WO2021228015A1 - Électrode en diamant dopé au bore à motifs ayant une surface spécifique élevée et procédé de fabrication et application d'une électrode en diamant dopé au bore à motifs - Google Patents

Électrode en diamant dopé au bore à motifs ayant une surface spécifique élevée et procédé de fabrication et application d'une électrode en diamant dopé au bore à motifs Download PDF

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WO2021228015A1
WO2021228015A1 PCT/CN2021/092641 CN2021092641W WO2021228015A1 WO 2021228015 A1 WO2021228015 A1 WO 2021228015A1 CN 2021092641 W CN2021092641 W CN 2021092641W WO 2021228015 A1 WO2021228015 A1 WO 2021228015A1
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doped diamond
boron
electrode
patterned
surface area
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PCT/CN2021/092641
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Chinese (zh)
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魏秋平
周科朝
马莉
李海超
杨万林
苗冬田
李志伸
陈尹豪
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中南大学
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Priority to JP2022568462A priority Critical patent/JP2023524867A/ja
Publication of WO2021228015A1 publication Critical patent/WO2021228015A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/277—Diamond only using other elements in the gas phase besides carbon and hydrogen; using other elements besides carbon, hydrogen and oxygen in case of use of combustion torches; using other elements besides carbon, hydrogen and inert gas in case of use of plasma jets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Definitions

  • the invention relates to a boron-doped diamond electrode with a high specific surface area and a preparation method and application thereof, in particular to a patterned boron-doped diamond electrode with a high specific surface area and a preparation method and application thereof, belonging to the field of electrode preparation.
  • Boron-doped diamond electrodes have been widely used in the fields of biosensing, water treatment and life detection due to their excellent electrochemical performance. Its low background current, high stability and low adsorption characteristics make it stand out among many electrode materials. Boron-doped diamond electrodes are electrochemical electrodes, which mainly convert biological, chemical and physical signals into electrical signals that can be identified and analyzed. In the field of low-concentration detection, diamond electrodes occupy a very important position due to their low background current characteristics.
  • the boron-doped diamond electrode with high specific surface area can be optimized for its excellent performance, it will be able to increase the response signal of the electrode itself, which will greatly amplify its detection advantage in the field of low concentration.
  • the patterned diamond electrode will be more flexible in size and shape design, and it will be easier to realize and optimize the electrode mass transfer design.
  • the existing methods for preparing patterned diamond electrodes mainly use plasma etching or photolithography methods, that is, the current top-down method is generally adopted: firstly, a diamond film of sufficient thickness is prepared, and then the above-mentioned method is used for the complete film. Perform patterning.
  • the purpose of the present invention is to provide a patterned boron-doped diamond electrode with a high specific surface area, and a preparation method and application thereof.
  • the patterned preparation method used in the present invention belongs to a bottom-up method, that is, a patterned mask is directly connected to the substrate as a whole, and then a patterned diamond electrode is directly grown on the substrate. This method has simpler design steps than etching and other methods, easier operation control, and lower manufacturing cost.
  • the method for preparing a patterned boron-doped diamond electrode with high specific surface area of the present invention includes the following steps.
  • the surface of the substrate with a metal sheet with a through-hole pattern, and then place it in a chemical vapor deposition furnace, and deposit and grow a patterned boron-doped diamond layer on the exposed part of the substrate surface to obtain a patterned boron-doped diamond electrode.
  • the surface temperature of the substrate is controlled to be 750-950°C
  • the growth pressure is 2.5-5KPa
  • the ratio of methane, borane, and hydrogen introduced is 1-20: 0.3-1: 45-49.
  • the exposed part of the surface of the substrate refers to the part of the through hole pattern exposed after the surface of the substrate is covered with a metal sheet with a through hole pattern.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • a metal sheet with a through hole pattern is covered on the surface of a substrate, and then they are placed in a chemical vapor deposition furnace together and fixed by a base plate.
  • the design method of the abutment is as follows: For example, the actual size of the electrode is 2-10 cm 2 , the size of the abutment designed for chemical vapor deposition is 4-15 cm 2 , and the surplus size is the surplus required for fixing. Measure the size, use high temperature resistant molybdenum wire to cut into corresponding size abutment accessories and complete the assembly.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the metal sheet is a stainless steel sheet.
  • the present invention is a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the preparation process of the metal sheet with a through-hole pattern is: according to the required pattern, a photolithography method is used to etch the corresponding surface of the metal sheet. Through hole pattern.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the pattern is one of a square array pattern, a rectangular array pattern, and a circular array pattern.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the substrate is a silicon wafer.
  • the substrate for growing diamond is a silicon substrate that can form a stable oxide intermediate layer. Compared with other metal substrates, the silicon substrate can form an intermediate oxide layer with a smaller thermal expansion coefficient than that of a pure substrate. The diamond is not easy to fall off.
  • the present invention is a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • a metal sheet with a through hole pattern is covered on the surface of a substrate, and then placed in a chemical vapor deposition furnace, and then 5-20°C/min Preferably, the temperature is increased at a rate of 5-15°C/min to make the surface temperature of the substrate reach 750-950°C.
  • the pattern is irregular or even fails to grow.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the chemical vapor deposition is hot wire chemical vapor deposition, the number of turns of the hot wire is 10-15, and the temperature of the hot wire is controlled during the chemical vapor deposition process. It is 2100-2400 °C.
  • the present invention is a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the ratio of methane, borane, and hydrogen introduced first is 10-20: 0.3-1: 45-49, deposition for 1-2 h, and then adjust the ratio of methane, borane, and hydrogen to 2-5: 0.3-1: 45-49, deposition for 6-10 h.
  • the invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the thickness of the boron-doped diamond layer is 5-20 ⁇ m, and the diameter of the diamond grains in the boron-doped diamond layer is 5-10 ⁇ m.
  • the method for preparing a patterned boron-doped diamond electrode with a high specific surface area is a porous boron-doped diamond layer, and the porous boron-doped diamond layer is patterned by deposition and growth. After the diamond layer, it is obtained by high-temperature etching treatment.
  • the high-temperature etching treatment is a high-temperature atmosphere etching treatment or a high-temperature metal etching treatment.
  • the boron-doped diamond layer forms a porous structure, even if micropores and/or sharp cones are distributed on the surface of the boron-doped diamond layer, thereby further expanding the specific surface area of the patterned boron-doped diamond electrode.
  • the high-temperature atmosphere etching treatment refers to depositing and growing the patterned boron-doped diamond layer on the exposed part of the substrate surface, and then placing it in an air or hydrogen atmosphere for heat treatment.
  • the heat treatment temperature is 600- 1000°C
  • the pressure is 10Pa-10 5 Pa
  • the treatment time is 5 ⁇ 180min.
  • High-temperature metal treatment etching refers to depositing and growing a patterned boron-doped diamond layer on the exposed part of the substrate surface, and then depositing a metal layer with a higher catalytic ability for carbon on the surface of the boron-doped diamond layer, and then treating the surface of the substrate.
  • the boron-doped diamond layer of the deposited metal layer is heat treated to spheroidize the metal layer at high temperature, forming a mass-distributed metal nanosphere or microsphere on the surface of the diamond; at high temperature, the carbon atoms in the diamond continuously dissolve into the metal nanometer In the spheres or microspheres, the solid carbon precipitated when the carbon atoms in the metal nanospheres or microspheres are supersaturated and solid-solved is etched by adding hydrogen atmosphere, so that the metal nanospheres or microspheres continue to migrate into the diamond, and finally the boron-doped diamond A large number of micropores and sharp cones are formed on the surface of the layer; the material of the metal layer is selected from one or a combination of metal iron, cobalt, and nickel; the heat treatment temperature is 600-1000°C, the time is 1min-3h, and the pressure is 0.1-1 Atmospheric pressure.
  • the invention also provides a patterned boron-doped diamond electrode with a high specific surface area prepared by the above-mentioned preparation method.
  • the invention also provides a patterned boron-doped diamond electrode with a high specific surface area prepared by the above preparation method as a working electrode and applied to an electrochemical sensor.
  • the boron-doped diamond electrode is used as the working electrode
  • the platinum sheet is used as the counter electrode
  • the Ag/AgCl electrode is used as the reference electrode to form an electrochemical sensor (three-electrode detection sensor).
  • the present invention provides a method for preparing a patterned boron-doped diamond electrode with a high specific surface area.
  • the preparation method of the present invention belongs to a bottom-up method, that is, directly connect the patterned mask to the substrate directly, and then directly A patterned diamond electrode is grown on the substrate.
  • the method has simpler design steps than etching and other methods, easier to control the operation, and lower manufacturing cost.
  • the stainless steel sheet is directly used as a mask to cover the silicon substrate, and the coefficient of thermal expansion of the stainless steel coating layer as a mask is much larger than that of the silicon substrate, so that it is easy to cause the original fixed during high temperature growth.
  • the mask appears to be shifted, deformed, etc., resulting in irregular growth of the diamond pattern or even growth failure.
  • a method combining the surrounding limit fixation and the slow temperature rise is cleverly designed to avoid the occurrence of the above phenomenon.
  • the patterned growth area is smaller than the traditional monolithic substrate growth area, there is a problem of difficulty in nucleation during the growth process. This is mainly because carbon atoms need sufficient thermodynamic motion to complete a series of processes such as nucleation, island formation, and film formation, but the growth of carbon atoms in a specific area is limited, which increases the difficulty of nucleation and film formation. , Prolong the entire growth cycle, even unable to form a regular pattern, the present invention overcomes the problem of difficulty in nucleation by adopting a method of high methane concentration in the early stage of growth.
  • the patterned diamond electrode prepared by the above method has a regular microstructure, the specific surface area of the electrode is large, and the response current of the electrode is greatly increased.
  • Figure 1 Schematic diagram of diamond electrode patterning.
  • Step 1 Pattern the stainless steel sheet.
  • the method is to etch the through hole pattern corresponding to the pattern on the stainless steel sheet according to the required square array pattern using a photolithography device to obtain the intermediate spacer layer.
  • Step 2 Design of hot wire chemical vapor deposition abutment.
  • the method is, according to the actual size of the detection electrode 2cm 2 , the design of the chemical vapor deposition base size is 4 cm 2 , the margin size is the margin size required when fixing, and the high temperature resistant molybdenum wire is used to cut into the corresponding size Abutment accessories and complete assembly.
  • Step 3 Depositing a boron-doped diamond film on the silicon wafer substrate by a chemical vapor method.
  • the method is to place the pattern sheet and silicon wafer substrate prepared in step 1 in an acetone solution, and ultrasonically clean for 10 minutes to remove oil stains on the surface; then ultrasonically clean in deionized water for 5 minutes, and then dry it in a drying oven.
  • the temperature of the surface of the silicon wafer substrate was raised to 750°C at a speed of 5°C/min, and the boron-doped diamond film was grown.
  • the number of turns of the hot wire is 10 turns, the temperature of the hot wire is controlled at 2100°C, and the cavity pressure is controlled to be about 2.5 kPa; first control the mass flow of methane 20 sccm, borane 0.3 sccm, and hydrogen 49 sccm; Grow for 1h. Then, the amount of borane and hydrogen introduced does not change, adjust the amount of methane introduced to 5 sccm and grow for 6 hours. Finally, the thickness of the boron-doped diamond film is 5-10 ⁇ m, and the grain size of the grown diamond film At 5-7 microns.
  • Step 4 The patterned diamond electrode obtained in step 3 is packaged, the platinum sheet is used as the counter electrode, and the Ag/AgCl electrode is used as the reference electrode to form a three-electrode detection sensor.
  • Step 5 Use the electrode prepared in step 4 to detect the dopamine solution.
  • the patterned electrode has a larger effective active area (the area of the patterned electrode is 0.25 cm 2 , the non-patterned electrode is 0.14 cm 2 , the index experiment is 2 mM potassium ferricyanide solution, and the scanning speed is 10mV/s), the charge transfer resistance is smaller (4.5 ⁇ for patterned electrodes, 10.5 ⁇ for non-patterned electrodes, the index experiment is electrochemical impedance test, specifically in 2 mM potassium ferricyanide solution, the test frequency is 1 Hz- 1MHz, open circuit voltage is 10 mV).
  • the detection object is a dopamine solution with a concentration range of 0.01-500 ⁇ M
  • the interference object is a 500 ⁇ M ascorbic acid solution. Both types of solutions use 0.01 M phosphate PBS solution as the substrate.
  • Interfering substances were added to dopamine solutions of different concentrations, and the encapsulated electrodes were used for detection and analysis.
  • the detection and analysis process used cyclic voltammetry (scanning speed of 20 mV per second) and square wave voltammetry (pulse amplitude of 30). mV, the frequency is 5 Hz).
  • the test results show that the detection limit of the electrode for dopamine is 60 nM.
  • the detection linear range is 5-50 ⁇ M.
  • Step 1 Pattern the stainless steel sheet.
  • the method is to use a photoetching equipment to etch the through hole pattern corresponding to the pattern on the stainless steel sheet according to the required square array pattern, rectangular array pattern, circular array pattern, etc., to obtain the intermediate spacer layer.
  • Step 2 Design of hot wire chemical vapor deposition abutment.
  • the method is, according to the actual size of the detection electrode 4cm 2 , the design of the chemical vapor deposition base size is 8 cm 2 , the margin size is the margin size required when fixing, and the high temperature resistant molybdenum wire is used to cut into the corresponding size Abutment accessories and complete assembly.
  • Step 3 Depositing a boron-doped diamond film on the silicon wafer substrate by a chemical vapor method.
  • the method is to place the pattern sheet and silicon wafer substrate prepared in step 1 in an acetone solution, and ultrasonically clean for 15 minutes to remove oil stains on the surface; then ultrasonically clean in deionized water for 10 minutes, and then dry it in a drying oven.
  • the temperature of the surface of the silicon wafer substrate was increased to 850°C at a speed of 10°C/min, and the boron-doped diamond film was grown.
  • the number of turns of the hot wire is 13 turns, the temperature of the hot wire is controlled at 2300 °C, and the cavity pressure is about 4 kPa; the mass flow of the gas is controlled to 15 sccm for methane, 0.5 sccm for borane, and 47 sccm for hydrogen; Growing for 1.5h. Then, the amount of borane and hydrogen introduced is unchanged, and the amount of methane introduced is adjusted to 3 sccm, and grown for 8 hours. Finally, the thickness of the boron-doped diamond film is 10-15 ⁇ m, and the grown diamond film crystal The particle size is 7-9 microns.
  • Step 4 The patterned diamond electrode obtained in step 3 is packaged, the platinum sheet is used as the counter electrode, and the Ag/AgCl electrode is used as the reference electrode to form a three-electrode detection sensor.
  • Step 5 Use the electrode prepared in step 4 to detect the dopamine solution.
  • the patterned electrode has a larger effective active area (the area of the patterned electrode is 0.3 cm 2 , the non-patterned electrode is 0.23 cm 2 , the index experiment is 2 mM potassium ferricyanide solution, and the scanning speed is 10mV/s), the charge transfer resistance is smaller (5.0 ⁇ for patterned electrodes and 14.0 ⁇ for non-patterned electrodes.
  • the index experiment is electrochemical impedance test, specifically in 2 mM potassium ferricyanide solution, the test frequency is 1 Hz- 1MHz, open circuit voltage is 10 mV).
  • the detection object is a dopamine solution with a concentration range of 0.01-500 ⁇ M
  • the interference object is a 1000 ⁇ M ascorbic acid solution.
  • the substrates of the two types of solutions are 0.01 M phosphate PBS solution.
  • Interfering substances were added to dopamine solutions of different concentrations, and the encapsulated electrodes were used for detection and analysis.
  • the detection and analysis process used cyclic voltammetry (scanning speed of 20 mV per second) and square wave voltammetry (pulse amplitude of 30). mV, the frequency is 5 Hz).
  • the test results show that the detection limit of the electrode for dopamine is 50 nM.
  • the detection linear range is 1-80 ⁇ M.
  • Step 1 Pattern the stainless steel sheet.
  • the method is to use a photolithography device to etch the through hole pattern corresponding to the pattern on the stainless steel sheet according to the required square array pattern, rectangular array pattern, circular array pattern, etc., to obtain the intermediate spacer layer.
  • Step 2 Design of hot wire chemical vapor deposition abutment.
  • the method is, according to the actual size of the detection electrode 10 cm 2 , the design of the chemical vapor deposition abutment size is 15 cm 2 , the margin size is the margin size required when fixing, and the high temperature resistant molybdenum wire is used to cut into the corresponding The size of the abutment accessories and complete the assembly.
  • Step 3 Depositing a boron-doped diamond film on the silicon wafer substrate by a chemical vapor method.
  • the method is to place the pattern sheet and silicon wafer substrate prepared in step 1 in an acetone solution, and ultrasonically clean for 20 minutes to remove oil stains on the surface; then ultrasonically clean in deionized water for 20 minutes, and then dry it in a drying oven.
  • the temperature of the silicon wafer substrate surface is increased to 950°C at a speed of 15 °C/min, and the boron-doped diamond film is grown.
  • the number of turns of the hot wire during the growth process is 15 turns, and the temperature of the hot wire is controlled.
  • the chamber pressure is about 5 kPa, first control the mass flow of the gas to be 10 sccm of methane, 1 sccm of borane, and 45 sccm of hydrogen; grow for 2 hours. Then, the amount of borane and hydrogen introduced does not change. , Adjust the input of methane to 2 sccm, grow for 10 hours, and finally obtain a boron-doped diamond film with a thickness of 15-20 ⁇ m, and the grown diamond film has a grain size of 9-10 microns in diameter.
  • Step 4 The patterned diamond electrode obtained in step 3 is packaged, the platinum sheet is used as the counter electrode, and the Ag/AgCl electrode is used as the reference electrode to form a three-electrode detection sensor.
  • Step 5 Use the electrode prepared in step 4 to detect the dopamine solution.
  • the patterned electrode has a larger effective active area (the area of the patterned electrode is 0.35 cm 2 , the non-patterned electrode is 0.27 cm 2 , the index experiment is 2 mM potassium ferricyanide solution, and the scanning speed is 10mV/s), the charge transfer resistance is smaller (the patterned electrode is 6.0 ⁇ , the non-patterned electrode is 16.0 ⁇ , the index experiment is electrochemical impedance test, specifically in the 2 mM potassium ferricyanide solution, the test frequency is 1 Hz- 1MHz, open circuit voltage is 10 mV).
  • the detection object is a dopamine solution with a concentration range of 0.01-500 ⁇ M
  • the interference object is a 1500 ⁇ M ascorbic acid solution. Both types of solutions use 0.01 M phosphate PBS solution as the substrate. Interfering substances were added to dopamine solutions of different concentrations, and the encapsulated electrodes were used for detection and analysis.
  • the detection and analysis process used cyclic voltammetry (scanning speed of 20 mV per second) and square wave voltammetry (pulse amplitude of 30). mV, the frequency is 5 Hz).
  • the test results show that the detection limit of the electrode for dopamine is 45 nM.
  • the detection linear range is 0.5-100 ⁇ M.
  • this comparative example 1 The other conditions of this comparative example 1 are the same as those of the embodiment 1, except that the pattern sheet and the silicon wafer substrate are not fixed around the periphery in step 3, and as a result, a diamond array consistent with the pattern cannot be grown.
  • the reason is that the thermal expansion coefficient of the silicon substrate and the stainless steel pattern sheet is quite different. If the limit is not good, it is easy to deform and shift and cause the growth of the diamond film to fail.
  • this comparative example 2 is the same as those of embodiment 1, except that the initial gas flow rate of methane in step 3 is 8 sccm, and as a result, a diamond array consistent with the pattern cannot be grown.
  • the reason is that the area between the silicon substrate and the stainless steel pattern sheet itself left for the nucleation of carbon atoms is relatively small. If the concentration of carbon atoms is not enough, it is difficult to nucleate and grow in a smaller area, and finally form a film, which leads to the failure of diamond film growth. .
  • this comparative example 3 is the same as those of example 1, except that in step 3, the temperature of the hot wire is adjusted to 1800°C. As a result, a diamond array cannot be grown. The reason is that the temperature of the hot wire is too low, which prevents the effective cracking of enough carbon atoms for diamond growth. In addition, the temperature of the hot wire is too low, which will also affect the substrate temperature, causing the nucleation of carbon atoms to be hindered, and further preventing the formation of carbon atoms. Membrane process.
  • this comparative example 3 is the same as those of embodiment 1, except that the temperature of the surface of the silicon wafer substrate is increased to 750°C at a speed of 30°C/min. As a result, it was found that the nucleation was not effective, and the diamond film could not be grown in the end. The reason is that the heating rate is too fast compared to the heating rate proposed in this patent. The thermal expansion coefficient between the substrate and the mask proposed earlier is very different. If the heating is too fast, it will cause serious thermal deformation. In the later patterning area, there was a very obvious displacement phenomenon, so that the carbon atoms could not effectively nucleate in the same area, and finally the growth failed.
  • this comparative example 5 The other conditions of this comparative example 5 are the same as those of example 3, except that the methane flow rate initially adopted in step 3 is 30 sccm. It turns out that the nucleation cannot be effectively formed on the substrate, and the growth of the diamond film fails. The reason is that the initial methane concentration used is too high. The excessively cracked carbon atoms are accumulated in the growth area, but the cracked atomic hydrogen cannot take away the excessive carbon atoms in time, and the excessive carbon atoms will form a graphite phase, resulting in The growth of the diamond film is stagnant, which eventually leads to more graphite phases observed in the growth area, and the growth of the diamond film fails.

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Abstract

L'invention concerne une électrode en diamant dopé au bore à motifs ayant une surface spécifique élevée et un procédé de fabrication et une application de l'électrode en diamant dopé au bore à motifs. Le procédé de fabrication consiste : à graver un motif régulier sur une feuille d'acier inoxydable à l'aide d'un procédé de photogravure ; à recouvrir la surface d'un substrat avec la feuille d'acier inoxydable ayant un motif de trou traversant, puis à placer la feuille d'acier inoxydable et le substrat ensemble dans un four de dépôt chimique en phase vapeur, et à délimiter et à fixer en utilisant une plateforme de base ; à déposer et à faire croître une couche de diamant dopé au bore à motifs sur une partie exposée de la surface du substrat pour obtenir l'électrode en diamant dopé au bore à motifs ; et dans le processus de dépôt chimique en phase vapeur, à réguler une température de surface du substrat à 750-950 °C, une pression d'air de croissance à 2,5-5 KPa, et un rapport entre le méthane, le borane et l'hydrogène introduits de (1-20):(0,3-1):(45-49) ; et enfin, à utiliser l'électrode en diamant dopé au bore fabriquée en tant qu'électrode de travail, une feuille de platine en tant que contre-électrode, et une électrode Ag/AgCl en tant qu'électrode de référence afin de les assembler dans un système d'électrode de détection. Par rapport à l'état de la technique, le procédé de fabrication selon la présente invention est plus simple, son fonctionnement est plus facile à réguler, et ses coûts de fabrication sont plus faibles.
PCT/CN2021/092641 2020-05-11 2021-05-10 Électrode en diamant dopé au bore à motifs ayant une surface spécifique élevée et procédé de fabrication et application d'une électrode en diamant dopé au bore à motifs WO2021228015A1 (fr)

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