CN109668948A - A kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method - Google Patents
A kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method Download PDFInfo
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Abstract
A kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method, technology is constructed using templates such as laser engraving, photosensitive seals, the electrod-array filtration zone of autonomous Design is constructed in filter membrane surface, conductive material is controlled using template work principle of filter and decorative material is formed on the surface of the filter membrane electrod-array, by subsequent transfer or encapsulation process, different types of carbon-based and electrode metal substrate array is prepared in batches.This method preparation process is simple, precision is high, material is saved, it is small, at low cost to pollute, and the conductive material of low concentration can be used to disperse solution, rapid batch prepares the electrod-array of various materials.Prepared electrod-array has low (carbon-based < 30 Ω/sq of resistance; Metal Substrate < 2 Ω/sq), structure composition easy-regulating, be applicable in substrate extensively, uniformity and the features such as favorable reproducibility; many deficiencies that commercialization screen printing electrode can effectively be overcome, are with a wide range of applications in fields such as environmental protection, food safety and medicals diagnosis on disease.
Description
Technical field
The present invention relates to electronic device preparation fields, and in particular to a kind of carbon-based and electrode metal substrate array low cost
High-precision preparation method.
Background technique
According to relevant statistics, China's in-vitro diagnosis market scale has reached annual tens billion of RMB.Currently, external
Diagnosis mostly uses the optical detecting methods such as chemiluminescence, and testing cost is higher and core technology is external trans-corporation ridge
It is disconnected.Compared with optical means, electrochemical sensing technology has the characteristics that portable devices, easy to use, testing cost is low, electrification
Extensive popularize for learning blood glucose meter is proved its application advantage in inexpensive, portable, quick biochemical analysis.However, electric
Screen printing carbon electrode used in chemical blood sugar test paper mostly uses the conductive carbon paste of high viscosity, complicated component to pass through screen printing
Brush mode produces, exist prepare low precision, it is electroactive poor, surface modification method is limited the deficiencies of.Meanwhile using silk-screen printing
When technology prepares the electrod-array of the precious metal materials such as gold, silver, platinum, since the consumption of its electrocondution slurry is big, prepared electrode at
This valuableness is of limited application.
In order to overcome the limitation of screen printing technique, some other types of electrod-arrays are constructed technology and are also applied to
Electrochemical sensing field, such as vacuum sputtering, vapor deposition, ion etching, inkjet printing, photoetching and various types of prints
Brush technology.However, these methods often exist, production equipment is expensive, preparation process is complicated, preparation condition is harsh, electrode material
The problems such as limited types.Template filtering technique is by constructing the electrod-array template of computer design in filter membrane surface, using decompression
Filter type realizes that the conductive material filtering of dispersion in the solution is fixed to template hollowed out area, so that being formed has specific shape
The high homogeneous electrode array of shape.For example, inviscid template is fixed to filter membrane surface by Lee etc., using template work principle of filter,
Realize the array (Adv.Mater.2012,24,3326-3332) of overlength nano-silver thread；It is beaten Deng using wax spray
Print machine directly constructs filtration zone array in filter membrane surface, realizes constructing for graphene oxide array, and pass through electronation
Convert it into conductive graphene array (ACS Nano 2016,10,853-860).However, there is also not for above scheme
Inviscid template is fixed to filter membrane surface by foot place, Lee, and filter device is complicated, is dfficult to apply to the big of conductive material
Volume weak solution；Etc. schemes need using expensive wax spray printer, template filter membrane preparation process is relatively multiple
It is miscellaneous, using paraffin as mould material there is also poor high temperature stabilities the problems such as.
Summary of the invention
The present invention provides a kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method, preparation costs
It is low, and the high-precision electrode array of various materials can in batches, be controllably prepared, effectively overcome existing commercial silk-screen printing electricity
Many deficiencies of pole.
Technical solution of the present invention can be realized by following technical measures:
A kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method, includes the following steps:
(1), insulating properties encapsulating material is fixed by way of pasting or printing on porous membrane surface, obtains filtering area
Domain is in electrode array shape, other regions by the closed filtering profile of insulating properties encapsulating material；
(2), decompression suction filtration is carried out using solution of step (1) the resulting filtering profile to conductive material, makes conductive material
Deposit to the filter array region of filtering profile；
(3), the filtering profile for being deposited with conductive material be dried, washed, re-dry, obtain be with filtering profile
The electrod-array of carrier.
Preferably, the method for the fixed insulating properties encapsulating material is laser engraving method, is included the following steps:
(1), the electrod-array region of blank is carved out on insulating properties macromolecule glue band using laser engraving machine；
(2), the sticking one side tiling of polymeric tape is fixed on to the surface of porous membrane, obtains filtering profile.It is excellent
The method of selection of land, the fixed insulating properties encapsulating material is the photosensitive marking art of composition, is included the following steps:
(1), it is closed using photosensitive seal preparation principle production electrod-array regional exposure, other unexposed prints in region
Chapter；
(2), oily insulating properties encapsulating material is coated on seal；
(3), insulating properties encapsulating material is printed on porous membrane surface using seal, by dry or curing process, obtained
To filtering profile.
Preferably, the porous membrane material includes cellulose acetate, nitrocellulose, cellulose mixture, polyvinylidene fluoride
Alkene (PVDF), polytetrafluoroethylene (PTFE) (PTFE), polysulfones (PSF) and anodised aluminium (AAO) filter membrane.
Preferably, the conductive material include carbon nanotube, graphene, carbon nano-fiber, nano-silver thread, gold nanowire,
One of nanometer platinum line is a variety of.
Preferably, the polymeric tape includes polyvinyl chloride (PVC), polyethylene terephthalate (PET), gathers
Methyl methacrylate (PMMA), polyimides (PI), brown paper and silica gel material adhesive tape.
Preferably, the insulating properties encapsulating material includes photosensitive stamp-pad ink, polyvinyl chloride (PVC) ink, polydimethylsiloxanes
Alkane (PDMS).
A kind of electrode material, adopts and is prepared with the aforedescribed process.
The invention also includes above-mentioned carbon-based and electrode metal substrate array low-cost and high-precision preparation methods in electrochemistry
Sensor, supercapacitor, electro-catalysis, the application in electroluminescent heating film field.
Compared with prior art, the invention has the following beneficial effects:
(1) this method preparation process is simple, preparation precision is high, material save (~100% utilization rate), environmental pollution it is small,
Production cost is low, electrod-array configuration can computer design, common low-cost equipment can be used.
(2) can use low concentration conductive material disperse solution, prepare quickly and in batch carbon nanotube, graphene,
The multiple types such as silver, gold, platinum are carbon-based, Metal Substrate or composite electrode array.
(3) electrod-array prepared by has resistance low (carbon-based array < 30 Ω/sq, Metal Substrate array < 2 Ω/sq), knot
Structure forms easy-regulating, is applicable in the features such as extensive substrate, uniformity and favorable reproducibility, can effectively overcome commercialization silk-screen printing electricity
Many deficiencies of pole, electrochemical sensor, supercapacitor, electro-catalysis, electroluminescent heating film, environmental protection, food safety and
The fields such as medical diagnosis on disease are with a wide range of applications.
(4) compared with the inviscid filtering profile of Lee report, filtering profile, energy are prepared using laser engraving insulating tape
Greatly enhancing template edge and filter membrane between bond strength, avoid template edge in conjunction with filter membrane loosely caused by filter
The coarse problem of array edges, to improve the precision that template filtering prepares electrod-array；Meanwhile prepared filtering profile
With the shape and property similar with filter membrane, energy compatible conventional filter device, the dispersion for being applicable in various concentration conductive material is molten
Liquid, to significantly enhance the universality of material.
(5) withThe wax spray printing of report prepares filtering profile and compares, and photosensitive seal technology is applicable in insulative water-proof
The high-temperature insulations encapsulating material such as ink, PDMS, the problems such as effectively olefin material capable of being overcome easily to melt；Meanwhile used mould
Plate Preparation equipment cost is lower, preparation process is simpler.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System.
Fig. 1 laser engraving template filtering prepares carbon-based electrode array process schematic (a. laser engraving adhesive tape template；b.
Fixation of the adhesive tape template on filter membrane；C. template filtering prepares carbon-based electrode array；D. removing template and obtaining filter membrane is carrier
Carbon-based electrode array；E. the encapsulation of single electrode array and electro-chemical test state)；
Fig. 2 laser engraving kraft paper gummed tape template prepares procedure chart (a. laser engraving of single-walled carbon nanotube electrod-array
Kraft paper gummed tape；B. removing of the kraft paper gummed tape from silica gel piece surface；C. the kraft paper gummed tape template that laser engraving obtains；d.
Attach to the kraft paper gummed tape template of filter membrane surface；E. the carbon-based electrode array that template is obtained by filtration)；
Fig. 3 laser engraving PVC tape template prepares single-walled carbon nanotube electrod-array and its transfers the sample drawing of substrate.
A. the PVC tape template of filter membrane surface is attached to；B. the single-walled carbon nanotube electrod-array after PVC template is removed；C. single wall carbon
Nanotube electrode array is transferred to PI one side glue surface；D. single-walled carbon nanotube electrod-array is transferred to rubber using double-sided adhesive
Glove surface.
Fig. 4 laser engraving PVC tape template prepare nano-silver thread electrod-array and its transfer substrate sample drawing (a. swash
Light carves PVC tape；B.PVC adhesive tape template is from silica gel piece sur-face peeling；C. the PVC tape template of filter membrane surface is attached to；
d.；Nano-silver thread electrod-array is obtained by filtration in PVC tape template；E. the nano-silver thread electrod-array with PVC adhesive tape template immerses
Ethyl alcohol is to remove PVC template；F. the nano-silver thread electrod-array after PVC template is removed；G. nano-silver thread electrode array passes through two-sided
Glue is transferred to rubber glove surface)；
Fig. 5 photosensitive seal template filtering prepares sample drawing (photosensitive marking of a. with electrod-array pattern of photosensitive seal
Chapter；B. the electrod-array template filter membrane of photosensitive seal preparation；C. the nano-silver thread electrod-array of template filtering preparation)；
Fig. 6 is using the single-walled carbon nanotube of template filtering preparation and the scanning electron microscope (SEM) photograph of nano-silver thread electrod-array
(a.PVDF filter membrane；B. single-walled carbon nanotube conductive film；C. nano-silver thread conductive film；D. nano-silver thread conductive film is by setting
Change the gold nanowire conductive film that reaction is converted to)；
Single pipe electrode that Fig. 7 is prepared using PDMS as photosensitive seal insulative potting material and thereon iron cyanogen
(a.PDMS encapsulates PTFE filter membrane, and interior illustration is to filter the single pipe electrode being prepared thereon for the volt-ampere response of change potassium
Array；Single single-walled carbon nanotube electrod-array is to 1.0M KCl (dotted line) and 5.0mM iron cyanogen on b.PDMS encapsulation PTFE filter membrane
Change the cyclic voltammogram of potassium (solid line), interior illustration is the single single-walled carbon nanotube electrochemical sensor that encapsulation obtains, scanning speed
Rate 100mV/s)；
The cyclic voltammogram of bisphenol-A on Fig. 8 single-walled carbon nanotube and single-walled carbon nanotube-acetylene black combination electrode array
(bisphenol A concentration, 20 μM；Electrolyte solution, 0.1M phosphate buffer solution (pH 7.4).Sweep speed, 100mV/s)；
0.1mM dopamine on Fig. 9 single-walled carbon nanotube (a, d), graphene (b, e) and gold nanowire (c, f) electrod-array
(dotted line is that above-mentioned electrod-array is molten in 0.1M phosphoric acid buffer to the cyclic voltammogram of (a, b, c) and 20mM hydrogen peroxide (d, e, f)
Cyclic voltammogram in liquid, solid line are electrod-array in the 0.1M phosphate buffer solution containing dopamine or hydrogen peroxide
Cyclic voltammogram, sweep speed 100mV/s).
Specific embodiment
To keep the present invention easier to understand, specific embodiments of the present invention are further illustrated below.
The preparation of conductive material dispersion liquid:
Dispersion liquid 1
60mg single-walled carbon nanotube (SWNTs) is added to lauryl sodium sulfate water (SDS) solution of 500mL 5mM
In, ultrasonic disperse 2 hours in 50W Ultrasound Instrument, obtained dark solution stands 2 days at room temperature, upper layer dark solution is collected,
Obtain the single-walled carbon nanotube stock solution being scattered in SDS aqueous solution.
Dispersion liquid 2
2.5g graphite powder is added in N-Methyl pyrrolidone (NMP) solvent of 500mL, it is ultrasonic in 50W Ultrasound Instrument
Dispersion 6 hours, obtained dark solution stands 2 days at room temperature, collects upper layer dark solution, obtains being scattered in the graphite in NMP
Alkene stock solution.
Dispersion liquid 3
25mg acetylene black is added in N-Methyl pyrrolidone (NMP) solvent of 5mL, the ultrasound point in 50W Ultrasound Instrument
It dissipates 1 hour, obtained dark solution stands 2 days at room temperature, collects upper layer dark solution, obtains being scattered in the acetylene black in NMP
Stock solution.
Dispersion liquid 4
200 μ L dispersion liquids 3 are first distributed in 5mL nmp solution, then dilution is distributed in 50mL water, by 100mL points
Dispersion liquid 1 is uniformly mixed with above-mentioned dispersion liquid 3, obtains compound conductive material dispersion liquid.
Dispersion liquid 5
Nano-silver thread disperses solution purchase from Nanjing Xian Feng Nono-material Science & Technology Ltd., design parameter are as follows: diameter
40nm, 20~60 μm of length, concentration 20mg/mL.
The preparation of filtering profile:
Filtering profile 1
By length about 150mm, width 70mm, thickness about 1mm clean silica gel piece on be laid in experiment table top on, will grow
It spends in the sticky glue surface tiling to silica gel piece of about 120mm, width 60mm, about 130 μm of thickness of kraft paper gummed tape, then by silicon
Film and kraft paper gummed tape are placed in 3020 laser engraving machine of giant dragon together, with its laser (10.6 μm of wavelength, practical cutting function
Rate is the 12% of 50W general power) the good electrod-array pattern of cutting computer design.Engraving finishes, by silica gel piece and brown paper glue
Band takes out together, and deionized water cleans up, in 60 DEG C of dryings of vacuum drying oven.By the kraft paper gummed tape template carved from silicon
It is carefully removed on film, obtains the filtering electrode array circle kraft paper gummed tape template of diameter 48mm, its adhesive faces tiled solid
Surely the round cellulose mixture filter membrane surface for arriving diameter 50mm, 0.22 μm of aperture, obtains the kraft paper gummed tape mould of laser engraving
Plate controls cellulose mixture filter membrane.
Filtering profile 2
By length about 150mm, width 70mm, thickness about 1mm clean silica gel piece on be laid in experiment table top on, then
The sticky glue surface tiling of length about 120mm, width 60mm, about 100 μm of thickness of PET adhesive tape is fixed on silica gel piece, then
According to 1 step of filtering profile engraving, cleaning and drying.The PET adhesive tape carved carefully is removed from silica gel piece, is obtained straight
The tiling of its adhesive faces is fixed to diameter 50mm, 0.22 μm of aperture by the filtering electrode array circle PET adhesive tape template of diameter 48mm
Circular nitrocellulose filter surface, obtain the PET adhesive tape template contral nitrocellulose filter of laser engraving.
Filtering profile 3
By length about 150mm, width 70mm, thickness about 1mm clean silica gel piece on be laid in experiment table top on, then
The sticky glue surface tiling of length about 120mm, width 60mm, about 150 μm of thickness of PVC tape is fixed on silica gel piece, then
According to 1 step of filtering profile engraving, cleaning and drying.The PVC tape template carved carefully is removed from silica gel piece, is obtained
To the filtering electrode array circle PVC tape template of diameter 48mm, tiled fixed to diameter 50mm, 0.22 μm of aperture
Among round PVDF filter membrane, the PVC tape template contral PVDF filter membrane of laser engraving is obtained.
Filtering profile 4
According to the filtering electrode array circle poly-methyl methacrylate of the making step production diameter 48mm of filtering profile 3
Ester (PMMA) adhesive tape template, tiled circular anode aluminium oxide (AAO) filter membrane fixed to diameter 48mm, 0.22 μm of aperture
On, obtain the PMMA adhesive tape template contral AAO filter membrane of laser engraving.
Filtering profile 5
Exposure mold is built: being printed on template electrod-array die plate pattern with laser printer, is formed electrode
The template template sample manuscript that array region is completely covered without printing, other region powdered black inks.It is covered on template sample manuscript
PET transparent film continues the photosensitive Stamp pad of circle for placing diameter about 48mm on transparent film, and three is put into the double-deck glass
It is compacted in glass exposure mold, the template sample manuscript back side is made to be close to the exposure glass plate of exposure mold, its print pattern front abutting
Transparent film is formed according to exposure glass plate, template sample manuscript, PET transparent film, photosensitive seal pad, back support glass plate
The exposure mold that sequence is placed.
The exposure of photosensitive seal forms: it is small that the exposure glass plate face for exposing mold being put into extra large enlightening board HD-00071 upward
In type seal exposure machine, ultraviolet photoetching processing is carried out according to exposure machine operation instruction.In exposure process, template sample manuscript
Black print region blocks ultraviolet light is irradiated to photosensitive seal pad, therefore the photosensitive seal of black region covering is not by ultraviolet
Light is irradiated and is exposed, to obtain electrod-array area of the pattern exposure closing, the unexposed photosensitive seal in other regions.
The coating of photosensitive stamp-pad ink: the photosensitive stamp-pad ink of capable board is coated to seal surface, is stood after absorbing a period of time, is used
Soft blotting paper or cloth wipes extra stamp-pad ink, obtains the internal electrod-array pattern photosensitive seal for containing photosensitive stamp-pad ink.
The printing of electrod-array template: the photosensitive seal is gently vertically impressed into the circle of diameter 50mm, 0.22 μm of aperture
It is removed after about 5 seconds among shape cellulose mixture filter membrane, the filter membrane for being printed on photosensitive stamp-pad ink is dried at room temperature for get electrode is arrived
The cellulose mixture template filter membrane that array region blank, the photosensitive stamp-pad ink in other regions cover.
Filtering profile 6
Photosensitive seal is made according to 5 step of filtering profile, deployed two-component PDMS glue introducing is had into electrod-array mould
In the photosensitive seal of plate, the photosensitive seal based on PDMS glue is prepared, is then printed on diameter 50mm, 0.22 μm of aperture
About 10 seconds among round polytetrafluoroethylene (PTFE) (PTFE) filter membrane, the filter membrane for being printed on PDMS glue is placed in 80 DEG C of vacuum drying oven solidifications 3
Hour, obtain the PTFE template filter membrane of PDMS encapsulation.
Filtering profile 7
Photosensitive seal is made according to 5 step of filtering profile, by the PVC ink of Heng Mei printing ink paint Co., Ltd, Zhongshan city
It is introduced into the photosensitive seal of electrod-array template, prepares the photosensitive seal based on PVC ink, be then printed on diameter
50mm, 0.22 μm of aperture round polysulfones (PSF) filter membrane among about 10 seconds, by the filter membrane for being printed on PVC ink be placed in vacuum dry
The drying 3 hours of 80 DEG C of case obtains the PSF template filter membrane of PVC ink encapsulation.
Embodiment 1
Filtering profile 1 is installed on the cup type filter of M50 of Shanghai Mo Su company, original diameter 50mm is stainless
Billet is replaced with the titanium plate of diameter 50mm, 0.45 μm of aperture.10mL dispersion liquid 1 is added in 100mL deionized water
It stirs evenly, ultrasound 5 minutes is directly poured into the solution in the filter cup of the cup type filter of M50, and decompression filters drying, then
The washing of 400mL deionized water is added for several times, to remove remaining SDS.Electrod-array area is deposited with single-walled carbon nanotube conduction
The brown paper template filter membrane of layer is put into 60 DEG C drying 2 hours in vacuum drying oven, and obtaining cellulose mixture filter membrane is carrier, ox-hide
The single-walled carbon nanotube electrod-array of paper segmentation, film resistance about 30 Ω/sq (see Fig. 2).
Embodiment 2
Filtering profile 2 is installed on the cup type filter of M50 of Shanghai Mo Su company, and with the ethyl alcohol of 25% volume ratio
Aqueous solution wetting, original stainless billet of 50mm are replaced with the titanium plate of diameter 50mm, 0.45 μm of aperture.By 10mL points
Dispersion liquid 1 is added in 100mL deionized water and stirs evenly, which is directly poured into and be mounted with template filter membrane by ultrasound 5 minutes
M50 filter cup in, be filtered under diminished pressure and drain, then be added 400mL deionized water washing for several times, to remove remaining SDS.It will
The PET template filter membrane that electrod-array area is deposited with single-walled carbon nanotube conductive layer, which is put into ethyl alcohol, to be impregnated 1 minute, from nitric acid fibre
It ties up carefully to remove on plain filter membrane and removes PET adhesive tape, 60 DEG C drying 2 hours in vacuum drying oven, obtaining nitrocellulose filter is
The single-walled carbon nanotube electrod-array of carrier, film resistance about 28 Ω/sq.
Embodiment 3
Filtering profile 3 is installed on the cup type filter of M50 of Shanghai Mo Su company, and with the ethyl alcohol of 25% volume ratio
Aqueous solution wetting, original stainless billet of 50mm are replaced with the titanium plate of diameter 50mm, 0.45 μm of aperture.By 10mL points
Dispersion liquid 2 is added in 300mL deionized water and stirs evenly, which is directly poured into the M50 filter cup for being mounted with template filter membrane
In, it is filtered under diminished pressure and drains, the ethanol water that 25% volume ratio of 400mL is then added washs for several times, remaining to remove
NMP.The PVC template filter membrane that electrod-array area is deposited with graphene conductive layer is put into ethyl alcohol and is impregnated 1 minute, is filtered from PVDF
Carefully removing removes PVC tape on film, and 60 DEG C of dryings in vacuum drying oven obtain the Graphene electrodes battle array that PVDF filter membrane is carrier
Column, film resistance about 60 Ω/sq.
Embodiment 4
Using dispersion liquid 1 and filtering profile 3, the single that PVDF filter membrane is carrier is prepared according to 2 step of embodiment
Pipe electrode array, film resistance about 26 Ω/sq.Single-walled carbon nanotube electrod-array on the filter membrane can transfer technique be transferred to
In one side glue, or double-sided adhesive is used to be transferred to rubber glove surface (see Fig. 3).
Embodiment 5
Filtering profile 3 is installed on the cup type filter of M50 of Shanghai Mo Su company, and with the ethyl alcohol of 25% volume ratio
Aqueous solution wetting, original stainless billet of 50mm are replaced with the titanium plate of diameter 50mm, 0.45 μm of aperture.By 80 μ L points
Dispersion liquid 5 is added in 90mL deionized water and is uniformly dispersed, which is directly poured into the M50 filter cup for being mounted with template filter membrane
In, it is filtered under diminished pressure and drains, the washing of 400mL deionized water is then added for several times.Electrod-array area is deposited with nano-silver thread conduction
The PVC template filter membrane of layer, which is put into ethyl alcohol, to be impregnated 1 minute, and carefully removing removes PVC tape, vacuum drying oven from PVDF filter membrane
In 60 DEG C of dryings, obtain PVDF filter membrane be carrier nano-silver thread electrod-array, film resistance about 1.8 Ω/sq.It can be used double
Nano-silver thread electrod-array is transferred to rubber glove surface (see Fig. 4) by face adhesive tape.
Embodiment 6
Using dispersion liquid 1 and filtering profile 4, the single that AAO filter membrane is carrier is prepared according to 2 step of embodiment
Pipe electrode array, film resistance about 21 Ω/sq.
Embodiment 7
Filtering profile 5 is installed on the cup type filter of M50 of Shanghai Mo Su company, original stainless billet of 50mm
It is replaced with the titanium plate of diameter 50mm, 0.45 μm of aperture.80 μ L dispersion liquids 5 are added in 90mL deionized water and are dispersed
It is even, which is directly poured into the M50 filter cup for being mounted with template filter membrane, is filtered under diminished pressure and drains, 400mL is then added and goes
Ion water washing is for several times.The photosensitive stamp-pad ink template filter membrane that electrod-array area is deposited with nano-silver thread conductive layer is put into vacuum to dry
60 DEG C of dryings in case obtain the nano-silver thread electrod-array that cellulose mixture filter membrane cuts for carrier, photosensitive marking oil, film electricity
It hinders about 2 Ω/sq (see Fig. 5).
Embodiment 8
It is uniformly dispersed in the 90mL aqueous solution for being 1:8 by the volume ratio that 80 μ L dispersion liquids 5 are added to water and ethyl alcohol, according to
The nano-silver thread electrod-array that PVDF filter membrane is carrier is prepared in the filtering of 5 step template of embodiment.By loading nano silvery line
The PVDF filter membrane of electrod-array, which is placed in the aqueous solution of chloraurate of 50mL 0.5wt%, to react 0.5 hour, anti-using chemistry displacement
Gold nanowire should be converted by nano-silver thread, be washed with deionized for several times, 60 DEG C of dryings of vacuum drying oven, it is porous to obtain PVDF
Filter membrane is the gold nanowire electrod-array of carrier, film resistance about 1.5 Ω/sq (its microscopic appearance is shown in Fig. 6).Using similar former
Reason, can be converted to platinum nanowire array for nano-silver thread electrod-array.
Embodiment 9
It is carrier, PDMS encapsulation point according to 2 step of embodiment preparation PTFE filter membrane using dispersion liquid 1 and filtering profile 6
The single-walled carbon nanotube electrod-array cut, film resistance about 16 Ω/sq (see Fig. 7 a).
Embodiment 10
Using dispersion liquid 4 and filtering profile 3, the single that PVDF filter membrane is carrier is prepared according to 3 step of embodiment
Pipe-acetylene black combination electrode array, film resistance about 50 Ω/sq.
The preparation and test of electrochemical sensor:
Sensor 1
Electrod-array prepared by embodiment 9 is cut into single three electrod-array, and is led with the segmentation of PTFE High temperature-resistanadhesive adhesive tape
Electric area and detection zone obtain single-walled carbon nanotube based electrochemical sensor.20 μ L are free of to respectively and are contained the 5mM potassium ferricyanide
The water-soluble drop-coated of 1.0M KCl to the detection zone of above-mentioned electrochemical sensor, carried out under 100mV/s potential scan rate
Volt-ampere test, volt-ampere test result are as shown in Figure 7b.
Sensor 2
Using method similar with sensor 1, three electrod-array of single-walled carbon nanotube prepared by embodiment 4 is cut out
It cuts and encapsulates, obtain single-walled carbon nanotube based electrochemical sensor.The 0.1M phosphoric acid buffer that 20 μ L are contained 20 μM of bisphenol-As is molten
Liquid (pH7.4) drop coating carries out volt-ampere survey to the detection zone of above-mentioned electrochemical sensor under 100mV/s potential scan rate
Examination, volt-ampere test result are as shown in phantom in Figure 8.
Sensor 3
Using method similar with sensor 1, compound three electricity of single-walled carbon nanotube-acetylene black prepared by embodiment 10
Pole array is cut and is encapsulated, and single-walled carbon nanotube-acetylene black base composite electric chemical sensor is obtained.20 μ L are contained into 20 μ
0.1M phosphate buffer solution (pH7.4) drop coating of M bisphenol-A to above-mentioned electrochemical sensor detection zone, 100mV/s electricity
It is shown in solid in progress volt-ampere test under bit scan rate, volt-ampere test result such as Fig. 8.
Sensor 4
Single-walled carbon nanotube based electrochemical sensor is prepared according to 2 step of sensor, 20 μ L are free of and are contained respectively
Detection zone of 0.1M phosphate buffer solution (pH7.4) drop coating of 0.1mM dopamine or 20mM hydrogen peroxide to the sensor
Domain carries out volt-ampere test, volt-ampere test result such as Fig. 9 (a), 9 (d) under 100mV/s potential scan rate.
Sensor 4
Graphene electrodes array prepared by embodiment 3 cuts and encapsulates according to the preparation step of sensor 1, obtains phase
The graphene sensor answered.Later, 20 μ L are free of respectively and the 0.1M phosphorus containing 0.1mM dopamine or 20 mM hydrogen peroxide
Acid buffering solution (pH7.4) drop coating carries out volt-ampere to the detection zone of the sensor under 100mV/s potential scan rate
Test, volt-ampere test result such as Fig. 9 (b), 9 (e).
Sensor 5
Gold nanowire electrod-array prepared by embodiment 8 cuts and encapsulates according to the preparation step of sensor 1, obtains
Corresponding nanogold based electrochemical sensor.Later, 20 μ L are free of to respectively and are contained 0.1mM dopamine or 20mM peroxidating
0.1M phosphate buffer solution (pH7.4) drop coating of hydrogen to the sensor detection zone, in 100mV/s potential scan rate
Lower progress volt-ampere test, volt-ampere test result such as Fig. 9 (c), 9 (f).
Fig. 3 and Fig. 4 is to prepare single-walled carbon nanotube and nano-silver thread respectively as template using laser engraving PVC tape
The preparation and transfer process of electrod-array.As can be seen that template filtering can rapid batch preparation autonomous Design electrod-array or
Pattern has and is applicable in that preparation process is simple, material saves (~100% utilization rate), is applicable in that conductive material range is wide, preparation essence
Spend the features such as higher.Meanwhile prepared electrod-array can be transferred on one-faced tapes or using double by transfer modes
Face glue is transferred in other substrates.
Fig. 5 is that the PVC template filter membrane of photosensitive seal technology production is applied to the preparation of nano-silver thread electrod-array.From figure
The electrod-array area of the pattern that 5a can be seen that the photosensitive seal by exposure-processed is fine and close smooth, and porous structure is exposing
Completely enclose in the process, and unexposed area is loose porous, photosensitive stamp-pad ink can penetrate into wherein, formed electrod-array region without
The photosensitive seal of stamp-pad ink, other regions infiltration stamp-pad ink.When in use, which can be as affixing one's seal, and rapid batch is by conventional filter
The high-precision template filter membrane that film is converted into electrod-array region blank, other regions are stamp-pad ink covering, so as to utilize template
Filtering prepares various high-precision conductive array.
It can be seen that from Fig. 2, Fig. 3 and Fig. 4 that the adhesive tape template prepared using laser carving method, can very strongly be attached
To porous membrane surface, formation and filter membrane shape, kin flexible filter template can be compatible with matched with filter membrane all
The conductive material dispersion solution of various concentration range can be used in filter device.Meanwhile the edge of adhesive tape template can be preferably
Filter membrane surface is fitted to, so that greatly improving inviscid template reported in the literature is bonded uncontrollable problem with filter membrane, is improved
Template filters the precision of prepared electrod-array.From fig. 5, it can be seen that when preparing filtering profile using photosensitive seal technology,
The equipment as needed for photosensitive seal technology is simple, (<) at low cost, prepares precision height, while the type of photosensitive stamp-pad ink is more
Sample, temperature tolerance with higher (> 100 DEG C).In contrast, wax spray printer apparatus valuableness (> $ reported in the literature
20000), preparation process is more complex, and the melt temperature of constructed paraffin filtering profile is low (47 DEG C~64 DEG C), storage and
There are inconveniences in use process.
Fig. 6 is PVDF filter membrane and the scanning electron microscope (SEM) photograph of various conductive material thin films thereon.It is obvious that being filtered using template
Method not only can efficiently prepare the electrod-array of various patterns, various materials, and prepared conductive film is with extraordinary
Uniformity and nanoporous.
Fig. 7 is single-walled carbon nanotube electrod-array and its volt-ampere response of photosensitive seal template filtering preparation.It can see
Out, photosensitive seal template filtering technique can prepare electrod-array, prepared single pipe electrode also with higher precision
The background of array is small, baseline is flat, has extraordinary electrochemical response to the potassium ferricyanide.
Fig. 8 is environmental contaminants bisphenol-A on single-walled carbon nanotube and single-walled carbon nanotube-acetylene black combination electrode array
Cyclic voltammetric response.Bisphenol-A all has very sensitive electrochemical response on this electrod-array, by using batch
The single-walled carbon nanotube being mixed with-acetylene black combination electrode array shows apparent effect of enhanced sensitivity.Therefore, with other electricity
Chemical sensitisation array technology of preparing is different, and template filtering can not only be used to prepare electrod-array, can also controllably realize in batches
The surface of electrod-array or noumenal modification.
Fig. 9 is a variety of materials electrod-array using template filtering preparation to common electroactive biological micromolecule dopamine
It is responded with the cyclic voltammetric of hydrogen peroxide.As can be seen that prepared single-walled carbon nanotube and Graphene electrodes array are to DOPA
Amine all shows good volt-ampere response, and nano-silver thread chemistry replaces to obtain gold nanowire electrod-array then to hydrogen peroxide
With apparent electro-catalysis phenomenon.Therefore, the various carbon-based and noble metal Ji Na with higher cost may be implemented in this method
The efficient array of rice conductive material, to effectively overcome the technical solutions such as existing silk-screen printing, inkjet printing different in preparation
Deficiency in terms of type electrode array.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination, letter
Change, should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of carbon-based and electrode metal substrate array low-cost and high-precision preparation method, which comprises the steps of:
(1), insulating properties encapsulating material is fixed by way of pasting or printing on porous membrane surface, obtains filtration zone in electricity
Pole array configuration, other regions are by the closed filtering profile of insulating properties encapsulating material；
(2), decompression suction filtration is carried out using solution of step (1) the resulting filtering profile to conductive material, deposits conductive material
To the filter array region of filtering profile；
(3), the filtering profile for being deposited with conductive material be dried, washed, re-dry, obtained using filtering profile as carrier
Electrod-array.
2. according to claim 1 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In the method for the fixed insulating properties encapsulating material is laser engraving method, is included the following steps:
(1), the electrod-array region of blank is carved out on insulating properties macromolecule glue band using laser engraving machine；
(2), the sticking one side tiling of polymeric tape is fixed on to the surface of porous membrane, obtains filtering profile.
3. according to claim 1 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In the method for the fixed insulating properties encapsulating material is the photosensitive marking art of composition, is included the following steps:
(1), it is closed using photosensitive seal preparation principle production electrod-array regional exposure, other unexposed seals in region；
(2), oily insulating properties encapsulating material is coated on seal；
(3), insulating properties encapsulating material is printed on porous membrane surface using seal, by dry or curing process, be obtained
Filter template.
4. according to claim 1 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In the porous membrane material includes cellulose acetate, nitrocellulose, cellulose mixture, Kynoar, polytetrafluoroethyl-ne
Alkene, polysulfones and anodised aluminium filter membrane.
5. according to claim 1 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In, the conductive material include carbon nanotube, graphene, carbon nano-fiber, nano-silver thread, gold nanowire, in nanometer platinum line
It is one or more.
6. according to claim 2 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In, the polymeric tape include polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polyimides,
The adhesive tape of brown paper and silica gel material.
7. according to claim 3 carbon-based and electrode metal substrate array low-cost and high-precision preparation method, feature exist
In the insulating properties encapsulating material includes photosensitive stamp-pad ink, polrvinyl chloride printing ink, dimethyl silicone polymer.
8. as claim 1-7 is described in any item carbon-based and the low-cost and high-precision preparation method of electrode metal substrate array is answered
With, which is characterized in that it is used for electrochemical sensor, supercapacitor, electro-catalysis, electroluminescent heating film field.
9. a kind of electrode material, which is characterized in that be prepared using the described in any item methods of claim 1-7.
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