CN101358941A - Double-face nanometer band electrode array integration sensor capable of being cut and method for manufacturing same - Google Patents
Double-face nanometer band electrode array integration sensor capable of being cut and method for manufacturing same Download PDFInfo
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- CN101358941A CN101358941A CNA2008101203506A CN200810120350A CN101358941A CN 101358941 A CN101358941 A CN 101358941A CN A2008101203506 A CNA2008101203506 A CN A2008101203506A CN 200810120350 A CN200810120350 A CN 200810120350A CN 101358941 A CN101358941 A CN 101358941A
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Abstract
The present invention discloses an electrode array integrated sensor which can cut two-sided nanobelts, and a preparation method thereof. Silicon or glass is selected as a base; the MEMS technology is adopted to deposit two different electrode materials onto the positive plane and the negative plane of the base; the lithography is used for forming a comb-shaped working electrode array and a reference electrode array, which are vertically symmetrical; the PECVD method is used for depositing a silicon nitride insulating layer respectively on two sides; the lithography extends out of the pad; the insulating layers on the two sides are provided with a plurality of cutting lines which are etched vertical to the electrodes. The sensor is used for regularly cutting and polishing, and can be repeatedly used so as to prolong the service life of the device and to enhance and maintain the consistency and stability of the electrodes. The sensor is fixed in the Teflon cavity, and adopts the differential pulse anodic stripping voltammetry to collect the impedance of the tested solution and complete the oxidation-reduction of current signals. The integrated sensor can be used for direct quantitative detection of the concentration of anions and cations in the solution in such fields as rivers and lakes, biomedicine, industrial wastewater and waste gas, and so on, and can be used for qualitative detection of biological molecules after completing the surface modification.
Description
Technical field
The present invention relates to be used for chemistry and detection of biological samples technology, but particularly relate to a kind of double-face nanometer band electrode array integration sensor of cutting.
Background technology
The biological and chemical material can bring about a wholesome effect to human body, also can produce harmful even fatal influence, and therefore the qualitative and quantitative detection of chemistry and biological specimen has very important meaning at aspects such as environment, food, medicine and clinical detection.Present detection method mainly contains atomic absorption spectrophotometry and mass spectroscopy etc., but adopt the equipment of these methods huge, and expensive, need complicated pretreatment, measuring period is long and need skilled operating personnel, and this brings many inconveniences in actual applications.
The structure of existing in the world ultramicroelectrode array comprises substrate 4, electrode 1, insulation course 3 and 2 four parts of pad as shown in Figure 1.The material of preparation electrode has comprised silver, platinum, iridium, gold and glass carbon.Thickness of electrode is generally at 1-2 μ m, and width is generally 10-20 μ m.Microelectrode array stability and repeatability better but generally need to cooperate reference electrode to constitute the electrode test system when being to use, and is comparatively complicated.
Summary of the invention
But the object of the present invention is to provide a kind of double-face nanometer band electrode array integration sensor (the following unified NanoBEA sensor of using) and preparation method who is used for the cutting of chemistry and biology sample detection, can directly carry out detection by quantitative, carry out to carry out qualitative detection to biomolecule (as antibody, DNA) after the finishing the zwitterion concentration in the solution.
In order to achieve the above object, the technical solution used in the present invention is as follows:
But one, a kind of double-face nanometer band electrode array integration sensor of cutting:
Comprise substrate, electrode, insulation course and pad.Select for use silicon chip or glass to do substrate, adopt the MEMS technology two kinds of different electrode materials to be deposited on positive and negative two planes of substrate, constitute working electrode and reference electrode respectively, adopt photoetching technique to form the pectination working electrode and the reference electrode array of top and bottom symmetry, adopt the PECVD method to deposit silicon nitride dielectric layer respectively at pectination working electrode and reference electrode both sides, the photoetching exposed pad is scribed many lines of cut vertical with electrode direction on the insulation course of two sides.
Described working electrode material is a gold, and described reference electrode material is a platinum, and two kinds of thickness of electrode are 80～150nm.
But two, a kind of preparation method of double-face nanometer band electrode array integration sensor of cutting, the step of this method is as follows:
1) select crystal orientation＜100〉diameter is that the N type silicon chip of 4inch is done substrate, cleans through standard technology to dry, and selects first dry oxidation, wet oxidation again, the thick silica dioxide medium layer of method growth 500nm of last dry oxidation;
2) method of employing magnetron sputtering at first deposits the thick titanium of 50nm as adhesion layer.Adopt the method for vacuum evaporation or magnetron sputtering then, pros and cons deposits thick gold of 100nm and platinum respectively, as working electrode with to electrode;
3) photoetching forms the arrays of comb electrodes and the land pattern of top and bottom symmetry, removes photoresist with acetone soln or plasma;
4) adopt the thick silicon nitride dielectric layer of PECVD method deposition 500nm, photoetching exposed pad zone;
5) pad goes between and seals with epoxy resin, and the eletrode tip that exposes polishes with the alumina powder of 0.3 μ m and 0.05 μ m successively.
The beneficial effect that the present invention has is: detection means is little, but cutting, sample solution is few, measures fast, and is easy to use, measures accurately, and the signal to noise ratio (S/N ratio) height disturbs few.This sensor can directly carry out detection by quantitative to the zwitterion concentration in the solution in fields such as rivers,lakes and seas, biomedicine (as blood, body fluid), industrial waste water, industrial gaseous waste, Chinese medicine, vegetables, fruit, tealeaves, carry out can carrying out qualitative detection to biomolecule (as antibody, DNA) after the finishing.
Description of drawings
Fig. 1 is the structural principle synoptic diagram of the ultramicroelectrode sensor array reported.
Fig. 2 is the double-face nanometer band electrode integrated sensor structural principle synoptic diagram that can reduce.
Fig. 3 is the side view of Fig. 2.
Fig. 4 is NanoBEA integrated sensor processing technology figure.
Fig. 5 is the skeleton view and the three-dimensional structure diagram in the integrated test of NanoBEA integrated sensor chamber.
Fig. 6 is the sem photograph of NanoBEA integrated sensor.
Fig. 7 is that a NanoBEA electrode surface of emission scan microscope FESEM test can spectrogram.
Fig. 8 is the cyclic voltammetric test result of NanoBEA integrated sensor.
Fig. 9 is the impedance operator test result of NanoBEA integrated sensor.
Among the figure: 1. electrode, 2. pad, 3. insulation course, 4. substrate, 5.Si
3N
4Insulation course, 6. line of cut, 7.Au working electrode, 8.Si/SiO
2Substrate, the 9.Pt reference electrode 10. goes between 11.SiO
2Dielectric layer, 12.Si substrate, 13. electrode tip holders, 14. solution cavities, 15. wire through-holes, 16.NanoBEA sensor, 17. fluid holes, 18. inlet openings, 19. fixed orifices, 20. electrode holders.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
As Fig. 2, shown in Figure 3, the present invention includes substrate, electrode, insulation course and pad.Select for use silicon chip or glass to make Si/SiO
2Substrate 8, adopt the MEMS technology two kinds of different electrode materials to be deposited on positive and negative two planes of substrate, constitute Au working electrode 7 and Pt reference electrode 9 respectively, adopt photoetching technique to form the pectination Au working electrode 7 and Pt reference electrode 9 arrays of top and bottom symmetry, adopt the PECVD method to deposit Si respectively at pectination working electrode and reference electrode both sides
3N
4Insulation course 5, photoetching exposed pad 2 is scribed many lines of cut 6 vertical with electrode direction on the insulation course of two sides.
The thickness of described Au working electrode 7 and Pt reference electrode is 80～150nm.
The preparation of sensor:
As shown in Figure 4, the preparation of NanoBEA sensor has mainly comprised thermal oxide, sputter, three steps of plasma reinforced chemical vapour deposition (PECVD), the preparation of corresponding oxide layer, electrode layer and insulation course.
(1) preparation of oxide layer (shown in Fig. 4 a):
Select crystal orientation＜100〉diameter is that 4 inches N type silicon chip is done substrate 12, cleans through standard technology to dry.Select first dry oxidation, again wet oxidation, the thick silica dioxide medium layer 11 of the method for dry oxidation growth 500nm at last.
(2) preparation of electrode layer (shown in Fig. 4 b):
Photoetching forms electrod-array and land pattern.Electrode and pad pattern are as shown in Figures 2 and 3.
Even glue: get rid of photoresist 10s with 3000 rev/mins speed;
Preceding baking: photoresist is preliminary drying 10min under 110 ℃ of temperature;
Exposure: time shutter 5s, exposure power 350W;
Develop: development time 10s, developer solution adopts the supporting developer solution of photoresist;
Post bake: taking out behind the post bake 5min under 130 ℃ of temperature;
Adopt the method for magnetron sputtering, at first deposit the thick titanium of 50nm as adhesion layer.Adopt the method for vacuum evaporation or magnetron sputtering then, pros and cons deposits thick gold of 100nm and platinum respectively, as working electrode 7 with to electrode 9;
Remove photoresist: remove photoresist with acetone soln or plasma, obtain electrod-array.
(3) preparation of insulation course
Adopt the thick silicon nitride of PECVD method deposition 500nm, photoetching exposes welding disking area, forms line of cut simultaneously.
Even glue: with 3000 rev/mins speed whirl coating 10s;
Preceding baking: photoresist is preliminary drying 10min under 110 ℃ of temperature;
Aim at and exposure: time shutter 5s, exposure power 350W.
Develop: development time 10s, developer solution adopts the supporting developer solution of photoresist.
Post bake: taking out behind the post bake 5min under 130 ℃ of temperature.
Corrosion: plasma etching silicon nitride dielectric layer 5 exposes land pattern and line of cut 6.
(4) encapsulation of sensor (shown in Fig. 4 c):
Behind the wafer dicing, from pad lead-in wire and use epoxy sealing.The eletrode tip that exposes polishes with the aluminum oxide polishing powder of 0.3 μ m and 0.05 μ m successively.
This Integrated electrode is fixed in the test chamber (as shown in Figure 5) that the Teflon material makes.Test chamber is made up of electrode tip holder 13 and solution cavity 14 two parts.Electrode tip holder is made up of threaded base 13 and electrode holder 20, and NanoBEA sensor 16 is clipped between the two plate electrodes folder 20, fixes by the fixed orifice 19 usefulness screws of electrode holder, and is tightened on the threaded base 13.Contact conductor is drawn by wire through-hole 15.Solution flows into by inlet opening 18, flows out from fluid hole 17.Eletrode tip can block along line of cut 6 according to behaviour in service in good time, reuses burnishing powder and polishes, and can obtain stable integrated electrode.
The chief component of modern stripping voltammetry analytical instrument comprises electrolytic cell, potentiostat and computing machine.Potentiostat is on computers integrated in some cases, and the system computer that has separates with A/D, D/A converter, microcontroller, and potentiostat can be operated separately.Potentiostat is the current potential on the may command working electrode both, and measurable flow is crossed the electric current of working electrode again.According to the parameter that computing machine sends, microcontroller is provided with the value of D/A, and scanning voltage outputs on the potentiostat, writes down the electric current that flows through working electrode that A/D records simultaneously, sends back computing machine and carries out data processing and demonstration.
The sign of sensor and characteristic
(1) characterization of size of NanoBEA sensor
The single dimension of picture 6mm * 1cm of NanoBEA sensor is made up of 50 nanometer band electrodes, and suprabasil oxidated layer thickness is 500nm.The long 9.5mm of each electrode, wide 10 μ m, thick 100nm, electrode separation 100 μ m; Silicon nitride dielectric layer is that 500nm is thick, pad size 0.4mm * 5.6mm.
Among Fig. 6, the edge thickness of single electrode is 121nm, and 150nm is approaching with adhesion layer, the metal level theoretic throat sum of electrode design.Among Fig. 7, the peak of Si, Au is all higher, also has simultaneously the peak of N, O to occur, this verified single metal working do electrode 7 near, the bag quilt of silicon nitride dielectric layer 5 and silicon dioxide is arranged really.
This proof, the NanoBEA sensor of preparation has reached designing requirement on bulk.
(2) NanoBEA sensor impedance characteristic
The NanoBEA sensor at the impedance characteristic in the 0.5mol/L sulfuric acid solution shown in Fig. 8 and 9.Initial potential is 0.5V, and the interchange amplitude is 0.005V, and frequency is from 10
5Hz sweeps to 1Hz.Fig. 8 is Nyquist figure, has comprised that (as Fig. 8 a) and phase-frequency response (as Fig. 8 b), the amplitude of impedance increases along with the reduction of frequency, and the phase place of impedance is along with the reduction capacitive of frequency reduces for the amplitude-frequency response of device; Fig. 9 is impedance complex plane figure, and real part of impedance and imaginary part are linear relationship.Because the capacitive interface that forms between electrode and the solution, low frequency part mainly shows as high impedance, and electrode impedance is 10
5Ω, and HFS is equivalent to electric capacity by short circuit, electrode impedance obviously is reduced to hundreds of ohm.When the test impedance of sensor does not meet impedance characteristic Fig. 8 and Fig. 9, can carry out cutting along the nearest 6 pairs of sensors of line of cut of sensor surface, polish again and pre-service, test curve should meet impedance characteristic.
Claims (3)
- But 1, a kind of double-face nanometer band electrode array integration sensor of cutting comprises substrate, electrode, insulation course and pad; It is characterized in that: select for use silicon chip or glass to do substrate, adopt the MEMS technology two kinds of different electrode materials to be deposited on positive and negative two planes of substrate, constitute working electrode and reference electrode respectively, adopt photoetching technique to form the pectination working electrode and the reference electrode array of top and bottom symmetry, adopt the PECVD method to deposit silicon nitride dielectric layer respectively at pectination working electrode and reference electrode both sides, the photoetching exposed pad is scribed many lines of cut vertical with electrode direction on the insulation course of two sides.
- But 2, the double-face nanometer band electrode array integration sensor of a kind of cutting according to claim 1 is characterized in that: described working electrode material is gold, and described reference electrode material is a platinum, and two kinds of thickness of electrode are 80～150nm.
- But 3, a kind of preparation method of double-face nanometer band electrode array integration sensor of cutting according to claim 1 is characterized in that the step of this method is as follows:1) select crystal orientation＜100〉diameter is that the N type silicon chip of 4inch is done substrate, cleans through standard technology to dry, and selects first dry oxidation, wet oxidation again, the thick silica dioxide medium layer of method growth 500nm of last dry oxidation;2) method of employing magnetron sputtering at first deposits the thick titanium of 50nm as adhesion layer.Adopt the method for vacuum evaporation or magnetron sputtering then, pros and cons deposits thick gold of 100nm and platinum respectively, as working electrode with to electrode;3) photoetching forms the arrays of comb electrodes and the land pattern of top and bottom symmetry, removes photoresist with acetone soln or plasma;4) adopt the thick silicon nitride dielectric layer of PECVD method deposition 500nm, photoetching exposed pad zone;5) pad goes between and seals with epoxy resin, and the eletrode tip that exposes polishes with the alumina powder of 0.3 μ m and 0.05 μ m successively.
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| CN102183645A (en) * | 2011-01-24 | 2011-09-14 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN102483422A (en) * | 2009-06-01 | 2012-05-30 | 康奈尔大学 | Integrated optofluidic system using microspheres |
| CN101713757B (en) * | 2009-11-19 | 2012-09-26 | 浙江大学 | Photoelectric compound integral sensor for detecting cell physiological parameters and preparation method thereof |
| CN107024509A (en) * | 2017-05-15 | 2017-08-08 | 中国科学院苏州生物医学工程技术研究所 | A kind of preparation method of blood coagulation test paper and its piezoelectric transducer chip |
| CN108254414A (en) * | 2018-03-09 | 2018-07-06 | 国家纳米科学中心 | A kind of flexible in vitro micro- raceway groove microelectrode array integrated chip and its preparation method and application |
| CN112666235A (en) * | 2021-01-19 | 2021-04-16 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
| CN112683967A (en) * | 2020-12-08 | 2021-04-20 | 中国科学院长春应用化学研究所 | Micro-nano charged electrode, preparation method thereof and enzyme-free biosensor |
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2008
- 2008-08-22 CN CNA2008101203506A patent/CN101358941A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483422A (en) * | 2009-06-01 | 2012-05-30 | 康奈尔大学 | Integrated optofluidic system using microspheres |
| CN102483422B (en) * | 2009-06-01 | 2014-07-23 | 康奈尔大学 | Integrated optofluidic system using microspheres |
| CN101713757B (en) * | 2009-11-19 | 2012-09-26 | 浙江大学 | Photoelectric compound integral sensor for detecting cell physiological parameters and preparation method thereof |
| CN102183645A (en) * | 2011-01-24 | 2011-09-14 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN102183645B (en) * | 2011-01-24 | 2013-12-11 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN107024509A (en) * | 2017-05-15 | 2017-08-08 | 中国科学院苏州生物医学工程技术研究所 | A kind of preparation method of blood coagulation test paper and its piezoelectric transducer chip |
| CN108254414A (en) * | 2018-03-09 | 2018-07-06 | 国家纳米科学中心 | A kind of flexible in vitro micro- raceway groove microelectrode array integrated chip and its preparation method and application |
| CN108254414B (en) * | 2018-03-09 | 2024-02-02 | 国家纳米科学中心 | Flexible in-vitro micro-channel microelectrode array integrated chip and preparation method and application thereof |
| CN112683967A (en) * | 2020-12-08 | 2021-04-20 | 中国科学院长春应用化学研究所 | Micro-nano charged electrode, preparation method thereof and enzyme-free biosensor |
| CN112683967B (en) * | 2020-12-08 | 2022-03-29 | 中国科学院长春应用化学研究所 | Micro-nano charged electrode, preparation method thereof and enzyme-free biosensor |
| CN112666235A (en) * | 2021-01-19 | 2021-04-16 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
| CN112666235B (en) * | 2021-01-19 | 2023-03-10 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
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