WO2017219771A1 - 一种微电极阵列及其制备方法 - Google Patents

一种微电极阵列及其制备方法 Download PDF

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WO2017219771A1
WO2017219771A1 PCT/CN2017/083627 CN2017083627W WO2017219771A1 WO 2017219771 A1 WO2017219771 A1 WO 2017219771A1 CN 2017083627 W CN2017083627 W CN 2017083627W WO 2017219771 A1 WO2017219771 A1 WO 2017219771A1
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platinum
microelectrode
microelectrode array
layer
modified
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English (en)
French (fr)
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夏凯
吴天准
孙滨
曾齐
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority claimed from CN201610460562.3A external-priority patent/CN106108891A/zh
Priority claimed from CN201610486521.1A external-priority patent/CN106037719B/zh
Priority claimed from CN201610858458.XA external-priority patent/CN106419906B/zh
Priority claimed from CN201710203187.9A external-priority patent/CN108652618B/zh
Application filed by Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Institute of Advanced Technology of CAS
Priority to EP17814509.0A priority Critical patent/EP3511706B1/en
Publication of WO2017219771A1 publication Critical patent/WO2017219771A1/zh
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/02—Details
    • A61N1/04—Electrodes
    • A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode

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  • the invention relates to the technical field of microelectrode surface modification, in particular to a microelectrode array and a preparation method thereof
  • nerve stimulation/recording electrodes are used to stimulate nerve tissue or record nerve electrical signals (electrocardiogram, brain electricity, cortical electrical signals, etc.), which are widely used in brain-computer interface, neurophysiology,
  • nerve electrical signals electrocardiogram, brain electricity, cortical electrical signals, etc.
  • the field of life sciences such as brain science research is a very important research and diagnosis tool.
  • nerve stimulation electrodes/recording are moving toward miniaturization and arraying---microelectrode arrays.
  • the reduction in electrode size leads to a problem of an increase in electrode impedance and ultimately affects the stimulation efficiency of the electrode.
  • the actual surface area of the electrode is increased mainly by surface modification, and the electrochemical performance of the electrode is improved.
  • the methods for surface modification of microelectrode arrays are generally as follows: 1. A layer of platinum black is modified on the surface of the electrode (Anal. Chem. 1987, 59, 217-218), which can electrochemically conduct the electrode. The impedance is reduced by at least an order of magnitude, but its mechanical stability is very poor, and its modified layer contains toxic substances such as lead, making it unsuitable for biomedical applications; 2. Modifying a layer of platinum ash on the surface of the electrode (US Patent 6974533, 2005), this coating has good mechanical stability and is non-toxic, but its surface roughness is not large enough, which makes it limited to the surface modification of ultra-high resolution electrodes; Eng.Med.Biol.Soc.
  • modified microelectrodes have excellent electrochemical properties (such as high Charge injection capability), but the adhesion of these materials is poor, and it is easy to fall off the electrode surface during the stimulation process.
  • the present invention is directed to providing a microelectrode array having a surface provided with a modifying layer, a bonding layer of the modified layer and a microelectrode substrate, a large surface area of the microelectrode, and a large surface roughness, and Green is non-toxic.
  • the present invention provides a microelectrode array, the electrode surface of which is provided with a modification layer comprising a platinum nano-pillar modification layer, a platinum nanowire modification layer or a dendritic platinum modification layer.
  • the thickness of the platinum nano-pillar modification layer is 500 nm to 5 ⁇ m, and the diameter of the platinum nano-column in the platinum nano-pillar modification layer is in the range of 50 nm to 500 nm.
  • the platinum nano column modification layer has a three-dimensional nanoporous structure.
  • the platinum nano-pillar modification layer is disposed by electrodeposition.
  • the surface of the platinum nano-pillar modification layer is provided with a ruthenium oxide layer, and the platinum nano-pillar modification layer and the ruthenium oxide layer form a ruthenium oxide/platinum nano-pillar composite coating layer, and the thickness of the ruthenium oxide layer is 10 nm. ⁇ 500nm.
  • the cerium oxide/platinum nanocolumn composite coating has a three-dimensional nanoporous structure, and the cerium oxide/platinum nanocolumn composite coating has a porous pore diameter of 50 nm to 500 nm.
  • the thickness of the platinum nanowire modification layer is 100 nm to 2 ⁇ m, and the diameter of the platinum nanowire in the platinum nanowire modification layer is in the range of 2 nm to 10 nm.
  • the platinum nanowire modification layer has a three-dimensional nanoporous structure.
  • the platinum nanowire modification layer is disposed by chemical deposition.
  • the dendritic platinum-modified layer has a thickness of 500 nm to 10 ⁇ m.
  • the dendritic platinum in the dendritic platinum-modified layer has a length of 200 nm to 10 ⁇ m, a width of 50 nm to 2 ⁇ m, and a thickness of 5 nm to 500 nm.
  • the dendritic platinum modification layer is disposed by electrodeposition.
  • the present invention provides a method for preparing a microelectrode array, wherein a modified layer is formed on a surface of a microelectrode to be modified by electrodeposition or chemical deposition to form a microelectrode array, and the modified layer includes a platinum nanocolumn A modification layer, a platinum nanowire modification layer or a dendritic platinum modification layer.
  • the method for preparing the microelectrode array includes:
  • Electrodeposition is carried out for 300-600 s under normal temperature and normal pressure conditions, and a platinum nano-column modified layer is formed on the surface of the microelectrode to obtain a microelectrode array.
  • the manner of electrodeposition is constant potential deposition, constant current deposition or pulse electrodeposition.
  • the platinum nano-column modified layer has a thickness of 500 nm to 5 ⁇ m, and the platinum nano-column modified layer has a diameter of 50 nm to 500 nm, and the platinum nano-column modified layer has a three-dimensional nanoporous structure.
  • the surface of the platinum nano-column modified layer is electrodeposited to prepare a ruthenium oxide layer, specifically comprising:
  • a platinum plate as a counter electrode, Ag/AgCl as a reference electrode, a microelectrode array provided with a platinum nano column modification layer as a working electrode, forming a three-electrode system with the electrodeposition solution B, and connecting with an electrochemical workstation;
  • electrodeposition is performed for 300 s to 600 s, and a surface of the platinum nano column modification layer forms a ruthenium oxide layer, and the platinum nano column modification layer and the ruthenium oxide layer form a ruthenium oxide/platinum nano column composite coating.
  • the strontium salt solution is chloroantimonic acid, cerium oxide, cerium chloride, cerium acetylacetonate, sodium hexachlorophthalate, potassium hexachloroantimonate, ammonium hexachloroantimonate, potassium hexanitrocitrate and ten One or more of dicarbonyl tetraindoles.
  • the oxidizing agent is one or more of hydrogen peroxide, oxygen, ozone, potassium peroxide and sodium peroxide;
  • the weak acid is one or more of formic acid, acetic acid, oxalic acid and carbonic acid.
  • the concentration of the cerium salt is 1 mmol/L to 5 mmol/L
  • the concentration of the oxidizing agent is 1 mmol/L to 5 mmol/L
  • the concentration of the weak acid is 1 mmol/L to 5 mmol. /L.
  • the method for preparing the microelectrode array includes:
  • microelectrode deposited with platinum nanowires was placed in water for 10 min to 50 min to remove the platinum nanowires with poor adhesion, and a platinum nanowire modification layer was obtained to obtain a microelectrode array.
  • the thickness of the platinum nanowire modification layer is 100 nm to 2 ⁇ m, and the diameter of the platinum nanowire in the platinum nanowire modification layer is in the range of 2 nm to 10 nm.
  • the platinum nanowire modification layer has a three-dimensional nanoporous structure.
  • the method for preparing the microelectrode array includes:
  • Electrodeposition is performed at a temperature of 35 ° C to 60 ° C for 3000 s to 6000 s, and a dendritic platinum-modified layer is formed on the surface of the microelectrode to obtain a microelectrode array.
  • the manner of electrodeposition is constant potential deposition, constant current deposition or pulse electrodeposition.
  • the voltage of the constant potential deposition is -0.3V to -0.8V
  • the current of the constant current deposition is -0.5 ⁇ A to -1.5 ⁇ A
  • the peak current density of the pulse electrodeposition is 0.8A/cm 2 to 2.5A/cm. 2 .
  • the voltage of the constant potential deposition is -0.7V to -0.8V
  • the current deposited by the constant current is -0.8 ⁇ A to -1.5 ⁇ A
  • the peak current density of the pulse electrodeposition is 1.5A/cm 2 to 2.5A/cm. 2 .
  • the platinum salt solution is one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate.
  • the weak reducing agent is one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol and 1,2,4 benzenetriol. .
  • the concentration of the platinum salt is 1 mmol/L to 20 mmol/L
  • the concentration of the weak reducing agent is 1 mmol/L to 20 mmol/L.
  • Example 1 is a scanning electron microscope (SEM) image of a platinum nano-pillar modified layer prepared in Example 1 of the present invention
  • Example 2 is a comparison diagram of cyclic voltammetry (CV) of a platinum nanocolumn modified microelectrode array prepared in Example 1 of the present invention and an unmodified microelectrode;
  • EIS electrochemical impedance
  • Example 4 is a scanning electron microscope (SEM) image of a ruthenium oxide layer prepared in Example 14 of the present invention
  • SEM scanning electron microscope
  • Example 6 is a comparison of cyclic voltammetry (CV) of a microelectrode array modified with a cerium oxide/platinum nanocolumn composite coating prepared by Example 14 of the present invention, an unmodified microelectrode, and a platinum nanocolumn modified microelectrode array. ;
  • EIS electrochemical impedance
  • Example 8 is a scanning electron microscope (SEM) image of a platinum nanowire modification layer (magnification 10,000 times) prepared in Example 27 of the present invention.
  • SEM scanning electron microscope
  • Example 10 is a scanning electron microscope (SEM) image of a platinum nanowire modification layer (magnified 20000 times) prepared in Example 27 of the present invention
  • FIG. 11 is a comparison diagram of cyclic voltammetry (CV) of a platinum nanowire-modified microelectrode array prepared in Example 27 of the present invention and an unmodified microelectrode;
  • EIS electrochemical impedance
  • FIG. 16 are scanning electron microscope (SEM) images of dendritic platinum-modified layers of different sizes prepared in Example 40 of the present invention.
  • Example 17 is a comparison diagram of cyclic voltammetry (CV) of a dendritic platinum-modified microelectrode array prepared in Example 40 of the present invention and an unmodified microelectrode;
  • EIS electrochemical impedance
  • Example 19 is a result of electrochemical stability test of a dendritic platinum-modified microelectrode array prepared in Example 40 of the present invention.
  • an embodiment of the present invention provides a microelectrode array, wherein a surface of an electrode of the microelectrode array is provided with a modification layer, and the modification layer comprises a platinum nano column modification layer, a platinum nanowire modification layer or a dendritic platinum modification.
  • the modification layer comprises a platinum nano column modification layer, a platinum nanowire modification layer or a dendritic platinum modification.
  • the platinum nano-pillar modification layer has a thickness of 500 nm to 5 ⁇ m, and the platinum nano-column modification layer has a diameter of the platinum nano-column of 50 nm to 500 nm.
  • the platinum nano-pillar modification layer has a three-dimensional nanoporous structure. The three-dimensional nanoporous structure can greatly increase the surface area of the microelectrode.
  • the platinum nano-pillar modification layer is disposed by electrodeposition. The bonding layer provided on the surface of the electrode by electrodeposition has a strong binding force to the surface of the electrode, and is not easily peeled off.
  • a platinum nanocolumn is used as a surface modification layer, and the binding layer of the modified layer and the microelectrode substrate is better, and the electrode is not easily detached, thereby causing electrode failure, and the surface area of the modified microelectrode is greatly increased.
  • the chemical impedance is significantly reduced, and the electrode charge injection capacity and charge storage capacity are greatly increased, which is advantageous for reducing the power consumption of the implanted system and improving the electrical stimulation effect, and the modified layer has good biocompatibility, making it in the biomedical field.
  • the application has greatly increased.
  • the surface of the platinum nano-pillar modification layer is provided with a ruthenium oxide layer, and the platinum nano-column modification layer and the ruthenium oxide layer form a ruthenium oxide/platinum nano-pillar composite coating, the ruthenium oxide
  • the thickness of the layer is from 10 nm to 500 nm.
  • the ruthenium oxide layer has a thickness of 50 nm to 400 nm and 100 nm to 300 nm.
  • a suitable thickness of the yttrium oxide layer allows the microelectrode array to have a higher charge storage capacity.
  • the cerium oxide/platinum nanocolumn composite coating layer has a thickness of 500 nm to 5 ⁇ m, and further optionally 1 ⁇ m to 4 ⁇ m and 2 ⁇ m to 3 ⁇ m. Different thicknesses result in microelectrodes having different sized surface areas.
  • the diameter of the platinum nanocolumn is 50 nm to 500 nm, and optionally, the diameter of the platinum nanocolumn is 200 nm to 300 nm. A suitable diameter ensures that the platinum nano-pillar layer has a good nanoporous structure, so that a suitable rough surface is obtained.
  • the cerium oxide/platinum nanocolumn composite coating layer has a three-dimensional nanoporous structure, and the porous pore diameter of the platinum nano-column layer ranges from 50 nm to 500 nm, and further optionally from 200 nm to 500 nm and from 100 nm to 300 nm.
  • the three-dimensional nanoporous structure can greatly increase the surface area of the microelectrode and greatly increase the charge storage capacity of the microelectrode.
  • the cerium oxide/platinum nanocolumn composite coating layer is obtained by sequentially depositing a platinum nano-pillar layer and a ruthenium oxide layer on the surface of the electrode.
  • the cerium oxide/platinum nanocolumn composite coating provided on the surface of the electrode by electrochemical deposition has strong binding force to the surface of the electrode and is not easy to fall off.
  • the yttrium oxide/platinum nanocolumn composite coating layer comprises a platinum nano-pillar layer and a ruthenium oxide layer which are sequentially disposed on the surface of the electrode, and the platinum nano-pillar layer has a nano-porous structure to provide a rough surface having a large surface area.
  • Platinum nanocolumn The layer acts as an adhesion layer between the electrode and the ruthenium oxide layer, which can adhere to more yttrium oxide and increase the adhesion between the ruthenium oxide layer and the electrode.
  • the ruthenium oxide layer has an extremely high charge storage. Therefore, the microelectrode array modified by the cerium oxide/platinum nanocolumn composite coating of the present invention has both high charge storage capacity and high stability.
  • the platinum nanowire-modifying layer has a thickness of 100 nm to 2 ⁇ m, and the platinum nanowire has a diameter of 2 nm to 10 nm. Different thicknesses result in microelectrodes having different sized surface areas.
  • the platinum nanowire modification layer has a three-dimensional nanoporous structure. Since the surface of the microelectrode has a large number of platinum nanowires, and the surface of the platinum nanowire and the microelectrode constitute a three-dimensional nanoporous structure, the three-dimensional nanoporous structure can greatly increase the surface area of the microelectrode.
  • the platinum nanowire modification layer is disposed by electrodeposition. The bonding layer provided on the surface of the electrode by chemical deposition has a strong binding force to the surface of the electrode and is not easily peeled off.
  • the platinum nanowire is used as a surface modification layer, and the bonding layer has strong binding force to the microelectrode substrate, is not easy to fall off, and causes electrode failure, and the surface area of the modified microelectrode is greatly increased, and the electrochemical The impedance is significantly reduced, and the electrode charge injection capacity and charge storage capacity are greatly increased, which is advantageous for reducing the power consumption of the implanted system and improving the electrical stimulation effect, and the modified layer has good biocompatibility, making it in the biomedical field.
  • the application has increased dramatically.
  • the dendritic platinum-modified layer has a thickness of 500 nm to 10 ⁇ m. Different dendritic platinum-modified layer thicknesses result in microelectrodes having different sized surface areas.
  • the dendritic platinum comprises a backbone and side branches grown orderly along the trunk, and the dendritic platinum may be a three-dimensional dendritic structure or a two-dimensional dendritic structure, when the dendritic platinum is a three-dimensional dendritic structure, The side branches grow laterally around the trunk in varying lengths in three dimensions.
  • dendritic platinum is a two-dimensional dendritic structure
  • dendritic platinum is a sheet-like structure.
  • the present invention can obtain dendritic platinum of different sizes and different specific shapes by adjusting the preparation process.
  • the dendritic platinum in the dendritic platinum-modified layer has a length of 200 nm to 10 ⁇ m, a width of 50 nm to 2 ⁇ m, and a thickness of 5 nm to 500 nm.
  • the dendritic platinum of the invention contains a large number of branched structures, the specific surface area of the dendritic platinum modified layer is greatly increased, and the performance of the dendritic platinum modified layer is relatively stable.
  • the dendritic platinum modification layer has a three-dimensional nanoporous structure.
  • the three-dimensional nanoporous structure can greatly increase the surface area of the microelectrode.
  • the dendritic platinum modifying layer is disposed by electrodeposition.
  • the bonding layer provided on the surface of the electrode by electrodeposition has strong binding force to the surface of the electrode, is not easy to fall off, and the performance is very stable.
  • dendritic platinum is used as a surface modification layer, and the bonding layer has good adhesion to the microelectrode substrate, is not easy to fall off, and causes electrode failure, and the surface area of the modified microelectrode is greatly increased.
  • the chemical impedance is significantly reduced, and the electrode charge injection capacity and charge storage capacity are greatly increased, which is advantageous for reducing the power consumption of the implanted system and improving the electrical stimulation effect, and the modified layer has good biocompatibility and mechanical stability, so that the modified layer has good biocompatibility and mechanical stability.
  • the application in the field of biomedicine has greatly increased.
  • a microelectrode array is provided in the first aspect of the present invention.
  • the surface of the electrode of the microelectrode array is provided with a modifying layer.
  • the bonding layer has good bonding force with the microelectrode substrate, and is not easy to fall off, resulting in electrode failure, and modification.
  • the surface area of the microelectrode is greatly increased, the electrochemical impedance is significantly reduced, and the charge injection capacity and charge storage capacity of the electrode are greatly increased, which is advantageous for reducing the power consumption of the implanted system and improving the electrical stimulation effect, and the modified layer has good properties. Biocompatibility has greatly increased its use in the biomedical field.
  • an embodiment of the present invention provides a method for preparing a microelectrode array, wherein a modified layer is prepared on a surface of a microelectrode to be modified by electrodeposition or chemical deposition to form a microelectrode array, and the modified layer includes platinum. Nano column modification layer, platinum nanowire modification layer or dendritic platinum modification layer.
  • the method for preparing the microelectrode array includes:
  • Electrodeposition is carried out for 300-600 s under normal temperature and normal pressure conditions, and a platinum nano-column modified layer is formed on the surface of the microelectrode to obtain a microelectrode array.
  • the platinum salt solution is one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate. .
  • the added weak reducing agent can react with the platinum salt to accelerate the electrochemical reduction of platinum ions and the formation of elemental platinum on the surface of the microelectrode, thereby forming a more porous structure.
  • the weak reducing agent is one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol, and pyromellit.
  • the concentration of the platinum salt is 1 mmol/L to 20 mmol/L
  • the concentration of the weak reducing agent is 1 mmol/L to 20 mmol/L.
  • the electrodeposition is performed by potentiostatic deposition (voltage is -0.1 V to -0.6 V), constant current deposition (current is -0.1 ⁇ A to -0.7 ⁇ A), or pulsed electrodeposition (peak current density is 0.1). A/cm 2 to 1 A/cm 2 ).
  • the platinum nano-pillar modification layer has a thickness of 500 nm to 5 ⁇ m, and the platinum nano-column modification layer has a platinum nano-column diameter ranging from 50 nm to 500 nm.
  • the platinum nano-pillar modification layer has a three-dimensional nanoporous structure.
  • the microelectrode to be modified may be a planar microelectrode, a pin microelectrode or the like.
  • preparing a ruthenium oxide layer by electrodeposition on the surface of the platinum nano-column modification layer specifically comprising:
  • a platinum plate as a counter electrode, Ag/AgCl as a reference electrode, a microelectrode array provided with a platinum nano column modification layer as a working electrode, forming a three-electrode system with the electrodeposition solution B, and connecting with an electrochemical workstation;
  • electrodeposition is performed for 300 s to 600 s, and a surface of the platinum nano column modification layer forms a ruthenium oxide layer, and the platinum nano column modification layer and the ruthenium oxide layer form a ruthenium oxide/platinum nano column composite coating.
  • the strontium salt solution is chloroantimonic acid, cerium oxide, cerium chloride, cerium acetylacetonate, sodium hexachlorophthalate, potassium hexachloroantimonate, ammonium hexachloroantimonate or potassium hexanitroguanadate. And one or more of the twelve carbonyl tetraindoles.
  • the oxidizing agent is one or more of hydrogen peroxide, oxygen, ozone, potassium peroxide, and sodium peroxide.
  • the weak acid is one or more of formic acid, acetic acid, oxalic acid, and carbonic acid.
  • the concentration of the platinum salt is from 1 mmol/L to 20 mmol/L (for example, may be 2 mmol/L, 5 mmol/L, 10 mmol/L, 15 mmol/L, and 18 mmol/L), which is weak.
  • the concentration of the reducing agent is from 1 mmol/L to 20 mmol/L (for example, it may be 2 mmol/L, 5 mmol/L, 10 mmol/L, 15 mmol/L, and 18 mmol/L).
  • the concentration of the cerium salt is 1 mmol/L to 5 mmol/L (for example, may be 1 mmol/L, 2 mmol/L, 3 mmol/L, 4 mmol/L, 5 mmol/L)
  • the concentration of the oxidizing agent is 1 mmol/L to 5 mmol/L (for example, 1 mmol/L, 2 mmol/L, 3 mmol/L, 4 mmol/L, 5 mmol/L)
  • the concentration of the weak acid is 1 mmol/L to 5 mmol. /L (for example, it may be 1 mmol/L, 2 mmol/L, 3 mmol/L, 4 mmol/L, 5 mmol/L).
  • the electrodeposition is performed by potentiostatic deposition (voltage is -0.1 V to -0.6 V), constant current deposition (current is -0.1 ⁇ A to -0.7 ⁇ A), or pulsed electrodeposition (peak current density is 0.1). A/cm 2 to 1 A/cm 2 ).
  • the cerium oxide/platinum nanocolumn composite coating has a thickness of 500 nm to 5 ⁇ m, further optionally 1 ⁇ m to 4 ⁇ m, 2 ⁇ m to 3 ⁇ m, and the platinum nanocolumn has a diameter of 50 nm to 500 nm, and the oxidation
  • the thickness of the ruthenium layer is 10 nm ⁇ 500 nm, optionally, the thickness of the yttrium oxide layer is 50 nm to 400 nm and 100 nm to 300 nm.
  • the platinum nano-pillar layer has a three-dimensional nanoporous structure.
  • the microelectrode to be modified may be a planar microelectrode, a pin microelectrode or the like.
  • the method for preparing the microelectrode array includes:
  • microelectrode deposited with platinum nanowires was placed in water for 10 min to 50 min to remove the platinum nanowires with poor adhesion, and a platinum nanowire modification layer was obtained to obtain a microelectrode array.
  • the platinum salt solution is one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate. .
  • the added weak reducing agent can react with the platinum salt to reduce the platinum ion to the platinum element, and the reaction rate is very slow due to the weak reducibility, thereby growing a large number of elongated platinum nanowires on the surface of the substrate. Form a more porous structure.
  • the weak reducing agent is one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol, and pyromellit.
  • the concentration of the platinum salt is 1 mmol/L to 20 mmol/L
  • the concentration of the weak reducing agent is 1 mmol/L to 20 mmol/L.
  • step (2) can be carried out in the dark.
  • the ultrasonic process has a power of 600 W and a frequency of 40 KHz.
  • the platinum nanowire modification layer has a thickness of 100 nm to 2 ⁇ m, and the platinum nanowire modification layer has a platinum nanowire diameter ranging from 2 nm to 10 nm.
  • the platinum nanowire modification layer has a three-dimensional nanoporous structure.
  • the microelectrode to be modified may be a planar microelectrode, a pin microelectrode or the like.
  • the method for preparing the microelectrode array includes:
  • Electrodeposition is performed at a temperature of 35 ° C to 60 ° C for 3000 s to 6000 s, and a dendritic platinum-modified layer is formed on the surface of the microelectrode to obtain a microelectrode array.
  • argon gas is introduced into the electrodeposition solution for 30 min to 1 h to remove air in the solution to prevent oxidation of the plating layer and to contribute to the structure of dendrites.
  • the electrode is surface activated
  • the surface activation operation is as follows:
  • the platinum plate is used as the counter electrode, Ag/AgCl is the reference electrode, and the microelectrode to be modified is the working electrode, which forms a three-electrode system and is connected with the electrochemical workstation.
  • the CV cycle cyclic voltammetry
  • the method is to cycle through 30 to 100 cycles in the range of -0.2V to 1.2V. Surface activation of the electrode to remove impurities from the electrode surface facilitates subsequent electrodeposition operations and improves the stability of the coating.
  • the platinum salt solution is one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate.
  • the concentration of the platinum salt is from 1 mmol/L to 20 mmol/L.
  • the weak reducing agent comprises formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbic acid One or more of a salt, hydroquinone, pyrogallol and pyrogallol; in the electrodeposition solution C, the concentration of the weak reducing agent is 1 mmol/L to 20 mmol/ L.
  • the weak reducing agent such as formic acid (HCOOH) added in the present invention can react with the platinum salt, in which HCOOH is oxidized to generate carbon dioxide (CO 2 ), and a porous platinum structure is formed, and the present invention has high temperature and high potential (or High current) promotes the reaction, accelerates the reduction of platinum ions, and forms a more porous platinum structure on the surface of the microelectrode.
  • HCOOH formic acid
  • the deposition temperature in the step (3) is from 50 ° C to 60 ° C.
  • the manner of electrodeposition is constant potential deposition, constant current deposition or pulse electrodeposition.
  • the voltage of the constant potential deposition is -0.3 V to -0.8 V
  • the current of the constant current deposition is -0.5 ⁇ A to -1.5 ⁇ A
  • the peak current density of the pulse electrodeposition is 0.8 A/cm 2 to 2.5. A/cm 2 .
  • the voltage of the constant potential deposition is -0.7V to -0.8V
  • the current of the constant current deposition is -0.8 ⁇ A to -1.5 ⁇ A
  • the peak current density of the pulse electrodeposition is 1.5A/cm 2 to 2.5A. /cm 2 .
  • the dendritic platinum modification layer has a thickness of 500 nm to 10 ⁇ m.
  • the dendritic platinum modification layer has a three-dimensional nanoporous structure.
  • the microelectrode to be modified may be a planar microelectrode, a pin microelectrode or the like.
  • the second aspect of the present invention provides a method for preparing a microelectrode array, wherein the solution is simple to prepare and has no other toxic substances (such as lead and other additives), and the condition is mild and simple, and the preparation can be quickly modified on the surface of the microelectrode array.
  • the layer has good adhesion to the microelectrode substrate, can greatly increase the surface area of the microelectrode, and has excellent electrochemical performance, thereby greatly expanding the application of the microelectrode array in the field of nerve stimulation.
  • a method for preparing a microelectrode array comprising the steps of:
  • FIG. 1 is a scanning electron microscope (SEM) image of a platinum nano-pillar modified layer of the present embodiment. It can be seen from the figure that the obtained platinum nano-column has a uniform morphology and a diameter of about 200 nm.
  • 2 is a comparison diagram of cyclic voltammetry (CV) of a platinum nanocolumn modified microelectrode array and an unmodified microelectrode according to the embodiment, wherein curve 1 is a cyclic voltammetry curve of an unmodified microelectrode, and curve 2 is a curve 2
  • the cyclic voltammetry curve of the platinum nanocolumn modified microelectrode array of this embodiment can be seen from FIG.
  • the platinum nano column modified layer has a larger CV area than the unmodified microelectrode, indicating that it has superiority.
  • the charge storage capability. 3 is a comparison diagram of electrochemical impedance (EIS) of a platinum nanocolumn modified microelectrode array and an unmodified microelectrode according to the embodiment, wherein curve 1 is an electrochemical impedance curve of an unmodified microelectrode, and curve 2 is The electrochemical impedance curve of the platinum nanocolumn modified microelectrode array of this embodiment can be seen from FIG. 3, the platinum nanocolumn modified layer has lower electrochemical impedance than the unmodified microelectrode, and it is at 1 KHz.
  • the electrochemical impedance can be as low as 2k ⁇ .
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to an electrochemical working phase, and deposited at a constant potential in a condition of -0.1 V (vsAg/AgCl).
  • a platinum nano-pillar modification layer is formed on the surface of the microelectrode, that is, a platinum nano-column modified microelectrode array is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to an electrochemical working phase, and deposited at a constant potential in a condition of -0.1 V (vsAg/AgCl).
  • a platinum nano-pillar modification layer is formed on the surface of the microelectrode, that is, a platinum nano-column modified microelectrode array is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to an electrochemical working phase, and deposited in a constant current at -0.3 ⁇ A (vsAg/AgCl).
  • a platinum nano-pillar modification layer is formed on the surface of the microelectrode, that is, a platinum nano-column modified microelectrode array is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to the electrochemical working phase, and deposited in a constant voltage at -0.1 V (vsAg/AgCl).
  • a platinum nano-pillar modification layer is formed on the surface of the microelectrode, that is, a platinum nano-column modified microelectrode array is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to an electrochemical working phase by pulse electrodeposition at a pulse current duty cycle of 5 ⁇ s: 500 ⁇ s.
  • a platinum nanocolumn modified layer was formed on the surface of the microelectrode under the condition of a peak current density of 2.5 A/cm 2 to obtain a platinum nanocolumn modified microelectrode array.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to an electrochemical working phase by pulse electrodeposition at a pulse current duty cycle of 5 ⁇ s: 500 ⁇ s.
  • a platinum nanocolumn modified layer was formed on the surface of the microelectrode under the condition of a peak current density of 2.5 A/cm 2 to obtain a platinum nanocolumn modified microelectrode array.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode are placed and connected to the electrochemical working phase, and deposited in a constant voltage at -0.1 V (vsAg/AgCl).
  • electrodeposition is performed for 300-600 s, and a platinum nano-column modified layer is formed on the surface of the microelectrode to obtain a platinum nano-column modified microelectrode array.
  • a method for preparing a microelectrode array comprising the steps of:
  • the platinum nanocolumn modified microelectrode array prepared in the above Examples 2 to 13 was tested by the same test method as in Example 1, and the test results showed that the prepared modified layer and the microelectrode substrate had better binding force.
  • a method for preparing a microelectrode array comprising the steps of:
  • yttrium oxide electrodeposition solution B a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-column modified layer-modified microelectrode are placed and connected to an electrochemical workstation to deposit at a constant potential.
  • electrodeposition was carried out for 300-600 s, and a ruthenium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by ruthenium oxide/platinum nano-column composite coating.
  • FIG. 4 is a scanning electron microscope (SEM) diagram of a ruthenium oxide layer according to Embodiment 14 of the present invention
  • FIG. 5 is a scanning electron microscope (SEM) diagram of a ruthenium oxide/platinum nanocolumn composite coating layer according to Example 14 of the present invention.
  • the platinum nano-pillar layer has a nano-porous surface structure, and the surface of the cerium oxide is very smooth.
  • the cerium oxide is electroplated on the surface of the platinum nano-column to form a cerium oxide/platinum nano-column composite coating
  • the composite coating also has nanoporous.
  • the surface has a porous pore diameter of 50 nm to 500 nm.
  • the thickness of the cerium oxide/platinum nanocolumn composite coating layer is 500 nm to 5 ⁇ m, and the thickness of the cerium oxide layer is 10 nm to 500 nm.
  • FIG. 6 is a comparison diagram of cyclic voltammetry (CV) of a ruthenium oxide/platinum nanocolumn composite coating modified microelectrode array and an unmodified microelectrode and a platinum nanocolumn according to Example 14 of the present invention, wherein the curve 1 is not Cyclic voltammetry curve of the modified microelectrode, curve 2 is the cyclic voltammetry curve of the platinum nanocolumn modified microelectrode array of the present embodiment, and curve 3 is the cycle of the microelectrode array modified by the yttrium oxide/platinum nanocolumn composite coating The voltammetric curve, as can be seen from FIG.
  • CV cyclic voltammetry
  • the CV area of the yttrium oxide/platinum nanocolumn composite coating of the embodiment of the present invention is larger than that of the unmodified microelectrode and the platinum nanocolumn modified microelectrode array, indicating It has superior charge storage capability.
  • FIG. 7 is a comparison diagram of electrochemical impedance (EIS) of a ruthenium oxide/platinum nanocolumn composite coating modified microelectrode array and an unmodified microelectrode and a platinum nanocolumn modified microelectrode array according to Example 14 of the present invention.
  • Curve 1 is the electrochemical impedance curve of the unmodified microelectrode
  • curve 2 is the electrochemical impedance curve of the platinum nanocolumn modified microelectrode array of the present embodiment
  • curve 3 is the cerium oxide/platinum nanocolumn composite coating of the present embodiment.
  • the electrochemical impedance curve of the layer-modified microelectrode array can be seen from FIG.
  • the cerium oxide/platinum nanocolumn composite coating of the embodiment of the present invention is compared to the unmodified microelectrode and the platinum nanocolumn modified microelectrode array.
  • the layer has a lower electrochemical impedance and its electrochemical impedance at 1 kHz is as low as 2 k ⁇ .
  • a method for preparing a microelectrode array comprising the steps of:
  • Electroposition solution A (1) Add 1 L of water, 5 mmol of ammonium hexachloroplatinate ((NH 4 ) 2 PtCl 6 ) and 5 mmol of sodium citrate (Na 3 C 6 H 5 O 7 ) to the vessel at room temperature and shake gently. Mixing to form electrodeposition solution A;
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the cerium oxide/platinum nanocolumn composite coating layer is 1 ⁇ m to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 200 to 300 nm
  • the thickness of the cerium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating layer is 2 to 4 ⁇ m
  • the diameter of the platinum nanocolumn is 200 to 400 nm
  • the thickness of the yttrium oxide layer is 200 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a porous pore diameter of 200 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition is carried out for 300-600 s, and a ruthenium oxide/platinum nano-column composite coating layer is formed on the surface of the microelectrode to obtain oxidation.
  • the thickness of the cerium oxide/platinum nanocolumn composite coating layer is 500 nm to 2 ⁇ m
  • the diameter of the platinum nanocolumn is 200 to 300 nm
  • the thickness of the cerium oxide layer is 200 nm to 400 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a porous pore diameter of 100 nm to 300 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and a microelectrode to be modified are placed and connected to an electrochemical workstation, and a constant potential deposition method is used to pulse electricity.
  • a platinum nanocolumn layer is formed on the surface of the microelectrode under the condition that the pulse current duty ratio is 5 ⁇ s: 500 ⁇ s and the peak current density is 2.5 A/cm 2 , thereby obtaining a platinum nanocolumn modified microelectrode array;
  • yttrium oxide electrodeposition solution B a platinum plate, an Ag/AgCl reference electrode, and a platinum nano-column modified microelectrode are placed and connected to an electrochemical workstation, and deposited at a constant potential at 0.5 Under V(vsAg/AgCl) conditions, a micro-electrode array modified by yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode by electrodeposition of 300-600 s.
  • the thickness of the cerium oxide/platinum nanocolumn composite coating layer is 1 ⁇ m to 3 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 200 nm
  • the thickness of the cerium oxide layer is 10 nm to 200 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 200 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 200 to 300 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • Electrodeposition solution A (1) In a container at room temperature, add 1 L of water, 5 mmol of sodium chloroplatinate (Na 2 PtCl 6 ) and 10 mmol of citric acid (C 6 H 8 O 7 ), gently shake and mix to form a platinum nanocolumn. Electrodeposition solution A;
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • a method for preparing a microelectrode array comprising the steps of:
  • platinum nanocolumn electrodeposition solution A a platinum plate, an Ag/AgCl reference electrode, and a microelectrode to be modified are placed and connected to an electrochemical workstation by pulse electrodeposition in a pulse current
  • a platinum nanocolumn modified microelectrode array was obtained by forming a platinum nanocolumn modified layer on the surface of the microelectrode under a condition of a duty ratio of 5 ⁇ s: 500 ⁇ s and a peak current density of 2.5 A/cm 2 .
  • a platinum plate, an Ag/AgCl reference electrode, and the above-mentioned platinum nano-pillar modified microelectrode are placed and connected to an electrochemical workstation, and deposited by a constant potential, Under the condition of 0.5V (vsAg/AgCl), electrodeposition was carried out for 300-600 s, and a yttrium oxide/platinum nano-column composite coating was formed on the surface of the microelectrode to obtain a microelectrode array modified by yttrium oxide/platinum nano-column composite coating.
  • the thickness of the yttrium oxide/platinum nanocolumn composite coating is 500 nm to 5 ⁇ m
  • the diameter of the platinum nanocolumn is 50 to 500 nm
  • the thickness of the yttrium oxide layer is 10 nm to 500 nm.
  • the porous ruthenium oxide/platinum nanocolumn composite coating has a pore diameter of 50 nm to 500 nm.
  • the platinum nanocolumn modified microelectrode array prepared in the above Examples 15 to 26 was tested by the same test method as in Example 14. The test results showed that the prepared modified layer and the microelectrode substrate had better binding force. Electrochemical resistance Low resistance, large charge injection and storage capacity, good biocompatibility, and good development potential in the field of nerve stimulation.
  • a method for preparing a microelectrode array comprising the steps of:
  • the microelectrode to be modified is placed in the above chemical deposition solution, and after being stored in a room temperature environment for 36 hours, the microelectrode is placed in water, and under the condition of a power of 600 W and a frequency of 40 KHz, ultrasonication is performed for 30 min to remove
  • the platinum nanowires with poor adhesion of the electrode substrate form a platinum nanowire modification layer with good biocompatibility, large surface area and good binding force on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • FIG. 9 and FIG. 10 are scanning electron microscope (SEM) images of the platinum nanowire-modified layer of the present embodiment at different magnifications. It can be seen from Fig. 8 that the obtained platinum nanowire modification layer has uniform morphology and no other impurities on the surface; as can be seen from Fig. 9, the surface of the obtained platinum nanowire modification layer is extremely porous and has a large surface area; It can be seen that the obtained platinum nanowires have a uniform morphology and a diameter of about 8 nm.
  • FIG. 11 is a comparison diagram of cyclic voltammetry (CV) of a platinum nanowire-modified microelectrode array and an unmodified microelectrode according to the embodiment, wherein curve 1 is a cyclic voltammetry curve of an unmodified microelectrode, and curve 2 is a curve 2
  • CV cyclic voltammetry
  • EIS electrochemical impedance
  • curve 1 is an electrochemical impedance curve of an unmodified microelectrode
  • curve 2 is The electrochemical impedance curve of the platinum nanowire-modified microelectrode array of this embodiment can be seen from FIG. 12, the platinum nanowire modification layer has lower electrochemical impedance than the unmodified microelectrode, and it is at 1 KHz.
  • the electrochemical impedance energy is as low as 1 k ⁇ .
  • a method for preparing a microelectrode array comprising the steps of:
  • the microelectrode to be modified is placed in the above chemical deposition solution, and stored in the room temperature for 36 hours in the dark, the microelectrode is placed in water, and the ultrasonic wave is 50 min under the condition of a power of 600 W and a frequency of 40 KHz.
  • the platinum nanowires with poor adhesion to the electrode substrate are removed, and a platinum nanowire modification layer with good biocompatibility, large surface area and good binding force is formed on the surface of the microelectrode, that is, a platinum nanowire-modified microelectrode array is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, and after being stored in a room temperature environment for 36 hours, the microelectrode is placed in water, and the ultrasonic wave is removed for 10 min under the condition of a power of 600 W and a frequency of 40 KHz.
  • Platinum nanowires with poor adhesion to the substrate, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 12 hours, the microelectrode is placed in water, and the ultrasonic wave is removed for 20 min under the condition of a power of 600 W and a frequency of 40 KHz.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 24 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 24 hours, and the microelectrode is placed in water at a power of 600 W and a frequency of 40 KHz, and ultrasonically removed for 30 min to remove the substrate.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • a method for preparing a microelectrode array comprising the steps of:
  • microelectrode to be modified is placed in the above chemical deposition solution, stored in a room temperature environment for 36 hours, the microelectrode is placed in water, and the ultrasonic wave is removed for 50 min under the condition of a power of 600 W and a frequency of 40 KHz.
  • Platinum nanowires with poor adhesion, and a platinum nanowire modification layer with good biocompatibility, large surface area and good adhesion are formed on the surface of the microelectrode, that is, a microelectrode array modified by platinum nanowires is obtained.
  • the platinum nanowire-modified microelectrode array prepared in the above Examples 28 to 39 was tested by the same test method as in Example 27, and the test results showed that the obtained platinum nanowire-modified layer and the microelectrode substrate were combined. Good, low electrochemical impedance, large charge injection and storage capacity, good biocompatibility, good development potential in the field of nerve stimulation force.
  • a method for preparing a microelectrode array comprising the steps of:
  • Fig. 13 is a scanning electron microscope (SEM) image of the dendritic platinum-modified layer in the present embodiment. It can be seen from the figure that after modification, dendritic platinum having a dendritic structure is formed on the surface of the microelectrode.
  • 14 to 16 are scanning electron microscope (SEM) images of dendritic platinum-modified layers of different sizes. Different sizes of dendritic platinum can be obtained by adjusting parameters such as deposition time and deposition temperature.
  • the electrodeposition time of the dendritic platinum in FIGS. 14 to 16 is 4000 s, 5000 s, and 6000 s, respectively, and the electrodeposition temperatures are 40 ° C, 50 ° C, and 60 ° C, respectively.
  • FIG. 17 is a comparison diagram of cyclic voltammetry (CV) of a dendritic platinum-modified microelectrode array and an unmodified microelectrode according to the present embodiment, wherein curve 1 is a cyclic voltammetry curve of an unmodified microelectrode, and curve 2 is a curve 2
  • the cyclic voltammetry curve of the dendritic platinum-modified microelectrode array of this example can be seen from FIG. 17 that the CV of the dendritic platinum modified layer is increased by about 44 times (from 3.7 mC/cm) compared to the unmodified microelectrode. 2 value added 162.4mC / cm 2 ), indicating that it has a superior charge storage capacity.
  • EIS electrochemical impedance
  • curve 1 is an electrochemical impedance curve of an unmodified microelectrode
  • curve 2 is The electrochemical impedance curve of the dendritic platinum-modified microelectrode array of this example.
  • the dendritic platinum modified layer has a lower electrochemical impedance than the unmodified microelectrode, which is at 1 kHz.
  • the electrochemical impedance energy is as low as 1.3k ⁇ .
  • FIG. 19 is an electrochemical stability test result of a dendritic platinum-modified microelectrode array according to the present embodiment, and a long-term high-frequency pulse experiment is performed on a microelectrode modified with dendritic platinum, and the charge storage capacity before and after the pulse is tested (calculation CV closure curve)
  • the change in the integral area of the cathode portion, the curve 1 in the figure is the CV curve of the dendritic platinum modified layer without pulse experiment, and the curve 2 is the CV after 48 h of the uninterrupted high frequency pulse of the dendritic platinum modified layer.
  • Curve, curve 3 is the CV curve after 96 hours of uninterrupted high frequency pulse of dendritic platinum modified layer. It can be seen from Fig.
  • microelectrodes used in this example were prepared by a series of micromachining processes such as photolithography (EVG 610 UV exposure machine, Austria), sputtering, etching, and the like.
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • a method for preparing a microelectrode array comprising the steps of:
  • the dendritic platinum-modified microelectrode array prepared in the above Examples 41-52 was tested by the same test method as in Example 40, and the test results showed that the prepared modified layer had better adhesion to the microelectrode substrate.

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Abstract

一种微电极阵列及其制备方法，所述微电极阵列的电极表面设置有修饰层，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。该修饰层与微电极基底的结合力较好，不容易脱落导致电极失效，且修饰后的微电极表面积增加，电化学阻抗降低，电极电荷注入容量和电荷存储能力增加，这有利于降低植入的系统功耗，改善电刺激效果。

Description

一种微电极阵列及其制备方法 技术领域
本发明涉及微电极表面修饰技术领域，特别是涉及一种微电极阵列及其制备方法
背景技术
神经刺激/记录电极作为最重要的植入式微器件之一，用以刺激神经组织或者记录神经电信号(心电、脑电、皮层电信号等等)，广泛用在脑机接口、神经生理、脑科学研究等生命科学领域，是非常重要的研究和诊疗工具。
为了减小植入创伤，同时给临床提供更多的刺激模式以及提高电刺激或记录的分辨率，神经刺激电极/记录正在朝着微型化以及阵列化方向发展----微电极阵列。然而，电极尺寸减小随着则带来电极阻抗增加的问题，并最终影响电极的刺激效率。目前，在不增加电极的几何尺寸的情况下，主要是通过表面修饰的方式增加电极的实际表面积，并改善电极的电化学性能。
具体地，目前微电极阵列表面修饰的方法大致有以下几种：1、在电极表面修饰一层铂黑(Anal.Chem.1987，59，217-218)，这种方式能使电极的电化学阻抗减小至少一个数量级，但其机械稳定性非常差，同时其修饰层中含有铅等有毒物质，使其不适用于生物医学领域的应用；2、在电极表面修饰一层铂灰(US Patent 6974533，2005)，这种涂层具有很好的机械稳定性且无毒，但其表面粗糙度不够大，使其在超高分辨率电极的表面修饰受到一定的限制；3、经氧化铱(Eng.Med.Biol.Soc.2004，4153-4156)或者导电聚合物(J.Biomed.Mater.Res.2001，56，261-272)修饰的微电极具有极好的电化学性能(如高的电荷注入能力)，但这些材料的粘附力较差，在刺激过程中，很容易从电极表面脱落下来。
发明内容
鉴于此，本发明旨在提供一种微电极阵列，所述微电极阵列的电极表面设置有修饰层，该修饰层与微电极基底的结合力好，微电极表面积大，表面粗糙度大，且绿色无毒。
第一方面，本发明提供了一种微电极阵列，所述微电极阵列的电极表面设置有修饰层，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
其中，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱的直径在50nm～500nm范围。
其中，所述铂纳米柱修饰层具有三维纳米多孔结构。
其中，所述铂纳米柱修饰层通过电沉积的方式设置。
其中，所述铂纳米柱修饰层的表面设置有氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层，所述氧化铱层的厚度为10nm～500nm。
其中，所述氧化铱/铂纳米柱复合涂层具有三维纳米多孔结构，所述氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
其中，所述铂纳米线修饰层的厚度为100nm～2μm，所述铂纳米线修饰层中的铂纳米线的直径在2nm～10nm范围。
其中，所述铂纳米线修饰层具有三维纳米多孔结构。
其中，所述铂纳米线修饰层通过化学沉积的方式设置。
其中，所述枝晶铂修饰层的厚度为500nm～10μm。
其中，所述枝晶铂修饰层中的枝晶铂的长度为200nm～10μm，宽度为50nm～2μm，厚度为5nm～500nm。
其中，所述枝晶铂修饰层通过电沉积的方式设置。
第二方面，本发明提供了一种微电极阵列的制备方法，采用电沉积或化学沉积的方法在待修饰的微电极的表面制备修饰层，形成微电极阵列，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
其中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到电沉积溶液A；
(2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液A形成三电极体系，并与电化学工作站相连接；
(3)在常温常压条件下，电沉积300～600s，所述微电极表面形成铂纳米柱修饰层，即得到微电极阵列。
其中，所述电沉积的方式为恒电位沉积、恒电流沉积或脉冲电沉积。
其中，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱直径在50nm～500nm范围，所述铂纳米柱修饰层具有三维纳米多孔结构。
其中，在所述铂纳米柱修饰层表面电沉积制备氧化铱层，具体包括：
提供铱盐溶液，在所述铱盐溶液中加入适量的氧化剂以及弱酸，混合混匀，得到电沉积溶液B；
以铂片为对电极，Ag/AgCl为参比电极，设置有铂纳米柱修饰层的微电极阵列为工作电极，与所述电沉积溶液B形成三电极体系，并与电化学工作站相连接；
在常温常压条件下，电沉积300s～600s，所述铂纳米柱修饰层表面形成氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层。
其中，所述铱盐溶液为氯铱酸、氧化铱、氯化铱、乙酰丙酮铱、六氯代铱酸纳、六氯铱酸钾、六氯铱酸铵、六硝基铱酸钾和十二羰基四铱中的一种或多种。
其中，所述氧化剂为过氧化氢、氧气、臭氧、过氧化钾和过氧化钠的一种或多种；所述弱酸为甲酸、乙酸、草酸和碳酸的一种或多种。
其中，所述电沉积溶液B中，所述铱盐的浓度为1mmol/L～5mmol/L，所述氧化剂的浓度为1mmol/L～5mmol/L，所述弱酸的浓度为1mmol/L～5mmol/L。
其中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到化学沉积溶液；
(2)将待修饰的微电极置于所述化学沉积溶液中，在室温环境中保存12～48小时，通过化学沉积的方式在微电极表面沉积大量的铂纳米线；
(3)将沉积有铂纳米线的微电极置于水中超声10min～50min，除去粘附力较差的铂纳米线，得到铂纳米线修饰层，即得到微电极阵列。
其中，所述铂纳米线修饰层的厚度为100nm～2μm，所述铂纳米线修饰层中的铂纳米线的直径在2nm～10nm范围。
其中，所述铂纳米线修饰层具有三维纳米多孔结构。
其中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入弱还原剂，混合混匀，得到电沉积溶液C；
(2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液C形成三电极体系，并与电化学工作站相连接；
(3)在35℃～60℃条件下，电沉积3000s～6000s，所述微电极表面形成枝晶铂修饰层，即得到微电极阵列。
其中，所述电沉积的方式为恒电位沉积、恒电流沉积或脉冲电沉积。
其中，所述恒电位沉积的电压为-0.3V～-0.8V，恒电流沉积的电流为-0.5μA～-1.5μA，脉冲电沉积的峰值电流密度为0.8A/cm2～2.5A/cm2。
其中，所述恒电位沉积的电压为-0.7V～-0.8V，恒电流沉积的电流为-0.8μA～-1.5μA，脉冲电沉积的峰值电流密度为1.5A/cm2～2.5A/cm2。
其中，所述铂盐溶液为硝酸铂、氯化铂、氯铂酸、六氯铂酸铵、氯铂酸钠、六氯铂酸钾和氯亚铂酸钾中的一种或多种。
其中，所述弱还原剂为甲酸、盐酸羟胺、柠檬酸、柠檬酸盐、抗坏血酸、抗坏血酸盐、对苯二酚、邻苯三酚及1，2，4苯三酚中的一种或多种。
其中，所述电沉积溶液中，所述铂盐的浓度为1mmol/L～20mmol/L，所述弱还原剂的浓度为1mmol/L～20mmol/L。
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例1制备的铂纳米柱修饰层的扫描电子显微镜(SEM)图；
图2为本发明实施例1制备的铂纳米柱修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图；
图3为本发明实施例1制备的铂纳米柱修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图；
图4为本发明实施例14制备的氧化铱层的扫描电子显微镜(SEM)图；
图5为本发明实施例14制备的氧化铱/铂纳米柱复合涂层的扫描电子显微镜(SEM)图；
图6为本发明实施例14制备的氧化铱/铂纳米柱复合涂层修饰的微电极阵列与未修饰的微电极、以及铂纳米柱层修饰的微电极阵列的循环伏安(CV)对比图；
图7为本发明实施例14制备的氧化铱/铂纳米柱复合涂层修饰的微电极阵列与未修饰的微电极、以及铂纳米柱层修饰的微电极阵列的电化学阻抗(EIS)对比图；
图8为本发明实施例27制备的铂纳米线修饰层(放大10000倍)的扫描电子显微镜(SEM)图；
图9为本发明实施例27制备的铂纳米线修饰层(放大15000倍)的扫描电子显微镜(SEM)图；
图10为本发明实施例27制备的铂纳米线修饰层(放大20000倍)的扫描电子显微镜(SEM)图；
图11为本发明实施例27制备的铂纳米线修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图；
图12为本发明实施例27制备的铂纳米线修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图；
图13～图16为本发明实施例40制备的不同尺寸枝晶铂修饰层的扫描电子显微镜(SEM)图；
图17为本发明实施例40制备的枝晶铂修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图；
图18为本发明实施例40制备的枝晶铂修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图；
图19为本发明实施例40制备的枝晶铂修饰的微电极阵列电化学稳定测试结果。
具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
第一方面，本发明实施例提供了一种微电极阵列，所述微电极阵列的电极表面设置有修饰层，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
本发明第一实施方式中，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱的直径在50nm～500nm范围。可选地，所述铂纳米柱修饰层具有三维纳米多孔结构。三维纳米多孔结构可极大地增大微电极的表面积。可选地，所述铂纳米柱修饰层通过电沉积的方式设置。通过电沉积方式设置在电极表面的修饰层与电极表面的结合力强，不易脱落。
本发明第一实施方式中，以铂纳米柱为表面修饰层，该修饰层与微电极基底的结合力较好，不容易脱落导致电极失效，并且修饰后的微电极表面积极大地增加，其电化学阻抗明显降低，电极电荷注入容量和电荷存储能力大大增加，这有利于降低植入的系统功耗，改善电刺激效果，同时该修饰层具有良好的生物相容性，使其在生物医学领域的应用大大增加。
本发明第一实施方式中，所述铂纳米柱修饰层表面设置有氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层，所述氧化铱层的厚度为10nm～500nm。可选地，氧化铱层的厚度为50nm～400nm、100nm～300nm。适合的氧化铱层厚度可以使微电极阵列具有较高的电荷存储能力。可选地，所述氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，进一步可选地为1μm～4μm、2μm～3μm。不同的厚度会使微电极具有不同大小的表面积。可选地，本发明中，所述铂纳米柱的直径为50nm～500nm，可选地，铂纳米柱的直径为200nm～300nm。适合的直径既能保证铂纳米柱层具有良好的纳米多孔结构，使其获得一个适宜的粗糙表面。可选地，所述氧化铱/铂纳米柱复合涂层具有三维纳米多孔结构，铂纳米柱层的多孔孔径在50nm～500nm范围，进一步可选地为200nm～500nm、100nm～300nm。三维纳米多孔结构可极大地增大微电极的表面积，大大增加微电极的电荷存储能力。可选地，本发明中，所述氧化铱/铂纳米柱复合涂层通过先后在所述电极表面电沉积铂纳米柱层和氧化铱层而得到。通过电化学沉积方式设置在电极表面的氧化铱/铂纳米柱复合涂层与电极表面的结合力强，不易脱落。
本发明中，所述氧化铱/铂纳米柱复合涂层包括依次设置于电极表面的铂纳米柱层和氧化铱层，由于铂纳米柱层具有纳米多孔结构，可提供一表面积较大的粗糙表面，使得铂纳米柱 层在电极与氧化铱层之间充当粘附层，既可附着更多的氧化铱，又能增加氧化铱层与电极之间的粘附力；同时，由于氧化铱层具有超高的电荷存储能力，因此本发明氧化铱/铂纳米柱复合涂层修饰的微电极阵列兼具高电荷存储能力和高稳定性。
本发明第二实施方式中，所述铂纳米线修饰层的厚度为100nm～2μm，铂纳米线的直径在2nm～10nm范围。不同的厚度会使微电极具有不同大小的表面积。可选地，所述铂纳米线修饰层具有三维纳米多孔结构。由于微电极表面具有大量的铂纳米线，从而铂纳米线与微电极表面构成三维纳米多孔结构，三维纳米多孔结构可极大地增大微电极的表面积。可选地，所述铂纳米线修饰层通过电沉积的方式设置。通过化学沉积方式设置在电极表面的修饰层与电极表面的结合力强，不易脱落。
本发明第二实施方式中，以铂纳米线为表面修饰层，该修饰层与微电极基底的结合力强，不容易脱落导致电极失效，并且修饰后的微电极表面积极大地增加，其电化学阻抗明显降低，电极电荷注入容量和电荷存储能力大大增加，这有利于降低植入的系统功耗，改善电刺激效果，同时该修饰层具有良好的生物相容性，使其在生物医学领域的应用大大增加。
本发明第三实施方式中，所述枝晶铂修饰层的厚度为500nm～10μm。不同的枝晶铂修饰层厚度会使微电极具有不同大小的表面积。
可选地，枝晶铂包括主干和沿着主干有序地生长的侧枝，枝晶铂可以为三维枝状结构也可以是二维枝状结构，当枝晶铂为三维枝状结构的时候，侧枝围绕主干在三维方向生长长度不等的侧枝。当枝晶铂为二维枝状结构的时候，枝晶铂为片状结构。本发明可以通过调整制备工艺得到不同大小和不同具体形状的枝晶铂。具体地，所述枝晶铂修饰层中的枝晶铂的长度为200nm～10μm，宽度为50nm～2μm，厚度为5nm～500nm。本发明枝晶铂中含有大量的分枝结构，枝晶铂修饰层的比表面积大大增加，且所述枝晶铂修饰层的性能较稳定。
可选地，所述枝晶铂修饰层具有三维纳米多孔结构。三维纳米多孔结构可极大地增大微电极的表面积。
可选地，所述枝晶铂修饰层通过电沉积的方式设置。通过电沉积方式设置在电极表面的修饰层与电极表面的结合力强，不易脱落，性能非常稳定。
本发明第三实施方式中，以枝晶铂为表面修饰层，该修饰层与微电极基底的结合力较好，不容易脱落导致电极失效，并且修饰后的微电极表面积极大地增加，其电化学阻抗明显降低，电极电荷注入容量和电荷存储能力大大增加，这有利于降低植入的系统功耗，改善电刺激效果，同时该修饰层具有良好的生物相容性以及机械稳定性，使其在生物医学领域的应用大大增加。
本发明实施例第一方面提供的一种微电极阵列，所述微电极阵列的电极表面设置有修饰层，该修饰层与微电极基底的结合力较好，不容易脱落导致电极失效，并且修饰后的微电极表面积极大地增加，其电化学阻抗明显降低，电极电荷注入容量和电荷存储能力大大增加，这有利于降低植入的系统功耗，改善电刺激效果，同时该修饰层具有良好的生物相容性，使其在生物医学领域的应用大大增加。
第二方面，本发明实施例提供了一种微电极阵列的制备方法，采用电沉积或化学沉积的方法在待修饰的微电极的表面制备修饰层，形成微电极阵列，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
本发明第一实施方式中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到电沉积溶 液A；
(2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液A形成三电极体系，并与电化学工作站相连接；
(3)在常温常压条件下，电沉积300～600s，所述微电极表面形成铂纳米柱修饰层，即得到微电极阵列。
可选地，所述铂盐溶液为硝酸铂、氯化铂、氯铂酸、六氯铂酸铵、氯铂酸钠、六氯铂酸钾和氯亚铂酸钾中的一种或多种。
本发明中，加入的弱还原剂可与铂盐发生反应，使电化学还原铂离子并在微电极表面形成单质铂的速度加快，从而形成更为多孔的结构。所述弱还原剂为甲酸、盐酸羟胺、柠檬酸、柠檬酸盐、抗坏血酸、抗坏血酸盐、对苯二酚、邻苯三酚及1，2，4苯三酚中的一种或多种。
可选地，所述电沉积溶液A中，铂盐的浓度为1mmol/L～20mmol/L，弱还原剂的浓度为1mmol/L～20mmol/L。
可选地，所述电沉积的方式为恒电位沉积(电压为-0.1V～-0.6V)、恒电流沉积(电流为-0.1μA～-0.7μA)或脉冲电沉积(峰值电流密度为0.1A/cm2～1A/cm2)。
可选地，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱直径在50nm～500nm范围。
可选地，所述铂纳米柱修饰层具有三维纳米多孔结构。
可选地，待修饰的微电极可以是平面微电极、针式微电极等。
可选地，在所述铂纳米柱修饰层表面电沉积制备氧化铱层，具体包括：
提供铱盐溶液，在所述铱盐溶液中加入适量的氧化剂以及弱酸，混合混匀，得到电沉积溶液B；
以铂片为对电极，Ag/AgCl为参比电极，设置有铂纳米柱修饰层的微电极阵列为工作电极，与所述电沉积溶液B形成三电极体系，并与电化学工作站相连接；
在常温常压条件下，电沉积300s～600s，所述铂纳米柱修饰层表面形成氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层。
可选地，所述铱盐溶液为氯铱酸、氧化铱、氯化铱、乙酰丙酮铱、六氯代铱酸纳、六氯铱酸钾、六氯铱酸铵、六硝基铱酸钾和十二羰基四铱中的一种或多种。
可选地，所述的氧化剂为过氧化氢、氧气、臭氧、过氧化钾和过氧化钠的一种或多种。
可选地，所述的弱酸为甲酸、乙酸、草酸和碳酸的一种或多种。
可选地，所述电沉积溶液A中，铂盐的浓度为1mmol/L～20mmol/L(例如可以是2mmol/L、5mmol/L、10mmol/L、15mmol/L、18mmol/L)，弱还原剂的浓度为1mmol/L～20mmol/L(例如可以是2mmol/L、5mmol/L、10mmol/L、15mmol/L、18mmol/L)。
可选地，所述电沉积溶液B中，所述铱盐的浓度为1mmol/L～5mmol/L(例如可以是1mmol/L、2mmol/L、3mmol/L、4mmol/L、5mmol/L)，所述氧化剂的浓度为1mmol/L～5mmol/L(例如可以是1mmol/L、2mmol/L、3mmol/L、4mmol/L、5mmol/L)，所述弱酸的浓度为1mmol/L～5mmol/L(例如可以是1mmol/L、2mmol/L、3mmol/L、4mmol/L、5mmol/L)。
可选地，所述电沉积的方式为恒电位沉积(电压为-0.1V～-0.6V)、恒电流沉积(电流为-0.1μA～-0.7μA)或脉冲电沉积(峰值电流密度为0.1A/cm2～1A/cm2)。
可选地，所述氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，进一步可选地为1μm～4μm、2μm～3μm，所述铂纳米柱的直径为50nm～500nm，所述氧化铱层的厚度为10nm～ 500nm，可选地，氧化铱层的厚度为50nm～400nm、100nm～300nm。
可选地，所述铂纳米柱层具有三维纳米多孔结构。
可选地，待修饰的微电极可以是平面微电极、针式微电极等。
本发明第二实施方式中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到化学沉积溶液；
(2)将待修饰的微电极置于所述化学沉积溶液中，在室温环境中保存12～48小时，通过化学沉积的方式在微电极表面沉积大量的铂纳米线；
(3)将沉积有铂纳米线的微电极置于水中超声10min～50min，除去粘附力较差的铂纳米线，得到铂纳米线修饰层，即得到微电极阵列。
可选地，所述铂盐溶液为硝酸铂、氯化铂、氯铂酸、六氯铂酸铵、氯铂酸钠、六氯铂酸钾和氯亚铂酸钾中的一种或多种。
可选地，加入的弱还原剂可与铂盐发生反应，将铂离子还原成铂单质，由于还原性很弱，导致反应速率很慢，从而生长出大量细长的铂纳米线并在基质表面形成更为多孔的结构。所述弱还原剂为甲酸、盐酸羟胺、柠檬酸、柠檬酸盐、抗坏血酸、抗坏血酸盐、对苯二酚、邻苯三酚及1，2，4苯三酚中的一种或多种。
可选地，所述化学沉积溶液中，铂盐的浓度为1mmol/L～20mmol/L，弱还原剂的浓度为1mmol/L～20mmol/L。
可选地，步骤(2)的化学沉积过程可在避光条件下进行。
可选地，超声过程的功率为600W，频率为40KHz。
可选地，所述铂纳米线修饰层的厚度为100nm～2μm，所述铂纳米线修饰层中的铂纳米线直径在2nm～10nm范围。
可选地，所述铂纳米线修饰层具有三维纳米多孔结构。
可选地，待修饰的微电极可以是平面微电极、针式微电极等。
本发明第三实施方式中，所述的微电极阵列的制备方法，包括：
(1)提供铂盐溶液，在所述铂盐溶液中加入弱还原剂，混合混匀，得到电沉积溶液C；
(2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液C形成三电极体系，并与电化学工作站相连接；
(3)在35℃～60℃条件下，电沉积3000s～6000s，所述微电极表面形成枝晶铂修饰层，即得到微电极阵列。
可选地，步骤(1)中，对电沉积溶液通入氩气30min～1h以去除溶液中的空气，防止镀层发生氧化，有助于产生枝晶的结构。
可选地，在步骤(2)之前，对电极进行表面活化，所述表面活化的操作如下：
以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，形成三电极体系，并与电化学工作站相连接，在稀硫酸溶液中，以CV循环(循环伏安法)的方式，在-0.2V～1.2V范围内，循环扫描30～100圈。对电极进行表面活化以去除电极表面的杂质，有助于后续电沉积操作，提高镀层的稳定性。
可选地，所述铂盐溶液为硝酸铂、氯化铂、氯铂酸、六氯铂酸铵、氯铂酸钠、六氯铂酸钾和氯亚铂酸钾中的一种或多种；所述电沉积溶液中，铂盐的浓度为1mmol/L～20mmol/L。
可选地，所述弱还原剂包括甲酸、盐酸羟胺、柠檬酸、柠檬酸盐、抗坏血酸、抗坏血酸 盐、对苯二酚、邻苯三酚和1，2，4苯三酚中的一种或多种；所述电沉积溶液C中，所述弱还原剂的浓度为1mmol/L～20mmol/L。
本发明中加入的弱还原剂如甲酸(HCOOH)可与铂盐发生反应，过程中HCOOH会被氧化而产生二氧化碳(CO2)，并形成多孔的铂结构，而本发明高温以及高电位(或者高电流)则可以促进反应发生，使铂离子还原速度加快，并在微电极表面形成更为多孔的铂结构。
可选地，步骤(3)中沉积温度为50℃～60℃。
可选地，所述电沉积的方式为恒电位沉积、恒电流沉积或脉冲电沉积。进一步可选地，所述恒电位沉积的电压为-0.3V～-0.8V，恒电流沉积的电流为-0.5μA～-1.5μA，脉冲电沉积的峰值电流密度为0.8A/cm2～2.5A/cm2。可选地，所述恒电位沉积的电压为-0.7V～-0.8V，恒电流沉积的电流为-0.8μA～-1.5μA，脉冲电沉积的峰值电流密度为1.5A/cm2～2.5A/cm2。
可选地，所述枝晶铂修饰层的厚度为500nm～10μm。
可选地，所述枝晶铂修饰层具有三维纳米多孔结构。
可选地，待修饰的微电极可以是平面微电极、针式微电极等。
本发明第二方面提供的一种微电极阵列的制备方法，该方法溶液配制简单，且无其他有毒物质(如铅等添加剂)，条件温和、简单易行，能够快速在微电极阵列表面制备修饰层，且该修饰层与微电极基底的结合力较好，能极大地增加微电极表面积，使其具有非常优越的电化学性能，因而大大地拓展了微电极阵列在神经刺激领域的应用。
实施例1
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯化铂(PtCl4)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
图1为本实施例铂纳米柱修饰层的扫描电子显微镜(SEM)图，从图中可以看出，所得的铂纳米柱形貌均一，直径约为200nm。图2为本实施例铂纳米柱修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图，图中，曲线1为未修饰的微电极的循环伏安曲线，曲线2为本实施例铂纳米柱修饰的微电极阵列的循环伏安曲线，从图2中可以看出，相比未修饰的微电极，铂纳米柱修饰层的CV面积更大，表明其具有更为优越的电荷存储能力。图3为本实施例铂纳米柱修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图，图中，曲线1为未修饰的微电极的电化学阻抗曲线，曲线2为本实施例铂纳米柱修饰的微电极阵列的电化学阻抗曲线，从图3中可以看出，相比未修饰的微电极，铂纳米柱修饰层具有更低的电化学阻抗，其在1KHz时的电化学阻抗能低至2kΩ。
实施例2
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的硝酸铂(Pt(NO3)4)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例3
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯铂酸(H2PtCl6)和20mmol盐酸羟胺(NH2OH·HCl)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电流的沉积方式，在-0.3μA(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例4
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸(H2PtCl6)和1mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例5
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的六氯铂酸铵((NH4)2PtCl6)和5mmol柠檬酸钠(Na3C6H5O7)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例6
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钠(Na2PtCl6)和10mmol柠檬酸(C6H8O7)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例7
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钾(K2PtCl6)和20mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例8
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯铂酸钾(K2PtCl6)和5mmol 甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电流的沉积方式，在-0.3μA(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例9
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯亚酸钾(K2PtCl4)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电压的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例10
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和5mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例11
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和10mmol柠檬酸(C6H8O7)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例12
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以恒电压的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
实施例13
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和1mmol甲酸(HCOOH)，轻轻摇晃混匀，形成电沉积溶液；
(2)在上述电沉积溶液中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
采用与实施例1中相同的测试方法对上述实施例2～13制备获得的铂纳米柱修饰的微电极阵列进行测试，测试结果表明所制得的修饰层与微电极基底的结合力较好，电化学阻抗低，电荷注入及存储能力大、生物相容性好，在神经刺激领域具有很好的发展潜力。
实施例14
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯化铂(PtCl4)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、1mmol的氯化铱(IrCl4)、2mmol的双氧水(H2O2)以及4mmol的草酸(H2C2O4)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰层修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱修饰层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
图4为本发明实施例14氧化铱层的扫描电子显微镜(SEM)图，图5为本发明实施例14氧化铱/铂纳米柱复合涂层的扫描电子显微镜(SEM)图，从图中可以看出，铂纳米柱层具有纳米多孔的表面结构，而氧化铱表面则很平滑，当氧化铱电镀在铂纳米柱表面形成氧化铱/铂纳米柱复合涂层，该复合涂层也具有纳米多孔的表面，多孔孔径为50nm～500nm。本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，所述氧化铱层的厚度为10nm～500nm。
图6为本发明实施例14的氧化铱/铂纳米柱复合涂层修饰的微电极阵列与未修饰的微电极以及铂纳米柱的循环伏安(CV)对比图，图中，曲线1为未修饰的微电极的循环伏安曲线，曲线2为本实施例铂纳米柱层修饰的微电极阵列的循环伏安曲线，曲线3为氧化铱/铂纳米柱复合涂层修饰的微电极阵列的循环伏安曲线，从图6中可以看出，相比未修饰的微电极以及铂纳米柱修饰的微电极阵列，本发明实施例的氧化铱/铂纳米柱复合涂层的CV面积更大，表明其具有更为优越的电荷存储能力。
图7为本发明实施例14的氧化铱/铂纳米柱复合涂层修饰的微电极阵列与未修饰的微电极以及铂纳米柱修饰的微电极阵列的电化学阻抗(EIS)对比图，图中，曲线1为未修饰的微电极的电化学阻抗曲线，曲线2为本实施例铂纳米柱层修饰的微电极阵列的电化学阻抗曲线，曲线3为本实施例氧化铱/铂纳米柱复合涂层修饰的微电极阵列的电化学阻抗曲线，从图7中可以看出，相比未修饰的微电极以及铂纳米柱修饰的微电极阵列，本发明实施例的氧化铱/铂纳米柱复合涂层具有更低的电化学阻抗，其在1KHz时的电化学阻抗能低至2kΩ。
实施例15
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的六氯铂酸铵((NH4)2PtCl6)和5mmol柠檬酸钠(Na3C6H5O7)，轻轻摇晃混匀，形成电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸钠(Cl6H12IrNa2O6)、5mmol的双氧水(H2O2)以及4mmol的甲酸(HCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱层修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为1μm～5μm，铂纳米柱的直径为200～300nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例16
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的硝酸铂(Pt(NO3)4)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸铵(Cl6H15IrN2O6)、5mmol的过氧化钾(K2O2)以及4mmol的乙酸(CH3COOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，以恒电流的沉积方式，在-0.3μA(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱层修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为2～4μm，铂纳米柱的直径为200～400nm，氧化铱层的厚度为200nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为200nm～500nm。
实施例17
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钾(K2PtCl6)和20mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯化铱(IrCl4)、5mmol的过氧化钠(Na2O2)以及4mmol的草酸(HOOCCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱层修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层修饰层，即得到氧化 铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～2μm，铂纳米柱的直径为200～300nm，氧化铱层的厚度为200nm～400nm。氧化铱/铂纳米柱复合涂层的多孔孔径为100nm～300nm。
实施例18
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯亚酸钾(K2PtCl4)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的乙酰丙酮铱(C15H21IrO6)、5mmol的双氧水(H2O2)以及4mmol的草酸(HOOCCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及铂纳米柱修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为1μm～3μm，铂纳米柱的直径为50～200nm，氧化铱层的厚度为10nm～200nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～200nm。
实施例19
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和20mmol乙酸(CH3COOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸(H2IrCl6·6H2O)、5mmol的过氧化钠(Na2O2)以及4mmol的甲酸(HCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电压的沉积方式，在-0.1V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层修饰层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为200～300nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例20
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的硝酸铂(Pt(NO3)4)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的六硝基铱酸钾(IrK3N6O12)、5mmol的过氧化钠(Na2O2)以及4mmol的乙酸(CH3COOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电流的沉积方式，在-0.3μA(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例21
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的六氯铂酸铵((NH4)2PtCl6)和5mmol柠檬酸钠(Na3C6H5O7)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的十二羰基四铱(Ir4(CO)12)、5mmol的双氧水(H2O2)以及4mmol的柠檬酸(C6H8O7)、轻轻摇晃混匀，形成氧化铱电沉积溶液B：
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电流的沉积方式，在-0.3μA(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例22
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钠(Na2PtCl6)和10mmol柠檬酸(C6H8O7)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸钠(Cl6H12IrNa2O6)、5mmol的过氧化钾(K2O2)以及4mmol的草酸(HOOCCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例23
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钾(K2PtCl6)和20mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol氯化铱(IrCl4)、5mmol的双氧水(H2O2)以及4mmol的柠檬酸(C6H8O7)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列；
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例24
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯亚酸钾(K2PtCl4)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸钠(Cl6H12IrNa2O6)、5mmol的双氧水(H2O2)以及4mmol的草酸(HOOCCOOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在-0.1V(vsAg/AgCl)条件下，在微电极表面形成铂纳米柱层，即得到铂纳米柱修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层修饰层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例25
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和5mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯铱酸钠(Cl6H12IrNa2O6)、5mmol的过氧化钾(K2O2)以及4mmol的柠檬酸(C6H8O7)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，在微电极表面形成铂纳米柱层，即得到铂纳米柱层修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
实施例26
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯铂酸(H2PtCl6)和20mmol盐酸羟胺(NH2OH·HCl)，轻轻摇晃混匀，形成铂纳米柱电沉积溶液A；
(2)在室温环境下，在容器中加入1L水、3mmol的氯化铱(IrCl4)、5mmol的过氧化钾(K2O2)以及4mmol的乙酸(CH3COOH)、轻轻摇晃混匀，形成氧化铱电沉积溶液B；
(3)在上述铂纳米柱电沉积溶液A中，置入铂片、Ag/AgCl参比电极以及待修饰的微电极，并与电化学工作站相连接，以脉冲电沉积的方式，在脉冲电流占空比为5μs：500μs，峰值电流密度为2.5A/cm2的条件下，在微电极表面形成铂纳米柱修饰层，即得到铂纳米柱修饰的微电极阵列。
(4)在上述氧化铱电沉积溶液B中，置入铂片、Ag/AgCl参比电极以及上述铂纳米柱层修饰的微电极，并与电化学工作站相连接，以恒电位的沉积方式，在0.5V(vsAg/AgCl)条件下，电沉积300～600s，在微电极表面形成氧化铱/铂纳米柱复合涂层，即得到氧化铱/铂纳米柱复合涂层修饰的微电极阵列。
本实施例中，氧化铱/铂纳米柱复合涂层的厚度为500nm～5μm，铂纳米柱的直径为50～500nm，氧化铱层的厚度为10nm～500nm。氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
采用与实施例14中相同的测试方法对上述实施例15～26制备获得的铂纳米柱修饰的微电极阵列进行测试，测试结果表明所制得的修饰层与微电极基底的结合力较好，电化学阻 抗低，电荷注入及存储能力大、生物相容性好，在神经刺激领域具有很好的发展潜力。
实施例27
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯化铂(PtCl4)和6mmol甲酸(HCOOH)，轻轻摇晃混匀，形成化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时后，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与电极基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
图8，图9以及图10为本实施例铂纳米线修饰层在不同放大倍率下的扫描电子显微镜(SEM)图。从图8可以看出，所得的铂纳米线修饰层形貌均一，表面没有其他杂质；从图9可以看出，所得的铂纳米线修饰层表面极为的粗糙多孔，表面积很大；从图10可以看出，所得的铂纳米线形貌均一，直径约为8nm。
图11为本实施例铂纳米线修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图，图中，曲线1为未修饰的微电极的循环伏安曲线，曲线2为本实施例铂纳米线修饰的微电极阵列的循环伏安曲线，从图4中可以看出，相比未修饰的微电极，铂纳米线修饰层的CV面积更大，表明其具有更为优越的电荷存储能力。图12为本实施例铂纳米线修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图，图中，曲线1为未修饰的微电极的电化学阻抗曲线，曲线2为本实施例铂纳米线修饰的微电极阵列的电化学阻抗曲线，从图12中可以看出，相比未修饰的微电极，铂纳米线修饰层具有更低的电化学阻抗，其在1KHz时的电化学阻抗能低至1kΩ。
实施例28
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、2mmol的硝酸铂(Pt(NO3)4)和8mmol甲酸(HCOOH)，轻轻摇晃混匀，形成化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中避光保存36小时后，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声50min，除去与电极基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例29
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的六氯铂酸铵((NH4)2PtCl6)和10mmol柠檬酸钠(Na3C6H5O7)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时后，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声10min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例30
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、14mmol的氯铂酸(H2PtCl6)和1mmol甲 酸(HCOOH)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存12小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声20min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例31
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯铂酸钠(Na2PtCl6)和5mmol柠檬酸(C6H8O7)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存24小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例32
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、8mmol的氯铂酸(H2PtCl6)和8mmol盐酸羟胺(NH2OH·HCl)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例33
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例34
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯亚酸钾(K2PtCl4)和1mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例35
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、15mmol的氯铂酸钾(K2PtCl6)和1mmol 柠檬酸(C6H8O7)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例36
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和15mmol甲酸(HCOOH)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例37
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和20mmol抗坏血酸(C6H8O6)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例38
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯铂酸钾(K2PtCl6)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存24小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声30min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
实施例39
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和10mmol柠檬酸(C6H8O7)，轻轻摇晃混匀，化学沉积溶液；
(2)将待修饰的微电极置于上述化学沉积溶液中，在室温环境中保存36小时，将微电极置于水中，在功率为600W，频率为40KHz的条件下，超声50min，除去与基底粘附力较差的铂纳米线，微电极表面则形成一层生物相容性好、表面积大以及结合力好的铂纳米线修饰层，即得到铂纳米线修饰的微电极阵列。
采用与实施例27中相同的测试方法对上述实施例28～39制备获得的铂纳米线修饰的微电极阵列进行测试，测试结果表明所制得的铂纳米线修饰层与微电极基底的结合力较好，电化学阻抗低，电荷注入及存储能力大、生物相容性好，在神经刺激领域具有很好的发展潜 力。
实施例40
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯化铂(PtCl4)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在35℃条件下，以恒电位的沉积方式，在-0.3V(vsAg/AgCl)条件下，电沉积3000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
图13为本实施例中枝晶铂修饰层的扫描电子显微镜(SEM)图，从图中可以看出，经修饰后，微电极表面形成了具有枝晶结构的枝晶铂。图14～图16为不同尺寸枝晶铂修饰层的扫描电子显微镜(SEM)图，通过调整沉积时间和沉积温度等参数可以得到不同尺寸的枝晶铂。图14～图16中的枝晶铂的电沉积时间分别是4000s，5000s以及6000s，电沉积温度分别是40℃，50℃以及60℃。图17为本实施例枝晶铂修饰的微电极阵列与未修饰的微电极的循环伏安(CV)对比图，图中，曲线1为未修饰的微电极的循环伏安曲线，曲线2为本实施例枝晶铂修饰的微电极阵列的循环伏安曲线，从图17中可以看出，相比未修饰的微电极，枝晶铂修饰层的CV增加约44倍(从3.7mC/cm2增值162.4mC/cm2)，表明其具有更为优越的电荷存储能力。图18为本实施例枝晶铂修饰的微电极阵列与未修饰的微电极的电化学阻抗(EIS)对比图，图中，曲线1为未修饰的微电极的电化学阻抗曲线，曲线2为本实施例枝晶铂修饰的微电极阵列的电化学阻抗曲线，从图18中可以看出，相比未修饰的微电极，枝晶铂修饰层具有更低的电化学阻抗，其在1KHz时的电化学阻抗能低至1.3kΩ。图19为本实施例枝晶铂修饰的微电极阵列的电化学稳定测试结果，对修饰有枝晶铂的微电极进行长期高频率脉冲实验，并测试脉冲前后的电荷存储能力(计算CV闭合曲线中，阴极部分的积分面积所得)的变化，图中曲线1为没有进行脉冲实验的枝晶铂修饰层的CV曲线图，曲线2为对枝晶铂修饰层不间断高频脉冲48h后的CV曲线图，曲线3为对枝晶铂修饰层不间断高频脉冲96h后的CV曲线图，从图19可以看出，经长时间高频脉冲(超过2×106次)，枝晶铂修饰层的电荷存储能力仅有很小的损失(小于2％)，表明本发明实施例所制备的枝晶铂修饰层具有极好的长期稳定性。
本实施例中所使用的微电极是通过一系列微加工工艺制备完成，如光刻(EVG610紫外曝光机，奥地利)、溅射、刻蚀等。
实施例41
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的硝酸铂(Pt(NO3)4)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在50℃条件下，以恒电位的沉积方式，在-0.5V(vsAg/AgCl)条件下，电沉积5000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例42
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、1mmol的氯铂酸(H2PtCl6)和8mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在60℃条件下，以恒电流的沉积方式，以-1.0μA(vsAg/AgCl)的电流，电沉积3000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例43
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸(H2PtCl6)和1mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在55℃环境中，以脉冲电沉积的方式，以占空比为5μs：500μs、峰值电流密度为2.5A/cm2的脉冲电流，电沉积3000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例44
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的六氯铂酸铵((NH4)2PtCl6)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在60℃条件下，以脉冲电沉积的方式，以占空比为5μs：500μs、峰值电流密度为1.5A/cm2的脉冲电流，电沉积5000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例45
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钠(Na2PtCl6)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在45℃条件下，以恒电位的沉积方式，以-0.8V(vsAg/AgCl)的电位，电沉积3000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例46
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、5mmol的氯铂酸钾(K2PtCl6)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在45℃条件下，以恒电位的沉积方式，以-0.6V(vsAg/AgCl)的电位，电沉积4000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例47
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯铂酸钾(K2PtCl6)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在50℃条件下，以恒电流的沉积方式，以-0.5μA(vsAg/AgCl)的电流，电沉积6000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例48
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、10mmol的氯亚酸钾(K2PtCl4)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在40℃条件下，以恒电流的沉积方式，以-1.5μA(vsAg/AgCl)的电流，电沉积5000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例49
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和5mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在60℃条件下，以脉冲电沉积的方式，以占空比为5μs：500μs、峰值电流密度为0.8A/cm2的脉冲电流，电沉积6000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例50
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯亚酸钾(K2PtCl4)和10mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在40℃条件下，以脉冲电沉积的方式，以占空比为5μs：500μs、峰值电流密度为2.5A/cm2的脉冲电流，电沉积5000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例51
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和20mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在50℃条件下，以恒电位的沉积方式，在-0.3V(vsAg/AgCl)条件下，电沉积6000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
实施例52
一种微电极阵列的制备方法，包括以下步骤：
(1)在室温环境下，在容器中加入1L水、20mmol的氯铂酸(H2PtCl6)和1mmol甲酸(HCOOH)，轻轻摇晃混匀，并通入氩气30min后，形成电沉积溶液C；
(2)在上述电沉积溶液C中，置入铂片、Ag/AgCl参比电极以及微电极，并与电化学工作站相连接，在40℃条件下，以恒电位的沉积方式，在-0.8V(vsAg/AgCl)条件下，电沉积3000s，在微电极表面形成枝晶铂修饰层，即得到枝晶铂修饰的微电极阵列。
采用与实施例40中相同的测试方法对上述实施例41-52制备获得的枝晶铂修饰的微电极阵列进行测试，测试结果表明所制得的修饰层与微电极基底的结合力较好，电化学阻抗低，电荷注入及存储能力大、生物相容性好，在神经刺激领域具有很好的发展潜力。

Claims (30)

  1. 一种微电极阵列，其特征在于，所述微电极阵列的电极表面设置有修饰层，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
  2. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱的直径在50nm～500nm范围。
  3. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米柱修饰层具有三维纳米多孔结构。
  4. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米柱修饰层通过电沉积的方式设置。
  5. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米柱修饰层的表面设置有氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层，所述氧化铱层的厚度为10nm～500nm。
  6. 如权利要求5所述的微电极阵列，其特征在于，所述氧化铱/铂纳米柱复合涂层具有三维纳米多孔结构，所述氧化铱/铂纳米柱复合涂层的多孔孔径为50nm～500nm。
  7. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米线修饰层的厚度为100nm～2μm，所述铂纳米线修饰层中的铂纳米线的直径在2nm～10nm范围。
  8. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米线修饰层具有三维纳米多孔结构。
  9. 如权利要求1所述的微电极阵列，其特征在于，所述铂纳米线修饰层通过化学沉积的方式设置。
  10. 如权利要求1所述的微电极阵列，其特征在于，所述枝晶铂修饰层的厚度为500nm～10μm。
  11. 如权利要求1所述的微电极阵列，其特征在于，所述枝晶铂修饰层中的枝晶铂的长度为200nm～10μm，宽度为50nm～2μm，厚度为5nm～500nm。
  12. 如权利要求1所述的微电极阵列，其特征在于，所述枝晶铂修饰层通过电沉积的方式设置。
  13. 一种微电极阵列的制备方法，其特征在于，采用电沉积或化学沉积的方法在待修饰的微电极的表面制备修饰层，形成微电极阵列，所述修饰层包括铂纳米柱修饰层、铂纳米线修饰层或枝晶铂修饰层。
  14. 如权利要求13所述的微电极阵列的制备方法，其特征在于，包括：
    (1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到电沉积溶液A；
    (2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液A形成三电极体系，并与电化学工作站相连接；
    (3)在常温常压条件下，电沉积300～600s，所述微电极表面形成铂纳米柱修饰层，即得到微电极阵列。
  15. 如权利要求14所述的微电极阵列的制备方法，其特征在于，所述电沉积的方式为恒电位沉积、恒电流沉积或脉冲电沉积。
  16. 如权利要求13所述的微电极阵列的制备方法，其特征在于，所述铂纳米柱修饰层的厚度为500nm～5μm，所述铂纳米柱修饰层中的铂纳米柱直径在50nm～500nm范围，所述铂纳米柱修饰层具有三维纳米多孔结构。
  17. 如权利要求14所述的微电极阵列的制备方法，其特征在于，在所述铂纳米柱修饰层表面电沉积制备氧化铱层，具体包括：
    提供铱盐溶液，在所述铱盐溶液中加入适量的氧化剂以及弱酸，混合混匀，得到电沉积溶液B；
    以铂片为对电极，Ag/AgCl为参比电极，设置有铂纳米柱修饰层的微电极阵列为工作电极，与所述电沉积溶液B形成三电极体系，并与电化学工作站相连接；
    在常温常压条件下，电沉积300s～600s，所述铂纳米柱修饰层表面形成氧化铱层，所述铂纳米柱修饰层和所述氧化铱层形成氧化铱/铂纳米柱复合涂层。
  18. 如权利要求17所述的微电极阵列的制备方法，其特征在于，所述铱盐溶液为氯铱酸、氧化铱、氯化铱、乙酰丙酮铱、六氯代铱酸纳、六氯铱酸钾、六氯铱酸铵、六硝基铱酸钾和十二羰基四铱中的一种或多种。
  19. 如权利要求17所述的微电极阵列的制备方法，其特征在于，所述氧化剂为过氧化氢、氧气、臭氧、过氧化钾和过氧化钠的一种或多种；所述弱酸为甲酸、乙酸、草酸和碳酸的一种或多种。
  20. 如权利要求17所述的微电极阵列的制备方法，其特征在于，所述电沉积溶液B中，所述铱盐的浓度为1mmol/L～5mmol/L，所述氧化剂的浓度为1mmol/L～5mmol/L，所述弱酸的浓度为1mmol/L～5mmol/L。
  21. 如权利要求13所述的微电极阵列的制备方法，其特征在于，包括：
    (1)提供铂盐溶液，在所述铂盐溶液中加入适量的弱还原剂，混合混匀，得到化学沉积溶液；
    (2)将待修饰的微电极置于所述化学沉积溶液中，在室温环境中保存12～48小时，通过化学沉积的方式在微电极表面沉积大量的铂纳米线；
    (3)将沉积有铂纳米线的微电极置于水中超声10min～50min，除去粘附力较差的铂纳米线，得到铂纳米线修饰层，即得到微电极阵列。
  22. 如权利要求13所述的微电极阵列的制备方法，其特征在于，所述铂纳米线修饰层的厚度为100nm～2μm，所述铂纳米线修饰层中的铂纳米线的直径在2nm～10nm范围。
  23. 如权利要求13所述的微电极阵列的制备方法，其特征在于，所述铂纳米线修饰层具有三维纳米多孔结构。
  24. 如权利要求13所述的微电极阵列的制备方法，其特征在于，包括：
    (1)提供铂盐溶液，在所述铂盐溶液中加入弱还原剂，混合混匀，得到电沉积溶液C；
    (2)以铂片为对电极，Ag/AgCl为参比电极，待修饰的微电极为工作电极，与所述电沉积溶液C形成三电极体系，并与电化学工作站相连接；
    (3)在35℃～60℃条件下，电沉积3000s～6000s，所述微电极表面形成枝晶铂修饰层，即得到微电极阵列。
  25. 如权利要求24所述的微电极阵列的制备方法，其特征在于，所述电沉积的方式为恒电位沉积、恒电流沉积或脉冲电沉积。
  26. 如权利要求25所述的微电极阵列的制备方法，其特征在于，所述恒电位沉积的电压 为-0.3V～-0.8V，恒电流沉积的电流为-0.5μA～-1.5μA，脉冲电沉积的峰值电流密度为0.8A/cm2～2.5A/cm2。
  27. 如权利要求26所述的微电极阵列的制备方法，其特征在于，所述恒电位沉积的电压为-0.7V～-0.8V，恒电流沉积的电流为-0.8μA～-1.5μA，脉冲电沉积的峰值电流密度为1.5A/cm2～2.5A/cm2。
  28. 如权利要求14、21或24所述的微电极阵列的制备方法，其特征在于，所述铂盐溶液为硝酸铂、氯化铂、氯铂酸、六氯铂酸铵、氯铂酸钠、六氯铂酸钾和氯亚铂酸钾中的一种或多种。
  29. 如权利要求14、21或24所述的微电极阵列的制备方法，其特征在于，所述弱还原剂为甲酸、盐酸羟胺、柠檬酸、柠檬酸盐、抗坏血酸、抗坏血酸盐、对苯二酚、邻苯三酚及1，2，4苯三酚中的一种或多种。
  30. 如权利要求14、21或24所述的微电极阵列的制备方法，其特征在于，所述电沉积溶液A、化学沉积溶液或电沉积溶液C中，所述铂盐的浓度为1mmol/L～20mmol/L，所述弱还原剂的浓度为1mmol/L～20mmol/L。
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