CN110358368A - A kind of stretchable microelectronic circuit electrically conductive ink and its synthetic method - Google Patents
A kind of stretchable microelectronic circuit electrically conductive ink and its synthetic method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/108—Hydrocarbon resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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Abstract
The invention belongs to stretchable microelectronic circuit electrically conductive ink preparation technical field more particularly to a kind of synthetic methods of stretchable microelectronic circuit electrically conductive ink, it is characterised in that, include the following steps: 1, the reducing agent of formula ratio is mixed with elastomer solution, and is uniformly dispersed, reaction base fluid is made；2, metal precursor is added into the reaction base fluid under agitation and is reacted, forms reaction mixture, reacts under stirring condition to fully reacting；The metal ion in the metal precursor is reduced during the reaction, and on the elastomer growth in situ at metal nanoparticle；3, the reaction mixture is centrifuged, obtained filter residue is elastic conductor material；4, by the elastic conductor material and dispersant.Beneficial effect is that stretchable microelectronic circuit electrically conductive ink provided by the present invention, preparation method is simple, and easy to operate, the requirement to technical staff is low, is easy to commercially produce, and can be used for the printing of high-precision electronic device.The film conductivity generated using the ink is good, and inoxidizability is high, and tensile property is good, fold resistant.
Description
Technical field
The invention belongs to stretchable microelectronic circuit electrically conductive ink preparation technical fields, and in particular to a kind of stretchable microelectronics
Circuit conductive ink and its synthetic method.
Background technique
With the development of contemporary scientific technology, traditional silicon-based electronic devices have been unable to satisfy the demand of people, be suitble to
Human body close contact or the microelectronic component carried convenient for human body gradually attract people's attention.Microelectronic component refers to device
Device of the line width above and below several microns in part chip, microelectronic component realize System on Chip/SoC using microelectronic process engineering
With the micromation of device, the performance of circuit and device, reliability can be made to increase substantially in this way, volume and cost significantly drop
It is low.The material for constituting this microelectronic component does not need only to have the electric property for meeting device property, most importantly full
The holding of foot performance under stretching or bending condition.
Elastic conductor is material a kind of not only conductive but also with draftability.Specifically refer to, material stretch, it is curved
In the case where bent, torsion, a kind of brand-new material that resistance is kept essentially constant.The special performance of elastic conductor material make its
Flexible electronic field is widely used.Conventional electronics mainly use silicone based circuit board and metal or ceramics envelope
Dress hits or interferes from the external world although effectively protecting internal circuit, but can not apply in nonplanar environment,
The package dimension of conventional electronics also limits the miniature integrated of device entirety simultaneously.The appearance of elastic conductor successfully solves
The two large problems that conventional electronics face always, therefore high performance elastic conductor is researched and developed to the development of flexible device with weight
Big meaning.
The rapid batch preparation of flexible electronic device may be implemented by printing technology, high-precision printing is in flexible microelectronics
There is great potential in field.Since high-precision printing reduces the package dimension of device, so that miniature being integrated into of device entirety
It may.But the electrically conductive ink for being presently available for printing stretchable microelectronic circuit is still a huge challenge.In general, may be used
Conductive ink for high-precision printing is mainly configured by evenly dispersed metal nanoparticle, due to the ruler of nanoparticle itself
Very little and shape advantage makes it that can easily pass through micron order syringe needle in printing, by the way that nanoparticle is printed upon stretchable base
On plate (such as PDMS, TPU etc.), construction stretch type elastic conductor can get.But the binding force between ink and substrate is poor,
It will lead to the separation between conductive metal and substrate in drawing process, on the other hand, the elastic conductor of building generally requires high temperature
Annealing, this may cause the decomposition of polymer and the sintering of nanoparticle, this is resulted in, can not in material drawing process
Stable high conductivity is kept, the practical application of flexible extensible electronic device is unfavorable for.
Silver is the highest metal of conductivity, and compared to gold, silver-colored price is lower, and compared to copper, silver is not easy to aoxidize in air,
Therefore it can be used as the desired metallic material of the elastic conductor of high-precision printing.In recent years, silver nanowires and Nano silver piece are in elasticity
Conductor field is widely studied application, but in high-precision printing, it is logical due to being unable to control silver nanowires and Nano silver piece
The direction of printing syringe needle is crossed, therefore causes the blocking of syringe needle, so that printing can not be normally carried out.Evenly dispersed silver in the ink
Nanoparticle works as polymer and Nanocomposites since the dimensional effect of itself can easily pass through micro-nano syringe needle
When, most polymers can make Nano silver grain that sedimentation occur or reunite, and make it can not be by micro-nano syringe needle, therefore, preparation can
Intrinsic stretchable elastic conductor for high-precision printing is still a huge challenge in flexible electronic field.
Volume seven page 803 of " natural nanotechnology " periodical 2012 rise report it is embedding with styrene-butadiene-styrene
Section copolymer is substrate, on it fabricated in situ silver particles, but when preparing film in 30um, film performance includes initial conductance
Rate and electric conductivity and draftability all degradations.
Volume 500 page 59 of " nature " periodical 2013 are risen and report evenly dispersed nanoparticle for the first time in polyurethane
Path is re-assemblied, so that material remains certain high conductivity.Researcher be prepared for two kinds based on gold nanoparticle with
The film of polyurethane compound LBL self-assembly and vacuum filtration, but its concrete application in terms of printing is not probed into
" research in nanotechnology " periodical is reported using Nano silver grain as filler, is prepared by elastic matrix of dimethyl silicone polymer
Elastic conductor, author is prepared for elastic conductor by simple blending method, when conductive filler volume fraction is very high, material
Preferable electric conductivity can be kept when stretching.
Some researchers prepare printing collectively as conductive filler using nanoparticle and other one-dimensional or two-dimensional materials
Electrically conductive ink, although this way improves the performance of the electronic device of preparation, due to the height of one-dimensional two-dimensional material itself
Aspect ratio, so the electrically conductive ink for resulting in preparation is not used to high-precision printing.Up to the present, it is based on pure nano grain of silver
Son, which prepares elastic conductor performance not yet, fine breakthrough, and preparation process is complicated, meanwhile, it can be used for the elastic conducting of high-precision printing
Body is still developed not successfully.On the one hand be due to, nanoparticle itself is relatively low in length and breadth, drawing process can make its be located remotely from each other and
Electric conductivity is lost, on the other hand, because of the reunion of nanoparticle in nanoparticle and the compound rear electrically conductive ink prepared of polymer,
Micro-nano syringe needle can not be passed through.
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of conductions that can be used as stretchable microelectronic circuit
Ink and its configuration method.
The invention discloses a kind of synthetic methods of stretchable microelectronic circuit electrically conductive ink, include the following steps:
Step 1, the reducing agent of formula ratio is mixed with elastomer solution, and be uniformly dispersed, reaction base fluid is made；
Step 2, metal precursor is added into the reaction base fluid under agitation to be reacted, forms reaction mixing
Liquid, reaction is to fully reacting under stirring condition；The metal ion in the metal precursor is reduced during the reaction, and
Growth in situ is at metal nanoparticle on the elastomer；
Step 3, the reaction mixture is centrifuged, obtained filter residue is elastic conductor material；
Step 4, by the elastic conductor material and dispersant.
Further, with volume fraction, metal nanoparticle accounts for the 20%-40% of elastic conductor material.
Preferably, with volume fraction, metal nanoparticle accounts for the 35% of elastic conductor material.
Further, the dispersing agent uses alcohols solvent, ketones solvent, n,N-Dimethylformamide, N- methylpyrrole
Alkanone.
Preferably, the dispersing agent uses isopropanol.
Further, the reducing agent uses at least one of ethylene glycol amine, sodium citrate, sodium borohydride.
Further, the elastomer uses soluble polyurethane, thermoplastic polyurethane, dimethyl silicone polymer, polyphenyl
Ethylene, one or more of at least one of arbitrary proportion mixture in polyacrylic acid.
Further, the metal precursor uses soluble metallic salt.
Preferably, the metal precursor uses silver nitrate.
Further, in step 1, the reaction base fluid is to stir not stratified to solution and be creamy white.
Preferably, step 1 prepares the stirring rate that uses of reaction base fluid as 1600rpm.
Further, in step 2, the stirring rate is 150-1200rpm.
Preferably, stirring rate gradually decreases as follows in step 2:
Stirring rate is 1200rpm when being initially added the metal precursor, until reaction mixture becomes faint yellow；
Stirring rate is adjusted to 800rpm, until reaction mixture becomes yellow；
Stirring rate is adjusted to 500rpm, until reaction mixture becomes rufous；
Stirring rate is adjusted to 300rpm, until reaction mixture becomes dark brown；
Stirring rate is adjusted to 150rpm, until reaction mixture becomes black.
Further, centrifugally operated described in step 3, revolving speed 5000rpm.
It the invention also discloses a kind of stretchable microelectronic circuit electrically conductive ink, is prepared using above-mentioned synthetic method.
The beneficial effects of the present invention are:
Stretchable microelectronic circuit electrically conductive ink provided by the present invention, preparation method is simple, easy to operate, to skill
The requirement of art personnel is low, is easy to commercially produce, and can be used for the printing of high-precision electronic device.The film generated using the ink
Good conductivity, inoxidizability are high, and tensile property is good, fold resistant.
Detailed description of the invention
Fig. 1 is reactive group liquid status figure of the present invention；
Fig. 2 is reaction mixture state diagram when step 2 of the present invention changes stirring rate；
Fig. 3 is state diagram after the present invention reacts abundant and stands；
Fig. 4 is elastic conductor materials behavior figure of the present invention；
Fig. 5 is scanning electron microscope (SEM) figure of elastic conductor material of the present invention；
Fig. 6 is the state diagram of various concentration product electrically conductive ink of the present invention；
Fig. 7 is the TEM phenogram of product electrically conductive ink of the present invention；
Fig. 8 is the grain size distribution of product electrically conductive ink of the present invention；
Fig. 9 is 1 product state diagram of comparative example of the present invention；
Figure 10 is scanning electron microscope (SEM) figure of 1 product of comparative example of the present invention；
Figure 11 is 2 product state diagram of comparative example of the present invention；
Figure 12 is 3 product state diagram of comparative example of the present invention；
Figure 13 is 4 product state diagram of comparative example of the present invention；
Figure 14 is 5 product state diagram of comparative example of the present invention；
Figure 15 is the conductivity data figure of ink when comparative example 7 selects IPA and THF as dispersing agent；
Figure 16 is SEM result after 7 tetrahydrofuran of comparative example film forming；
Figure 17 is 1 product Erichsen test result figure of the embodiment of the present invention；
Figure 18 is that 1 product of the embodiment of the present invention prints product figure；
Figure 19 is 1 product conductivity test result figure of the embodiment of the present invention；
Figure 20 is 1 product load-deformation curve of the embodiment of the present invention；
Figure 21 is 1 product oxidation resistance test result figure of the embodiment of the present invention
Figure 22 is that 1 product of the embodiment of the present invention stretches conductivity test result figure
Figure 23 is 1 product fatigability test result figure of the embodiment of the present invention
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention, and following embodiment is only used for more
Technical em- bodiments of the invention are clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
The invention discloses a kind of synthetic methods of stretchable microelectronic circuit electrically conductive ink, include the following steps:
Step 1, the aqueous positive electricity polyurethane solutions that 1g mass fraction is 35% are weighed, 10g diethanolamine solution is weighed, it will
The two kinds of solution weighed pour into 50ml beaker, and 12.5g deionized water is then added and obtains reaction stoste, stirring is mixed at room temperature
Close reaction stoste.Stoste is stirred to react two hours using IKA mixing platform, and mixing speed 1600rpm, stirring can make aqueous
Polyurethane solutions are sufficiently mixed with diethanol amine, and milky and no lamination is presented in the mixed solution obtained after stirring
(such as attached drawing 1)；As react base fluid；
Step 2,3.14g silver nitrate solid is weighed, 3.14g deionized water is added, silver nitrate solution is used into ultrasonic wave
Cleaning machine ultrasonic disperse obtains the precursor solution of metallic silver.
The precursor solution of the metallic silver is added in the reaction base fluid (such as part Fig. 2 (a)), mixing platform is adjusted
Revolving speed is 1200rpm, and faint yellow (such as part Fig. 2 (b)) is presented in solution after stirring 20min, then adjusts mixing platform revolving speed and is
800rpm continues to stir 2h, obtains brown yellow solution (such as part Fig. 2 (c)), continues to adjust mixing platform revolving speed to 500rpm, stirs
Rufous is presented in solution after mixing 2h, and extremely light silver-colored simple substance is begun in walls of beaker and forms (such as part Fig. 2 (d)), and then will
Mixing platform revolving speed is adjusted to 300rpm, continues to obtain dark brown solution (such as part Fig. 2 (e)) after stirring 3h, have in walls of beaker bright
Aobvious silver-colored simple substance is formed, and finally adjusts mixing platform revolving speed to 150rpm, continues to stir 17h, black is presented (such as in obtained solution
The part Fig. 2 (f)), beaker bottom has a large amount of precipitatings, and the silver-colored simple substance formed in walls of beaker is extremely thick, and silver mirror reaction phenomenon is extremely obvious.
The solution left standstill 1h or so that entire reaction process obtains after reaction is observed that extremely apparent lamination (as schemed
3), upper solution is as clear as crystal, and black puffy precipitating is arranged at bottom.
Step 3, the mixed liquor in beaker after reaction is transferred to 50ml centrifuge tube, centrifugal condition are as follows: revolving speed
5000rpm, time 10min, after centrifugation, centrifuge tube upper solution is transparent whites, and centrifuge tube bottom sidewall obtains composite precipitation,
Obtained composite precipitation is elastic conductor material (such as Fig. 4)；
Step 4, elastic conductor material and isopropanol are mixedly configured into solution, contain polyurethane 1% based on mass fraction.
Getting the product electrically conductive ink.
The invention also discloses a kind of stretchable microelectronic circuit electrically conductive inks, are prepared using above-mentioned synthetic method.
Resulting composite precipitation will be centrifuged and do scanning electron microscope (SEM) test.Test result (such as Fig. 5).
The precipitating main component that test result shows is Nano silver grain and polyurethane, Nano silver grain and poly- ammonia
Ester it is compound also fairly obvious.Nano silver grain in composite precipitation shows as zero dimension ball shape, between Nano silver grain by
Polyurethane bonding.In addition, in obtained composite precipitation, without obvious agglomeration between Nano silver grain.
To prove creativeness of the invention, spy tests the performance of the present embodiment product as follows:
1, draftability is tested
Such as Figure 17, polytetrafluoroethylene (PTFE) is chosen as substrate, using casting filming therapy by the obtained electrically conductive ink of embodiment 1
Preparation film forming.And obtained film is supported on 3M adhesive tape and carries out tension test, as a result such as Figure 17.It can be seen that embodiment 1
Film made of product can be stretched to 12cm not broken (stretching 6 times) by 2cm.Tensile property is good.
2, printing precision is tested
Such as Figure 18, the method printed by direct write can directly print the pattern of needs, line thickness always, lines
Corner is without accumulation, it is seen that the product printing precision is high.
3, the acquisition of seepage flow threshold
Percolation phenomenon is prevalent in polymer composite material, for conducting particles and the compound bullet of polymer
In property conductor material, conductive path can not be formed when content is low in the composite for conducting particles, materials conductive performance is poor,
When content is increased to a certain concentration to conducting particles in the composite, conductive path can be formed, and composite material has conduction
Property, the content of conducting particles is known as percolation threshold at this time, this to make when the volume fraction of conducting particles increases to a certain critical value
The behavior for obtaining the physical property mutation of integral composite is referred to as percolation phenomenon.The content of conducting particles continues to increase later
The conductivity of height, composite material can be gradually increased therewith.As Figure 19 is obtained when the volume fraction of Nano silver grain is 15%
Composite elastic conductor thin film electric conductivity is very poor, and conductivity is 2.62 × 10-4S·cm-1Left and right, but work as the body of Nano silver grain
When fraction increases to 20%, conductivity rapidly rises to 268.625Scm-1, later with Nano silver grain volume fraction
Increase, the conductivity of composite elastic conductor constantly rises, and is rising initial stage rate quickly, is tending towards stability later.
4, load-deformation curve is tested
With sharp blade by the strip form film sample of the film cut growth 15mm, wide 2mm that are prepared.Thickness of sample
It is obtained by SEM photograph measurement, stretches former length using vernier caliper measurement sample, then carry out extension test.As a result such as Figure 20,
When stretching the initial stage, load-deformation curve meets Hooke's law, with the increase of stretching distance, composite elastic conductor thin film
Strain increases stress and also sharply increases, and does not occur yield phenomenon, is directly entered strain.When the volume fraction of Nano silver grain
When being 20%, the extensibility of composite elastic conductor thin film is about 887%, with nano grain of silver daughter in composite elastic conductor thin film
The extensibility of the rising of fraction, film is gradually reduced, when Nano silver grain volume fraction is 40%, the extensibility drop of film
Down to 336%.This is because volume fraction of nanoparticles increases so that fragile material is gathered in composite elastic conductor, drawing
It is more easier to be broken during stretching, therefore composite elastic conductor thin film extensibility is caused to decline rapidly.
5, oxidation resistance test
In air by film exposure, the resistance variations of 85 days films are continuously recorded at room temperature, obtain result such as Figure 21 institute
Show.The conductivity of different volumes score film is although different, but there is no under obvious for the conductivity of all films
Drop.Stablize constant conductivity and shows that the composite elastic conductor thin film being prepared has good inoxidizability, it is this excellent
Performance can it be more widely used in flexible electronic device.
6, conductivity test is stretched
Stretch conductivity, i.e., the variation of conductivity in elastic conductor film drawing process.For intrinsic stretchable elasticity
For conductor, it is the most accurate that its elastic conductor performance is measured with conductivity variations in stretching.This is because, it is extrinsic can
Tensile elasticity conductor kind can make the resistance variations of integral material little due to the flexibility of substrate itself in drawing process kind, but
This is not in fact tensility possessed by material itself, for intrinsic elastic conductor, although during stretching
Resistance variations are larger, but the variation of this resistance be not be based only on material electric conductivity variation cause, there are also materials itself
The variation of length, width and thickness causes.For obtain electrically conductive ink intrinsic stretching conductivity variation, we select silver nanoparticle
The elastic conductor film of electrically conductive ink manufactured in the present embodiment preparation stretch the test of conductivity.
It the use of width is 3mm, length 7mm, with a thickness of 30 μm of elastic conductor film.Test obtained 22 institute of result figure
Show, in the case where stretching 100%, the conductivity of elastic conductor film is changed to 500S/cm by initial 2761S/cm, electricity
Conductance only has dropped 18%.Composite elastic compared to Nano silver grain under the same thickness for using in-situ synthesis to prepare is led
Body, elastic conductor film produced herein have a higher conductivity in 100% stretching.
7, fatigability is tested
PDMS after using film-forming is as package substrate.Two-sided conductive tape is placed at both ends on PDMS, in adhesive tape
Upper smearing elargol places elastic conductor film when elargol is not dry, and continues to smear one layer of conductive silver glue on upper layer, to protect
The contact for demonstrate,proving film edge when stretching smears liquid metal in the two edges that film stretches.Later when elargol is not dry in film
Upper layer covers one layer of PDMS being cured again, finally overturns two-sided conductive tape, compresses PDMS film, finally obtains upper layer and lower layer
The elastic conductor film of encapsulation.
Use 100 μm of s-1Speed by film extensibility be 50% when recycle 4000 times, as a result such as Figure 23 institute
Show, as the result is shown: elastic conductor film has excellent fatigue resistance.Stretch 4000 times when, the resistance variations of film only by
What is started is changed to 11 times or so more 3 times.It is analyzed in conjunction with the scanned photograph (Figure 23) of film after circulation terminates, film is repeatedly following
This variation of resistance variations under ring not just merely because material resistance under multiple circulation itself variation, also as PDMS base
Plate has already appeared fatigue under multiple circulation, and this point will be seen that from the photo for amplifying 1000 times in the part Figure 23 (a), separately
Outside, in the photo (part Figure 23 (b)) of amplification 50000, the closs packing state of nanoparticle is still high-visible.Stretch circulation
Former long side surface view film is returned to after 4000 times, and there is no apparent bendings, that is to say, that film was still done over numerous cycles
It is to stretch circulation, i.e., the elastic conductor film that the present invention is prepared has good fatigue resistance.
Embodiment 2-5
Embodiment 2-5 is identical as the synthesis process of embodiment 1, and only the variation in reaction raw materials selection, is detailed in table
1:
1 embodiment 2-5 raw material of table chooses table
In order to illustrate the creativeness of synthetic method in the embodiment of the present invention, following comparative example is specially designed:
Comparative example 1
Be added without aqueous polyurethane in reaction base fluid, remaining experimental procedure process with it is completely the same when embodiment 1.Reaction
After obtain transparent clear solution (such as Fig. 9), there is silver mirror reaction to generate for obtained clear transparent solutions to be added dropwise and exists on reaction vessel
On glass slide, after drying at room temperature, directly tested using multimeter, as the result is shown the solution conductivity.Obtained clear is molten
The drying on silicon wafer is directly added dropwise in liquid, does scanning electron microscope test (such as Figure 10).By comparative analysis, polyurethane is not added
Obtained Nano silver grain is also zero dimension spherical structure, identical when particle size is with addition polyurethane, therefore aqueous polyurethane is not
Change original reduction reaction, i.e., diethanol amine restore silver nitrate during, have not been changed generate Nano silver grain size with
Distribution.
Comparative example 2
Aqueous positive electricity polyurethane is replaced with into other aqueous positive electric polymers, has chosen diallyl dimethyl ammoniumchloride
(PDDA) with polyetherimide (PEI) aqueous solution as reference.Aqueous positive electricity polyurethane solutions are replaced in liquid before the reaction
PDDA solution and PEI solution, remaining experimental procedure are identical as embodiment 1.Obtained reaction product (such as Figure 11), from a left side to
The right side is followed successively by aqueous polyurethane product, PDDA product, PEI product.
Use PDDA as the experiment of aqueous positive electric polymer.When PDDA is added in liquid before the reaction, reaction obtains afterwards for 24 hours
Solution be black, there is the generation of silver mirror reaction in solution bottom without obvious sediment in walls of beaker, solution is in black.By what is obtained
Solution is centrifuged under conditions of 5000rpm, 10min, and black attachment occurs in centrifuge tube side wall after centrifugation, and attachment is few,
Centrifugation bottom of the tube obtains shown without spawn.
For the experiment of aqueous positive electricity polymer P EI is added in liquid before reacting, the solution obtained after reaction is presented yellow, burns
Cup sidewall equally has the formation of silver mirror reaction, and adrift a small amount of black precipitate occur to solution surface in silvery white film, bottom.It is right
Obtained suspension is centrifuged, and yellow is presented in upper liquid after centrifugation, and centrifuge tube side wall still has black attachment to be formed.
Thus it proves, not all aqueous positive electric polymer all has the function of being nucleated template, aqueous positive electricity polyurethane
Selection be inventor creative work.
Comparative example 3
It is added without reducing agent diethanol amine during the reaction, remaining experiment condition process embodiments 1 is identical.What is obtained is molten
Liquid (such as Figure 12).The suspended shape of the white particle of solution, upper liquid is transparent after centrifugation, and centrifuge tube bottom sidewall has white sponge production
Object, it is non-conductive.
Find that white product is urethane solid after analysis, this is because salting-out effect has occurred during the reaction, i.e.,
The polyurethane for not having reduction is precipitated silver nitrate as metal salt from aqueous solution.
Comparative example 4
It is added without aqueous polyurethane in liquid before the reaction, directly obtains nano grain of silver using diethanol amine reduction silver nitrate
Son obtains the nanoparticle dispersion liquid (such as part Figure 13 (a)) of clear after reaction.Silver nanoparticle in reaction system at this time
Particle nucleation and growth process is added the polyurethane solutions of equivalent in this reaction system later, continues to stir, molten after stirring 3 days
Liquid becomes brown color, and solution is interior to form (such as part Figure 13 (b)) without obvious particulate material or precipitating.After stirring 9 days
It reacts (such as part Figure 13 (c)), high-visible small black particle shape substance in reaction vessel, it is suspended that solution also becomes black
Liquid, but container bottom does not have precipitating to be formed, this is because diethanol amine fails all to go back silver nitrate after reacting 24 hours before
It is former, that is to say, that the silver nitrate for still thering is minute quantity not to be reduced in reaction system, after polyurethane is added, unreduced silver nitrate
Starting to be restored by diethanol amine, the Nano silver grain that minute quantity restores starts the nucleating growth in the polyurethane of rear addition, but
It is that Nano silver grain is less at this time, so just initially forming answering for Nano silver grain and polyurethane in container after reaction in 9 days
Object is closed, simultaneously as nanoparticle is less, the compound of formation can not be settled.After 50 days stirring tests, reaction container bottom is still
There is not black precipitate to be formed, on the contrary, reaction vessel inner wall has further thick and heavy silver mirror reaction to generate (such as part Figure 13 (d)).
It is proved by this comparative example: being unable to get composite precipitation by reacting the method that polyurethane is added afterwards again, that is,
Say that the nanoparticle of nucleation and growth process cannot be mixed with polyurethane, this experiment demonstrates polyurethane in reaction system from side
In be as nucleation substrate directly with Nano silver grain it is compound.
Comparative example 5
Whether the polyurethane to be added in liquid before confirmatory reaction all participates in reaction, does following experiment: will be upper after centrifugation
Layer liquid collects (such as part Figure 14 (a)) again, continues to be placed on mixing platform and stir, and undergoes 3 days (such as part Figure 14 (b)), 6 days
(such as part Figure 14 (c)) and 9 days (such as part Figure 14 (d)) stirring after as a result, analysis experimental phenomena: experience for a long time
After stirring, reaction container bottom does not have the formation of black precipitate, but has all the more thick and heavy silver mirror reaction on reaction vessel inner wall
It generates.This explanation after reaction, still has part silver nitrate not restored completely by diethanol amine, with the lengthening of time, nitre
Sour silver continues to be restored by diethanol amine, but the polyurethane due to being added in reaction system all settles, and continues to restore
To Nano silver grain be not nucleated substrate, can not settle, so the solution clear caused.Me is tested by this
Demonstrate reaction the initial stage be added polyurethane all with nanoparticle sedimentation.
Comparative example 6
To explore whether all common solvents can act as dispersing agent and be used to prepare, this comparative example is specially set.It presses
It is tested according to following steps and observes state when each step terminates.
1, the elastic conductor material point that different solvents (as shown in table 2) is prepared with 1 step 3 of embodiment is chosen respectively
It does not mix, observes dispersity afterwards.
2, by mixed liquor ultrasonic disperse 30min, dispersity is observed afterwards.
3, the observation state after standing 15min, 30min, 36h respectively.
The selection of 2 solvent of table and dispersibility test table
It can be seen that dehydrated alcohol, DMF, IPA, NMP, THF can be such that elastic conductor material disperses, wherein dehydrated alcohol
Stability is worst, and THF stability is best.
Since metal nanoparticle (especially silver nano-grain) can reunite at high temperature, accordingly, it is preferred that dispersion
Agent uses low-boiling IPA, THF.
Comparative example 7
When further directed to using different dispersing agents, the electric conductivity of the mixture (ink) of generation is explored, specially
This comparative example is set.According to the test of comparative example 6, chooses preferred IPA, THF and tested.The oil that will be obtained in comparative example 6
Ink drying and forming-film at normal temperature, and test using multimeter the electric conductivity (such as Figure 15) of the film.
There is this courseware THF very poor for the film conductivity prepared when solvent, when the volume fraction of Nano silver grain increases to
When 40%, still there is a very poor electric conductivity.
It chooses the film that volume fraction is 35% and does scanning electron microscope test, as a result as shown in figure 16.SEM result
Primary explanation film conductivity very poor reason.Shown in the part Figure 16 (a), nanoparticle in the SEM photograph of 50000 times of amplification
Son is uniformly dispersed, and in the photo of 2000 times of amplification shown in the part Figure 16 (b), nanoparticle is in single now dispersed in the polymer
State, but due to this monodisperse excessively so that do not accumulate between nanoparticle, or even mutually from far, does not have between each other
Contact.Preparation-obtained film is caused not have good electric conductivity.
Above-mentioned comparative example 1-7 illustrates that selection, the addition of raw material of reaction raw materials are suitable in synthetic method disclosed in this invention
It is isolated not existing between sequence and opportunity, reaction time, an organic whole.Each technical characteristic is mutually coordinated can
Generate the electrically conductive ink.This also embodies the creative work of inventor.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of synthetic method of stretchable microelectronic circuit electrically conductive ink, which comprises the steps of:
Step 1, the reducing agent of formula ratio is mixed with elastomer solution, and be uniformly dispersed, reaction base fluid is made；
Step 2, metal precursor is added into the reaction base fluid under agitation to be reacted, forms reaction mixture,
It reacts under stirring condition to fully reacting；The metal ion in the metal precursor is reduced during the reaction, and in institute
Growth in situ is stated on elastomer into metal nanoparticle；
Step 3, the reaction mixture is centrifuged, obtained filter residue is elastic conductor material；
Step 4, by the elastic conductor material and dispersant.
2. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that with volume
Score meter, metal nanoparticle account for the 20%-40% of elastic conductor material.
3. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that with volume
Score meter, metal nanoparticle account for the 35% of elastic conductor material.
4. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that described point
Powder uses alcohols solvent, ketones solvent, n,N-Dimethylformamide, N-Methyl pyrrolidone.
5. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that described point
Powder uses isopropanol.
6. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that the bullet
Property body use soluble polyurethane, thermoplastic polyurethane, dimethyl silicone polymer, polystyrene is a kind of or several in polyacrylic acid
At least one of the arbitrary proportion mixture of kind.
7. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that the gold
Belong to presoma and uses soluble metallic salt.
8. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that step 2
In, the stirring rate is 150-1200rpm.
9. the synthetic method of stretchable microelectronic circuit electrically conductive ink according to claim 1, which is characterized in that step 2
Middle stirring rate gradually decreases as follows:
Stirring rate is 1200rpm when being initially added the metal precursor, until reaction mixture becomes faint yellow；
Stirring rate is adjusted to 800rpm, until reaction mixture becomes yellow；
Stirring rate is adjusted to 500rpm, until reaction mixture becomes rufous；
Stirring rate is adjusted to 300rpm, until reaction mixture becomes dark brown；
Stirring rate is adjusted to 150rpm, until reaction mixture becomes black.
10. a kind of stretchable microelectronic circuit electrically conductive ink, which is characterized in that using described in any one of claim 1-9
It is prepared by the synthetic method of stretchable microelectronic circuit electrically conductive ink.
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| CN111148363A (en) * | 2019-12-31 | 2020-05-12 | 浙江理工大学 | Method for preparing flexible circuit board by etching-writing nano conductive material on surface of polymer film |
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Application publication date: 20191022 |