CN115615965B - Hydrogen sensor, preparation method thereof and method for detecting hydrogen concentration - Google Patents
Hydrogen sensor, preparation method thereof and method for detecting hydrogen concentration Download PDFInfo
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- CN115615965B CN115615965B CN202211437009.XA CN202211437009A CN115615965B CN 115615965 B CN115615965 B CN 115615965B CN 202211437009 A CN202211437009 A CN 202211437009A CN 115615965 B CN115615965 B CN 115615965B
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/59—Transmissivity
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Abstract
The invention belongs to the technical field of sensors, and particularly relates to a hydrogen sensor, a preparation method of the hydrogen sensor and a method for detecting hydrogen concentration. The invention provides a hydrogen sensor, which comprises a laminated substrate, a sensitive unit and a protective film layer; the sensitive unit is a palladium-gold alloy nano array; the molar percentage content of gold in the palladium-gold alloy is 30 to 40 percent; the nano array consists of a plurality of array units which are orderly arranged, and the cross section area of a single array unit is 0.0078 to 0.65 mu m 2 (ii) a The nanometer isThe distance between two adjacent array units in the array is 300 to 1000nm. The method selects the palladium-gold alloy with specific components as the material of the sensitive unit, simultaneously limits the sensitive unit to be the palladium-gold alloy nano array, eliminates the memory effect when the palladium-based material is used for hydrogen sensing, and can quickly and accurately obtain the hydrogen concentration by measuring the light transmittance by using the hydrogen sensor provided by the invention.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a hydrogen sensor, a preparation method thereof and a method for detecting hydrogen concentration.
Background
Hydrogen is an important chemical raw material and a potential energy carrier, is colorless, tasteless, inflammable and explosive, has a wide explosion limit range in air (4 to 75 percent by vol), and therefore, the hydrogen concentration in the environment needs to be monitored in real time in the production, storage and use processes of the hydrogen, and the hydrogen leakage is prevented from causing explosion risks.
Conventional hydrogen sensors mainly include electrochemical sensors, semiconductor-type metal oxide (MOx) sensors, metal-oxide-type (MOS) semiconductor sensors, thermal conductivity sensors, and catalytic combustion sensors. The traditional hydrogen sensor can convert the hydrogen concentration into electrical signals of a sensitive unit, such as voltage, resistance and the like, is very convenient for subsequent signal transmission, processing and output, but is easily interfered in a radiation environment, and meanwhile, the hydrogen response selectivity is weak, and the detection result accuracy is poor.
In order to improve the accuracy of the detection result of the hydrogen sensor, a class of optical hydrogen sensors is researched and developed, and the sensitive units of the optical hydrogen sensors are made of palladium and palladium alloy. The optical hydrogen sensor has strong interaction with hydrogen at room temperature, and can realize the detection of the hydrogen concentration by detecting the reflectivity, the transmittance and the surface plasmon resonance characteristic of the optical hydrogen sensor or some characteristics of a carrier (such as an optical fiber waveguide) of a sensitive unit. The response of palladium and palladium alloy is based on the process of absorbing and releasing hydrogen, so that the selectivity is high, the response process only involves the introduction and extraction of light, the optical hydrogen sensor has strong anti-interference capability, and the detection result accuracy is high. However, the hydrogen absorption and desorption processes of the existing palladium and palladium alloy (palladium-silver alloy, palladium-copper-silicon alloy, palladium-nickel alloy, palladium-yttrium alloy and the like) used as sensitive unit materials are not completely reversible, so that a memory effect is generated, and the repeatability of optical hydrogen sensing is poor.
Disclosure of Invention
In view of the above, the invention provides a hydrogen sensor, a preparation method thereof and a method for detecting hydrogen concentration, and the palladium-gold alloy nanoarray in the hydrogen sensor provided by the invention does not generate a memory effect in the process of absorbing and releasing hydrogen, and can continuously and accurately detect the hydrogen concentration in a gas sample to be detected.
In order to solve the above technical problems, the present invention provides a hydrogen sensor comprising a stacked substrate, a sensing unit and a protective film layer;
the sensitive unit is a palladium-gold alloy nano array; the molar percentage content of gold in the palladium-gold alloy is 30 to 40 percent; the nano array consists of a plurality of array units which are orderly arranged, and the cross section area of a single array unit is 0.0078 to 0.65 mu m 2 (ii) a The distance between two adjacent array units in the nano array is 300 to 1000nm.
Preferably, the protective film layer includes a polymethylmethacrylate film or a polytetrafluoroethylene film.
Preferably, the thickness of the protective film layer is 10 to 50nm.
Preferably, the height of the array unit is 15 to 40nm;
the shape of the array unit comprises a cylinder or a prism.
Preferably, the substrate is a hard transparent material;
the thickness of the substrate is 0.3-1mm.
The invention also provides a preparation method of the hydrogen sensor in the technical scheme, which comprises the following steps:
etching the surface of the substrate to obtain the substrate containing the nano-array template;
depositing a gold film layer and a palladium film layer on the surface of the nano array template to obtain a substrate attached with gold-palladium;
alloying the substrate attached with the gold-palladium to obtain a primary hydrogen sensor;
and arranging a protective film layer on the surface of the primary hydrogen sensor to obtain the hydrogen sensor.
Preferably, the etching comprises photolithography or electron beam etching.
Preferably, the alloying is to perform annealing treatment on the substrate attached with the gold-palladium, wherein the temperature of the annealing treatment is 330 to 370 ℃, and the heat preservation time of the annealing treatment is 11 to 13h.
Preferably, the deposition method comprises electron beam evaporation deposition, magnetron sputtering deposition or pulsed laser deposition.
The invention also provides a method for detecting the hydrogen concentration, which comprises the following steps:
placing a hydrogen sensor and a gas sample to be detected in a closed space, introducing light beams from any side of the hydrogen sensor, detecting the emergent light power penetrating through the hydrogen sensor, and calculating to obtain the light transmittance to be detected; the hydrogen sensor is the hydrogen sensor in the technical scheme or the hydrogen sensor prepared by the preparation method in the technical scheme;
substituting the light transmittance to be measured into a standard curve, and calculating to obtain the pressure of hydrogen in the gas sample to be measured; the standard curve is a relation curve of light transmittance and hydrogen pressure in a standard gas sample;
and calculating the concentration of the hydrogen in the gas sample to be detected according to the pressure of the hydrogen in the gas sample to be detected.
The invention provides a hydrogen sensor, which comprises a laminated substrate, a sensitive unit and a protective film layer; the sensitive unit is a palladium-gold alloy nano array; the molar percentage content of gold in the palladium-gold alloy is 30 to 40 percent; the nano array consists of a plurality of array units which are orderly arranged, and the cross section area of a single array unit is 0.0078 to 0.65 mu m 2 (ii) a The distance between two adjacent array units in the nano array is 300 to 1000nm. In the present invention, the reduction in the formation of an alloy of palladium and gold is achievedThe bonding strength with hydrogen is improved, and the nano structure has a larger specific surface area. In the invention, the palladium-gold alloy eliminates the difference between the activation energy of the hydrogen absorption and the hydrogen desorption processes, can realize completely reversible hydrogen absorption and desorption, and eliminates the memory effect. According to the invention, the palladium-gold alloy with specific components is selected as the material of the sensitive unit, and the sensitive unit is defined as the palladium-gold alloy nano array, so that the memory effect during sensing of the hydrogen sensor is eliminated, and the hydrogen concentration can be rapidly and accurately obtained by measuring the light transmittance of the hydrogen sensor.
Drawings
FIG. 1 is an atomic force microscope image of a sensitive unit of a hydrogen sensor prepared in example 1;
FIG. 2 shows that the pressure ranges of the hydrogen sensors prepared in examples 1 to 2 and comparative examples 1 to 3 are 40 to 10 5 A light transmittance curve chart when primary hydrogen absorption and desorption circulation detection is carried out in a Pa hydrogen environment;
fig. 3 is a graph showing the response of the hydrogen sensor prepared in example 1 to a standard gas with a low hydrogen pressure, in which (a) is a graph showing the light transmittance at different times during the detection process, and (b) is a histogram showing the hydrogen pressure at different times during the detection process;
FIG. 4 is a point line graph showing response times of the hydrogen sensor prepared in example 1 to standard gases of different hydrogen pressures;
fig. 5 is a point line graph showing recovery times of the hydrogen sensor prepared in example 1 for standard gases of different hydrogen pressures.
Detailed Description
The invention provides a hydrogen sensor which comprises a laminated substrate, a sensitive unit and a protective film layer.
In the present invention, the substrate is preferably a hard transparent material; the hard transparent material preferably comprises quartz or glass, more preferably quartz. In the present invention, the quartz is preferably a quartz wafer. In the present invention, the hard transparent material is transparent to visible light and near infrared light.
In the present invention, the thickness of the substrate is preferably 0.3 to 1mm, and more preferably 0.5 to 0.8mm.
The size and the shape of the substrate are not specially limited, and the substrate can be set according to the actual requirement of the hydrogen sensor.
In the invention, the sensitive unit is a nano array of palladium-gold alloy; the molar percentage of gold in the palladium-gold alloy is 30 to 40 percent, and preferably 33 to 36 percent. In the present invention, the nano-array is composed of a plurality of array units arranged in an ordered manner, and the shape of the array units preferably includes a cylinder or a prism, and more preferably a cylinder. In the invention, the diameter of the cross section of the cylinder is preferably 100 to 500nm, and more preferably 200 to 300nm. In the invention, the cross-sectional area of a single array unit is 0.0078 to 0.65 mu m 2 Preferably 0.03 to 0.24 μm 2 (ii) a The distance between two adjacent array units is 300 to 1000nm, and preferably 400 to 600nm.
In the invention, the height of the array unit is preferably 15 to 40nm, and more preferably 25 to 35nm.
In the invention, the nano arrays of the palladium-gold alloy are spaced, and the palladium-gold alloy only covers part of the substrate area, so that enough light can be transmitted, and the detection of optical signals is facilitated.
In the present invention, the protective film layer preferably includes a polymethyl methacrylate film or a polytetrafluoroethylene film, more preferably a polymethyl methacrylate film; the thickness of the protective film layer is preferably 10 to 50nm, more preferably 20 to 40nm, and still more preferably 30nm.
In the invention, the protective film layer has selective permeability to hydrogen, can prevent other gases from interfering the hydrogen sensor, and avoids the other gases from influencing the sensitive unit, thereby improving the detection accuracy of the hydrogen sensor.
The invention also provides a preparation method of the hydrogen sensor in the technical scheme, which comprises the following steps:
etching the surface of the substrate to obtain the substrate containing the nano-array template;
depositing a gold film layer and a palladium film layer on the surface of the nano-array template to obtain a substrate attached with gold-palladium;
alloying the substrate attached with the gold-palladium to obtain a primary hydrogen sensor;
and arranging a protective film layer on the surface of the primary hydrogen sensor to obtain the hydrogen sensor.
The invention etches on the surface of the substrate to obtain the substrate containing the nano-array template. In the present invention, the etching preferably includes photolithography or electron beam etching, and more preferably photolithography. In the invention, the photoetching is preferably holographic ultraviolet photoetching. In the present invention, the holographic ultraviolet etching process preferably further comprises the following steps:
and sequentially coating an anti-reflection layer and photoresist on the surface of the substrate, performing holographic ultraviolet light etching, and then sequentially performing development and fixation to obtain the substrate containing the nano-array template.
In the present invention, the coating preferably further comprises: the substrate is cleaned. In the present invention, the cleaning is preferably oxygen plasma cleaning. In the invention, the flow rate of the oxygen for oxygen plasma cleaning is preferably 500 to 700sccm, and more preferably 600sccm; the power of the oxygen plasma cleaning is preferably 550 to 650W, and more preferably 600W; the time for cleaning the oxygen plasma is preferably 8 to 12min, and more preferably 10min.
In the present invention, the anti-reflection layer is preferably an AZ BARLI-II anti-reflection layer. In the present invention, the photoresist is preferably an Ultra-i-123-0.8 photoresist. In the present invention, the coating is preferably spin coating. In the invention, the thickness of the anti-reflection layer is preferably 180 to 220nm, and more preferably 200nm; the thickness of the photoresist is preferably 680 to 720nm, and more preferably 700nm.
In the invention, the rotation speed of the spin coating of the anti-reflection layer is preferably 3500 to 4500r/min, and more preferably 4000r/min. After the anti-reflection layer is coated in a spinning mode, the anti-reflection layer is preferably baked, wherein the baking temperature is preferably 160 to 200 ℃, and more preferably 180 ℃; the baking time is preferably 50 to 70s, and more preferably 60s. In the present invention, the baking is preferably performed on a hot plate.
In the invention, the rotation speed of the spin-coating photoresist is preferably 3500 to 4500r/min, and more preferably 4000r/min. The photoresist is preferably baked after being spin-coated, and the baking temperature is preferably 85 to 95 ℃, and more preferably 90 ℃; the baking time is preferably 1.2 to 1.7min, and more preferably 1.5min. In the present invention, the baking is preferably performed on a hot plate.
In the invention, the equipment adopted by the holographic ultraviolet lithography is preferably Eulitha PhableR 100S equipment, the wavelength of the light source for holographic ultraviolet lithography is preferably 377nm, and the light intensity of the light source for holographic ultraviolet lithography is preferably 2mW/cm 2 (ii) a The exposure time of the holographic ultraviolet photoetching is preferably 35s.
The present invention has no particular requirement for the development and fixing, and may be carried out in a manner conventional in the art.
In the invention, the shape and the size of the nano array template are consistent with those of the palladium-gold alloy nano array. The method adopts holographic ultraviolet light etching, can improve the accuracy of the size of the palladium-gold alloy nano array, and can realize large-area and batch preparation.
After the substrate containing the nano-array template is obtained, the invention deposits a gold film layer and a palladium film layer on the surface of the nano-array template to obtain the substrate attached with gold-palladium. In the invention, the thicknesses of the gold film layer and the palladium film layer are set according to the molar percentage content ratio of palladium to gold in the palladium-gold alloy. In the present invention, the deposition method preferably includes electron beam evaporation deposition, magnetron sputtering deposition, or pulsed laser deposition, and more preferably electron beam evaporation deposition. The invention has no special requirements on the electron beam evaporation deposition and can adopt a conventional mode in the field.
After the substrate with the gold-palladium is obtained, the substrate with the gold-palladium is alloyed to obtain the primary hydrogen sensor. The invention preferably further comprises, before alloying: and stripping the photoresist and the gold film layer and the palladium film layer which cover the surface of the photoresist, and then removing the anti-reflection layer except the gold-palladium nano array. The present invention is not particularly limited to the manner of peeling, and may be performed in a manner conventional in the art. In the present invention, the method of removing the anti-reflection layer is preferably oxygen plasma dry etching. In the invention, the flow rate of the oxygen for the oxygen plasma dry etching is preferably 45 to 55sccm, and more preferably 50sccm; the power of the oxygen plasma dry etching is preferably 25 to 35W, and more preferably 30W; the time of the oxygen plasma dry etching is preferably 18 to 22s, and more preferably 20s.
In the present invention, the alloying is preferably to anneal the substrate to which gold-palladium is attached; the temperature of the annealing treatment is preferably 330 to 370 ℃, and more preferably 350 ℃; the heat preservation time of the annealing treatment is preferably 11 to 13h, and more preferably 12h.
After the primary hydrogen sensor is obtained, the surface of the primary hydrogen sensor is provided with a protective film layer to obtain the hydrogen sensor. In the present invention, when the protection film layer is a polymethyl methacrylate film, the present invention preferably spin-coats a polymethyl methacrylate solution on the surface of the primary hydrogen sensor to obtain the polymethyl methacrylate film. In the present invention, the polymethyl methacrylate solution is preferably prepared according to the following method: and dissolving polymethyl methacrylate in an organic solvent to obtain the polymethyl methacrylate solution. In the present invention, the organic solvent preferably includes chlorobenzene, anisole or ethyl lactate, more preferably anisole. In the present invention, the mass percentage content of the polymethyl methacrylate solution is preferably 0.8 to 1.2%, and more preferably 1%. In the invention, the rotation speed of the spin coating is preferably 2000 to 6000r/min, and more preferably 4000r/min. In the present invention, after the spin coating, it is preferable to further include: baking the spin-coated product, wherein the baking temperature is preferably 140-160 ℃, and more preferably 150 ℃; the baking time is preferably 170 to 190s, and more preferably 180s. In the present invention, the baking is preferably performed on a hot plate.
In the invention, when the protective film layer is a polytetrafluoroethylene film, magnetron sputtering deposition is preferably carried out on the surface of the primary hydrogen sensor to obtain the polytetrafluoroethylene film. In the invention, the target material for magnetron sputtering deposition is polytetrafluoroethylene. The invention has no special requirements on the magnetron sputtering deposition and can be carried out by adopting a conventional mode in the field.
The preparation method provided by the invention can be used for producing the hydrogen sensor in batches.
The invention also provides a method for detecting the hydrogen concentration, which comprises the following steps:
placing a hydrogen sensor and a gas sample to be detected in a closed space, and introducing light beams into any side of the hydrogen sensor to obtain the light transmittance to be detected; the hydrogen sensor is the hydrogen sensor in the technical scheme or the hydrogen sensor prepared by the preparation method in the technical scheme;
substituting the light transmittance to be measured into a standard curve, and calculating to obtain the pressure of hydrogen in the gas sample to be measured; the standard curve is a relation curve of light transmittance and hydrogen pressure in a standard gas sample;
and calculating the concentration of the hydrogen in the gas sample to be detected according to the pressure of the hydrogen in the gas sample to be detected.
According to the invention, a hydrogen sensor and a gas sample to be measured are arranged in a closed space, light beams are introduced from any side of the hydrogen sensor, the emergent light power penetrating through the hydrogen sensor is detected, and the light transmittance to be measured is calculated; the hydrogen sensor is the hydrogen sensor in the technical scheme or the hydrogen sensor prepared by the preparation method in the technical scheme. In the invention, the closed space is provided with a window for leading in and leading out light. In the present invention, the light beam is preferably provided by a light source, which preferably comprises an LED light source or a white light source, more preferably an LED light source. In the present invention, the white light source preferably includes a tungsten lamp light source or a xenon lamp light source. In the present invention, the power of the LED light source is preferably 2 to 20mw, and more preferably 10mW. In the present invention, the wavelength of the light beam is preferably 700 to 800nm, and more preferably 750 to 780nm.
The present invention preferably utilizes a silicon-based diode optical power detector to detect optical power; the corresponding range of the silicon-based diode optical power detector is preferably 400-1100 nm, the detection range is preferably 1nW-20mW, and the sensitivity is not less than 10mA/W.
In the invention, the method for calculating the light transmittance to be measured comprises the following steps:
detecting the optical power of the closed space without the light beam passing through and recording as a noise signal;
detecting the optical power of the light beam directly passing through the closed space, and recording as a reference signal;
recording the emergent light power penetrating through the hydrogen sensor as a working signal;
according to equation 1: light transmittance to be measured = (working signal-noise signal)/(reference signal-noise signal) calculate light transmittance to be measured.
In the invention, the performance parameters of the light beam used for obtaining the reference signal are consistent with the performance parameters of the light beam used for obtaining the working signal.
After the light transmittance to be measured is obtained, substituting the light transmittance to be measured into a standard curve, and calculating to obtain the pressure of hydrogen in the gas sample to be measured; the standard curve is a relation curve of light transmittance and hydrogen pressure in the standard gas sample. In the present invention, the standard curve is preferably obtained as follows:
placing a hydrogen sensor and standard gas samples with different hydrogen pressures in a closed space, introducing light beams into any side of the hydrogen sensor, detecting emergent light power penetrating through the hydrogen sensor, and respectively calculating to obtain standard light transmittance; the hydrogen sensor is the hydrogen sensor in the technical scheme or the hydrogen sensor prepared by the preparation method in the technical scheme;
and establishing a relation curve of the standard light transmittance and the hydrogen pressure in the standard gas sample to obtain a standard curve.
In the invention, the pressure of hydrogen in the standard gas sample is preferably 40Pa to 10 5 Pa。
The method for calculating the standard light transmittance is preferably consistent with the method for calculating the light transmittance to be measured.
The method has no special requirement on the mode of establishing the relation curve of the standard light transmittance and the hydrogen pressure in the standard gas sample, and can be realized by adopting the conventional mode in the field.
After the pressure of the hydrogen in the gas sample to be detected is obtained, the concentration of the hydrogen in the gas sample to be detected is calculated according to the pressure of the hydrogen in the gas sample to be detected. The invention has no special requirement on the calculation method, and the conventional calculation method in the field can be adopted.
The hydrogen sensor provided by the invention has high selective responsiveness to hydrogen, the sensitive unit in the sensor adopts a palladium-gold alloy nano array, the sensor has the property of reversible hydrogen absorption and desorption, and meanwhile, in order to avoid surface poisoning and performance reduction possibly caused by other gases to the sensitive unit, the surface of the sensitive unit is covered with a layer of polymer protective film which can selectively permeate the hydrogen and simultaneously block other gases. The hydrogen sensor provided by the invention has a wide response range, and the pressure range of the hydrogen sensor to hydrogen is 40Pa to 10 5 Pa of gas to be measured all respond.
The hydrogen sensor provided by the invention has no memory effect, and the sensitive unit is made of palladium-gold alloy materials, and the hydrogen absorption and desorption curves of the sensitive unit are basically overlapped, so that the hydrogen sensor is different from other hydrogen sensors based on palladium materials, and has no memory effect on the response of hydrogen.
The hydrogen response basis of the hydrogen sensor provided by the invention is a reversible hydrogen absorption and desorption process of the palladium-gold alloy nano array, so that oxygen or air is not required to participate in the detection process, and the hydrogen sensor is suitable for certain closed, oxygen-free or hypoxic environments.
The hydrogen sensor provided by the invention realizes the detection of the hydrogen concentration by detecting the transmittance of the palladium-gold alloy nano array to light with specific wavelength, avoids the introduction of electric signals, and is suitable for hydrogen sensing in a radiation environment.
The sensitive unit palladium-gold alloy nano array of the hydrogen sensor can be manufactured in batch by the conventional semiconductor manufacturing technology, and in addition, a light source and an optical power detector for detection can be selected from commercially available mature products, so that the manufacturing cost of the sensor is lower.
In order to further illustrate the present invention, the following technical solutions provided by the present invention are described in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Using oxygen plasmaCleaning (oxygen flow of 600sccm, power of 600W, time of 10 min) the quartz wafer; spin-coating an anti-reflection layer AZ BARLi-II on the surface of the cleaned quartz wafer at the rotating speed of 4000r/min, and baking the quartz wafer on a heating plate at 180 ℃ for 1min after spin-coating to obtain an anti-reflection layer film with the thickness of 200nm; spin-coating photoresist Ultra-i-123-0.8 on the surface of the anti-reflection layer film at the rotating speed of 4000r/min, and baking the anti-reflection layer film for 1.5min at 90 ℃ on a heating plate after spin-coating to obtain a photoresist layer with the thickness of 700 nm; holographic UV lithography (light source wavelength 377nm, light intensity 2 mW/cm) of spin-coated antireflective and photoresist layers substrates using a Eulitha PhableR 100S equipment system 2 Exposure time is 35 s), baking at 120 ℃ for 1.5min, and developing for 1min by using AZ 300MIF developing solution; washing and fixing with deionized water after developing to generate a nanometer circular hole array (the diameter of the circular hole is 300nm, and the distance between two adjacent circular holes is 600 nm) to obtain a substrate containing a nanometer circular hole array template;
sequentially performing electron beam evaporation deposition on a gold film with the thickness of 10nm and a palladium film with the thickness of 15nm in the nano round hole array template at the deposition rate of 0.3A/s, and soaking in acetone for 12h to strip the photoresist layer and the gold film layer and the palladium film layer covering the photoresist layer, thereby obtaining a substrate attached with gold-palladium;
performing oxygen plasma dry etching on the substrate attached with the gold-palladium under the conditions that the oxygen flow is 50sccm and the power is 30W for 20s to remove the anti-reflection layer outside the nano circular hole array, and then annealing at 350 ℃ for 12h to alloy the gold and the palladium (the molar percentage content of the gold in the palladium-gold alloy is 36%) to obtain a primary hydrogen sensor; the height of a single cylinder in the palladium-gold alloy nanometer circular hole array in the primary hydrogen sensor is 25nm;
spin-coating 1% polymethyl methacrylate anisole solution on the surface of the primary hydrogen sensor at the rotating speed of 4000r/min, baking the primary hydrogen sensor on a heating plate at 150 ℃ for 180s to form a protective film with the thickness of 30nm, and cutting the baked product into square samples of 9mm multiplied by 9mm according to actual needs to obtain the hydrogen sensor.
The surface of the hydrogen sensor prepared in example 1 was examined by an atomic force microscope to obtain a picture of a sensitive cell atomic force microscope, as shown in fig. 1. It can be seen from fig. 1 that the palladium-gold alloy cylindrical nanoarrays have uniform diameter, height and periodic distribution.
Example 2
A hydrogen sensor was fabricated according to the method of example 1, except that the thickness of the deposited gold film was 8nm, the thickness of the deposited palladium was 16nm, and the molar percentage of gold in the palladium-gold alloy of the palladium-gold alloy nanoarray was 30%.
Comparative example 1
A hydrogen sensor was prepared according to the method of example 1, except that palladium was deposited without depositing gold and with a deposition thickness of 25nm.
Comparative example 2
A hydrogen sensor was fabricated according to the method of example 1, except that the thickness of the deposited gold film was 7.2nm, the thickness of the deposited palladium was 17.8nm, and the molar percentage of gold in the palladium-gold alloy of the palladium-gold alloy nanoarray was 26%.
Comparative example 3
A hydrogen sensor was fabricated according to the method of example 1, except that the thickness of the deposited gold film was 6.2nm, the thickness of the deposited palladium was 18.8nm, and the molar percentage of gold in the palladium-gold alloy of the palladium-gold alloy nanoarray was 22%.
Detecting a gas sample to be detected by using the hydrogen sensors prepared in the examples 1 to 2 and the comparative examples 1 to 3; the detection device used for detection comprises a closed chamber, wherein the upper surface and the lower surface of the closed chamber are provided with transparent windows, the transparent windows are connected with optical fibers, the upper optical fibers are connected with an LED light source (the power is 10mW, and the wavelength of a light beam is 780 nm), and the lower optical fibers are connected with a silicon-based diode light power detector; the left side and the right side of the closed chamber are connected with an air inlet pipe and an air outlet pipe, and the gas to be measured enters the closed chamber through the air inlet pipe. The hydrogen sensor is arranged at the center above the window on the lower bottom surface, and the plane of the sensitive unit is parallel to the plane of the window;
detecting the optical power of the closed space without the light beam passing through and recording as a noise signal;
introducing an LED light source with the power of 10mW and the light beam wavelength of 780nm into the closed space, and detecting the light power of the light beam directly passing through the closed space and recording as a reference signal;
respectively introducing standard hydrogen samples with different pressures into the closed space, detecting the emergent light power penetrating through the hydrogen sensor, and recording as a working signal; the pressure of hydrogen in the standard hydrogen sample is gradually increased to 100000Pa along 40Pa and then gradually decreased to 40Pa; wherein for comparative examples 1 to 3, the hydrogen pressure increased from 100Pa and finally decreased to 100Pa;
according to equation 2: the standard light transmittance = (working signal-noise signal)/(reference signal-noise signal) calculates the standard light transmittance, and establishes a relation curve between the standard light transmittance and the hydrogen pressure in the standard gas sample to obtain a standard curve, as shown in fig. 2, and specific point values in the standard curve are listed in table 1.
Introducing a gas sample to be measured into the closed space containing the hydrogen sensor, and calculating according to a formula 1 to obtain the light transmittance to be measured; and substituting the light transmittance to be measured into the corresponding standard curve to obtain the hydrogen pressure of the gas sample to be measured.
TABLE 1 Point values of standard curves obtained in examples 1 to 2 and comparative examples 1 to 3
It can be seen from table 1 and fig. 2 that the light transmittance of the hydrogen sensor increases nonlinearly with the increase of the hydrogen pressure, the hysteresis of the palladium-gold alloy in the hydrogen absorption and desorption process is significantly suppressed with the doping of gold, and the hysteresis is completely eliminated for examples 1 to 2. The hydrogen sensor provided by the invention eliminates the memory effect during sensing.
Introducing a gas sample to be measured into the closed space containing the hydrogen sensor prepared in the embodiment 1, and calculating according to a formula 1 to obtain the light transmittance to be measured; the light transmittance to be measured was substituted into the standard curve of example 1 to obtain the hydrogen pressure of the gas sample to be measured, and the results are shown in table 2.
Table 2 results of measuring light transmittance of gas to be measured using hydrogen sensor of example 1
| Light transmittance (%) | 63．27349 | 63.37928 | 63.85022 | 64.89216 | 65.33592 | 65.53837 | 65.65021 | 65.78859 | 66.02377 |
| Hydrogen pressure (Pa) | 40.3 | 101.2 | 496 | 1010 | 1990 | 4990 | 10100 | 39900 | 99000 |
The response performance of the hydrogen sensor prepared in example 1 to a standard gas sample with low hydrogen pressure is detected, and a response performance curve diagram of the hydrogen sensor to a gas to be detected with low hydrogen pressure is obtained as shown in fig. 3, in which (a) is a curve diagram of light transmittance at different times in the detection process, and (b) is a histogram of hydrogen pressure at different times in the detection process. It can be seen from fig. 3 that as the hydrogen pressure is gradually reduced from 2000Pa to 40Pa, the light transmittance of example 1 is gradually reduced, and example 1 still responds to 40Pa hydrogen compared to the case of no hydrogen (background pressure is 4 Pa), indicating that the lower limit of detection of hydrogen obtained under the existing conditions is 40Pa.
The response time of the hydrogen sensor prepared in example 1 to standard gas samples of different hydrogen pressures was measured, and the results are shown in fig. 4; wherein t is 90 In response to hydrogen gas, the time required for the light transmittance to increase by 90% of the maximum increase range was obtained. The recovery time of the hydrogen sensor prepared in example 1 for the standard gas samples having different hydrogen pressures was measured, and the results are shown in fig. 5; wherein, t 10 The time required for the light transmittance to decrease by 90% of the maximum decrease range is required for the hydrogen-free state to be recovered. FIG. 4The specific values for-5 are listed in Table 3.
Table 3 response time and recovery time of hydrogen sensors prepared in example 1 at different hydrogen pressures
It can be seen from table 3, fig. 4 and fig. 5 that the response time of example 1 to hydrogen gas shows a trend of increasing and then decreasing with the increase of hydrogen pressure, the response time of 906Pa is the longest, and the response time when 59s and 3980pa are reached (the lower limit of pressure when hydrogen gas in air explodes) is 9s. The recovery time of the embodiment 1 also shows a change trend of increasing and then decreasing along with the increase of the hydrogen pressure, the recovery time from the hydrogen environment of 400Pa is longest and reaches 116s, and the recovery time from the hydrogen environment of 80050Pa is shortest and reaches 47s.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments are included in the scope of the present invention.
Claims (8)
1. A hydrogen sensor comprises a laminated substrate, a sensitive unit and a protective film layer;
the sensitive unit is a palladium-gold alloy nano array; the molar percentage content of gold in the palladium-gold alloy is 30 to 40 percent; the nano array consists of a plurality of array units which are orderly arranged, and the cross section area of a single array unit is 0.0078 to 0.65 mu m 2 (ii) a Two adjacent arrays in the nano array are singleThe distance between the elements is 300 to 1000nm;
the protective film layer is a polymethyl methacrylate film; the thickness of the protective film layer is 10 to 50nm.
2. The hydrogen sensor according to claim 1, wherein the height of the array unit is 15 to 40nm;
the shape of the array unit comprises a cylinder or a prism.
3. The hydrogen sensor according to claim 1, wherein the substrate is a hard transparent material;
the thickness of the substrate is 0.3 to 1mm.
4. The method for producing a hydrogen sensor according to any one of claims 1 to 3, comprising the steps of:
etching the surface of the substrate to obtain the substrate containing the nano-array template;
depositing a gold film layer and a palladium film layer on the surface of the nano-array template to obtain a substrate attached with gold-palladium;
alloying the substrate attached with the gold-palladium to obtain a primary hydrogen sensor;
and arranging a protective film layer on the surface of the primary hydrogen sensor to obtain the hydrogen sensor.
5. The method of claim 4, wherein the etching comprises photolithography or electron beam etching.
6. The preparation method of the alloy material as claimed in claim 4, wherein the alloying is carried out by annealing the substrate attached with gold-palladium, the temperature of the annealing is 330 to 370 ℃, and the holding time of the annealing is 11 to 13h.
7. The method of claim 4, wherein the deposition comprises electron beam evaporation deposition, magnetron sputtering deposition or pulsed laser deposition.
8. A method of detecting hydrogen concentration, comprising the steps of:
placing a hydrogen sensor and a gas sample to be detected in a closed space, introducing light beams from any side of the hydrogen sensor, detecting the emergent light power penetrating through the hydrogen sensor, and calculating to obtain the light transmittance to be detected; the hydrogen sensor is prepared by the preparation method of any one of claims 1 to 3 or 4 to 7;
substituting the light transmittance to be measured into a standard curve, and calculating to obtain the pressure of hydrogen in the gas sample to be measured; the standard curve is a relation curve of light transmittance and hydrogen pressure in a standard gas sample;
and calculating the concentration of the hydrogen in the gas sample to be detected according to the pressure of the hydrogen in the gas sample to be detected.
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