CN104341860B - Nanometer conductive ink and preparation method thereof - Google Patents
Nanometer conductive ink and preparation method thereof Download PDFInfo
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- CN104341860B CN104341860B CN201310332132.XA CN201310332132A CN104341860B CN 104341860 B CN104341860 B CN 104341860B CN 201310332132 A CN201310332132 A CN 201310332132A CN 104341860 B CN104341860 B CN 104341860B
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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
Abstract
The invention discloses a kind of nanometer conductive ink and preparation method thereof, which includes: organic copper salt, solvent, surfactant and nano metal conducting particles；Preparation method includes: step 1: after organic copper salt, solvent, surfactant, nano metal conducting particles are mixed in proportion, forming solution；Step 2: by step 1 acquired solution by the screen to filtrate, nanometer conductive ink is made.The low-temperature sintering and low-resistivity of present invention realization conductive ink, keep higher conductivity and good at model, efficiently solve the problems, such as that sintering temperature is restricted by nano particle diameter, expand the applicable substrate of ink jet printing and substrate range, and the effective solution problem that copper nanometer conductive ink synthesis technology of the existing technology is complicated, sintering temperature is excessively high.
Description
Technical field
The present invention relates to a kind of conductive inks and preparation method thereof, more particularly to a kind of nanometer conductive ink and its preparation
Method.
Background technique
Last century the fifties start, and copper foil etching method becomes most widely used printed circuit board manufacturing technology.By
It is more serious for the pollution of environment in a large amount of water for cleaning of needs and solvent, this method, and a large amount of material is etching
It is lost in cleaning process, causes that stock utilization is very low, wastes of raw material, so that the cost of product dramatically increases.Meanwhile it is multiple
High energy consumption caused by general labourer's skill is but also need to find new alternative techniques.
The rise of silk-screen printing technique, the production equipment for solving etching method from part is at high cost, utilization rate is low etc. lacks
Point.However, the technology of waste and contact for slurry, having still resulted in this processing method, there are certain disadvantages
End.
The eighties in last century, with the rapid development of nanotechnology, nanosecond science and technology already make human society many
Huge variation has occurred in industrial field.Based on the ink jet printing circuit engineering that nanometer conductive ink is risen, because can directly exist
Circuit is made on substrate, compared with traditional copper foil etching method, there is low energy consumption, low cost, low pollution, high efficiency, narrow linewidth
Etc. a series of advantage, the efficiency of existing printed circuit manufacture can be greatly improved, becomes and is nowadays in high speed development
RFID tag (RFID), printed circuit (PCB), flexible circuit (FPC), flexible display and Organic Thin Film Transistors
(OTFT), the fields such as wearable electronic product, Organic Light Emitting Diode, organic solar material and other flexible electronic devices are ground
One of emphasis studied carefully.In today that device element constantly develops towards densification, miniaturization and lightweight, ink jet printing
Circuit engineering can become the core technology of the following printed circuit manufacturing industry surely, push the development and research of entire electronic component.
Promotion ink jet printing circuit engineering is exploitation low fever in the prerequisite that flexible electronic device process industryization is applied
The conductive ink of junction temperature, low-resistivity.Because the substrate of flexible electronic device is generally the lower plastics of heat resisting temperature or paper
, if processing temperature is excessively high, it is easy to make substrate deformation that irreversible destruction even occur.Therefore, as ink jet printing electricity
The basal core on road, the preparation of conductive ink are wherein the most key steps.By by conductive particle such as conducting polymer,
Ceramics, metal and carbon pipe etc. orderly disperse to form stable ink in a solvent to be the main flow direction studied at present.Wherein, golden
Belonging to nanometer ink is most to have application prospect in all conductive inks, because it has good electric conductivity and due to dimensional effect
Conductive film can be sintered at a lower temperature.Currently, the research of metallic conduction ink is concentrated mainly on exploitation gold, silver and copper
Nanometer conductive ink.Gold nano conductive ink only rests on the laboratory research stage since cost is excessively high, and is received based on elemental silver
The conductive ink research of rice grain is more, if CN101805538A discloses silver nanoparticle conductive ink in 150 DEG C of sintering, resistance
Rate is down to 10-5Ω cm is fully available for wiring, and there is also relevant reports to the research of elemental copper nanometer particle ink.
Since silver nanoparticle conductive ink cost is high, and silver atoms easily shift so as to cause circuit malfunction.Therefore,
At low cost, stability is good and becomes field recent years because having compared with silver nanoparticle conductive ink for copper nanometer conductive ink
Research hotspot.Disclosing such as CN101386723A, CN101608077A and prepare copper nanometer conductive ink by chemical means
Method, but its shortcoming is that the copper nano particles of synthesis need the dedoping step such as electrodialysis of complexity；CN101880493A and
CN102558944A individually discloses the method for being not required to the synthesis copper conductive ink of subsequent removal of impurities, but does not all study the conductive ink
Electric conductivity；Chinese patent CN102558954A discloses a kind of method for simply preparing copper nanometer conductive ink, but should
Conductive ink just has preferable electric conductivity after being sintered only at up to 200-250 DEG C；In addition, as CN102093774A is also public
Some technologies and implementation are opened.However, comprehensively considering from the basic demand conductivity, sintering temperature of conductive ink, especially
It is cannot all to fully achieve the good sintering of low temperature in sintering temperature, this be just bound to so that ink application substrate by
Certain limitation is arrived.Therefore, how while guaranteeing conductivity, make great efforts to reduce the research weight that sintering temperature is conductive ink
One of heart.
CN101010388A and article Thin Solid Films519(2011) 6530-6533 proposes a kind of utilization
Organic copper salt, copper complex formazan decomposition obtain that the organic copper ink to form a film can be sintered in lower temperature.However, sending out in an experiment
It is existing, since the copper that thermal decomposition generates is fluidised form, it will affect the effect of printing and the uniformity of film forming to a certain extent,
This suffers from apparent influence for high density, super-narrow line width printed circuit etc. is mass produced.This just needs to develop a kind of tool
There is the simple nanometer conductive ink of sintering temperature and low, low-resistivity, preparation process.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nanometer conductive inks and preparation method thereof.Conductive ink tool
Have the advantages that sintering temperature and low, low-resistivity, preparation process are simple.
In order to solve the above technical problems, nanometer conductive ink of the invention, comprising: organic copper salt, solvent, surfactant
With nano metal conducting particles.
The main component of the organic copper salt is copper-amine complex, content of the copper-amine complex in nanometer conductive ink
For 0.1mol/L~2mol/L.Wherein, copper-amine complex is the reaction product of presoma the first mantoquita and amine；First mantoquita
It include: one of copper formate, copper acetate, cupric oxalate, capric acid copper, lauric acid copper or a variety of；The amine includes: ammonium hydroxide, just pungent
One of amine, ethylenediamine, ethanol amine, dibutyl amine are a variety of；The molar ratio of first mantoquita and the amine is 1:0.5~1:
2。
The solvent is methanol, ethyl alcohol, ethylene glycol, diglycol, glycol monoethyl ether, ethylene glycol monoethyl ether, goes
One of ionized water, glycerine, toluene, dimethylbenzene are a variety of.
The surfactant is polyethylene glycol, polyvinylpyrrolidone, acid polyethylene sodium, polyvinyl alcohol, polystyrene
One of sodium sulfonate, ascorbic acid are a variety of.The molar ratio of the surfactant and the nano metal conducting particles is
0.1:1~5:1.
The nano metal conducting particles, is dispersed in organic copper salt, is copper, silver, Kufil, copper and indium alloy nanometer
One of particle is a variety of, preferably copper nano-particle；The partial size S of nano metal conducting particles are as follows: 20nm≤S≤200nm,
Preferably 20nm≤S≤100nm.Mass fraction of the nano metal conducting particles in nanometer conductive ink is 5wt%~95wt%.
The nano metal conducting particles can be used commercially produced product or as obtained by the preparation such as electrolysis, ball milling, wet chemical method, preferably logical
Wet chemical method is crossed to be prepared.Wherein, the method that wet chemical method prepares copper nano-particle, comprising:
At 30~100 DEG C, the second mantoquita is added in the polyol systems containing reducing agent and organic protective agent, is stirred
It after mixing 5~180 minutes, is cooled to room temperature, by being centrifuged or filtering, obtains copper nano-particle.
Second mantoquita includes: one of copper sulphate, copper nitrate, copper chloride or a variety of.
The reducing agent is one of sodium borohydride, hydrazine hydrate, ascorbic acid, sodium hypophosphite, glucose or a variety of；
The molar ratio of reducing agent and the second mantoquita is 3:1~10:1.
The organic protective agent be ascorbic acid, citric acid, lauric acid, cinnamic acid, capric acid, the basic sodium sulfonate of dodecane,
Dodecyl sodium sulfate, cetyl trimethylammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid
One of sodium, kayexalate, acid polyethylene sodium are a variety of；Organic protective agent and the molar ratio of the second mantoquita are
0.0001:1~0.1:1.
Conventional polyalcohol, such as ethylene glycol, glycerol can be used in the polyalcohol.
The partial size P of the copper nano-particle are as follows: 20nm≤P≤100nm.
In addition, the invention also discloses the preparation methods of above-mentioned nanometer conductive ink, comprising:
Step 1: in proportion (such as aforementioned proportion) by organic copper salt, solvent, surfactant, nano metal conducting particles
After mixing, solution is formed；
Step 2: by step 1 acquired solution by the screen to filtrate, nanometer conductive ink is made.
In the step 1, uniformly mixed method, comprising: ultrasound, ball milling, grinding or magnetic agitation.Wherein, preferably
Ground, ultrasonic frequency are 20~50KHz, and the time is 30~120 minutes；The revolving speed of ball milling be 200~400rpm, ratio of grinding media to material 10~
20:1, time are 0.5~6 hour；The time of grinding is 0.5~6 hour；The revolving speed of magnetic agitation is 60~120rpm, time
It is 1~24 hour.
In the step 1, nano metal conducting particles is preferably by copper nanoparticle made from above-mentioned wet chemical method
Son, it is preferable that mass fraction of the copper nano-particle in nanometer conductive ink is 5wt%-95wt%.
Furthermore the invention also discloses one kind to contain metal conductive film, wherein it is according to the following steps that this, which contains metal conductive film,
It is prepared:
Nanometer conductive ink as described above is applied in substrate (i.e. film molding), (such as in 110~180 DEG C of sintering
The time of sintering can be 30~120min), it is formed and contains metal conductive film, or will be inorganic in nanometer conductive ink as described above
Ink portion is applied in substrate form inorganic ink film after, it is dry, then will be organic in nanometer conductive ink as described above
Part is applied on inorganic ink film, is sintered in 110~180 DEG C, is formed and is contained metal conductive film；
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, surfactant and nano metal are conductive
Particle；Organic moiety in nanometer conductive ink includes: organic copper salt.
The method of the coating, comprising: from spin-coating method, slot coated method, letterpress printing method, gravure printing method, screen printing
Brush method, ink-jet application method, any one in distributor rubbing method.These coating methods can be as printed wiring board etc.
Conductive wires pattern formation coating technique use.
The substrate can be flexible substrates, if heat resisting temperature is in 200 DEG C of materials below, specifically can include: paper, modeling
Material etc.；Wherein, plastics include: polyimide film；
The sintering can also carry out in reducing atmosphere, wherein the reducing atmosphere includes: the mixed of argon gas and hydrogen
Close the gaseous mixture that gas and the reducibility gas provided by formic acid or formaldehyde and inert gas form；Wherein, inert gas packet
It includes: nitrogen or argon gas.
In addition, the invention also discloses a kind of preparation methods containing metal conductive film, comprising:
Nanometer conductive ink as described above is applied in substrate (i.e. film molding), is sintered in 110~180 DEG C, shape
At containing metal conductive film, or the inorganic ink portion in nanometer conductive ink as described above is applied in substrate formed it is inorganic
It is dry after ink film, then the organic moiety in nanometer conductive ink as described above is applied on inorganic ink film, in 110
~180 DEG C of sintering, form and contain metal conductive film；
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, surfactant and nano metal are conductive
Particle；Organic moiety in nanometer conductive ink includes: organic copper salt.
In the present invention, the technology of preparing of organic fluxing low-temperature sintering nanometer conductive ink is combined using organic-inorganic
Principle is thermally decomposed by organic copper salt, is formed the fluxing alloy nano-powder sintering of melt copper, is realized the low-temperature sintering of conductive ink
And low-resistivity.This organic its basic sintering theory of fluxing low-temperature sintering nanometer conductive ink is illustrated in fig. 1 shown below, when being heated to
When certain temperature when (such as 160 DEG C), organic copper salt carries out being decomposed to form melt copper.Melt copper has certain mobility, when it
When flowing through nano conducting powders, due to the high-energy and fluidised form of melt copper, can effectively fluxing and Encapsulation nanoparticle, formed
Apparent fluxing effect, assists effective sintering of conducting particles to form a film；Simultaneously as nanoparticle be ink primary solids at
Point, when melt copper flows through nanoparticle, the effect of pinning fluid can be effectively acted as, reduces the mobility of melt copper, from
And effectively guarantee the consistency and stability of film forming.
In addition to this, the way of realization of this organic fluxing low-temperature sintering nanometer conductive ink, can also be in sintering step
Before rapid beginning, upper a certain amount of organic copper salt solution is uniformly effectively sprayed in the inorganic nano conductive ink moisture film that spraying is completed,
Fluxing sintering is carried out again.
The present invention is thermally decomposed by organic metal mantoquita, is formed the fluxing alloy nano-powder sintering of melt copper, is realized conductive
The low-temperature sintering and low-resistivity of ink.The experimental results showed that sintering temperature can be reduced to 160 DEG C, sintering metal film (copper
Film) lowest resistivity is up to 10-5Ωcm。
In addition, being asked for copper nanometer conductive ink synthesis technology complexity of the existing technology, sintering temperature excessively high two
Topic, what the present invention innovated, which propose, uses copper-amine complex as dispersing agent, so that the copper nanometer through wet chemical method synthesis
Only appropriate solvent need to be dispersed to can prepare copper nanometer conductive ink to grain.In addition, the addition of copper-amine complex also unexpectedly reduces
The sintering temperature of copper nanometer conductive ink.Experiment shows to lead through what the resulting copper nano-particle of wet chemical method was prepared
Electric ink can sinter electrically conductive film into reducing atmosphere, and when sintering temperature is 110 DEG C, which is 3 ×
10-3Ωcm；When sintering temperature is 160 DEG C, conductive film volume resistivity is 3.0 × 10-5Ωcm。
Therefore, the invention has the following beneficial effects:
(1) low-temperature sintering of conductive ink is effectively realized, meanwhile, keep higher conductivity and good at model；
(2) efficiently solve the problems, such as that sintering temperature is restricted by nano particle diameter；
(3) the applicable substrate of ink jet printing and substrate range are expanded；
(4) preserving type of ink can divide for organic copper salt solution and nano metal particles suspension are prepared respectively
Open preservation, proportion is used in mixed way by a certain percentage when use, can also be prepared into finished product conductive ink and be saved；
(5) copper nano-particle can also be prepared by wet chemical method, then, copper-amine complex is used to carry out as dispersing agent
The preparation of conductive ink, effective solution copper nanometer conductive ink synthesis technology of the existing technology is complicated, sintering temperature
Excessively high problem.
Detailed description of the invention
Present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments:
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 the sintering of copper nanometer conductive ink) figure；
Fig. 4 is the XRD(X x ray diffraction before the sintering of copper nanometer conductive ink) figure；
Fig. 5 is copper nanometer conductive ink in 160 DEG C of sintered FE-SEM figures；
Fig. 6 is copper nanometer conductive ink in 160 DEG C of sintered XRD diagram.
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).
Specific embodiment
In following embodiment, four probe resistance rate testers use the MCP-T370 model of Mitsubishi.
In following embodiment conductive ink is applied in substrate, the method for coating can be to apply from spin-coating method, slit
Cloth method, letterpress printing method, gravure printing method, silk screen print method, ink-jet application method, any one in distributor rubbing method.
Embodiment 1
Commercial electrolytic copper nanoparticle 1g(partial size is weighed as 40nm), polyvinylpyrrolidone (K30) 0.1g, is added extremely
3.5g methanol adds four water copper formate 0.23g, ethylenediamine after ultrasound is completely dispersed for 120 minutes under 20KHz frequency
0.12g, mixed solution ultrasound after sixty minutes, through 800 mesh net filtrations, obtain conductive ink.
Take a small amount of above-mentioned conductive ink, coating (as using from spin-coating method) flexible substrates polyimide film (PI,
Kapton, Dupoint) on (film molding), and 160 DEG C be sintered 30 minutes after, the copper film of sinter molding is obtained, with four probes
The volume resistivity that resistivity tester measures gained copper film is about 1 × 10-4Ω cm(0.1 Ω/).Take a small amount of sinter molding
Copper film carries out SEM observation, as a result as shown in Fig. 2, being in obvious sintering state.
Embodiment 2
Commercial electrolytic copper nanoparticle 1g(partial size is weighed as 100nm), acid polyethylene sodium 0.05g, is added to 3.5g and mixes
Solution (ethylene glycol in mixed solution: methanol: molar ratio=5:1:4 of glycol monoethyl ether), the ultrasound 80 under 40KHz frequency
After minute is completely dispersed, cupric oxalate 0.15g, n-octyl amine 0.26g, mixed solution ball milling 60 minutes under 400rpm revolving speed are added
(ratio of grinding media to material 20:1) afterwards obtains conductive ink through 800 mesh net filtrations.
A small amount of above-mentioned conductive ink is taken, coating (as used slot coated method) is in PI(polyimide film) (film in substrate
Molding), and after 160 DEG C are sintered 30 minutes, the copper film of sinter molding is obtained, measures gained copper with four probe resistance rate testers
The volume resistivity of film is about 0.45 × 10-4Ω cm(0.045 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation,
Its result is similar to shown in Fig. 2, is in apparent sintering state.
Embodiment 3
Business Nano silver grain 1g(partial size is weighed as 20nm), polyvinyl alcohol 0.05g, is added to 3.5g deionized water,
After ultrasound is completely dispersed for 30 minutes under 50KHz frequency, four water copper formate 0.23g, n-octyl amine 0.26g are added, mixed solution exists
Under the speed of 120rpm after magnetic agitation 1 hour, through 800 mesh net filtrations, conductive ink is obtained.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the silverskin of sinter molding, the volume resistivity that gained silverskin is measured with four probe resistance rate testers is about 0.65 × 10-4Ω
Cm(0.065 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, is burnt in apparent
Knot state.
Embodiment 4
The copper nano-particle 2g(partial size for weighing the preparation of commercialized ball-milling method is 200nm), kayexalate 0.2g,
It is added to 2.5g glycerol and adds four water copper formate 0.23g, ethanol amine after ultrasound is completely dispersed for 30 minutes under 50KHz frequency
0.12g, mixed solution after magnetic agitation 8h, through 800 mesh net filtrations, obtain conductive ink under 80rpm revolving speed.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the copper film of sinter molding, the volume resistivity that gained copper film is measured with four probe resistance rate testers is about 0.25 × 10-4Ω
Cm(0.025 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, is burnt in apparent
Knot state.
Embodiment 5
Business copper and indium alloy nanoparticle 1g(partial size is weighed as 150nm), polyethylene glycol (10000) 0.15g, four water beetles acid
Copper 0.23g, n-octyl amine 0.07g are added to the 3.5g mixed solution (ethylene glycol in mixed solution: methanol: ethylene glycol monoethyl ether
Molar ratio=5:1:4), mixed solution is under 200rpm revolving speed after ball milling 6 hours (ratio of grinding media to material 10:1), through 800 mesh net filtrations,
Obtain conductive ink.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the copper and indium alloy film of sinter molding, it is about with the volume resistivity that four probe resistance rate testers measure gained copper and indium alloy film
1.50×10-4Ω cm(0.15 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2,
In apparent sintering state.
Embodiment 6
The copper nano-particle 2.8g(average grain diameter of Low Temperature Wet chemistry method preparation is weighed as 50nm), ascorbic acid 0.5g, is added
Enter to 3.5g ethyl alcohol, after ultrasound is completely dispersed for 30 minutes under 40KHz frequency, adds four water copper formate 2.3g, ethanolamine
Body 0.6g, mixed solution after ball milling 0.5 hour (ratio of grinding media to material 15:1), through 800 mesh net filtrations, are led under 300rpm revolving speed
Electric ink.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the copper film of sinter molding, the volume resistivity that gained copper film is measured with four probe resistance rate testers is about 1.0 × 10-4Ωcm
(0.1 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, in apparent sintering shape
State.
Embodiment 7
Business copper Nano silver grain 1g(partial size is weighed as 200nm), polyvinylpyrrolidone (K30) 0.05g, ascorbic acid
0.05g is added to 3.5g ethyl alcohol, after ultrasound is completely dispersed for 30 minutes under 40KHz frequency, add four water copper formate 0.46g,
After n-octyl amine 0.52g, mixed solution 60rpm magnetic agitation 24 hours, through 800 mesh net filtrations, conductive ink is obtained.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the silverskin of sinter molding, measuring its resistivity with the volume resistivity that four probe resistance rate testers measure gained silverskin is about
2.35×10-4Ω cm(0.235 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to Fig. 2 institute
Show, is in apparent sintering state.
Embodiment 8
Commercial electrolytic copper nanoparticle 1g(partial size is weighed as 40nm), polyvinylpyrrolidone (K30) 5g, is added to 8.5g
Ethyl alcohol adds a water copper acetate 0.2g, n-octyl amine 0.26g after ultrasound is completely dispersed for 30 minutes under 40KHz frequency, mixes
Solution ultrasound after sixty minutes, through 800 mesh net filtrations, obtains conductive ink.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 180 DEG C are sintered 30 minutes, is obtained
To the copper film of sinter molding, the volume resistivity that gained copper film is measured with four probe resistance rate testers is about 0.70 × 10-3Ω
Cm(0.7 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, in apparent sintering
State.
Embodiment 9
Commercial electrolytic copper nanoparticle 1g(partial size is weighed as 40nm), polyvinylpyrrolidone (K30) 1g, is added to 3.5g
Ethyl alcohol adds four water copper formate 0.23g, n-octyl amine 0.26g after ultrasound is completely dispersed for 30 minutes under 40KHz frequency, mixes
Solution ultrasound after sixty minutes, through 800 mesh net filtrations, obtains conductive ink.
A small amount of above-mentioned conductive ink is taken, is coated in PI substrate (film molding), and after 160 DEG C are sintered 30 minutes, is obtained
To the copper film of sinter molding, the volume resistivity that gained copper film is measured with four probe resistance rate testers is about 0.90 × 10-4Ω
Cm(0.09 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, is burnt in apparent
Knot state.
Embodiment 10
Commercial electrolytic copper nanoparticle 1g(partial size is weighed as 40nm), polyvinylpyrrolidone (K30) 0.1g, is added extremely
3.9g ethyl alcohol, through 800 mesh net filtrations, obtains inorganic conductive ink after ultrasound is completely dispersed for 60 minutes under 40KHz frequency.
Meanwhile copper formate 0.46g, n-octyl amine 0.52g are weighed, it is added in 4g ethyl alcohol, ultrasound is completely dissolved for 30 minutes, is obtained
To organic conductive ink.
Take a small amount of above-mentioned inorganic conductive ink, be coated in PI substrate (film molding), using vacuum drying oven at 40 DEG C slightly
After micro- drying, a small amount of organic conductive emitting ink is sintered 30 points on inorganic ink film, and at 160 DEG C using Minitype atomizing spray head
Zhong Hou obtains the copper film of sinter molding, and the volume resistivity that gained copper film is measured with four probe resistance rate testers is about 2.35
×10-4Ω cm(0.0235 Ω/).The copper film of a small amount of sinter molding is taken to carry out SEM observation, result is similar to shown in Fig. 2, is in
Apparent sintering state.
Embodiment 11
By 0.06mol NaH2PO2·H2O, 0.0002mol polyvinylpyrrolidone and 0.0002mol ascorbic acid are dissolved in
In 100mL ethylene glycol.Solution is heated to 90 DEG C under mechanical stirring, 1mL concentration, which is added, after system temperature is stablized is
The CuSO of 0.02mol/ml4·5H2O solution.Solution became carmetta by blue in 2-5 minutes, showed to have generated copper nanometer
Particle.Reaction is terminated after the reaction was continued 1h, copper nano particles is obtained by centrifugation, and be dried under vacuum 6 hours.Use FE-SEM
Electronic Speculum observation gained copper nano particles, obtain Fig. 3, and carry out material phase analysis to the copper nano particles after drying with XRD, obtain figure
4.Fig. 3 shows that prepared copper nano particles diameter is less than 100nm, and average grain diameter is about 80nm.Fig. 4 shows that prepared copper is received
Rice grain purity is higher, is free of other miscellaneous phases.
Copper nano particles 0.080g, four water copper formate 1.13g, n-octyl amine 1.30g after taking above-mentioned drying, are added appropriate second
Alcohol/ethylene glycol (volume ratio 80/20) mixed solvent arrives nano-copper conductive ink after ground 30min.In addition, it is necessary to
Illustrate, surfactant of the invention is not added in the nano-copper conductive ink prepared at this, is because being received in synthesis copper
It is had been added to when rice grain.
Gained copper nanometer conductive ink is coated in polyimide film substrate, in Ar-H2Gaseous mixture (the hydrogen containing 5% volume
Gas) in 160 DEG C of sintering 120min to get arrive copper film.The volume resistivity of gained copper film is measured with four probe resistance rate testers
It is 3.0 × 10-5Ωcm(0.03Ω/□).Sintered copper film is observed with FE-SEM, obtains Fig. 5；With XRD to gained copper film into
Row material phase analysis, obtains Fig. 6.Fig. 5 shows that part nano copper particle connects together after melt surface after sintering, and partial size is in 50nm
Copper particle below derives from the decomposition of organic copper salt.Fig. 6 shows sintered electrically conductive film metallic copper very high purity and by most
High half-peak breadth narrows, and copper nano particles partial size increases after can speculating sintering.
Embodiment 12
Copper nano particles 0.080g made from Example 11, four water copper formate 2.26g, n-octyl amine 2.60g, add suitable
Ethyl alcohol/ethylene glycol (volume ratio 80/20) mixed solvent is measured, arrives nano-copper conductive ink after ground 30min.
Gained copper nanometer conductive ink is coated on flexible substrates polyimide film (PI, Kapton, Dupoint),
Ar-H2In gaseous mixture (hydrogen containing 5% volume) 110 DEG C of sintering 120min to get arrive copper film.With four probe resistance rate testers
The volume resistivity for measuring gained copper film is 5 × 10-3Ωcm(5Ω/□)。
Embodiment 13
Copper nano particles 0.080g made from Example 11, four water copper formate 2.26g, n-octyl amine 2.60g, add suitable
Ethyl alcohol/ethylene glycol (volume ratio 80/20) mixed solvent is measured, arrives nano-copper conductive ink after ground 30min.By institute
It obtains copper nanometer conductive ink to be coated on flexible substrates polyimide film (PI, Kapton, Dupoint), in Ar-H2Gaseous mixture
In (hydrogen containing 5% volume) 130 DEG C of sintering 120min to get arrive copper film.Gained copper film is measured with four probe resistance rate testers
Volume resistivity be 3 × 10-3Ωcm(3Ω/□)。
Embodiment 14
Copper nano particles 1.13g made from Example 11, four water copper formate 2.26g, n-octyl amine 2.60g, add suitable
Ethyl alcohol/ethylene glycol (volume ratio 80/20) mixed solvent is measured, arrives nano-copper conductive ink after ground 30min.By institute
It obtains copper nanometer conductive ink to be coated on flexible substrates polyimide film (PI, Kapton, Dupoint), in Ar-H2Gaseous mixture
In (hydrogen containing 5% volume) 130 DEG C of sintering 120min to get arrive copper film.Gained copper film is measured with four probe resistance rate testers
Volume resistivity be 3 × 10-4Ωcm(0.3Ω/□)。
Claims (15)
1. a kind of nanometer conductive ink, which is characterized in that by organic copper salt, solvent, surfactant and nano metal conductive particle
Son composition；The organic copper salt is copper-amine complex；The copper-amine complex is the reaction product of the first mantoquita and amine, the copper
Content of the amine complex in nanometer conductive ink is 0.1mol/L~2mol/L；Wherein, first mantoquita is selected from: formic acid
One of copper, copper acetate, cupric oxalate, capric acid copper, lauric acid copper are a variety of, and the amine is selected from: ammonium hydroxide, n-octyl amine, ethylenediamine,
One of ethanol amine, dibutyl amine are a variety of；The molar ratio of first mantoquita and the amine is 1:0.5~1:2；The surface
Activating agent is polyethylene glycol, in polyvinylpyrrolidone, acid polyethylene sodium, polyvinyl alcohol, kayexalate, ascorbic acid
It is one or more；The molar ratio of the surfactant and the nano metal conducting particles is 0.1:1~5:1；Nanogold
Belonging to conducting particles is one of copper, silver, Kufil, copper and indium alloy nanoparticle or a variety of；Nano metal conducting particles
Partial size S are as follows: 20nm≤S≤200nm；Mass fraction of the nano metal conducting particles in nanometer conductive ink be 5wt%~
95wt%.
2. nanometer conductive ink as described in claim 1, it is characterised in that: the solvent is methanol, ethyl alcohol, ethylene glycol, one
One of diglycol ethylene, glycol monoethyl ether, ethylene glycol monoethyl ether, deionized water, glycerine, toluene, dimethylbenzene are more
Kind.
3. nanometer conductive ink as described in claim 1, it is characterised in that:
Nano metal conducting particles is commercially produced product, or as obtained by electrolysis, ball milling or wet chemical method preparation.
4. nanometer conductive ink as claimed in claim 3, it is characterised in that: the partial size S of the nano metal conducting particles are as follows:
20nm≤S≤100nm。
5. nanometer conductive ink as claimed in claim 3, it is characterised in that: the nano metal conducting particles is copper nanoparticle
Son.
6. nanometer conductive ink as claimed in claim 5, it is characterised in that: the copper nano-particle passes through wet chemical method system
It is standby to obtain, preparation method, comprising:
At 30~100 DEG C, the second mantoquita is added in the polyol systems containing reducing agent and organic protective agent, stirring 5
It after~180 minutes, is cooled to room temperature, by being centrifuged or filtering, obtains copper nano-particle.
7. nanometer conductive ink as claimed in claim 6, it is characterised in that: second mantoquita includes: copper sulphate, nitric acid
One of copper, copper chloride are a variety of.
8. nanometer conductive ink as claimed in claim 6, it is characterised in that: the reducing agent is sodium borohydride, hydrazine hydrate, resists
One of bad hematic acid, sodium hypophosphite, glucose are a variety of；
The molar ratio of reducing agent and the second mantoquita is 3:1~10:1.
9. nanometer conductive ink as claimed in claim 6, it is characterised in that: the organic protective agent is ascorbic acid, lemon
Acid, lauric acid, cinnamic acid, capric acid, dodecane basic sodium sulfonate, cetyl trimethylammonium bromide, gather dodecyl sodium sulfate
One of ethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, Sodium Polyacrylate, kayexalate, acid polyethylene sodium or
It is a variety of；
Organic protective agent and the molar ratio of the second mantoquita are 0.0001:1~0.1:1.
10. nanometer conductive ink as claimed in claim 6, it is characterised in that: the partial size P of the copper nano-particle are as follows: 20nm
≤P≤100nm。
11. a kind of preparation method of nanometer conductive ink as described in claim 1 characterized by comprising
Step 1: it after organic copper salt, solvent, surfactant, nano metal conducting particles are mixed in proportion, is formed molten
Liquid；
Step 2: by step 1 acquired solution by the screen to filtrate, nanometer conductive ink is made.
12. method as claimed in claim 11, it is characterised in that: in the step 1, uniformly mixed method, comprising: super
Sound, ball milling, grinding or magnetic agitation；
Wherein, ultrasonic frequency is 20~50KHz, and the time is 30~120 minutes；The revolving speed of ball milling is 200~400rpm, ball material
Than 10~20:1, the time is 0.5~6 hour；The time of grinding is 0.5~6 hour；The revolving speed of magnetic agitation be 60~
120rpm, time are 1~24 hour.
13. method as claimed in claim 11, it is characterised in that: in the step 1, nano metal conducting particles is to pass through
The copper nano-particle that wet chemical method is prepared, mass fraction of the copper nano-particle in the nanometer conductive ink are
5wt%-95wt%.
14. one kind contains metal conductive film, it is characterised in that: the metal conductive film that contains is made of being prepared according to the following steps:
Nanometer conductive ink as described in claim 1 is applied in substrate, is sintered in 110~180 DEG C, formation is led containing metal
Electrolemma, or the inorganic ink portion in nanometer conductive ink as described in claim 1 is applied in substrate and forms inorganic ink
It is dry after moisture film, then the organic moiety in nanometer conductive ink as described in claim 1 is applied on inorganic ink film,
It is sintered in 110~180 DEG C, is formed and contain metal conductive film；
Wherein, the inorganic ink portion in nanometer conductive ink, comprising: solvent, surfactant and nano metal conducting particles；
Organic moiety in nanometer conductive ink includes: organic copper salt.
15. containing metal conductive film as claimed in claim 14, it is characterised in that: the method for the coating, comprising: from spin coating
Method, slot coated method, letterpress printing method, gravure printing method, silk screen print method, ink-jet application method, appointing in distributor rubbing method
It anticipates one kind；
The substrate, comprising: paper, plastics；Wherein, plastics include: polyimide film；
The sintering carries out in reducing atmosphere, wherein the reducing atmosphere include: argon gas and hydrogen gaseous mixture, with
And the gaseous mixture that the reducibility gas provided by formic acid or formaldehyde and inert gas form；Wherein, inert gas includes: nitrogen
Or argon gas.
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| WO2016197234A1 (en) * | 2015-06-11 | 2016-12-15 | National Research Council Of Canada | Preparation of high conductivity copper films |
| CN105127609B (en) * | 2015-10-15 | 2017-03-08 | 哈尔滨工业大学 | Copper/galactic nucleus core-shell nanoparticles low-temperature sintering composite solder paste and preparation method thereof |
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| CN106147405A (en) * | 2016-07-06 | 2016-11-23 | 复旦大学 | Copper electrically conductive ink and the preparation method of copper electrically conductive ink, copper conductive film |
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| CN106590173A (en) * | 2016-12-01 | 2017-04-26 | 南京大学 | Nano-metal ink capable of being cured at low temperatures, preparation method therefor and application of nano-metal ink |
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| CN106700735B (en) * | 2016-12-02 | 2020-06-02 | 东北大学 | Particle-free conductive copper ink capable of being heated in air and preparation and use methods thereof |
| CN107186222A (en) * | 2017-05-11 | 2017-09-22 | 佛山实瑞先导材料研究院（普通合伙） | A kind of method that supersonic liquid phase reduction prepares Nanometer Copper |
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| CN108652753A (en) * | 2018-02-02 | 2018-10-16 | 浙江清华柔性电子技术研究院 | It is used to form the pattern material and labeling method of organism surface label |
| CN112789331A (en) * | 2018-08-03 | 2021-05-11 | 加拿大国家研究委员会 | UV sinterable molecular inks and processing thereof using broad spectrum UV light |
| CN109651892B (en) * | 2019-01-28 | 2021-10-15 | 哈尔滨工业大学（威海） | Preparation method of nano-copper conductive ink |
| CN109732099B (en) * | 2019-03-08 | 2022-04-05 | 辽宁大学 | Preparation method of antioxidant micron copper |
| JP7355313B2 (en) | 2019-03-28 | 2023-10-03 | 石川県 | Metal paste, electronic components, and electronic component manufacturing method |
| CN110028830A (en) * | 2019-04-23 | 2019-07-19 | 深圳市华星光电技术有限公司 | A kind of preparation method of copper-based ink and preparation method thereof, electrode |
| CN110446336B (en) * | 2019-09-11 | 2022-03-01 | 哈尔滨工业大学 | In-situ electro-reduction reaction connection method of metal nano ink and application of metal nano ink in printed electronic device |
| CN110408268B (en) * | 2019-09-11 | 2021-11-23 | 哈尔滨工业大学 | Water system nano ink and preparation method thereof |
| CN113327721B (en) * | 2021-08-04 | 2021-11-30 | 宁波维柔电子科技有限公司 | Preparation method of low-temperature cured conductive copper paste |
| CN114231092A (en) * | 2021-12-15 | 2022-03-25 | 深圳先进技术研究院 | Copper conductive ink, flexible substrate and preparation method of flexible substrate |
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