JP6339976B2 - Method for producing carbon microelectrode - Google Patents

Description

  The present invention relates to a method for producing a carbon microelectrode used in electrochemical measurement.

  Electrochemical measurement is an excellent measurement method for highly sensitive detection of hydrogen ions, trace metal ions, and biomolecules in solution. In the analysis and biosensor based on the electrochemical method, it is important to measure a small amount of sample and to measure a target substance having a lower concentration with high sensitivity. As a technique for analyzing a small amount of sample, miniaturization of an electrode can be mentioned. Furthermore, by incorporating the microelectrode into the microchannel, the electrode area increases with respect to the sample volume and the diffusion rate of the substance, so that an advantage of quick response and high response current density can be expected. On the other hand, since the electrochemical current increases or decreases in proportion to the electrode area, there is a drawback that the absolute value of the response current generally decreases. In order to solve these problems, microelectrodes having various electrode shapes have been studied.

  In order to increase the sensitivity of the microelectrode, it is also effective to use a pattern electrode produced by bringing the microelectrode close to each other. For example, there is a technique in which a working electrode is composed of two electrodes (a generator electrode and a collector electrode) that are configured close to each other on the order of μm (see, for example, Patent Document 1 and Non-Patent Document 1). In this technique, an electrochemical redox cycle is generated on the electrode, and the redox current is repeatedly extracted from one target molecule, thereby increasing the apparent current value and enabling highly sensitive measurement. . By using the above electrode structure, highly sensitive electrochemical detection is possible, and a highly sensitive biosensor using the above electrode structure can be realized.

  On the other hand, in the analysis based on the electrochemical method, selection of the electrode material is important. It is important to use a material that is stable in a wide potential range for the electrode used for measurement. The measurable potential range, i.e. the potential window, also depends on the electrode, solvent and supporting electrolyte. In the most common aqueous solution system, when the electrolyte type is the same, (1) hydrogen overvoltage (difference between actual hydrogen generation potential and theoretical equilibrium potential) is large, (2) oxygen overvoltage (actual The larger the difference between the generation potential of oxygen and the theoretical equilibrium potential) and (3) the higher the dissolution potential of the electrode, the wider the potential window.

Under the circumstances described above, noble metals such as gold, platinum and palladium, semiconductors such as mercury, SnO ₂ and In ₂ O _3, and carbon materials such as glassy carbon and crystalline carbon are used as electrode materials. Among these materials, noble metals have high oxygen overvoltage and are difficult to oxidize and dissolve, so that they can be used as measurement electrodes within a wide potential range on the oxidation side. However, since noble metals have a small hydrogen overvoltage, their use is limited due to the disadvantage that they are difficult to use for measurement on the reduction side. Moreover, it is an expensive material. On the other hand, the mercury electrode has a large hydrogen overvoltage and is suitable for measurement on the reduction side, but cannot be used for measurement of oxidation reaction because dissolution occurs on the oxidation side. In addition, the environmental load is large. SnO ₂ and In ₂ O ₃ are used as transparent electrodes, and the measurable potential range is considerably wide, but on the reduction side, there is a drawback that the electrodes are reduced to tin or indium.

Carbon materials have strong corrosion resistance and a wide potential window on both the oxidation and reduction sides. This feature enables electrochemical detection of many types of substances compared to electrodes made of other materials, which is an advantage when used as an electrode for electrochemical use.
On the other hand, the disadvantage of the carbon material electrode is that the structure is indefinite. Even if it is a carbon electrode in a word, its manufacturing method varies, and there are various forms known by names such as glassy carbon, amorphous carbon, sputtered carbon, diamond-like carbon, and graphite.

  Since the electrochemical reaction is an electron transfer reaction on the electrode surface in solution, the shape of the electrode surface has an important influence on the efficiency of the electrochemical reaction and the selectivity of the reactant. However, the surface structures of the carbon materials described above are diverse and have not been fully identified. This is a limitation that hinders the functionalization of electrochemical electrodes made of carbon materials.

  In recent years, in order to satisfy the demand for miniaturization and integration of an electrochemical detection device or the demand for a small amount of an object to be measured, it is desired to use a miniaturized microelectrode of the electrochemical electrode itself. In manufacturing a microelectrode using a carbon material, the microfabrication characteristics of the carbon material are important. Therefore, regarding the fabrication of these microelectrodes, the structural control of the carbon material is inevitable as the size is reduced.

In the carbon material, an increase in hardness sp ³ bond moiety represented by diamond structure, to reduce hardness in the sp ² -bonded moiety represented by graphite, in the configuration ratio of sp ³ bonds is high material, microfabrication The problem arises that is difficult. The downsizing of the electrochemical electrode is more remarkably affected by the above-described structural indefiniteness, which causes variations in the precision of microfabrication. In order to supply an electrode that exhibits an electrochemical response stably, a carbon material having a defined structure is desired.

Currently, a material called graphene is attracting attention as a new form of carbon material. Graphene is a planar carbon material having a thickness corresponding to one atomic layer composed only of carbon sp ² bonds. Graphene has high mobility, and research has accelerated worldwide since the elucidation of unique electronic properties resulting from its two-dimensional structure.
A method for producing graphene is generally a method in which graphite having a structure in which a large number of graphenes are stacked is pressed onto a substrate and peeled off and transferred (for example, see Non-Patent Document 2). Many methods for generating graphene using a carbon-containing raw material have been developed, such as thermal decomposition of silicon carbide (see, for example, Non-Patent Document 3), chemical vapor deposition on a catalytic metal surface such as nickel or copper (for example, Non-Patent Documents 4 and 5) and molecular beam epitaxy (see Non-Patent Document 6 for example) are known.

Here, the carbon electrode for electrochemical measurement using graphene as a carbon material can be said to be a carbon electrode whose structure is truly defined. Only the surface and edges constitute graphene. Therefore, when miniaturizing the electrode, it is possible to predict electrode characteristics that cannot be controlled because the surface structure of other carbon materials is indefinite, and to design an electrode based thereon. As a result, high sensitivity and high selectivity can be added. Furthermore, it can be expected to be applied to a measurement object that has been difficult or impossible to realize.
A graphene microelectrode can be obtained by processing a graphene generated or transferred onto an electrode substrate by a processing process using a lithography method and a lift-off method (for example, see Patent Document 2). A general processing process is to apply a photoresist on a graphene film, expose and develop, process the graphene film into a desired shape using a dry etching method or a chemical etching method, and then add an organic solvent or the like. Use to remove surface photoresist.

Japanese Patent Laid-Open No. 01-272958 JP 2013-242214 A

C. E. Chidsey et al. , Anal. Chem. , Vol. 58, 1986, 601-607. K. S. Novoselov et al. , Science, vol. 306, 2004, 666-669. A. J. et al. van Bummel et al. , Surface Science, vol. 48, 1975, 463-472. A. Reina et al. , Nano Letters, vol. 9, 2009, 30-35. X. Li et al. , Science, vol. 324, 2009, 1312-1314. F. Maeda et al. , Japan Journal of Applied Physics, vol. 49, 2010, 04DH13.

  However, although the graphene is composed of the surface and the edge, the characteristics of the edge of the graphene film newly created by the processing process are different from the edge that can be spontaneously generated at the time of film formation. There was a problem that the accuracy decreased. In addition, since the grown graphene film undergoes a multi-step process such as resist coating, baking, exposure, development, resist removal, and cleaning, the surface part of the graphene film is also accurate in structural control due to damage and resist residue adhesion. It was difficult to avoid the decline.

  In view of the above circumstances, an object of the present invention is to provide a carbon microelectrode capable of realizing highly accurate electrochemical measurement.

One embodiment of the present invention includes a first step of growing a graphene layer according to a pattern by a chemical vapor deposition method (CVD method) on the surface of a catalytic metal layer patterned into the shape of a microelectrode , In order to maintain the pattern shape, a third step of forming a support layer on the graphene layer, and a step of peeling the graphene layer grown in the pattern shape from the catalytic metal layer and placing it on the electrode substrate 2 steps in this order, and the support layer is a method for producing a carbon microelectrode, which is a paraxylylene-based polymer vapor-deposited film comprising at least one of polyparaxylene and derivatives thereof .

  One embodiment of the present invention is the above-described method for manufacturing a carbon microelectrode, wherein the catalytic metal layer is formed by a lithography method and a lift-off method.

  One embodiment of the present invention is the above-described method for producing a carbon microelectrode, wherein the catalytic metal layer is produced by treating nickel or copper on the surface of a commercially available microelectrode pattern by a plating method.

One aspect of the present invention is a method for producing the carbon microelectrode, wherein the support layer formed of the paraxylylene-based polymer vapor deposition film is patterned into an arbitrary shape after the first step and before the third step. And further comprising a fourth step of ning.

One aspect of the present invention is a method for producing the carbon microelectrode, wherein in the second step, the graphene layer on which the support layer is formed is peeled from the catalyst metal layer by chemical etching , and the graphene A layer is placed on the electrode substrate.

  One aspect of the present invention is the above-described carbon microelectrode manufacturing method, wherein the graphene layer in which the support layer made of the insulating film is formed from the catalytic metal layer by a physical technique in the second step. And the graphene layer is placed on the electrode substrate.

One aspect of the present invention is a method of manufacturing the carbon microelectrodes, in the second step, using a pre-Symbol support layer directly as the electrode substrate.

  According to the present invention, it is possible to provide a carbon microelectrode capable of realizing highly accurate electrochemical measurement.

It is a flowchart explaining one Embodiment of the manufacturing method of the carbon microelectrode in this invention. It is sectional drawing which shows typically the structure in the process for demonstrating the manufacturing method of the carbon microelectrode in Example 1 of this invention. It is sectional drawing which shows typically the structure in the process for demonstrating the manufacturing method of the carbon microelectrode in Example 2 of this invention. It is sectional drawing which shows typically the structure in the process for demonstrating the manufacturing method of the carbon microelectrode in Example 2 of this invention.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart for explaining an embodiment of a method for producing a carbon microelectrode according to the present invention.

(First embodiment)
In one embodiment, the present invention includes a first step of growing a graphene layer in a pattern by a chemical vapor deposition method (CVD method) on the surface of a catalytic metal layer patterned in the shape of a microelectrode, and the pattern A carbon microelectrode manufacturing method comprising: a second step of peeling a graphene layer grown in a shape and placing the graphene layer on an electrode substrate.

  According to this embodiment, it is possible to obtain a carbon microelectrode in which the electrode characteristics and the uniformity of the microfabrication characteristics and the uniformity of the microfabrication characteristics are enhanced by the carbon material having a high structure controllability. Furthermore, highly accurate electrochemical measurement can be realized by the carbon microelectrode obtained by the present embodiment.

  First, in the first step, a pattern of the catalyst metal layer is formed. What is necessary is just to produce the pattern of a catalyst metal layer by the lithography method and the lift-off method. Moreover, when utilizing a commercially available microelectrode pattern, you may produce these surfaces by processing nickel and copper by the plating method. However, when using the plating method, a platinum electrode having a melting point higher than the growth temperature of the CVD method may be used.

Subsequently, a graphene layer is grown according to a pattern on the surface of the patterned catalytic metal layer by a chemical vapor deposition method (CVD method). By using the graphene layer that has been grown in a pattern in advance, it is possible to avoid the mixing of the edges of the graphene film newly formed by the processing process, and to prevent the accuracy of the structure control from being lowered.
In this specification, “Chemical Vapor Deposition (CVD)” is one of the vapor deposition methods for forming thin films of various materials on a substrate material heated in a reaction tube made of quartz or the like. In addition, it means a method of depositing a film by a chemical reaction on the surface of a substrate or in a gas phase by supplying a raw material gas containing a target thin film component. For example, when forming a silicon thin film, there are three stages: a process of decomposing stable molecules such as silane, which is a raw material gas, a process in which decomposed species (radical species) in the gas phase react, and a process of depositing on a substrate. Through this process, a silicon thin film can be formed.

  Next, in the second step, the graphene layer grown in the pattern is peeled off and placed on the electrode substrate. Details of the peeling method will be described in the fourth and fifth embodiments described later.

(Second embodiment)
In one embodiment, the present invention further includes forming a support layer on the graphene layer in order to maintain the pattern shape of the graphene layer after the first step and before the second step. A method for producing a carbon microelectrode comprising the steps is provided.

  According to this embodiment, since the process is performed via the support layer, the process load on the surface of the graphene that operates as an electrode can be reduced, and the deterioration of the accuracy of the structure control can be reduced as compared with the conventional case.

What is necessary is just to perform a 1st process and a 2nd process similarly to the above-mentioned 1st embodiment. In the present embodiment, a third step of forming a support layer on the graphene layer is provided after the first step and before the second step. The support layer in the third step is preferably a polymer film that can be removed by a remover or an insulating film having high adhesion to graphene. The remover used for removing the polymer film is preferably an organic solvent such as acetone or N-methyl-2-pyrrolidone.
Examples of the “polymer film removable with an organic solvent” include resins such as polymethyl methacrylate (PMMA).
Examples of the “insulating film having high adhesion to graphene” include a paraxylylene-based polymer vapor deposition film made of at least one of polyparaxylene and derivatives thereof (fluoride, chloride, etc.).

(Third embodiment)
In one embodiment, the present invention includes a fourth step of patterning the support layer made of the paraxylylene-based polymer deposited film into an arbitrary shape after the first step and before the third step. An electrode manufacturing method is provided.

  According to this embodiment, since the process is performed via the support layer, the process load on the surface of the graphene that operates as an electrode can be reduced, and the deterioration of the accuracy of the structure control can be reduced as compared with the conventional case.

  The first step, the second step, and the third step may be performed in the same manner as in the first embodiment and the second embodiment described above. In this embodiment, when the insulating film forming the support layer is a paraxylylene polymer vapor deposition film, the paraxylylene polymer vapor deposition film is deposited on the electrode substrate after the first step and before the third step. Then, patterning can be performed by a dry etching method. After forming the electrode substrate / support layer, it may be pressure-bonded to the graphene film to form the electrode substrate / support layer / graphene / metal layer, but the graphene layer in the portion where there is no polyparaxylene layer having high adhesion to graphene is Depending on the difference in adhesion with graphene, it may be removed in subsequent steps.

(Fourth embodiment)
In one embodiment, the present invention provides a method for producing a carbon microelectrode, wherein, in the second step, the graphene layer is peeled off by chemical etching of the catalytic metal layer, and the graphene layer is placed on the electrode substrate. provide.

  According to the present embodiment, damage to the surface portion of the graphene film and deterioration in the accuracy of structure control due to film residue adhesion can be reduced as compared with the conventional case.

  As used herein, “chemical edging” means that a chemical is used to corrode or dissolve the sample surface. For example, the catalyst metal layer may be removed using an acid or a base.

What is necessary is just to perform a 1st process and a 3rd process similarly to the above-mentioned 1st embodiment and 2nd embodiment. In the present embodiment, when the support layer is a polymer film that can be removed by a remover such as a solvent, the support layer / graphene / metal layer after the first step and the third step are diluted with a dilute acid solution (for example, The support layer / graphene may be peeled off by immersing in FeCl ₃ in a solution of 0.05 g / mL to dissolve the metal. The support layer / graphene / electrode substrate is obtained by removing the acid by floating the support layer / graphene on the surface in a container containing pure water, and then scooping it up with the electrode substrate and mounting it. Next, the surface of the graphene is exposed by removing the polymer film of the support layer with an organic solvent, and an electrode having a configuration of a graphene / electrode substrate may be formed. In this transfer process, the only process load on the graphene surface acting as an electrode is the application and removal process of the polymer film, so the damage to the surface of the graphene film and the deterioration of structure control accuracy due to film residue adhesion are reduced compared to the conventional process. can do.

  When the support layer is an insulating film having high adhesion to graphene, after the first step and the third step, the support layer is previously deposited on the electrode substrate to form the electrode substrate / support layer. After that, the electrode substrate / support layer / graphene / metal layer may be formed by pressure bonding with the graphene film. The electrode substrate / support layer / graphene may be peeled off by immersing this in a dilute acid solution and dissolving the metal. Since the graphene surface is exposed, the supporting layer does not need to be removed and can be used as an electrode as it is. In this process, the process load on the surface of the graphene acting as an electrode is only the deposition of the insulating film and the removal of the metal layer. Therefore, it is possible to reduce the accuracy of structure control due to the damage of the surface portion of the graphene film compared to the conventional method. . Moreover, since a polymer film is not used, residue adhesion can be avoided.

(Fifth embodiment)
In one embodiment, in the second step, in the second step, the graphene layer on which the support layer made of the insulating film is formed is peeled from the catalytic metal layer by a physical technique, and the graphene layer is removed from the catalyst metal layer. A method for producing a carbon microelectrode to be placed on an electrode substrate is provided.

  According to this embodiment, it is possible to avoid moisture adsorption and etching agent residue adhesion that occur during chemical etching, so that the structure controllability can be further enhanced.

  In the present specification, the “physical method” means a method using physical action such as light, heat, water, electricity, magnetism, and mechanical. For example, a method of peeling off the catalyst metal layer using a magnet or the like, or a method of peeling off the catalyst metal layer by applying a pulling force in a vertical direction with a machine or the like can be used.

What is necessary is just to perform a 1st process and a 3rd process similarly to the above-mentioned 1st embodiment and 2nd embodiment. In this embodiment, after the first step and the third step, a support layer is previously deposited on the electrode substrate, and after forming the electrode substrate / support layer, it is pressure-bonded to the graphene film, and the electrode substrate / support layer / graphene / A metal layer may be formed. Thereafter, the electrode substrate / support layer / graphene may be peeled from the catalyst metal layer using the physical method described above. In this case, it is possible to avoid moisture adsorption and etching agent residue adhesion that occur during chemical etching, thereby further improving the structure controllability. In addition, since all the processes are dry processes, it is possible to use a material (such as paper or cellulose film) that has low resistance to wet processes such as a shape change due to moisture as an electrode substrate.
Furthermore, when the strength of the insulating film having high adhesion to graphene is sufficient, it may be used as it is as an electrode substrate.
In each process of the first embodiment to the fifth embodiment described above, the shape and film structure of the graphene layer may be confirmed in a non-contact and non-destructive manner using a Raman imaging method or the like.

  The embodiment of the present invention has been described in detail with reference to the drawings. However, the specific configuration is not limited to this embodiment, and includes designs and the like that do not depart from the gist of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example.

[Example 1]
FIG. 2 is a cross-sectional view schematically showing a configuration in a process for explaining a method of manufacturing a carbon microelectrode in Example 1 of the present invention. First, a resist pattern layer was formed on an insulating substrate (preferably quartz). The resist pattern layer has an opening at a pattern portion where a microelectrode is formed. Next, the metal layer was deposited on the insulating layer and the resist pattern by depositing a metal layer on the resist pattern layer by sputtering (or deposition such as vapor deposition). The condition of the metal layer at this time was set to be about 0.5 μm to 100 μm in thickness with a nickel layer (or a copper layer). Subsequently, the resist pattern layer was removed by a lift-off method to selectively remove the metal layer formed thereon. As a result, a micropattern composed of a metal layer was obtained (see FIG. 2A).
Instead of the above method, nickel or copper may be formed on these surfaces by plating using a commercially available microelectrode pattern. However, in this case, a platinum electrode having a melting point higher than the growth temperature of the CVD method is used.

Next, a graphene layer was grown on the micropatterned metal film. The substrate on which the metal layer was formed was washed with acetone (or an organic solvent such as isopropyl alcohol (IPA)), and then placed in a heating furnace for CVD. Until the metal substrate is taken out from the heating furnace after the graphene is grown, the argon gas at about 1000 sccm and the H ₂ gas at a flow rate of _{2 to} 35 sccm are set so that the pressure in the heating furnace becomes about 1 atm (760 Torr, 1013 hPa). It flowed continuously. sccm is the unit of flow rate, indicating a 1013hPa fluid at 0 ℃ is 1 cm ³ Flowing to 1 minute.

The substrate was heated from room temperature to about 1000 ° C. over about 15 minutes, then heated to graphene growth temperature (desirably 1075 ° C.) over about 10 minutes, and the surface of the metal layer was cleaned for about 30 minutes while maintaining the temperature. Next, CH ₄ gas diluted to 1% was flowed at a flow rate of about 1 sccm for a predetermined time (preferably about 30 minutes), and graphene was grown on the surface of the metal layer on the substrate. The pressure during graphene growth is about 1 atm, but it may be grown under low pressure conditions. Next, the introduction of CH ₄ gas and the heating of the heater were stopped, and the mixture was left as it was. The temperature dropped to around 100 ° C. in about 2 hours. After confirming that the temperature reached about 100 ° C., the introduction of H ₂ gas was stopped, and H ₂ and CH ₄ gas were exhausted, and then the substrate was taken out from the heating furnace. By the above method, one to several layers of graphene could be produced according to the pattern of the metal layer. (First step) (see FIG. 2B). Confirmation that the graphene layer was formed was performed using a Raman imaging method.

Next, a process of peeling the graphene layer grown in a pattern shape was performed. Polymethyl methacrylate (PMMA) was applied on graphene grown on a metal substrate by a CVD method, and heated at about 170 ° C. to be solidified (see FIG. 2C). Subsequently, the PMMA / graphene / metal substrate was immersed in a dilute acid solution (for example, a solution in which FeCl ₃ was dissolved at a concentration of 0.05 g / mL), and the metal was dissolved over about 1 to several hours. By this treatment, patterned graphene peeled from the metal layer and supported by the resin layer was obtained (see FIG. 2D).

After this PMMA / graphene was immersed in pure water to remove the acid, it was scooped up and placed on an electrode substrate (preferably quartz or glass) made of any insulating material (see FIG. 2E). On the electrode substrate, an electrode pad for connection to an electrochemical measurement device was formed in advance, and a graphene film was placed so as to be in contact with the electrode pad. The electrode pad was formed from a metal layer by a lithography method and a lift-off method.
Next, after the moisture was evaporated, the resin layer was removed, and a microelectrode composed of a graphene layer grown in a pattern was obtained (second step) (see FIG. 2F). In order to evaporate the moisture, it may be only dried at room temperature and in the atmosphere, but it was evaporated by heating to about 40-80 ° C. in a vacuum. The evaporation of moisture due to heating removes adsorbed water between the electrode substrate and the graphene layer better, and improves the adhesion between the substrate and the graphene film. The resin layer is removed by heating acetone (or N-methyl-2-pyrrolidone (NMP) or the like) to room temperature (25 ° C.) (or a temperature of 25 ° C. or more and 50 ° C. or less). Used. The PMMA resin can also be removed by heating from 350 ° C. to 450 ° C. in a hydrogen atmosphere.
Confirmation that the patterned graphene layer was formed on the electrode substrate was performed using a Raman imaging method.
From the above, it has been clarified that a carbon microelectrode using a graphene layer with high structure controllability is provided.

[Example 2]
3 and 4 are cross-sectional views schematically showing a configuration in a process for explaining a method of manufacturing a carbon microelectrode in Example 2 of the present invention. The process up to the first step was performed in the same manner as in Example 1 (FIGS. 3A-B and 4A-B).
Next, a process of peeling the graphene layer grown in a pattern shape was performed. A polyparaxylene layer was formed by evaporation on an arbitrary electrode substrate (preferably quartz or glass) (see FIG. 3C).
On the electrode substrate, an electrode pad for connection with an electrochemical measuring instrument was formed in advance. The electrode pad was formed from a metal layer by a lithography method and a lift-off method. The electrode pad portion was covered with a mask at the time of polyparaxylene deposition in order to prevent deposition of the polyparaxylene layer as an insulating material.
Graphene / metal was bonded onto the polyparaxylene / electrode substrate in a direction in which the polyparaxylene layer and the graphene layer were bonded (see FIG. 3D). A hydraulic press machine was used for bonding. Prior to bonding, a polyparaxylene layer was also formed on the graphene layer by a vapor deposition method, and this was used as a support film (see FIG. 4C). The thickness was about 2 μm. The polyparaxylene layers were bonded together in the direction in which they were bonded (see FIG. 4D).

The bonded substrate (metal / graphene / polyparaxylene / electrode substrate) is immersed in a dilute acid solution (for example, a solution in which FeCl ₃ is dissolved at a concentration of 0.05 g / mL), and takes about 1 to several hours. Only the metal layer was dissolved. By this treatment, patterned graphene peeled from the metal layer and supported by the polyparaxylene / electrode substrate layer was obtained (see FIGS. 3E and 4E). After removing the acid by immersion in pure water, the water was evaporated. Confirmation that the patterned graphene layer was formed on the electrode substrate was performed using a Raman imaging method.
As described above, a carbon microelectrode using a graphene layer with high structure controllability can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the carbon microelectrode which can implement | achieve highly accurate electrochemical measurement can be provided.

Claims (7)

On the surface of the catalytic metal layer patterned into the shape of a microelectrode,
A first step of growing a graphene layer according to a pattern by chemical vapor deposition (CVD);
A third step of forming a support layer on the graphene layer in order to maintain the pattern shape of the graphene layer;
A second step of peeling off the graphene layer grown in the pattern from the catalytic metal layer and placing it on the electrode substrate;
In this order ,
The method for producing a carbon microelectrode , wherein the support layer is a paraxylylene-based polymer vapor deposition film made of at least one of polyparaxylene and derivatives thereof .   The method for producing a carbon microelectrode according to claim 1, wherein the catalytic metal layer is produced by a lithography method and a lift-off method.   The said catalyst metal layer is a manufacturing method of the carbon microelectrode of Claim 1 which processes nickel or copper by the plating method on the surface of a commercially available microelectrode pattern. Before the third step even after the first step, any one of claims 1 to 3, further comprising a fourth step of patterning the support layer made of the paraxylene based polymer deposited film into a desired shape A method for producing a carbon microelectrode as described in 1. above. In the second step, from the catalytic metal layer by chemical etching, and stripping the graphene layer the support layer is formed, any one of claims 1-4 for placing said graphene layer on the electrode substrate The method for producing a carbon microelectrode according to one item. In the second step, from the catalytic metal layer by physical means, and separating the graphene layer before Symbol supporting layer is formed, of claims 1 to 4, placing the graphene layer on the electrode substrate The manufacturing method of the carbon microelectrode as described in any one. Wherein in the second step, the manufacturing method of the carbon microelectrode according to any one of claims 1 to 6, using a pre-Symbol support layer directly as the electrode substrate.

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