CN104034773A - Gold film microelectrode array and manufacture method thereof - Google Patents
Gold film microelectrode array and manufacture method thereof Download PDFInfo
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- CN104034773A CN104034773A CN201410280120.1A CN201410280120A CN104034773A CN 104034773 A CN104034773 A CN 104034773A CN 201410280120 A CN201410280120 A CN 201410280120A CN 104034773 A CN104034773 A CN 104034773A
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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, relate to a kind of golden film microelectrode array and preparation method thereof.
Background technology
Microelectrode refers to that the one dimension of electrode is of a size of micro-electricity (10
-6m) level is to nanometer (10
-9m) a class electrode of level.In the time that the one dimension size of electrode is reduced to micron order from grade, show many good electrochemical characteristics, as high steady-state current density, extremely short response time, polarization current is little, ohm voltage drop is little, mass transfer velocity is high, signal to noise ratio (S/N ratio) is large, can be used for transient state electrode process study, high impedance electrolyte system and current system.Microelectrode array is to be formed in parallel by multiple microelectrodes, and it had both retained physics and the electrochemical properties of original single microelectrode excellence, can obtain again high current density and good output signal.On microelectrode array, can record simultaneously and stimulate multiple sites, this has expanded the visual field of research widely, keep again single celled accurate recording simultaneously, be easy to detect unicellular and many kinds of parameters cellular network, bio-compatibility is good, is with a wide range of applications.
The method of preparing at present microelectrode array mainly contains etching method, offset printing method and construction from part.The most frequently used etching method has soft lithographic technique, comprise [the Xia Y N such as micro-contact printing, duplicating molded, the micro-molding of transfer and Micromolding in Capillaries, Whitesides G M " Soft Lithography " [J] .Angew.Chem.Int.Ed.1998,37:550-575].Although these class methods can be applied on the surface of various materials and different chemical character, exist as problems such as the distortion of elastomeric stamp, the little elastomeric high precision alignment alignment difficulties of small scale, still need to carry out deep research and development.Although can be used for constructing regular metal or the microelectrode array of carbon for the photoetching process in etching method, its process complexity, needs ultra-clean working environment and expensive equipment.Offset printing method can be prepared disposable microelectrode and array in batches, but can only obtain the relatively large microelectrode array of size, can not construct the microelectrode array that spatial accuracy is high.Physics construction from part does not need special experimental facilities, different electrode materials can be formed to microelectrode or array as the materials such as gold, platinum, silver, nickel, tungsten and carbon are fixed on insulation support body inside, and method is simple, is widely used.
At present, the method for preparing microelectrode array based on construction from part is mainly to use the high hydrocarbon gas thermal cracking of carbon content to prepare microelectrode and the array of carbon back, and the method need to be used high temperature naked light, has potential inflammable and explosive risk.Need to develop a kind of preparation method of microelectrode and the array of preparing gold copper-base alloy under temperate condition.
Summary of the invention
The object of this invention is to provide a kind of golden film microelectrode array and preparation method thereof.
The method of preparing gold copper-base alloy microelectrode and/or microelectrode array provided by the invention, comprises the steps:
1) under the impetus of micro-injection pump, supporter is cleaned, with hydroxylation reagent, the inwall of supporter is carried out after hydroxylation and silanization successively again, push nano gold sol, again with after washed with de-ionized water, push again the mixed liquor being formed by the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride, in the inwall deposition of described supporter and layer of gold film;
Described supporter is the supporter of single microelectrode or the supporter of microelectrode array;
2) by step 1) the gained supporter that deposits golden film dries, after copper wire is inserted and contact with golden film in supporter, by the tip of supporter and tail end sealing, curing, obtains described gold copper-base alloy microelectrode and/or microelectrode array.
The step 1 of said method) in, the material that forms described microelectrode supporter is glass, quartz or organic polymer;
Described supporter is the kapillary with micron tip; The most advanced and sophisticated diameter of described micron is specially 10-50 μ m;
The thickness of described golden film is 500nm-15 μ m.
Wherein, the supporter of described single microelectrode is to obtain according to the method preparation comprising the steps: the tip of a capillary is drawn into micron-sized tip and obtains;
The supporter of described microelectrode array is to obtain according to the method preparation comprising the steps: the tip of at least two capillaries is drawn into a micron-sized tip and obtains.
Described step 1) in cleaning step, clean solvent for use and be 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 8-25 μ L/min, is specially 15 μ L/min, 20 μ L/min, 15-20 μ L/min;
In described hydroxylation step, the H that hydroxylation reagent used is 7:3 by volume ratio
2sO
4: H
2o
2composition, the hydroxylated time is 10-30min, is specially 20min, 10-20min; The flow velocity that hydroxylation reagent pushes is 8～25 μ L/min, is specially 15 μ L/min, 20 μ L/min, 15-20 μ L/min;
In described silanization step, silylating reagent used is methyl alcohol or the aqueous solution of 3-TSL 8330, and mass percentage concentration is 1%-5%, is specially 3%; The time of silanization is 10-30min, is specially 10,15,25,10-25 or 15-25min, and the flow velocity that silylating reagent pushes is 10-25 μ L/min, is specially 15 μ L/min;
In the described step that pushes nano gold sol, the flow velocity pushing is 10-25 μ L/min, is specially 15 μ L/min, 17 μ L/min or 15-17 μ L/min; The consumption of nano gold sol is 5-10mL, is specially 7ml, 5-7ml;
In the described mixed liquor being formed by the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride, the mass percentage concentration of the aqueous solution of gold chloride is 0.01%-0.1%, be specially 0.05%, 0.05-0.1%, the concentration of the aqueous solution of oxammonium hydrochloride is 2-16mmol/L, be 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, is specially 0.5ml, 2.5ml, 0.5-2.5ml or 2.5-5ml;
The flow velocity pushing is 4-20 μ L/min, is 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, is specially 80 DEG C, the time is 6-12 hour, specifically can be 10 hours.
In addition, described step 1) in, nano gold sol is to obtain according to the method preparation comprising the steps:
After the aqueous solution of gold chloride is heated to boil, refluxes and react with the aqueous solution of sodium citrate, react complete and obtain; Wherein, the mass percentage concentration of the aqueous solution of described gold chloride is 0.01%-0.1%, and the mass percentage concentration of the aqueous solution of described sodium citrate is 0.1%-1.0%;
The volume ratio of the aqueous solution of described gold chloride and the aqueous solution of sodium citrate is 40-100:1;
In described reactions steps, the time is 9-12min, is specially 10min.
In addition, the gold copper-base alloy microelectrode and/or the microelectrode array that prepare according to the method described above, also belong to protection scope of the present invention.
The invention provides a kind of method of preparing gold copper-base alloy microelectrode and microelectrode array.The method can form continuously at the capillary tube inner wall of different size and shapes, equal controlled gold layers of even thickness.Compared with preparing Technology of Microelectrodes with existing pyrolysis acetylene gas, the method is without thermal source, avoid thermal cracking carbon source to prepare the potential inflammable and explosive risk of microelectrode array, operation is simple for the method simultaneously, nontoxic, size is controlled, with low cost, can expand to preparing other metals as microelectrode and the microelectrode array of silver, alloy platinum material, be easy to realize batch production.
Brief description of the drawings
Fig. 1 is that capillary tube inner wall self-assembled nanometer aurosol and growth gold copper-base alloy nano thin-film are prepared microelectrode schematic diagram (A) and sectional view (B)
Fig. 2 is (figure below) photo comparison diagram after (upper figure) before single glass capillary (A) and capillary array (B) deposited gold film that contains three capillaries.
Fig. 3 is for the microelectrode that deposited the kapillary of golden film and form is at 1mol/L H
2sO
4the cyclic voltammogram (A) activating in solution, the single golden film microelectrode forming after encapsulation are containing 1mmol/L K
3fe (CN)
6in solution, in the array of the cyclic voltammogram (B) of (supporting electrolyte solution, 0.1mol/L KCl) and formation after encapsulation, three golden film microelectrodes are containing 1mmol/L K respectively
3fe (CN)
6the cyclic voltammogram (C) of (supporting electrolyte solution, 0.1mol/L KCl) in solution.(A) in, illustration is viewed quartz ampoule under scanning electron microscope and the gold layer depositing, and golden layer thickness can reach 10 μ m.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Embodiment 1, prepare golden film microelectrode
1) preparation of nano gold sol:
After the aqueous solution of the gold chloride that is 0.1% by 100mL mass percentage concentration is heated to boil, adding 2.5mL mass percentage concentration is the aqueous solution of 1% sodium citrate, backflow 10min, solution becomes aubergine from golden yellow, remove thermal source, treat solution cool to room temperature, obtain nano gold sol, low-temperature dark is preserved.
2) preparation of supporter:
The tip of a quartz capillary is drawn under naked light condition to micron-sized tip with butane fire maker, the diameter at this micron order tip is 10 μ m, prepares the supporter of gold film electrode as next step.
3) capillary tube inner wall wet method deposited gold:
Under the impetus of micro-injection pump, 2mL acetone, 1mL deionized water are pushed to 2 successively) in the supporter that drawn clean, the flow velocity of cleaning is 20 μ L/min;
Again by the H that is 7:3 by volume ratio
2sO
4: H
2o
2the piranha solution of composition, pushes capillary tube inner wall with the flow velocity of 20 μ L/min by suction function and carries out after surface hydroxylation 20min;
Under the impetus of micro-injection pump, the aqueous solution of the silylating reagent 3-TSL 8330 that is 1% by 5mL mass percentage concentration, pushing inwall with the flow velocity of 15 μ L/min carries out, after silanization processing 25min, cleaning up afterwards with deionized water in hydroxylated kapillary supporter;
Again under the impetus of micro-injection pump, 5mL aurosol solution is pushed to inwall in the kapillary supporter of silanization with the flow velocity of 15 μ L/min, make nm of gold be fixed on capillary tube inner wall, clean up with deionized water afterwards;
Again under the impetus of micro-injection pump, the mixed liquor 5ml that the aqueous solution that is the aqueous solution of 0.01% gold chloride and the oxammonium hydrochloride of 4mmol/L by mass percentage concentration that is 10:1 by volume ratio forms pushes inwall with the flow velocity of 15 μ L/min and has fixed in the kapillary of nm of gold, and capillary tube inner wall can grow into the nanometer of continuous uniform and outward appearance light to the Au film of micron thickness.
As shown in Figure 1, the photo figure in kind before and after capillary tube inner wall deposited gold film as shown in Figure 2 A for the chemical process of capillary surface functionalization and deposited gold layer.
Shown in Fig. 3 (A) is in this embodiment, to have deposited the kapillary of golden film at 1mol/L H
2sO
4the cyclic voltammogram activating in solution, in sulfuric acid, what 1.4V left and right was corresponding is the oxidizing process of Au, what 0.9V left and right was corresponding is the reduction process of Au, has illustrated that Au film is successfully fixed on capillary tube inner wall.
4) conducting of microelectrode and microelectrode array is made with encapsulation:
By step 3) the gained supporter that deposits golden film dries after 12 hours in 70 DEG C, copper wire is inserted in supporter and contacted with golden film, utilize epoxy resin that tip capillaceous and tail end are sealed, baking and curing, obtains the gold copper-base alloy microelectrode with the preparation of wet method deposition provided by the invention.
According to as above method, the number of supporter is increased to 3, obtain gold copper-base alloy microelectrode array provided by the invention.
In Fig. 3 (A), illustration is viewed quartz ampoule under scanning electron microscope and the golden film depositing, and the thickness of golden film can reach 10 μ m.
Fig. 3 (B) is that the single golden film microelectrode forming after encapsulating is containing 1mmol/L K
3fe (CN)
6the cyclic voltammogram of (supporting electrolyte solution, 0.1mol/L KCl) in solution, can see that gold film electrode demonstrates the steady-state current response of typical microelectrode, the microelectrode that illustrate method based on deposited gold film has successfully been prepared into.
Embodiment 2, prepare golden film microelectrode
1) preparation of nano gold sol: with embodiment 1 step 1) identical, the consumption of the aqueous solution of the sodium citrate that is only 1% by mass percentage concentration replaces with 1mL by 2.5mL;
2) preparation of supporter: three quartz capillaries are reversed under naked light condition to the array being drawn into there being most advanced and sophisticated three capillaries to form with butane fire maker, tip diameter is 50 μ m, prepares the supporter of gold film electrode as next step.
3) capillary tube inner wall wet method deposited gold: under the impetus of micro-injection pump, 2mL acetone, 2mL deionized water are pushed to 2 successively) in the supporter that drawn clean, the flow velocity of cleaning is 20 μ L/min;
Again by the H that is 7:3 by volume ratio
2sO
4: H
2o
2the piranha solution of composition, pushes capillary tube inner wall with the flow velocity of 15 μ L/min by suction function and carries out after surface hydroxylation 30min;
Under the impetus of micro-injection pump, the aqueous solution of the silylating reagent 3-TSL 8330 that is 5% by 10mL mass percentage concentration, push inwall with the flow velocity of 25 μ L/min and in hydroxylated kapillary supporter, carry out silanization processing 15min, clean up with deionized water afterwards;
Again under the impetus of micro-injection pump, 10mL aurosol solution is pushed to inwall in the kapillary supporter of silanization with the flow velocity of 25 μ L/min, make nm of gold be fixed on capillary tube inner wall, clean up with deionized water afterwards;
Again under the impetus of micro-injection pump, the mixed liquor 0.5ml that the aqueous solution of the aqueous solution of the gold chloride that is 0.1% by mass percentage concentration that is 10:2 by volume ratio and the oxammonium hydrochloride of 16mmol/L forms pushes inwall with the flow velocity of 4 μ L/min and has fixed in the kapillary of nm of gold, and capillary tube inner wall can grow into the nanometer of continuous uniform and outward appearance light to the Au film of micron thickness.
As shown in Figure 1, the photo figure in kind before and after capillary array inwall deposited gold film as shown in Figure 2 B for the chemical process of the surface-functionalized and deposited gold layer of capillary array.
4) conducting of microelectrode and microelectrode array is made with encapsulation: by step 3) the gained supporter that deposits golden film dries after 6 hours in 90 DEG C, three copper wires are inserted respectively in three supporters and contacted with golden film, utilize epoxy resin that tip capillaceous and tail end are sealed, baking and curing, obtains the gold copper-base alloy microelectrode array with the preparation of wet method deposition provided by the invention.
Fig. 3 (C) is that in the array forming after encapsulating, three golden film microelectrodes are containing 1mmol/LK respectively
3fe (CN)
6(supporting electrolyte solution in solution, 0.1mol/L KCl) cyclic voltammogram, can see that three gold film electrodes all demonstrate the steady-state current response of typical microelectrode, illustrate that the method based on deposited gold film has successfully been prepared into the microelectrode array being made up of three microelectrodes.
Embodiment 3, prepare golden film microelectrode
1) preparation of nano gold sol: according to embodiment 1 step 1), the aqueous solution of the gold chloride that is only 0.1% by mass percentage concentration replaces with the aqueous solution of 0.05% gold chloride, and the aqueous solution of the sodium citrate that is 1% by 2.5mL mass percentage concentration 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 deposited gold:
Under the impetus of micro-injection pump, 2mL acetone, 2.5mL deionized water are pushed to 2 successively) in the supporter that drawn clean, the flow velocity of cleaning is 15 μ L/min;
Again by the H that is 7:3 by volume ratio
2sO
4: H
2o
2the piranha solution of composition, pushes capillary tube inner wall with the flow velocity of 10 μ L/min by suction function and carries out after surface hydroxylation 10min;
Under the impetus of micro-injection pump, the aqueous solution of the silylating reagent 3-TSL 8330 that is 3% by 2mL mass percentage concentration, push inwall with the flow velocity of 10 μ L/min and in hydroxylated kapillary supporter, carry out silanization processing 10min, clean up with deionized water afterwards;
Again under the impetus of micro-injection pump, 7mL aurosol solution is pushed to inwall in the kapillary supporter of silanization with the flow velocity of 17 μ L/min, make nm of gold be fixed on capillary tube inner wall, clean up with deionized water afterwards;
Again under the impetus of micro-injection pump, the mixed liquor 2.5ml that the aqueous solution that is the aqueous solution of 0.05% gold chloride and the oxammonium hydrochloride of 2mmol/L by mass percentage concentration that is 10:1 by volume ratio forms pushes inwall with the flow velocity of 10 μ L/min and has fixed in the kapillary of nm of gold, and capillary tube inner wall can grow into the nanometer of continuous uniform and outward appearance light to the Au film of micron thickness.
The chemical process of capillary surface functionalization and deposited gold layer as shown in Figure 1.
4) conducting of microelectrode and microelectrode array is made with encapsulation:
By step 3) the gained supporter that deposits golden film dries after 10 hours in 80 DEG C, copper wire is inserted in supporter and contacted with golden film, utilize epoxy resin that tip capillaceous and tail end are sealed, baking and curing, obtains the gold copper-base alloy microelectrode with the preparation of wet method deposition provided by the invention.
Claims (8)
1. a method of preparing gold copper-base alloy microelectrode and/or microelectrode array, comprises the steps:
1) under the impetus of micro-injection pump, clean after supporter, the inwall of supporter is carried out to hydroxylation with hydroxylation reagent, carry out again silanization, push again nano gold sol, with after washed with de-ionized water, then push the mixed liquor being formed by the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride, in the inwall deposition of described supporter and layer of gold film;
Described supporter is the supporter of single microelectrode or the supporter of microelectrode array;
2) by step 1) the gained supporter that deposits golden film dries, after copper wire is inserted and contact with golden film in supporter, by the tip of supporter and tail end sealing, curing, obtains described gold copper-base alloy microelectrode and/or microelectrode array.
2. method according to claim 1, is characterized in that: described step 1) in, the material that forms described supporter is glass, quartz or organic polymer;
Described supporter is the kapillary with micron order tip; The diameter at described micron order tip is specially 10-50 μ m;
The thickness of described golden film is 500nm-15 μ m, is specially 10 μ m.
3. method according to claim 1 and 2, is characterized in that: the supporter of described single microelectrode is to obtain according to the method preparation comprising the steps: the tip of a capillary is drawn into micron-sized tip and obtains;
The supporter of described microelectrode array is to obtain according to the method preparation comprising the steps: the tip of at least two capillaries is drawn into a micron-sized tip and obtains.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: described step 1) in cleaning step, clean solvent for use and be 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 10-25 μ L/min;
In described hydroxylation step, the H that hydroxylation reagent used is 7:3 by volume ratio
2sO
4: H
2o
2composition, the hydroxylated time is 10-30min; The flow velocity that hydroxylation reagent pushes is 8-25 μ L/min;
In described silanization step, silylating reagent used is methyl alcohol or the aqueous solution of 3-TSL 8330, and mass 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 that pushes nano gold sol, the flow velocity pushing is 10-25 μ L/min; The consumption of nano gold sol is 5-10mL;
In the described mixed liquor being formed by the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride, the mass percentage concentration of the aqueous solution of gold chloride is 0.01%-0.1%, the concentration of aqueous solution of oxammonium hydrochloride is 2-16mmol/L, and the volume ratio of the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride is 10:1-2; The consumption of the described mixed liquor being made up of the aqueous solution of gold chloride and the aqueous solution of oxammonium hydrochloride is 0.5-5mL; The flow velocity pushing is 4-20 μ L/min, is specially 15 μ L/min.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: described step 2) in baking step, temperature is 70-90 DEG C, the time is 6-12 hour.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described step 1) in, nano gold sol is to obtain according to the method preparation comprising the steps:
After the aqueous solution of gold chloride is heated to boil, refluxes and react with the aqueous solution of sodium citrate, react complete and obtain.
7. method according to claim 6, is characterized in that: the mass percentage concentration of the aqueous solution of described gold chloride is 0.01%-0.1%, and the mass percentage concentration of the aqueous solution of described sodium citrate is 0.1%-1.0%;
The volume ratio of the aqueous solution of described gold chloride and the aqueous solution of sodium citrate is 40-100:1;
In described reactions steps, the time is 9-12min, is specially 10min.
8. the arbitrary described method of claim 1-7 prepares gold copper-base alloy microelectrode and/or microelectrode array.
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| CN106480436A (en) * | 2015-08-31 | 2017-03-08 | 中国科学院大连化学物理研究所 | A kind of preparation method of coating EFI pin |
| CN106480436B (en) * | 2015-08-31 | 2021-02-19 | 中国科学院大连化学物理研究所 | Preparation method of plating electric spray needle |
| CN105575752A (en) * | 2016-03-04 | 2016-05-11 | 北京工业大学 | Dual-functional equal-inner-diameter skin flow mass spectrum spray needle and preparation method thereof |
| CN105575752B (en) * | 2016-03-04 | 2017-09-22 | 北京工业大学 | A kind of difunctional uniform internal diameter skin liquid spectrum nozzle needle and preparation method |
| CN105806907A (en) * | 2016-05-13 | 2016-07-27 | 首都师范大学 | Method for preparing microelectrodes |
| CN105806907B (en) * | 2016-05-13 | 2018-06-29 | 首都师范大学 | A kind of method for preparing microelectrode |
| CN107200604A (en) * | 2017-05-10 | 2017-09-26 | 北京海光仪器有限公司 | The production method of gold-plated quartz sand |
| CN108906041A (en) * | 2018-07-24 | 2018-11-30 | 上海理工大学 | A kind of preparation method for the single layer golden film can be used for photocatalytic degradation 4- nitrophenol |
| CN108906041B (en) * | 2018-07-24 | 2021-07-13 | 上海理工大学 | Preparation method of single-layer gold film for photocatalytic degradation of 4-nitrophenol |
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