KR101325212B1 - Preparation method of carbon nanotube electrode, and the carbon nanotube electrode thereby - Google Patents
Preparation method of carbon nanotube electrode, and the carbon nanotube electrode thereby Download PDFInfo
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- KR101325212B1 KR101325212B1 KR1020100116840A KR20100116840A KR101325212B1 KR 101325212 B1 KR101325212 B1 KR 101325212B1 KR 1020100116840 A KR1020100116840 A KR 1020100116840A KR 20100116840 A KR20100116840 A KR 20100116840A KR 101325212 B1 KR101325212 B1 KR 101325212B1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The present invention relates to a method for producing a carbon nanotube electrode and a carbon nanotube electrode manufactured according to this, in detail, forming a bottom electrode on an insulating substrate (step 1); Forming a catalyst layer on the bottom electrode of step 1 (step 2); And growing a carbon nanotube on the substrate on which the catalyst layer is formed in step 2 (step 3), and a carbon nanotube electrode prepared according to the present invention.
The carbon nanotube electrode manufacturing method of the present invention and the carbon nanotube electrode prepared according to the present invention has an effect that does not require expensive metals and deposition process by manufacturing the electrode by deteriorating the polymer resin with optical functional group, carbon nanotube When grown, there is an effect having excellent contact resistance properties with carbon nanotubes. In addition, the carbon nanotube electrode of the present invention has excellent electrochemical properties and excellent contact resistance properties, and thus can be applied to high sensitivity electrochemical sensors, fuel cells, and electron beam sources.
Description
The present invention relates to a method for producing a carbon nanotube electrode and a carbon nanotube electrode produced accordingly.
Carbon nanotubes are a tube-like structure composed of carbon, and because all carbon atoms are exposed to the surface, they are sensitive to minute physicochemical reactions and are known to have the mechanical robustness of carbon materials. Because of these properties, carbon nanotubes are in the spotlight in the field of nanotechnology, and research on various device applications using them has been reported.
In particular, since carbon nanotube transistors are composed of source, drain, and gate electrodes, they can measure the electrical conductivity of carbon nanotubes. Change in current flow can be detected as a signal. Therefore, it can be used in various fields such as biosensor for detecting E. coli or gas sensor that can detect dangerous gas leakage.It is a high-sensitivity sensor that can measure in real time, so it can be applied in various fields and is relatively inexpensive compared to other sensor manufacturing methods. This has the advantage of being possible.
In the case of the carbon nanotube transistor as described above, a device manufactured using one strand grown horizontally or a small number of carbon nanotubes can be used as an electrode having excellent characteristics by vertically growing carbon nanotubes. When the carbon nanotubes are above a certain density, they grow in a vertically aligned (VA) form due to the strong interaction between the tubes. In this case, the maximum surface area of the carbon nanotube, which is a one-dimensional nanostructure, is maximized. At the same time, it also has the advantages of three-dimensional structure electrodes. The nano-carbon electrode manufactured as described above has a large surface area and at the same time less diffusion limiting effect when used in an electrochemical sensor, thereby making it possible to manufacture an electrode having much higher sensitivity than conventional sensors. In addition, it is expected to exhibit high efficiency as an electrode of a fuel cell, and is also useful as a biological application for measuring or stimulating a signal of minute cells. In addition, carbon nanotubes made on metal can be used as electron guns or micro X-ray sources that can be used for displays.
Korean Patent No. 10-2000-0035702 discloses a nano-sized vertical transistor in which carbon nanotubes such as the above are grown vertically through chemical vapor deposition, and are applied to semiconductors to achieve high density and high integration. It is.
In addition, Korean Patent No. 10-2007-0057150 discloses an electronic device in which carbon nanotubes are vertically oriented, and has been shown to have an effect of realizing a highly integrated device more than twice as large as a horizontal structure because of vertical structure.
However, despite the excellent characteristics and wide applications as shown above, the development of carbon nanotube three-dimensional electrodes is not rapidly achieved. This is due to the difficulty in vertically connecting carbon nanotubes to metals. In order to fabricate the carbon nanotube three-dimensional electrode, the carbon nanotubes may be directly grown on the prefabricated metal electrode, or assembled on the metal electrode through a linker or a molecule serving as a pool. However, when carbon nanotubes are grown directly on a metal electrode, the growth of carbon nanotubes on a metal surface is very difficult, and thus it is not easy to realize them. This is because they lose their activity as. In addition, in the case of manufacturing a nano carbon electrode using a linker or other polymer, the alignment of the carbon nanotubes is not good, and the contact resistance between the metal electrode and the carbon nanotubes may be very large due to the linker molecules.
In order to solve the problems described above, the inventors of the present invention form an electrode of carbon material of the present invention, and form a catalyst layer having a multilayer structure such that carbon nanotubes can be vertically grown on top of the carbon nanotubes. The carbon nanotube electrode grown to the top was completed.
An object of the present invention is to provide a method for producing a carbon nanotube electrode and a carbon nanotube electrode produced accordingly.
In order to achieve the above object, the present invention comprises the steps of forming a bottom electrode on an insulating substrate (step 1); Forming a catalyst layer on the bottom electrode of step 1 (step 2); And growing a carbon nanotube on the substrate on which the catalyst layer is formed in step 2 (step 3), and a carbon nanotube electrode prepared through the same.
The carbon nanotube electrode manufacturing method of the present invention and the carbon nanotube electrode prepared according to the present invention has an effect that does not require expensive metals and deposition process by manufacturing the electrode by deteriorating the polymer resin with optical functional group, carbon nanotube When grown, there is an effect having excellent contact resistance properties with carbon nanotubes.
In addition, the carbon nanotube electrode of the present invention has excellent electrochemical properties and excellent contact resistance properties, and thus can be applied to high sensitivity electrochemical sensors, fuel cells, and electron beam sources.
1 is a schematic view of a carbon nanotube electrode produced by the present invention;
Figure 2 is a schematic diagram showing the carbon nanotube electrode produced by the manufacturing step according to the present invention;
3 is a photograph of a carbon nanotube electrode prepared according to Example 2 of the present invention under a scanning electron microscope;
4 is a photograph of a carbon pillar electrode prepared according to Example 3 of the present invention with a scanning electron microscope;
5 is a photograph of an electrode manufactured by Comparative Example 1 of the present invention observed with a scanning electron microscope;
FIG. 6 is a
7 is a graph of electrochemical characterization of electrodes prepared by Comparative Example 1 of the present invention;
FIG. 8 is a
9 is a graph of the electrochemical characteristic evaluation of the carbon pillar electrode manufactured by Example 3 of the present invention.
Hereinafter, the present invention will be described in detail.
The present invention comprises the steps of forming a bottom electrode on an insulating substrate (step 1);
Forming a catalyst layer on the bottom electrode of step 1 (step 2); And
It provides a method for producing a carbon nanotube electrode comprising the step of growing carbon nanotubes on the substrate on which the catalyst layer is formed in step 2 (step 3), the schematic diagram of the carbon nanotube electrode produced by the manufacturing method of the
Hereinafter, the present invention will be described in detail by steps.
The substrate of
In addition, the bottom electrode of
At this time, the bottom electrode of
The polymer may be coated on the substrate, patterned, and then heat-treated to form a bottom electrode made of carbon.
The polymer is preferably a polymer having a photo functional group, more preferably SU8-2002 photoresist. By using the polymer having the optical functional group there is an effect that can be easily patterned through exposure and development through a mask.
On the other hand, the coating is preferably carried out through spin coating. Spin coating has the effect of coating the polymer onto the substrate in a short time.
In addition, the heat treatment is preferably performed for 20 to 40 minutes at a temperature of 800 to 1000 ℃.
If the heat treatment is performed at a temperature of less than 800 ℃ has a problem that the specific resistance of the formed carbon electrode is too large, if the heat treatment is performed at a temperature exceeding 1000 ℃ there is a problem that the process is difficult to perform due to unnecessarily high temperature . In addition, when the heat treatment is performed for less than 20 minutes, the resistance of the formed electrode is too large, there is a problem that unnecessary time waste may occur when the heat treatment is performed for more than 40 minutes.
On the other hand, the bottom electrode of
Growing a graphene thin film (step a);
Separating the graphene thin film of step a (step b);
Transferring the graphene thin film separated in the step B to an upper portion of the substrate (step c);
Performing patterning on the graphene thin film transferred in the step c (step d); And
The bottom electrode of the graphene material may be formed through a process including the step (step ㅁ) of etching the graphene thin film on which the patterning has been performed in the step d with oxygen plasma, thereby providing excellent electrical properties. There is an effect that can form an electrode.
In addition, the bottom electrode of
Preparing a raw material solution by dispersing carbon nanotubes, graphene flakes, or nano-sized activated carbon in an organic solvent (step A);
Patterning the electrode form over the substrate (step B);
Coating the raw material solution prepared in step A into the electrode pattern patterned in step B (step C); And
Through the process comprising the step of forming a self-assembled film to the outside of the patterning of step B (step D) can be formed of a carbon nanotube or an activated carbon bottom electrode, thereby forming a bottom electrode having excellent electrical characteristics It can be effective.
Further, the bottom electrode of
The method of manufacturing a carbon nanotube electrode according to the present invention may further include forming an insulating layer on a portion except the bottom electrode after the bottom electrode is formed in
The insulating layer is to insulate all the portions except the portion where the carbon nanotubes are to be grown. The insulating layer is preferably formed of a material selected from the group consisting of SiO 2 , Si 3 N 4 and Al 2 O 3 . .
Although the formation of the insulating layer is not necessarily required in the manufacturing method of the present invention, the formation of the insulating layer has an effect of further improving the characteristics of the electrode manufactured by the manufacturing method of the present invention. That is, by forming the insulating layer, the reaction can be controlled to occur only in the carbon nanotubes, so an electrochemical sensor can expect a much larger signal-to-noise ratio and can minimize leakage current regardless of the reaction.
In addition, the method of manufacturing a carbon nanotube electrode according to the present invention may further include coating a polymer on the bottom electrode and patterning it before the catalyst layer is formed in
In this case, the patterning is to open the portion where the catalyst layer is to be deposited and the connection portion with the bottom electrode, and the polymer is preferably a polymer having an optical functional group, and the coating is preferably performed by spin coating.
By using the polymer having the optical functional group, it is possible to pattern the portion where the catalyst layer is to be deposited and the connection portion with the bottom electrode through exposure and development through a mask, and to shorten the execution time of the process by coating the polymer through spin coating. It can be effective.
The catalyst layer of
In addition, the catalyst layer of
By using at least one material selected from the group consisting of transition metal compounds, metals and semiconducting nanoparticles as the catalyst layer, there is an effect of growing a small diameter nanotube.
Further, the catalyst layer of
This improves the problem that the existing catalyst molecules and the metal electrode react with each other to lose activity as a catalyst, thereby enabling the carbon nanotubes to grow vertically.
At this time, the thickness of the aluminum thin film is preferably 5 to 15 nm.
If the thickness of the aluminum thin film is less than 5 nm, there is a problem that the electrical contact is bad as the aluminum thin film is oxidized, and if the thickness of the aluminum thin film exceeds 15 nm, the process cost of growing carbon nanotubes increases, and also the bottom electrode and There is a problem in that the contact resistance becomes large.
In addition, the thickness of the iron thin film is preferably 1 to 10 nm.
If the thickness of the iron thin film is less than 1 nm, there is a problem that the carbon nanotubes do not grow well horizontally or vertically well. If the thickness exceeds 10 nm, the diameter of the carbon nanotubes is too large or the carbon nanotubes are well grown. There is a problem that does not grow.
At this time, the carbon nanotubes grown through the
Carbon nanotubes are classified into single-ply single-layered carbon nanotubes and multi-ply carbon nanotubes in which multiple layers of carbon nanotubes form concentric circles depending on the structure. There is also a tube.
Single-ply carbon nanotubes are simply a roll of graphite plate, with a diameter of 0.5 to 3 nm, and double-ply carbon nanotubes are concentric with two single-ply carbon nanotubes, with a diameter of 1.4 to 3 nm. The multi-ply carbon nanotubes are characterized by 3 to 15 ply layers with diameters ranging from 5 to 100 nm.
Carbon nanotubes of the present invention is a single-ply or multi-ply carbon nanotubes due to the excellent electrical properties and high specific surface area, there is an effect that can exhibit more excellent properties than conventional electrical materials.
On the other hand, the carbon nanotubes of
This has the effect that carbon nanotubes grow vertically, thereby achieving a higher contact area as compared to carbon nanotubes growing horizontally, thereby making the most of the high specific surface area of carbon nanotubes. There is.
In addition, the growth of the carbon nanotubes in
Plasma chemical vapor deposition is a method performed by using a plasma to generate a glow discharge in a chamber or a reactor by a high frequency power source applied to a positive electrode. This has the advantage of synthesizing carbon nanotubes at a low temperature compared to the thermochemical vapor deposition method, and has the advantage of growing carbon nanotubes oriented perpendicular to the substrate.
In
On the other hand, the present invention provides a carbon nanotube electrode produced through the above manufacturing method.
The carbon nanotube electrode of the present invention is formed of a carbon electrode such as carbon degradation, the bottom electrode, and by growing the carbon nanotube vertically to the top there is an effect that shows an excellent electrical characteristics compared to the conventional electrode In terms of its manufacturing process, it is characterized by having a concise process.
In addition, the carbon nanotube electrode of the present invention has the effect that the junction between the carbon nanotubes and the carbon electrode is well formed, the electrochemical signal is well transmitted, through which the effect is applicable to high sensitivity electrochemical sensor, fuel cell, electron beam source, etc. have.
Furthermore, the present invention comprises the steps of coating and patterning the polymer on the insulating substrate (step a);
Coating and patterning the polymer on top of the patterned portion of
It provides a method for producing a carbon pillar electrode comprising the step (step c) of heat-treating the polymer laminated in the pillar structure of step b.
Step a is a step of coating and patterning the polymer on the insulating substrate, the substrate of step a is an insulating substrate selected from the group consisting of silicon, quartz, sapphire, glass and alumina, The polymer is coated onto the substrate and patterned into the desired electrode form.
In addition, the polymer is preferably a polymer having a photo functional group, more preferably SU8-2002 photoresist. By using the polymer having the optical functional group there is an effect that can be easily patterned through exposure and development through a mask.
In addition, the coating of step a is preferably carried out through spin coating. Spin coating has the effect of coating the polymer onto the substrate in a short time.
Step b is a step of laminating a pillar structure by coating and patterning the polymer on top of the patterned part in step a.
The polymer used in step b is preferably a polymer having a photo functional group, more preferably SU8-2010 photoresist. By using the polymer having the optical functional group there is an effect that can be easily patterned through exposure and development through a mask.
In addition, the coating of step b is preferably carried out through spin coating. Spin coating has the effect of coating the polymer onto the substrate in a short time, but there is no limitation.
Step c is a step of carbonizing the heat-treated polymer patterned and laminated in step b.
Through step c, the polymer patterned and stacked in step b may be carbonized to be made into deteriorated carbon having a filler structure, and thus carbon pillar electrodes may be manufactured.
At this time, the heat treatment of step c is preferably carried out for 20 to 40 minutes at a temperature of 800 to 1000 ℃.
If the heat treatment is performed at a temperature of less than 800 ℃ has a problem that the specific resistance of the formed carbon electrode is too large, if the heat treatment is performed at a temperature exceeding 1000 ℃ there is a problem that the process is difficult to perform due to unnecessarily high temperature . In addition, when the heat treatment is performed for less than 20 minutes, the resistance of the formed electrode is too large, there is a problem that unnecessary time waste may occur when the heat treatment is performed for more than 40 minutes.
In addition, the present invention provides a carbon pillar electrode prepared through the above manufacturing method.
The carbon pillar electrode of the present invention can form a pillar structure by patterning and stacking a polymer having an optical functional group and forming a pillar structure by heating and carbonizing it to form a pillar structure. Since the carbon pillar electrode of the present invention has excellent electrical properties, there is an effect that can be applied as an electrochemical sensor.
Hereinafter, the present invention will be described in more detail by the following examples.
However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
Example 1 Preparation of
Step 1: The SU8-2002 photoresist was spin-coated on the silicon substrate coated with the silicon oxide film at 4000 rpm for 30 seconds, and heat-treated for 1 minute and 3 minutes at a temperature of 65 ° C. and 95 ° C., respectively. After the exposure using a mask according to the pattern of the electrode, and then heat-treated for 1 minute and 3 minutes at a temperature of 65 ℃ and 95 ℃, respectively, immersed it in a developing solution to remove the patterned photoresist was patterned, 900 ℃ Heat treatment for 30 minutes at the temperature of to form a carbon-based bottom electrode.
Step 2: The SU8-2002 photoresist was spin coated on the bottom electrode formed in
Step 3: A 10 nm thin film of aluminum was deposited on the substrate on which the patterning of
Step 4: A carbon nanotube electrode was prepared by vertically growing carbon nanotubes on the substrate on which the catalyst layer of
Example 2 Preparation of
A carbon nanotube electrode was manufactured in the same manner as in Example 1 except that the method further includes forming an insulating layer through the silicon nitride film after forming the bottom electrode of
Example 3 Fabrication of Carbon Pillar Electrode
Step 1: The SU8-2002 photoresist was spin-coated on the silicon oxide coated silicon substrate at 4000 rpm for 30 seconds, and heat-treated at 65 ° C. and 95 ° C. for 1 minute and 3 minutes, respectively. After the exposure using a mask according to the pattern of the electrode and heat treatment for 1 minute and 3 minutes at a temperature of 65 ℃ and 95 ℃ respectively, and then immersed it in a developer solution to remove the unnecessary pattern photoresist patterned.
Step 2: The SU8-2010 photoresist was spin-coated on the substrate subjected to the patterning of
Step 3: The carbon pillar electrode was manufactured by heat-treating the substrate on which the polymer was laminated in the pillar structure for 30 minutes at a temperature of 900 ° C. in the furnace.
≪ Comparative Example 1 &
An electrode was manufactured in the same manner as in Example 2, except that carbon nanotubes were grown on the platinum electrode instead of the degraded carbon electrode of the present invention.
Experimental Example 1 Scanning Electron Microscope Analysis
The electrodes prepared by Examples 2 and 3 of the present invention and the electrodes prepared by Comparative Example 1 were observed through a scanning electron microscope, and the results are shown in FIGS. 3, 4, and 5.
As shown in Figures 3, 4 and 5, it can be seen that the electrode produced by the embodiment of the present invention was well manufactured in the desired pattern. In particular, in the case of the electrode manufactured by Example 2, it can be seen that the carbon nanotubes were grown vertically, and in the case of the electrode manufactured by Example 3, it was found that the entire electrode was made of a deteriorated carbon electrode having a pillar structure. .
In addition, it can be seen that the electrode manufactured through Comparative Example 1 was also made of an electrode having a desired pattern.
Experimental Example 2 Evaluation of Electrochemical Properties
(1)
Potassium ferricyanide (K 3 [Fe (CN) 6 ]) was added to deionized water (DI) and 100 mM KCl solution, respectively. Cyclic voltammetry was measured by addition of redox reaction molecules, and cyclic voltammetry in pure deionized water without potassium ferricyanide was measured. The results are shown in FIG. 6. At this time, the carbon nanotube electrode was used as the working electrode for cyclic voltammetry measurement, and the electrochemical signal was measured using a three-electrode system of a counter electrode made of platinum and an Ag / AgCl reference electrode.
As shown in FIG. 6, when the ferricyanide is added as a redox reaction molecule to measure cyclic voltammetry, an electrochemical reaction can be observed, and the electrode prepared according to Example 2 of the present invention has microelectrode characteristics. It could be confirmed that it represents. On the other hand, pure deionized water without potassium ferricyanide was found to have no current flow between the electrode and the solution.
In the cyclic voltammetry measurement, when a potential is applied to a carbon nanotube electrode, which is a working electrode, electrons are transferred from the carbon nanotube electrode to active species in the solution according to the voltage value applied to reduce molecules in the solution, or vice versa. From the molecules in the electrons are transferred to the carbon nanotube electrode to see that the molecules in the solution is oxidized. The cyclic voltammetry is an analytical tool for observing the oxidation and reduction of such molecules. The cyclic voltammetry circulates a potential at a constant speed to the working electrode based on the reference electrode, and measures the current between the working electrode and the counter electrode. Is done. Cyclic voltammetry is a method widely used as a method of directly knowing the reaction occurring on the surface of the electrode. As shown in the above results, it was confirmed that the carbon nanotubes were electrically connected to the degraded carbon bottom electrode of the present invention. It was found that the carbon nanotube electrode functions as an electrode.
(2)
The redox reaction of potassium ferricyanide (K 3 [Fe (CN) 6 ]) with deionized water (DI) and 100 mM KCl solution was carried out in the electrode prepared according to Comparative Example 1 of the present invention. Cyclic voltammetry was measured by addition of molecules, and cyclic voltammetry in pure deionized water without potassium periyanide and cyclic voltammetry in 100 mM KCl solution were measured. The results are shown in FIG. 7.
As shown in FIG. 7, the electrode manufactured by Comparative Example 1 did not have a clear electrochemical characteristic, which is why the electrical bonding between the platinum electrode and the carbon nanotube is not good, unlike the carbon nanotube electrode of the present invention. It seems to be.
Accordingly, it could be confirmed that the electric carbon exhibited excellent electrical properties due to the bonding of the carbon deteriorated carbon electrode and the bottom electrode according to the present invention.
(3) electrochemical signal change measurement
In order to measure the electrochemical signal change of the carbon nanotube electrode prepared according to Example 2 of the present invention and the electrode in which no carbon nanotubes are present, the same procedure as in the Cyclic voltammetry analysis method was performed. The electrochemical signal change was measured, and the result is shown in FIG. 8.
As shown in FIG. 8, it can be seen that the electrochemical signal is increased in the carbon nanotube electrode of Example 2 rather than the case where the carbon nanotube is not present until the
(4) electrochemical characterization
The carbon pillar electrode prepared by Example 3 of the present invention was redoxed with potassium ferricyanide (K 3 [Fe (CN) 6 ])) in deionized water (DI) and 100 mM KCl solution. It was added as a reaction molecule, but the amount was changed and analyzed the electrochemical properties, the results are shown in Figure 9 below.
As shown in Figure 9 it can be seen that the carbon pillar electrode prepared by Example 3 of the present invention exhibits the electrochemical properties. At this time, it can be seen that as the amount of potassium ferricyanide added increases, the electrochemical characteristics are further improved.
Through this, it can be seen that the carbon pillar electrode of the present invention has sufficient electrochemical characteristics to be applied as an electrochemical sensor.
1: substrate
2: carbon electrode
3: insulation layer
4: catalyst layer
5: carbon nanotube
Claims (30)
Forming a catalyst layer on the bottom electrode of step 1 (step 2); And
In the carbon nanotube electrode manufacturing method comprising the step (step 3) of growing carbon nanotubes on the substrate on which the catalyst layer is formed in step 2,
The bottom electrode is a carbon nanotube electrode manufacturing method, characterized in that formed of at least one carbon material selected from the group consisting of deteriorated carbon, carbon nanotube film, activated carbon, diamond thin film and graphite.
The method of manufacturing a carbon nanotube electrode, characterized in that formed by the bottom electrode of the carbon material by coating and patterning the polymer on the substrate and heat treatment.
Forming a catalyst layer on the bottom electrode of step 1 (step 2); And
In the carbon nanotube electrode manufacturing method comprising the step (step 3) of growing carbon nanotubes on the substrate on which the catalyst layer is formed in step 2,
The bottom electrode of step 1,
Growing a graphene thin film (step a);
Separating the graphene thin film of step a (step b);
Transferring the graphene thin film separated in the step B to an upper portion of the substrate (step c);
Performing patterning on the graphene thin film transferred in the step c (step d); And
Fabrication of carbon nanotube electrodes, characterized in that formed in the graphene bottom electrode through a process comprising the step of etching the (graph) the graphene thin film subjected to the patterning in the step d (step ㅁ) Way.
Preparing a raw material solution by dispersing carbon nanotubes, graphene flakes, or nano-sized activated carbon in an organic solvent (step A);
Patterning the electrode form over the substrate (step B);
Coating the raw material solution prepared in step A into the electrode pattern patterned in step B (step C); And
Method of manufacturing a carbon nanotube electrode, characterized in that formed in the bottom electrode of carbon nanotubes or activated carbon through a process comprising the step (step D) of forming a self-assembled film outside the patterning of step B.
After coating and patterning the polymer over the substrate to form a catalyst layer into the patterning and growing the carbon nanotubes on the catalyst layer formed carbon nanotube electrode, characterized in that formed as a planar bottom electrode.
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| KR100851950B1 (en) * | 2006-05-18 | 2008-08-12 | 경희대학교 산학협력단 | Manufacturing Method of Electron Emission Source with Selective Aarray |
| KR20120053797A (en) * | 2010-11-18 | 2012-05-29 | 경희대학교 산학협력단 | Electrode for electrochemical biosensor and biosensor including the same |
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| KR100851950B1 (en) * | 2006-05-18 | 2008-08-12 | 경희대학교 산학협력단 | Manufacturing Method of Electron Emission Source with Selective Aarray |
| KR20120053797A (en) * | 2010-11-18 | 2012-05-29 | 경희대학교 산학협력단 | Electrode for electrochemical biosensor and biosensor including the same |
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| ABDOLLAH SALIMI 등, Analytical Biochemistry, Vol. 333, pp. 49-56 (2004)* |
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