JP2023524867A - Patterned boron-doped diamond electrode with high specific surface area, and its manufacturing method and application - Google Patents

Abstract

The present invention discloses a patterned boron-doped diamond electrode with high specific surface area and its manufacturing method and application. The manufacturing method includes etching a regular pattern on a stainless steel sheet by a photoetching method, covering the surface of a substrate with a stainless steel sheet having a through-hole pattern, and then placing both the stainless steel sheet and the substrate in a chemical vapor deposition furnace. a patterned boron-doped diamond layer is deposited and grown on the exposed portion of the surface of the substrate to obtain a patterned boron-doped diamond electrode; The temperature of the surface is controlled to 750 to 950° C., the growth pressure is controlled to 2.5 to 5 KPa, and the ratio of methane, borane, and hydrogen gas to be introduced is (1 to 20):(0.3 to 1):(45 to 49), and finally assemble a sensing electrode system with the fabricated boron-doped diamond electrode as the working electrode, the platinum sheet as the counter electrode, and the Ag/AgCl electrode as the reference electrode. Compared with the prior art, the manufacturing method of the present invention is simple, easy to control operation and low manufacturing cost.

Description

The present invention relates to a boron-doped diamond electrode with high specific surface area and its manufacturing method and application, in particular, to a patterned boron-doped diamond electrode with high specific surface area and its manufacturing method and application, and belongs to the field of electrode manufacturing.

Boron-doped diamond electrodes are widely used in biosensing, water treatment, life detection, etc. due to their excellent electrochemical performance. Due to its low background current, high stability and low adsorption properties, boron-doped diamond electrodes stand out among numerous electrode materials. Boron-doped diamond electrode belongs to electrochemical electrodes, which mainly converts biological, chemical and physical signals into electrical signals that can be recognized and analyzed. It occupies an important position in the field of detection.

Based on its own excellent performance, if the boron-doped diamond electrode with high specific surface area can be designed through optimization, the response signal of the electrode itself can be enhanced, which greatly enhances its detection merit in the low concentration field. improve to Compared to traditional porous diamond electrodes, patterned diamond electrodes are more flexible in designing dimensions and shapes, and are easier to implement and optimize in terms of electrode mass transfer design. The conventional method for producing patterned diamond electrodes mainly adopts the plasma etching method or the photo-etching method, that is, at present, a sufficiently thick diamond film is produced, and then the whole film is patterned by the above method. A top-down approach is usually used.

SUMMARY OF THE INVENTION Overcoming the shortcomings of the prior art, the present invention aims to provide a patterned boron-doped diamond electrode with high specific surface area and its manufacturing method and application. The patterning fabrication method adopted in the present invention belongs to the bottom-up approach, that is, directly integrally connecting the patterned mask and the base, and then directly growing the patterned diamond electrode on the base. The design steps of the method are simpler than methods such as etching, the operation is more controlled, and the manufacturing cost is lower.

A method for manufacturing a patterned boron-doped diamond electrode with high specific surface area according to the present invention includes the following steps.

Coating the surface of the substrate with a metal sheet having a through-hole pattern, and then placing the metal sheet and the substrate together in a chemical vapor deposition furnace to deposit and grow a patterned boron-doped diamond layer on the exposed portions of the surface of the substrate. to obtain a patterned boron-doped diamond electrode, and in the chemical vapor deposition process, the temperature of the surface of the substrate is controlled to 750-950 ° C., the growth pressure is controlled to 2.5-5 KPa, and the introduced methane, borane, hydrogen The gas ratio is 1-20:0.3-1:45-49.

In the present invention, the exposed portion of the surface of the substrate means the portion of the through-hole pattern exposed after the surface of the substrate is coated with the metal sheet having the through-hole pattern.

In the method of manufacturing a patterned boron-doped diamond electrode having a high specific surface area according to the present invention, a metal sheet having a through-hole pattern is coated on the surface of a substrate, and then both the metal sheet and the substrate are placed in a chemical vapor deposition furnace. Place it, and position and fix it with the base.

During actual operation, the base is designed to have a base size of 4-15 cm ² for chemical vapor deposition, if the actual size required for the electrode is 2-10 cm ² , and the rest of the dimensions are fixed. It is designed to be cut into base fittings of the required size and assembled using molybdenum wire with high temperature resistance to complete the assembly.

In the method of manufacturing a patterned boron-doped diamond electrode with high specific surface area according to the present invention, the metal sheet is a stainless steel sheet.

In the manufacturing method of the patterned boron-doped diamond electrode with high specific surface area according to the present invention, the manufacturing process of said metal sheet with through-hole pattern is photo-etching on the surface of the metal sheet according to the desired pattern. Etching a corresponding through-hole pattern.

In the method for manufacturing a patterned boron-doped diamond electrode with high specific surface area according to the present invention, said pattern is one of a square array pattern, a rectangular array pattern and a circular array pattern.

In the method for manufacturing a patterned boron-doped diamond electrode with high specific surface area according to the present invention, said substrate is a silicon sheet. In the present invention, the base for growing diamond adopts a silicon base that can form a stable oxide intermediate layer, and compared with other metal-based bases, the silicon base has a higher thermal expansion coefficient It is possible to form an intermediate oxide layer with a small , and the diamond grown in this way is difficult to come off.

In the method of manufacturing a patterned boron-doped diamond electrode having a high specific surface area according to the present invention, a metal sheet having a through-hole pattern is coated on the surface of a substrate, and then both the metal sheet and the substrate are placed in a chemical vapor deposition furnace. Then, the surface temperature of the substrate is raised to 750-950° C. at a rate of 5-20° C./min, preferably 5-15° C./min.

The present inventors have found that by positioning and fixing the substrate around it, and by gradually raising the temperature, phenomena such as displacement and deformation of the metal sheet due to differences in the thermal expansion coefficients of the metal sheet and the substrate. It has been found that this avoids irregularities in the grown diamond pattern and thus failure to grow.

In the method for manufacturing a patterned boron-doped diamond electrode with high specific surface area according to the present invention, the chemical vapor deposition is hot filament chemical vapor deposition, the number of turns of the hot filament is 10-15, and the number of turns of the hot filament is 10-15. The temperature of the hot filament is controlled at 2100-2400° C. in the phase growth process.

In the method for manufacturing a patterned boron-doped diamond electrode with a high specific surface area according to the present invention, the ratio of methane, borane and hydrogen gases initially introduced in the chemical growth process is 10-20:0.3-1. : 45 to 49, and after 1 to 2 hours of deposition, the ratio of methane, borane and hydrogen gas introduced is adjusted to 2 to 5:0.3 to 1:45 to 49, and 6 to 10 hours deposit.

The extent of the patterned growth area is very small relative to the growth area of the entire traditional base, which makes it difficult to nucleate in the growth process. This is mainly because carbon atoms require sufficient thermodynamic motion to complete a series of processes such as nucleation, island formation, and film formation. This is because the growth is limited to within a region, which increases the difficulty of nucleation and film formation and lengthens one growth cycle. The inventors have found that the problem of difficulty in nucleation can be overcome by increasing the concentration of methane at the initial stage of growth.

During the actual operation, both the metal sheet with through-hole pattern and the silicon sheet substrate were first placed in an acetone solution, ultrasonically cleaned for 10-20 minutes to remove surface oil stains, and then deionized water. Ultrasonic clean for 5-20 minutes and bake prior to deposition.

In the method for manufacturing a patterned boron-doped diamond electrode having a high specific surface area according to the present invention, the boron-doped diamond layer has a thickness of 5 to 20 μm, and the boron-doped diamond layer has a diamond crystal grain size of 5 to 10 μm. is.

Preferably, in the method for fabricating a patterned boron-doped diamond electrode with high specific surface area according to the present invention, said boron-doped diamond layer is a porous boron-doped diamond layer, said porous boron-doped diamond layer comprises: After depositing and growing a boron-doped diamond layer, a high-temperature etching process is performed, wherein the high-temperature etching process is a high-temperature atmosphere etching process or a high-temperature metal etching process.

By subjecting the boron-doped diamond layer to a high-temperature etching treatment, the boron-doped diamond layer becomes a porous structure, that is, micropores and/or cones are distributed on the surface of the boron-doped diamond layer, and patterned. Further increase the specific surface area of the boron-doped diamond electrode.

During the actual operation, the high temperature atmosphere etching process refers to depositing and growing a patterned boron-doped diamond layer on the exposed portion of the surface of the substrate, and then placing it in an air or hydrogen gas atmosphere at a temperature of 600-1000° C. and a pressure of 600-1000° C. is 10 Pa to 10 ⁵ Pa and the treatment time is 5 to 180 min.

High-temperature metal etching involves depositing and growing a patterned boron-doped diamond layer on the exposed portion of the surface of the substrate, then depositing a metal layer having high catalytic activity on carbon on the surface of the boron-doped diamond layer, and then The boron-doped diamond layer deposited with the metal layer is heat-treated, the metal layer is spheroidized at high temperature to form metal nanospheres or microspheres dispersedly distributed on the surface of the diamond, and the carbon atoms in the diamond are reduced at high temperature. is subsequently solid-dissolved in the metal nanospheres or microspheres, and by adding a hydrogen gas atmosphere, the solid carbon deposited when the carbon atoms in the metal nanospheres or microspheres are supersaturated solid solution is etched, and the metal nanospheres or It means that the micron spheres continue to move into the diamond, and finally form a large number of micropores and cones on the surface of the boron-doped diamond layer, and the material of the metal layer is metallic iron, cobalt, nickel The heat treatment temperature is 600 to 1000° C., the time is 1 min to 3 hours, and the pressure is 0.1 to 1 atmospheric pressure.

The present invention further provides a patterned boron-doped diamond electrode having a high specific surface area produced by the above production method.

The present invention further provides an application of the patterned boron-doped diamond electrode having a high specific surface area produced by the above production method as a working electrode to an electrochemical sensor.

During application, an electrochemical sensor (three-electrode detection sensor) is assembled with a boron-doped diamond electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag/AgCl electrode as the reference electrode.

The present invention provides a patterned boron-doped diamond electrode manufacturing method with high specific surface area, the manufacturing method of the present invention belongs to the bottom-up approach, that is, the patterned mask and the base are directly connected as one. Afterwards, a patterned diamond electrode is grown directly on the base, and the design steps of the method are simpler than methods such as etching, the operation is easier to control, and the manufacturing cost is lower.

In the manufacturing process, the stainless steel sheet is directly adopted as a mask to cover the silicon base, and the stainless steel coating layer used as the mask has a much larger coefficient of thermal expansion than the silicon base, thus, it is inherently fixed during high temperature growth. Since the mask is likely to cause phenomena such as displacement and deformation, the grown diamond pattern becomes irregular, and eventually the growth fails. In the present invention, the occurrence of the above phenomenon is avoided by skillfully designing a method of combining position regulation and fixing in the surroundings and gradual temperature rise.

On the other hand, the extent of the patterned growth area is very small relative to the growth area of the entire traditional base, which makes it difficult to nucleate in the growth process. This is mainly because carbon atoms require sufficient thermodynamic motion to complete a series of processes such as nucleation, island formation, and film formation. This is because the growth is limited to within the region, which increases the difficulty of nucleation and film formation, lengthens one growth cycle, and thus makes it impossible to form a regular pattern. Overcome the problem of difficulty in nucleation by increasing the concentration of methane in the early stage of the process.

The patterned diamond electrode produced by the above method has a regular microstructure, the electrode has a large specific surface area, and the response current of the electrode is greatly improved.

It is a schematic diagram of patterning of a diamond electrode.

The following examples illustrate substantial features and significant progress of the present invention, but the present invention is not limited to the examples.

Example 1

In step 1, a stainless steel sheet is patterned. The method is to etch through-hole patterns with corresponding patterns in the stainless steel sheet according to the desired square array pattern by photo-etching equipment to obtain the intermediate space layer.

Step 2 designs a hot filament chemical vapor deposition platform. The method is to design the size of the base for chemical vapor deposition to be 4 cm ² according to the actual size of 2 cm ² required for the detection electrode, and the remaining size is the margin required for fixing, and the high temperature resistance It is to use a certain molybdenum wire and cut it into the base bracket of the corresponding size to complete the assembly.

In step 3, a boron-doped diamond film is deposited on the silicon sheet substrate by chemical vapor deposition. The method is to put the pattern sheet and silicon sheet substrate produced in step 1 into an acetone solution, ultrasonically clean for 10 minutes to remove surface oil stains, and then ultrasonically clean with deionized water for 5 minutes. 1) After baking in a baking furnace, it is put into a chemical vapor deposition chamber, and the temperature of the surface of the silicon sheet substrate is raised to 750° C. at a rate of 5° C./min to grow a boron-doped diamond film.

The number of turns of the hot filament in the growth process was set to 10, the temperature of the hot filament was controlled at 2100° C., the room pressure was controlled at about 2.5 kpa, and the mass flow of the introduced gas was 20 sccm of methane and 0.0 sccm of borane. After growing for 1 hour under the conditions of 3 sccm and 49 sccm of hydrogen gas, the amount of methane introduced was adjusted to 5 sccm without changing the amounts of borane and hydrogen gas, and the amount of methane introduced was adjusted to 5 sccm. The thickness of the obtained boron-doped diamond film is 5-10 μm, and the grain size of the grown diamond film is 5-7 μm.

In step 4, the patterned diamond electrodes obtained in step 3 are packaged to construct a three-electrode detection sensor with the platinum sheet as the counter electrode and the Ag/AgCl electrode as the reference electrode.

In step 5, dopamine solution is detected by the electrode produced in step 4. The patterned electrodes have a larger effective active area than non-porous electrodes (0.25 cm ² area for patterned electrodes and 0.14 cm ² for non-patterned electrodes). , the pointer experiment is with 2 mM potassium ferricyanide solution, the scan rate is 10 mV/s), low charge transfer resistance (4.5 Ω for patterned electrodes and is 10.5Ω, and the pointer experiment is an electrochemical resistance test, specifically performed in a 2mM potassium ferricyanide solution, the frequency of the test is 1Hz~1MHz, and the open-circuit voltage is 10mV). The detection target was a dopamine solution with a concentration range of 0.01 to 500 μM, and the interference target was a 500 μM ascorbic acid solution, both of which had a 0.01 M phosphate PBS solution as the base solution. adopted as Interfering substances are added to dopamine solutions with different concentrations, and the packed electrodes are used for detection analysis. The pulse width value is 30 mV and the frequency is 5 Hz). The detection results showed that the electrode had a detection limit of 60 nM for dopamine, with a linear detection range of 5-50 μM.

Example 2

In step 1, a stainless steel sheet is patterned. The method is to etch through-hole patterns with corresponding patterns according to the desired square array pattern, rectangular array pattern, circular array pattern, etc. on the stainless steel sheet by photoetching equipment to obtain the intermediate space layer. .

Step 2 designs a hot filament chemical vapor deposition platform. The method is to design the size of the base for chemical vapor deposition to be 8 cm ² according to the actual size of 4 cm ² required for the detection electrode, and the remaining size is the margin required for fixing, and the high temperature resistance It is to use a certain molybdenum wire and cut it into the base bracket of the corresponding size to complete the assembly.

In step 3, a boron-doped diamond film is deposited on the silicon sheet substrate by chemical vapor deposition. The method is to put the pattern sheet and silicon sheet substrate produced in step 1 into an acetone solution, ultrasonically clean for 15 minutes to remove surface oil stains, and then ultrasonically clean with deionized water for 10 minutes. 1) After baking in a baking furnace, it is put into a chemical vapor deposition chamber, and the temperature of the surface of the silicon sheet substrate is increased to 850° C. at a rate of 10° C./min to grow a boron-doped diamond film.

The number of turns of the hot filament in the growth process is 13, the temperature of the hot filament is controlled at 2300° C., the room pressure is controlled at about 4 kilopascals, and the mass flow of the introduced gas is 15 sccm of methane, 0.5 sccm of borane, After growing for 1.5 hours with the hydrogen gas controlled to 47 sccm, the amount of methane introduced was adjusted to 3 sccm without changing the introduction amounts of borane and hydrogen gas, and the growth was continued for 8 hours. The thickness of the obtained boron-doped diamond film is 10-15 μm, and the grain size of the grown diamond film is 7-9 μm.

In step 4, the patterned diamond electrodes obtained in step 3 are packaged to construct a three-electrode detection sensor with the platinum sheet as the counter electrode and the Ag/AgCl electrode as the reference electrode.

In step 5, dopamine solution is detected by the electrode produced in step 4. The patterned electrodes have a larger effective active area than non-porous electrodes (0.3 cm ² area for patterned electrodes and 0.23 cm ² for non-patterned electrodes). , the pointer experiment is with 2 mM potassium ferricyanide solution, the scan rate is 10 mV/s), low charge transfer resistance (5.0 Ω for patterned electrodes and , and the pointer experiment is an electrochemical resistance test, specifically performed in a 2 mM potassium ferricyanide solution, the frequency of the test is 1 Hz to 1 MHz, and the open-circuit voltage is 10 mV). The detection target is a dopamine solution with a concentration range of 0.01 to 500 μM, and the interference target is a 1000 μM ascorbic acid solution, both of which are 0.01 M phosphate PBS solution as the base solution. adopted as Interfering substances are added to dopamine solutions with different concentrations, and the packed electrodes are used for detection analysis. The pulse width value is 30 mV and the frequency is 5 Hz). The detection results showed that the electrode had a detection limit of 50 nM for dopamine, with a linear detection range of 1-80 μM.

Example 3

In step 1, a stainless steel sheet is patterned. The method is to etch through-hole patterns with corresponding patterns according to the desired square array pattern, rectangular array pattern, circular array pattern, etc. on the stainless steel sheet by photoetching equipment to obtain the intermediate space layer. .

Step 2 designs a hot filament chemical vapor deposition platform. The method is to design the size of the chemical vapor deposition base to 15 cm ² according to the actual size of 10 cm ² required for the detection electrode, and the remaining size is the margin required for fixing, and the high temperature resistance It is to use a certain molybdenum wire and cut it into the base bracket of the corresponding size to complete the assembly.

In step 3, a boron-doped diamond film is deposited on the silicon sheet substrate by chemical vapor deposition. The method is to put the pattern sheet and silicon sheet substrate produced in step 1 into an acetone solution, ultrasonically clean for 20 minutes to remove surface oil stains, and then ultrasonically clean with deionized water for 20 minutes. 1) baking in a baking furnace, then placing in a chemical vapor deposition chamber, raising the temperature of the surface of the silicon sheet substrate to 950° C. at a rate of 15° C./min to grow a boron-doped diamond film; The number of turns of the hot filament in the growth process is 15, the temperature of the hot filament is controlled at 2400° C., the room pressure is controlled at about 5 kilopascals, and the mass flows of the introduced gases are methane 10 sccm, borane 1 sccm, and hydrogen gas. After growing for 2 hours under the control of 45 sccm, the introduction amount of methane was adjusted to 2 sccm without changing the introduction amounts of borane and hydrogen gas, and growth was continued for 10 hours. The thickness of the doped diamond film is 15-20 μm and the grain size of the grown diamond film is 9-10 microns in diameter.

In step 4, the patterned diamond electrodes obtained in step 3 are packaged to construct a three-electrode detection sensor with the platinum sheet as the counter electrode and the Ag/AgCl electrode as the reference electrode.

In step 5, dopamine solution is detected by the electrode produced in step 4. The patterned electrodes have a larger effective active area than the non-porous electrodes (0.35 cm ² for patterned electrodes and 0.27 cm ² for non-patterned electrodes). , the pointer experiment is with 2 mM potassium ferricyanide solution, the scan rate is 10 mV/s), low charge transfer resistance (6.0 Ω for patterned electrodes and The pointer experiment is an electrochemical resistance test, specifically performed in a 2 mM potassium ferricyanide solution, the test frequency is 1 Hz to 1 MHz, and the open-circuit voltage is 10 mV). The detection target was a dopamine solution with a concentration range of 0.01 to 500 μM, and the interference target was a 1500 μM ascorbic acid solution, both of which had a 0.01 M phosphate PBS solution as the base solution. adopted as Interfering substances are added to dopamine solutions with different concentrations, and the packed electrodes are used for detection analysis. The pulse width value is 30 mV and the frequency is 5 Hz). The detection results showed that the electrode had a detection limit of 45 nM for dopamine, resulting in a linear detection range of 0.5-100 μM.

Comparative example 1

Comparative Example 1 is carried out under the same conditions as in Example 1, except that the pattern sheet and the silicon sheet substrate are not positioned or fixed around them in step 3, and as a result, a diamond array is grown to match the pattern. I couldn't. This is because the coefficient of thermal expansion of the silicon base and the patterned stainless steel sheet differ greatly from each other. Therefore, if the position cannot be properly regulated, phenomena such as deformation and displacement occur, resulting in failure in the growth of the diamond film. This is because it is easy to lead to things being put away.

Comparative example 2

Comparative Example 2 was conducted under the same conditions as in Example 1, except that the initial flow rate of methane in step 3 was 8 sccm, and as a result, it was not possible to grow a patterned diamond array. This is because the area for carbon atom nucleation is originally small between the silicon base and the stainless steel pattern sheet, so unless the concentration of carbon atoms is sufficiently high, nucleation and growth occur within the small area, resulting in the final This is because the growth of the diamond film fails because it becomes difficult to form a film on a regular basis.

Comparative example 3

Comparative Example 3 was carried out under the same conditions as in Example 1 except that the temperature of the hot filament was adjusted to 1800° C. in step 3, and as a result, the diamond array could not be grown. This is because the temperature of the hot filament is too low to effectively decompose enough carbon atoms for diamond growth; This is because the nucleation of carbon atoms is inhibited, and further the film forming process of carbon atoms is inhibited.

Comparative example 4

Comparative Example 4 was carried out under the same conditions as in Example 1, except that the surface temperature of the silicon sheet substrate was raised to 750° C. at a rate of 30° C./min. As a result, it was found that the nucleation could not be effectively performed, and finally the diamond film was not grown. This raises the problem that the temperature rise rate is too fast as pointed out in the present application. When the temperature is too high, the thermal deformation becomes serious, and an obvious displacement phenomenon occurs in the region of the patterning at the beginning and the end of the temperature rise, so that the carbon atoms cannot nucleate effectively in the same region and eventually grow. This is because the

Comparative example 5

Comparative Example 5 was conducted under the same conditions as in Example 3, except that in step 3 the methane flow rate was initially set to 30 sccm. As a result, it was found that nucleation could not be effectively performed on the base, and finally the growth of the diamond film failed. This is because the initial concentration of methane used is too high and the decomposed carbon atoms are deposited in excess in the growth region, whereas the decomposed atomic hydrogen can immediately carry the excess carbon atoms away. This is because excess carbon atoms form a graphite phase and stop the growth of the diamond film. be.

Claims (10)

Coating the surface of the substrate with a metal sheet having a through-hole pattern, and then placing the metal sheet and the substrate together in a chemical vapor deposition furnace to deposit and grow a patterned boron-doped diamond layer on the exposed portions of the surface of the substrate. to obtain a patterned boron-doped diamond electrode, and in the chemical vapor deposition process, the temperature of the surface of the substrate is controlled to 750-950 ° C., the growth pressure is controlled to 2.5-5 KPa, and the introduced methane, borane, hydrogen A method for fabricating a patterned boron-doped diamond electrode with a high specific surface area, comprising the step of setting the gas ratio to 1-20:0.3-1:30-49. After coating the surface of the substrate with a metal sheet having a through-hole pattern, the metal sheet and the substrate are placed together in a chemical vapor deposition furnace, positionally regulated and fixed by a base, the metal sheet being a stainless steel sheet, 2. The method of manufacturing a patterned boron-doped diamond electrode with high specific surface area according to claim 1, wherein the substrate is a silicon sheet. Etching a corresponding through-hole pattern on the surface of the metal sheet by photoetching according to a desired pattern, wherein the pattern is one of a square array pattern, a rectangular array pattern and a circular array pattern. A method for manufacturing a patterned boron-doped diamond electrode with high specific surface area according to claim 1. After coating the surface of the substrate with a metal sheet having a through-hole pattern, the metal sheet and the substrate are placed together in a chemical vapor deposition furnace, and the temperature of the surface of the substrate is increased to 750~ at a rate of 5~20°C/min. The method for manufacturing a patterned boron-doped diamond electrode having a high specific surface area according to claim 1, characterized in that the temperature is raised to 950°C. The chemical vapor deposition is hot filament chemical vapor deposition, the number of turns of the hot filament is 10 to 15, and the temperature of the hot filament is controlled to 2100 to 2400 ° C. in the chemical vapor deposition process. 2. The method of manufacturing a patterned boron-doped diamond electrode with a high specific surface area according to claim 1. In the chemical growth process, the ratio of methane, borane, and hydrogen gas initially introduced is 10-20:0.3-1:45-49, and the methane, borane introduced after deposition for 1-2 h. , The ratio of hydrogen gas is adjusted to 2-5:0.3-1:45-49, and the patterned film having a high specific surface area is deposited for 6-10 hours. A method for manufacturing a boron-doped diamond electrode. 7. The method according to claim 1, wherein the boron-doped diamond layer has a thickness of 5 to 20 μm, and the grain size of diamond in the boron-doped diamond layer is 5 to 10 μm. A method for producing a patterned boron-doped diamond electrode having a high specific surface area. Said boron-doped diamond layer is a porous boron-doped diamond layer, said porous boron-doped diamond layer is obtained by depositing and growing a patterned boron-doped diamond layer and then performing a high temperature etching treatment, wherein said high temperature 2. The method for manufacturing a patterned boron-doped diamond electrode having a high specific surface area according to claim 1, wherein the etching treatment is high temperature atmosphere etching treatment or high temperature metal etching treatment. A patterned boron-doped diamond electrode having a high specific surface area produced by the production method according to any one of claims 1 to 8. Application of the patterned boron-doped diamond electrode with high specific surface area produced by the production method according to any one of claims 1 to 8, characterized in that it is applied in an electrochemical sensor as a working electrode.

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