 1 mm, and the drying tank body is communicated with the sealing cavity through the air inlet holes in the mounting part.
Example 1:
the preparation method of the high-sensitivity hydrogen sensor comprises the following steps:
(1) Preparing an insulating substrate: the polyimide-covered epoxy resin with a smooth surface is selected as an insulating substrate, and the stable resistivity is 10 19 Ω·m；
(2) Printing a conductive microelectrode on the surface of an insulating substrate: after a layer of thin adhesive is coated on the surface of an insulating substrate, a layer of copper foil with the thickness of 15 mu m is adhered on the surface of the insulating substrate, so that an electrode conducting layer is ensured to be stably attached on the surface of the insulating substrate, and an interdigital electrode with the gap of 100 mu m is manufactured to be used as a conducting microelectrode by adopting a mask etching method;
(3) Depositing a palladium cluster film between the conductive microelectrodes: generating stable palladium cluster beam current by adopting a magnetic control plasma gas aggregation method, depositing the stable palladium cluster beam current into gaps of the interdigital conductive microelectrodes, and measuring the resistance between the conductive microelectrodes in real time in the deposition process until the palladium cluster film resistance reaches a preset value, wherein the preset value is 1MΩ; the evolution curve of the palladium cluster film resistance along with the deposition time is shown in fig. 3, a micrograph of the palladium cluster film is shown in fig. 4, the average cluster particle diameter is 5nm, the average nearest neighbor distance between palladium clusters is 1nm, and the coverage rate of the palladium cluster film is 44.56%;
(4) Placing the insulating substrate on which the palladium cluster film is deposited in a sealed cavity, respectively connecting the conductive microelectrode with one end of the wiring terminal, which is positioned in the sealed cavity, with the wiring terminal, and connecting one end of the wiring terminal, which is positioned outside the sealed cavity, with an external circuit by using the wiring terminal, so as to realize real-time monitoring of the macroscopic resistance of the palladium cluster film by the external circuit; during connection, two ends of an enameled wire with the diameter of 50 mu m are respectively welded at the inner end of a connecting terminal cavity and the pin of an interdigital conductive microelectrode in a sealed cavity; outside the sealed cavity, connecting an external circuit with the outer end of the connecting terminal cavity by using a BNC-crocodile clip cable;
(5) Assembling the drying unit, namely clamping the mounting part of the drying tank body in the connecting through hole on the side wall of the sealing cavity, and communicating the drying unit with the sealing cavity to obtain the assembled hydrogen sensor;
(6) The assembled hydrogen sensor is sequentially placed in an air environment with hydrogen concentration of 1000ppm, 2000ppm, 3000ppm, 5000ppm, 10000ppm and 12000ppm, the resistance change of the palladium cluster film is measured in real time through an electric signal measuring device in an external circuit, as shown in fig. 5, the average value of the resistance at different hydrogen concentrations is taken as a response resistance value, the average value of the resistance of the palladium cluster film before each section of hydrogen response is taken as a common resistance value, and the relative resistance change is obtained according to calculation:
drawing a calibration curve corresponding to different hydrogen concentrations one by one, and fitting the calibration curve through polynomials to obtain the following calibration relations: hydrogen concentration=1.43×10 6 X (relative resistance change) 2 +20253×relative resistance change
Inputting the hydrogen sensor into a programmable and visual output device in an external circuit to finish the calibration of the hydrogen sensor;
(7) The calibrated hydrogen sensor is placed in an air environment to be tested, and the hydrogen concentration is read through a programmable and visual output device in an external circuit; the change in resistance of the palladium cluster film is shown in fig. 7, with the relative resistance change being about 0.065797, the response being initiated within about 1 second, the equilibrium being reached within about 10 seconds, and the hydrogen concentration in the current environment being sensed from the programmable and visual output device display being about 8000ppm.
Example 2:
when the palladium cluster film is deposited in the step (3) of example 2, the preset resistance value is 50kΩ, and the coverage rate of the palladium cluster film is 85%; the average cluster particle diameter was 7nm, and the average nearest neighbor distance between palladium clusters was 0.5nm, and the rest was the same as in example 1.
Example 3:
when the palladium cluster film is deposited in the step (3) of example 3, the preset resistance value is 15mΩ, and the coverage rate of the palladium cluster film is 34%; the average cluster particle diameter was 9nm, and the average nearest neighbor distance between palladium clusters was 3nm, and the rest was the same as in example 1.
The sensitivity of the hydrogen sensors in example 2 and example 3 was tested to obtain the fitting curve results shown in fig. 8 and 9.
Wherein the response curve fitting formula of the hydrogen sensor prepared in example 2 is:
hydrogen concentration=2.95×10 5 X (relative resistance change) 2 5769 x relative resistance change.
The response curve fitting formula for the hydrogen sensor prepared in example 3 is:
hydrogen concentration=15011× (relative resistance change) 2 +11576 x relative resistance change.
Examples 1-3 differ in sensitivity to demonstrate that coverage of the palladium cluster thin film, average cluster particle size, average nearest neighbor distance between palladium clusters has an effect on the sensitivity of the sensor.
Claims (8)
1. A high-sensitivity hydrogen sensor used in an air environment, which is characterized by comprising a drying unit (7), a sensing unit and an external circuit (6); the sensing unit comprises a sealing cavity (1) and a sensing assembly arranged in the sealing cavity, wherein the sensing assembly comprises an insulating substrate (2) arranged at the bottom of the sealing cavity, a palladium cluster film (3) arranged on the upper surface of the insulating substrate and two conductive microelectrodes (4) arranged at two ends of the palladium cluster film, two wiring terminals (5) are arranged on the sealing cavity, one end of each wiring terminal is positioned outside the sealing cavity, one end of each wiring terminal is positioned inside the sealing cavity and is connected with the conductive microelectrode through a wire, and one end of each wiring terminal is positioned outside the sealing cavity and is connected with an external circuit through a wire; the sealed cavity is communicated with a drying unit, and an air inlet is arranged on the drying unit;
the diameter distribution of palladium clusters in the palladium cluster film is 1-10 nm, the average nearest neighbor distance between the palladium clusters is 0.5-5 nm, and the transmission mode of electrons among the clusters in the palladium cluster film is quantized tunneling jump;
the drying unit is used for absorbing the original water vapor in the mixed gas to be detected, so that the interference to the subsequent detection is avoided; after the mixed gas is diffused into the sealed cavity, hydrogen molecules and oxygen molecules are adsorbed on the surfaces of the palladium cluster films, at the moment, bias voltage is applied to two sides of the conductive microelectrodes through a power supply in an external circuit, electrons of the palladium clusters d in the films are excited to a higher energy level under the action of the bias voltage, the hydrogen molecules and the oxygen molecules are dissociated into active hydrogen atoms and active oxygen atoms respectively, then water molecules are catalytically synthesized, the generated water molecules belong to purified water and are enriched on the surfaces of the palladium clusters and filled between the clusters, so that tunneling resistance of electron transmission is enhanced, and macroscopic resistance of the palladium cluster films is increased;
the preparation method of the high-sensitivity hydrogen sensor comprises the following steps:
(1) Preparing an insulating substrate;
(2) Printing a conductive microelectrode on the surface of an insulating substrate;
(3) Depositing a palladium cluster film between the conductive microelectrodes;
(4) Placing the insulating substrate with the deposited palladium cluster film in a sealed cavity, respectively connecting the conductive microelectrode with one end of the wiring terminal, which is positioned in the sealed cavity, by using a wire, and connecting one end of the wiring terminal, which is positioned outside the sealed cavity, with an external circuit by using the wire;
(5) Assembling a drying unit, and communicating the drying unit with the sealed cavity to obtain the assembled hydrogen sensor;
(6) Placing the assembled hydrogen sensor in hydrogen environments with different concentrations, recording macroscopic resistance changes of the palladium cluster film in the hydrogen environments with different concentrations through an external circuit, fitting a response relation, and inputting the response relation into the external circuit to finish the calibration of the hydrogen sensor;
(7) And placing the calibrated hydrogen sensor in an air environment to be measured, and measuring the hydrogen concentration through an external circuit.
2. A high sensitivity hydrogen sensor for use in an air environment according to claim 1, wherein said insulating substrate is of a material selected from the group consisting of flexible and rigidInsulating material, insulating substrate stable resistivity not less than 10 9 Omega, m; the flexible insulating material is selected from one of polyimide, polydimethylsiloxane and polyethylene terephthalate; the rigid insulating material is selected from one of quartz, glass, ruby, sapphire, resin and monocrystalline silicon piece with silicon oxide insulating layer.
3. The high-sensitivity hydrogen sensor for air environment according to claim 1, wherein the conductive microelectrode is in the shape of an interdigital electrode or a spiral electrode, the thickness of the conductive microelectrode is 50 nm-10 μm, and the distance between two conductive microelectrodes is 2-100 μm.
4. A highly sensitive hydrogen sensor for use in an air environment according to claim 1 or 3, wherein the conductive microelectrode is made of a material selected from the group consisting of gold, silver, copper, iron, aluminum and indium tin oxide.
5. The high-sensitivity hydrogen sensor for use in an air environment according to claim 1, wherein the coverage of the palladium cluster film is 30-95%, and the resistance of the palladium cluster film is 50k Ω -1 gΩ.
6. A high sensitivity hydrogen sensor for use in an air environment according to claim 1, wherein the external circuit comprises a power supply connected by a wire, an electrical signal measuring device, and a programmable and visual output device capable of converting the measured electrical signal into a hydrogen concentration signal and visually outputting and displaying.
7. The high-sensitivity hydrogen sensor for air environment according to claim 1, wherein the drying unit comprises a drying tank body and a drying agent arranged in the drying tank body, a plurality of air inlets are arranged on the drying tank body, and the drying tank body is communicated with the sealing cavity.
8. The high sensitivity hydrogen sensor according to claim 1, wherein the palladium cluster film in step (3) is deposited by nano-printing, physical vapor deposition, chemical vapor deposition or block self-assembly.
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