JPH02268265A - Electrode cell having minute hole for electrochemical measurement and manufacture thereof - Google Patents

Abstract

PURPOSE:To perform measurement characterized by high sensitivity and excellent response by using at least two working electrodes where an electrode is arranged at the bottom part, the intermediate part or the upper part of each of many minute holes. CONSTITUTION:Many circular minute holes 5 reaching a lower electrode 2 at the lowermost layer through an insulating film 3 from the surface are provided in a surface electrode 4. The surface electrode is used as an upper working electrode. The lower electrode 2 is insulated with the walls of the minute holes in the film 3 and provided at the bottom parts of the hole 5 so as to face the electrode 4. The lower electrode 2 is used as a lower working electrode. Thus, an electrode cell for minute use is constituted. These electrodes are formed of metal, half-metal or semiconductors. In this constitution, high sensitivity, high response speed and a large current are obtained. This cell has an excellent effect in high sensitivity analysis of low concentration samples.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a minute electrode cell for electrochemical measurement used in electrochemical analysis, flow cells, liquid phase chromatography, etc., and a method for manufacturing the same.

[Conventional technology]

In general, electrode cells for electrochemical measurements, so-called microelectrodes, are suitable for analyzing microscopic areas such as in living organisms and microscopic solution samples, so attempts have been made to combine them with various organic or inorganic materials and apply them to sensors, etc. There is. Most microelectrodes are made by enclosing metal wires of platinum, gold, etc., carbon fiber metal chlorides, etc. in glass capillary tubes.

The response behavior of this fine electrode varies depending on the shape of the electrode.The response speed increases as the size of the electrode decreases.Therefore, various electrode shapes and miniaturization of electrodes have been studied for the purpose of measuring high-speed electrochemical reactions. ing.

However, when the electrode radius is reduced to 1 μm and 11 degrees, the detectable current drops to below the nA order, which increases noise and decreases sensitivity during measurement, making it difficult to measure low-concentration samples. It was rare that measurements were required.

Finally, in order to improve the sensitivity of the electrodes, it has been proposed to increase the number of working electrodes. This electrode has a structure in which a large number of carbon fibers are encapsulated in an insulating resin, and the encapsulated carbon fibers are etched to remove the influence of solution agitation and contamination. It is.

However, with this method, it is not possible to obtain electrodes with the exact same shape or shapes other than disk electrodes, it is time-consuming to manufacture, difficult to obtain in large quantities, and there are drawbacks such as deterioration of the resin used for encapsulation. Atsuku.

On the other hand, in recent years, the application of phosphorography technology has been proposed as a method for creating microelectrodes. In this method, a resist is applied to a substrate, an image mask with an electrode pattern is placed over it, exposed and developed, and a thin metal film is formed by vapor deposition, etc., and then the resist is peeled off to form minute electrodes on the substrate. After creating a metal thin film on an insulating substrate, a resist is applied, an electrode pattern and an image mask are overlapped, exposed and developed, and the remaining resist is used as a mask to remove the exposed metal. An etching method is known in which a film is etched to obtain an electrode pattern.

With this method, a large amount of microelectrodes with arbitrary shapes and a constant distance between the electrodes can be fabricated on the substrate with good reproducibility. Electrode pairs that can perform measurements similar to poles, and! It can be applied to vaporization elements, sensor base electrodes, etc. Applying this microelectrode fabrication method, microelectrochemical transistors (e.g. J, Phya, C
HSM, 89°5133 (1985)), Electrochemical measurement of low molecules or polymer complexes using an L-type deposit electrode (Anal.

Ch@w, 58, 601 (1986), etc. have been carried out.

Furthermore, a resist (polymethyl methacrylate: PMMA) is coated on a conductive substrate, and many fine circular holes are made in the resist by exposure and development to produce a working electrode having many fine circular patterns (J , El
@ctroch@m, Soe, Vol, 133°752 (1986), ).

[Problem to be solved by the invention]

However, if such fine electrodes are simply arranged densely, they will become similar to normal-sized electrodes, and the characteristics as fine electrodes will be lost. Therefore, it is necessary to arrange the fine electrodes at a certain distance, and there is a drawback that the electrode becomes large as a whole in order to obtain a measurable current.

In view of the above points, the present invention has been made to solve such problems, and its purpose is to provide at least two working electrodes arranged at the bottom, middle, or top of each of a large number of micropores. It is an object of the present invention to provide a microporous electrode cell that can perform electrochemical measurements with high sensitivity and good responsiveness by using the present invention, and a method for manufacturing the same.

[Means to solve the problem]

To achieve the above object, the present invention provides an electrode cell for electrochemical measurement having a working electrode for substance detection, in which a thin film surface electrode formed of a metal, semimetal or semiconductor having a large number of micropores, or an insulating surface and at least one other metal insulated from each other by a pore wall at the bottom or middle of the pore;

It is characterized in that it is composed of a working electrode having an electrode made of a semi-metal F4 or a semiconductor.

Further, the manufacturing method of the present invention includes sequentially laminating conductive thin films and insulating films of metal, semimetal pA, or semiconductor at least once each on a substrate whose surface or entire surface is insulating,
Next, a fine hole resist pattern is formed thereon, and then a large number of fine holes are made by etching until the bottom layer of the conductive film surface is exposed.

[Effect]

Therefore, in the present invention, whereas in conventional electrodes, the target substance diffused perpendicularly to the electrode surface, it took time to reach a steady state and the current density was low.
By making the electrodes finer and making the diffusion more hemispherical, it is possible to shorten the time it takes to reach a steady state and increase the current density. Furthermore, by using two or more working electrodes, one of the adjacent electrodes is at the oxidation potential of the target substance, and the other is at the oxidation potential of the target substance.
By setting one electrode to a reduction potential, oxidation and reduction are repeated between the adjacent electrodes, so the effective current can be significantly increased.

〔Example〕

Hereinafter, the present invention will be explained in detail by way of examples with reference to the drawings.

FIG. 1 is a schematic diagram of a microporous electrode cell for electrochemical measurement according to an embodiment of the present invention. In the figure, 1 is an insulating substrate, for example, an oxide film 1b is deposited on the main surface of a silicon substrate 1a.

It consists of a so-called silicon substrate with an oxide film. 2 is a lower electrode as a working electrode formed of a metal, semimetal or semiconductor on the oxidized M1b surface, that is, the insulating surface, on the substrate 1;
3 is an insulating film formed on this lower electrode 2; 4 is a surface electrode as another working electrode formed of the same metal, semimetal, or semiconductor as the lower electrode 2 on the surface of the insulating film 3; be.

Reference numeral 5 denotes a large number of micro holes (also referred to as micro circular holes) formed in a circular shape to reach the film surface of the lower electrode 2 in the lowest layer through the surface insulation M3 on the surface electrode 4. The surface electrode 4 having micropores 5 of 1 to 3 is used as an upper working electrode, and the lower electrodes 2 that are insulated from each other by the micropore walls of the insulating film 3 are placed at the bottoms of the micropores 5 as lower working electrodes. A micropore electrode cell is constructed by the working electrode.

In FIG. 1, T is an opening for connecting an external lead to one end of the lower electrode 2 for leading out the electrode.

Here, as the group &1 whose surface or whole is insulating,
In addition to silicon substrates with oxide films, quartz plates.

Examples include aluminum oxide substrates, glass substrates, and plastic substrates. Metals for the lower and surface electrodes 2.4 include gold, platinum, silver, chromium, titanium, stainless steel, etc. 1. Semiconductors for the electrodes include p- and n-type silicon, p- and n-type germanium, cadmium sulfide, Titanium dioxide, zinc oxide, gallium phosphide, gallium arsenide, indium phosphide, cadmium selenide, cadmium telluride, molybdenum diarsenide, tungsten selenide.

Examples include steel dioxide, tin oxide, indium oxide, indium tin oxide, and conductive carbon as a semimetal for electrodes. Examples of the insulating film 3 include silicon oxide, silicon dioxide, silicon nitride, silicone resin, polyimide and derivatives thereof, epoxy resin, and thermoset polymers.

Also, fine/]・/,! When producing a microporous electrode cell as a pole, a conductive thin film and an insulating film 3 are alternately laminated to form an electrode 2 or 4 on a substrate 1. , a coating method, etc. can be used. Then, a resist is applied onto this substrate, and an image mask having an electrode pattern is overlaid thereon, or the pattern is directly exposed using an electron beam, etc., and the pattern is transferred to the resist on the substrate by development. ,
Using the remaining resist pattern as a mask, the laminated film of each conductive film and insulating film is etched to form microscopic holes to form a large number of microscopic working electrodes. That is, a lower electrode 2. is placed on an insulating substrate 1. After sequentially laminating the insulating film 3 and the surface electrode 4, a resist is applied thereon, and exposure and
Develop to form a microporous resist pattern. Thereafter, by etching the laminated film of the surface electrode 4 and the insulating film 3 based on this pattern, a large number of fine holes 5 can be opened in which the film surface of the bottom electrode 2, which is the lowest layer, is exposed.

According to this example, in the conventional electrode, the target substance diffused perpendicularly to the electrode surface, so it took time to reach a steady state, and the current density was low.
On the other hand, by making the electrode thinner and making the diffusion hemispherical, the time required to reach a steady state can be shortened and the current density can be increased. In addition, the working electrode is composed of two lower electrodes 22 and a surface electrode 4, and by setting one of the adjacent electrodes to the oxidation potential of the 1j substance and the other to the reduction potential, oxidation occurs between the adjacent electrodes. Since the reduction is repeated, the effective current can be increased significantly.

In the above embodiments, two surface electrodes and a lower electrode are used as the working electrodes, but the present invention is not limited to this, and the present invention is not limited to this, but may be applied to the bottoms of each of a large number of micropores.

It is also possible to arbitrarily combine two or more working electrodes in which electrodes are arranged in the middle or upper part.

Further, when manufacturing a microporous electrode cell, in addition to integrating only two or more working electrodes on a substrate, a reference electrode and a counter electrode can also be manufactured integrally.

That is, after a conductive thin film and an insulating film are alternately laminated one or more times on a substrate, this laminated film is etched in the same manner as in the above-described embodiment to form a large number of minute working electrodes. After that, a resist is applied to the upper insulating film, and an image mask having an electrode pattern is placed thereon, or a pattern is exposed directly to areas without micropores using an electron beam and developed, and the pattern is transferred to the substrate. Transfer to the upper resist. Thereafter, a thin metal, semiconductor, or semimetal thin film is formed by sputtering, vapor deposition, CVD, coating, etc., and then a reference electrode and a counter electrode are produced by a lift-off method in which the resist is peeled off, and a working electrode, a reference electrode, It is also possible to obtain a microporous electrode cell for electrochemical measurements in which a counter electrode is integrated.

In this case, to produce a reference electrode, one of the two electrodes other than the microporous working electrode in the electrode cell is plated with a metal or organic redox polymer as a supporting material, and electrolytically Form and produce legally. Furthermore, examples of the reference substance on the reference electrode include silver silver chloride, polyvinylferrocene, and the like.

A microporous electrode cell constructed by such a method allows three electrodes, a working electrode, a reference electrode, and a counter electrode, to be formed on the same substrate, and is therefore suitable for measuring a small amount of sample or a minute area.

Next, specific examples of implementing the method of the present invention will be described below with reference to FIG. 2, but it goes without saying that the present invention is not limited to these examples.

Example 1 A 1 μm oxidized silicon wafer (manufactured by Osaka Titanium Co., Ltd.) was used as the substrate 1 (Fig. 2 (a)), and a sputtering device (
Anelva: 5PF-332H) was installed in a specified position with a metal mask, and the pressure was 1.3 Pa.

Chromium was sputtered in argon for 10 seconds at a power of 50 W, followed by sputtering at a power of 70 W for 10 seconds without breaking the vacuum.
Platinum was sputtered for 1 minute, and a chromium film with a thickness of 1100 nm was applied.
A lower electrode 2 of platinum film was formed (FIG. 2(b)). Next, remove the metal mask and use silicon dioxide as an insulating film [
3 was deposited by sputtering method (FIG. 2(C)). At this time, the power is 50W.

Sputtering was performed for 10 minutes to form a silicon dioxide film with a thickness of 300 nm. Put on another metal mask again and chrome-
1100n of platinum surface electrode 4 was deposited (Fig. 2(d)
).

Thereafter, a photoresist 6 (MP1400-27 manufactured by Ntspray Co., Ltd.) was applied 1. It was applied to a thickness of am. This resist-coated silicon wafer was placed in an oven and baked at 80° C. for 30 minutes. Then, using a chrome mask, mask aligner (manufactured by Canon)
Contact exposure was carried out for 20 seconds. The exposed silicon wafer was treated with a resist solution (manufactured by Shipley, MP-319).
2o'c inside.

Development was performed for 60 seconds, washed with water, and dried to transfer the mask pattern to the resist (Fig. 2 (•)).

After development, the substrate was placed in a reactive ion etching device (manufactured by Anelpa, OEM-451), and sputter etched with platinum under the conditions of an argon gas flow rate of 50 SCCM and a pressure of IPa and Pa-100W. Gas flow rate 258 CCM, pressure 0.25 Pa, 150
Silicon dioxide was etched for 10 minutes under W conditions to form a large number of disk electrode patterns having micro holes 5 (FIG. 2(f)). At this time, the diameter of each disk electrode was 1 μm and the number of disk electrodes was 10,000. Thereafter, the substrate was immersed in methyl ethyl ketone and subjected to ultrasonic treatment, and the resist other than the electrode forming portion was peeled off to obtain an electrode pattern. FIG. 1 shows an outline of the microporous electrode cell for electrochemical measurements produced in this manner.

This electrode cell for microelectrochemical measurement (hereinafter referred to as an electrochemical cell) was prepared using 0-1 flo 1/1 7erocene.

The lower and surface electrodes 2 and 4 were immersed in an acetonitrile solution containing 0.1 mol/1 of the supporting electrolyte (tetraethylammonium bichlorate) and connected to the solitual botensiostat via lead wires. is fixed at 10.IV, and the lower electrode 2fOV is set at 0.
The current value was measured by scanning the potential at 100 mV/w up to 5 V, and compared with the case where only 100 working electrodes of 1 μm disk electrodes were used.

As a result, a limiting current corresponding to the oxidation of ferrocene having a rise at O, a V (based on a silver reference electrode) was obtained in both cases. However, with a disk electrode of 1 μm diameter, a limiting current of only 0.46 #AL can be obtained;
With the electrode of this example, a value of 15 μA was obtained. On the other hand, the working electrode (diameter: 0.10101 t
When compared with an electrochemical cell having the same area, a limiting current was observed in the former, whereas a peak associated with the redox reaction of ferrocene was observed in the latter. and received a quick response. Furthermore, when measuring the current value by stepping the potential from Ov to 0.5V, the electrochemical cell of this example has a diameter of 0.10V.
It was found that 5.2 times the current value was obtained after 0.4 seconds of voltage application compared to the disk electrode of No. m, and the sensitivity was also improved.

Example 2 In Example 1, spin-on glass 11 was used instead of the sputtering method when forming the silicon dioxide layer. Spin-on glass (Tokyo Ohka ocD'ryp-7) about 1 μm
After spin-coding to a thickness of , baking was performed at 450° C. for 1 hour. Thereafter, an electrode was produced in the same manner as in Example 1. The diameter of each micropore was 2 μm, and the number of micropores was 2,500.

Next, electrochemical measurements were performed under the same conditions as in the above example, and comparison was made with 2,500 disk electrodes each having a diameter of 2 μm. In both cases, limiting currents having curves similar to those shown in Example 1 were obtained. While a disc electrode with a diameter of 2 μm can provide a limiting current of only 0.83 μA, the electrode of this example showed a value of 2.4 μA. Furthermore, even when the solution is stirred, the change in the potential-current curve is small and round. On the other hand, a working electrode (diameter: 0.2
When compared with an electrochemical cell with 0°, ), a limiting current was observed in the former, whereas a peak associated with the redox reaction of ferrocene was observed in the latter. A faster response was obtained compared to conventional electrodes. Furthermore, when measuring the current value by stepping the potential from OV to 0.5 V, the electrochemical cell of this example has a voltage application of 0 compared to a disk electrode with a diameter of 0.20 W or m.
, 4.7 times the current value was obtained after 4 seconds, indicating that the sensitivity was improved.

Example 3 A quartz substrate with a thickness of 0.3 mm was placed in a vacuum evaporation apparatus (manufactured by JEOL Ltd.) together with a metal mask, and chromium and gold were vacuum evaporated into circles. The film thickness was 200°C. Next, the CVO device (A
NELVAgPED-401) was used, and 1μ
9. Form a silicon nitride film with a thickness of m. Using another metal mask again, a chromium-gold surface electrode was formed. After that, electron beam resist (φ-MAC, Daikin Industries, Ltd. ju
) was applied to a thickness of 1 μm. This resist-coated quartz substrate was placed in an open chamber and baked at 180° C. for 60 minutes.

After that, an electronic m exposure device (JEOL: JSM-840
), electron beam acceleration voltage: 10KV, exposure amount: 5μ
Exposure was performed under c/crIL conditions.

After development, the substrate was placed in a reactive ion etching device (manufactured by Anelpa, DEM-451), and gold was sputter etched under the conditions of an argon gas flow rate of 50 SCCM, a pressure Tpa, and a power of 100 W. The etchant was a 10:1 mixture of gas and oxygen, and the gas pressure z,
An electrode was obtained by etching silicon nitride for 10 minutes under the conditions of apa, flow rate of 508 CCM, and power of 100 W. The diameter of the prepared disk electrodes was 0.5 μm, and the number of disk electrodes was 40,000.

Next, an electrochemical measurement was performed under the same conditions as in the above example, and a circle was compared with a disk electrode having a diameter of 0.5 μm and 40,000 pieces. Both examples! A limiting current curve similar to that shown in was obtained. While a disc electrode with a diameter of 0.5 μm could provide a limiting current of only 0.92 μA, the electrode of this example showed a value of 3.5 μA. On the other hand, the working electrode (diameter: 0.10 m) has the same area as the many microporous disk electrodes of the fabricated electrochemical cell of this example.
When compared with an electrochemical cell having the same area, a limiting current was observed in the former, whereas a peak associated with the redox reaction of ferrocene was observed in the latter. It was found that the response speed was fast.

i9. When measuring the current value by stepping the potential from Ov to 0.5V, the electrochemical cell of this example has a diameter of 0.1
5 after 0.4 seconds of voltage application compared to a disk electrode with zero
．． It was found that a current value five times higher was obtained, and the sensitivity was improved.

Example 4 A silicon wafer with a 1 μm oxide film (manufactured by Osaka Titanium Co., Ltd.) was used as a substrate, and a sputtering device (manufactured by ANELVA: 5P) was used.
F-332H), installed with a metal mask at a specified position in argon at a pressure of 1.3 Pa.

Sputtering of chromium was performed for 10 seconds with a power of 7-50 W for 10 seconds, and then sputtering of platinum was performed for 1 minute at a power of 70 W without breaking the vacuum to form a lower electrode of a chromium-platinum film with a thickness of 100 nm. Next, the metal mask was removed and a silicon dioxide film was deposited by sputtering. At this time, sputtering was performed with a power of sow and io to form a film of silicon dioxide with a thickness of 300 nm. Put on another metal mask again, deposit 1100n of chromium-platinum surface electrode, then remove the metal mask and deposit 300n of silicon dioxide film.
It was deposited by m sputtering method. Thereafter, a 7-photoresist (Silapray IJ MP1400-
27) to a thickness of 1 μm and form a circle. This resist-coated silicon wafer was placed in an open chamber at 80°C.

It was baked for 30 minutes. Thereafter, contact exposure was performed for 20 seconds using a chrome mask and a mask aligner (manufactured by Canon). The exposed silicon wafer was incubated at 20°C in a resist developer (MF-319 manufactured by Shipley Publishing Co., Ltd.).
Development was performed for 60 seconds, washed with water, and dried to transfer the mask pattern to the resist. After development, the substrate was placed in a reactive ion etching equipment f (manufactured by Anelpa, OEM-4151), and the flow rate of c1ii' gas was 25 SCCM, and the pressure was 0.
．． Silicon dioxide was etched for 10 minutes under conditions of 25 Pa and power of 150 W, and then argon gas flow of 3150 SCCM, pressure of IPA, and power of 100 W was performed.
After sputter etching platinum under the following conditions, C
2F, a large number of disk electrode patterns with micro holes were formed by etching with gas. At this time, the diameter of each disk electrode was 1 μm, and the number of disk electrodes was 10,000. after that,
The substrate was immersed in methyl ethyl ketone and subjected to ultrasonic treatment, and the resist other than the electrode formation portion was peeled off to obtain an electrode pattern.

The electrode of this example was prepared by adding 0.1 mmol/l of 7erocene and 0.1 mmol/l.
Dissolve 1 mol/1 of the supporting electrolyte (tetraethylammonium barchlorate) and submerge it in 9 acetonitrile solution, connect the bottom and surface electrodes to a dual potentiostat via lead wires, and connect the surface electrode to 10 and 1 V. and lower electrode from OV to Q, 1V to 5V.
The current value was measured by scanning the potential at 00 mV/see, and compared with the case where only 10,000 working electrodes of 1 μm disk electrodes were used. In both cases, a limiting current corresponding to the oxidation of ferrocene, which has a rise to O, a V (based on a silver reference electrode), was obtained. In contrast to the disk electrode with a diameter of 1 μm, the limiting current magnitude was only α46 μA, whereas the electrode of this example obtained a value of 1.3 μA. on the other hand,
Comparing the fabricated electrochemical cell of this example with a large number of microporous disk electrodes and an electrochemical cell with the same working electrode (diameter: 0.10 mm), a limiting current was observed in the former; On the other hand, in the latter case, a peak associated with the redox reaction of ferrocene was observed, and the electrochemical cell of this example had a faster response than an electrode having the same area. Furthermore, when measuring the current value by stepping the potential from OV to 0.5vt, the electrochemical cell of this example has a diameter of 0.10m.
Compared to the disk electrode shown in FIG.

Example 5 Using the electrode cell prepared in Example 1, the concentration was 3 μm o
Immerse the surface electrode in an aqueous solution containing 1/l epinephrine, 50 μnet, 1 mol/1 ascorbic acid, and 0.1 mol/1 supporting electrolyte (sodium phosphate).
3VK, lower electrode 100m V from Ov to 0.7V
/see to perform potential scanning and measure the current value.
9 compared to using a working electrode with only 10,000 μm disk electrodes.

In the 1 μm disk electrode, the response of epinephrine was hidden due to the oxidation current of ascorbic acid, whereas in the lower electrode of the electrode cell of this example, the response of the transient response of ascorbic acid superimposed on the limiting current of epinephrine appeared on the surface. On the electrode side, only the limiting current of epinephrine reduction was observed, and quantification was possible without interference from ascorbic acid.

〔Effect of the invention〕

As explained above, the microporous electrode cell for electrochemical measurements of the present invention is made of a metal having a large number of micropores.

Semimetal - & circles are thin film surface electrodes made of semiconductor.

Alternatively, it is constructed of a working electrode that has an insulating surface and at least one other electrode formed of a metal, semimetal, or semiconductor that is insulated from each other by a micropore wall at the bottom or middle of the pore, so that it can be used as a conventional microelectrode. It has many advantages such as high sensitivity, high response speed and current value compared to working electrodes with the same electrode area, and can be measured with a simple device, making it suitable for high-sensitivity analysis of low-concentration samples. It also has a very noticeable effect.

Furthermore, according to the method of the present invention, in order to fabricate a microporous electrode cell for electrochemical measurement consisting of a working electrode patterned with many micropores using phosphorography technology, a working electrode of any size and shape can be used. It has the advantage that it can be obtained in large quantities at low cost.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a microporous electrode cell for electrochemical measurement according to an embodiment of the present invention, and FIGS. 2(a) to 2(f) are cross-sectional views of the manufacturing process of this embodiment. 1...Substrate, 1a @・so silicon substrate, 1b・
... Oxide film, 2 ... Lower electrode, 3 ... Insulation M
(Silicon dioxide capture), 4...Surface electrode, 5...Automatic micropores, 6...Yutaka regimen. Diagram

Claims (2)

[Claims] (1) In an electrode cell for electrochemical measurement having a working electrode for substance detection, the working electrode is a thin film surface electrode having a large number of micropores, or an insulating surface and a micropore wall that is mutually connected to the bottom or midway of the micropores. 1. A microporous electrode cell for electrochemical measurement, comprising a working electrode having at least one other electrode insulated with a metal, the material of the electrode being a metal, a semimetal, or a semiconductor. (2) Conductive thin films and insulating films of metal, semimetal, or semiconductor are alternately laminated at least once each on a substrate whose surface or entire surface is insulating, and then a microporous resist pattern is formed thereon. A method for producing a microporous electrode cell for electrochemical measurement, comprising the step of subsequently drilling a large number of micropores by etching until the bottom layer of the conductive film surface is exposed.