CN117907396A - Microelectrode system of three-dimensional micro-column array, electrochemical sensor and preparation method - Google Patents
Microelectrode system of three-dimensional micro-column array, electrochemical sensor and preparation method Download PDFInfo
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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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Abstract
The embodiment of the application relates to the technical field of electrochemical detection, in particular to a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method, wherein the microelectrode system comprises: a substrate, an electrode layer and an insulating layer arranged on the substrate; the electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array is adopted as a working electrode; the pattern of the ultra-micro circular electrode array is obtained by performing alignment on the three-electrode pattern, and the electrode units of the ultra-micro circular electrode array are mutually isolated through an insulating layer. The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, which greatly increases the specific surface area, improves the sensitivity of an electrode to a target substance, can provide continuous electric field distribution and improves the response stability.
Description
Technical Field
The embodiment of the application relates to the technical field of electrochemical detection, in particular to a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method.
Background
The electrode system is a core component of the electrochemical sensor and the detection instrument, not only the carrier fixed by the sensitive film, but also the transducer of the electrochemical signal, and the performance of the electrode system directly influences the detection performance of the electrochemical luminescence sensor. In the electrode system, the microelectrode has excellent electrochemical characteristics of high mass transfer rate, high current density, high response speed and the like. However, due to miniaturization of the electrode, the area of the sensitive surface of the electrode is greatly reduced, and the sensitivity is also reduced. Also, as the electrode size decreases, edge effects and tip effects significantly increase, so that stability of the electrode system is deteriorated. How to improve the sensitivity and stability of detection as much as possible while miniaturizing the electrode system, to realize better detection performance, and gradually becomes a research hot spot.
The conventional electrochemical luminescence sensor uses a separated working electrode, reference electrode and counter electrode three-electrode system, is not compatible with a back-end circuit, is not easy to miniaturize, integrate and mass-produce, and limits the practical progress of the electrochemical sensor. The traditional electrochemical sensor uses a discrete electrode system with conventional size, is difficult to be compatible with an integrated circuit at the rear end, is not easy to miniaturize, integrate and produce in batches, and greatly limits the practical application and development of the sensor.
Disclosure of Invention
The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method.
To solve the above technical problem, in a first aspect, an embodiment of the present application provides a microelectrode system of a three-dimensional micro-column array, including: a substrate, an electrode layer and an insulating layer arranged on the substrate; the electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array is adopted as a working electrode; the ultra-micro circular disk array is formed by overlapping three electrode patterns, and the ultra-micro circular electrode array units are mutually isolated through an insulating layer.
In some exemplary embodiments, the electrode layer includes a disk-shaped working electrode and a circular ring-shaped counter electrode in concentric symmetric distribution; the disc-shaped working electrode adopts a three-dimensional ultramicroelectrode array, and the radius of the disc of the three-dimensional ultramicroelectrode array is 5-20 mu m; the micro-electric column spacing of the disc-shaped working electrode is 50-300 mu m.
In some exemplary embodiments, the counter electrode comprises three electrodes; the working radius of the three electrodes is 1 mm-3 mm; the radius of the working electrode is 2 mm-6 mm.
In some exemplary embodiments, the spacing between the three electrode microcolumns in the ultramicrodisc array is 50 μm to 300 μm; the space between the working electrode micro-electric columns is 50-300 mu m.
In some exemplary embodiments, the materials of the working electrode and the counter electrode are both sensitive metallic materials, which are one or both of gold or platinum; or the working electrode and the counter electrode both comprise a main body of non-sensitive metal material and a sensitive metal material layer positioned on the side surface of the main body of non-sensitive metal material, wherein the material of the main body of non-sensitive metal material is nickel, and the material of the sensitive metal material layer is one or two of gold and platinum.
In some exemplary embodiments, the material of the insulating layer is silicon nitride; the thickness of the insulating layer is 100 nm-300 nm.
In a second aspect, an embodiment of the present application further provides an electrochemical sensor, including a microelectrode system of the three-dimensional micro-pillar array described above.
In a third aspect, an embodiment of the present application further provides a method for preparing a microelectrode system of a three-dimensional micro-column array, including the steps of: first, a substrate is provided; then, forming a layer of reverse glue on the substrate, and developing the reverse glue by photoetching by adopting a first layer of mask to form a three-electrode pattern; next, forming a metal layer on the three-electrode pattern and the remaining reverse adhesive; the metal layer covers the three-electrode pattern and the residual reverse glue; then, stripping the residual reverse glue and the metal layer above the reverse glue to form a three-electrode pattern on the substrate; next, an insulating layer is formed on the three electrode pattern; the insulating layer covers the three electrode patterns and is positioned between the ultra-micro circular electrode arrays of the three electrode patterns; then forming photoresist on the three electrode patterns and the insulating layer, and developing the patterns on the front surface of the photoresist by adopting a second layer of mask through photoetching to form patterns of an ultra-micro circular electrode array in an alignment manner; then, the photoresist developed in the previous step is used as a mask for reactive ion etching; etching part of the insulating layer to expose the surface of the ultra-micro circular electrode array; forming a bimetal layer on the surface of the ultra-micro circular electrode array by taking the photoresist as a mask; finally, after removing the residual photoresist, insulating the lead wire by adopting a third layer of mask plate and the photoresist, and etching an insulating wire, a reference electrode micro-cell and an electrolyte micro-cell on the photoresist through photoetching development.
In some exemplary embodiments, the bi-metallic layer includes a first metallic nickel layer and a second metallic gold layer disposed in a stack; the material of the first metal layer is nickel, and the material of the second metal layer is gold; the first metal layer is disposed adjacent to a surface of the array of ultra-micro circular electrodes.
In some exemplary embodiments, after the insulating lines, the reference electrode microchamber, and the electrolyte microchamber are etched on the photoresist by photolithographic development, further comprising: first, integrating a reference electrode on an ultramicro circular electrode array; then, the preparation of the ultra-microelectrode array chip is completed through scribing, assembling and gold wire pressure welding treatment in sequence.
The technical scheme provided by the embodiment of the application has at least the following advantages:
The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method, wherein the microelectrode system comprises the following components: a substrate, an electrode layer and an insulating layer arranged on the substrate; the electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array is adopted as a working electrode; the ultra-micro circular disk array is formed by overlapping three electrode patterns, and the ultra-micro circular electrode array units are mutually isolated through an insulating layer.
According to the microelectrode system of the three-dimensional microelectrode array, a disc-ring-shaped concentrically and symmetrically distributed micro working electrode and a counter electrode are formed on a substrate to serve as electrode layers, and a three-dimensional micro immune reaction tank is manufactured on the periphery of the working electrode by utilizing SU-8 insulating negative photoresist. The microelectrode system of the three-dimensional microelectrode array not only effectively improves the uniformity of the electric field intensity and the electric potential distribution on the surface of the working electrode, but also enables the electric field distribution to be consistent with the diffusion direction of the electron mediator in the electrode surface solution, enables the electrode response to be more easy to reach a steady state and well inhibit current noise, and is beneficial to improving the uniformity and consistency of the morphology of the electrode surface modifier. Meanwhile, the distance between the microelectrodes is only in the micron level, and an electric field is concentrated on the reaction surface, so that electrons are quickly exchanged, the amplification effect of the microelectrode array is effectively utilized, and a response signal is improved. The upper surface of the microelectrode is modified with an insulating layer, which can shield the longitudinal electric field part, and the radial electric field part is reserved to weaken linear diffusion current, and the nonlinear diffusion current is reserved, so that the response current can reach a steady state rapidly.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, which are not to be construed as limiting the embodiments unless specifically indicated otherwise.
FIG. 1 is a schematic diagram of a three-dimensional micro-column array micro-electrode system according to an embodiment of the present application;
FIG. 2 is a schematic plan view of a first layer of a mask for an electrode chip of an array of ultra-microelectrodes according to an embodiment of the present application;
FIG. 3 is a schematic plan view of a second layer of a mask for an electrode chip of an array of ultra-microelectrodes according to one embodiment of the present application;
FIG. 4 is a schematic plan view of a third layer of a mask for an electrode chip of an array of ultra-microelectrodes according to one embodiment of the present application;
FIG. 5 is a flow chart of a method for fabricating a microelectrode system of a three-dimensional micro-column array according to one embodiment of the present application;
FIG. 6 is a schematic cross-sectional view of a method for fabricating a microelectrode system of a three-dimensional microarray according to an embodiment of the present application;
Fig. 7 is a schematic diagram of a processing process flow of a microelectrode system integrated on a chip of a three-dimensional micro-post array according to an embodiment of the present application.
Detailed Description
As known from the background art, the conventional electrochemical sensor uses a discrete electrode system with conventional size, is difficult to be compatible with the integrated circuit at the rear end, is not easy to miniaturize, integrate and mass-produce, and greatly limits the practical application and development of the sensor
The size of the electrode has a close relationship with the mass transfer mode of the electrode surface material and the electrochemical performance of the electrode, for example, the smaller the electrode size, the greater the steady state current density of the electrode surface. As electrode dimensions are reduced to the micrometer and even sub-micrometer range, the electrodes will exhibit a number of unique and superior properties, such as greater current density, higher signal to noise ratio, smaller time constant, faster mass transfer rate and electron transfer rate, etc., which will help to increase the sensitivity of the sensor, lower detection limit and increase response time.
Since the output electrical signal of a single microelectrode is small, a collection of microelectrodes, i.e. an array of microelectrodes, is used. The mass transfer mode of the ultramicroelectrode array is different from that of the ultramicroelectrode, and the ultramicroelectrode array is easily influenced by the diffusion of adjacent electrodes, and the size and the distance of the electrodes are required to be optimized so as to obtain the optimal electrochemical performance. With the increasing maturity of the micro-processing technology, three electrodes can be integrated on the same chip, and the miniaturization and integration of an electrode system are promoted.
In order to solve the above technical problems, an embodiment of the present application provides a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method, where the microelectrode system includes: a substrate, an electrode layer and an insulating layer arranged on the substrate; the electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array is adopted as a working electrode; the ultra-micro circular disk array is formed by overlapping three electrode patterns, and the ultra-micro circular electrode array units are mutually isolated through an insulating layer. The microelectrode system of the three-dimensional microelectrode array can provide continuous electric field distribution, and response stability is improved. The distance between microelectrodes is only in the micron level, and an electric field is concentrated on the reaction surface, so that electrons are quickly exchanged, the amplification effect of the microelectrode array is effectively utilized, and a response signal is improved.
Embodiments of the present application will be described in detail below with reference to the attached drawings. However, it will be understood by those of ordinary skill in the art that in various embodiments of the present application, numerous specific details are set forth in order to provide a thorough understanding of the present application. The claimed application may be practiced without these specific details and with various changes and modifications based on the following embodiments.
Referring to fig. 1, an embodiment of the present application provides a microelectrode system of a three-dimensional micro-column array, comprising: a substrate 100, and an electrode layer 101 and an insulating layer 102 provided over the substrate 100; the electrode layer 101 comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three-electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array 103 is adopted as a working electrode; the ultra-micro circular disk array is obtained by performing overlay on the three-electrode pattern, and the ultra-micro circular electrode array units are mutually isolated through the insulating layer 102.
The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array for electrochemical detection, which comprises the following components: the substrate 100 (silicon dioxide base), the insulating layer (silicon nitride) and the Micro working electrode and the counter electrode which are concentrically and symmetrically distributed are designed and prepared by utilizing the standard processing technology of Micro Electro MECHANICAL SYSTEMS, MEMS, and a three-dimensional Micro immune reaction tank is manufactured on the periphery of the working electrode by utilizing SU-8 insulating negative photoresist. The microelectrode system of the three-dimensional microelectrode array can provide continuous electric field distribution, and response stability is improved. The distance between microelectrodes is only in the micron level, and an electric field is concentrated on the reaction surface, so that electrons are quickly exchanged, the amplification effect of the microelectrode array is effectively utilized, and a response signal is improved.
It should be noted that, the three-electrode pattern in the electrode layer 101 of the present application is obtained by sequentially forming a three-electrode pattern on the reverse adhesive on the substrate by using the first layer mask, forming a metal layer on the three-electrode pattern and the residual reverse adhesive, and then stripping the residual reverse adhesive and the metal layer above the residual reverse adhesive; the ultra-micro circular array is used for carrying out overlay on the three-electrode pattern by adopting a second layer of mask plate to obtain a pattern of the ultra-micro circular electrode array; the reaction tank is a three-dimensional miniature immune reaction tank with a three-dimensional structure; the miniature immunoreaction pool comprises a reference electrode micrococcus and an electrolyte micrococcus, wherein the miniature immunoreaction pool is formed by adopting a third layer of mask and photoresist to insulate a lead, and an insulating wire, the reference electrode micrococcus and the electrolyte micrococcus are carved on the photoresist through photoetching and developing.
The working electrode of the prior art is basically a planar ultramicroelectrode array, and the microelectrode system of the three-dimensional microcolumn array provided by the application has the advantages that the surface of the working electrode adopts a three-dimensional ultramicroelectrode array structure, the specific surface area is greatly increased, and the sensitivity of the electrode to target substances is improved. Therefore, in order to obtain larger current density, higher signal-to-noise ratio, smaller time constant, faster mass transfer rate and electron transfer rate, the embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, which utilizes the microelectrode array to prepare a micro-sensing chip and combines a portable detector to research the clinical detection significance of an electrochemical micro-sensing chip. Meanwhile, aiming at the small reaction area of the micro-sensing device, how to improve the sensitivity of the sensing chip by utilizing the three-dimensional microstructure is researched, and the microelectrode characteristics and the sensitization effect of the three-dimensional microelectrode are researched.
The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, which is mainly used for electrochemical detection and comprises the following components: because the output electrical signal of a single microelectrode is small, the working electrode adopts a set of microelectrodes, namely an array of microelectrodes. The mass transfer mode of the ultramicroelectrode array is different from that of the ultramicroelectrode, and the ultramicroelectrode array is easily influenced by the diffusion of adjacent electrodes, and the size and the distance of the electrodes are required to be optimized so as to obtain the optimal electrochemical performance. The application prepares the ultra-microelectrode array chip by utilizing the MEMS processing technology, and can provide continuous electric field distribution in order to improve the response speed of the electrode, thereby improving the response stability in electrochemical measurement.
The electrode is an important element of the electrochemical sensor, not only the carrier fixed by the sensitive film, but also the transducer of the electrochemical signal, and the performance of the electrode directly influences the detection performance of the electrochemical sensor. The conventional electrochemical sensor uses a separated working electrode, reference electrode and counter electrode three-electrode system, is not compatible with a back-end circuit, is not easy to miniaturize, integrate and mass produce, and limits the practical progress of the electrochemical sensor.
With the increasing maturity of the micro-processing technology, three electrodes can be integrated on the same chip, and the miniaturization and integration of an electrode system are promoted. The size of the electrode influences the mass transfer mode of the electrode surface substances, and when the electrode size is reduced to the micrometer or even nanometer range, the electrode system can show unique characteristics, such as large current density, high signal-to-noise ratio, small time constant, fast mass transfer rate, low IR drop and the like, and the characteristics can improve the sensitivity of the sensor, reduce the detection limit, accelerate the response time and the like.
In some embodiments, the electrode layer comprises a disc-shaped working electrode and a circular counter electrode in concentric symmetric distribution; the disc-shaped working electrode adopts a three-dimensional ultramicroelectrode array, and the radius of the disc of the three-dimensional ultramicroelectrode array is 5-20 mu m; the micro-electric column spacing of the disc-shaped working electrode is 50-300 mu m. Illustratively, the disk radius of the three-dimensional microelectrode array may be 5 μm, 8 μm, 10 μm, 15 μm or 20 μm; the microcolumn spacing of the disk-shaped working electrode may be 50 μm, 100 μm, 150 μm, 200 μm, 250 μm or 300 μm. Preferably, the radius of the disc of the three-dimensional ultramicroelectrode array is 10 μm; the micro-electrode spacing of the disc-shaped working electrode was 200 μm.
The working electrode surface of the application adopts a three-dimensional ultramicroelectrode array structure, thus greatly increasing the specific surface area, improving the sensitivity of the electrode to target substances and improving the response stability.
In some embodiments, the counter electrode comprises three electrodes; the working radius of the three electrodes is 1 mm-3 mm; the radius of the working electrode is 2 mm-6 mm. By way of example, the working radius of the three electrodes may be 1mm, 1.5mm, 2mm, 2.5mm or 3mm; the working electrode may have a radius of 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm or 6mm. Preferably, the working radius of the three electrodes is 1.5mm; the radius of the working electrode was 3.5mm.
In some embodiments, the spacing between the three electrode microelectrodes in the array of supermicro disks is 50 μm to 300 μm; the space between the working electrode micro-electric columns is 50-300 μm. Illustratively, the spacing between the three electrode microcolumns in the array of the ultramicrodisk is 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, or 300 μm; the space between the working electrode micro-electric columns is 50-300 μm. Preferably, the spacing between three electrode micro-electric columns in the ultramicro disc array is 200 μm; the spacing between the individual working electrode microcolumns is 80 μm, 140 μm, 200 μm, respectively.
The application designs two electrodes, namely three electrodes and a single working electrode; the working radius of the three electrodes is 1.5mm, and the radius of a single working electrode is 3.5mm; an array of ultra-micro disk electrodes, the disk radius r being 10 μm. Fig. 2,3 and 4 show schematic plan views of a first layer of mask, a second layer of mask and a third layer of mask (for example, 4 inch pieces) of the microelectrode array electrode chip respectively. Specifically, three electrodes and a single working electrode are respectively manufactured on the first layer of mask plate; the second layer of mask layout is used for drawing an ultramicro disc array, the spacing between three electrode microcolumns is 200 mu m, and the spacing between single working electrode microcolumns is 80 mu m, 140 mu m and 200 mu m respectively; and the third layer of mask plate is used for throwing SU-8 negative photoresist (the thickness is 20 mu m) to form an insulating wire for a lead wire, a reference electrode micro-cell and an electrolyte micro-cell.
In some embodiments, the materials of the working electrode and the counter electrode are both sensitive metallic materials, which are one or both of gold (Au) or platinum (Pt); or the working electrode and the counter electrode both comprise a main body of non-sensitive metal material and a sensitive metal material layer positioned on the side surface of the main body of non-sensitive metal material, wherein the material of the main body of non-sensitive metal material is nickel (Ni), and the material of the sensitive metal material layer is one or two of gold or platinum. In a specific embodiment, a layer of metallic Ni is typically deposited on the electrode surface, followed by a layer of metallic Au on the metallic Ni.
For example, the three-electrode microcolumn has a height of 10 μm to 50 μm, the thickness of the electrochemically deposited metal Ni on the electrode surface is 10 μm to 30 μm, and the thickness of the metal Au is 1 μm to 5 μm. Preferably, the three-electrode microcolumn has a height of 20 μm, the thickness of the electrochemically deposited metal Ni on the electrode surface is 18 μm to 19 μm, and the thickness of the metal Au is 1 μm to 2 μm.
In some embodiments, the material of the insulating layer is silicon nitride (SiN x); the thickness of the insulating layer is 100 nm-300 nm.
In some embodiments, the material of the substrate is silicon dioxide (SiO 2).
The embodiment of the application also provides an electrochemical sensor, which comprises the microelectrode system of the three-dimensional micro-column array. The microelectrode system provided by the application is used for an electrochemical sensor and high-sensitivity electrochemical detection, the detection method is simple and low in cost, and can detect acute myocardial infarction markers with extremely low concentration, and the microelectrode system can be used for but is not limited to protein detection based on bioaffinity and has a huge application prospect. In addition, electrochemical detection is an important integration in the microelectrode system of the application, not only does not need a complex optical detection module, but also can realize the detection of the target object more sensitively.
Referring to fig. 5, the embodiment of the application further provides a preparation method of the microelectrode system of the three-dimensional micro-column array, which comprises the following steps:
Step S1, providing a substrate.
And S2, forming a layer of reverse glue on the substrate, and forming a three-electrode pattern on the reverse glue by photoetching development through a first layer of mask.
Step S3, forming a metal layer on the three-electrode pattern and the residual reverse adhesive; the metal layer covers the three electrode pattern and the remaining reverse paste.
And S4, stripping the residual reverse glue and the metal layer above the reverse glue to form a three-electrode pattern on the substrate.
S5, forming an insulating layer on the three-electrode pattern; the insulating layer covers the three electrode patterns and is positioned between the ultra-micro circular electrode arrays of the three electrode patterns.
And S6, forming photoresist on the three-electrode pattern and the insulating layer, and performing photoetching development on the front surface of the photoresist by adopting a second layer of mask to form a pattern of the ultra-micro circular electrode array in an alignment mode.
Step S7, taking the photoresist developed in the previous step as a mask for reactive ion etching; portions of the insulating layer are etched to expose the surface of the array of ultra-micro circular electrodes.
And S8, forming a bimetal layer on the surface of the ultra-micro circular electrode array by taking the photoresist as a mask.
And S9, after removing the residual photoresist, insulating the lead wire by adopting a third layer of mask plate and the photoresist, and etching an insulating wire, a reference electrode micro-cell and an electrolyte micro-cell on the photoresist through photoetching development.
In some embodiments, the bimetal layer in step S8 includes a first metallic nickel layer and a second metallic gold layer disposed in a stack; the material of the first metal layer is nickel, and the material of the second metal layer is gold; the first metal layer is disposed adjacent to a surface of the array of ultra-micro circular electrodes.
Fig. 6 shows a schematic cross-sectional view of a method for preparing a microelectrode system of a three-dimensional micro-column array provided by the application. Wherein, the substrate adopts a SiO 2/Si base, gold represents a metal Au layer, sun1303 represents photoresist (reverse photoresist) formed on the first layer mask, siN x represents an insulating layer, nickel represents a metal Nickel layer electroplated on the surface of the electrode, 4620 represents photoresist (positive photoresist) formed on the second layer mask, and SU-8 represents photoresist formed on the second layer mask and the third layer mask respectively. As shown in fig. 6, a method for preparing the microelectrode system of the three-dimensional micro-column array according to the present application will be described in detail by way of specific examples.
(1) Using single-sided polished silicon dioxide as a substrate (base); the first step of the preparation process is to clean the silicon dioxide sheet according to a standard cleaning flow, thoroughly remove dirt attached to the surface and keep absolute dryness, improve the cleanliness and flatness of the surface, and strengthen the adhesiveness of the surface.
(2) The method comprises the steps of adopting a first layer of mask to throw negative photoresist sun1303 (5 mu m), referring to fig. 2, performing steps of pre-baking, exposure, development, post-baking and the like, transferring the pattern of the mask to photoresist on the surface of a glass sheet, etching a three-electrode pattern on the photoresist, then adopting an oxygen plasma etching process to clean the surface of a substrate which is not protected by the photoresist, removing residual photoresist, and improving the adhesive strength between a sputtered metal layer and the substrate.
(3) Cr (30 nm)/Au (200 nm) is deposited using a radio frequency magnetron sputtering process, wherein Cr is used as an adhesion layer to improve adhesion between gold and a substrate, and gold (Au) is used to prepare a microelectrode.
(4) Soaking the flakes in a developing solution, stripping to form a three-electrode pattern, and then cleaning the surface by oxygen plasma to remove residues.
(5) Preparation of an insulating layer: siN x was deposited to a thickness of 1 μm using a Plasma Enhanced Chemical Vapor Deposition (PECVD) process and used as an insulating layer between the microelectrode array units. The preparation principle of the SiN x film is as follows: 3SiH 4+4NH3→Si3N4+12H2.
(6) Photoetching: and (3) throwing 4620 positive photoresist (20 mu m) by adopting a second layer of mask plate, wherein the second layer of mask plate is shown in fig. 3, and performing pre-baking, exposure, development and hardening processes, wherein patterns of the ultra-micro circular electrode array are formed on the front surface in an overlapping manner, and the developed photoresist is used as a mask for reactive ion etching. .
(7) Etching: siN x insulating layer was processed using a trifluoromethane (CHF 3) plasma Reactive Ion Etch (RIE) to expose a gold ultra-micro circular electrode array.
(8) By using an electroplating process, a layer of metallic nickel (about 18-19 mu m) is firstly electroplated on the surface of an electrode by using 20 mu m SU-8 thick glue as a mask, and then a layer of metallic Au (1-2 mu m) is electroplated, so that a stable bimetal layer (three-dimensional electrode) is formed on the surface of the electrode, and the electrochemical performance of the electrode can be further inspected.
(9) Removing photoresist and cleaning: and removing the SU-8 thick glue layer by adopting a reagent, and removing residual photoresist by oxygen plasma etching.
(10) And (3) forming insulation for the lead by throwing SU-8 negative photoresist (20 mu m) on the third layer of mask, wherein the insulation wire, the reference electrode micro-cell and the electrolyte micro-cell are carved on the photoresist by performing pre-baking, exposure, development and hardening processes, as shown in figure 4.
In some embodiments, after the insulating lines, the reference electrode microchamber, and the electrolyte microchamber are etched on the photoresist by photolithography development in step S9, the method further comprises the steps of:
step S10, integrating a reference electrode on the ultra-micro circular electrode array.
And S11, sequentially performing scribing, assembly and gold wire pressure welding treatment to finish the preparation of the ultra-microelectrode array chip.
When the microelectrode system of the three-dimensional microelectrode array prepared by adopting the process is tested, the self-assembly method is adopted to fix the object to be tested on the surface of the gold electrode, so that the three-dimensional microelectrode system of the three-dimensional microelectrode array capable of detecting the object to be tested is formed. By integrating the reference electrode on-chip, miniaturization and integration of the electrode system is facilitated.
Fig. 7 shows a schematic diagram of a process flow of a microelectrode system integrated on-chip with a three-dimensional micropillar array. It should be noted that the position and the arrangement shape of the three-dimensional micro-electrode array on the working electrode can be changed and adjusted according to specific requirements. In addition, the number and the height of the three-dimensional micro-electrode column arrays on the working electrode can be changed according to the detection target. In electrochemical detection, the module for detecting the electrode can be changed to a fluorescence detection module, and the detection of the signal based on the electrode is changed to a detection method based on the fluorescence signal.
Simulation is performed by using the electric field distribution of the ANSYS three-dimensional ultra-micro electrode array. The height and the distance of the micro-electric columns are controlled by controlling variables, the electric field distribution at the edges of the electrodes is not consistent in theory, the electric field intensity at the right angle part of the electrodes is large, and the electric field intensity at the edges of the electrodes is small. Considering abrupt changes in the electric field at right angles to the electrodes, it is possible to be an unstable factor in the response signal of the electrodes. Due to the central symmetry of the disk electrode patterns, the electric field distribution of the disk electrode is uniform along the edge of the electrode without abrupt change. However, the electric field strength is greater at the portion closer to the disk electrode, and the electric field strength is much attenuated at the portion farther from the disk electrode, and such a field strength distribution is not favorable for rapid diffusion of substances and transfer of electrons. In theory, the electric field of the electrode is uniformly distributed along the center symmetry, and has stronger electric field distribution in the whole electrode working area, so that the uniform electric field is more beneficial to the stability of response signals, and the diffusion of substances and the electron transfer between adjacent electrodes are ensured.
According to the influence of the electrode shape and the relative position on the electric potential distribution, the electric field intensity and the solution diffusion, a micro working electrode and a counter electrode which are concentrically and symmetrically distributed and provided with ultra-micro electric columns are designed and prepared by utilizing an MEMS standard processing technology, and a three-dimensional micro immune reaction tank is manufactured on the periphery of the working electrode by utilizing SU-8 insulating negative photoresist. The concentric symmetric distributed disk working electrode and circular counter electrode structure not only effectively improves the uniformity of the electric field intensity and the electric potential distribution on the surface of the working electrode, but also enables the electric field distribution to be consistent with the diffusion direction of the electron mediator in the electrode surface solution, enables the electrode response to be more easy to reach a steady state and well inhibit current noise, and is beneficial to improving the uniformity and consistency of the morphology of electrode surface modifiers. In addition, the design of the miniature immune reaction tank improves the operation of antibody fixation and immune reaction, greatly reduces the use amount of antibodies and antigens, improves the efficiency of immune reaction, and is also helpful for improving the repeatability and consistency of detection.
The surface morphology of the prepared microelectrode chip is characterized by using a scanning electron microscope, and the electrochemical characteristics of the microelectrode are examined by using a cyclic voltammetry. SEM image shows that the microelectrode has good surface evenness, clear and tidy edge, even coverage of the insulating layer and three-dimensional structure of the micro immune reaction cell. The optical signal can be measured by a photomultiplier or an EMCCD and other detection devices, so that the object to be detected can be qualitatively analyzed.
The microelectrode system of the three-dimensional microelectrode array provided by the application designs and prepares a micro working electrode and a counter electrode which are concentrically and symmetrically distributed by using an MEMS standard processing technology, and a three-dimensional micro immune reaction tank is manufactured at the periphery of the working electrode by using SU-8 insulating negative photoresist, and has the following beneficial effects:
(1) The distance between microelectrodes is only in the micron level, and an electric field is concentrated on the reaction surface, so that electrons are quickly exchanged, the amplification effect of the microelectrode array is effectively utilized, and a response signal is improved.
(2) The concentric symmetric distributed disk working electrode and circular counter electrode structure not only effectively improves the uniformity of the electric field intensity and the electric potential distribution on the surface of the working electrode, but also enables the electric field distribution to be consistent with the diffusion direction of the electron mediator in the electrode surface solution, enables the electrode response to be more easy to reach a steady state and well inhibit current noise, and is beneficial to improving the uniformity and consistency of the morphology of electrode surface modifiers.
(3) The upper surface of the microelectrode is modified with an insulating layer, which can shield the longitudinal electric field part, and the radial electric field part is reserved to weaken linear diffusion current, and the nonlinear diffusion current is reserved, so that the response current can reach a steady state rapidly.
(4) The design of the miniature immune reaction tank improves the operation of antibody fixation and immune reaction, greatly reduces the use amount of antibodies and antigens, improves the efficiency of immune reaction, and is also beneficial to improving the repeatability and consistency of detection.
The embodiment of the application provides a microelectrode system of a three-dimensional micro-column array, an electrochemical sensor and a preparation method, wherein the microelectrode system comprises the following components: a substrate, an electrode layer and an insulating layer arranged on the substrate; the electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and a three-dimensional ultramicro electrode array is adopted as a working electrode; the ultra-micro circular disk array is formed by overlapping three electrode patterns, and the ultra-micro circular electrode array units are mutually isolated through an insulating layer.
According to the technical scheme, in the microelectrode system of the three-dimensional microelectrode array, the disc-circular ring concentric symmetrically distributed micro working electrode and counter electrode are formed on the substrate to serve as electrode layers, and the SU-8 insulating negative photoresist is utilized to manufacture a three-dimensional micro immune reaction tank at the periphery of the working electrode. The microelectrode system of the three-dimensional microelectrode array not only effectively improves the uniformity of the electric field intensity and the electric potential distribution on the surface of the working electrode, but also enables the electric field distribution to be consistent with the diffusion direction of the electron mediator in the electrode surface solution, enables the electrode response to be more easy to reach a steady state and well inhibit current noise, and is beneficial to improving the uniformity and consistency of the morphology of the electrode surface modifier. Meanwhile, the distance between the microelectrodes is only in the micron level, and an electric field is concentrated on the reaction surface, so that electrons are quickly exchanged, the amplification effect of the microelectrode array is effectively utilized, and a response signal is improved. The upper surface of the microelectrode is modified with an insulating layer, which can shield the longitudinal electric field part, and the radial electric field part is reserved to weaken linear diffusion current, and the nonlinear diffusion current is reserved, so that the response current can reach a steady state rapidly.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of carrying out the application and that various changes in form and details may be made therein without departing from the spirit and scope of the application. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the application, and the scope of the application is therefore intended to be limited only by the appended claims.
Claims (10)
1. A microelectrode system of a three-dimensional array of micropillars, comprising:
A substrate, an electrode layer and an insulating layer arranged on the substrate;
The electrode layer comprises an electrode pattern layer, an ultramicro disc array and a reaction tank, wherein the electrode pattern layer, the ultramicro disc array and the reaction tank are sequentially overlapped on the substrate; wherein, three electrode patterns are formed on the electrode pattern layer, and the working electrode adopts a three-dimensional ultramicro electrode array;
The ultra-micro circular disk array is a pattern of an ultra-micro circular electrode array obtained by performing alignment on the three electrode patterns, and the ultra-micro circular electrode array units are mutually isolated through the insulating layer.
2. The microelectrode system of the three-dimensional micropillar array according to claim 1, wherein the electrode layer comprises a disk-shaped working electrode and a circular counter electrode that are concentrically and symmetrically distributed;
The disc-shaped working electrode adopts a three-dimensional ultramicroelectrode array, and the radius of a disc of the three-dimensional ultramicroelectrode array is 5-20 mu m;
the distance between the micro-electric columns of the disc-shaped working electrode is 50-300 mu m.
3. The microelectrode system of the three-dimensional micropillar array of claim 2, wherein the counter electrode comprises three electrodes; the working radius of the three electrodes is 1 mm-3 mm; the radius of the working electrode is 2 mm-6 mm.
4. The microelectrode system of the three-dimensional micro-column array according to claim 2, wherein the spacing between the three electrode micro-electric columns in the ultramicro disk array is 50 μm to 300 μm; the space between the working electrode micro-electric columns is 50-300 mu m.
5. The microelectrode system of the three-dimensional micropillar array according to claim 2, wherein the materials of the working electrode and the counter electrode are both sensitive metal materials, and the sensitive metal materials are one or two of gold or platinum; or the working electrode and the counter electrode both comprise a main body of non-sensitive metal material and a sensitive metal material layer positioned on the side surface of the main body of non-sensitive metal material, wherein the material of the main body of non-sensitive metal material is nickel, and the material of the sensitive metal material layer is one or two of gold and platinum.
6. The microelectrode system of the three-dimensional micropillar array according to claim 1, wherein the material of the insulating layer is silicon nitride; the thickness of the insulating layer is 100 nm-300 nm.
7. An electrochemical sensor comprising a microelectrode system of the three-dimensional micropillar array of any one of claims 1-6.
8. The preparation method of the microelectrode system of the three-dimensional micro-column array is characterized by comprising the following steps of:
Providing a substrate;
forming a layer of reverse glue on the substrate, and developing the reverse glue by photoetching by adopting a first layer of mask to form a three-electrode pattern;
Forming a metal layer on the three electrode patterns and the residual reverse adhesive; the metal layer covers the three-electrode pattern and the residual reverse glue;
stripping the residual reverse glue and the metal layer above the reverse glue to form a three-electrode pattern on the substrate;
Forming an insulating layer on the three electrode patterns; the insulating layer covers the three electrode patterns and is positioned between the ultra-micro circular electrode arrays of the three electrode patterns;
Forming photoresist on the three electrode patterns and the insulating layer, and performing photoetching development on the front surface of the photoresist by adopting a second layer of mask to form patterns of an ultra-micro circular electrode array in an overlapping manner;
Taking the photoresist developed in the previous step as a mask for reactive ion etching; etching part of the insulating layer to expose the surface of the ultra-micro circular electrode array;
forming a bimetal layer on the surface of the ultra-micro circular electrode array by taking the photoresist as a mask;
After the residual photoresist is removed, a third layer of mask plate and the photoresist are adopted to form insulation for the lead, and an insulation wire, a reference electrode micro-cell and an electrolyte micro-cell are carved on the photoresist through photoetching development.
9. The method for preparing a microelectrode system of a three-dimensional micro-column array according to claim 8, wherein the bimetal layer comprises a first metallic nickel layer and a second metallic gold layer which are arranged in a stacked manner; the material of the first metal layer is nickel, and the material of the second metal layer is gold; the first metal layer is disposed adjacent to a surface of the array of ultra-micro circular electrodes.
10. The method of manufacturing a microelectrode system of a three-dimensional micro-column array according to claim 8, further comprising, after etching the insulating wire, the reference electrode micro-cell, and the electrolyte micro-cell on the photoresist by photolithography and development:
Integrating a reference electrode on the ultra-micro circular electrode array;
The preparation of the ultra-microelectrode array chip is completed through scribing, assembling and gold wire pressure welding treatment in sequence.
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