WO2014200306A1 - Method for manufacturing piled nano-electrode pairs and suspended sensor using same - Google Patents

Method for manufacturing piled nano-electrode pairs and suspended sensor using same Download PDF

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Publication number
WO2014200306A1
WO2014200306A1 PCT/KR2014/005209 KR2014005209W WO2014200306A1 WO 2014200306 A1 WO2014200306 A1 WO 2014200306A1 KR 2014005209 W KR2014005209 W KR 2014005209W WO 2014200306 A1 WO2014200306 A1 WO 2014200306A1
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Prior art keywords
photoresist
electrode
mesh
nano
substrate
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PCT/KR2014/005209
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French (fr)
Korean (ko)
Inventor
신흥주
임영진
Original Assignee
에스케이이노베이션 주식회사
국립대학법인 울산과학기술대학교 산학협력단
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Publication of WO2014200306A1 publication Critical patent/WO2014200306A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells

Definitions

  • the present invention relates to a method of manufacturing a stacked nano-electrode pair and an airborne type sensor using the same. More specifically, the present invention effectively adjusts the spacing between a carbon flat electrode and an airborne carbon nanomesh through thin and dense through the present invention.
  • Hankuk Heavy Industries Hankuk Heavy Industries
  • the present invention relates to a method for manufacturing a nested nanoelectrode pair in which carbon nanomeshes are formed in high yield, and to an aerial type biosensor or an electrochemical sensor manufactured using the same.
  • Semiconductor sensors are being developed in the midst of development of biomaterial sensors, and their manufacturing is simplified and their performance is improved. All sensors are aimed at improving the sensitivity to improve performance, and efforts to achieve these goals are also made. Is increasing.
  • electrochemical sensors or optical sensors are mainly used for biosensing.
  • the optical sensor has a disadvantage in that the reaction speed is higher than that of other sensors, and the detection degree is also high or large, resulting in poor space utilization and inconvenience in use.
  • An end point of the optical sensor can be overcome by using an electrochemical sensor, which electrochemically oxidizes or reduces an object to measure current flowing to an external circuit, or dissolves or silvers it in an electrolyte solution or solid state.
  • the gas phase utilizes electromotive force generated by the action of the ion ion, which is small in size, but has a very slow reaction rate and a low sensitivity.
  • the electrochemical sensor measures the concentration of the component to be analyzed in an aqueous liquid sample by placing a sample in the reaction zone in an electrochemical cell containing two electrodes with impedances to make current measurements appropriate. React directly or indirectly with the redox agent to determine the concentration of the component to be analyzed. The amount of oxidative or reducible material present is then measured electrochemically.
  • the above method does not allow the electrolytic product to touch other electrodes and react at the next electrode while it is measurable. It requires a separate separation between the electrodes so that they do not interfere. Despite the high cost, the manufacturing process is complicated.
  • the present invention improves the sensing sensitivity of existing airborne nano-type nanowire sensors and effectively improves the manufacturing limits of overlapping nanoelectrode pairs.
  • the present invention provides a method of manufacturing a superimposed nano-electrode pair
  • the contact between the carbon nanomesh and the electrode is physically and electrically stable by using the overlapping nanoelectrode pair of the present invention, so that the sensing sensitivity is improved, and the production cost and productivity of the nanowire-based sensor are low.
  • the aim is to provide biosensors or electrochemical sensors that can be dramatically increased in mass production.
  • a space-separation layer covering the electrode, c) a photoresist-like backside and a mesh-shaped photoresist such as a spacer and spaced apart from the photoresist electrode. Forming a mesh and d) the substrate formed photoresist electrode,
  • the step a) includes applying a first photoresist on the substrate and exposing the first photoresist. And developing a photoresist electrode on the substrate.
  • the first photoresist may be a negative photoresist, more specifically SU-8.
  • the method may include forming a spaced space securing layer, which is an unexposed second photomask region covering the photoresist electrode.
  • the step b) may further include exposing and enabling the spaced space securing layer.
  • the second photoresist may be a positive photoresist, more specifically
  • the method of manufacturing a stacked nano-electrode pair according to an embodiment of the present invention, wherein c) includes: applying a third photoresist onto a substrate on which the spaced layer is formed. Exposing the resist to form a photoresist back portion, which is two light-shaped exposure regions spaced apart from the photoresist electrode by a predetermined distance with the photoresist electrode interposed therebetween; and reexposing the photoresist.
  • the photoresist electrode may be formed to cross the photoresist electrode to form a photoresist mesh, which is a mesh-shaped exposure region that connects the two lamp-shaped exposure regions of the photoresist pillar.
  • the step c) may include forming the photoresist mesh. After the resist light register and the photoresist mesh are formed, the development removes the unexposed region and the space-separation layer, which are unexposed third photoresist regions, in the step c). It may further include the steps to do so.
  • the third photoresist may be a negative photoresist, and more specifically, SU ⁇ 8.
  • the angle ⁇ between the wires of the photoresist mesh may be 40 ° to 60 °.
  • a chamber of the present invention The method of manufacturing a nested nano-electrode pair according to an embodiment described above.
  • multi-stage heat treatment in the step may include a second phase which is performed, at 300 to 400 o C for 30 to 90 minutes in the first stage and 900 to 1000 ° C is performed for 30 to 90 minutes.
  • a method of manufacturing a nested nano-electrode pair According to an embodiment of the present invention, a method of manufacturing a nested nano-electrode pair,
  • the second photoresist may be thicker than the first photoresist.
  • the third photoresist may be thicker than the second photoresist.
  • a notary type sensor comprising a pair of electrodes and a glucose enzyme as a sensing material, wherein the glucose enzyme may be glucose oxidase.
  • the present invention provides a method for manufacturing a superimposed nano-electrode pair, which includes
  • a superposed nano-electrode pair can be manufactured to minimize the gap between the carbon electrode and the carbon nanomesh.
  • the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention physically and electrically stabilizes the contact between the nanowires and the electrode, thereby ensuring a higher sensing sensitivity than the conventional one. have.
  • the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention has the advantage of low production cost and increased productivity due to the nanowire-based mass production.
  • FIG. 1 illustrates a manufacturing process of a method for manufacturing a superposed nano-electrode pair according to the present invention.
  • Figure 2 is an airborne type formed by manufacturing overlapping nano-electrode pairs of the present invention.
  • FIG. 3 is a schematic view showing the planar electrode and the airborne carbon nanomesh of the overlapping nanoelectrode pair formed by the method of manufacturing the overlapping nanoelectrode pair according to the present invention.
  • FIG. 4 illustrates a dense overlapping type formed by an embodiment of the present invention.
  • Fig. 5 shows the results of a cyclic-current voltage experiment to show the electrochemical characteristics and characteristics of the overlapping carbon nanoelectrode pairs as electrochemical sensors.
  • a method of manufacturing a superposed nano-electrode pair according to the present invention comprises: a) photoresist on a substrate;
  • Forming an electrode b) forming a space replenishment to cover the photoresist electrode; c) forming a dorsal photoresist back and mesh-shaped photoresist mesh so as to be spaced apart from the photoresist electrode; and d) the substrate-formed photoresist electrode, the photoresist back, and the photoresist mesh. And thermally decomposing the exposed area of the substrate.
  • a photoresist electrode 12 is formed on the first substrate 10 for the production of the overlapped nano-electrode pair of the present invention.
  • a substrate 10 having an insulating surface 10b is prepared as in (1).
  • the substrate 10 has an insulating surface 10b in order to prevent electrical connection between the carbon lamp 30 and the planar electrode 20 produced by the present invention.
  • a substrate having such an insulating surface 10b. (U)) does not place any special limitation on the aspect for achieving the object of the present invention, but preferably silicon substrate 10a or insulator substrate 10 is coated with insulating material 10b. Can be used.
  • the silicon substrate 10a coated with the insulating material 10b when used, all of the coated insulating material 10b can be used as long as it can prevent any electrical connection.
  • silicon dioxide Alternatively, a silicon nitride column may be used.
  • quartz or aluminum oxide is used as the insulator substrate 10.
  • washing process Before application of the first photoresist 11, it is preferable to perform an additional washing process to remove fine impurities.
  • the substrate having the insulating surface 10b (hereinafter, the substrate having the insulating surface is described as 'substrate 10') is completed, the substrate as shown in FIG.
  • the first photoresist 11 is coated on the top.
  • photoresist (U) may be carried out in a non-limiting manner known to the skilled person, for example by a variety of methods such as spin coating, dip coating or gravure coating.
  • one photoresist (U) is not limited in principle, it is preferable to use a negative photoresist, for example, SU-8 photoresist may be used.
  • the thickness of the first photoresist 11 is 0.5 to ⁇ , preferably 3 to 5 ⁇ .
  • the coating thickness of the first photoresist (II) is limited to 0.5 ⁇ or more. It is for easy formation of the electrode 20, and the coating thickness of the first photoresist 11 is limited to ⁇ because the effect as a biosensor or an electrochemical sensor is not greatly improved even if the thickness exceeds ⁇ . . Therefore, it is natural that the overlapping nanoelectrode pair of the present invention in which the coating thickness of the first photoresist 11 is formed between 3 and 5 mu m is excellent in electrode formation and sensor as a biosensor or an electrochemical sensor.
  • the substrate 10 is sufficiently cooled down. After confirming that silver is in the same state as the temperature before step (a), the subsequent process is performed.
  • the specific conditions of soft bake are applicable for 80 to 120 to 3 to 5 minutes.
  • the first photoresist 11 is exposed and developed as shown in (3) and (4) of FIG.
  • the photoresist electrode 12 is formed on the substrate 10.
  • the exposure was performed by irradiating UV or the like to the first photoresist 11 through a photomask window in the shape of a planar electrode 20.
  • the shape of the planar electrode 20 is predetermined according to the design to be manufactured.
  • the straight pattern having a constant width is formed in a form spaced apart at regular intervals to form a constant shape of the carbon nanomesh 40 of the present invention and to increase the yield.
  • the first photoresist 11 is cured.
  • Photoresist electrode 12 is formed. At this time, the exposed light energy
  • first photoresist 11 can be cured from the top of the first photoresist 11 to just above the substrate 10.
  • the first photoresist 11 of the remaining portion except for the photoresist electrode 12 formed by the exposure is removed by development.
  • various types of developers known to those skilled in the art may be used, and for example, a SU-8 developer may be used.
  • the photoresist is formed on the substrate 10 through the development.
  • the second photoresist 14 is coated on the substrate 10 on which the photoresist electrode 12 is formed, as shown in FIG.
  • the method of coating may be performed by a non-limiting method known to those skilled in the art, for example, it may be carried out by various methods such as spin coating, dip coating, or gravure coating.
  • the second photoresist 14 is not limited in principle, but it is preferable to use a positive photoresist.
  • the AZ-9260 photoresist may be used.
  • the thickness of the second photoresist 14 is applied is 3 to 12 ⁇ , preferably 5 to 7 ⁇ thicker than the first photoresist (1 1) of step (a). If the thickness of the second photoresist 14 is not thicker than that of the first photoresist 11, the second photoresist 14 is uniformly coated on the outer surface of the photoresist electrode 12 in a subsequent process. It may not be.
  • the photoresist electrode 12 and the substrate 10 in which the second photoresist 14 is applied are weakly applied before the subsequent process is performed. It is desirable to proceed with a soft bake. At this time, when the soft bake process is terminated, the substrate 10 is naturally cooled down, and after confirming that the temperature is the same as the temperature before the step (a), the subsequent process is performed. The specific conditions of soft bake at this time correspond to the application for 6 to 8 minutes at 80 to 120 ° C. Subsequently, as shown in (6) and (7) of FIG. 1, the second photoresist 14 is exposed and developed to cover the photoresist electrode 12, which is an unexposed second photomask region.
  • Spacer space securing layers 14a and 14b are formed.
  • the photomask used for exposure is designed to cover the photoresist electrode 12, and is designed to be largely masked at regular intervals along the array of the photoresist electrode 12.
  • the secondary exposure is performed through the designed photomask and the development is performed, the unexposed region remains as it is, and the space-separation layer having a predetermined thickness coated on the outer surface of the photoresist electrode 12 ( 14a) is formed.
  • the space-separation layer 14a is preferably formed with a thickness of at least 2 ⁇ .
  • the mask is designed to increase the width above ⁇ .
  • Forming the space-separating layer 14a with a thickness of 2 ⁇ or more is to effectively prevent physical and electrical contact with the photoresist electrode 1.2 during the manufacture of the photoresist mesh 18 in a subsequent process.
  • the space-separation replenishment 14a, 14b is used to form the photoresist substrate 17 and the photoresist mesh 18 so as to be spaced apart from the photoresist electrode 12 on the substrate 10 in a subsequent process. Electrode 12 and photoresist lamp 17; and
  • a space between the photoresist electrode and the photoresist mesh is formed by forming a space between the photoresist electrodes at a predetermined interval and then forming a photoresist mesh. The distance between the carbon plane electrode and the carbon nanomesh can be adjusted efficiently, and this process can minimize the gap between the carbon plane electrode and the carbon nanomesh.
  • the area is removed and only the space securing layer 14a is left.
  • AZ developer can be used.
  • the specific method of washing in the washing is not limited, and it is also possible to perform sequential washing in order of isopropyl alcohol and methanol, for example, or washing using a photoresist asher. .
  • the space-separation layer 14a Upon completion, as shown in (8) of FIG. 1, the space-separation layer 14a is exposed and solubilized.
  • This gap-separation layer 14b solubilized by exposure is completely removed during development of the subsequent process. That is, since the nanoelectrode pair of the present invention is manufactured in a superposition type, when the exposure is performed in a state where the photoresist mesh 18 is supported, it is difficult to completely remove the gap space securing layer 14a. There is this. Therefore, in the subsequent process, the space-separation layer 14b is sufficiently solubilized in advance and deformed into a solubilized space-separation layer 14b.
  • a third photoresist 16 is applied onto the substrate 10 on which the solubilized separation space 14b is formed, as shown in FIG.
  • the coating method may be performed by a non-limiting method known to those skilled in the art, for example, it may be carried out by various methods such as spin coating, dip coating, or gravure coating.
  • the third toresist is not limited in principle, but negative
  • a photoresist for example, SU-8 photoresist.
  • the thickness of the third photoresist 16 is 6 to 15 ⁇ , preferably 8 to
  • ⁇ is formed sufficiently thicker than the two photoresist 14 of step (c). This is because the thickness of the third photoresist 16 must be sufficiently provided to secure the thickness of the third photoresist 16 and to form the photoresist mesh 18 in an air-lifted form in a subsequent process. to be.
  • the substrate 00) is sufficiently cooled down naturally to confirm that the temperature is the same as the temperature before the step (a).
  • the specific conditions of soft bake are applicable for 6 to 8 minutes at 80 to 120 ° C.
  • the photoresist light emitting part ⁇ which is an exposure area of two lamps, which is spaced apart from the electrode 12 and is spaced apart from each other by a distance, is formed. 10) It should be divided enough to harden up to the top.
  • the substrate (K) is sufficiently cooled to confirm that the temperature is the same as the temperature before performing step (a).
  • the specific conditions of bake are applicable for 6 to 8 minutes at 80 to 120 0C.
  • the third photoresist 16 is reexposed as shown in FIG. 1 (11).
  • a photoresist mesh 18 is formed across the photoresist electrode 1.2, which is a mesh-shaped exposure region that connects the two lamp-shaped exposure regions of the photoresist lamp portion 17.
  • the re-exposure energy is transferred to the photoresist lamp back ( 17) Only the top of the photoresist was cured, with a limit to less than the exposure energy to form.
  • the re-exposure energy is the exposure energy for forming the photoresist light emitting part 17.
  • the re-exposure energy may be hardened to match the thickness of the photoresist mesh desired to be obtained, and the size to be cured from the top of the photoresist to the spacing layer.
  • the photoresist may be formed as described above. From cast top board 10 which will be added to a size which is cured to just above it is also possible.
  • the thickness of the photoresist mesh formed in the present invention is the thickness of the photoresist mesh formed in the present invention.
  • the angle ⁇ between the wires of the photoresist mesh 18 is 40 ° in order to form a thinner and denser airborne carbon nanomesh 40. It is preferable to adopt a range of from 60 °. This indicates that the carbon nanomesh 40, which is finally formed when the angle ⁇ between the wires of the photoresist mesh 18 is adopted in the range of 40 ° to 60 °, has the most compact shape through FIG. can confirm.
  • the specific conditions of the post exposure bake corresponds to the application for 1 to 15 minutes at 80 to 120 ° C.
  • the specific method of washing in washing is non-limiting, and it is also possible to perform sequential washing in order of isopropyl alcohol and methanol, for example. Alternatively, it is also possible to clean using a photoresist asher.
  • the photoresist electrode 12 formed on the substrate 10, the photoresist light emitting portion 17 and the photoresist mesh 18 are subjected to multi-stage heat treatment.
  • the pyrolysis is performed in the photoresist mesh 18 as shown in FIG.
  • the photoresist light emitting portion 17 and the photoresist electrode 12 are transformed into a planar electrode 20, a carbon pillar 30, and an airborne carbon nanomesh 40.
  • the planar electrode 20 and the airborne carbon nanomesh 40 can be seen in FIG. 3.
  • the photoresist electrode 12 is transformed into a planar electrode 20, and the photoresist group lamp 17 has a carbon post;
  • the carbon column 30 thus formed is an airborne type.
  • the carbon nanomesh 40 is subjected to a predetermined interval from the substrate 10.
  • the thermal decomposition occurs simultaneously at the photoresist mesh 18 and the photoresist lamp 17 supporting the photoresist mesh.
  • the resist mesh 18 is transformed to carbon nanomesh 40, it is subjected to tension from both edges so that the photoresist mesh 18 is deformed to carbon nanomesh 40 without sagging.
  • the purpose of the overlapping nanoelectrode pair manufacturing method according to the present invention is thin and compact
  • the present inventors have adopted a particular form of the pyrolysis feature for this purpose.
  • the thermal decomposition is the first step and is performed in two steps of the second step, the second step is conducted at a temperature greater than the first.
  • the first step is from 300 to 400 30 to 90 minutes at U C.
  • the second stage is run for 30 to 90 minutes at 900 to 1000 o C. More specifically, the temperature is raised to 1 ° C / min (min) from 300 to 400 ° C, while maintaining 30 to 90 minutes at 300 to 400 ° C.
  • the above] step is carried out, after which 1 to 900 to 1000 0 C
  • the second step is performed while raising the temperature to 0 C / min (min) and maintaining 30 to 90 minutes at 900 to 1000 ° C.
  • the photoresist mesh (1.8), the photoresist back part ( ⁇ ) and the photoresist electrode 12 are put into an electric furnace, and a low vacuum pump and a high vacuum pump are used. It is also possible to create an atmosphere of 7 to 10-5 torr and then reproduce this particular type.
  • the airborne carbon nanomesh 40 is naturally cooled and then removed from the atmosphere of pyrolysis.
  • a photoresist asher can be used to remove the carbon particles generated during the pyrolysis process.
  • the airborne carbon nanomesh 40 manufactured by the above manufacturing method is shown in FIG.
  • the type of air is manufactured as such.
  • the carbon nanomesh 40 has a width of 200 to 400 nm and a carbon nanowire spacing of 3 to 7 ⁇ .
  • the manufacturing method is simple and economical, and the yield of the overlapping nano electrode pair finally formed by the manufacturing method is Corresponding to a high yield of 70% or more, preferably 80% or more.
  • the above manufacturing method has the phenomena of providing thin and dense airborne carbon nanomesh 40 in high yield.
  • a biosensing material or an electrochemical sensing material is laminated on the overlapping nanoelectrode pair manufactured by the manufacturing method, and the sensing property is improved and the size and volume are reduced.
  • a biosensor or electrochemical sensor employing a superposed nano-electrode pair.
  • the bio-sensing material is not particularly limited as long as it adopts various ones known to those skilled in the art. However, it is preferable to select a substance that generates a redox substance capable of measuring electrochemical current in response to a specific biomaterial, such as a glucose enzyme, and specifically, adopts a glucose oxidase. It is good.
  • the electrochemical sensing material is also not limited as long as it adopts various ones known to those skilled in the art.
  • the mask is designed to cover the photoresist electrode on top of the photoresist electrode, and then exposed. [7] The exposed part was removed by developing using AX developer (AZ developer). [8] Then, exposure was carried out in the absence of the photomask, so as to solubilize AZ-9260, a second photoresist that was not removed by development in the previous step.
  • AX developer AZ developer
  • the third photoresist SU-8 was evenly coated on the insulating layer, the photoresist electrode and the solubilized second photoresist with a thickness of 9 ⁇ by spin coating.
  • a photoresist mesh was formed. [12] After exposure, the remaining parts except the exposed part using SU-8 developer (SU-8 developer)
  • the atmosphere was made up to 10-6 torr by using a low vacuum pump and a high vacuum pump, and then Pyrolysis was carried out in stages. Specifically up to 350 ° C ⁇ minutes (min) were raised to maintain the 60 minutes at 350 ° C. After the first step, the temperature was raised to 1 0 C / min (min) to 900 ° C and maintained at 900 ° C 60 minutes I proceeded to the second stage. After the pyrolysis, the flat electrode 20, the carbon lamp 30, and the airborne carbon nanomesh 40 were naturally cooled and removed from the electric furnace.
  • the overlapped nano-electrode pair finally formed in Example 1 has a yield of 75%.
  • the shape and structural features of the airborne carbon nanomesh 40 are SEM (Quanta 200, FEI company USA), HRTEM (JEM-2100F, JEOL Ltd., Japan), FIB (Quanta 3D FEG, FEI company, USA), And Raman spectroscopy system (alpha300R, WITec GmbH, Germany).
  • the measured width of the carbon nanomesh corresponds to 300 nm and the carbon nanowire spacing corresponds to 4.5 ⁇ .
  • the redox repeat means between the planar electrode and the carbon nanomesh.
  • the redox material repeats the oxidation and reduction reactions to amplify the current signal value. As the distance between the planar electrode and the carbon nanomesh decreases, the redox repetition effect is increased to increase the current signal amplification degree. .
  • the orange graph and the red graph represent current values obtained from the carbon nanomesh and the planar electrode when redox repetition does not occur.
  • the upper green graph and the lower green graph respectively represent the carbon nanomesh and the carbon plane.
  • the current value amplified through the redox repeat obtained from the electrode is shown.
  • the solution used in the experiment is 10 mM Ferrocyanide.
  • the gap between the planar electrode and the carbon nanomesh of the superposed nanoelectrode pair of the present invention was minimized to confirm that the redox repetition effect was increased and the current signal was amplified. Can be.
  • ⁇ Effectively control the distance between carbon flat electrode and airborne carbon nanomesh while effectively blocking the contact of carbon nanomesh, it is easy to manufacture high yield thin and dense airborne carbon nanomesh easily.
  • a superposed nano-electrode pair can be manufactured to minimize the gap between the carbon electrode and the carbon nanomesh.
  • the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention can physically and electrically stabilize the contact between the nanowires and the electrode, thereby ensuring a higher sensitivity than the conventional one.
  • the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention has the advantage of low production cost and increased productivity due to nanowire-based, which enables mass production.
  • insulator substrate 10a silicon substrate

Abstract

The present invention provides a method for manufacturing piled nano-electrode pairs, which is an application form of a suspended carbon nanowire capable of efficiently solving the problems of conventional suspended nanowire sensors, such as yield reduction and manufacturing limitation. Further, the present invention provides piled nano-electrode pairs in which a suspended carbon nano-mesh with a thin and compact form is manufactured with high yield. The present invention also provides a biosensor or an electrochemical sensor with improved sensitivity, in which a carbon nano-mesh is in a physically and electrically stable contact with an electrode by applying the piled nano-electrode pairs manufactured in accordance with the present invention.

Description

명세서  Specification
발명의명칭:중첩형나노전극쌍제조방법및이를이용한  NAME OF THE INVENTION: METHOD OF MANUFACTURING Nested Nano Electrode Pairs
공중부유형센서  Airborne Type Sensor
기술분야  Field of technology
[1] 본발명은증첩형나노전극쌍제조방법및이를이용한공중부유형센서에 관한것으로서，보다상세하게는본발명을통하여탄소평면전극과공중부유형 탄소나노메쉬의간격을효과적으로조절하여얇고조밀한공중부유형  [1] The present invention relates to a method of manufacturing a stacked nano-electrode pair and an airborne type sensor using the same. More specifically, the present invention effectively adjusts the spacing between a carbon flat electrode and an airborne carbon nanomesh through thin and dense through the present invention. Hankuk Heavy Industries
탄소나노메쉬가고수율로형성된중첩형나노전극쌍을제조하는방법과이를 이용하여제조된공중부유형바이오센서또는전기화학센서에관한것이다.  The present invention relates to a method for manufacturing a nested nanoelectrode pair in which carbon nanomeshes are formed in high yield, and to an aerial type biosensor or an electrochemical sensor manufactured using the same.
[2]  [2]
배경기술  Background
[3] 최근환경문제에대한관심증가와정보통신기기의발전과더불어다양한  [3] Along with the growing interest in environmental issues and the development of information and communication equipment,
바이오물질에대한센서가개발되고있는가운데반도체기슬을접목함으로써 제조가간편해지고그성능이향상되고있다.모든센서는성능향상을위하여 감지도를높이는것이최대목표이며，이러한목표를달성하기위한노력도 증가되고있다.  Semiconductor sensors are being developed in the midst of development of biomaterial sensors, and their manufacturing is simplified and their performance is improved. All sensors are aimed at improving the sensitivity to improve performance, and efforts to achieve these goals are also made. Is increasing.
[4] 한편,바이오센싱에는전기화학적센서또는광센서가주로사용되어지고 있다.  On the other hand, electrochemical sensors or optical sensors are mainly used for biosensing.
[5] 상기광센서는，여타의센서에비하여반웅속도가빠르고,그감지도도높은 편이나크기가큰편이어서공간활용성이떨어지고사용에불편함에있다는 단점이있다.  [5] The optical sensor has a disadvantage in that the reaction speed is higher than that of other sensors, and the detection degree is also high or large, resulting in poor space utilization and inconvenience in use.
[6] 상기광센서의단점은전기화학적센서를사용하여극복할수있는데，상기 전기화학적센서는대상물질을전기화학적으로산화또는환원하여외부 회로에흐를전류를측정하거나전해질용액이나고체에용해또는이은화한 가스상의이은이이온전극에작용하여생기는기전력을이용하는것으로이는 그크기는작으나，매우느린반응속도를나타냄과더불어감도가낮다는단점이 있다.  [6] An end point of the optical sensor can be overcome by using an electrochemical sensor, which electrochemically oxidizes or reduces an object to measure current flowing to an external circuit, or dissolves or silvers it in an electrolyte solution or solid state. The gas phase utilizes electromotive force generated by the action of the ion ion, which is small in size, but has a very slow reaction rate and a low sensitivity.
[7] 즉한국등록특허제 074U87호에따르면,분석물의농도를측정하는  [7] In other words, according to Korean Patent No. 074U87, the concentration of analyte is measured.
전기화학센서는전류측정을적절하도록하는임피던스를가진두개의전극을 포함하는전기화학셀에서반응영역에샘플을놓음으로써수성액체샘플중 분석하고자하는성분의농도를측정한다.상기분석하고자하는성분은 산화환원제와직접또는간접적으로반응하여분석할성분의농도에상웅하는 . 양으로산화또는환원가능한물질을형성한다.이어서，존재하는산화또는 환원가능한물질의양은전기화학적으로측정된다.일반적으로상기방법은 전기분해생성물이다른전극에닿지못하고측정가능한동안에는다음 전극에서반응을간섭하지못하도록전극간의층분한격리를요구하고,그제조 원가가고가인데다제조공정이복잡하다는문제점이있다. The electrochemical sensor measures the concentration of the component to be analyzed in an aqueous liquid sample by placing a sample in the reaction zone in an electrochemical cell containing two electrodes with impedances to make current measurements appropriate. React directly or indirectly with the redox agent to determine the concentration of the component to be analyzed. The amount of oxidative or reducible material present is then measured electrochemically. In general, the above method does not allow the electrolytic product to touch other electrodes and react at the next electrode while it is measurable. It requires a separate separation between the electrodes so that they do not interfere. Despite the high cost, the manufacturing process is complicated.
[8]  [8]
발명의상세한설명  Detailed description of the invention
기술적과제  Technical task
[9] 본발명은기존의공중부유형나노와이어센서의센싱감도를향상시키고， 제조적한계문제둥을효과적으로개선할수있는중첩형나노전극쌍  [9] The present invention improves the sensing sensitivity of existing airborne nano-type nanowire sensors and effectively improves the manufacturing limits of overlapping nanoelectrode pairs.
제조방법을제공하기위한것이다.  It is intended to provide a manufacturing method.
[10] 구체적으로본발명은중첩형나노전극쌍제조시，탄소전극과  [10] Specifically, the present invention provides a method of manufacturing a superimposed nano-electrode pair,
탄소나노메쉬의접촉을효과적으로차단하면서도，탄소전극과탄소나노메쉬의 간격을조절하여얇고조밀한공중부유형탄소나노메쉬를고수율로형성하기 위한중첩형나노전극쌍을제조하는방법을제공하기위한것이다.  It is to provide a method of manufacturing overlapping nanoelectrode pairs to form thin and dense airborne carbon nanomeshes in high yield by controlling the gap between carbon electrodes and carbon nanomeshes while effectively blocking the contact of carbon nanomeshes. .
[11] 또한，본발명의중첩형나노전극쌍을이용하여탄소나노메쉬와전극과의 접촉이물리적，전기적으로안정하여센싱감도가향상뿐만아니라,나노와이어 기반의센서의생산비용이적으며생산성을획기적으로높여대량생산이 가능한바이오센서또는전기화학센서를제공하기위한것이다.  [11] In addition, the contact between the carbon nanomesh and the electrode is physically and electrically stable by using the overlapping nanoelectrode pair of the present invention, so that the sensing sensitivity is improved, and the production cost and productivity of the nanowire-based sensor are low. The aim is to provide biosensors or electrochemical sensors that can be dramatically increased in mass production.
[12]  [12]
과제해결수단  Task solution
[13] 본발명에따른중첩형나노전극쌍제조방법은，  [13] The manufacturing method of the overlapped nano-electrode pair according to the present invention is
[14] a)기판상부에포토레지스트전극을형성하는단계, b)상기포토레지스트  [14] a) forming a photoresist electrode on the substrate, b) the photoresist
전극을덮는이격공간확보층을형성하는단계, c)상기포토레지스트전극과 이격되도록두기등형상의포토레지스트기등부와메쉬형상의포토레지스트. 메쉬를형성하는단계및 d)상기기판상형성된포토레지스트전극,  Forming a space-separation layer covering the electrode, c) a photoresist-like backside and a mesh-shaped photoresist such as a spacer and spaced apart from the photoresist electrode. Forming a mesh and d) the substrate formed photoresist electrode,
포토레지스트기등부및포토레지스트메쉬의노광영역을다단열처리하여 열분해하는단계;를포함할수있다.  And thermally decomposing the exposed portions of the photoresist back and the photoresist mesh.
[15] 구체적으로，본발명의일실시예에따른중첩형나노전극쌍제조방법에있어， 상기 a)단계는，상기기판상부에제 1포토레지스트를도포하는단계및상기 제 1포토레지스트를노광및현상하여,상기기판상부에포토레지스트전극을 형성하는단계를포함할수있다.여기서,상기제 1포토레지스트는네거티브형 포토레지스트일수있으며，보다구체적으로는 SU-8일수있다.  Specifically, in the method for manufacturing a superposed nano-electrode pair according to an embodiment of the present invention, the step a) includes applying a first photoresist on the substrate and exposing the first photoresist. And developing a photoresist electrode on the substrate. Here, the first photoresist may be a negative photoresist, more specifically SU-8.
[16] 본발명의일실시예에따른중첩형나노전극쌍제조방법에있어,상기  [16] A method of manufacturing a nested nanoelectrode pair according to an embodiment of the present invention, wherein
b)단계는，상기포토레지스트전극이형성된기판상부에저 12포토레지스트를 도포하는단계및상기제 2포토레지스트를노광및현상하여，상기  b) the step of applying a low 12 photoresist on the substrate on which the photoresist electrode is formed and the exposure and development of the second photoresist,
포토레지스트전극을덮는미노광제 2포토마스크영역인이격공간확보층을 형성하는단계를포함할수있다.그리고，상기 b)단계는，상기이격공간확보층을 노광하여가용화시키는단계를더포함할수있다.여기서，상기  The method may include forming a spaced space securing layer, which is an unexposed second photomask region covering the photoresist electrode. The step b) may further include exposing and enabling the spaced space securing layer. Where
제 2포토레지스트는포지티브형포토레지스트일수있으며，보다구체적으로는 The second photoresist may be a positive photoresist, more specifically
AZ-9260일수있다. [17] 본발명의일실시예에따른증첩형나노전극쌍제조방법에있어,상기 c)단계는，상기이격공간확보층이형성된기판상부로제 3포토레지스트를 도포하는단계，상기,제 3포토레지스트를노광하여，상기포토레지스트전극을 사이에두고포토레지스트전극과일정거리이격되며서로대향하는두 기등형상의노광영역인포토레지스트기등부를형성하는단계및상기 거 13포토레지스트를재노광하여，상기포토레지스트전극을가로질러상기 포토레지스트기둥부의상기두기등형상의노광영역을연결하는메쉬형상의 노광영역인포토레지스트메쉬를형성하는단계를포함할수있다.그리고，상기 c)단계는，상기포토레지스트기등부및상기포토레지스트메쉬가형성된 이후에，현상을통해상기 c)단계에서미노광된제 3포토레지스트영역인 미노광영역및상기이격공간확보층을제거하는단계를더포함할수있다. 여기서，상기제 3포토레지스트는네거티브형포토레지스트일수있으며，보다 구체적으로는 SU— 8일수있다.또한，상기포토레지스트메쉬의와이어사이의 각도 (Θ)는 40。내지 60°일수있다. May be AZ-9260. [17] The method of manufacturing a stacked nano-electrode pair according to an embodiment of the present invention, wherein c) includes: applying a third photoresist onto a substrate on which the spaced layer is formed. Exposing the resist to form a photoresist back portion, which is two light-shaped exposure regions spaced apart from the photoresist electrode by a predetermined distance with the photoresist electrode interposed therebetween; and reexposing the photoresist. The photoresist electrode may be formed to cross the photoresist electrode to form a photoresist mesh, which is a mesh-shaped exposure region that connects the two lamp-shaped exposure regions of the photoresist pillar. The step c) may include forming the photoresist mesh. After the resist light register and the photoresist mesh are formed, the development removes the unexposed region and the space-separation layer, which are unexposed third photoresist regions, in the step c). It may further include the steps to do so. Here, the third photoresist may be a negative photoresist, and more specifically, SU − 8. In addition, the angle Θ between the wires of the photoresist mesh may be 40 ° to 60 °.
[18] 본발명의일실.시예에따른중첩형나노전극쌍제조방법에있어,상기 [18] A chamber of the present invention. The method of manufacturing a nested nano-electrode pair according to an embodiment described above.
d)단계에서상기다단열처리는, 300내지 400oC에서 30내지 90분동안시행되는 제 1단계및 900내지 1000°C에서 30내지 90분동안시행되는제 2단계를포함할 수있다. d) multi-stage heat treatment in the step may include a second phase which is performed, at 300 to 400 o C for 30 to 90 minutes in the first stage and 900 to 1000 ° C is performed for 30 to 90 minutes.
[19] 본발명의일실시예에따론중첩형나노전극쌍제조방법에있어,상기  According to an embodiment of the present invention, a method of manufacturing a nested nano-electrode pair,
제 2포토레지스트는상기제 1포토레지스트보다두껍게형성될수있다.  The second photoresist may be thicker than the first photoresist.
[20] 본발명의일실시예에따른중첩형나노전극쌍제조방법에있어,상기  [20] A method of manufacturing a nested nanoelectrode pair according to an embodiment of the present invention, wherein
제 3포토레지스트는상기제 2포토레지스트보다두껍게형성될수있다-.  The third photoresist may be thicker than the second photoresist.
[21] 한편，상기된방법으로제조된본발명의일실시예에따른중첩형나노  [21] On the other hand, a nested nano according to an embodiment of the present invention manufactured by the method described above
전극쌍을포함하며，감지물질로서글루코스효소 (glucose enzyme)를포함하는 공증부유형센서를제조할수있다.여기서,글루코스효소는글루코스 옥시다아제 (glucose oxidase)일수있다.  It is possible to manufacture a notary type sensor comprising a pair of electrodes and a glucose enzyme as a sensing material, wherein the glucose enzyme may be glucose oxidase.
[22]  [22]
발명의효과  Effects of the Invention
[23] 본발명의중첩형나노전극쌍제조방법은제조공정증탄소전극과  [23] The present invention provides a method for manufacturing a superimposed nano-electrode pair, which includes
탄소나노메쉬의접촉을효과적으로차단하면서탄소평면전극과공중부유형 탄소나노메쉬의간격을효과적으로조절하여고수율의얇고조밀한공중부유형 탄소나노메쉬를쉽게제조할수있는효과가있다.  It effectively blocks the contact between carbon nanomeshes and effectively controls the gap between carbon plane electrodes and airborne carbon nanomeshes, making it easy to manufacture high yield thin and dense airborne carbon nanomeshes.
[24] 또한,본발명에의하면,탄소전극과탄소나노메쉬의간격을최소화하도록 중첩형나노전극쌍을제조할수있다.  In addition, according to the present invention, a superposed nano-electrode pair can be manufactured to minimize the gap between the carbon electrode and the carbon nanomesh.
[25] 또한，본발명의중첩형나노전극쌍이채용된공중부유형바이오센서또는 전기화학센서는나노와이어와전극과의접촉이물리적，전기적으로안정하여 ■ 종래의것보다높은센싱감도를보장할수있다. [26] 또한，본발명의중첩형나노전극쌍이채용된공중부유형바이오센서또는 전기화학센서는나노와이어기반으로생산비용이적으며생산성이증대되어 대량생산이가능한장점이있다. [25] In addition, the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention physically and electrically stabilizes the contact between the nanowires and the electrode, thereby ensuring a higher sensing sensitivity than the conventional one. have. In addition, the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention has the advantage of low production cost and increased productivity due to the nanowire-based mass production.
[27]  [27]
도면의간단한설명  Brief description of the drawings
[28] 도 1은본발명의중첩형나노전극쌍제조방법의제조과정을도시한  1 illustrates a manufacturing process of a method for manufacturing a superposed nano-electrode pair according to the present invention.
도면이다.  Drawing.
[29] 도 2는본발명의중첩형나노전극쌍제조에의해형성되는공중부유형  [29] Figure 2 is an airborne type formed by manufacturing overlapping nano-electrode pairs of the present invention.
포토레지스트메쉬와탄소나노메쉬의조밀도를나타낸것이다.  It shows the density of photoresist mesh and carbon nano mesh.
[30] 도 3은본발명의중첩형나노전극쌍제조방법에의해형성되는중첩형나노 전극쌍의평면전극과공중부유형탄소나노메쉬를나타낸개략도이다. FIG. 3 is a schematic view showing the planar electrode and the airborne carbon nanomesh of the overlapping nanoelectrode pair formed by the method of manufacturing the overlapping nanoelectrode pair according to the present invention.
[31] 도 4는본발명의실시예에의하여형성된조밀한형태의중첩형 4 illustrates a dense overlapping type formed by an embodiment of the present invention.
포토레지스트전극쌍과탄소나노전극쌍의형상을나타낸다.  The shape of the photoresist electrode pair and the carbon nanoelectrode pair is shown.
[32] 도 5는중첩형탄소나노전극쌍의전기화학적특성및전기화학적센서로서의 특징을보여주기위한순환-전류전압실험결과이디—. [32] Fig. 5 shows the results of a cyclic-current voltage experiment to show the electrochemical characteristics and characteristics of the overlapping carbon nanoelectrode pairs as electrochemical sensors.
[33]  [33]
발명의실시를위한형태  Mode for Carrying Out the Invention
[34] 이하첨부한도면들을참조하여본발명에따른중첩형나노전극쌍제조방법 및이를이용한공중부유형센서를상세히설명한다.다음에소개되는도면들은 당업자에게본발명의사상이층분히전달될수있도록하기위해예로서 제공되는것이다.따라서，본발명은이하제시되는도면들에한정되지않고 다른형태로구체화될수도있으며，이하제시되는도면들은본발명의사상올 명확히하기위해과장되어도시될수있다.또한명세서전체에걸쳐서동일한 참조번호들은동일한구성요소들을나타낸다.  [34] Hereinafter, the method of manufacturing an overlapping nano-electrode pair according to the present invention and an airborne type sensor using the same will be described in detail with reference to the accompanying drawings. The drawings described below are provided to further convey the concept of the present invention to those skilled in the art. Therefore, the present invention may be embodied in other forms, not limited to the drawings presented below, and the drawings presented below may be exaggerated to clarify the spirit of the invention. Like numbers refer to like elements throughout.
[35] 이때，사용되는기술용어및과학용어에있어서다른정의가없다면，이  [35] At this time, unless otherwise defined in the technical and scientific terms used,
발명이속하는기술분야에서통상의지식을가진자가통상적으로이해하고 있는의미를가지며，하기의설명및첨부도면에서본발명의요지를  Meaningful understanding of a person having ordinary knowledge in the technical field to which the invention belongs, and the gist of the present invention in the following description and attached drawings.
불필요하게흐릴수있는공지기능및구성에대한설명은생략한다.  Omit descriptions of known functions and configurations that may be unnecessarily blurred.
[36] 본발명의중첩형나노전극쌍제조방법은 a)기판상부에포토레지스트  [36] A method of manufacturing a superposed nano-electrode pair according to the present invention comprises: a) photoresist on a substrate;
전극을형성하는단계; b)상기포토레지스트전극을덮는이격공간확보충을 형성하는단계; c)상기포토레지스트전극과이격되도록두기등형상의 포토레지스트기등부와메쉬형상의포토레지스트메쉬를형성하는단계;및 d) 상기기판상형성된포토레지스트전극,포토레지스트기등부및포토레지스트 메쉬의노광영역을다단열처리하여열분해하는단계를포함한다.  Forming an electrode; b) forming a space replenishment to cover the photoresist electrode; c) forming a dorsal photoresist back and mesh-shaped photoresist mesh so as to be spaced apart from the photoresist electrode; and d) the substrate-formed photoresist electrode, the photoresist back, and the photoresist mesh. And thermally decomposing the exposed area of the substrate.
[37] 구체적으로,본발명의중첩형나노전극쌍의제조를위하여우선기판 (10) 상부에포토레지스트전극 (12)을형성한다 .(a) Specifically, a photoresist electrode 12 is formed on the first substrate 10 for the production of the overlapped nano-electrode pair of the present invention. (A)
[38] 여기서，먼저도 1의 (1)과같이절연성표면 (10b)을갖는기판 (10)을준비한다. 상기기판 (10)이절연성표면 (10b)을갖는것은본발명에의하여제조된탄소 기등 (30)및평면전극 (20)간의전기적연결을방지하기위함이다.이와같은 절연성표면 (10b)을갖는기판 (U))은본발명의목적달성을위한측면에있어서 종류에특별한제한을두지는않으나,바람직하게는절연물질 (10b)이표면에 코팅된실리콘기판 (10a)또는절연체기판 (10)증선택적으로사용될수있다. First, a substrate 10 having an insulating surface 10b is prepared as in (1). The substrate 10 has an insulating surface 10b in order to prevent electrical connection between the carbon lamp 30 and the planar electrode 20 produced by the present invention. A substrate having such an insulating surface 10b. (U)) does not place any special limitation on the aspect for achieving the object of the present invention, but preferably silicon substrate 10a or insulator substrate 10 is coated with insulating material 10b. Can be used.
[39] 이때절연물질 (10b)이표면에코팅된실리콘기판 (10a)을사용하는경우， 코팅되는절연물질 (10b)은전기적연결을방지할수있는임의의물질이면모두 사용가능하며,일례로이산화규소또는실리콘나이트라이드둥을사용할수 있다.또는,절연체기판 (10)을사용하는경우，절연체기판 (10)으로는석영또는 산화알루미늄등이사용되는것이바람직하다. [39] In this case, when the silicon substrate 10a coated with the insulating material 10b is used, all of the coated insulating material 10b can be used as long as it can prevent any electrical connection. For example, silicon dioxide Alternatively, a silicon nitride column may be used. Alternatively, when the insulator substrate 10 is used, it is preferable that quartz or aluminum oxide is used as the insulator substrate 10.
[40] 한편，절연성표면 (10b)을갖는기판 (10)이준비되면후속공정인  [40] On the other hand, when the substrate 10 having the insulating surface 10b is prepared,
제 1포토레지스트 (11)를도포시키기전에세척공정을추가로실시하여미세 불순물을제거하기위한세척을실시함이바람직하다.이때세척의구체적인 방법은비제한적이며,예를들면피라나용액 (Piranha solution - 황산 (H2S04):과산화수소 (H202)=4:i흔합용액)에의한세척도가능하다.  Before application of the first photoresist 11, it is preferable to perform an additional washing process to remove fine impurities. The specific method of washing is non-limiting, for example, a Piranha solution (Piranha solution). Washing with sulfuric acid (H2S04): hydrogen peroxide (H202) = 4: i mixed solution) is also possible.
[41] 그리고이와같이절연성표면 (10b)을깆-는기판 (10;이하，절연성표면을갖는 기판을 '기판 (10)'으로기재함)의준비가완료되면도 1의 (2)와같이기판 (10) 상부에제 1포토레지스트 (11)를도포한디ᅳ.이때도포하는방법은통상의 [41] As described above, when the preparation of the substrate having the insulating surface 10b (hereinafter, the substrate having the insulating surface is described as 'substrate 10') is completed, the substrate as shown in FIG. The first photoresist 11 is coated on the top.
기술자에게공지된비제한적인방법으로시행될수있으며,예를들면스핀 코팅,딥코팅，또는그라비아코팅등의다양한방법에의하여시행될수있다. 또한，상기게 1포토레지스트 (U)는원칙적으로제한을두지않으나,네가티브 포토레지스트를이용함이바람직하며，일례로는 SU-8포토레지스트를이용할 수있다.  It may be carried out in a non-limiting manner known to the skilled person, for example by a variety of methods such as spin coating, dip coating or gravure coating. In addition, although one photoresist (U) is not limited in principle, it is preferable to use a negative photoresist, for example, SU-8 photoresist may be used.
[42] 또한,제 1포토레지스트 (11)가도포되는두께는 0.5내지 ΙΟμπι，바람직하게는 3 내지 5μιη이다.여기서,제 1포토레지스트 (I I)의도포두께가 0.5μιτι이상으로 제한되는것은평면전극 (20)의용이한형성을위함이며，제 1포토레지스트 (11)의 도포두께가 ΙΟμπι이하로제한되는것은두께가 ΙΟμπι를초과하더라도 바이오센서또는전기화학적센서로서의효과가크게향상되지않기때문이다. 따라서,제 1포토레지스트 (11)의도포두께가 3내지 5μιη사이로형성된본 발명의중첩형나노전극쌍은바이오센서또는전기화학적센서의전극형성및 센서로서의효과가우수함은당연하다.  In addition, the thickness of the first photoresist 11 is 0.5 to ΙΟμπι, preferably 3 to 5μιη. Here, the coating thickness of the first photoresist (II) is limited to 0.5 μιτι or more. It is for easy formation of the electrode 20, and the coating thickness of the first photoresist 11 is limited to ΙΟμπι because the effect as a biosensor or an electrochemical sensor is not greatly improved even if the thickness exceeds ΙΟμπι. . Therefore, it is natural that the overlapping nanoelectrode pair of the present invention in which the coating thickness of the first photoresist 11 is formed between 3 and 5 mu m is excellent in electrode formation and sensor as a biosensor or an electrochemical sensor.
[43] 한편,상기기판 (10)상에제 1포토레지스트 (1.1)의도포가완료되면，상기  On the other hand, when the application of the first photoresist (1.1) on the substrate 10 is completed, the
계 1포토레지스트 (U)가도포된상태의기판 (10)에약하게굽기 (soft bake)를더 시행함이바람직하다.이때약하게굽기 (soft bake)과정을종료하면，기판 (10)을 충분히자연냉각시켜상기 (a)단계를시행하기전의온도와동일한상태의 은도임을확인한후에후속공정을시행한다.이때약하게굽기 (soft bake)의 구체적조건은 80내지 120 에서 3내지 5분동안의적용에해당한다.  It is preferable to perform a soft bake on the substrate 10 with the photoresist (U) applied thereon. When the soft bake process is completed, the substrate 10 is sufficiently cooled down. After confirming that silver is in the same state as the temperature before step (a), the subsequent process is performed. The specific conditions of soft bake are applicable for 80 to 120 to 3 to 5 minutes.
[44] 이어,도 1의 (3)및 (4)와같이상기제 1포토레지스트 (11)를노광및현상하여, 상기 기판 (10) 상부에 포토레지스트 전극 (12)을 형성한다. 이 때 노광은 평면 전극 (20) 모양의 포토마스크 창을 통하여 제 1포토레지스트 ( 1 1)에 UV 등을 조사하여 실시된디-. 여기서 , 평면 전극 (20) 모양은 제조하고자 하는 설계에 따라 미 리 결정된다. 바람직하게는 일정 너 비를 갖는 일자형 패턴이 일정 간격으로 이격 된 형 태로 형성 되는 것이 본 발명 의 탄소나노메쉬 (40)의 형 태를 일정하게 형성시키고 수득률을 높이는 데 좋다. Subsequently, the first photoresist 11 is exposed and developed as shown in (3) and (4) of FIG. The photoresist electrode 12 is formed on the substrate 10. The exposure was performed by irradiating UV or the like to the first photoresist 11 through a photomask window in the shape of a planar electrode 20. Here, the shape of the planar electrode 20 is predetermined according to the design to be manufactured. Preferably, the straight pattern having a constant width is formed in a form spaced apart at regular intervals to form a constant shape of the carbon nanomesh 40 of the present invention and to increase the yield.
[45] 이와 같이 노광이 실시됨 에 따라，상기 제 1포토레지스트 ( 1 1)가 경화되어  As the exposure is performed in this manner, the first photoresist 11 is cured.
포토레지스트 전극 ( 12)이 형성 된다. 이 때 노광 된 광 에 너지는  Photoresist electrode 12 is formed. At this time, the exposed light energy
제 1포토레지스트 (11)가 제 1포토레지스트 (11) 최상부부터 기판 (10) 바로 위까지 경화될 수 있을 만큼 충분하여 야 한다.  It should be sufficient so that the first photoresist 11 can be cured from the top of the first photoresist 11 to just above the substrate 10.
[46] 다음으로 상기 노광에 의하여 형 성된 포토레지스트 전극 (12)을 제외 한 나머지 부분의 제 1포토레지스트 (11)를 현상 (development)으로 제거 한다. 이때 현상 (development)의 방법으로는 통상의 기술자에 게 공지된 다양한 종류의 현상액 (developer)의 사용이 가능하며 , 예를 들면 SU-8 현상액 (SU-8 developer)을 사용할 수도 있다,  Next, the first photoresist 11 of the remaining portion except for the photoresist electrode 12 formed by the exposure is removed by development. In this case, as a development method, various types of developers known to those skilled in the art may be used, and for example, a SU-8 developer may be used.
[47] 이 로써 , 상기 현상 (development)을 통하여 기판 (10) 상에는 포토레지스트  Thus, the photoresist is formed on the substrate 10 through the development.
전극 (12)만이 남는다.  Only the electrode 12 remains.
[48] 이와 같이 포토레지 스트 전극 (12)의 형성 이 완료되면，다음으로 상기  When formation of the photoresist electrode 12 is completed as described above,
포토레지스트 전극 ( 12)을 덮는 이 격공간확보층 (1.4a, 14b)을 형성한다. (b)  The space securing layers 14a and 14b covering the photoresist electrode 12 are formed. (b)
[49] 이를 위하여 우선，도 1의 (5)와 같이 상기 포토레지스트 전극 (12)이 형성된 기판 (10) 상부에 계 2포토레지스트 (14)를 도포한다. 이 때 도포의 방법은 통상의 기술자에 게 공지된 비제한적 인 방법으로 시 행 될 수 있으며，예를 들면 스핀 코팅，딥 코팅，또는 그라비아 코팅 등의 다양한 방법 에 의하여 수행될 수 있다. 여기서 , 상기 제 2포토레지스트 (14)는 원칙 적으로 제한을 두지 않으나，포지티브 포토레지스트를 이용함이 바람직하며 , 일례로는 AZ-9260 포토레지스트를 사용할 수 있다.  To this end, first, the second photoresist 14 is coated on the substrate 10 on which the photoresist electrode 12 is formed, as shown in FIG. At this time, the method of coating may be performed by a non-limiting method known to those skilled in the art, for example, it may be carried out by various methods such as spin coating, dip coating, or gravure coating. Here, the second photoresist 14 is not limited in principle, but it is preferable to use a positive photoresist. For example, the AZ-9260 photoresist may be used.
[50] 이 때 상기 제 2포토레지스트 (14)가 도포되는 두께는 3 내지 12μηι, 바람직하게는 5 내지 7μηι으로 상기 (a)단계의 제 1포토레지스트 (1 1 ) 보다 두껍 게 형성된다. 여기서 제 2포토레지스트 (14)의 두께가 상기 제 1포토레지스트 (11) 보다 두껍 게 되 지 않으면, 후속공정에서 상기 제 2포토레지스트 (14)가 포토레지스트 전극 (12) 외표면에 균일하게 코팅되 지 않을 수 있다.  At this time, the thickness of the second photoresist 14 is applied is 3 to 12μηι, preferably 5 to 7μηι thicker than the first photoresist (1 1) of step (a). If the thickness of the second photoresist 14 is not thicker than that of the first photoresist 11, the second photoresist 14 is uniformly coated on the outer surface of the photoresist electrode 12 in a subsequent process. It may not be.
[51] 이와 같이 제 2포토레지스트 (14)의 도포가 완료되 면，후속공정을 수행하기 전에 제 2포토레지스트 (14)가 도포된 상태의 포토레지스트 전극 (12) 및 기판 (10)에 약하게 굽기 (soft bake)를 진행함이 바람직하다. 이 때 약하게 굽기 (soft bake) 과정을 종료하면, 기판 (10)을 층분히 자연 냉각시켜 상기 (a)단계를 수행하기 전의 온도와 동일한 상태의 온도임을 확인한 후에 후속공정을 수행한다. 이 때 약하게 굽기 (soft bake)의 구체적 조건은 80 내지 120 °C에서 6 내지 8분 동안의 적용에 해당한다. [52] 이어,도 1의 (6)및 (7)과같이상기제 2포토레지스트 (14)를노광및현상하여， 상기포토레지스트전극 (12)을덮는미노광제 2포토마스크영역인 When the application of the second photoresist 14 is completed as described above, the photoresist electrode 12 and the substrate 10 in which the second photoresist 14 is applied are weakly applied before the subsequent process is performed. It is desirable to proceed with a soft bake. At this time, when the soft bake process is terminated, the substrate 10 is naturally cooled down, and after confirming that the temperature is the same as the temperature before the step (a), the subsequent process is performed. The specific conditions of soft bake at this time correspond to the application for 6 to 8 minutes at 80 to 120 ° C. Subsequently, as shown in (6) and (7) of FIG. 1, the second photoresist 14 is exposed and developed to cover the photoresist electrode 12, which is an unexposed second photomask region.
이격공간확보층 (14a, 14b)을형성한다.  Spacer space securing layers 14a and 14b are formed.
[53] 이때노광시에사용되는포토마스크는상기포토레지스트전극 (12)을덮도록 마스크디자인된것으로서,상기포토레지스트전극 (12)의들레를따라일정 간격으로크게마스크디자인된다.그리고,이와같이마스크디자인된 포토마스크를통해 2차노광을실시하고이를현상하면,미노광영역이그대로 남아상기포토레지스트전극 (12)의외표면에미노광제 2포토마스크영역이 일정두께코팅된형태로이격공간확보층 (14a)이형성된다.  In this case, the photomask used for exposure is designed to cover the photoresist electrode 12, and is designed to be largely masked at regular intervals along the array of the photoresist electrode 12. When the secondary exposure is performed through the designed photomask and the development is performed, the unexposed region remains as it is, and the space-separation layer having a predetermined thickness coated on the outer surface of the photoresist electrode 12 ( 14a) is formed.
[54] 이러한이격공간확보층 (14a)은적어도 2μηι이상의두께로형성되는것이  [54] The space-separation layer 14a is preferably formed with a thickness of at least 2μηι.
바람직하며,이를위하여상기포토레지스트전극 (12)의둘레를따라  Preferably, along the circumference of the photoresist electrode 12
ΙΟμηι이상의너비가늘어나도록마스크디자인된다.여기서,  The mask is designed to increase the width above ΙΟμηι.
이격공간확보층 (14a)을 2μπι이상의두께로형성시키는것은후속공정에서 포토레지스트메쉬 (18)의제조시에상기포토레지스트전극 (1.2)과의물리적， 전기적접촉을효과적으로방지하기위함이디-.  Forming the space-separating layer 14a with a thickness of 2 μπι or more is to effectively prevent physical and electrical contact with the photoresist electrode 1.2 during the manufacture of the photoresist mesh 18 in a subsequent process.
[55] 아울러,이렇게상기포토레지스트전극 (12)의표면에형성된상기  In addition, the formed on the surface of the photoresist electrode 12 as described above
이격공간확보충 (14a, 14b)은후속공정에서기판 (10)상단에포토레지스트 전극 (12)과이격되도록포토레지스트기등부 (17)및포토레지스트메쉬 (18)를 형성시킬때，포토레지스트전극 (12)과포토레지스트기등부 (17)및  The space-separation replenishment 14a, 14b is used to form the photoresist substrate 17 and the photoresist mesh 18 so as to be spaced apart from the photoresist electrode 12 on the substrate 10 in a subsequent process. Electrode 12 and photoresist lamp 17; and
포토레지스트메쉬 (18)사이의접촉을효과적으로차단하여,별도의미세한 수치계산등의과정이없이도포토레지스트전극 (12)과포토레지스트 기등부 (17)및포토레지스트메쉬 (18)사이의이격공간이효과적으로확보될수 있도록한다ᅳ게다가,이와같이포토레지스트전극주변에일정간격으로 이격공간확보층을형성시킨이후에포토레지스트메쉬를형성시키는공정을 통하여，포토레지스트전극과포토레지스트메쉬의간격,나아가최종형성되는 탄소평면전극과탄소나노메쉬사이의거리를효율적으로조정할수있고，이와 같은공정을통하여탄소평면전극과탄소나노메쉬의간격을최소화시킬수도 있다.  The contact between the photoresist mesh 18 is effectively blocked, so that the space between the photoresist electrode 12, the photoresist light emitting portion 17 and the photoresist mesh 18 is eliminated without any detailed numerical calculation or the like. In addition, a space between the photoresist electrode and the photoresist mesh is formed by forming a space between the photoresist electrodes at a predetermined interval and then forming a photoresist mesh. The distance between the carbon plane electrode and the carbon nanomesh can be adjusted efficiently, and this process can minimize the gap between the carbon plane electrode and the carbon nanomesh.
[56] 또한이와같이포토레지스트전국 (12)과포토레지스트기둥부 (17)및  [56] Likewise, the photoresist station 12 and the photoresist pillar 17 and
포토레지스트메쉬 (18)사이의이격공간을확보함으로써탄소전극및 탄소나노메쉬 (40)의제조를위한열처리시에도제조되는탄소전극및 탄소나노메쉬 (40)사이의접촉이방지된다.그리고이로써고수율의  By securing the space between the photoresist mesh 18, the contact between the carbon electrode and the carbon nanomesh 40, which is produced even during the heat treatment for the production of the carbon electrode and the carbon nanomesh 40, is prevented. Yield
탄소나노메쉬 (40)를수득하여본발명의중첩형나노전극쌍의전기적，물리적인 안정을더욱효과적으로도모하게된다.  By acquiring carbon nanomesh 40, the electrical and physical stability of the overlapping nanoelectrode pair of the present invention can be more effectively achieved.
[57] 이어 ,상기노광이완료된이후에는현상 (development)을실시하여，노광  Subsequently, after the exposure is completed, a development is performed to expose the exposure.
영역을제거하고상기이격공간확보층 (14a)만을남긴다.이때  The area is removed and only the space securing layer 14a is left.
현상 (development)의방법으로는통상의기술자에게공지된다양한종류의 현상액 (developer)의사용이가능하며，예를들면 AZ현상액 (AZ developer)을 사용할 수도 있다. As a method of development, a variety of developers can be used. For example, AZ developer can be used. Can also be used.
[58] 한편，상기 현상 (development)을 통하여 이격공간확보충 (14a)이 코팅 된  On the other hand, through the development (development) the space-filling supplement (14a) is coated
포토레지스트 전극 (12) 형성 이 완료된 후에는，현상으로 남는 부분을 세척함이 바람직하다. 세척에 있어 세척의 구체적 인 방법은 비 제한적 이며 , 예를 들면 이소프로필 알코올과 메탄올 순서로 순차적 인 세척을 하는 것도 가능하다ᅳ 또는 포토레지스트 애셔 (Photoresist asher)를 이용하여 세 척하는 것 또한 가능하다.  After the formation of the photoresist electrode 12 is completed, it is preferable to wash the remaining portions. The specific method of washing in the washing is not limited, and it is also possible to perform sequential washing in order of isopropyl alcohol and methanol, for example, or washing using a photoresist asher. .
[59] 그리 고, 이 격공간확보층 (14a)이 코팅된 포토레지스트 전극 ( 12) 형성 이  Then, the formation of the photoresist electrode 12 coated with the space-separation layer 14a
완료되 면 도 1의 (8)과 같이 상기 이 격공간확보층 ( 14a)을 노광하여 가용화시 키는 단계를 더 수행한다. 이와 같이 노광으로 가용화 된 상기 이 격공간확보층 (14b)은 후속공정의 현상 (development) 시 , 완전히 제거된다. 즉，본 발명 의 나노 전극쌍은 중첩 형으로 제작되기 때문에 포토레지스트 메쉬 (18)가 부양 형성된 상태에서 노광을 실시하였을 때，상기 이 격공간확보층 (14a)을 완전히 제거시 키는 데 어 려움이 있다. 따라서，상기 이 격공간확보층을 미 리 충분히 가용화시켜 가용화 된 이 격공간확보층 (14b)로 변형시킨 상태에서 후속공정 에서  Upon completion, as shown in (8) of FIG. 1, the space-separation layer 14a is exposed and solubilized. This gap-separation layer 14b solubilized by exposure is completely removed during development of the subsequent process. That is, since the nanoelectrode pair of the present invention is manufactured in a superposition type, when the exposure is performed in a state where the photoresist mesh 18 is supported, it is difficult to completely remove the gap space securing layer 14a. There is this. Therefore, in the subsequent process, the space-separation layer 14b is sufficiently solubilized in advance and deformed into a solubilized space-separation layer 14b.
현상 (development)을 통하여 완전히 제거되도록 하는 것 이 다.  It is to be completely removed through development.
[60] 이 때 상기 이 격공간확보층 ( 14a)을 가용화 시 키 기 위 한 노광은 별도의  [60] At this time, the exposure to solubilize the space-separation layer 14a is separate.
포토마스크가 없는 상태에서 실시하여，상기 이 격공간확보층 (14a)이 표면에 코팅된 포토레지스트 전극 ( 12)에 노광된 광 에너 지가 충분히 조사될 수 있도록 한다.  It is carried out in the absence of a photomask, so that the light energy exposed to the photoresist electrode 12 coated on the surface of the space securing layer 14a can be sufficiently irradiated.
[61] 이어，상기 포토레지스트 전극 (12)과 이격되도록 두 기둥형상의 포토레지스트 기등부 (Π)와 메쉬 형상의 포토레지스트 메쉬 (18)를 형성 한다. (c)  Next, two columnar photoresist lamps Π and a mesh-shaped photoresist mesh 18 are formed to be spaced apart from the photoresist electrode 12. (c)
[62] 이를 위하여 먼저，도 I 의 (9)와 같이 가용화 된 이격공간확보 (14b)이 형성된 기 판 (10) 상부로 제 3포토레지스트 (16)를 도포한다. 이 때 도포 방법은 통상의 기술자에 게 공지 된 비 제한적 인 방법 으로 시 행될 수 있으며，예를 들면 스핀 코팅 , 딥 코팅，또는 그라비아 코팅 등의 다양한 방법에 의하여 수행될 수 있다. 상기 제 3토레지스트는 원칙 적으로 제한을 두지 않으나, 네가티브  To this end, first, a third photoresist 16 is applied onto the substrate 10 on which the solubilized separation space 14b is formed, as shown in FIG. At this time, the coating method may be performed by a non-limiting method known to those skilled in the art, for example, it may be carried out by various methods such as spin coating, dip coating, or gravure coating. The third toresist is not limited in principle, but negative
포토레지스트를 이용함이 바람직하며 , 일례로 SU-8 포토레지스트를 이용하는 것이 좋다.  It is preferable to use a photoresist, for example, SU-8 photoresist.
[63] 이 때 제 3포토레지스트 (16)의 두께는 6 내지 15μιη, 바람직하게는 8 내지  At this time, the thickness of the third photoresist 16 is 6 to 15μιη, preferably 8 to
ΙΟμιη으로 상기 (c)단계의 게 2포토레지스트 (14) 보다 충분히 두껍 게 형성 한다. 왜냐하면，이와 같이 제 3포토레지스트 ( 16)의 두께를 확보하여 후속공정에서 포토레지스트 메쉬 (18)를 공중부양 된 형 태로 형성 시 킬 제 3포토레지스트 (16) 두께가 층분히 마련되어 있어 야 하기 때문이다.  ΙΟμιη is formed sufficiently thicker than the two photoresist 14 of step (c). This is because the thickness of the third photoresist 16 must be sufficiently provided to secure the thickness of the third photoresist 16 and to form the photoresist mesh 18 in an air-lifted form in a subsequent process. to be.
[64] 상기 제 3포토레지스트 ( 16)의 도포가 완료되면，후속공정을 수행하기 전에 상기 제 3포토레지스트 (16)가 도포 된 상기 포토레지스트 전극 (12) 및 기판 (10)에 약하게 굽기 (soft bake)를 진행함이 바람직하다. 이때 약하게 굽기 (soft bake) 과정을 종료하면，기판 00)을 충분히 자연 냉각시 켜 상기 (a)단계를 수행하기 전의 온도와 동일한 상태의 온도임을 확인한 후에 후속공정을 수행함이 바람직하다.이때약하게굽기 (soft bake)의구체적조건은 80내지 120oC에서 6 내지 8분동안의 적용에해당한다. When the application of the third photoresist 16 is completed, weakly baking the photoresist electrode 12 and the substrate 10 to which the third photoresist 16 is applied before performing the subsequent process ( soft bake). At this time, when the soft bake process is completed, the substrate 00) is sufficiently cooled down naturally to confirm that the temperature is the same as the temperature before the step (a). Preferably, the specific conditions of soft bake are applicable for 6 to 8 minutes at 80 to 120 ° C.
[65] 이와같이상기제 3포토레지스트 (16)의도포가완료되면,도 1의 (10)과같이 상기제 3포토레지스트 (16)를노광하여,상기포토레지스트전극 (12)을사이에 두고포토레지스트전극 (12)과일정거리 이격되며서로대향하는두기등형상의 노광영역인포토레지스트기등부 (Π)를형성시킨다.이때노광된광에너지는 제 3포토레지스트 (16)가포토레지스트최상부부터기판 (10)바로위까지 경화될 수있을만큼층분하여야한다.  When the application of the third photoresist 16 is completed as described above, the third photoresist 16 is exposed as shown in FIG. The photoresist light emitting part Π, which is an exposure area of two lamps, which is spaced apart from the electrode 12 and is spaced apart from each other by a distance, is formed. 10) It should be divided enough to harden up to the top.
[66] 그리고,상기포토레지스트기등부 (17)가형성된상태의포토레지스트  In addition, the photoresist in a state where the photoresist group lamp portion 17 is formed.
전극 (12)및기판 (10)에노광후굽기 (post exposure bake)를진행함이바람직하다. 이때노광후굽기 (post exposure bake)과정을종료하면，기판 (K))을층분히자연 냉각시켜상기 (a)단계를수행하기 전의온도와동일한상태의 온도임을 확인한다.이때노광후굽기 (post exposure bake)의구체적조건은 80내지 120 0C에서 6내지 8분동안의 적용에해당한다ᅳ  It is desirable to carry out post exposure bake on the electrode 12 and the substrate 10. At the end of the post exposure bake process, the substrate (K) is sufficiently cooled to confirm that the temperature is the same as the temperature before performing step (a). The specific conditions of bake are applicable for 6 to 8 minutes at 80 to 120 0C.
[67] 이어,도 1의 (11)과같이상기 제 3포토레지스트 (16)를재노광하여，상기  Subsequently, the third photoresist 16 is reexposed as shown in FIG. 1 (11).
포토레지스트전극 (1.2)을가로질러상기포토레지스트기등부 (17)의상기두 기등형상의노광영역을연결하는메쉬 형상의노광영역인포토레지스트 메쉬 (18)를형성시킨다.  A photoresist mesh 18 is formed across the photoresist electrode 1.2, which is a mesh-shaped exposure region that connects the two lamp-shaped exposure regions of the photoresist lamp portion 17.
[68] 종래에는상기포토레지스트메쉬를형성시킬때，상기 기판 (10)으로부터 일정 간격부양된형태의포토레지스트메쉬 (18)를형성시킬수있도록하기위하여, 재노광에너지를상기포토레지스트기등부 (17)를형성시키기위한노광 에너지보다적도록제한하여포토레지스트의상단만을경화시켰디-.  In the related art, in order to form the photoresist mesh 18 having a predetermined interval from the substrate 10 when the photoresist mesh is formed, the re-exposure energy is transferred to the photoresist lamp back ( 17) Only the top of the photoresist was cured, with a limit to less than the exposure energy to form.
[69] 그러나，본발명의중첩형나노전극쌍의 제조에 있어서，재노광에너지는제한 없이 비교적크게가하여지더라도,포토레지스트주변에 이격공간확보층이 이미형성되어 있기 때문에 이격공간확보층하단의포토레지스트전극과 이격공간확보층상단의포토레지스트메쉬간의 접촉이차단된상태로 포토레지스트메쉬가형성되는것이다.이때상기 재노광에너지는상기 포토레지스트기등부 ( 17)를형성시키기 위한노광에너지보다적도록제한하는 것이요구되지않는다,구체적으로，상기 이때 재노광에너지는얻고자하는 포토레지스트메쉬의두께에 맞추어경화되도록가하여 질수도있고,상기 포토레지스트최상부에서상기 이격공간확보층까지 경화되는크기로가하여 질 수도있으며，전술된상기포토레지스트기등부 (17)의 형성시의 노광에너지의 크기와같이 포토레지스트최상부부터 기판 (10)바로위까지 경화되는크기로 가하여지는것또한가능하다.  However, in the manufacture of the overlapped nano-electrode pair of the present invention, even if the re-exposure energy is relatively large without limitation, since the space-separation layer is already formed around the photoresist, The photoresist mesh is formed while the contact between the photoresist electrode and the photoresist mesh on the space-separation layer is blocked. The re-exposure energy is the exposure energy for forming the photoresist light emitting part 17. No less limit is required, specifically, the re-exposure energy may be hardened to match the thickness of the photoresist mesh desired to be obtained, and the size to be cured from the top of the photoresist to the spacing layer. The photoresist may be formed as described above. From cast top board 10 which will be added to a size which is cured to just above it is also possible.
[70] 이와같이본발명에서 형성되는상기포토레지스트메쉬의두께는  Thus, the thickness of the photoresist mesh formed in the present invention is
이격공간확보층상단에코팅된포토레지스트의두께로결정되며,  Determined by the thickness of the photoresist coated on top of the spacing layer,
포토레지스트에가하여지는재노광에너지의크기에따라결정되는것이 아니다. [71] 한편 본 발명의 중첩 형 나노 전극쌍 제조방법 에서는 보다 얇고 조밀한 공중부유형 탄소나노메쉬 (40)를 형성하기 위하여，포토레지스트 메쉬 (18)의 와이어 사이의 각도 (Θ)는 40°내지 60°의 범위를 채 택함이 바람직하다. 이는 도 2를 통하여 , 상기 포토레지스트 메쉬 (18)의 와이어 사이 의 각도 (Θ)가 40°내지 60°의 범위 에서 채택될 때 최종 형성되는 탄소나노메쉬 (40)가 가장 조밀한 형 태를 띰을 확인할 수 있다. It is not determined by the amount of re-exposure energy applied to the photoresist. In the method of manufacturing a superposed nanoelectrode pair according to the present invention, the angle Θ between the wires of the photoresist mesh 18 is 40 ° in order to form a thinner and denser airborne carbon nanomesh 40. It is preferable to adopt a range of from 60 °. This indicates that the carbon nanomesh 40, which is finally formed when the angle Θ between the wires of the photoresist mesh 18 is adopted in the range of 40 ° to 60 °, has the most compact shape through FIG. can confirm.
[72] 그리고, 상기 포토레지스트 기둥부 ( 17) 및 상기 포토레지스트 메쉬 (18)의  And the photoresist pillar portion 17 and the photoresist mesh 18
형성 이 완료되 면, 후속공정을 수행하기 전에 포토레지스트 기등부 (17)와 포토레지스트 메쉬 (18) 및 포토레지스트 전극 (12)이 형성된 상태의 기판 (10)에 노광 후 굽기 (post exposure bake)를 진행함이 바람직하다. 이 때 노광 후 굽기 (post exposure bake) 과정을 종료하면, 기판 (10)을 충분히 자연 냉각시켜 상기  Once formation is complete, post exposure bake on the substrate 10 with the photoresist light 17, photoresist mesh 18, and photoresist electrode 12 formed thereon before subsequent processing. It is preferable to proceed. At this time, when the post exposure bake process is completed, the substrate 10 is sufficiently naturally cooled to
(a)단계를 수행하기 전의 온도와 동일한 상태의 온도임을 확인한다. 충분히 냉각되 지 않으면 후속공정으로 이어지는 현상 (development)에서 포토레지스트 기등부 (17)와 포토레지스트 메쉬 (18) 및 포토레지스트 전극 (12)이 열웅력에 의해 크랙이나 파괴 가 일어날 수도 있기 때문이다. 이 때 노광 후 굽기 (p0st exposure bake)의 구체적 조건은 80 내지 120 oC에 서 1 내지 15분 동안의 적용에 해당한다. Confirm that the temperature is the same as the temperature before the step (a). This is because the photoresist lamp 17, the photoresist mesh 18, and the photoresist electrode 12 may be cracked or destroyed by thermal forces in a development that leads to a subsequent process if it is not sufficiently cooled. At this time, the specific conditions of the post exposure bake (p 0s t exposure bake) corresponds to the application for 1 to 15 minutes at 80 to 120 ° C.
[73] 이 렇게 기판 (10) 상에 포토레지스트 전극 -(12) 뿐만 아니 라 포토레지스트  [73] The photoresist electrode -12 as well as the photoresist on the substrate 10
기등부 (17)와 포토레지스트 메쉬 (18)까지 모두 형성되면, 도 1의 (12)와 같이 현상 (development)을 통해 상기 c) 단계에서 미 노광된 제 3포토레지스트 ( 16) 영 역 인 미 노광영 역 및 상기 이 격공간확보층 (14b)을 제거 한다.  When both the light emitting portion 17 and the photoresist mesh 18 are formed, the third photoresist 16 region which is not exposed in the step c) through development as shown in FIG. The exposure area and the space-separation layer 14b are removed.
[74] 그리고 상기 현상 (development)이 완료되면, 포토레지스트 전극 (12)，  And when the development is completed, the photoresist electrode 12,
포토레지스트 기둥부 (17) 및 기판 (10)으로부터 일정 간격 부유된 상태의 포토레지스트 메쉬 (18) 만이 남는다. 이 때 현상 (development)의 방법으로는 통상의 기술자에 게 공지된 다양한 종류의 현상액 (developer)의 사용이 가능하며 , 예를 들면 SU-8 현상액 (SU-8 developer)을 사용할 수도 있다.  Only the photoresist mesh 18 in a state in which the photoresist pillar portion 17 and the substrate 10 are suspended at regular intervals remains. In this case, as a development method, various types of developers known to those skilled in the art may be used, and for example, a SU-8 developer may be used.
[75] 한편，상기 현상 (development)을 수행한 후에는，후속공정을 수행하기 전에  On the other hand, after the development is performed, before the subsequent process is performed,
현상으로 남는 포토레지스트 부분을 세척함이 바람직하다. 세척에 있어 세척의 구체적 인 방법은 비 제한적 이며 , 예를 들면 이소프로필 알코올과 메탄올 순서로 순차적 인 세척을 하는 것도 가능하다. 또는，포토레지스트 애셔 (Photoresist asher)를 이용하여 세척하는 것 또한 가능하다.  It is desirable to clean the portion of the photoresist that remains in development. The specific method of washing in washing is non-limiting, and it is also possible to perform sequential washing in order of isopropyl alcohol and methanol, for example. Alternatively, it is also possible to clean using a photoresist asher.
[76] 마지 막으로，상기 기판 (10)상 형성된 포토레지스트 전극 ( 12), 포토레지스트 기등부 (17) 및 포토레지스트 메쉬 (18)의 노광영 역을 다단 열처리하여  Finally, the photoresist electrode 12 formed on the substrate 10, the photoresist light emitting portion 17 and the photoresist mesh 18 are subjected to multi-stage heat treatment.
열분해한다 .(d)  Pyrolyses (d)
[77] 상기 열분해는 도 1의 (13)에서 보듯이，상기 포토레지스트 메쉬 (18)，  The pyrolysis is performed in the photoresist mesh 18 as shown in FIG.
포토레지스트 기등부 (17) 및 포토레지스트 전극 (12)을 평면 전극 (20)과 탄소 기둥 (30) 및 공중부유형 탄소나노메쉬 (40)로 변형시킨다. 이와 같이 열분해를 통하여 형성 되는 중첩 형 나노 전극쌍으로서，평면 전극 (20)과 공중부유형 탄소나노메쉬 (40)는 도 3에서 확인할 수 있다. [78] 구체적으로,상기열분해를통하여포토레지스트전극 (12)은평면 전극 (20)으로변형되고，포토레지스트기등부 (17)는탄소기등 (carbon post; The photoresist light emitting portion 17 and the photoresist electrode 12 are transformed into a planar electrode 20, a carbon pillar 30, and an airborne carbon nanomesh 40. As the superposed nano-electrode pair formed by thermal decomposition as described above, the planar electrode 20 and the airborne carbon nanomesh 40 can be seen in FIG. 3. Specifically, through the thermal decomposition, the photoresist electrode 12 is transformed into a planar electrode 20, and the photoresist group lamp 17 has a carbon post;
30)으로변형되며，포토레지스트메쉬 (18)는공중부유형탄소나노메쉬 (40)로 변형된다.그리고,이와같이형성된탄소기둥 (30)은공중부유형  30), and the photoresist mesh 18 is transformed into an airborne carbon nanomesh 40. The carbon column 30 thus formed is an airborne type.
탄소나노메쉬 (40)를기판 (10)으로부터소정간격부양되게한다.또한상기 열분해과정에있어，포토레지스트메쉬 (18)와이를지탱하고있는포토레지스트 기등부 (17)에서동시에열분해가일어나면서포토레지스트메쉬 (18)가 탄소나노메쉬 (40)로변형될때양쪽가장자리로부터인장웅력을받게되어 포토레지스트메쉬 (18)는처짐없이탄소나노메쉬 (40)로변형된다.  The carbon nanomesh 40 is subjected to a predetermined interval from the substrate 10. In the thermal decomposition process, the thermal decomposition occurs simultaneously at the photoresist mesh 18 and the photoresist lamp 17 supporting the photoresist mesh. When the resist mesh 18 is transformed to carbon nanomesh 40, it is subjected to tension from both edges so that the photoresist mesh 18 is deformed to carbon nanomesh 40 without sagging.
[79] 한편본발명에따른중첩형나노전극쌍제조방법의목적은얇고조밀한  [79] On the other hand, the purpose of the overlapping nanoelectrode pair manufacturing method according to the present invention is thin and compact
공중부유형탄소나노메쉬 (40)를형성하기위한것에있는만큼，본발명자들은 상기열분해의특징으로특정형태의것을채택함이상기목적에보다  As it is intended to form the airborne carbon nanomesh 40, the present inventors have adopted a particular form of the pyrolysis feature for this purpose.
바람직함을알게되었다 ·.상기열분해는제 1단계및제 2단계의두단계로 시행되며，제 2단계가제 ].단계보다높은온도에서시행된다.구체적으로는 상기제 1단계는 300내지 400UC에서 30내지 90분동안시행되며，상기저】Preferably discovered that, The thermal decomposition is the first step and is performed in two steps of the second step, the second step is conducted at a temperature greater than the first. Steps: specifically, the first step is from 300 to 400 30 to 90 minutes at U C.
2단계는 900내지 1000oC에서 30내지 90분동안시행된다.보다구체적으로 300 내지 400°C까지 1 °C/분 (min)으로승온되어 300내지 400°C에서 30내지 90분을 유지하면서상기제 ]단계가시행되며，이후에는 900내지 10000C까지 1The second stage is run for 30 to 90 minutes at 900 to 1000 o C. More specifically, the temperature is raised to 1 ° C / min (min) from 300 to 400 ° C, while maintaining 30 to 90 minutes at 300 to 400 ° C. The above] step is carried out, after which 1 to 900 to 1000 0 C
0C/분 (min)으로승온되어 900내지 1000°C에서 30내지 90분을유지하면서상기 제 2단계가행해진다. The second step is performed while raising the temperature to 0 C / min (min) and maintaining 30 to 90 minutes at 900 to 1000 ° C.
[80] 상기열분해가재현될구체적분위기는상기특정형태의것의 재현을  [80] The specific atmosphere in which the pyrolysis is to be reproduced is used to reproduce the specific type.
방해하지않는한특별한제한은없으며，예를들면상기포토레지스트메쉬 (1.8), 포토레지스트기등부 (Π)및포토레지스트전극 (12)을전기로에넣고저진공 펌프및고진공펌프를이용하여 10-7내지 10-5토르 (torr)까지분위기를만든후 상기특정형태의것을재현할수도있다.  There is no special limitation as long as it does not interfere. For example, the photoresist mesh (1.8), the photoresist back part (Π) and the photoresist electrode 12 are put into an electric furnace, and a low vacuum pump and a high vacuum pump are used. It is also possible to create an atmosphere of 7 to 10-5 torr and then reproduce this particular type.
[81] 한편,상기 (d)단계가완료되면，열분해에의하여형성된평면전극 (20)과  On the other hand, when the step (d) is completed, the planar electrode 20 formed by pyrolysis and
공중부유형탄소나노메쉬 (40)를자연냉각한후열분해의분위기에서꺼낸다. 추가적으로바람직하게는포토레지스트애셔 (Photoresist asher)를이용하여 열분해과정에서발생된탄소입자를제거할수있다.  The airborne carbon nanomesh 40 is naturally cooled and then removed from the atmosphere of pyrolysis. In addition, a photoresist asher can be used to remove the carbon particles generated during the pyrolysis process.
[82] 상기제조방법에의하여제조되는공중부유형탄소나노메쉬 (40)는도 3의  The airborne carbon nanomesh 40 manufactured by the above manufacturing method is shown in FIG.
개략도에서보는바와같은형태이며,이와같이제조되는공중부유형  As shown in the schematic, the type of air is manufactured as such.
탄소나노메쉬 (40)은너비가 200내지 400 nm,탄소나노와이어간격이 3내지 7 μηι이디、또한상기제조방법은간단하고경제적이며，상기제조방법으로최종 형성되는중첩형나노전극쌍의수율은 70%이상,좋게는 80%이상의고수율에 해당한다.따라서상기제조방법은얇고조밀한공중부유형탄소나노메쉬 (40)를 고수율로제공하는현저성이있다.  The carbon nanomesh 40 has a width of 200 to 400 nm and a carbon nanowire spacing of 3 to 7 μηι. In addition, the manufacturing method is simple and economical, and the yield of the overlapping nano electrode pair finally formed by the manufacturing method is Corresponding to a high yield of 70% or more, preferably 80% or more. Thus, the above manufacturing method has the phenomena of providing thin and dense airborne carbon nanomesh 40 in high yield.
[83] 나아가상기제조방법에의하여제조된중첩형나노전극쌍에바이오감지물질 또는전기화학감지물질을적층하여，감지성이향상되고크기및부피가감소된 중첩형 나노 전극쌍을 적용한 바이오센서 또는 전기화학센서가 제공된다. [83] Furthermore, a biosensing material or an electrochemical sensing material is laminated on the overlapping nanoelectrode pair manufactured by the manufacturing method, and the sensing property is improved and the size and volume are reduced. There is provided a biosensor or electrochemical sensor employing a superposed nano-electrode pair.
[84] 이 때 바이오 감지물질 또는 전기화학 감지물질은 중첩 형 나노 전극쌍을 [84] At this time, the biosensor or electrochemical sensing material is used for
구성하는 평면 전극과 공중부유형 탄소나노메쉬 (40) 모두에 적층 될 수 있으며 , 어 느 일방에만 적층 될 수도 있디 상기 바이오 감지물질은 통상의 기술자에 게 공지된 다양한 것을 채택하는 한 특별한 제한은 없지 만，글루코스 효소 (glucose enzyme)와 같이 특정 바이오 물질에 반응하여 전기화학 전류를 측정할 수 있는 산화환원 물질을 발생시키는 물질을 채 택함이 바람직하며，구체적으로는 글루코스 옥시다아제 (glucose oxidase)를 채택하는 것이 좋다. 상기 전기화학 감지 물질 역시 통상의 기술자에 게 공지된 다양한 것을 채택하는 한 별도의 제한은 없다.  It can be laminated on both the flat electrode and the airborne carbon nanomesh 40 constituting, and may be laminated on only one side. The bio-sensing material is not particularly limited as long as it adopts various ones known to those skilled in the art. However, it is preferable to select a substance that generates a redox substance capable of measuring electrochemical current in response to a specific biomaterial, such as a glucose enzyme, and specifically, adopts a glucose oxidase. It is good. The electrochemical sensing material is also not limited as long as it adopts various ones known to those skilled in the art.
[85]  [85]
[86] 이하, 본 발명과 관련된 실시 예 및 비교예를 상세히 설명 한다.  Hereinafter, examples and comparative examples related to the present invention will be described in detail.
[87] Γ실시 예 Π 중첩 형 나노？ -ᅵ극쌍의 제조 [87] Γ EXAMPLE Π Overlapping Nano?
[88] [1]일반적 인 6인치의 실리콘 웨이 퍼위에 절연층으로 이산화규소를  [88] [1] Silicon dioxide as an insulating layer over a typical 6-inch silicon wafer.
열산화방법 (Thermal oxidation)으로 증착 한 후， [2]제 1포토레지스트인 SU-8을 스핀 코팅으로 절연층 위 에 두께 4μτη로 고르게 코탕하였다.  After deposition by thermal oxidation, [2] SU-8, the first photoresist, was evenly coated with a thickness of 4 μτη on the insulating layer by spin coating.
[3]제 1포토레지스트인 SU-8을 코팅 한 후 포토레지스트 전극 모양의 포토마스크 창을 통하여 자외선에 층분히 노출시켜 노광을 수행하고， [4JSU-8 현상액 (SU-8 developer)을 이용하여 노광 된 부분을 제외 한 나머 지 부분을  [3] After coating SU-8, which is the first photoresist, exposure is carried out by exposure to ultraviolet rays through a photomask window in the form of a photoresist electrode, followed by exposure using [4JSU-8 developer (SU-8 developer). Rest of the rest except the exposed part
현상 (development)으로 제거 했다. [5]현상 후 남은 포토레지 스트 전극 부분 및 기판 상부에 제 2포토레지스트인 AZ-9260 포토레 지스트를 스핀 코팅으로 두께 It was removed as a phenomenon. [5] spin coating of AZ-9260 photoresist, a second photoresist, on photoresist electrode and substrate
6μιη로 고르게 코팅하였다. [6]제 2포토레지스트인 ΑΖ-9260올 코팅 한 후 상기 에서 형성된 포토레지스트 전극을 덮되 포토레지스트 전극 보다 너비가Coated evenly to 6μιη. [6] After coating the second photoresist AX-9260ol, the photoresist electrode formed above is covered, but the width of the photoresist electrode is
ΙΟμηι 더 넓 게 마스크 디자인 된 포토마스크를 포토레지스트 전극 상부에 덮고 노광을 실시하고，. [7]ΑΖ 현상액 (AZ developer)을 이용하여 노광 된 부분을 현상으로 제거 했다. [8]이 어，포토마스크가 없는 상태에서 노광을 실시하여 이 전 단계에서 현상으로 제거되지 않은 제 2포토레지스트인 AZ-9260을 가용화하였다. ΙΟμηι The mask is designed to cover the photoresist electrode on top of the photoresist electrode, and then exposed. [7] The exposed part was removed by developing using AX developer (AZ developer). [8] Then, exposure was carried out in the absence of the photomask, so as to solubilize AZ-9260, a second photoresist that was not removed by development in the previous step.
[9]이후 제 3포토레지스트인 SU-8을 스핀 코팅으로 절연층，포토레지스트 전극 및 가용화된 제 2포토레 지스트 상부에 두께 9 μηι로 고르게 코팅하였다.  [9] Subsequently, the third photoresist SU-8 was evenly coated on the insulating layer, the photoresist electrode and the solubilized second photoresist with a thickness of 9 μηι by spin coating.
[1이제 3포토레지스트인 SU-8을 코팅 한 후 기등 형 성을 위한 포토마스크 창을 통하여 노광을 수행하여 포토레지스트 기등부를 형 성시 키고， [11]와이 어 사이의 각도 (Θ)가 45도인 메쉬 형상의 포토마스크를 통하여 노광을 수행하여  [1 Now, after coating SU-8, a third photoresist, exposure is performed through a photomask window for forming a photoresist to form a photoresist lamp, and [11] the angle between the wires is 45 degrees. Exposure through a mesh-shaped photomask
포토레지스트 메쉬를 형성 시 켰다. [12]노광을 수행한 후， SU-8 현상액 (SU-8 developer)을 이용하여 노광된 부분을 제외한 나머지 부분을  A photoresist mesh was formed. [12] After exposure, the remaining parts except the exposed part using SU-8 developer (SU-8 developer)
현상 (development)으로 제거 했다. [13]현상 후 포토레 지스트 메쉬 (18),  It was removed as a phenomenon. [13] photoresist mesh after development (18),
포토레 지스트 기둥부 (Π) 및 포토레지스트 전극 (12)을 전기로에 넣고 저진공 펌프 및 고진공펌프를 이용하여 10-6 토르 (torr)까지 분위 기를 만든 후, 제 I 단계 및 제 2 단계의 두 단계로 열분해를 진행했다. 구체적으로 350°C까지 Γ 분 (min)으로 승은되 어 350°C에서 60분을 유지하면서 제 1단계를 진행했으며 , 이후에는 900 °C까지 10C/분 (min)으로 승온되어 900°C에서 60분을 유지하면서 제 2단계를 진행했다. 열분해 후 형성된 평면 전극 (20)과 탄소 기등 (30) 및 공중부유형 탄소나노메쉬 (40)를 자연 냉각한 후 전기로에서 꺼 냈다. After putting the photoresist pillar (Π) and the photoresist electrode 12 into the electric furnace, the atmosphere was made up to 10-6 torr by using a low vacuum pump and a high vacuum pump, and then Pyrolysis was carried out in stages. Specifically up to 350 ° C Γ minutes (min) were raised to maintain the 60 minutes at 350 ° C. After the first step, the temperature was raised to 1 0 C / min (min) to 900 ° C and maintained at 900 ° C 60 minutes I proceeded to the second stage. After the pyrolysis, the flat electrode 20, the carbon lamp 30, and the airborne carbon nanomesh 40 were naturally cooled and removed from the electric furnace.
[89]  [89]
[90] Γ심시 예 21 심시 예 1의 중첩 형 나노 저극쌍의 물성 분석  [90] Analysis of physical properties of superposed nano low pole pairs
[91] 실시 예 1에 의하여 최종적으로 형성된 중첩형 나노 전극쌍은 수율이 75% 이다. 공중부유형 탄소나노메쉬 (40)의 모양과 구조적 특징은 SEM(Quanta 200, FEI company USA), HRTEM(JEM-2100F, JEOL Ltd., Japan), FIB(Quanta 3D FEG, FEI company, USA), 및 라만 분광 시스템 (alpha300R, WITec GmbH, Germany)을 이용하여 측정하였다.  The overlapped nano-electrode pair finally formed in Example 1 has a yield of 75%. The shape and structural features of the airborne carbon nanomesh 40 are SEM (Quanta 200, FEI company USA), HRTEM (JEM-2100F, JEOL Ltd., Japan), FIB (Quanta 3D FEG, FEI company, USA), And Raman spectroscopy system (alpha300R, WITec GmbH, Germany).
[92] 도 4를 참조하면，본 발명의 실시 예 1에 의하여 형성된 중첩 형 4, the superposition type formed by Embodiment 1 of the present invention.
포토레지스트전극쌍의 실제 형 태는 도 4-(a)를 통하여 확인할 수 있으며，이를 열분해 하여 제조된 평면 전극 및 공중부유형 탄소나노메쉬는 도 4-(b)를 통하여 확인할 수 있다. 구체적으로 본 발명 에 의 하여 제조된 공중부유형  The actual shape of the photoresist electrode pair can be confirmed through Fig. 4- (a), and the planar electrode and airborne carbon nanomesh prepared by pyrolysis thereof can be seen through Fig. 4- (b). Specifically airborne type produced by the present invention
탄소나노메쉬의 측정된 너 비는 300nm，탄소나노와이어 간격은 4.5μπι에 해당한다.  The measured width of the carbon nanomesh corresponds to 300 nm and the carbon nanowire spacing corresponds to 4.5 μπι.
[93]  [93]
[94] Γ심시 예 31 심시 예 1의 중첩 형 나노 전극쌍의 ？—ᅵ기 적 특성 파참  [94] Γ apocalyptic example 31？ — ᅵ Magnetic characteristics of superimposed nanoelectrode pair
[95] 실시 예 1의 중첩 형 나노 전극쌍의 센서로의 특징을 보여주기 위하여， [95] To show the characteristics of the superposed nanoelectrode pair as a sensor of Example 1,
순환-전류전압 실험을 실시하여 도 5의 그래프에 나타내었다. 이와 같은 순환-전류전압 실험 에서는 산화환원반복을 통한 전류값을 측정하게 된다.  Cyclic-current voltage experiments were carried out and are shown in the graph of FIG. 5. In this cyclic-current voltage experiment, the current value through redox reduction is measured.
[96] 여기서 산화환원반복이 란, 평면 전극 및 탄소나노메쉬 사이 에서 [96] Here, the redox repeat means between the planar electrode and the carbon nanomesh.
산화환원물질이 산화와 환원 반응을 반복하여 전류신호값이 증폭되 게 하는 기 법으로，평면 전극과 탄소나노메쉬 의 간격 이 줄어들수록 산화환원반복 효과가 증대되어 전류신호 증폭도가 상승되는 특징 이 있다.  The redox material repeats the oxidation and reduction reactions to amplify the current signal value. As the distance between the planar electrode and the carbon nanomesh decreases, the redox repetition effect is increased to increase the current signal amplification degree. .
[97] 본 도 5에서 주황색 그래프와 적 색 그래프는 산화환원반복이 일어나지 않을 경우 탄소나노메쉬와 평면 전극으로부터 얻어지는 전류값을 나타내며 , 상부 녹색 그래프와 하부 녹색 그래프는 각각 탄소나노메쉬와 탄소 평 면  In FIG. 5, the orange graph and the red graph represent current values obtained from the carbon nanomesh and the planar electrode when redox repetition does not occur. The upper green graph and the lower green graph respectively represent the carbon nanomesh and the carbon plane.
전극으로부터 얻어지는 산화환원반복을 통해 증폭된 전류값을 나타낸다. 한편, 실험에 사용된 용액은 10 mM Ferrocyanide이다.  The current value amplified through the redox repeat obtained from the electrode is shown. On the other hand, the solution used in the experiment is 10 mM Ferrocyanide.
[98] 도 5를 참조하면，본 발명 의 중첩 형 나노 전극쌍의 평 면 전극과 탄소나노메쉬의 간격 이 최소화 된 상태로 제조되어 , 산화환원반복 효과가 증대되고 전류신호가 증폭되 었음을 확인할 수 있다.  Referring to FIG. 5, the gap between the planar electrode and the carbon nanomesh of the superposed nanoelectrode pair of the present invention was minimized to confirm that the redox repetition effect was increased and the current signal was amplified. Can be.
[99] 본 발명의 중첩형 나노 전극쌍 제조방법은 제조 공정 중 탄소전극과  [99] The method of manufacturing a superposed nanoelectrode pair of the present invention is characterized in that
■： 탄소나노메쉬의 접촉을 효과적으로 차단하면서 탄소 평면 전극과 공중부유형 탄소나노메쉬 의 간격을 효과적으로 조절하여 고수율의 얇고 조밀한 공중부유형 탄소나노메쉬를 쉽 게 제조할 수 있는 효과가 있다. 또한,본발명에의하면，탄소전극과탄소나노메쉬의간격을최소화하도록 중첩형나노전극쌍을제조할수있다. , ■ : Effectively control the distance between carbon flat electrode and airborne carbon nanomesh while effectively blocking the contact of carbon nanomesh, it is easy to manufacture high yield thin and dense airborne carbon nanomesh easily. In addition, according to the present invention, a superposed nano-electrode pair can be manufactured to minimize the gap between the carbon electrode and the carbon nanomesh. ,
또한,본발명의중첩형나노전극쌍이채용된공중부유형바이오센서또는 전기화학센서는나노와이어와전극과의접촉이물리적,전기적으로안정하여 종래의것보다높은센싱감도를보장할수있다.  In addition, the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention can physically and electrically stabilize the contact between the nanowires and the electrode, thereby ensuring a higher sensitivity than the conventional one.
또한,본발명의중첩형나노전극쌍이채용된공중부유형바이오센서또는 전기화학센서는나노와이어기반으로생산비용이적으며생산성이증대되어 대량생산이가능한장점이있다. In addition, the airborne type biosensor or electrochemical sensor employing the overlapping nanoelectrode pair of the present invention has the advantage of low production cost and increased productivity due to nanowire-based, which enables mass production.
Figure imgf000016_0001
이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐,본발명은상기의실시예에한정되는것은아니며，본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
Figure imgf000016_0001
As described above, the present invention has been described in terms of specific details and limited embodiments and drawings, but the present invention has been provided only to assist the general understanding of the present invention, and the present invention is not limited to the above embodiments. Anyone with ordinary knowledge in this field can make various modifications and variations from these materials.
따라서,본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형 있는모든것들은본발명사상의범주에속한다고할것이다.  Accordingly, the spirit of the present invention should not be limited to the described embodiments, and all claims that are equivalent to or equivalent to the scope of the claims as well as the following claims are intended to fall within the scope of the present invention.
(부호의설명)  (Description of the sign)
10:절연체기판 10a:실리콘기판  10: insulator substrate 10a: silicon substrate
10b:절연성표면 11:제 1포토레지스트  10b: insulating surface 11: first photoresist
12:포토레지스트전극 14:제 2포토레지스트  12 photoresist electrode 14 second photoresist
14a:비가용성이격공간확보층 14b:가용성이격공간확보층 14a: Unavailable Spacing Layer 14b: Unavailable Spacing Layer
Figure imgf000016_0002
16:제 3포토레지스트 17:포토레지스트기등부
Figure imgf000016_0002
16: Third photoresist 17: Photoresist light register
18:포토레지스트메쉬 20:평면전극  18: photoresist mesh 20: plane electrode
30:탄소기둥 40:공중부유형탄소나노메쉬  30: carbon column 40: air type carbon nano mesh

Claims

청구범위 Claim
[청구항 1] a)기판상부에포토레지스트전극을형성하는단계；  Claim 1 a) forming a photoresist electrode on the substrate;
b)상기포토레지스트전극을덮는이격공간확보층을형성하는 단계;  b) forming a space securing layer covering the photoresist electrode;
c)상기포토레지스트전극과이격되도록두기둥형상의 포토레지스트기등부와메쉬형상의포토레지스트메쉬를 형성하는단계；및  c) forming two pillar-shaped photoresist back portions and a mesh-shaped photoresist mesh to be spaced apart from the photoresist electrode; and
d)상기기판상형성된포토레지스트전극，포토레지스트기등부 및포토레지스트메쉬의노광영역을다단열처리하여열분해하는 단계;를포함하는중첩형나노전극쌍제조방법 .  and d) thermally decomposing the exposed region of the substrate-formed photoresist electrode, photoresist back part, and photoresist mesh, and thermally decomposing the overlapped nano-electrode pair.
[청구항 2] 제 1항에있어서，  [Claim 2] In paragraph 1,
상기 a)단계는，  In step a),
상기기판상부에제 1포토레지스트를도포하는단계;및 상기제 1포토레지스트를노광및현상하여，상기기판상부에 포토레지스트전극을형성하는단계;를포함하는중첩형나노 전극쌍제조방법. ' Coating a first photoresist on the substrate; and exposing and developing the first photoresist to form a photoresist electrode on the substrate. '
[청구항 3] 제 2항에있어서， [Claim 3] In paragraph 2,
상기제 1포토레지스트는네거티브형포토레지스트인중첩형나노 전극쌍제조방법.  The method of claim 1, wherein the first photoresist is a negative photoresist.
[청구항 4] 제 1항에있어서，  [Claim 4] In paragraph 1,
상기 b)단계는,  Step b),
상기포토레지스트전극이형성된기판상부에  On the substrate on which the photoresist electrode is formed
제 2포토레지스트를도포하는단계;및  Applying a second photoresist; and
상기제 2포토레지스트를노광및현상하여，상기포토레지스트 전극을덮는미노광제 2포토마스크영역인이격공간확보층을 형성하는단계 ;를포함하는중첩형나노전극쌍제조방법 .  Exposing and developing the second photoresist to form a space-separation layer that is an unexposed second photomask region covering the photoresist electrode.
[청구항 5] 제 4항에있어서,  [Claim 5] In paragraph 4,
상기 b)단계는，  In step b),
상기이격공간확보층을노광하여가용화시키는단계;를더 포함하는중첩형나노전극쌍제조방법 .  Exposing and solubilizing the space-separation layer.
[청구항 6] 제 4항에있어서，  [Claim 6] In paragraph 4,
상기제 2포토레지스트는포지티브형포토레지스트인중첩형나노 전극쌍제조방법.  And the second photoresist is a positive photoresist.
[청구항 7] 제 1항에있어서，  [Claim 7] In paragraph 1,
상기 c)단계는,  Step c) is
상기이격공간확보층이형성된기판상부로제 3포토레지스트를 도포하는단계; 상기제 3포토레지스트를노광하여,상기포토레지스트전극을 사이에두고포토레지스트전극과일정거리이격되며서로 대향하는두기등형상의노광영역인포토레지스트기등부를 형성하는단계；및 Applying a third photoresist onto the substrate on which the space securing layer is formed; Exposing the third photoresist to form a photoresist lamp portion, which is a two-lighted exposure region spaced apart from the photoresist electrode by a distance, with the photoresist electrode interposed therebetween; and
상기제 3포토레지스트를재노광하여，상기포토레지스트전극을 가로질러상기포토레지스트기등부의상기두기등형상의 노광영역을연결하는메쉬형상의노광영역인포토레지스트 메쉬를형성하는단계;를포함하는증첩형나노전극쌍제조방법. Re-exposing the third photoresist to form a photoresist mesh that is a mesh-shaped exposure area that connects the two light-emitting exposure areas of the photoresist light dorsal portion across the photoresist electrode; Folded nano-electrode pair manufacturing method.
[청구항 8] 제 7항에있어서, [Claim 8] In paragraph 7,
상기 c)단계는，  Step c) is
상기포토레지스트기등부및상기포토레지스트메쉬가형성된 이후에,현상을통해상기 c)단계에서미노광된제 3포토레지스트 영역인미노광영역및상기이격공간확보충을제거하는단계；를 더포함하는중첩형나노전극쌍제조방법.  After the photoresist light register and the photoresist mesh are formed, removing the unexposed region and the space replenishment space, which are the third photoresist regions unexposed in the step c), through the development; Nested nano-electrode pair manufacturing method.
[청구항 9] 제 7항에있어서,  [Claim 9] In paragraph 7,
상기제 3포토레지스트는네거티브형포토레지스트인중첩형나노 전극쌍제조방법.  And the third photoresist is a negative photoresist.
[청구항 10] 제 7항에있어서,  [Claim 10] In paragraph 7,
상기포토레지스트메쉬의와이어사이의각도 (Θ)는 40°내지 60°인 중첩형나노전극쌍제조방법.  The angle (Θ) between the wires of the photoresist mesh is 40 ° to 60 ° superimposed nano-electrode pair manufacturing method.
[청구항 11] 제 I항에있어서，  [Claim 11] In Section I,
상기 d)단계에서상기다단열처리는，  In step d), the multi-stage heat treatment is,
300내지 400°C에서 30내지 90분동안시행되는제 1단계;및 900내지 1000oC에서 30내지 90분동안시행되는제 2단계;를 포함하는중첩형나노전극쌍제조방법 . A first step of 30 to 90 minutes at 300 to 400 ° C; and a second step of 30 to 90 minutes at 900 to 1000 ° C .;
[청구항 12] 제 i항내지제 11항중어느한항의방법으로제조된중첩형나노 전극쌍을포함하며，  12. A nested nano-electrode pair manufactured by the method of any of claims i to 11,
감지물질로서글루코스효소 (glucose enzyme)를포함하는 공중부유형센서.  Airborne type sensor comprising a glucose enzyme (sensing substance).
[청구항 13] 제 12항에있어서，  13. In claim 12,
상기글루코스효소는글루코스옥시다아제 (glucose oxidase)인 공중부유형센서.  The glucose enzyme is glucose oxidase (glucose oxidase) airborne type sensor.
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