CN105651837A - Microelectrode system and preparation method thereof as well as electrochemical sensor - Google Patents

Microelectrode system and preparation method thereof as well as electrochemical sensor Download PDF

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Publication number
CN105651837A
CN105651837A CN201511021604.5A CN201511021604A CN105651837A CN 105651837 A CN105651837 A CN 105651837A CN 201511021604 A CN201511021604 A CN 201511021604A CN 105651837 A CN105651837 A CN 105651837A
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electrode
microelectrode
insulating substrate
microelectrode system
spiral
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CN201511021604.5A
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CN105651837B (en
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蒋莉娟
魏清泉
刘文文
李钊
俞育德
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Institute of Semiconductors of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells

Abstract

The invention discloses a microelectrode system with three microelectrode array structures, namely the microelectrode system with a two-dimensional interdigital structure, a spiral interdigital structure and a spiral cross interdigital structure, an electrochemical sensor and a preparation method of the microelectrode system. According to the devices, continuous electric field distribution is provided, and the response performance is improved.

Description

Microelectrode system and its preparation method, electrochemical sensor
Technical field
The present invention relates to technical field of electrochemical detection, particularly relate to a kind of microelectrode system and its preparation method, electrochemical sensor.
Background technology
Electrochemical sensor and detection system have due to it be easy to miniatureization, the advantage that highly sensitive, specificity is good, have important using value in biology, medical science, food safety, environmental monitoring, military affairs, medicine and other fields.
The key part of electrochemical sensor and electrode system. Compared to conventional electrodes, the electrochemical properties that the while that super microelectrode having that the speed of response is fast, strength of current is little, current density is big, coefficient of mass transfer is big.
Ultra-micro array electrode refers to that the electrode that the outward appearance being together made up of multiple super microelectrode boundling is single, its electric current are the summations of each single super microelectrode electric current. This kind of electrode had both maintained the characteristic of original single super microelectrode, can obtain again bigger strength of current, it is to increase the sensitivity of electroanalysis. Wherein, fork finger-type micro-strip electrode array has generation-collection effect, can improve the sensitivity of detection, it is achieved lower concentration detects.
But the reduction of the size due to electrode, fringing effect and point effect obviously increase, the bad stability of the electrode system being. How while electrode system miniatureization, improve sensitivity and the stability of detection as far as possible, it is achieved better detection perform, becomes research focus gradually.
In the process realizing the present invention, applicant recognizes the technological deficiency that prior art exists: adopting the electrode also inequality one that the electrode system of the fork super microelectrode array of finger-type produces, therefore the response stability of testing sample can be affected.
Summary of the invention
(1) technical problem solved
In order to address the aforementioned drawbacks, the present invention provides the microelectrode system of three kinds of Microelectrode array architecture, it is that a kind of two dimension interdigital structure, a kind of spiral interdigital structure and a kind of spiral intersect the microelectrode system of interdigital structure, electrochemical sensor and its preparation method respectively, providing continuous print electric field distribution, it is to increase response performance.
(2) technical scheme
According to an aspect of the present invention, it provides a kind of microelectrode system, comprising: insulating substrate; And first, second two electrodes in insulating substrate, forming pair of electrodes, single electrode is comb arrays structure, insulated from each other, and the first and second electrodes are mutually nested.
According to another aspect of the present invention, it provides a kind of microelectrode system, comprising: insulating substrate; Spiral interdigital electrode in insulating substrate, it is first, second two electrodes, forms pair of electrodes, and single electrode is spiral list side pectination, and insulated from each other, both are mutually nested.
According to another aspect of the present invention, it provides a kind of microelectrode system, comprising: insulating substrate; Spiral intersection interdigital electrode in insulating substrate, it is first, second two electrodes, forms pair of electrodes, and single electrode is spiral two sides pectinations, and insulated from each other, both are mutually nested.
According to another aspect of the present invention, it provides a kind of electrochemical sensor, this electrochemical sensor comprises above-mentioned microelectrode system.
According to another aspect of the present invention, it provides a kind of method preparing microelectrode system, comprises step: revolve resist coating in the insulating substrate of cleaning; The photoresist material of revolved painting is carried out photoetching, exposes microelectrode pattern; Utilize sputtering or steam the method for plating, form the microelectrode pattern of the microelectrode system that the present invention proposes on an insulating substrate; Remove remaining photoresist material.
(3) useful effect
The microelectrode system of the present invention's two dimension interdigital structure, spiral interdigital structure, spiral intersection interdigital structure has one pair of size to form microelectrode at micron, symmetrical nested stereo electrod respectively, it has following useful effect: 1) two-dimentional interdigital structure in the present invention, spiral interdigital structure, spiral intersect the microelectrode system of interdigital structure can provide continuous print electric field distribution, it is to increase the stability of response in Electrochemical Detection; 2) three kinds of microelectrode systems in the present invention, the size of electrode concentrates on electrode surface in micron or submicron order, the electric field overwhelming majority so that electrode exchanges rapidly, effectively make use of the scale effect of microelectrode array, it is to increase sensitivity. 3) the two-dimentional interdigital structure in the present invention, spiral interdigital structure, spiral intersect interdigital structure microelectrode system, it is possible in electrode two-dimensional surface, it is provided that the electric field of equal so that whole microelectrode system is more stable.
Accompanying drawing explanation
Fig. 1 is the structural representation of two-dimentional interdigital structure microelectrode system according to a first embodiment of the present invention;
Fig. 2 is the structural representation of spiral interdigital structure microelectrode system according to a second embodiment of the present invention;
Fig. 3 is the structural representation of the intersection interdigital structure microelectrode system of spiral according to a third embodiment of the present invention;
Fig. 4 is the schematic diagram of microelectrode system preparation method of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
According to an aspect of the present invention, it is proposed to a kind of microelectrode system. Fig. 1 is the structural representation of the first embodiment of this microelectrode system.
With reference to Fig. 1, this microelectrode system is two dimension interdigital structure, comprising: insulating substrate; Two dimension intersection fork in insulating substrate refers to, it is two electrodes, and single electrode is comb arrays structure, insulated from each other, and mutually nested formation crossed structure.
Fig. 2 is the structural representation of the 2nd embodiment of this microelectrode system.
With reference to Fig. 2, this microelectrode system is spiral interdigital structure, comprising: insulating substrate; Spiral interdigital electrode in insulating substrate, it is two electrodes, and single electrode is spiral pectination, insulated from each other, and mutually nested one-tenth spiral interdigital structure.
Fig. 3 is the structural representation of the 3rd embodiment of this microelectrode system.
With reference to Fig. 3, this microelectrode system is spiral intersection interdigital structure, comprising: insulating substrate; Spiral intersection interdigital electrode in insulating substrate, it is two electrodes, and single electrode is spiral pectination, insulated from each other, and mutually nested one-tenth spiral decussate texture.
In the microelectrode system of the present invention, insulation layer is preferably silicon dioxide layer, and the thickness of this silicon dioxide layer is between 1 micron to 10 microns. The material of microelectrode is sensitive conductive material, it may be preferred that this sensitive conductive material is gold, platinum and silver. In addition, in order to ensure that sensitive conductive material and insulating substrate effectively bond, it may be preferred that before steaming plating, sputtering or deposition sensitive metal material, first form one layer of bonding metal layer. For gold, bonding metal layer selects chromium or titanium, and the thickness of bonding metal layer is between 10 nanometers to 50 nanometers.
Pectination microelectrode is mutually nested, and its comb width and mutually adjacent comb tooth spacing are all between 10 nanometers to 20 microns, and the height of comb is between 50 nanometers to 1 micron. In the microelectrode system of the present embodiment, spacing between electrodes is micron order or nano level only, and electrode concentrates on reaction surface so that electron exchange is rapid, effectively make use of the scale effect of microelectrode array, thus improves the sensitivity of electrode system. Preferably, comb width and mutually adjacent comb tooth spacing are all between 5 microns to 20 microns, and its height is between 50 nanometers to 300 nanometers.
The microelectrode system of the present invention can provide continuous print electric field distribution, is different from inequality one electric field distribution that general fork refers to microstrip array electrode, thus provides more stable response performance. Preferably, the pair of electrodes in the microelectrode system of different structure includes the wiring end of connection, and this wiring end is used for the connection with external detection equipment.
According to a further aspect in the invention, also proposing a kind of electrochemical sensor, this electrochemical sensor comprises any one microelectrode system in above-mentioned three kinds of structures that the present invention proposes.
In accordance with a further aspect of the present invention, a kind of microelectrode system preparation method is also proposed, size is made up of in submicron or micron-sized electrode by three kinds of microelectrode systems of the present invention insulating substrate and one, two electrodes are mutually nested, prepared by employing semiconductor technology, concrete preparation method comprises: step S01, gets out clean insulating substrate. Step S02, the insulating substrate in cleaning revolves resist coating; Step S03, carries out photoetching to the photoresist material of revolved figure, exposes target pattern; Step S04 and step S05, utilizes magnetron sputtering or steams the technique of plating, tackiness agent and sensitive metal material are sputtered respectively or steams on the substrate exposed, and forms two dimension interdigital structure, spiral interdigital structure or spiral intersection and pitches the figure referred to; Step S06, removes remaining photoresist material.
The concrete example of according to the method one, the preferred quartz substrate of insulating substrate. In quartz substrate, steaming plating two dimension interdigital structure microelectrode, electrode sensitive metallic substance is gold, and fixing through follow-up bio-sensing element forms the two-dimentional interdigital structure microelectrode system to alpha-fetoprotein detection. In step S02, revolving resist coating in the quartz substrate of cleaning, thickness is 4 microns; In step S03, UV-light photoetching forms microelectrode pattern, as the mould of microelectrode; In step S04 and step S05, the quartz substrate after photoetching sputtering 30nm chromium and 200nm gold, wherein layer gold is as sensitive metal layer, and layers of chrome is as the bonding coat between layer gold and quartz substrate; In step S06, with acetone soak, remove photoresist material mould, retain the microelectrode system of the two-dimentional interdigital structure being made up of chromium, gold; In step S07, when the two dimension fork adopting above-mentioned technique to prepare refers to that microelectrode system is tested, adopt the method for white assembling at the antibody of the fixing alpha-fetoprotein of gold electrode surfaces, form the impedance biological sensing system that the two dimension fork to alpha-fetoprotein detection refers to microelectrode.
Above-described specific embodiment; the object of the present invention, technical scheme and useful effect have been further described; it it should be understood that; the foregoing is only specific embodiments of the invention; it is not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (13)

1. a microelectrode system, comprising: insulating substrate; And first, second two electrodes in insulating substrate, forming pair of electrodes, single electrode is comb arrays structure, insulated from each other, and the first and second electrodes are mutually nested.
2. a microelectrode system, comprising: insulating substrate; Spiral interdigital electrode in insulating substrate, it is first, second two electrodes, forms pair of electrodes, and single electrode is spiral list side pectination, and insulated from each other, both are mutually nested.
3. a microelectrode system, comprising: insulating substrate; Spiral intersection interdigital electrode in insulating substrate, it is first, second two electrodes, forms pair of electrodes, and single electrode is spiral two sides pectinations, and insulated from each other, both are mutually nested.
4. microelectrode system according to claim 1,2 or 3, it is characterized in that, the first described electrode and the 2nd electrode are three-dimensional structure, and the spacing between its width and adjacent electrode is between 200 nanometers to 20 microns, and height is between 20 nanometers to 1 micron.
5. microelectrode system according to claim 1,2 or 3, it is characterized in that, the first described electrode and the 2nd electrode are three-dimensional structure, and the spacing between its width and adjacent electrode is between 200 nanometers to 20 microns, and height is between 20 nanometers to 1 micron.
6. microelectrode system according to claim 1,2 or 3, it is characterised in that, the microelectrode system of three kinds of described structures, first, second electrode all extends to the wiring end of connection, and this wiring end is used for the connection with external detection equipment.
7. microelectrode system according to claim 2, it is characterised in that, first, second electrode is involute urve spiral list side pectination.
8. microelectrode system according to claim 3, it is characterised in that, first, second electrode is involute urve spiral two sides pectinations.
9. microelectrode system according to claim 1,2 or 3, it is characterised in that, described insulating substrate is silicon dioxide layer, and the thickness of this silicon dioxide layer is between 1 micron to 200 microns.
10. microelectrode system according to claim 1,2 or 3, it is characterised in that, the material of first, second described electrode is metal sensitive material, and this metal sensitive material is gold, platinum or silver.
The 11. microelectrode systems according to the arbitrary item of claim 1 to 10, it is characterised in that, described insulating substrate is quartz, glass or the silicon substrate through insulation processing.
12. 1 kinds of electrochemical sensors, it is characterised in that, this electrochemical sensor comprises the microelectrode system described in 1 to 11 arbitrary item of claim.
Prepare the method for microelectrode system, comprise step for 13. 1 kinds:
The insulating substrate of cleaning revolves resist coating;
The photoresist material of revolved painting is carried out photoetching, exposes microelectrode pattern;
Utilize sputtering or steam the method for plating, form the microelectrode pattern of the microelectrode system as according to any one of claim 1 to 11 on an insulating substrate;
Remove remaining photoresist material.
CN201511021604.5A 2015-12-31 2015-12-31 Microelectrode system and preparation method thereof, electrochemical sensor Active CN105651837B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107144744A (en) * 2017-04-25 2017-09-08 云南大学 A kind of electrode system for measuring the electron transport performance in nanometer sized materials/structure
WO2018014719A1 (en) * 2016-07-20 2018-01-25 广州易活生物科技有限公司 Detection electrode structure, detection aperture plate, and prefabricated detection aperture plate
CN108414592A (en) * 2018-02-05 2018-08-17 北京科技大学 A kind of preparation method of polymer brush microelectrode array
CN109809359A (en) * 2019-01-10 2019-05-28 北方工业大学 2.5D interdigital electrode manufacturing method and interdigital electrode
CN111122683A (en) * 2019-12-12 2020-05-08 同济大学 Electrochemical method for detecting cephalosporin by three-dimensional interdigital printed electrode

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CN102326078A (en) * 2009-01-09 2012-01-18 技术研究及发展基金有限公司 Volatile organic compounds as diagnostic markers in the breath for lung cancer
CN102405409A (en) * 2008-12-23 2012-04-04 3M创新有限公司 Organic chemical sensor with microporous organosilicate material
CN102692439A (en) * 2011-03-25 2012-09-26 中国科学院电子学研究所 Microelectrode system having double-spiral structure, electrochemical sensor and preparation method of the microelectrode system having double-spiral structure

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009106906A1 (en) * 2008-02-27 2009-09-03 Budapesti Müszaki És Gazdaságtudományi Egyetem Interdigitated electrode
CN102405409A (en) * 2008-12-23 2012-04-04 3M创新有限公司 Organic chemical sensor with microporous organosilicate material
CN102326078A (en) * 2009-01-09 2012-01-18 技术研究及发展基金有限公司 Volatile organic compounds as diagnostic markers in the breath for lung cancer
CN102692439A (en) * 2011-03-25 2012-09-26 中国科学院电子学研究所 Microelectrode system having double-spiral structure, electrochemical sensor and preparation method of the microelectrode system having double-spiral structure

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018014719A1 (en) * 2016-07-20 2018-01-25 广州易活生物科技有限公司 Detection electrode structure, detection aperture plate, and prefabricated detection aperture plate
CN107144744A (en) * 2017-04-25 2017-09-08 云南大学 A kind of electrode system for measuring the electron transport performance in nanometer sized materials/structure
CN107144744B (en) * 2017-04-25 2018-07-20 云南大学 A kind of electrode system measuring the electron transport performance in nanometer sized materials/structure
CN108414592A (en) * 2018-02-05 2018-08-17 北京科技大学 A kind of preparation method of polymer brush microelectrode array
CN109809359A (en) * 2019-01-10 2019-05-28 北方工业大学 2.5D interdigital electrode manufacturing method and interdigital electrode
CN111122683A (en) * 2019-12-12 2020-05-08 同济大学 Electrochemical method for detecting cephalosporin by three-dimensional interdigital printed electrode

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