CN104341860A - Nanometer conductive ink and preparing method thereof - Google Patents
Nanometer conductive ink and preparing method thereof Download PDFInfo
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- CN104341860A CN104341860A CN201310332132.XA CN201310332132A CN104341860A CN 104341860 A CN104341860 A CN 104341860A CN 201310332132 A CN201310332132 A CN 201310332132A CN 104341860 A CN104341860 A CN 104341860A
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- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Abstract
Nanometer conductive ink and a preparing method thereof are disclosed. The nanometer conductive ink comprises an organic copper salt, a solvent, a surfactant and nanometer metal conductive particles. The preparing method includes: a first step of uniformly mixing the organic copper salt, the solvent, the surfactant and the nanometer metal conductive particles according to a ratio to form a solution; and a second step of filtering the solution obtained in the first step through a screen to obtain the nanometer conductive ink. According to the nanometer conductive ink and the preparing method thereof, low-temperature sintering and a low specific resistance of the conductive ink are achieved, the high specific conductance and a good film-forming property are maintained, the problem that the sintering temperature is restricted by the particle size of the nanometer particles is effectively overcome, the range of a substrate and a base plate which are suitable for ink jet printing is broadened, and the problem that the synthesis process of copper nanometer conductive ink in the prior art is complex in process and overhigh in sintering temperature is effectively overcome.
Description
Technical field
The present invention relates to a kind of conductive ink and preparation method thereof, particularly relate to a kind of nanometer conductive ink and preparation method thereof.
Background technology
Last century, the fifties started, and Copper Foil etching method becomes most widely used printed circuit board (PCB) manufacturing technology.Owing to needing a large amount of water for cleaning and solvent, this method is comparatively serious for the pollution of environment, and a large amount of materials is lost in etch cleaner process, causes very low, the raw-material waste of material use efficiency, the cost of product is significantly increased.Meanwhile, the high energy consumption that complicated technology causes also makes to need to find new alternative techniques.
The rise of silk-screen printing technique, solves the shortcomings such as the production unit cost of etching method is high, utilization ratio is low from part.But, for the waste of slurry and the Technology of contact, still result in this working method and there is certain drawback.
The eighties in last century, along with developing rapidly of nanotechnology, nanosecond science and technology make the many industrial fields of human society there occurs huge change already.Based on the ink jet printing circuit engineering that nanometer conductive ink is risen, because directly circuit can be made on substrate, compared with traditional Copper Foil etching method, there is less energy-consumption, low cost, low stain, high-level efficiency, the a series of advantage such as narrow linewidth, greatly can improve the efficiency that existing printed wiring manufactures, become the RFID tag (RFID) being nowadays in high speed development, printed wiring (PCB), flexible circuit (FPC), flexible display and OTFT (OTFT), wearable electronic product, Organic Light Emitting Diode, one of emphasis for the area researches such as organic solar material and other flexible electronic devices.At device element constantly towards today that densification, miniaturization and lightweight develop, ink jet printing circuit engineering can become the core technology of following printed wiring manufacturing industry surely, promotes development and the research of whole electronic component.
Promote the conductive ink that ink jet printing circuit engineering is exploitation sintering temperature and low, low-resistivity in the prerequisite that flexible electronic device process industryization is applied.Because the substrate of flexible electronic device is generally the lower plastics of heat resisting temperature or paper, if processing temperature is too high, easily make substrate deformation that irreversible destruction even occurs.Therefore, as the basal core of ink jet printing circuit, the preparation of conductive ink is wherein the most key step.By conductive particle such as conducting polymer, pottery, the orderly dispersion of metal and carbon pipe etc. are formed the main flow direction that stable ink is research at present in a solvent.Wherein, metal nano ink has application prospect most in all conductive inks, because it possesses good electroconductibility and can sinter conductive film at a lower temperature due to dimensional effect.At present, the research of metallic conduction ink mainly concentrates on exploitation gold and silver and copper nanometer conductive ink.Gold nano conductive ink, due to high cost, only rests on the laboratory study stage, and more based on the conductive ink research of elemental silver nanoparticles, and as CN101805538A discloses silver nanoparticle conductive ink when sintering for 150 DEG C, resistivity is low to moderate 10
-5Ω cm, can be used for distribution completely, and also there is relevant report to the research of elemental copper nanometer particle ink.
Because silver nanoparticle conductive ink cost remains high, and silver atoms very easily shifts thus causes circuit malfunction.Therefore, copper nanometer conductive ink because have compared with silver nanoparticle conductive ink that cost is low, good stability and become the study hotspot in this field recent years.As CN101386723A, CN101608077A disclose the method being prepared copper nanometer conductive ink by chemical means, but the copper nano particles that its weak point is synthesis needs complicated dedoping step as electrodialysis; CN101880493A and CN102558944A individually discloses the method for the synthesis copper conductive ink not needing follow-up removal of impurities, but does not all study the conductivity of this conductive ink; Chinese patent CN102558954A discloses a kind of method simply preparing copper nanometer conductive ink, but this conductive ink only just has good electroconductibility after sintering at up to 200-250 DEG C; In addition, as CN102093774A also discloses some technology and implementation.But consider from the basic demand electric conductivity of conductive ink, sintering temperature, especially in sintering temperature, all can not realize the good sintering of low temperature completely, this just certainly will make to receive certain limitation at the bottom of the fired basis of ink.Therefore, how while guarantee electric conductivity, making great efforts to reduce sintering temperature is one of research center of gravity of conductive ink.
CN101010388A and article Thin Solid Films519(2011) 6530-6533 all propose a kind ofly utilize organic copper salt, organic copper ink that copper complex formazan decomposition obtains to sinter at lesser temps film forming.But find in an experiment, the copper produced due to thermolysis is fluidised form, and therefore, can affect the effect of printing and the homogeneity of film forming to a certain extent, this is for scale operation high-density, and super-narrow line width printed wiring etc. has obvious impact.This just needs to develop a kind of nanometer conductive ink with advantages such as sintering temperature and low, low-resistivity, preparation technology are simple.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nanometer conductive ink and preparation method thereof.This conductive ink has the advantages such as sintering temperature and low, low-resistivity, preparation technology be simple.
For solving the problems of the technologies described above, nanometer conductive ink of the present invention, comprising: organic copper salt, solvent, tensio-active agent and nano metal conducting particles.
The main component of described organic copper salt is copper-amine complex, and the content of this copper-amine complex in nanometer conductive ink is 0.1mol/L ~ 2mol/L.Wherein, copper-amine complex is the reaction product of presoma first mantoquita and amine; Described first mantoquita comprises: one or more in Tubercuprose, venus crystals, cupric oxalate, capric acid copper, lauric acid copper; Described amine comprises: one or more in ammoniacal liquor, n-octyl amine, quadrol, thanomin, dibutylamine; The mol ratio of described first mantoquita and described amine is 1:0.5 ~ 1:2.
Described solvent is one or more in methyl alcohol, ethanol, ethylene glycol, glycol ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, deionized water, glycerol, toluene, dimethylbenzene.
Described tensio-active agent is one or more in polyoxyethylene glycol, polyvinylpyrrolidone, acid polyethylene sodium, polyvinyl alcohol, sodium polystyrene sulfonate, xitix.The mol ratio of this tensio-active agent and described nano metal conducting particles is 0.1:1 ~ 5:1.
Described nano metal conducting particles, dispersibles in organic copper salt, is one or more in copper, silver, Kufil, copper and indium alloy nanoparticle, is preferably copper nano-particle; The particle diameter S of nano metal conducting particles is: 20nm≤S≤200nm, is preferably 20nm≤S≤100nm.The massfraction of nano metal conducting particles in nanometer conductive ink is 5wt% ~ 95wt%.This nano metal conducting particles can adopt commercially produced product or prepare gained by electrolysis, ball milling, wet chemical method etc., prepares preferably by wet chemical method.Wherein, wet chemical method prepares the method for copper nano-particle, comprising:
At 30 ~ 100 DEG C, the second mantoquita is joined in the polyol systems containing reductive agent and organic protective agent, stir after 5 ~ 180 minutes, be cooled to room temperature, through centrifugal or suction filtration, obtain copper nano-particle.
Described second mantoquita comprises: one or more in copper sulfate, cupric nitrate, cupric chloride.
Described reductive agent is one or more in sodium borohydride, hydrazine hydrate, xitix, inferior sodium phosphate, glucose; The mol ratio of reductive agent and the second mantoquita is 3:1 ~ 10:1.
Described organic protective agent is one or more in xitix, citric acid, lauric acid, styracin, capric acid, the basic sodium sulfonate of dodecane, sodium laurylsulfonate, cetyl trimethylammonium bromide, polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, sodium polyacrylate, sodium polystyrene sulfonate, acid polyethylene sodium; The mol ratio of organic protective agent and the second mantoquita is 0.0001:1 ~ 0.1:1.
Described polyvalent alcohol, can adopt conventional polyvalent alcohol, as ethylene glycol, glycerine etc.
The particle diameter P of described copper nano-particle is: 20nm≤P≤100nm.
In addition, the invention also discloses the preparation method of above-mentioned nanometer conductive ink, comprising:
Step one: after (as aforementioned proportion) mixes in proportion by organic copper salt, solvent, tensio-active agent, nano metal conducting particles, forms solution;
Step 2: by step one gained solution by screen filtration, obtained nanometer conductive ink.
In described step one, the method mixed, comprising: ultrasonic, ball milling, grinding or magnetic agitation.Wherein, preferably, ultrasonic frequency is 20 ~ 50KHz, and the time is 30 ~ 120 minutes; The rotating speed of ball milling is 200 ~ 400rpm, ratio of grinding media to material 10 ~ 20:1, and the time is 0.5 ~ 6 hour; The time of grinding is 0.5 ~ 6 hour; The rotating speed of magnetic agitation is 60 ~ 120rpm, and the time is 1 ~ 24 hour.
In described step one, the copper nano-particle that nano metal conducting particles obtains preferably by above-mentioned wet chemical method, preferably, the massfraction of described copper nano-particle in nanometer conductive ink is 5wt%-95wt%.
Moreover the invention also discloses a kind of containing metal conducting film, wherein, this containing metal conducting film is prepared from according to following steps:
Nanometer conductive ink as above is applied to (namely film is shaping) in substrate, in 110 ~ 180 DEG C of sintering (time as sintering can be 30 ~ 120min), form containing metal conducting film, or after the inorganic ink portion in nanometer conductive ink as above being applied to substrate forming inorganic ink film, dry, again the organic moiety in nanometer conductive ink as above is applied on inorganic ink film, in 110 ~ 180 DEG C of sintering, forms containing metal conducting film;
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, tensio-active agent and nano metal conducting particles; Organic moiety in nanometer conductive ink comprises: organic copper salt.
The method of described coating, comprising: any one in spin-coating method, slot coated method, toppan printing, woodburytype, silk screen print method, ink-jet application method, divider coating method.The coating technique that these coating processes all can be formed as the conductive wires pattern of printed wiring board etc. uses.
Described substrate, can be flexible substrates, as the material of heat resisting temperature below 200 DEG C, specifically can comprise: paper, plastics etc.; Wherein, plastics comprise: polyimide film;
Described sintering also can carry out in reducing atmosphere, and wherein, described reducing atmosphere comprises: the gas mixture that the gas mixture of argon gas and hydrogen and the reducing gas provided by formic acid or formaldehyde and rare gas element form; Wherein, rare gas element comprises: nitrogen or argon gas.
In addition, the invention also discloses a kind of preparation method of containing metal conducting film, comprising:
Nanometer conductive ink as above is applied to (namely film is shaping) in substrate, in 110 ~ 180 DEG C of sintering, form containing metal conducting film, or after the inorganic ink portion in nanometer conductive ink as above being applied to substrate forming inorganic ink film, dry, again the organic moiety in nanometer conductive ink as above is applied on inorganic ink film, in 110 ~ 180 DEG C of sintering, forms containing metal conducting film;
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, tensio-active agent and nano metal conducting particles; Organic moiety in nanometer conductive ink comprises: organic copper salt.
In the present invention, the technology of preparing of organic low-temperature sintering nanometer conductive ink of fluxing is the principle utilizing organic-inorganic to combine, and by organic copper salt thermolysis, forms melt copper and to flux alloy nano-powder sintering, realize low-temperature sintering and the low-resistivity of conductive ink.This organic its basic sintering theory of low-temperature sintering nanometer conductive ink of fluxing is illustrated in fig. 1 shown below, and when being heated to certain temperature time (as 160 DEG C), organic copper salt carries out being decomposed to form melt copper.Melt copper has certain mobility, when it flows through nano conducting powders, due to high-energy and the fluidised form of melt copper, can effectively flux and Encapsulation nanoparticle, forms effect of significantly fluxing, and assists effective sintering film forming of conducting particles; Meanwhile, because nanoparticle is the primary solids composition of ink, when melt copper flows through nanoparticle, effectively can play the effect of pinning fluid, reduce the mobility of melt copper, thus effectively ensure consistence and the stability of film forming.
In addition, the way of realization of this organic low-temperature sintering nanometer conductive ink of fluxing, for before sintering step starts, evenly effectively can also spray a certain amount of organic copper salt solution at the inorganic nano conductive ink moisture film sprayed, then carry out sintering of fluxing.
The present invention by the thermolysis of organo-metallic mantoquita, forms melt copper and to flux alloy nano-powder sintering, realize low-temperature sintering and the low-resistivity of conductive ink.Experimental result shows, sintering temperature can be reduced to 160 DEG C, and sintering metal film (copper film) lowest resistivity can reach 10
-5Ω cm.
In addition, the copper nanometer conductive ink synthesis technique existed for prior art is complicated, the too high two problems of sintering temperature, proposing of the present invention's innovation uses copper-amine complex as dispersion agent, makes the copper nano particles through wet chemical method synthesis only need be dispersed to appropriate solvent and can prepare copper nanometer conductive ink.In addition, the interpolation of copper-amine complex also reduces the sintering temperature of copper nanometer conductive ink unexpectedly.Experiment shows, the conductive ink that the copper nano-particle through wet chemical method gained is prepared from can sinter electrically conductive film in reducing atmosphere, and when sintering temperature is 110 DEG C, this conducting film volume specific resistance is 3 × 10
-3Ω cm; When sintering temperature is 160 DEG C, conducting film volume specific resistance is 3.0 × 10
-5Ω cm.
Therefore, the present invention has following beneficial effect:
(1) effectively realize the low-temperature sintering of conductive ink, meanwhile, keep higher specific conductivity to become model with good;
(2) problem that sintering temperature is restricted by nano particle diameter is efficiently solved;
(3) the applicable substrate of ink jet printing and substrate scope is expanded;
(4) preserving type of ink can for preparing organic copper salt solution and the separately preservation of nano metal particles suspension liquid respectively, and during use, proportioning is used in combination by a certain percentage, also can be prepared into finished product conductive ink to preserve;
(5) also copper nano-particle is prepared by wet chemical method, then, use copper-amine complex to carry out the preparation of conductive ink as dispersion agent, effectively solve the problem that copper nanometer conductive ink synthesis technique is complicated, sintering temperature is too high that prior art exists.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and embodiment, the present invention is further detailed explanation:
Fig. 1 is sintering theory schematic diagram;
Fig. 2 is scanning electron microscope (SEM) figure of copper film after sintering;
Fig. 3 is the FE-SEM(field emission scanning electron microscope before copper nanometer conductive ink sintering) figure;
Fig. 4 is the XRD(X ray diffraction before copper nanometer conductive ink sintering) figure;
Fig. 5 is the FE-SEM figure of copper nanometer conductive ink after 160 DEG C of sintering;
Fig. 6 is the XRD figure of copper nanometer conductive ink after 160 DEG C of sintering.
Wherein, the INSTRUMENT MODEL in SEM, FE-SEM, XRD is as follows:
SEM:Phenom G2Pro[Fu Na scientific instrument (Shanghai) Co., Ltd. (Phenom China)];
FE-SEM: Hitachi S-4800;
XRD:DX-2800（Hao Yuan Optical Instruments CO.,LTD）。
Embodiment
In following examples, four point probe resistivity tester adopts the MCP-T370 model of Mitsubishi.
Following examples that conductive ink is applied to substrate is upper, the method for coating can be in spin-coating method, slot coated method, toppan printing, woodburytype, silk screen print method, ink-jet application method, divider coating method any one.
Embodiment 1
Taking commercial electrolytic copper nanoparticle 1g(particle diameter is 40nm), polyvinylpyrrolidone (K30) 0.1g, be added to 3.5g methyl alcohol, after within ultrasonic 120 minutes under 20KHz frequency, disperseing completely, add four water Tubercuprose 0.23g, quadrol 0.12g again, mixing solutions is after ultrasonic 60 minutes, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, coating (as adopted from spin-coating method) is at flexible substrates polyimide film (PI, Kapton, Dupoint) upper (film is shaping), and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 1 × 10
-4Ω cm(0.1 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, result as shown in Figure 2, in obvious sintering state.
Embodiment 2
Taking commercial electrolytic copper nanoparticle 1g(particle diameter is 100nm), acid polyethylene sodium 0.05g, be added to 3.5g mixing solutions (ethylene glycol in mixing solutions: methyl alcohol: the mol ratio=5:1:4 of ethylene glycol monomethyl ether), after within ultrasonic 80 minutes under 40KHz frequency, disperseing completely, add cupric oxalate 0.15g, n-octyl amine 0.26g again, mixing solutions ball milling after 60 minutes (ratio of grinding media to material 20:1) under 400rpm rotating speed, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, coating (as adopted slot coated method) is at PI(polyimide film) in substrate (film is shaping), and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 0.45 × 10
-4Ω cm(0.045 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 3
Taking commercial silver nanoparticle 1g(particle diameter is 20nm), polyvinyl alcohol 0.05g, be added to 3.5g deionized water, after within ultrasonic 30 minutes under 50KHz frequency, disperseing completely, add four water Tubercuprose 0.23g, n-octyl amine 0.26g again, mixing solutions is after the speed lower magnetic force of 120rpm stirs 1 hour, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 160 DEG C of sintering after 30 minutes, obtain the silverskin of sinter molding, the volume specific resistance recording gained silverskin with four point probe resistivity tester is about 0.65 × 10
-4Ω cm(0.065 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 4
Taking copper nano-particle 2g(particle diameter prepared by business-like ball milled is 200nm), sodium polystyrene sulfonate 0.2g, be added to 2.5g glycerine, after within ultrasonic 30 minutes under 50KHz frequency, disperseing completely, add four water Tubercuprose 0.23g, thanomin 0.12g again, mixing solutions is after 80rpm rotating speed lower magnetic force stirs 8h, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 0.25 × 10
-4Ω cm(0.025 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 5
Taking business copper and indium alloy nanoparticle 1g(particle diameter is 150nm), polyoxyethylene glycol (10000) 0.15g, four water Tubercuprose 0.23g, n-octyl amine 0.07g, be added to 3.5g mixing solutions (ethylene glycol in mixing solutions: methyl alcohol: the mol ratio=5:1:4 of ethylene glycol monoethyl ether), mixing solutions ball milling after 6 hours (ratio of grinding media to material 10:1) under 200rpm rotating speed, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 160 DEG C of sintering after 30 minutes, obtain the copper and indium alloy film of sinter molding, the volume specific resistance recording gained copper and indium alloy film with four point probe resistivity tester is about 1.50 × 10
-4Ω cm(0.15 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 6
Taking the standby copper nano-particle 2.8g(median size of Low Temperature Wet chemistry legal system is 50nm), xitix 0.5g, be added to 3.5g ethanol, after within ultrasonic 30 minutes under 40KHz frequency, disperseing completely, add four water Tubercuprose 2.3g, thanomin liquid 0.6g again, mixing solutions ball milling after 0.5 hour (ratio of grinding media to material 15:1) under 300rpm rotating speed, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 1.0 × 10
-4Ω cm(0.1 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 7
Taking business copper Nano silver grain 1g(particle diameter is 200nm), polyvinylpyrrolidone (K30) 0.05g, xitix 0.05g, be added to 3.5g ethanol, after within ultrasonic 30 minutes under 40KHz frequency, disperseing completely, add four water Tubercuprose 0.46g, n-octyl amine 0.52g again, mixing solutions 60rpm magnetic agitation is after 24 hours, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and after 30 minutes, obtain the silverskin of sinter molding at 160 DEG C of sintering, measures its resistivity be about 2.35 × 10 with the volume specific resistance that four point probe resistivity tester records gained silverskin
-4Ω cm(0.235 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 8
Taking commercial electrolytic copper nanoparticle 1g(particle diameter is 40nm), polyvinylpyrrolidone (K30) 5g, be added to 8.5g ethanol, after within ultrasonic 30 minutes under 40KHz frequency, disperseing completely, add a water venus crystals 0.2g, n-octyl amine 0.26g again, mixing solutions is after ultrasonic 60 minutes, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 180 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 0.70 × 10
-3Ω cm(0.7 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 9
Taking commercial electrolytic copper nanoparticle 1g(particle diameter is 40nm), polyvinylpyrrolidone (K30) 1g, be added to 3.5g ethanol, after within ultrasonic 30 minutes under 40KHz frequency, disperseing completely, add four water Tubercuprose 0.23g, n-octyl amine 0.26g again, mixing solutions is after ultrasonic 60 minutes, filter through 800 eye mesh screens, obtain conductive ink.
Take a morsel above-mentioned conductive ink, is coated on (film is shaping) in PI substrate, and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 0.90 × 10
-4Ω cm(0.09 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 10
Taking commercial electrolytic copper nanoparticle 1g(particle diameter is 40nm), polyvinylpyrrolidone (K30) 0.1g, be added to 3.9g ethanol, under 40KHz frequency ultrasonic 60 minutes completely dispersion after, through 800 eye mesh screens filter, obtain inorganic conductive ink.
Meanwhile, take Tubercuprose 0.46g, n-octyl amine 0.52g, join in 4g ethanol, within ultrasonic 30 minutes, dissolve completely, obtain organic conductive ink.
Take a morsel above-mentioned inorganic conductive ink, be coated on (film is shaping) in PI substrate, utilize vacuum drying oven after 40 DEG C a little drying, utilize Minitype atomizing spray head by a small amount of organic conductive emitting ink on inorganic ink film, and at 160 DEG C of sintering after 30 minutes, obtain the copper film of sinter molding, the volume specific resistance recording gained copper film with four point probe resistivity tester is about 2.35 × 10
-4Ω cm(0.0235 Ω/).The copper film of the sinter molding that takes a morsel carries out SEM observation, and its result is similar to shown in Fig. 2, in obvious sintering state.
Embodiment 11
By 0.06mol NaH
2pO
2h
2o, 0.0002mol polyvinylpyrrolidone and 0.0002mol xitix are dissolved in 100mL ethylene glycol.Under mechanical stirring solution is heated to 90 DEG C, after system temperature is stablized, adds the CuSO that 1mL concentration is 0.02mol/ml
45H
2o solution.Solution became carmetta by blueness in 2-5 minute, showed to generate copper nano particles.Termination reaction after continuation reaction 1h, obtains copper nano particles by centrifugal, and dry 6 hours under vacuo.With FE-SEM electron microscopic observation gained copper nano particles, obtain Fig. 3, and with XRD, material phase analysis is carried out to dried copper nano particles, obtain Fig. 4.Fig. 3 shows that prepared copper nano particles diameter is less than 100nm, and median size is about 80nm.Fig. 4 shows that prepared copper nano particles purity is higher, not containing other dephasign.
Get above-mentioned dried copper nano particles 0.080g, four water Tubercuprose 1.13g, n-octyl amine 1.30g, add ethanol in proper amount/ethylene glycol (volume ratio is 80/20) mixed solvent, after grinding 30min, namely obtain nano-copper conductive ink.In addition, it should be noted that, do not add tensio-active agent of the present invention in nano-copper conductive ink prepared by this place, is because add when synthesizing copper nano particles.
Gained copper nanometer conductive ink is coated in polyimide film substrate, at Ar-H
2in gas mixture (hydrogen containing 5% volume), 160 DEG C of sintering 120min, namely obtain copper film.The volume specific resistance recording gained copper film with four point probe resistivity tester is 3.0 × 10
-5Ω cm (0.03 Ω/).Observe the copper film after sintering with FE-SEM, obtain Fig. 5; With XRD, material phase analysis is carried out to gained copper film, obtain Fig. 6.Fig. 5 shows that part nano copper particle connects together after sintering rear surface melting, particle diameter at the copper particle source of below 50nm in the decomposition of organic copper salt.Fig. 6 is shown the electrically conductive film metallic copper very high purity after sintering and is narrowed by the highest peak width at half height, and after can inferring sintering, copper nano particles particle diameter increases.
Embodiment 12
The copper nano particles 0.080g that Example 11 obtains, four water Tubercuprose 2.26g, n-octyl amine 2.60g, then add ethanol in proper amount/ethylene glycol (volume ratio is 80/20) mixed solvent, after grinding 30min, namely obtain nano-copper conductive ink.
Gained copper nanometer conductive ink is coated on flexible substrates polyimide film (PI, Kapton, Dupoint), at Ar-H
2in gas mixture (hydrogen containing 5% volume), 110 DEG C of sintering 120min, namely obtain copper film.The volume specific resistance recording gained copper film with four point probe resistivity tester is 5 × 10
-3Ω cm (5 Ω/).
Embodiment 13
The copper nano particles 0.080g that Example 11 obtains, four water Tubercuprose 2.26g, n-octyl amine 2.60g, then add ethanol in proper amount/ethylene glycol (volume ratio is 80/20) mixed solvent, after grinding 30min, namely obtain nano-copper conductive ink.Gained copper nanometer conductive ink is coated on flexible substrates polyimide film (PI, Kapton, Dupoint), at Ar-H
2in gas mixture (hydrogen containing 5% volume), 130 DEG C of sintering 120min, namely obtain copper film.The volume specific resistance recording gained copper film with four point probe resistivity tester is 3 × 10
-3Ω cm (3 Ω/).
Embodiment 14
The copper nano particles 1.13g that Example 11 obtains, four water Tubercuprose 2.26g, n-octyl amine 2.60g, then add ethanol in proper amount/ethylene glycol (volume ratio is 80/20) mixed solvent, after grinding 30min, namely obtain nano-copper conductive ink.Gained copper nanometer conductive ink is coated on flexible substrates polyimide film (PI, Kapton, Dupoint), at Ar-H
2in gas mixture (hydrogen containing 5% volume), 130 DEG C of sintering 120min, namely obtain copper film.The volume specific resistance recording gained copper film with four point probe resistivity tester is 3 × 10
-4Ω cm (0.3 Ω/).
Claims (18)
1. a nanometer conductive ink, is characterized in that, comprising: organic copper salt, solvent, tensio-active agent and nano metal conducting particles.
2. nanometer conductive ink as claimed in claim 1, is characterized in that: the main component of described organic copper salt is copper-amine complex; The content of described copper-amine complex in nanometer conductive ink is 0.1mol/L ~ 2mol/L.
3. nanometer conductive ink as claimed in claim 2, is characterized in that: described copper-amine complex is the reaction product of the first mantoquita and amine;
Wherein, described first mantoquita comprises: one or more in Tubercuprose, venus crystals, cupric oxalate, capric acid copper, lauric acid copper; Described amine comprises: one or more in ammoniacal liquor, n-octyl amine, quadrol, thanomin, dibutylamine; The mol ratio of described first mantoquita and described amine is 1:0.5 ~ 1:2.
4. nanometer conductive ink as claimed in claim 1, is characterized in that: described solvent is one or more in methyl alcohol, ethanol, ethylene glycol, glycol ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, deionized water, glycerol, toluene, dimethylbenzene.
5. nanometer conductive ink as claimed in claim 1, is characterized in that: described tensio-active agent is one or more in polyoxyethylene glycol, polyvinylpyrrolidone, acid polyethylene sodium, polyvinyl alcohol, sodium polystyrene sulfonate, xitix;
The mol ratio of described tensio-active agent and described nano metal conducting particles is 0.1:1 ~ 5:1.
6. nanometer conductive ink as claimed in claim 1, is characterized in that: described nano metal conducting particles is one or more in copper, silver, Kufil, copper and indium alloy nanoparticle;
The particle diameter S of nano metal conducting particles is: 20nm≤S≤200nm;
The massfraction of nano metal conducting particles in nanometer conductive ink is 5wt% ~ 95wt%;
Nano metal conducting particles is commercially produced product, or prepares gained by electrolysis, ball milling or wet chemical method.
7. nanometer conductive ink as claimed in claim 6, is characterized in that: the particle diameter S of described nano metal conducting particles is: 20nm≤S≤100nm.
8. nanometer conductive ink as claimed in claim 6, is characterized in that: described nano metal conducting particles is copper nano-particle.
9. nanometer conductive ink as claimed in claim 8, it is characterized in that: described copper nano-particle is prepared by wet chemical method, its preparation method comprises:
At 30 ~ 100 DEG C, the second mantoquita is joined in the polyol systems containing reductive agent and organic protective agent, stir after 5 ~ 180 minutes, be cooled to room temperature, through centrifugal or suction filtration, obtain copper nano-particle.
10. nanometer conductive ink as claimed in claim 9, is characterized in that: described second mantoquita comprises: one or more in copper sulfate, cupric nitrate, cupric chloride.
11. nanometer conductive ink as claimed in claim 9, is characterized in that: described reductive agent is one or more in sodium borohydride, hydrazine hydrate, xitix, inferior sodium phosphate, glucose;
The mol ratio of reductive agent and the second mantoquita is 3:1 ~ 10:1.
12. nanometer conductive ink as claimed in claim 9, is characterized in that: described organic protective agent is one or more in xitix, citric acid, lauric acid, styracin, capric acid, the basic sodium sulfonate of dodecane, sodium laurylsulfonate, cetyl trimethylammonium bromide, polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, sodium polyacrylate, sodium polystyrene sulfonate, acid polyethylene sodium;
The mol ratio of organic protective agent and the second mantoquita is 0.0001:1 ~ 0.1:1.
13. nanometer conductive ink as claimed in claim 9, is characterized in that: the particle diameter P of described copper nano-particle is: 20nm≤P≤100nm.
The preparation method of 14. 1 kinds of nanometer conductive ink as claimed in claim 1, is characterized in that, comprising:
Step one: after organic copper salt, solvent, tensio-active agent, nano metal conducting particles being mixed in proportion, forms solution;
Step 2: by step one gained solution by screen filtration, obtained nanometer conductive ink.
15. methods as claimed in claim 14, it is characterized in that: in described step one, the method mixed, comprising: ultrasonic, ball milling, grinding or magnetic agitation;
Wherein, ultrasonic frequency is 20 ~ 50KHz, and the time is 30 ~ 120 minutes; The rotating speed of ball milling is 200 ~ 400rpm, ratio of grinding media to material 10 ~ 20:1, and the time is 0.5 ~ 6 hour; The time of grinding is 0.5 ~ 6 hour; The rotating speed of magnetic agitation is 60 ~ 120rpm, and the time is 1 ~ 24 hour.
16. methods as claimed in claim 14, it is characterized in that: in described step one, nano metal conducting particles is the copper nano-particle prepared by wet chemical method, and the massfraction of described copper nano-particle in described nanometer conductive ink is 5wt%-95wt%.
17. 1 kinds of containing metal conducting films, is characterized in that: described containing metal conducting film is prepared from according to following steps:
Nanometer conductive ink as claimed in claim 1 is applied in substrate, in 110 ~ 180 DEG C of sintering, form containing metal conducting film, or after the inorganic ink portion in nanometer conductive ink as claimed in claim 1 being applied to substrate forming inorganic ink film, dry, again the organic moiety in nanometer conductive ink as claimed in claim 1 is applied on inorganic ink film, in 110 ~ 180 DEG C of sintering, forms containing metal conducting film;
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, tensio-active agent and nano metal conducting particles; Organic moiety in nanometer conductive ink comprises: organic copper salt.
18. containing metal conducting films as claimed in claim 17, it is characterized in that: the method for described coating, comprising: any one in spin-coating method, slot coated method, toppan printing, woodburytype, silk screen print method, ink-jet application method, divider coating method;
Described substrate, comprising: paper, plastics; Wherein, plastics comprise: polyimide film;
Described sintering carries out in reducing atmosphere, and wherein, described reducing atmosphere comprises: the gas mixture that the gas mixture of argon gas and hydrogen and the reducing gas provided by formic acid or formaldehyde and rare gas element form; Wherein, rare gas element comprises: nitrogen or argon gas.
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