CN104034773B - Gold film microelectrode array and manufacture method thereof - Google Patents
Gold film microelectrode array and manufacture method thereof Download PDFInfo
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Abstract
The invention discloses a gold film microelectrode array, a microelectrode array and a manufacture method of the microelectrode array. The method comprises the steps of self-assembling amino silane on the inner wall of a hydroxylated capillary, assembling single-layer gold sol nano particles under the static action of amidogen and nanogold, and slowly injecting chemical plating liquid containing chloroauric acid and hydroxylamine hydrochloride in the capillary to grow a gold thin film. Wet process deposition is adopted to prepare the gold film microelectrode and the microelectrode array, a heat source is not required, the operation is simple and easy, the size is controllable, the potential flammable and combustible risk of thermal cracking of a carbon source for preparation of the microelectrode array is avoided, and a continuous uniform gold layer with the controllable thickness can be formed on the inner wall of glass or the capillaries with different sizes and shapes. The single microelectrode and the electrode array containing three microelectrodes, prepared by adopting the method, can be potentially applied to the micro-zone analysis of chemical release on cell surfaces, and have important functions of knowing cell surface kinetics and deeply understanding cell surface physiological status, processes and mechanisms.
Description
Technical field
The invention belongs to microelectrode and microelectrode array preparation field, it is related to a kind of golden film microelectrode array and its making side
Method.
Background technology
Microelectrode refers to one-dimensional a size of micro- electricity (10 of electrode-6M) level is to nanometer (10-9M) a class electrode of level.Work as electricity
The one-dimensional size of pole, when grade is reduced to micron order, shows many excellent electrochemical characteristics, and such as high stable state is electric
Current density, extremely short response time, current of polarization are little, ohm voltage drop is little, mass transfer velocity is high, signal to noise ratio is big, can be used for transient state electricity
Pole process study, high impedance electrolyte system and current system.Microelectrode array is to be formed in parallel by multiple microelectrodes, and it was both
Remain the excellent physically and electrically chemical characteristic of single microelectrode originally, high current density and good output can be obtained again
Signal.On microelectrode array, can record simultaneously and stimulate multiple sites, this greatly extends the visual field of research, simultaneously
Maintain to single celled accurate recording it is easy to detect unicellular and cellular network many kinds of parameters, bio-compatibility is good, tool again
Have wide practical use.
The method preparing microelectrode array at present mainly has etching method, lithographic methods and construction from part.The most frequently used etching
Method has Soft lithograph technology, including micro-contact printing, duplicating molded, microtransfer molding and Micromolding in Capillaries etc. [xia y n,
whitesides g m“soft lithography”[j].angew.chem.int.ed.1998,37:550-575].Such side
Although method can be applied on the surface of various materials and different chemical property, there is the such as deformation of elastomeric stamp, little yardstick
The problems such as high accuracy alignment alignment difficulties of small body, is it is still necessary to carry out in-depth study and development.For in etching method
Although photoetching process can be used to construct the microelectrode array of regular metal or carbon, its process is complicated, needs ultra-clean work
Environment and expensive equipment.Lithographic methods can prepare disposable microelectrode and array in batches, but can only obtain
Relatively large sized microelectrode array is it is impossible to construct the high microelectrode array of spatial accuracy.It is special that physics construction from part does not need
Experimental facilitiess, different electrode material such as gold, platinum, silver, nickel, tungsten and carbon etc. material can be fixed on inside insulation support body
Form microelectrode or array, method is simple, is widely used.
At present, the high hydrocarbon gas thermal cracking of phosphorus content is mainly used based on the method that construction from part prepares microelectrode array
Prepare carbon-based microelectrode and array, the method needs, using high temperature naked light, there is potentially inflammable and explosive risk.Need to send out
Open up the preparation method of a kind of microelectrode preparing golden material in a mild condition and array.
Content of the invention
It is an object of the invention to provide a kind of golden film microelectrode array and preparation method thereof.
The golden material microelectrode of preparation and/or the method for microelectrode array that the present invention provides, comprise the steps:
1) under the impetus of micro-injection pump, supporter is carried out, then with hydroxylating agent to supporter
After inwall carries out hydroxylating and silanization successively, push nano gold sol, then after deionized water cleaning, then push by gold chloride
Aqueous solution and oxammonium hydrochloride. aqueous solution composition mixed liquor, that is, described supporter inwall deposit and one layer of golden film；
Described supporter is the supporter of single microelectrode or the supporter of microelectrode array；
2) by step 1) the gained deposition supporter that has golden film dries, by copper wire insertion support internal contact with golden film after,
By the tip of supporter and tail end sealing, solidify, obtain described gold material microelectrode and/or microelectrode array.
The step 1 of said method) in, the material constituting described microelectrode supporter is glass, quartzy or organic polymer；
Described supporter is the capillary tube most advanced and sophisticated with micron；The most advanced and sophisticated diameter of described micron is specially 10-50 μm；
The thickness of described golden film is 500nm-15 μm.
Wherein, the supporter of described single microelectrode is to be prepared according to the method comprising the steps: by a hair
The tip of tubule is drawn into micron-sized most advanced and sophisticated and obtains；
The supporter of described microelectrode array is to be prepared according to the method comprising the steps: will at least two capillarys
The tip of pipe is drawn into a micron-sized tip and obtains.
Described step 1) in cleaning step, cleaning solvent for use is followed successively by acetone and deionized water；Described acetone and go from
The volume of sub- water is 1.0-6.0ml, and the flow velocity of cleaning is 8-25 μ l/min, specially 15 μ l/min, 20 μ l/min, 15-
20μl/min；
In described hydroxylation steps, hydroxylating agent used h for 7:3 by volume ratio2so4: h2o2Composition, hydroxylated
Time is 10-30min, specially 20min, 10-20min；The flow velocity that hydroxylating agent pushes is 8～25 μ l/min, specially
15μl/min、20μl/min、15-20μl/min；
In described silylation step, silylating reagent used is the methanol or water-soluble of 3- TSL 8330
Liquid, mass percentage concentration is 1%-5%, and specially 3%；The time of silanization be 10-30min, specially 10,15,25,
10-25 or 15-25min, the flow velocity that silylating reagent pushes is 10-25 μ l/min, specially 15 μ l/min；
In the described step pushing nano gold sol, the flow velocity pushing is 10-25 μ l/min, specially 15 μ l/min, 17 μ
L/min or 15-17 μ l/min；The consumption of nano gold sol is 5-10ml, specially 7ml, 5-7ml；
In the mixed liquor that the aqueous solution of the described aqueous solution by gold chloride and oxammonium hydrochloride. forms, the aqueous solution of gold chloride
Mass percentage concentration is 0.01%-0.1%, specially 0.05%, 0.05-0.1%, the concentration of the aqueous solution of oxammonium hydrochloride. is 2-
16mmol/l, specially 4mol/l, the volume ratio of the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride. is 10:1-2；
The consumption of mixed liquor is 0.5-5ml, specially 0.5ml, 2.5ml, 0.5-2.5ml or 2.5-5ml；
The flow velocity pushing is 4-20 μ l/min, specially 15 μ l/min, 4-15 μ l/min, 10 μ l/min, 4-10 μ l/min
Or 10-15 μ l/min.
Described step 2) in baking step, temperature is 70-90 DEG C, specially 80 DEG C, the time is 6-12 hour, concretely
10 hours.
In addition, described step 1) in, nano gold sol is to be prepared according to the method comprising the steps:
Reacted with the aqueous solution backflow of sodium citrate after the aqueous solution of gold chloride is heated to boiling, reaction finishes
And obtain；Wherein, the mass percentage concentration of the aqueous solution of described gold chloride is 0.01%-0.1%, the aqueous solution of described sodium citrate
Mass percentage concentration be 0.1%-1.0%；
The aqueous solution of described gold chloride is 40-100:1 with the volume ratio of the aqueous solution of sodium citrate；
In described reactions steps, the time is 9-12min, specially 10min.
In addition, the golden material microelectrode preparing according to the method described above and/or microelectrode array, fall within the present invention's
Protection domain.
The invention provides a kind of method preparing golden material microelectrode and microelectrode array.The method can be in different size
With the capillary tube inner wall of shape formed continuously, the controlled layer gold of all even thickness.Prepare microelectrode with existing pyrolysis acetylene gas
Technology is compared, and the method is without thermal source, it is to avoid thermal cracking carbon source prepares the potential inflammable and explosive risk of microelectrode array, simultaneously
Operation is simple for the method, nontoxic, and size is controlled, with low cost, can expand to prepare other metals as silver, alloy platinum material
Microelectrode and microelectrode array, it is easy to accomplish batch production.
Brief description
Fig. 1 is capillary tube inner wall self-assembled nanometer aurosol and the golden material nano film preparation microelectrode schematic diagram of growth
(a) and sectional view (b)
Fig. 2 is before individual glass capillary tube (a) and capillary array (b) deposited gold film containing three capillaries (upper figure)
(figure below) photo comparison figure afterwards.
Fig. 3 is to deposited the microelectrode that the capillary tube of golden film formed in 1mol/l h2so4The circulation volt of activation in solution
Antu (a), the single golden film microelectrode being formed after encapsulation are in k containing 1mmol/l3fe(cn)6(supporting electrolyte in solution
Solution, 0.1mol/l kcl) cyclic voltammogram (b) and the array that formed after encapsulation in three golden film microelectrodes distinguish
In k containing 1mmol/l3fe(cn)6The cyclic voltammogram (c) of (supporting electrolyte solution, 0.1mol/l kcl) in solution.In (a)
Illustration is quartz ampoule observed under scanning electron microscope and the layer gold being deposited, and layer gold thickness is up to 10 μm.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
Method of stating is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1, preparation golden film microelectrode
1) preparation of nano gold sol:
After the aqueous solution of the gold chloride that 100ml mass percentage concentration is 0.1% is heated to boiling, add 2.5ml mass hundred
Point concentration is the aqueous solution of 1% sodium citrate, and flow back 10min, and solution is changed into aubergine from golden yellow, removes thermal source, treats molten
Liquid is cooled to room temperature, obtains nano gold sol, and low-temperature dark preserves.
2) preparation of supporter:
The tip butane fire maker of a piece quartz capillary is drawn into micron-sized tip under the conditions of naked light, this is micro-
A diameter of 10 μm of meter level tip, prepare the supporter of gold film electrode as next step.
3) capillary tube inner wall wet method deposition gold:
Under the impetus of micro-injection pump, 2ml acetone, 1ml deionized water are pushed 2 successively) in has drawn prop up
Support body is carried out, and the flow velocity of cleaning is 20 μ l/min；
Again by the h for 7:3 by volume ratio2so4: h2o2The piranha solution of composition, is passed through negative with the flow velocity of 20 μ l/min
Pressure effect pushes after capillary tube inner wall carries out surface hydroxylation 20min；
Under the impetus of micro-injection pump, the silylating reagent 3- aminopropyl that 5ml mass percentage concentration is 1%
The aqueous solution of trimethoxy silane, pushes inwall with the flow velocity of 15 μ l/min and carries out silicon in hydroxylated capillary tube supporter
After alkanisation processes 25min, deionized water cleans up afterwards；
Again under the impetus of micro-injection pump, 5ml aurosol solution is pushed inwall with the flow velocity of 15 μ l/min
Through in the capillary tube supporter of silanization, making nanometer gold be fixed on capillary tube inner wall, deionized water cleans up afterwards；
Again under the impetus of micro-injection pump, volume ratio is golden for 0.01% chlorine by mass percentage concentration for 10:1
Aqueous acid pushes inwall with the mixed liquor 5ml of the aqueous solution composition of the oxammonium hydrochloride. of 4mmol/l with the flow velocity of 15 μ l/min
Fix in the capillary tube of nanometer gold, capillary tube inner wall can grow into continuous uniform and the nanometer of shiny appearance is thick to micron
The au film of degree.
The chemical process of capillary surface functionalization and deposition thereof is as shown in figure 1, before and after capillary tube inner wall deposited gold film
Photo figure in kind as shown in Figure 2 a.
Shown in Fig. 3 (a) is the capillary tube that deposited golden film in this embodiment in 1mol/l h2so4In solution, activation follows
Ring voltammogram, in sulphuric acid, 1.4v about corresponding be au oxidizing process, 0.9v about corresponding be au reduction process,
Illustrate that au film is successfully fixed on capillary tube inner wall.
4) conducting of microelectrode and microelectrode array and encapsulation make:
By step 3) after gained deposition has the supporter of golden film to dry 12 hours in 70 DEG C, by copper wire insertion support internal with
Golden film contacts, and is sealed the tip of capillary tube and tail end using epoxy resin, baking and curing, that is, obtain present invention offer
Golden material microelectrode with wet method deposition preparation.
According to as above method, the number of supporter is increased to 3, the golden material microelectrode battle array of present invention offer is provided
Row.
In Fig. 3 (a), illustration is quartz ampoule observed under scanning electron microscope and the golden film being deposited, the thickness of golden film
Degree is up to 10 μm.
Fig. 3 (b) is the single golden film microelectrode being formed after encapsulation in k containing 1mmol/l3fe(cn)6In solution (
Hold electrolyte solution, 0.1mol/l kcl) cyclic voltammogram it can be seen that gold film electrode shows the steady of typical microelectrode
State current-responsive, illustrates the microelectrode being successfully prepared into based on the method for deposited gold film.
Embodiment 2, preparation golden film microelectrode
1) preparation of nano gold sol: with embodiment 1 step 1) identical, the citric acid being only 1% by mass percentage concentration
The consumption of the aqueous solution of sodium replaces with 1ml by 2.5ml；
2) preparation of supporter: three quartz capillary butane fire makers are reversed to be drawn under the conditions of naked light carry
There is the array that three most advanced and sophisticated capillaries are formed, tip diameter is 50 μm, prepares the support of gold film electrode as next step
Body.
3) capillary tube inner wall wet method deposition gold: under the impetus of micro-injection pump, by 2ml acetone, 2ml deionized water
Push 2 successively) in the supporter that drawn be carried out, the flow velocity of cleaning is 20 μ l/min；
Again by the h for 7:3 by volume ratio2so4: h2o2The piranha solution of composition, is passed through negative with the flow velocity of 15 μ l/min
Pressure effect pushes after capillary tube inner wall carries out surface hydroxylation 30min；
Under the impetus of micro-injection pump, the silylating reagent 3- aminopropan that 10ml mass percentage concentration is 5%
The aqueous solution of base trimethoxy silane, pushes inwall with the flow velocity of 25 μ l/min and carries out in hydroxylated capillary tube supporter
Silanization treatment 15min, afterwards deionized water clean up；
Again under the impetus of micro-injection pump, 10ml aurosol solution is pushed inwall with the flow velocity of 25 μ l/min
Through in the capillary tube supporter of silanization, making nanometer gold be fixed on capillary tube inner wall, deionized water cleans up afterwards；
Again under the impetus of micro-injection pump, the chlorine that volume ratio is 0.1% for 10:2 by mass percentage concentration
Golden aqueous acid is pushed with the flow velocity of 4 μ l/min with the mixed liquor 0.5ml of the aqueous solution composition of the oxammonium hydrochloride. of 16mmol/l
Inwall has been fixed in the capillary tube of nanometer gold, and capillary tube inner wall can grow into continuous uniform and the nanometer of shiny appearance is extremely micro-
The au film of meter Hou Du.
The surface-functionalized chemical process with deposition thereof of capillary array is as shown in figure 1, capillary array inwall deposits
Photo figure in kind before and after golden film is as shown in Figure 2 b.
4) conducting of microelectrode and microelectrode array and encapsulation make: by step 3) gained deposition have the supporter of golden film in
After 90 DEG C dry 6 hours, three copper wires are inserted three supports respectively and contacts with golden film in vivo, using epoxy resin by capillary tube
Tip and tail end sealed, baking and curing, that is, obtain the present invention offer with wet method deposition preparation golden material microelectrode
Array.
Fig. 3 (c) be through encapsulation after formation array in three golden film microelectrodes respectively containing 1mmol/lk3fe(cn)6
In solution, the cyclic voltammogram of (supporting electrolyte solution, 0.1mol/l kcl) is it can be seen that three gold film electrodes all show
The steady-state current response of typical microelectrode, the method based on deposited gold film that illustrates successfully has been prepared into and has been made up of three microelectrodes
Microelectrode array.
Embodiment 3, preparation golden film microelectrode
1) preparation of nano gold sol: according to embodiment 1 step 1), the gold chloride being only 0.1% by mass percentage concentration
Aqueous solution replace with 0.05% gold chloride aqueous solution, the sodium citrate that 2.5ml mass percentage concentration is 1% water-soluble
Liquid replaces with the aqueous solution of the sodium citrate of 2ml0.6%；
2) preparation of supporter: with embodiment 1 step 2)；
3) capillary tube inner wall wet method deposition gold:
Under the impetus of micro-injection pump, 2ml acetone, 2.5ml deionized water are pushed 2 successively) in drawn
Supporter is carried out, and the flow velocity of cleaning is 15 μ l/min；
Again by the h for 7:3 by volume ratio2so4: h2o2The piranha solution of composition, is passed through negative with the flow velocity of 10 μ l/min
Pressure effect pushes after capillary tube inner wall carries out surface hydroxylation 10min；
Under the impetus of micro-injection pump, the silylating reagent 3- aminopropyl that 2ml mass percentage concentration is 3%
The aqueous solution of trimethoxy silane, pushes inwall with the flow velocity of 10 μ l/min and carries out silicon in hydroxylated capillary tube supporter
Alkanisation processes 10min, and deionized water cleans up afterwards；
Again under the impetus of micro-injection pump, 7ml aurosol solution is pushed inwall with the flow velocity of 17 μ l/min
Through in the capillary tube supporter of silanization, making nanometer gold be fixed on capillary tube inner wall, deionized water cleans up afterwards；
Again under the impetus of micro-injection pump, volume ratio is golden for 0.05% chlorine by mass percentage concentration for 10:1
The mixed liquor 2.5ml of the aqueous solution composition of the oxammonium hydrochloride. of aqueous acid and 2mmol/l is pushed interior with the flow velocity of 10 μ l/min
Wall has been fixed in the capillary tube of nanometer gold, and capillary tube inner wall can grow into the nanometer of continuous uniform and shiny appearance to micron
The au film of thickness.
The chemical process of capillary surface functionalization and deposition thereof is as shown in Figure 1.
4) conducting of microelectrode and microelectrode array and encapsulation make:
By step 3) after gained deposition has the supporter of golden film to dry 10 hours in 80 DEG C, by copper wire insertion support internal with
Golden film contacts, and is sealed the tip of capillary tube and tail end using epoxy resin, baking and curing, that is, obtain present invention offer
Golden material microelectrode with wet method deposition preparation.
Claims (22)
1. a kind of method preparing golden material microelectrode, comprises the steps:
1) under the impetus of micro-injection pump, after cleaning supporter, with hydroxylating agent, hydroxyl is carried out to the inwall of supporter
Base, then carry out silanization, then push nano gold sol, after deionized water cleaning, then push by gold chloride aqueous solution and
The mixed liquor of the aqueous solution composition of oxammonium hydrochloride., obtains one layer of golden film in the inwall deposition of described supporter；
Described supporter is the supporter of single microelectrode；
The material constituting described supporter is glass, quartzy or organic polymer；
Described supporter is the capillary tube most advanced and sophisticated with micron order；
2) by step 1) the gained deposition supporter that has golden film dries, by copper wire insertion support internal contact with golden film after, will prop up
The tip of support body and tail end sealing, solidification, obtain described gold material microelectrode.
2. method according to claim 1 it is characterised in that: described step 1) in, most advanced and sophisticated a diameter of of described micron order
10-50μm；
The thickness of described golden film is 500nm-15 μm.
3. method according to claim 2 it is characterised in that: the thickness of described golden film be 10 μm.
4. method according to claim 1 it is characterised in that: the supporter of described single microelectrode be according to include as follows
The method of step is prepared: the tip of a capillary is drawn into micron-sized most advanced and sophisticated and obtains.
5. method according to claim 1 it is characterised in that: described step 1) in cleaning step, cleaning solvent for use according to
Secondary for acetone with deionized water；The volume of described acetone and deionized water is 1.0-6.0ml, and the flow velocity of cleaning is 10-25 μ
l/min；
In described hydroxylation steps, hydroxylating agent used h for 7:3 by volume ratio2so4: h2o2Composition, the hydroxylated time is
10-30min；The flow velocity that hydroxylating agent pushes is 8-25 μ l/min；
In described silylation step, silylating reagent used is methanol or the aqueous solution of 3- TSL 8330, matter
Amount percentage concentration is 1%-5%；The time of silanization is 10-30min, and the flow velocity that silylating reagent pushes is 10-25 μ l/
min；
In the described step pushing nano gold sol, the flow velocity pushing is 10-25 μ l/min；The consumption of nano gold sol is 5-
10ml；
In the mixed liquor that the aqueous solution of the described aqueous solution by gold chloride and oxammonium hydrochloride. forms, the quality of the aqueous solution of gold chloride
Percentage concentration is 0.01%-0.1%, and the concentration of aqueous solution of oxammonium hydrochloride. is 2-16mmol/l, the aqueous solution of gold chloride and hydrochloric acid
The volume ratio of the aqueous solution of azanol is 10:1-2；The mixing that the aqueous solution of the described aqueous solution by gold chloride and oxammonium hydrochloride. forms
The consumption of liquid is 0.5-5ml；The flow velocity pushing is 4-20 μ l/min.
6. method according to claim 5 it is characterised in that: described push by the aqueous solution of gold chloride and oxammonium hydrochloride.
In the step of mixed liquor of aqueous solution composition, the flow velocity pushing is 15 μ l/min.
7. method according to claim 1 it is characterised in that: described step 2) in baking step, temperature is 70-90 DEG C,
Time is 6-12 hour.
8. according to the arbitrary described method of claim 1-7 it is characterised in that: described step 1) in, nano gold sol be according to
The method comprising the steps is prepared:
Reacted with the backflow of the aqueous solution of sodium citrate after the aqueous solution of gold chloride is heated to boiling, reaction finish and
?.
9. method according to claim 8 it is characterised in that: the mass percentage concentration of the aqueous solution of described gold chloride is
0.01%-0.1%, the mass percentage concentration of the aqueous solution of described sodium citrate is 0.1%-1.0%；
The aqueous solution of described gold chloride is 40-100:1 with the volume ratio of the aqueous solution of sodium citrate；
In described reactions steps, the time is 9-12min.
10. method according to claim 9 it is characterised in that: in described reactions steps, the time be 10min.
A kind of 11. methods preparing golden material microelectrode array, comprise the steps:
1) under the impetus of micro-injection pump, after cleaning supporter, with hydroxylating agent, hydroxyl is carried out to the inwall of supporter
Base, then carry out silanization, then push nano gold sol, after deionized water cleaning, then push by gold chloride aqueous solution and
The mixed liquor of the aqueous solution composition of oxammonium hydrochloride., obtains one layer of golden film in the inwall deposition of described supporter；
Described supporter is the supporter of microelectrode array；
The material constituting described supporter is glass, quartzy or organic polymer；
Described supporter is the capillary tube most advanced and sophisticated with micron order；
2) by step 1) the gained deposition supporter that has golden film dries, by copper wire insertion support internal contact with golden film after, will prop up
The tip of support body and tail end sealing, solidification, obtain described gold material microelectrode array.
12. methods according to claim 11 it is characterised in that: described step 1) in, the most advanced and sophisticated diameter of described micron order
For 10-50 μm；
The thickness of described golden film is 500nm-15 μm.
13. methods according to claim 12 it is characterised in that: the thickness of described golden film be 10 μm.
14. methods according to claim 11 it is characterised in that: the supporter of described microelectrode array be according to include as
The method of lower step is prepared: the tip of at least two capillaries is drawn into a micron-sized tip and obtains.
15. methods according to claim 11 it is characterised in that: described step 1) in cleaning step, clean solvent for use
It is followed successively by acetone and deionized water；The volume of described acetone and deionized water is 1.0-6.0ml, and the flow velocity of cleaning is 10-
25μl/min；
In described hydroxylation steps, hydroxylating agent used h for 7:3 by volume ratio2so4: h2o2Composition, the hydroxylated time is
10-30min；The flow velocity that hydroxylating agent pushes is 8-25 μ l/min；
In described silylation step, silylating reagent used is methanol or the aqueous solution of 3- TSL 8330, matter
Amount percentage concentration is 1%-5%；The time of silanization is 10-30min, and the flow velocity that silylating reagent pushes is 10-25 μ l/
min；
In the described step pushing nano gold sol, the flow velocity pushing is 10-25 μ l/min；The consumption of nano gold sol is 5-
10ml；
In the mixed liquor that the aqueous solution of the described aqueous solution by gold chloride and oxammonium hydrochloride. forms, the quality of the aqueous solution of gold chloride
Percentage concentration is 0.01%-0.1%, and the concentration of aqueous solution of oxammonium hydrochloride. is 2-16mmol/l, the aqueous solution of gold chloride and hydrochloric acid
The volume ratio of the aqueous solution of azanol is 10:1-2；The mixing that the aqueous solution of the described aqueous solution by gold chloride and oxammonium hydrochloride. forms
The consumption of liquid is 0.5-5ml；The flow velocity pushing is 4-20 μ l/min.
16. methods according to claim 15 it is characterised in that: described push by the aqueous solution of gold chloride and oxammonium hydrochloride.
The step of mixed liquor of aqueous solution composition in, the flow velocity that pushes is 15 μ l/min.
17. methods according to claim 11 it is characterised in that: described step 2) in baking step, temperature is 70-90
DEG C, the time is 6-12 hour.
18. methods according to claim 11 it is characterised in that: described step 1) in, nano gold sol is according to inclusion
The method of following steps is prepared:
Reacted with the backflow of the aqueous solution of sodium citrate after the aqueous solution of gold chloride is heated to boiling, reaction finish and
?.
19. methods according to claim 18 it is characterised in that: the mass percentage concentration of the aqueous solution of described gold chloride is
0.01%-0.1%, the mass percentage concentration of the aqueous solution of described sodium citrate is 0.1%-1.0%；
The aqueous solution of described gold chloride is 40-100:1 with the volume ratio of the aqueous solution of sodium citrate；
In described reactions steps, the time is 9-12min.
20. methods according to claim 19 it is characterised in that: in described reactions steps, the time be 10min.
The golden material microelectrode that the arbitrary methods described of 21. claim 1-10 prepares.
22. the microelectrode array that the arbitrary methods described of claim 11-20 prepares.
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