CN105802345A - Nano-metal conductive printing ink and its preparation method and printed circuit board - Google Patents
Nano-metal conductive printing ink and its preparation method and printed circuit board Download PDFInfo
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- CN105802345A CN105802345A CN201410849618.5A CN201410849618A CN105802345A CN 105802345 A CN105802345 A CN 105802345A CN 201410849618 A CN201410849618 A CN 201410849618A CN 105802345 A CN105802345 A CN 105802345A
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Abstract
The invention provides nano-metal conductive printing ink and its preparation method. The nano-metal conductive printing ink comprises nano-metal particles with ellipsoidal shapes. The invention also provides a printed circuit board prepared from the nano-metal conductive printing ink. Through use of the nano-metal conductive printing ink, the ellipsoidal conductive nano-metal particles in a printing liquid drop are pulled each other under a morphology-caused strong capillary force between particles so that a large force field is formed, a loose aggregation structure of the ellipsoidal particles is formed on the liquid surface under the strong and remote attraction between particles, and viscosity of the liquid drop surface is fast increased and can resist a capillary flow in the liquid so that the particles are not conveyed into the boundary through the capillary flow and the suspending particles are not moved to the liquid drop edge and thus coffee-ring effects are well inhibited and uniform printing ink printing quality is realized.
Description
Technical field
The invention belongs to printed wiring technical field, be specifically related to a kind of nano metal electrically conductive ink and preparation method thereof and printed wiring board.
Background technology
The ink that electrically conductive ink conductive material is made, has to a certain degree conduction property, as the use of printing conductiving point or conducting wire in printed wiring board of being therefore everlasting.Kind according to its main conductive composition, is generally divided into gold system, silver system, copper system or even carbon system ink.
And for ink product too, its print on substrate after effect, ink will be affected print on substrate the quality of pattern；After inkjet printing, the uniform deposition of ink function solute is all extremely important with application to the formation of patterns of high precision and the performance of prepared device.And existing ink is due to the spherical particle form of solute so that it is substrate completes the dry run after inkjet printing and can there are some effects causing its uniformity to change, such as coffee toroidal effect.
Wherein, the Crack cause of coffee ring can according to Kelvin formula: RTlnPr/P0=2 γ M/ ρ r=2 γ Vm/r；In formula, P0It is liquid vapour pressure in the plane, PrIt it is liquid vapour pressure on curved surface；R is the radius of curvature of curved surface, convex surface r is taken on the occasion of, concave surface r is taken negative value；γ, M and ρ are the surface tension of liquid, molal weight and density respectively.Therefore, under the implication expressed by above-mentioned formula, the droplet of ink surface of printing is in the less place of curvature, and the vapour pressure on its liquid level is more big, and hydrone more easily escapes in air, and in other words evaporation intensity herein is more big.The radius of curvature of solid-liquid-vapour three-phase intersection drop is minimum, in evaporation process, the evaporation rate of liquid level boundary is very fast, therefore the rate of volatilization of edge's drop is more than the rate of volatilization at drop centered place, the edge of drop is fixed on the surface of solids, under surface tension effects, liquid internal just creates and is constantly flowed extrorse capillary flow to compensate this partial loss to maintain balance by the middle part of drop, when evaporation terminates, the particle set suspended is deposited on drop edge, form the coffee annular state of edge thickness intermediate thin, as shown in Figure 1.
Therefore, in the scenario above, it is achieved surface improves pattern accuracy, it is necessary to suppress coffee toroidal effect.In existing way, scattered spherical nanoparticles in overwhelming majority metallic conductive inks is modified more by adopt, as by using surfactant or high boiling point solution to change the character of its whole surface and intermolecular stress in ink, to reach the coffee toroidal effect in printing process is well suppressed.But in existing way, although after adding modifying agent, surface tension and intermolecular stress are changed and make the effect of coffee ring be inhibited, but add these modified measures, influence whether other character of ink, such as the adhesiveness etc. of electric conductivity and substrate.So, existing do not have and suppressing coffee toroidal effect and can not affect the ink product of other performance such as electric conductivity, viscosity.
Summary of the invention
The above-mentioned deficiency aiming to overcome that prior art of the embodiment of the present invention, there is provided a kind of to be made without modified and there is suitable superficiality, printed wiring board prepared by energy self nano metal electrically conductive ink suppressing coffee toroidal effect and preparation method thereof and this electrically conductive ink of employing.
In order to realize foregoing invention purpose, the technical scheme of the embodiment of the present invention is as follows:
A kind of nano metal electrically conductive ink, including nano-metal particle, described nano-metal particle is elliposoidal shape.
The nano metal electrically conductive ink of the present invention, in the drop printed, ellipsoid electrical-conductive nanometer metallic particles relies on its pattern and produces capillary tube interaction force between stronger particle, rely on its interparticle long range interaction power, draw each other, being monolithically fabricated a large force field, this strong and long-range interparticle attraction makes elliposoidal particle form loose aggregate structure at liquid level；And then cause that the viscosity on drop top layer increases rapidly, and contend with the capillary flow of liquid internal, it is prevented that granule is transported to border by capillary flow, prevents the particle of suspension to shift to drop edge, therefore can suppress coffee toroidal effect well, form uniform ink print quality.
The present invention also proposes a kind of method preparing above-mentioned nano metal electrically conductive ink further, comprises the steps:
Compound containing described nano metal and reducing agent are carried out liquid-phase reduction under the atmosphere of nano metal etchant；
In described liquid-phase reduction process, add the reagent for restraining nucleation for controlling nano metal crystallite dimension to reaction system.
The above-mentioned preparation method of the present invention, by polycrystalline crystal seed quantity and type being controlled in the experiment incipient stage, when polycrystalline crystal seed number reach to a certain degree relief its enter directly into rapid growth stage, after the crystal seed speed of growth in all directions improves rapidly, preferential growth becomes no longer obvious, and this process consumes the silver atoms restored in a large number, make reaction fulfil ahead of schedule, form required axiolitic nano-metal particle；Course of reaction simplicity is controlled.
Present invention further propose that a kind of printed wiring board adopting above-mentioned nano conductive printing ink to prepare.
Adopt printed wiring board prepared by the axiolitic nano metal electrically conductive ink of the present invention, the droplet of ink printed on substrate, the capillary flow relying on its interparticle long range interaction power and liquid internal contends with, it is prevented that granule is transported to border by capillary flow, effectively suppresses coffee toroidal effect；And the nano metal electrode surface of the printed wiring board prepared is smooth, compactness good, strong with the adhesive force of substrate, the electric conductivity of electrode is excellent, can be greatly promoted the quality of wiring board.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the dried droplet morphology schematic diagram of spherical conductive droplet of ink under coffee toroidal effect；
Fig. 2 is field of force schematic diagram between the interior molecules of drop in elliposoidal nano metal electrically conductive ink droplet drying process of the present invention；
Fig. 3 is the droplet morphology schematic diagram formed after elliposoidal nano metal electrically conductive ink droplet drying of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of nano metal electrically conductive ink, it is transformed based on existing metal system electrically conductive ink, difference is in that the spherical nano-metal particle solute comparing in existing ink, and the nano-metal particle of the metallic conductive inks of the present invention is ellipsoid shape.
The nano metal electrically conductive ink of the present invention, the form printing droplet drying process and the weather formed may refer to shown in Fig. 2-3；In the drop printed, ellipsoid electrical-conductive nanometer metallic particles relies on its pattern and produces capillary tube interaction force between stronger particle, rely on its interparticle long range interaction power, draw each other, being monolithically fabricated a large force field, this strong and long-range interparticle attraction makes elliposoidal particle form loose aggregate structure at liquid level；And then cause that the viscosity on drop top layer increases rapidly, and contend with the capillary flow of liquid internal, it is prevented that granule is transported to border by capillary flow, prevents the particle of suspension to shift to drop edge, therefore can suppress coffee toroidal effect well, form uniform ink print quality.
Form the effect of solute for ink and form the circuit quality printed, the present invention further to the size Control of above-mentioned axiolitic nano metal in certain size size, it is preferred that the short-axis direction diameter of ellipsoid shape nano-metal particle is 30～40nm, long axis direction diameter is 60nm～120nm.After elliposoidal shape is further change in, its granule is excessive or too small, it all can affect the smooth surface printing the printed wiring formed and homogeneity and the associativity on substrate, and is also possible to cause the shower nozzle in ink jet printing process to block after oversize；Therefore in conjunction with, on the basis of the intergranular stress of its formation, adopting above-mentioned size as the nano metal ink particle of best applications on the basis of repetition test.Certainly, further testing its caking property and the result of coffee toroidal effect, the more excellent short-axis direction diameter that is of a size of be about 40nm, long axis direction diameter is about 100nm.
Simultaneously variable based on pattern in the present invention, and preparation process can be beneficial to the situation controlled, the above-mentioned metallic conductive inks of the present invention is silver system or copper system electrically conductive ink.
The preparation method that the further present invention also proposes a kind of above-mentioned nano metal electrically conductive ink, comprises the steps:
S10, obtains containing the raw materials of compound of the metal ingredient in metallic conductive inks to be prepared, reducing agent, nano metal etchant；
S20, carries out liquid-phase reduction by raw materials of compound and reducing agent under the atmosphere of nano metal etchant；
S30, adds the reagent for restraining nucleation for controlling to generate nanocrystalline grain size in the liquid-phase reduction process of nano metal.
In the preparation process of the nano metal electrically conductive ink of the present invention, compare the liquid-phase reduction preparation process of existing nano metal, focus on controlling the formation pattern of nano-metal particle, after theoretical research repeatedly and test, based on existing liquid phase reduction, by the controlling factors to nucleation and the induction to grain morphology in the process of liquid-phase reduction, finally give ellipsoid shape nano-metal particle required in the present invention.
In process prepared by said method, carry out based on existing common liquid-phase reduction, such as prepare nanometer silver system electrically conductive ink for liquid-phase reduction, the compound solution raw material of the argentiferous being generally adopted, it is possible to it is comparatively suitable for AgNO to select3For material solution, in this compound, the form of Ag is relatively stable ionic forms, and dissolubility is best；Certainly, other can also being adopted in preparation to can be suitably used for the Ag-containing solution of liquid-phase reduction as preparing raw material, in enforcement, technical staff can select according to the convenience of resource.When preparing copper system electrically conductive ink, the raw material of compound is replaced by copper nitrate, copper sulfate etc., all can according to the type of the electrically conductive ink of required preparation and.
Adding nano metal etchant in further step S20 in compound makes reaction system carry out under etchant atmosphere；Process at liquid-phase reduction adopts the nucleus type that the nano metal that the reduction initial stage is formed by nano metal etchant is assembled to process；Because forming the pattern of nano metal, with in the early stage can tuberculosis form relevant, reduction process starts rear monovalence silver/or cupric reduction obtains zero-valent silver atom/or copper atom, and the concentration of silver atoms/or copper atom reaches critical point phase interpolymerized collection and condenses nucleation, and then absorb the zeroth order atom continued growth around newly restored.Normal when being not added with intervening, the pattern of its crystalline polymeric growth mostly is random multiaspect and combines, and ultimately generates spherical nano-particle.And it can at the initial stage of nucleation to add nano metal etchant in step S20, for the more crystal seed of some defects (owing to defect can be higher, more unstable, therefore easily etched), crystal seed such as twin Yu polycrystalline, by the little crystal seed with twin plane high for this class activity, it is etched；And the metastable mono-crystalline structures of structure is easily retained and grows up, the metal atom concentration gone out at reduction initial reduction is not high, they optionally can grow on each crystal face of single crystal seed, the nanostructured such as bar-shaped, linear, the threadiness that therefore can obtain some pattern comparison rule.
Certainly, it should be pointed out that the material variety owing to containing is more, being added in the process of reaction raw materials and function etchant in a solvent, precedence can be selected according to the situation of solvent etc.；As long as can guarantee that it can carry out under the atmosphere of etchant when reaction starts, it is ensured that the nucleus shape at its initial stage can in the particular type of application claims.
Under the atmosphere of the etchant of step S20, in the less situation of metallic atom amount that the reduction initial stage generates, control the pattern of its tuberculosis.And in the process of said method, after reaction carries out in a large number, nucleation rate further speeds up, the further fast growth of nano-particle；And normally only that particle diameter is relatively effective at the seed ratio of below 5nm due to etching action own, when crystal grain look excessive after its structure basicly stable, etching has been not easy there is impact again.In this situation, step S30 adds reagent for restraining nucleation in nano metal reduction process, better prevent crystal seed from forming bigger granule in growth course because of reunion, the size finally making metal nanoparticle can be controlled well, forms required axiolitic nano-metal particle.
Adopt above-mentioned process, its by the length that controls nanocrystal to pattern for the purpose of, after the effect of etchant cannot act on, used reagent for restraining nucleation to control fast-growth and the arrowhead of crystal grain.By polycrystalline crystal seed quantity being controlled in the experiment incipient stage, when polycrystalline crystal seed number reach to a certain degree relief its enter directly into rapid growth stage, after the crystal seed speed of growth in all directions improves rapidly, preferential growth becomes no longer obvious, and this process consumes the metallic atom restored in a large number, make reaction fulfil ahead of schedule, form required axiolitic nano-metal particle.
On the basis of above-mentioned embodiment party, the present invention considers effect in implementation process further, the reagent for restraining nucleation adopted is PEG, because own PEG (Polyethylene Glycol) is as a kind of donor with reduction H proton, itself there is good reproducibility, be a kind of highly reduced property solution, reaction rate can be promoted on the one hand, accelerate the reduction efficiency of whole metallic atom so that the increasing number of crystal seed.And on the other hand, itself there is higher viscosity in nature, by the viscosity that it is higher, it is possible to and the speed that restriction metallic atom is reunited, thus preventing crystal seed from forming bigger granule in growth course because of reunion.By the effect of two aspects, the size of metal nanoparticle is finally made to be controlled well, so preferably employing this PEG in the present invention as reagent for restraining nucleation.Certainly, based on this effect of the size pattern becoming nuclear control size, its reagent for restraining nucleation can also adopt poly(propylene oxide) and polybutylene oxide to be replaced or be used in conjunction with, and also can realize controlling the purpose of crystallite dimension.Wherein, based on the general knowledge implementing requirement and technical staff of the present invention, the Polyethylene Glycol PEG of employing is required to be the Polyethylene Glycol that relative molecular weight is relatively low, such as PEG400.Because its form of wax-like Polyethylene Glycol that relative molecular weight is high is solid-state, it is usually used in the viscosity increasing low-molecular-weight liquid PEG and becomes solidity, being not particularly suitable in the liquid phase of the present invention and use as functional additive.
Meanwhile, wherein based on the difference of above-mentioned metal species and etchant etching effect in conjunction with the elementary process preparing nanometer silver in the present invention based on liquid-phase reduction, etchant preferably employs HCl；Because in the nanoparticle conductive ink preparation of silver system, adopting the reduction of reproducibility Hydrogen Proton to generate in the process of silver atoms, most process all can produce H ion, adopts HCl as etchant, one, it is possible to introduces H in the reaction mixture of reduction reaction+So that the reaction of reduction can reduced rate；Its two, when silver compound is AgNO3Solution, then in the above-described embodiment, H+In conjunction with NO3For HNO3, its silver that can further partial reaction be obtained, more again it is oxidized to ionic species, principle is: 4HNO3+3Ag→3AgNO3+NO+2H2O, can remove high crystal seed more for the defects such as newly-generated twin and polycrystalline, active.Certainly, due to Cl own-Ion is deposited in case a large amount of interpolation, its energy and Ag+Generate precipitation.Certainly, the HCl added as etchant needs amount is controlled, and the amount of interpolation needs to control the trace scope not producing precipitation according to this area common sense.And ability effect of the stage that etchant tells on and etching, it is preferred to use etchant and the amount of substance ratio of original metal compound control to float between 1:25～1:35.Conception based on above-mentioned acid system metal etch, it would however also be possible to employ other acid that can replace carry out such as H2S or HNO3Etc. acid solution；When certainly not adopting acid as etchant, it would however also be possible to employ the high activity twin of existing defects and the etching solution of polycrystalline can be destroyed equally.Meanwhile, based on the conception carrying out size Control after the etching effectiveness nonsignificance that above-mentioned etchant addition produces, the addition of reagent for restraining nucleation can adopt amount of substance ratio between 45:1～50:1 compared with the addition of etchant.
The reaction of the liquid phase that reaction system needs carries out, as the solvent of silver compound in reaction, adopt in the present invention ethylene glycol, ethanol, deionized water or other solvent of liquid phase environment can be provided.Certainly, wherein, preferably employ ethylene glycol (EG), because ethylene glycol own self also has good reproducibility, it is possible to simultaneously as reducing agent function, and boiling point higher (197.2 DEG C), raise temperature and can improve reaction rate, carry out back flow reaction under high temperature and can improve the crystalline form of Silver nanoparticles, produce the particle of uniform particle sizes, even can control crystalline form.Therefore, it has more function value to compare other solvents.
And in conjunction with the process of above-mentioned reaction, the selection of the reducing agent in liquid-phase reduction process, the speed of association reaction generation and the effect of reduction, reducing agent preferably employs NaBH4, sodium citrate, glucose, ethylene glycol, dimethyl sulfoxide (HCON (CH3)2) etc..Mechanism based on above-mentioned solvent ethylene glycol is set forth, it can promote the temperature of reduction process further, the final form assisting to control crystallization；And ethylene glycol is in reduction process, at high temperature decomposing and produce the Biformyl that reproducibility is stronger, then the monovalence silver in solution reduced and obtain zero-valent silver atom by Biformyl；Its process is beneficial to reaction controlling comparatively gently, and therefore reducing agent is it is also preferred that adopt ethylene glycol to carry out.Simultaneously, owing to reducing agent and dicyandiamide solution are as primary response process, etchant or reagent for restraining nucleation that function is added only control on the product of reaction, the interpolation of the quantity of solvent therefore reacted and reduction dosage can necessarily be limited in the preferable range of above-mentioned functions additive, can guarantee that being normally carried out of reaction.If the effect of speed and product really in order to make reaction is comparatively controlled, amount of substance ratio (molar ratio) of the addition of reducing agent EG and the addition of etchant can control to float in the scope of 715:1～5:1.
Simultaneously as in the process of reduction reaction, if the reproducibility of reducing agent is stronger, then just produce silver atoms in the early stage in a large number, be unfavorable for etching and morphology control；Therefore in this situation; in the present invention further before step S20 reduces; nanometer silver dispersant it is added with in reaction system; reduction reaction generating process is so made to carry out under the protection atmosphere of dispersant; and the dispersant in the present invention is macromolecule or the larger molecular organics with silver-colored adsorption functional group; adsorption is had between these functional group and metallics; after ion is reduced into metal; dispersant is just adsorbed on particle surface; between metallic particles, form steric hindrance, stop particle to be assembled when collision.Based on above-mentioned purpose, the dispersant adopted further can be: at least one in polyvinylpyrrolidone (PVP), dodecyl sodium sulfate (SDS), polyvinyl alcohol (PVA), cetyl trimethylammonium bromide (CTAB).Wherein most preferably adopting PVP as dispersant, monomer whose forms chemical absorption containing O, N functional group with silver, therefore the PVP of long-chain multipoint adsorption mode uniformly can envelope nanometer silver and remain stable for a long time, and nanometer silver is had preferably dispersion effect by it.Additionally, due to PVP is long chain macromolecule, when the nanometer silver spray printing being dispersant with PVP is on substrate, PVP also has the effect of adhesive agent, is beneficial to the print quality promoting ink.Certainly, carrying out in a large number to after to a certain degree when reaction, the concentration of silver atoms increases further, and the effectiveness of dispersant plays and tends to slowing down；So just acceleration and size Control that above-mentioned reagent for restraining nucleation reacts can be added.
Certainly, wherein in the process that above-mentioned steps is implemented, the opportunity of various functional additives needs the control principle according to the explanation in above steps and effect, the particularly interpolation of reagent for restraining nucleation, it can not or add prior to etchant with etchant before the reduction step simultaneously, such as PEG and HCl, in system, first with the addition of PEG can cause that reduction reaction is just relatively more violent in the incipient stage, the polycrystalline crystal seed huge number that the same time produces, the size and the degree of stability that add its crystal grain during HCl have been difficult to be etched agent etching so that the morphology control step of reaction is directly skipped.So, prepare the stage that axiolitic nano-Ag particles must produce in conjunction with reduction process in the reaction, by various functional additives, the pattern of crystal seed and the direction of growth are controlled.Certainly, if being required to more excellent carrying out in force, then carry out, in the process of initial reduction reaction, just having started response speed unsuitable too fast at interpolation reducing agent, can suitably turn down reaction temperature, it is to avoid the size of crystal grain and degree of stability are rapidly achieved the degree that cannot etch.And after adding reagent for restraining nucleation, be easy to react the control being rapidly completed and being more favorable for size, it is more preferable to reaction temperature can control adding reaction temperature before reagent for restraining nucleation to control being 135～145 DEG C, adds the Liquid reduction reaction process temperature after reagent for restraining nucleation to be 155～165 DEG C.
Present invention further propose that printed wiring board prepared by electrically conductive ink prepared by a kind of present invention of employing, the method for preparation can adopt the mode of common printing to carry out on substrate, finally prints line pattern on substrate, forms printed wiring board.
Adopt printed wiring board prepared by the axiolitic nano metal electrically conductive ink of the present invention, the droplet of ink printed on substrate, the capillary flow relying on its interparticle long range interaction power and liquid internal contends with, it is prevented that granule is transported to border by capillary flow, effectively suppresses coffee toroidal effect；And the nano metal electrode surface of the printed wiring board prepared is smooth, compactness good, strong with the adhesive force of substrate, the electric conductivity of electrode is excellent, can be greatly promoted the quality of wiring board.
For make the above-mentioned preparation process of the present invention clearly complete, be prone to the enforcement reference of those skilled in the art, and make the prominent progressive effect of material of the present invention more significantly, by the following examples the enforcement of said process carried out concrete example explanation.
Embodiment 1
Reducing with the liquid phase nanometer silver of silver system electrically conductive ink in this embodiment and be illustrated, according to the foregoing description in the present invention, those skilled in the art can expand on some similar electrically conductive inks such as copper system.
S1, is first dissolved in 100mg polyvinylpyrrolidone (PVP) in 20ml ethylene glycol (EG) and pours in the flask of a 50ml capacity；
S2, adds glycerol in heat collecting type constant temperature blender with magnetic force, and temperature is set as 140 DEG C；After glycerol temperature constant in device to be mixed, the flask with PVP and EG of preparation in step S10 is placed in one, stirs 1h.
S3, is then rapidly injected flask by 0.5mlHCl (concentration is 10mmol/L), waits 10min then the AgNO newly prepared by 15ml3EG solution (concentration is 39mmol/L) with 0.5ml min-1Speed be slowly added dropwise in flask, heated and stirred 4h reduces: its chemical equation is as follows:
2HOCH2CH2OH→2CH3CHO+2H2O
2Ag++2CH3CHO→CH3CHO-OHCCH3+2Ag+2H+；
Certainly the H in the HCl wherein added+Can as the product of second step reaction, it is suppressed that response speed, and 4H++4NO3 -+3Ag→3AgNO3+NO(g)+2H2O, also can further enhance the etch effect of nanometer silver nucleus to newly-generated pattern defect.
S4, subsequently by 10ml PEG400 (PEG) with 0.5ml min-1Speed inject flask；Complete when PEG injects temperature brought up to 160 DEG C and ensures continuously stirred 1h.
S5, takes out flask, at room temperature natural cooling；Again through high speed centrifugation (8000rpm) by the reagent medicament remained in reaction and Impurity removal after product in flask is diluted with dehydrated alcohol, this process can be repeatedly, supernatant liquid after centrifugal become as clear as crystal till, lower sediment is the axiolitic nano-Ag particles of preparation；
S6, clean ellipsoid nano-Ag particles is re-dispersed in dehydrated alcohol with the proportion of 25wt%, on the substrate cleaned up, (substrate can be the flexible base boards such as PI, PEN, PET in the method preparation of employing inkjet printing, can also be silicon chip, glass), then carry out heat cure and can obtain mimic bus plate.
By the ink layer of the solidification after above-mentioned steps heat cure, choose edge, center respectively choose 1cm2The region of size, carry out the outcome measurement of metal dust content, in its measurement result, the difference of content is less than 5%, compares the content difference of the center and peripheral position printing the drop with coffee toroidal effect after solidifying of existing spherical ink, greatly reduces.Substantially may be considered the effect with very good uniformity.And using its shape of scanning electron microscopic observation to after being re-dispersed into ethanol solution spin coating with the proportion of 25wt% under the microscope, its overwhelming majority is ellipsoid shape.Therefore, from the result of test, also the axiolitic Nano silver conductive ink drawing the present invention of highly significant can have good coffee ring inhibition, compare existing spherical conductive particle, there is significant progressive.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, all should include within protection scope of the present invention.
Claims (10)
1. a nano metal electrically conductive ink, including nano-metal particle, it is characterised in that described nano-metal particle is elliposoidal shape.
2. the nano metal electrically conductive ink as described in right 1, it is characterised in that the short-axis direction diameter of the nano-metal particle of described elliposoidal shape is 30～40nm, long axis direction diameter is 60nm～120nm.
3. the preparation method of nano metal electrically conductive ink as claimed in claim 1 or 2, it is characterised in that comprise the steps:
Compound containing described nano metal and reducing agent are carried out liquid-phase reduction under the atmosphere of nano metal etchant；
In described liquid-phase reduction process, add the reagent for restraining nucleation for controlling nano metal crystallite dimension to reaction system.
4. the preparation method of nano metal electrically conductive ink as claimed in claim 3, it is characterized in that, compound containing described nano metal and reducing agent being carried out under the atmosphere of nano metal etchant in liquid-phase reduction step, described Liquid reduction reaction process carries out when being added with nano metal dispersant in reaction system.
5. the preparation method of nano metal electrically conductive ink as claimed in claim 4, it is characterised in that described nano metal dispersant is at least one in polyvinylpyrrolidone, dodecyl sodium sulfate, polyvinyl alcohol or cetyl trimethylammonium bromide.
6. the preparation method of the nano metal electrically conductive ink as described in any one of claim 3 to 5, it is characterised in that described nano metal etchant is HCl, H2S or HNO3In at least one；
And/or, described reagent for restraining nucleation is at least one in Polyethylene Glycol, poly(propylene oxide) or polybutylene oxide.
7. the preparation method of the nano metal electrically conductive ink as described in any one of claim 3 to 5, it is characterised in that described reducing agent is NaBH4, sodium citrate, glucose, at least one in ethylene glycol or dimethyl sulfoxide；
And/or, described Liquid reduction reaction process carries out in ethylene glycol solvent.
8. the preparation method of the nano metal electrically conductive ink as described in any one of claim 3 to 5, it is characterized in that, in described Liquid reduction reaction process process, add the Liquid reduction reaction process temperature before reagent for restraining nucleation be 135～145 DEG C, to add the Liquid reduction reaction process temperature after reagent for restraining nucleation be 155～165 DEG C.
9. the preparation method of the nano metal electrically conductive ink as described in any one of claim 3 to 5, it is characterised in that the addition of described etchant is 1:25～1:35 with the mol ratio of metallic element in described compound；
And/or, the mol ratio of the addition of described reagent for restraining nucleation and described etchant addition is 45:1～50:1.
10. printed wiring board prepared by the nano metal electrically conductive ink that a kind utilizes described in claim 1 or 2.
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| CN110484058A (en) * | 2019-08-20 | 2019-11-22 | 深圳市华星光电半导体显示技术有限公司 | Composition for ink |
| CN113498427A (en) * | 2019-03-11 | 2021-10-12 | 卡尔斯鲁厄技术研究所 | High conductivity printable inks for highly stretchable soft electronic devices and high conductivity super-stretchable conductors obtainable therefrom |
| TWI832490B (en) * | 2022-01-06 | 2024-02-11 | 日商海上股份有限公司 | Wiring device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113498427A (en) * | 2019-03-11 | 2021-10-12 | 卡尔斯鲁厄技术研究所 | High conductivity printable inks for highly stretchable soft electronic devices and high conductivity super-stretchable conductors obtainable therefrom |
| CN113498427B (en) * | 2019-03-11 | 2023-06-02 | 卡尔斯鲁厄技术研究所 | High conductivity printable inks for highly stretchable soft electronic devices and high conductivity superstretchable conductors obtainable therefrom |
| CN110484058A (en) * | 2019-08-20 | 2019-11-22 | 深圳市华星光电半导体显示技术有限公司 | Composition for ink |
| WO2021031247A1 (en) * | 2019-08-20 | 2021-02-25 | 深圳市华星光电半导体显示技术有限公司 | Ink composition |
| TWI832490B (en) * | 2022-01-06 | 2024-02-11 | 日商海上股份有限公司 | Wiring device |
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