CN102323314A - Production and detection method of plated bismuth gold micro-array electrode for detecting heavy metals - Google Patents
Production and detection method of plated bismuth gold micro-array electrode for detecting heavy metals Download PDFInfo
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Abstract
The invention relates to a production and detection method of a plated bismuth gold micro-array electrode for detecting heavy metals, which is characterized in that: in a bismuth plating process of a production machine of a gold micro-array electrode, when 0.015mol/L Bi (NO3) 3 . 5H2O, 1 mol / L KNO3 and 1% HNO3 are used to plate heavy metals, magnetic stirring is added to improve the plating efficiency. The micro-array electrode is used as a wok electrode of stripping voltammetry to form a sensor for detecting the heavy metals, liquid is prepared, and parameter values of the voltammetry are set to complete the detection of the heavy metals lead, cadmium or nickel, and the sensitivity is up to the national drinking water standards.
Description
Technical field
The present invention relates to a kind of simple and easy, be used for the method for making and the detection method of the plating bismuth tiny array electrode that heavy metal detects cheaply, belong to micro processing field.
Background technology
Stripping voltammetry in the electrochemical method can be used for detecting heavy metal; At the initial stage that this method is developed out; Mercury commonly used is as the medium of enriching heavy metal, but well-known, mercury itself is exactly a kind of heavy metal that human body is had harm; And have volatility, so this has brought significant limitation to the application that stripping voltammetry detects heavy metal.
Calendar year 2001, people such as Jung-Yuen Choi utilize silk-screen printing technique to produce a kind of working electrode, Ag/AgCl contrast electrode and carbon of the HgO of containing modification heavy metal detecting sensor [Choi, J., the Seo to electrode; K., Cho, S., Oh; J., Kahng, S.; And Park, J., Analytica Chimica Acta; Screen-printed anodic stripping voltammetric sensor containing HgO for heavymetal analysis.2001,443,241-247.].Backing material is the polycarbonate bar, and wherein the bottom of working electrode is a silver, and the middle layer is a carbon, and the superiors are mercury.When can well being used for lead, cadmium and copper heavy metal ion, this electrode detects.
Bismuth is a kind of material of low toxicity, detects in the method for heavy metal at stripping voltammetry, and bismuth can be used for replacing mercury to be used for the enrichment of heavy metal, and whole like this testing process just can not work the mischief to human body.2007, people such as Christos Kokkinos utilized the sputtering technology in the fine process, have produced the bismuth film as heavy metal testing electrode [Kokkinos; C., Economou, A., Raptis; I., Efstathiou, C., and Speliotis; T., Electrochemistry Communications, Noveldisposable bismuth-sputtered electrodes for the determination of trace metals bystripping voltammetry.2007; 9,2795-2800.], its manufacture craft is: earlier on silicon oxidation to go out a bed thickness be 1 micron oxide layer; As the restraining barrier of bismuth metal and silicon, direct sputter bismuth on silicon dioxide insulate part bismuth film with the photoresist that insulate then then.Utilize kind electrode to lead, the cadmium heavy metal ion detects simultaneously, and concentration wherein plumbous, cadmium is 0-125 μ g/L, and gradient is 25 μ g/L, and end liquid is acetate buffer solution, and PH is 4.5.
2010, people such as Uthaitip Injang made the bismuth film and have accomplished lead on CNT, the detection of cadmium and zinc heavy metal ion, and the detection range of linearity wherein plumbous, cadmium is 2-100ug/L; Zinc is 12-100ug/L [Injang, U., Noyrod, P.; Siangproh, W., Dungchai; W., Motomizu, S.; And Chailapakul, O., Analytica Chimica Acta; Determination of trace heavy metalsin herbs by sequential injection analysis-anodic stripping voltammetry usingscreen-printed carbon nanotubes electrodes.2010,668,54-60.].CNT has high conductivity, bigger surface area and better chemical stability, therefore CNT can effectively be improved detection sensitivity as the substrate of bismuth.
In stripping voltammetry, can adopt tiny array electrode as working electrode, this tiny array electrode is formed by the regular arrangement of a lot of microelectrodes.Microelectrode is compared following advantage with grand electrode: can reach the stable state of redox reaction rapidly, have higher faradic currents and charging current ratio, the ohmmic drop IR of electrolytic solution reduces, and tiny array electrode is more suitable for the detection in the electrolytic solution that flows.[KAREL
CHRISTIAN?AMATORE，KAREL?HOLUB，
and?KUTNER，A.W.，Pure?Appl.Chem，Microelectrodes.Definitions，characterization，and?applications.2000，72，1483-1492.]
The present invention just is based on above background exploitation, is used for the making and the detection method of the plating bismuth gold tiny array electrode of heavy metal detection, carries out the measurement to heavy metal concentration and kind with the working electrode as stripping voltammetry.
Summary of the invention
The objective of the invention is at SiO
2On produce tiny array electrode, this electrode substrate is a gold thin film, photo-sensistive polyimide is an insulation course; Then that polyimide is graphical, make the part gold expose out, other parts still insulate; Exposed part forms golden array electrode, because this part conduction, so can carry out the plating of bismuth in the above; On microelectrode, plate one deck bismuth film at last, accomplish detection heavy metal with this working electrode.
Innovative point of the present invention is only just can accomplish the making to golden tiny array electrode with Twi-lithography; Method for making is very simple and practical; Significantly reduced fabrication cycle, and because the cause of microelectrode, plating bismuth technology also can be very quick; Just can accomplish in about one minute, and so just can make this method be tending towards practical more.
The gordian technique that the present invention need solve is:
1. the manufacture craft of golden tiny array electrode cheaply
What make micron-sized microelectrode employing is Micrometer-Nanometer Processing Technology, and in general this technology all can have the too high problem of cost, and we adopt method only to use Twi-lithography at this, and method for making is quite simple.
2. the configuration of bismuth electroplate liquid and electroplating process
The configuration of electroplate liquid directly has influence on the effect of bismuth metal plating, is plated in gold surface so the selection of electroplate liquid must guarantee the bismuth rapid and reliable, and wanting simultaneously can long preservation and repeatedly use.
The technical scheme that the present invention adopts is:
1. the production program of golden tiny array electrode: at SiO
2On at first produce metallic pattern, and then on metallic pattern the polyimide of spin coating one deck Photosensitive, carry out the photoetching second time then, polyimide is a kind of good insulating material, carries out etching and obtains tiny array electrode.
2. the configuration of electroplate liquid: 0.015mol/L Bi (NO
3)
35H
2O+1mol/L KNO
3+ 1%HNO
3The time of plating bismuth is 2min, and current potential be-0.3V, should add magnetic agitation during plating, and electroplating current can obviously increase, and this shows that electroplating effect can be better.
Advantage then of the present invention and beneficial effect are:
1. the present invention adopts silica-based fine process, and its source is abundant, and processing technology is ripe, can produce in batches, and can reuse.
2. microelectrode has all advantages of conventional microelectrode, is suitable as very much the working electrode of stripping voltammetry.
3. detecting electrode itself harm has improved the detection security.
4. microelectrode is convenient to microminiaturized and integrated.
Description of drawings
Fig. 1 electrode synoptic diagram: (a) platinum is to electrode, (b) golden tiny array electrode.
Fig. 2 tiny array electrode is made process flow diagram: (a) oxidation goes out SiO2 (b) photoetching for the first time on monocrystalline silicon, and gold graphical (c) photoetching is for the second time produced microelectrode array (d) plating bismuth with polyimide.
Fig. 3 plates bismuth effect schematic three dimensional views.
Embodiment
One, makes golden tiny array electrode
1) silicon oxidation
A. cleaning silicon chip
At first with silicon slice placed at 30% H
2O
2And H
2SO
4By in 1: 5 proportional arrangement cleaning fluid, carry out electric furnace heating 20 minutes, clean up with deionized water again after the cooling, dry up with nitrogen then, put into the baking oven baking 30 minutes of 120 ° of C at last again, to go out water vapor.
B. oxidation produces silicon dioxide
At silicon face growth SiO
2Method chemical vapor deposition and thermal oxide are generally arranged.The instrument of chemical vapor deposition oxide is relatively expensive, and the cost of manufacture of production oxide layer is than higher, uses under the situation of low temperature needing usually.The manufacturing cost of thermal oxide is cheap relatively, but structure must can withstand pyroprocessing, and silicon thermal oxidation has two kinds of wet-oxygen oxidation and dry-oxygen oxidations.
Wet-oxygen oxidation: Si (s)+2H
2O (g)-＞SiO
2+ 2H
2(g)
Dry-oxygen oxidation: Si (s)+O
2(g)-＞SiO
2(s)
The thermal oxide of silicon is normally accomplished in the tubular type stove, and its operating temperature is approximately 850 ℃-1150 ℃.Dry-oxygen oxidation uses pure oxygen as oxygenant, during oxidation with pure oxygen with as the nitrogen of the thinning agent oxidation furnace of flowing through together.Therefore oxidation rate depends on that oxygen is diffused into the speed of silicon-silicon oxide interface, and along with the increase of oxidated layer thickness, oxidation rate is also got off with regard to slow, so dry-oxygen oxidation is very slowly.If there is water vapor, oxygen will improve through the rate of diffusion of oxide layer greatly.Hydrone can destroy the atomic link between silicon-oxygen-silicon and form 2-OH group.This scission of link structure is with respect to making oxygen molecule move more easily, so oxidation rate is very fast.The quality of oxide layer that dry-oxygen oxidation obtains is better than the oxide layer of wet-oxygen oxidation, in order to obtain good oxide layer and oxidation fast, and dried-wet-dried method for oxidation oxidation that the present invention adopts, actual temp and step are as shown in table 1 below.
Table 1 silicon dioxide oxide layer making step and temperature
| | Temperature | Time | |
| 1. dry oxidation | ?1100℃ | ? |
|
| 2. wet oxidation | ?1100℃ | ? |
|
| 3. dry oxidation | ?1100℃ | ?30min |
2) making of gold electrode and graphical
The making of gold electrode will be adopted lift-off technology, and concrete processing step is following:
A. substrate is prepared: according to above-mentioned silicon chip cleaning silicon chip is cleaned; Nitrogen dries up; Oven dry (120 ℃ of 30min)
B. gluing
Photoresist is selected the AZ4620 positive photoresist for use, carries out spin coating with the whirl coating platform, and the spin coating proceeding program is followed successively by: 1000rpm, 10s and 3000rpm, 30s.
C. baking before
Spin coating is accomplished the back and directly silicon chip is put into 80 ℃ baking oven and place behind 30～40min directly taking-up and carry out photoetching.
D. exposure
Time shutter is chosen as 35s.
E. develop
At first dispose developer solution, volume ratio is AZ400K: H
2O=1: 3, the silicon chip after the exposure is put into developer solution rock 40s, clean in the deionized water then, flush time is approximately 10s, dries up with nitrogen at last.Should examine under a microscope development effect after accomplishing above step,, should append development time, until developing fully if do not develop fully.
F. steam gold
Steam Jin Qianying and carry out plasma treatment, increase the adhesiveness of metal with the effect that reaches activating surface.Because gold is not strong with the adhesiveness of silicon chip, therefore should steam one deck titanium earlier before the steaming gold in addition, its thickness is 5～15nm, is steaming gold then, and the thickness of gold is 200nm.
G. remove photoresist
The silicon chip that steamed gold is put into acetone, after placement a period of time (approximately 30min), have the part photoresist to roll, just wash silicon face,,, and then use alcohol wash up to remaining fully gold electrode so that residual photoresist is washed out with injection needle if observe.
3) the polyimide layer array is made
A. simply clean
Earlier with silicon chip immerse sonicated in the acetone (1～5min), take out then and put into alcohol and shake 1～5min, use washed with de-ionized water at last; Nitrogen dries up; Put into baking oven and dry, temperature is that 120 ℃ of times are 20～40min.
B. gluing
Photoresist is selected AP2210 for use, and polyimide (PI) positive photoresist carries out spin coating with the whirl coating platform, and the spin coating proceeding program is followed successively by: 1000rpm, 10s and 2000rpm, 30s.
C. baking before
On hot plate, hot plate temperature is set at 100 ℃ with the silicon slice placed that has been coated with glue, and be 5～10min heat time heating time.
D. exposure
Time shutter is 65s.
E. develop
Developer solution is configured to 2.38%TMAH, and development time is 35s.
F. solidify
Silicon slice placed after developing is heated to 350 ℃ in curing oven, the annealing solidification process has been accomplished in cooling rapidly then.
Above step is carried out scribing after accomplishing, and with tiny array electrode, platinum combines the formation three-electrode system to accomplish following electroplating technology to electrode and Ag/AgCl contrast electrode.
Two, electroplate the bismuth film
1) electroplate liquid configuration
The bismuth of reporting in the document is electroplated supporting electrolyte has multiple [Legeai, S., Soropogui, K.; Cretinon, M., Vittori, O.; Heeren De Oliveira, A., Barbier, F.; And Grenier-Loustalot, M.F., Analytical and bioanalytical chemistry, Economic bismuth-film microsensor foranodic stripping analysis of trace heavy metals using differential pulsevoltammetry.2005; 383,839-847.], as shown in table 1.
Several kinds of configuration modes of table 1 bismuth electroplate liquid supporting electrolyte
| Supporting electrolyte |
| KNO31mol?L -1+HNO31％ |
| Acetate?buffer?0.1mol?L -1 |
| HCl?5mol?L -1+NH4OH?1.5mol?L -1+gelatin?1.5g?L -1 |
| HNO30.125mol?L -1+H2NSO3H?0.04mol?L -1+gelatin?1.5g?L -1 |
The present invention selects for use following electroplate liquid to carry out the plating of bismuth:
0.015mol/L Bi (NO
3)
35H
2O+1mol/L KNO
3+ 1%HNO
3(mass percent)
2) electroplate
Step is following:
A. dispose the sulfuric acid solution of 1M, three electrodes are put into wherein, carry out cyclic voltammetry scanning (scope :-0.2V～1.5V, sweep velocity is 50mV/s, cycle index is 5).The configuration of the sulfuric acid of 1mol/L: select 98% the concentrated sulphuric acid for use, density is 1.84kg/L, and amount of substance is 18.4mol/L, the sulfuric acid of the 1mol/L of configuration 500ml
0.5L×1mol/L＝x×18.4mol/L
x＝27.174ml
The volume of promptly getting the concentrated sulphuric acid is 27.174ml.
B. electroplate liquid is put on the magnetic stirring apparatus, three-electrode system is put into electroplate liquid, begins to stir.Size of current during according to plating shows that adding to stir and do not add the stirring electroplating current has very big difference, adds stirring and can improve electroplating efficiency.
C. setting-up time is 2min, sets the plating current potential to be-0.3V.
Three, heavy metal detects
Constitute the heavy metal detecting sensor by the plating bismuth of above preparation gold tiny array electrode as the working electrode of stripping voltammetry,, set the stripping voltammetry parameter value, detect with the heavy metal of accomplishing plumbous cadmium or nickel through the configuration damping fluid, wherein,
1) damping fluid configuration
Acetate-sodium acetate buffer: pH value 4.4, prescription: the 0.3mol/L acetate (mass percent) of the sodium acetate of 3.7% 0.2mol/L+6.3%
2) set the stripping voltammetry parameter
Parameter such as following table:
| The parameter title | Parameter value |
| Enrichment time | 2min |
| Accumulating potential | -1.5V |
| Resting potential | -1.35V |
| The tranquillization time | 15s |
| The scanning take-off potential | -1.35V |
| Scanning stops current potential | -0.05V |
| Sweep velocity | 8mV/s |
| Recurrence interval | 500ms |
| Pulse-response amplitude | 50mV |
| Sampling time | 50ms |
| Pulse width | 100ms |
3) measurement result analysis
Heavy metal sensor by plating bismuth gold tiny array electrode constitutes has replaced mercury and other heavy metals to react with bismuth, can be like this detect safer.
The introducing of tiny array electrode can be brought lot of advantages in addition: be swift in response, signal to noise ratio (S/N ratio) is high, to advantages such as end liquid degree of dependence are low.The result shows: sensor can well be accomplished the detection to common heavy metal such as lead, cadmium, nickel, measures sensitivity and can reach national drinking water standard, does not need operation bidirectional can accomplish the detection to heavy metal ion in the orange juice simultaneously.
Claims (6)
1. a method for making that is used for the plating bismuth gold tiny array electrode of heavy metal detection is characterized in that comprising the making of golden tiny array electrode and the plating bismuth technology two parts on the golden tiny array electrode, wherein:
(1) making of golden microelectrode is at SiO
2On at first produce metallic pattern, and then on metallic pattern the polyimide of spin coating one deck Photosensitive, carry out the photoetching second time then, carry out etching and obtain tiny array electrode;
(2) plating bismuth technology comprises the selected of electroplate liquid configuration and electroplating technological parameter, the configuration of electroplate liquid: 0.015mol/L Bi (NO
3) 5H
2O+1mol/L KNO
3+ 1%HNO
3, the time of electroplating bismuth is 2min, current potential is-0.3V should add magnetic agitation during plating.
2. by the described method of claim 1, it is characterized in that comprising:
A. the making of golden tiny array electrode:
1) silicon oxidation
A. cleaning silicon chip
At first with silicon slice placed at 30% H
2O
2And H
2SO
4By in 1: 5 proportional arrangement cleaning fluid, carry out electric furnace heating 20 minutes, clean up with deionized water again after the cooling, dry up with nitrogen then, put into 120 ℃ baking oven baking 30 minutes at last again, to remove water vapor;
B. oxidation generates silicon dioxide
The dry method that adopts dry oxidation-wet oxidation-dry oxidation and wet oxidation be method of mixing mutually, specifically is earlier at 1100 ℃ of dry oxidation 30min, follows 1100 ℃ of wet oxidation 6h, last 1100 ℃ of dry oxidation 30min;
2) making of gold electrode and figure ratio
Adopt lift-off technology to make gold electrode
A. substrate is prepared: clean according to the silicon chip of above-mentioned silicon chip cleaning a) after to oxidation; Nitrogen dries up and dries;
B. gluing
Select the AZ4620 positive photoresist for use, carry out spin coating with the whirl coating platform, the spin coating proceeding program is followed successively by: 1000rpm, 10s and 3000rpm, 30s;
C. baking before
Spin coating is accomplished the back and directly silicon chip is put into 80 ℃ baking oven and carry out preceding baking, after the preceding baking directly taking-up carry out photoetching;
D. exposure
Time shutter is chosen as 35s;
E. develop
Silicon chip after the exposure is put into developer solution rock 40s, in deionized water, clean then, dry up with nitrogen at last; Should examine under a microscope development effect after accomplishing above step,, should append development time, until developing fully if do not develop fully;
F. steam gold
Steam Jin Qianying and carry out plasma treatment, increase the adhesiveness of metal with the effect that reaches activating surface, silicon chip should steam one deck titanium earlier before steaming gold, and then steams golden;
G. remove photoresist
The silicon chip that steamed gold is put into acetone, behind placement 30～40min, have the part photoresist to roll, just wash silicon face,,, and then use alcohol wash up to remaining fully gold electrode so that residual photoresist is washed out with injection needle if observe;
3) the polyimide layer array is made
A. clean
The silicon chip that will steam earlier behind the gold immerses sonicated in the acetone, takes out then to put into alcohol and shake, and uses washed with de-ionized water at last; Nitrogen dries up; Put into baking oven, bake out temperature is 120 ℃;
B. gluing
Select AP2210 for use, the polyimide positive photoresist carries out spin coating with the whirl coating platform, and the spin coating proceeding program is followed successively by: 1000rpm, 10s and 2000rpm, 30s;
C. baking before
Be to heat on 100 ℃ the hot plate the silicon slice placed that has been coated with glue in temperature;
D. exposure
Time shutter is 65s;
E. develop
Developer solution is configured to 2.38%TMAH, and development time is 35s;
F. solidify
Silicon slice placed after developing is heated to 350 ℃ in curing oven, cooling is solidified to accomplish annealing rapidly then;
G. above step is carried out scribing after accomplishing, and with golden tiny array electrode, platinum combines the formation three-electrode system to accomplish following electroplating technology to electrode and Ag/AgCl contrast electrode;
B. plate bismuth technology
1) electroplate liquid configuration
The electroplate liquid that uses consists of: 0.015mol/L Bi (NO
3)
35H
2O+1mol/L KNO
3+ 1%HNO
3
2) electroplating technology step
A. dispose the sulfuric acid solution of 1M earlier, the three-electrode system that steps A is made is put into wherein, carry out cyclic voltammetry scanning, sweep limit :-0.2V～1.5V, sweep velocity is 50mV/s;
B. electroplate liquid is put on the magnetic stirring apparatus, three-electrode system is put into electroplate liquid and is begun and stirs; Size of current during according to plating shows, adds stirring and can improve electroplating efficiency;
C. setting electroplating time is 2min, and the plating current potential of setting is-0.3V.
3. press the described method of claim 2, when it is characterized in that gold electrode is made,
1) the described substrate drying condition of step a is 120 ℃, 30min;
2) the described preceding baking time of step c is 30～40min;
3) the described developer solution volume ratio of step e is A2400K: H
2O=1: 3;
4) the described thickness that steams the preceding steaming earlier of gold one deck titanium of step f is 5～15min.
4. press the described method of claim 2, when it is characterized in that polyimide array is made,
1) the described immersion acetone of step a sonicated 1～5min, concussion time 1～5min in the alcohol; Drying time is 20～40min;
2) step c described before baking be 5～10min heat time heating time.
5. the plating bismuth gold tiny array electrode that uses each described method of claim 1～4 to make detects the method for heavy metal; It is characterized in that at first constituting heavy metal detecting sensor, configuration damping fluid, setting the stripping voltammetry parameter value by the working electrode of plating bismuth gold tiny array electrode as stripping voltammetry; The heavy metal to lead, cadmium or nickel detects in the orange juice to accomplish, wherein
1. damping fluid is acetate-sodium acetate solution, consists of the 0.3mol/L acetate of 3.7% 0.2mol/L sodium acetate+6.3%, the pH=4.4 of described damping fluid
2. the stripping voltammetry parameter of setting is enrichment time 2min, and accumulating potential-1.5, resting potential-1.35V, tranquillization time 15s, scanning take-off potential-1.35V, scanning stop current potential-0.05V, sweep velocity 8mV/s, recurrence interval 500ms, pulse-response amplitude 50mV, sampling time 50ms, pulse width 100ms.
6. by the method for the described detection heavy metal of claim 5, it is characterized in that detection sensitivity reaches national drinking water standard.
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| CN105388201A (en) * | 2015-10-21 | 2016-03-09 | 浙江大学 | Three-electrode integrated electrochemical sensor based on microelectrode array |
| CN105606673A (en) * | 2016-02-03 | 2016-05-25 | 北京大学 | Chip applicable to electrochemical real-time PCR and preparation method of chip |
| CN106198625A (en) * | 2016-06-02 | 2016-12-07 | 东北电力大学 | One heavy metal species on-line monitoring system device in situ |
| CN108658035A (en) * | 2018-04-28 | 2018-10-16 | 北京航天控制仪器研究所 | MEMS air flow meter manufacturing method of chip with back cavity structure |
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