KR20170114985A - Method of measuring hydrogen gas using sensor for hydrogen gas - Google Patents

Method of measuring hydrogen gas using sensor for hydrogen gas Download PDF

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KR20170114985A
KR20170114985A KR1020170044141A KR20170044141A KR20170114985A KR 20170114985 A KR20170114985 A KR 20170114985A KR 1020170044141 A KR1020170044141 A KR 1020170044141A KR 20170044141 A KR20170044141 A KR 20170044141A KR 20170114985 A KR20170114985 A KR 20170114985A
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hydrogen gas
hydrogen
carbon
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pair
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신흥주
임영진
서준영
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울산과학기술원
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract

A method for measuring hydrogen gas using a hydrogen gas sensor, comprising the steps of measuring a concentration of hydrogen gas using a hydrogen gas sensor and generating a joule heat in a hydrogen gas sensor measuring the concentration of the hydrogen gas Wherein the hydrogen gas sensor comprises a pair of electrode portions facing each other with a predetermined gap therebetween on the substrate, carbon nanowires connecting the pair of electrode portions and supported by the pair of electrode portions, And hydrogen sensing particles positioned on the surface of the carbon nanowire in an island shape and having an average particle diameter of 1 nm to 500 nm.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for measuring hydrogen gas using a hydrogen gas sensor,

The present invention relates to a method for measuring hydrogen gas using a hydrogen gas sensor, and more particularly, to a method for measuring hydrogen gas using a hydrogen gas sensor whose efficiency is remarkably improved by using joule heat.

Generally, hydrogen is expected to open the popularization of hydrogen energy because it can solve the finite fossil fuel fineness and environmental pollution problem which are widely used now as promising renewable energy in the future.

However, hydrogen is an explosive gas, which contains more than 4% of the air and is in danger of explosion, requiring initial detection of hydrogen gas.

However, it is necessary to develop a new type of sensor having high efficiency and high sensitivity that can overcome the commerciality due to low yield and a complicated production process.

In recent years, in order to compensate for the disadvantages of commercialized hydrogen sensing sensors, development of nanotechnology-based gas sensors is actively proceeding as disclosed in Patent Document 1. [

Nanomaterials have properties such as quantum confinement effect and very high surface-to-volume ratio, which were not seen in micrometer-sized materials. It is possible to develop a sensor having a quick response, and it is advantageous for miniaturization of a device and development of a portable device due to its small size.

Palladium has been proposed as such a nanomaterial, and a palladium-based hydrogen sensor has recently been proposed.

Palladium-based hydrogen sensor is a hydrogen gas sensor that utilizes the property that electric conductivity changes with respect to external hydrogen environment at room temperature. More specifically, the external hydrogen molecule is separated into an atomic form on the surface of the palladium, adsorbed on the surface thereof, and then the palladium hydride (PdHx) is formed by diffusion of the palladium atom into the vacancy space between the palladium atoms to change the electrical conductivity of the palladium .

The sensitivity of the palladium-based hydrogen gas sensor is greatly influenced by the solubility of the hydrogen gas relative to the solid palladium. That is, the lower the temperature, the higher the solubility of hydrogen gas in the solid phase palladium, and thus the hydrogen gas can be measured even at room temperature.

However, if the temperature is lowered, even if the solubility of the hydrogen gas with respect to the solid palladium is increased, the diffusion of the hydrogen absorbed in the solid palladium is slow. That is, the reaction time of the gas sensor (the time until the resistance change of the palladium after the gas injection is increased to the maximum point) and the recovery time (the time it takes for the resistance change value of the palladium after the gas removal to return to the initial value) are increased.

Therefore, in the case of the palladium-based hydrogen gas sensor used at room temperature, in the environment where the hydrogen gas concentration continuously changes, the resistance value does not depend on the rate of change of the gas concentration, .

Korean Patent No. 10-0655640 (December 4, 2006)

In order to solve the above problems, the present invention provides a hydrogen gas measurement method using a hydrogen gas sensor capable of measuring concentration in real time even at a low power by heating only a sensor structure made of nano size because of using joule heat .

According to an aspect of the present invention, there is provided a method for controlling a hydrogen gas sensor, comprising: measuring a concentration of hydrogen gas using a hydrogen gas sensor; and generating joule heat in a hydrogen gas sensor measuring the concentration of the hydrogen gas, The hydrogen gas sensor includes a pair of electrode portions facing each other at a predetermined interval on a substrate, carbon nanowires connecting the pair of electrode portions and supported by the pair of electrode portions, Wherein the hydrogen-sensing particle has an average particle diameter of 1 nm to 500 nm in the form of an island on the surface of the hydrogen-gas sensing element.

The step of generating the joule heat may be performed by applying a voltage to both ends of the carbon nanowire in which the hydrogen sensing particles are formed.

The step of applying a voltage to both ends of the carbon nanowire can be performed for 1 second to 10 seconds in the range of 1V to 15V.

The step of generating the joule heat may be performed to generate joule heat in the range of 1 μW to 100 μW.

The hydrogen sensing particles may be located on the surface of the carbon nanowires in the form of primary particles.

The hydrogen sensing particles may be located on the surface of the carbon nanowire in the form of secondary particles formed by collecting primary particles.

The average particle size of the secondary particles may range from 1 nm to 500 nm.

The area where the hydrogen sensing particles are located may be in the range of 90% to 100% of the area of the entire surface of the carbon nanowire.

The hydrogen sensing particles may be palladium particles.

The specific surface area of the hydrogen sensing particles may range from 0.5 m 2 / g to 250 m 2 / g.

The aspect ratio of the carbon nanowires may range from 40: 1 to 2000: 1.

According to another aspect of the present invention, there is provided a method for controlling a hydrogen gas sensor comprising the steps of detecting a concentration of hydrogen gas using a hydrogen gas sensor including a plurality of sensor modules and generating a joule heat in the hydrogen gas sensor measuring the concentration of the hydrogen gas Wherein the hydrogen gas sensor includes a pair of first electrode portions facing each other with a predetermined gap therebetween on the substrate and a pair of first electrode portions connected to the pair of first electrode portions, A first carbon nanowire supported by a pair of first electrode portions, and a first hydrogen sensing particle located in an island shape on the surface of the first carbon nanowire and having an average particle diameter of 1 nm to 10 nm, module; And a pair of second electrode units spaced apart from the pair of first electrode units and facing each other with a predetermined gap therebetween, a pair of second electrode units connected to the pair of second electrode units, A second carbon nanowire supported by the first carbon nanowire, and a second hydrogen sensing particle located on the surface of the second carbon nanowire in an island shape and having an average particle diameter of more than 10 nm and not more than 500 nm. A hydrogen gas measuring method using a hydrogen gas sensor is provided.

In the present embodiment, the step of generating Joule heat may include the step of forming both the first ends of the first carbon nanowires having the first hydrogen sensing particles and the second ends of the second carbon nanowires having the second hydrogen sensing particles formed thereon Respectively. ≪ / RTI >

The step of applying a voltage to both ends of the first and second carbon nanowires may be performed in a range of 1 V to 15 V for 1 second to 10 seconds.

The step of generating the joule heat may be performed to generate joule heat in the range of 1 μW to 100 μW.

The area where the first hydrogen sensing particles are located may be in the range of 90% to 100% by area, based on 100% of the surface area of the entire surface of the first carbon nanowire.

The area occupied by the second hydrogen sensing particles may be in the range of 90% to 100% of the area of the entire surface of the second carbon nanowire.

The specific surface area of the first hydrogen sensing particles may range from 25 m 2 / g to 250 m 2 / g.

The specific surface area of the second hydrogen sensing particles may range from 0.5 m 2 / g to 25 m 2 / g.

According to the hydrogen gas measurement method using the hydrogen gas sensor according to the embodiment of the present invention, even if the hydrogen concentration of the hydrogen gas sensor is increased, the performance of the hydrogen gas sensor can be restored within a short time by using the joule heat Therefore, high reproducibility can be secured in hydrogen gas measurement.

In addition, since the hydrogen gas sensor used in the hydrogen gas measuring method of the present invention includes the public part type carbon nanowire, the joule heat generated is limited to the outside and the heating is performed in a short time, It is possible to heat in a short time even with low power joule heat. Therefore, it is possible to easily recover the resistance value of the hydrogen sensing particles raised by the sensing of the hydrogen gas to the initial resistance value even by applying the low-power string current, and the time required for the hydrogen sensing particles can be remarkably shortened.

FIG. 1 illustrates an example of a hydrogen gas sensor used in a hydrogen gas measurement method according to an embodiment of the present invention.
FIG. 2 illustrates an example of a hydrogen gas sensor used in a hydrogen gas measurement method according to another embodiment of the present invention.
FIG. 3 illustrates a process of manufacturing a hydrogen gas sensor used in a hydrogen gas measurement method according to an embodiment.
Fig. 4A shows an example of a pair of photoresist electrode portions and a photoresist micro-wire structure before thermal decomposition in Fig.
FIG. 4B exemplarily shows a pair of carbon electrode portions and a carbon nanowire structure after pyrolysis in FIG.
FIG. 5 is a view illustrating a state in which palladium nanoparticles are deposited on a carbon nanowire by an electroplating method in the process of manufacturing a hydrogen gas sensor used in a hydrogen gas measurement method according to an embodiment.
6A to 6C illustrate palladium nanoparticles deposited on the carbon nanowire according to the voltage applied in the electroplating method shown in FIG.
FIG. 7 shows changes in the measured current according to the applied voltage before and after deposition of the palladium nanoparticles on the aerial carbon nanowire included in the hydrogen gas sensor used in the hydrogen gas measurement method according to the embodiment.
FIG. 8 is a graph showing the rate of change in resistance according to the hydrogen concentration of the hydrogen gas sensor used in the method for measuring hydrogen gas according to an embodiment.
FIG. 9A is an electron microscope image of a hydrogen gas sensor manufactured in the form shown in FIG. 2. FIG.
FIG. 9B is an exemplary view of an electron microscope image of a side of a sensor module for high sensitivity in a hydrogen gas sensor manufactured in the form shown in FIG. 2; FIG.
FIG. 9C is an exemplary view of an electron microscope image of a side of a sensor module for high sensitivity in a hydrogen gas sensor manufactured in the form shown in FIG. 2. FIG.
FIG. 9D is an electron microscope image of the first carbon nanowire having the first hydrogen sensing particles deposited thereon of the sensor module for high sensitivity in the hydrogen gas sensor manufactured in the form shown in FIG. 2.
FIG. 9E is an electron microscope image of the second carbon nanowire deposited with the second hydrogen sensing particles of the sensor module for high concentration in the hydrogen gas sensor manufactured in the form shown in FIG. 2. FIG.
FIG. 10A is a graphical representation of a current flowing through the first carbon nanowire NW1 or the second carbon nanowire NW2.
FIG. 10B shows changes in the measured currents according to the applied voltages for the carbon nanowires (CNW), the first and second carbon nanowires (NW1 and NW2) on which hydrogen sensing particles are not deposited.
FIG. 11 is a graph showing a time when the resistance of the hydrogen sensing sensor including the second carbon nanowire is restored to its initial value when the resistance changed in the hydrogen environment of 1000 ppm concentration is compared with the case where the external heat source device is used and the case where the string heat is generated to be.
12A is a graph showing changes in resistance value by generating a string of heat for a hydrogen gas sensor including a first carbon nanowire in a hydrogen gas injection and removal environment at various concentrations.
FIG. 12B is a graph showing changes in the resistance value by generating a string of heat for a hydrogen gas sensor including a second carbon nanowire in a hydrogen gas injection and removal environment at various concentrations.
FIG. 13 is a graph showing the hydrogen concentration detection rate when the hydrogen gas concentration varies in various directions for the hydrogen sensor including both of the first and second carbon nanowires.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, at the time of the present application, It should be understood that variations can be made.

An embodiment of the present invention is a hydrogen gas sensor comprising a hydrogen gas sensor for measuring the concentration of hydrogen gas and a hydrogen gas sensor for measuring the concentration of the hydrogen gas to generate Joule heat, A method for measuring hydrogen gas using a sensor is provided.

FIG. 1 shows an example of a hydrogen gas sensor used in the hydrogen gas measuring method according to the present embodiment.

Referring to FIG. 1, the hydrogen gas sensor 100 used in the method for measuring hydrogen gas according to the present embodiment includes a pair of electrode portions 41 positioned on a substrate at a predetermined interval, (42) connected to the electrode part (41) of the carbon nanowire and supported by the pair of electrode parts, and hydrogen sensing particles (51) having an average particle diameter of 1 nm to 500 nm 50). A specific description of the hydrogen gas sensor will be described later.

First, the step of measuring the concentration of hydrogen gas using the hydrogen gas sensor can be performed by a conventional method known in the art, and is not particularly limited.

The step of generating joule heat in the hydrogen gas sensor may include measuring the concentration of hydrogen gas in real time using a hydrogen gas sensor and then resetting the hydrogen gas sensing performance of the hydrogen gas sensor .

For example, in order to measure the concentration of hydrogen gas in real time using a hydrogen gas sensor and then to maintain the sensing performance of the hydrogen gas concentration sensor, the carbon nanowires 42 coated with the hydrogen sensing particles 50 ) Needs to be restored to its initial state quickly.

In the present invention, a voltage is applied to the carbon nanotubes coated with the hydrogen sensing particles 50 to generate Joule heat in the carbon nanowires 42, The resistance value of the hydrogen gas sensor can be quickly restored to its initial value by improving the external release rate of hydrogen.

Specifically, the step of generating the joule heat may be performed by applying a voltage to both ends of the carbon nanowire 42 on which the hydrogen sensing particles 50 are formed. For example, it can be performed by applying a voltage to both ends of the carbon nanowire 42 in the range of 1 V to 15 V for 1 second to 10 seconds.

Joule heat generated in this way can range, for example, from 1 μW to 100 μW. The carbon nanowires are spaced apart from the substrate by a certain distance so that they can reach the sufficiently high temperature in a short time with low power because of excellent insulation characteristics.

However, the voltage applied to both ends of the carbon nanowire 42 and the values of the generated line heat and the like are illustrative, and the length, diameter, conductivity, and the like of the carbon nanowire 42, And may be appropriately changed depending on the size.

Next, the hydrogen gas sensor 100 will be described.

The hydrogen sensing particles 50 may be palladium particles. However, the present invention is not limited thereto, and any material that can change the electric resistance by hydrogen can be used. Accordingly, the portion referred to in the following description for palladium is only a description of the specific example of the hydrogen sensing particle 50, but is not limited to palladium.

The hydrogen sensing particles 50 may be positioned on the surface of the carbon nanowires in the form of primary particles.

The particle size of the primary particles may be in the range of 1 to 10 nm. This range implies that hydrogen sensitivity can be increased.

Alternatively, the hydrogen sensing particles 50 may be located on the surface of the carbon nanowires in the form of secondary particles formed by collecting primary particles. The particle diameter of the secondary particles may be 10 nm to 500 nm. This range has the significance that it is not saturated with a high concentration of hydrogen.

These primary particles or secondary particles can be determined by the electroplating method described below. The sensitivity of sensing the hydrogen of the hydrogen gas sensor 100 by the particle diameter of the hydrogen sensing particles 50 (for example, palladium) to be plated and the area where the hydrogen sensing particles 50 are located on the carbon nanowires 42 And a difference in detection concentration may occur. This can be adjusted according to the desired specification.

More specifically, the formation process of the hydrogen-sensing particles 50 will be described in detail in the production method described later.

Meanwhile, the area where the hydrogen sensing particles 50 are positioned may be 90 to 100% by area based on 100% of the surface area of the entire surface of the carbon nanowires 42. The ratio of the area of the hydrogen sensing particles 50 occupying the surface of the carbon nanowires 42 may influence the specification of the sensor. The above range is considered to be a practical commercial sensor.

The specific surface area of the hydrogen sensing particles 50 may be 0.5 m 2 / g to 250 m 2 / g. This range has the significance of showing a quick response to hydrogen.

The aspect ratio of the carbon nanowires 42 may be in the range of, for example, 40: 1 to 2000: 1, and the average diameter of the carbon nanowires 42 may be in the range of 200 nm to 500 nm. Joule heat generated from the carbon nanowires 42 is transmitted to the carbon electrode portions 41 supporting the carbon nanowires 42 when the aspect ratios and diameters of the carbon nanowires 42 satisfy the above- It is possible to heat the carbon nanowires 42 in a short period of time even at a very low power of string. Also, if the average diameter of the carbon nanowires 42 is small, the influence on the current flow of the hydrogen sensing particles 50 becomes large, and high-sensitivity hydrogen sensing becomes possible.

In an embodiment of the present invention, a hydrogen gas sensor is used to measure a hydrogen gas using a hydrogen gas sensor including a hollow carbon nanowire. Therefore, when the hydrogen gas sensor approaches a saturated state and generates heat, The heating can be performed in a short time.

As the temperature of the carbon nanowire increases due to the string heat, the saturated hydrogen gas sensor improves the mass transfer (diffusion) rate in the hydrogen gas sensing particles adsorbed by the hydrogen gas. Therefore, The recovery time can be remarkably shortened. That is, the hydrogen gas sensor in a saturated state can be recovered quickly and can be reused for measuring hydrogen gas.

According to another embodiment of the present invention, there is provided a method for controlling a hydrogen gas sensor, comprising: detecting a concentration of hydrogen gas using a hydrogen gas sensor including a plurality of sensor modules; generating joule heat in the hydrogen gas sensor measuring the concentration of the hydrogen gas And a hydrogen gas sensor for measuring a hydrogen gas concentration.

In this embodiment, the same configuration as the hydrogen gas measuring method using the hydrogen gas sensor according to the above-described embodiment is the same as that described above, and thus will not be described here.

FIG. 2 exemplarily shows a hydrogen gas sensor used in the hydrogen gas measurement method according to the present embodiment.

Referring to FIG. 2, the hydrogen gas sensor 200 including a plurality of sensor modules used in the hydrogen gas measurement method according to the present embodiment may include a sensor module for high sensitivity and a sensor module for high concentration. This can be divided by the average particle diameter range of the hydrogen sensing particles plated on the carbon nanowires included in each sensor module.

That is, the high-sensitivity sensor module includes, for example, a pair of first electrode portions 41a located on the substrate 11 with a predetermined gap therebetween, a pair of first electrode portions 41a, A first carbon nanowire 42a connected to the pair of first electrode portions 41a and supported by the pair of first electrode portions 41a and a second carbon nanowire 42a disposed on the surface of the first carbon nanowires 42a in an island- And the first hydrogen sensing particles 50a having a thickness of 10 nm.

The sensor module for high concentration includes a pair of second electrode portions 41b which are located apart from the pair of first electrode portions 41a and are positioned facing each other with a predetermined gap therebetween, A second carbon nanowire 42b connected to the second electrode portion 41b and supported by the pair of second electrode portions 41b, and a second carbon nanowire 42b connected to the second carbon nanowire 42b, And second hydrogen sensing particles 50b having an average particle diameter of more than 10 nm and not more than 500 nm.

When the first hydrogen sensing particle 50a having a small particle diameter is used as in the high sensitivity sensor module, it is possible to detect a small concentration of hydrogen, but since the first hydrogen sensing particle 50a has a small size, have.

On the contrary, when the second hydrogen sensing particles 50b are used as the large-sized sensor module, the second hydrogen sensing particles 50b are large in size. Therefore, the electric conductivity change may be insufficient for a small concentration of hydrogen However, it may be effective in detecting high concentration of hydrogen.

The area where the first hydrogen sensing particles 50a are positioned may be 90% to 100% of the area of the entire surface of the first carbon nanowire 42a. When the area where the first hydrogen sensing particles 50a are positioned satisfies the above range, most of the current is very effective to bypass the palladium when the first hydrogen sensing particles 50a is made of palladium.

The area occupied by the second hydrogen sensing particles may be 90% to 100% by area based on 100% by area of the entire surface of the second carbon nanowire. When the area where the second hydrogen sensing particles 50b are located satisfies the above range, most of the current is very effective to bypass the palladium when the palladium is used as the second hydrogen sensing particles 50b.

The specific surface area of the first hydrogen sensing particles 50a may be 25 m 2 / g to 250 m 2 / g. This range may be effective in increasing the reaction rate with the high sensitivity of the hydrogen gas sensor 200.

The specific surface area of the second hydrogen sensing particles 50b may be 0.5 m 2 / g to 25 m 2 / g. This range can be effective in increasing the degree of saturation of the hydrogen gas sensor 200 and increasing the reaction rate.

The step of generating joule heat in the hydrogen gas sensor 200 may include the step of forming both ends of the first carbon nanowire 42a on which the first hydrogen sensing particles 50a are formed, And then applying a voltage to both ends of the second carbon nanowires 42b on which the hydrogen sensing particles 50b are formed.

The step of applying a voltage to both ends of the first and second carbon nanowires 42a and 42b may be performed in a range of 1 to 15 V for 1 to 10 seconds. When the voltage applied to both ends of the first carbon nanowire satisfies the above range in order to generate a string of heat, it is possible to reach a sufficiently high temperature with low power.

In this way, the string of lines generated in the first and second carbon nanowires 42a and 42b may be in the range of 1 to 100 μW. When the string of lines generated in the first and second carbon nanowires 42a and 42b satisfies the above range, it is possible to reach a sufficiently high temperature with low power.

When hydrogen gas is measured using a hydrogen gas sensor including a plurality of sensor modules having different average particle diameter ranges of hydrogen sensing particles as in the present embodiment, in addition to the effect of the embodiment, the hydrogen gas concentration is periodically changed It is possible to measure the hydrogen concentration accurately in real time even in environments having various hydrogen gas concentrations, so that high sensitivity and high concentration hydrogen gas measurement are possible.

Meanwhile, the hydrogen gas sensor 100 used in the hydrogen gas measurement method according to an embodiment of the present invention can be manufactured using a photoresist, for example, as shown in FIG.

First, referring to FIG. 3, an insulating layer 11 is formed on the upper surface of the silicon wafer 10 in (a) and (s10).

The insulating layer 11 is formed by thermal oxidation. The upper surface of the silicon wafer 10 whose elemental symbol is Si is oxidized by applying heat at 800 to 1200 ° C., An insulating layer 11 having an elemental symbol SiO 2 is deposited on the upper surface of the substrate 10 by vapor deposition.

Here, the thickness of the insulating layer 11 to be deposited may be 0.1 to 10 占 퐉, and the thickness of the insulating layer 11 may be selectively selected depending on the thickness of the silicon wafer 10 and the measurement capacity of the sensor.

Next, in step (b) (step s20), on the insulating layer 11 of the silicon wafer 10 formed by the step (a), a pair of photoresist electrode parts 21 are formed by photolithography, The photoresist electrode portions 21 of the photoresist micro-wires 22 are formed.

The photolithography is a step of forming a pattern on a substrate by transferring a pattern engraved in a photomask onto a photoresist when ultraviolet rays are irradiated to a substrate coated with a photosensitive resin through a photomask, ) Is composed of a plurality of steps, which will be described in more detail as follows.

First, in step (b-1) (s21), a photoresist is applied on the insulating layer 11 formed by the step (a) to form a photoresist layer 20.

At this time, SU-8 is used as the photoresist material applied to the insulating layer 11, and the photoresist is evenly coated on the insulating layer 11 by a spin coating method, A photoresist layer 20 is formed.

Here, the thickness of the formed photoresist layer 20 is 5 to 100 占 퐉, and the thickness of the photoresist layer 20 is selectively selected according to the measured capacitance of the sensor.

Next, in step (b-2), a photoresist layer 20 formed by the step (b-1) (s21) is exposed to a first port After the mask 31 is placed, ultraviolet light is irradiated to perform primary exposure.

At this time, it is preferable that the primary exposure is performed with sufficient energy to perform optical polymerization to the bottom of the photoresist layer 20 corresponding to the electrode area of the photoresist layer 20. [

Next, in step (b-3), a pair of electrode regions are formed on the first-exposed photoresist layer 20 by the step (b-2) After the second photomask (32) is buried in the region, secondary exposure is performed with ultraviolet light.

At this time, the photoresist microwire 22 connecting the pair of photoresist electrode portions 21 has a photoresist layer 20 corresponding to the photoresist microwave region in the secondary exposure in order to be formed in the form of a micro-sized wire, The thickness of the photoresist microwire 22 may be controlled according to the ultraviolet exposure energy.

Next, in step (b-4) (step s24), the photoresist layer 20 except for the area exposed by the steps (b-2) and (a-3) The photoresist microelectrode 22 connecting the pair of photoresist electrode portions 21 and the photoresist electrode portions 21 is formed on the insulating layer 11 of the wafer 10. [

Type photoresist micro-wire 22 and a photoresist micro-wire 22 (hereinafter referred to as " photoresist micro-wire ") polymerized using a developer capable of selectively etching portions excluding the optically- A pair of photoresist electrode portions 21 are formed.

Next, in step (c) (step s30), the pair of photoresist electrode parts 21 and the photoresist micro-wires 22 formed on the insulating layer 11 by the step (b) And is converted into a pair of carbon electrode portions 41 and carbon nanowires 42 by pyrolysis.

At this time, the pair of photoresist electrode portions 21 and the photoresist microwire 22 structure of the polymerized photoresist material are accommodated in the chamber so that the internal atmosphere of the chamber is maintained at a temperature of 500 DEG C or higher in a vacuum or an inert gas environment To thereby perform a polymer pyrolysis process.

The shape of the pair of photoresist electrode portions 21 and the structure of the photoresist micro-wires 22 through the polymer pyrolysis process is changed due to the volume reduction. FIG. 4A shows a state in which a pair of photoresist electrode portions FIG. 4B shows a pair of photoresist electrode portions 21 and a photoresist microwire 22 structure after pyrolysis. FIG.

As shown in FIGS. 4A and 4B, in the polymer pyrolysis process, the pair of the photoresist electrode portions 21 and the photoresist microwire 22 structure are reduced in volume by about 80% .

Here, the thermal decomposition process can control the volume reduction of the pair of photoresist electrode portions 21 and the photoresist micro-wire 22 structure according to conditions such as time, temperature, heating rate, cooling rate, have.

Accordingly, the shape of the final carbon nanowire can be controlled by adjusting the size and exposure energy of the photomask for polymer micro fabrication and the polymer pyrolysis conditions.

In this case, the size of the photoresist microwire is 1 mu m to several mu m in diameter, several to several hundred mu m in length, and the spacing between the conducting cone wafer and the airborne photoresist microwire is 1 mu m to several hundred mu m, The size of the carbon nanowire through the process is several tens of nanometers to several micrometers in diameter, several to several hundred micrometers in length, and the distance between the substrate and the wire is several hundred nanometers to several hundred micrometers.

Next, in step (d) (step s40), palladium nanoparticles 42 are formed on the surfaces of the carbon nanowires 42 among the pair of carbon electrode parts 41 and the carbon nanowires 42 converted by the step (c) (50). ≪ / RTI >

As shown in FIG. 5, the deposition of the palladium nanoparticles is performed by electroplating. The electroplating includes a counter electrode (counter electrode) 1, a reference electrode 2, a working electrode 3 is required to flow an electric current to the sample when an electrode reaction occurs. In this case, platinum (Pt) is used as a counter electrode (counter electrode) A working electrode 3 is used as a reference electrode 2 and silver or silver chloride is used as a reference electrode 2. The working electrode 3 is brought into contact with one side or both sides of the pyrolyzed carbon electrode unit 41, The palladium nanoparticles 50 are deposited on the carbon nanowires 42 exposed to the palladium plating solution (electrolytic solution) by electrodeposition by applying a voltage to the carbon electrodes 42.

More specifically, the carbon nanowires 42 suspended in air on the insulating layer 11 of the silicon wafer 10 manufactured according to an embodiment of the present invention are immersed in a sodium palladium plating solution (Na2PdCl4) The working electrode 3 is brought into contact with the carbon electrode 41 on one side or both sides and the counter electrode 1 made of platinum and the reference electrode 2 made of silver-silver chloride are combined with the carbon nanowires 42 to form palladium A voltage (electricity) is applied to the working electrode 3 in a state where the working electrode 3 is immersed in the plating liquid.

At this time, the concentration of the palladium plating solution is preferably 10 nM to 100 mM, and as the concentration of the palladium plating solution increases, the rate of formation of the palladium nanoparticles increases and particles larger than the nano size can be formed.

The size and spacing of the palladium nanoparticles vary with the voltage of the working electrode 3 and the deposition time.

6A to 6C illustrate palladium nanoparticles deposited on the carbon nanowire according to the voltage applied in the electroplating method shown in FIG.

Referring to FIG. 6A, for example, a voltage of -0.8 V, which is a high voltage, is applied to the working electrode 2 for 5 seconds to deposit palladium nanoparticles on a carbon surface having relatively low electrochemical activity, V is applied for 20 seconds to restrict the growth rate of the deposited palladium nanoparticles 50 to form relatively small-sized palladium nanoparticles on the carbon nanowires 42.

6B shows a state in which palladium nanoparticles 50 are secondarily deposited on the carbon nanowires 42 by applying a voltage of -0.8 V to the working electrode 2 for 5 seconds and then applying a voltage of -0.2 V for 80 seconds FIG. 4C shows a state in which a voltage of -0.8 V is applied to the working electrode 2 for 5 seconds, a voltage of -0.2 V is applied successively for 120 seconds, and a voltage of -0.8 V is applied again to the electrode 10 And finally a voltage of -0.2 V is applied for 60 seconds to deposit palladium nanoparticles 50 on the carbon nanowires 42.

6B, after a voltage of -0.8 V was applied to the working electrode 2 for 5 seconds, a voltage of -0.2 V was applied for 80 seconds to the palladium nanoparticles 50 ) Are secondarily deposited. In this case, it can be seen that a relatively large median of the palladium nanoparticles are formed at the carbon nanowires at regular intervals.

6C, a voltage of -0.8 V is applied to the working electrode 2 for 5 seconds, a voltage of -0.2 V is applied continuously for 120 seconds, a voltage of -0.8 V is applied again for 10 seconds, Finally, a voltage of -0.2 V is applied for 60 seconds to deposit the palladium nanoparticles 50 on the carbon nanowires 42. In this case, it can be seen that large size palladium nanoparticles are continuously deposited along the outer circumferential surface of the carbon nanowire.

The size and spacing of the palladium nanoparticles can be controlled by the voltage of the working electrode 3 and the deposition time.

In an embodiment of the present invention, in order to further increase the adhesion between the palladium nanoparticles 50 deposited by the electrochemical (electroplating) method and the carbon nanowires 42, Annealing treatment can be performed at a temperature of 100 占 폚 or higher.

FIG. 7 is a graph showing the change in the measured current according to the applied voltage for the air-bearing type carbon nanowires before and after the deposition of the palladium nanoparticles by the above-described method. Referring to FIG. 7, a public-type carbon nanowire hydrogen gas sensor fabricated by the above-described exemplary method includes palladium nanoparticles 50 deposited on a carbon nanowire 42, The resistance is reduced. The decrease in electrical resistance of the carbon nanowires is because the electrical resistance of the palladium nanoparticles 50 is lower than that of the carbon nanowires 42.

In the aerosol type carbon nanowire included in the hydrogen gas sensor used in the measurement method according to the embodiment of the present invention, the current flows not only through the carbon nanowires 42 but also through the palladium nanoparticles 50 , When the external hydrogen gas concentration changes, the electric resistance of the airborne type carbon nanowire changes to enable the hydrogen to be detected based on the change.

FIG. 8 is a graph showing a rate of change in resistance according to a hydrogen concentration of a carbon nanowire hydrogen gas sensor of a public part type carbon nanowire according to an embodiment of the present invention. As shown in FIG. 8, It is observed that the carbon nanowire hydrogen gas sensor changes the electrical resistance according to the hydrogen concentration.

A hydrogen gas sensor including a plurality of sensor modules used in a hydrogen gas measurement method according to another embodiment of the present invention is manufactured in the same manner as described above. For example, as shown in FIG. 2, The first and second carbon nanowires 42a and 42b coated with the first and second hydrogen sensing particles 50a and 50b may be fabricated and integrated into a single chip.

FIG. 9A is an electron microscope image of a hydrogen gas sensor manufactured in the form of FIG. 2, FIG. 9B is an exemplary electron microscope image of a side surface of the sensor module for high sensitivity in FIG. 2, An electron microscope image of the side surface of the sensor module for high sensitivity is shown.

FIG. 9D is an electron microscope image of the first carbon nanowire 42a deposited with the first hydrogen sensing particles 50a of the sensor module for high sensitivity in FIG. 2. FIG. And an electron microscope image of the second carbon nanowire 42b on which the second hydrogen sensing particles 50b of the sensor module for the first carbon nanowire 42b are deposited.

9D, the first carbon nanowires 42a and NW 1 are formed by, for example, applying a voltage of-1.2 V to the working electrode for 5 seconds, applying a voltage of -0.8 V successively for 5 seconds And may be a first carbon nanowire 42a (NW 1) on which a few nanometers of palladium nanoparticles are deposited.

Referring to FIG. 9E, the second carbon nanowires 42b and NW 2 are formed by, for example, applying a voltage of-1.2 V to the working electrode for 5 seconds, applying a voltage of -0.8 V successively for 25 seconds And second carbon nanowires 42b and NW 2 on which palladium nanoparticles having a size of several tens of nanometers are deposited.

The size and spacing of the palladium nanoparticles formed in Figures 9d and 9e may vary depending on the voltage of the working electrode and the deposition time. In addition, the size of the palladium nanoparticles can be determined according to the resistance of the carbon nanowires, the concentration of the palladium solution, the applied voltage and time of the electroplating.

FIG. 10A is a graphical representation of a current flowing through the first carbon nanowire NW1 or the second carbon nanowire NW2, FIG. 10B is a graph showing a state in which the carbon nanowires CNW, 1 and the second carbon nanowires NW1 and NW2, respectively.

Referring to FIGS. 10A and 10B, when the hydrogen sensing particles, for example, palladium nanoparticles are deposited, the total resistance of the first or second carbon nanowires decreases. In addition, since the electric current is bypassed by the high electric conductivity of the carbon nanowires having lower electric conductivity, the entire resistance of the carbon nanowires coated with the palladium nanoparticles due to the change of the external hydrogen concentration is sensitively changed, Lt; / RTI >

FIG. 11 is a graph showing a time when the resistance of the hydrogen sensing sensor including the second carbon nanowire is restored to its initial value when the resistance changed in the hydrogen environment of 1000 ppm concentration is compared with the case where the external heat source device is used and the case where the string heat is generated to be. In Fig. 11, the gray shaded portion indicates a hydrogen environment with a concentration of 1000 ppm.

Specifically, five samples of the second carbon nanowires were prepared and placed in the gas chamber. After injecting hydrogen gas at a concentration of 1000 ppm into the gas chamber, gas injection was stopped after a certain time, The change in resistance to the sample was measured.

Referring to FIG. 11, it can be seen that, in the case of no external and internal heat source application (Sample 1), it takes a considerable time to recover the resistance value increased after the hydrogen gas injection into the initial resistance value. On the other hand, in the case where heat of 35 ° C was applied for 5 seconds (Sample 2) using an external heat source and heat of 45 ° C was applied for 5 seconds using an external heat source (Sample 3) It can be confirmed that the time required to recover the initial value is shortened when the heat is applied for 5 seconds (Sample 4).

Particularly, according to the embodiment of the present invention, it can be confirmed that the time required for recovering the initial resistance value in the case where the string is heated, that is, when the string heat of 30 μW is generated (Example 1) .

In other words, according to the present invention, by applying low power without using an external heat source to generate heat, it is possible to drastically shorten the time required to recover the hydrogen sensing performance of the hydrogen gas sensor.

12A and 12B are graphs showing a change in resistance value by generating a string of heat for a hydrogen gas sensor including first and second carbon nanowires NW1 and NW2 in a hydrogen gas injection and removal environment of various concentrations. to be.

That is, FIGS. 12A and 12B are obtained by measuring the hydrogen concentration by detecting the hydrogen concentration after recovering the initial resistance by applying a string of heat when the resistance of the hydrogen gas sensor increases according to the hydrogen concentration.

For example, in the case of FIG. 12A, a change in resistance value is measured using a hydrogen gas sensor including a first carbon nanowire NW1. That is, the initial resistance of the hydrogen gas sensor including the first carbon nanowire (NW1) was 6.48 MΩ, but when the hydrogen concentration was 50,000 ppm, the resistance of the hydrogen gas sensor was increased to 18.53 MΩ, To restore the initial resistance to 6.48MΩ. In addition, the minimum change resistance of the first carbon nanowire (NW1) was 6.78 M ?. In this way, the resistance value change was measured in a hydrogen concentration atmosphere of 50,000 ppm to 10 ppm.

In the case of FIG. 12B, a change in resistance value is measured using a hydrogen gas sensor including a second carbon nanowire NW2. That is, the initial resistance of the hydrogen gas sensor including the second carbon nanowire (NW2) was 1.54 MΩ, but when the hydrogen concentration was 50,000 ppm, the resistance of the hydrogen gas sensor was increased to 2.97 MΩ, And the initial resistance was restored to 1.54 MΩ. The minimum change resistance of the second carbon nanowire (NW2) was 1.58 M ?. In this way, the resistance value change was measured in a hydrogen concentration atmosphere of 50,000 ppm to 10 ppm.

Referring to FIGS. 12A and 12B, it can be confirmed that the string resistance is immediately restored to the initial resistance value.

FIG. 13 shows the rate of change in resistance by measuring the hydrogen concentration detection rate when the hydrogen gas concentration varies variously with respect to the hydrogen sensor including both the first and second carbon nanowires NW1 and NW2.

Referring to FIG. 13, when the concentration changes from low concentration to high concentration or when concentration changes from high concentration to low concentration, the same resistance change occurs at the same concentration. In other words, it can be seen that hydrogen gas sensor has reliable high reproducibility and can measure hydrogen concentration in real time by applying heat to the hydrogen gas sensor as in the embodiments of the present invention.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: counter electrode
2: Reference electrode
3: working electrode
10: Silicon wafer
11: Insulating layer
20: photoresist layer
21: Photoresist electrode portion
22: Photoresist microwire
31: First photo mask
32: Second photomask
41: carbon electrode part
42: Carbon nanowire
50: hydrogen-sensing particle
41a: a first electrode portion
41b: the second electrode portion
50a: first hydrogen sensing particle
50b: second hydrogen sensing particle
42a, NW1: a first carbon nanowire
42b, NW2: a second carbon nanowire

Claims (19)

Measuring a concentration of hydrogen gas using a hydrogen gas sensor; And
And generating Joule heat in the hydrogen gas sensor measuring the concentration of the hydrogen gas,
Wherein the hydrogen gas sensor comprises:
A pair of electrode portions positioned on the substrate facing each other with a predetermined gap therebetween,
Carbon nanowires connected to the pair of electrode portions and supported by the pair of electrode portions, and
And hydrogen sensing particles having an average particle diameter of 1 nm to 500 nm, which are located on the surface of the carbon nanowire in an island shape. The method according to claim 1,
The step of generating Joule heat comprises:
Wherein the hydrogen gas sensing is performed by applying a voltage to both ends of the carbon nanowire on which the hydrogen sensing particles are formed. 3. The method of claim 2,
The step of applying a voltage to both ends of the carbon nanowire includes:
Wherein the measurement is performed for 1 to 10 seconds in the range of 1 V to 15 V. The method according to claim 1,
The step of generating Joule heat comprises:
Wherein the joule heat is generated in a range of 1 μW to 100 μW. The method according to claim 1,
Wherein the hydrogen sensing particles are located on the surface of the carbon nanowires in the form of primary particles. The method according to claim 1,
Wherein the hydrogen sensing particles are located on the surface of the carbon nanowires in the form of secondary particles formed by collecting primary particles. The method according to claim 6,
Wherein the secondary particles have an average particle diameter of 1 nm to 500 nm. The method according to claim 1,
Wherein the area of the hydrogen sensing particles is 90% by area to 100% by area based on 100% by area of the entire surface of the carbon nanowire. The method according to claim 1,
Wherein the hydrogen sensing particles are palladium particles. The method according to claim 1,
Wherein the specific surface area of the hydrogen sensing particles is 0.5 m 2 / g to 250 m 2 / g. The method according to claim 1,
Wherein the aspect ratio of the carbon nanowires is in the range of 40: 1 to 2000: 1. Detecting a concentration of hydrogen gas using a hydrogen gas sensor including a plurality of sensor modules; And
And generating Joule heat in the hydrogen gas sensor measuring the concentration of the hydrogen gas,
A hydrogen gas sensor including the plurality of sensor modules,
A first carbon nanowire connected to the pair of first electrode parts and supported by the pair of first electrode parts, and a second carbon nanowire connected to the pair of first electrode parts, A sensor module for high sensitivity, comprising a first hydrogen sensing particle having an average particle size of 1 nm to 10 nm and located in an island shape on the surface of the first carbon nanowire; And
A pair of second electrode parts spaced apart from the pair of first electrode parts and positioned facing each other with a predetermined gap therebetween, a pair of second electrode parts connected to the pair of second electrode parts, A second carbon nanowire supported by the second carbon nanowire, a second hydrogen sensing particle having an average particle size of more than 10 nm and less than 500 nm, which is located in an island shape on the surface of the second carbon nanowire;
Wherein the hydrogen gas is a hydrogen gas. 13. The method of claim 12,
The step of generating Joule heat comprises:
The first carbon nanowire having the first hydrogen sensing particle formed thereon
Wherein the second carbon nanowire is formed by applying a voltage to both ends of the second carbon nanowire on which the second hydrogen sensing particles are formed. 14. The method of claim 13,
The step of applying a voltage to both ends of the first and second carbon nanowires includes:
Wherein the measurement is performed for 1 to 10 seconds in the range of 1 V to 15 V. 13. The method of claim 12,
The step of generating Joule heat comprises:
Wherein the joule heat is generated in a range of 1 μW to 100 μW. 13. The method of claim 12,
Wherein the area where the first hydrogen sensing particles are located is from 90% by area to 100% by area, with respect to 100% by area of the entire surface of the first carbon nanowires. 13. The method of claim 12,
Wherein an area where the second hydrogen sensing particles are located is from 90% by area to 100% by area based on 100% by area of the entire surface of the second carbon nanowires. 13. The method of claim 12,
Wherein a specific surface area of the first hydrogen sensing particles is 25 m 2 / g to 250 m 2 / g. 13. The method of claim 12,
And the specific surface area of the second hydrogen sensing particles is 0.5 m 2 / g to 25 m 2 / g.
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KR20210075824A (en) * 2019-12-13 2021-06-23 울산대학교 산학협력단 Hydrogen sensor and method for producing the same
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