CN106700735B - Particle-free conductive copper ink capable of being heated in air and preparation and use methods thereof - Google Patents
Particle-free conductive copper ink capable of being heated in air and preparation and use methods thereof Download PDFInfo
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Abstract
A particle-free conductive copper ink capable of being heated in air and a preparation method and a use method thereof belong to the technical field of conductive ink. The conductive copper ink comprises the following components in percentage by mass: 20-73%, complexing agent: 15-60%, solvent: 10-51%, and auxiliary agent: 0 to 10 percent; the preparation method comprises the following steps: adding a complexing agent into an auxiliary agent and a solvent, uniformly mixing, adding a copper precursor, stirring, and filtering by using a microporous filter membrane; the using method comprises the following steps: and printing or coating conductive copper ink on the substrate, and performing heat treatment in air at 130-350 ℃ for 1-15 min for sintering to obtain the copper film/copper wire adhered on the substrate. The ink does not contain any solid particles, has high stability and good conductivity, and the preparation method is simple and easy to operate. The preparation method can be used for heating in the air to obtain the elemental copper, and has the advantages of low curing temperature, short time, no pollution, low cost and easy realization of industrialization.
Description
Technical Field
The invention belongs to the technical field of conductive ink, and particularly relates to particle-free conductive copper ink capable of being heated in air, and a preparation method and a use method thereof.
Background
Printed electronics (printed electronics) is a technology for manufacturing circuits and electronic devices at low cost and high efficiency by printing functional material inks such as conductive polymers, nano-metal inks, or nano-inorganic substances on a substrate by printing means.
Among many conductive inks, conductive polymers have the advantage of low sintering temperature, but their low conductivity and chemical stability have limited their development. In recent years, carbon material inks have received much attention, mainly due to their low cost, but their low conductivity is not satisfactory for devices requiring high conductivity. Gold, silver and copper inks are widely concerned with metal-based inks having wide applications. Gold and silver inks are favored for their high oxidation resistance. However, in order to reduce the cost, researchers have also selected copper with lower resistivity to replace gold and silver, but due to the easy oxidation property of copper in air, most copper-based inks are sintered and densified in an inert gas, a reducing gas or a vacuum environment, which inevitably complicates the operation steps, and the reducing gas is dangerous. The copper-based conductive ink is a blue liquid, does not contain any particulate matter, has high stability, can be printed into lines or patterns on a substrate by various means of printing electrons or a coating technology, and can be subjected to subsequent heat treatment to obtain a conductive copper wire in the air, thereby having wide application prospect in the aspect of printing electrons.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides particle-free conductive copper ink capable of being heated in air and a preparation method and a use method thereof. The preparation method can be used for heating in the air to obtain the elemental copper, and has the advantages of low curing temperature, short time, no pollution, low cost and easy realization of industrialization.
The particle-free conductive copper ink capable of being heated in air is prepared from a copper precursor, a complexing agent, a solvent and an auxiliary agent; wherein, the copper precursor comprises the following components in percentage by mass: 20-73%, complexing agent: 15-60%, solvent: 10-51%, and auxiliary agent: 0 to 10 percent;
the copper precursor is one or a mixture of more of copper nitrate, copper oxide, aliphatic carboxylic acid copper without hydroxyl, aromatic carboxylic acid copper or alicyclic carboxylic acid copper;
the complexing agent is one or a mixture of several of aliphatic amine, alcohol amine, amide, aromatic amine and alicyclic amine with 1-6N atoms;
the solvent is one or a mixture of water and alcohol compounds;
the auxiliary agent is one or a mixture of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, Arabic gum, ethyl cellulose, hydroxymethyl cellulose, span or tween.
The span is one of span 85, span 80, span 60, span 40 or span 20;
one of tween 85, tween 80, tween 60, tween 40 or tween 20 of the tween;
when the copper precursor is a mixture of several kinds of copper precursors, the mixing ratio is any ratio.
When the complexing agent is a mixture of a plurality of complexing agents, the mixing ratio is any ratio.
In the solvent, the alcohol compound is an alcohol compound which contains 1-3 hydroxyl functional groups and has 1-12 carbon atoms. When the solvent is water, the particle-free copper-based conductive ink needs to be added with an auxiliary agent.
When the auxiliary agent is a mixture of a plurality of kinds of additives, the mixing proportion is any ratio.
The particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 1-1000 mPa & s, the contact angle of 15-65 degrees and the surface tension of 20-60 mN/m, and does not have any color change and precipitate generation after being stored for 2 years at room temperature.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink which can be heated in the air, adding a complexing agent into an auxiliary agent and a solvent, and uniformly mixing to obtain a mixed solution;
(2) and adding a copper precursor into the mixed solution, stirring until the copper precursor is completely dissolved, and filtering by using a microporous filter membrane to obtain the particle-free conductive copper ink capable of being heated in the air.
In the step (1), the mixture is uniformly mixed for 15-30 min.
In the step (2), the stirring is carried out at room temperature for 0.5-12 h.
In the step (2), the pore size of the microporous filter membrane is 220nm or 450 nm.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: printing or coating a particle-free conductive copper ink which can be heated in air on a substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 130-350 ℃, and carrying out heat treatment for 1-15 min to obtain the copper film/copper wire adhered on the substrate.
The resistivity of the prepared copper film/copper wire is 4.1-56.7 mu omega cm. The prepared copper film adhered on the substrate is torn by a 3M adhesive tape and a 600M adhesive tape, the copper film does not fall off, the copper film generated on the flexible substrate cannot be damaged after being bent for 200 times, and the resistivity ratio is more than 1 and less than R/R0< 2.5 (where R is the resistivity of the copper film after each bending, R0Resistivity before bending).
In the using method, the substrate is one of polyethylene terephthalate (PET), polyether sulfone resin (PES), polyethylene naphthalate (PEN), Polyimide (PI), glass, monocrystalline silicon, a quartz plate, a ceramic plate or photographic paper.
In the step (2), when the copper precursor is added into the mixed solution, the following reaction occurs:
Cu-R+4R’-NH2→Cu(R’-NH2)4R
wherein R represents a functional group other than copper in copper nitrate, copper oxide, aliphatic carboxylic acid copper having no hydroxyl group, aromatic carboxylic acid copper or alicyclic carboxylic acid copper, and R' represents a functional group other than an amine functional group in aliphatic amine, alcohol amine, amide, aromatic amine or alicyclic amine having 1 to 6N atoms.
Compared with the prior art, the particle-free conductive copper ink capable of being heated in air and the preparation and use methods thereof have the beneficial effects that:
1. the particle-free conductive copper ink capable of being heated in the air does not contain any solid particles, overcomes the defects (low stability and high sintering temperature) inherent in the traditional particle type copper ink, and has the advantages of high stability, simple and easy operation of the manufacturing method, low curing temperature, short time, no pollution, good conductivity, low cost and easy realization of industrialization.
2. The particle-free conductive copper ink capable of being heated in the air can be sintered in the air to obtain simple substance copper by adjusting the sequence between the decomposition temperature of a complex and the volatilization temperature of a solvent, and is not required to be sintered in inert gas, reducing gas and vacuum atmosphere, so that the danger is reduced, and the cost and the operation steps are saved.
3. The resistivity of the copper film obtained after the heat treatment is 4.1-56.7 mu omega-cm, has almost the same value with the resistivity of the copper film obtained by sintering a particle type and other particle-free types under inert gas or reducing gas, the adhesion of the copper film and the substrate is good, the copper film does not fall off after being torn by a 3M or 600M adhesive tape, the copper film generated by the flexible substrate cannot be damaged after being bent for 200 times, and the resistivity ratio is 1 to R/R0 to 2.5 (wherein R is the resistivity of the copper film after each bending, and R0 is the resistivity before bending).
4. The particle-free conductive copper ink capable of being heated in air has the viscosity of 1-1000 mPa & s, the contact angle of 15-65 degrees and the surface tension of 20-60 mN/m, and does not have any color change or precipitate generation after being stored for 2 years at room temperature. In addition, the conductive copper film prepared by the particle-free conductive copper ink capable of being heated in the air can be used for various materials, such as plastics, silicon, glass, ceramics, paper and the like, and can also be applied to various printing methods or various coating methods. Printing methods such as screen printing, ink jet printing, gravure printing, letterpress printing, flexography, lithography, and the like; coating methods such as blade coating, wire rod coating, spin coating, spray coating, dip coating, and the like. Among them, inks having a viscosity in the range of 1 to 20 mPas are suitable for ink jet printing, and inks having a viscosity higher than 20 mPas are suitable for printing methods such as screen printing and flexo printing.
Drawings
Fig. 1 is an XRD pattern of the copper thin film of example 1.
FIG. 2 is an SEM topography of the copper film of example 2.
FIG. 3 is a Cu 2p XPS plot of the copper film of example 3.
FIG. 4 is an SEM topography of the copper film of example 4.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples, viscosity of a particle-free conductive copper ink heatable in air was measured using a viscometer of type LVDV-II + Pro, Brookfield Engineering Labs Inc., USA, contact angle and surface tension of a particle-free conductive copper ink heatable in air were measured using a contact angle meter SL200KS, Keno industries, Inc., USA, resistivity of a copper film was measured using a RTS 8 four-probe resistance tester, Guangzhou four-probe technologies, Inc., JSM-700IF, Japan JEOL, Inc., field emission scanning electron microscope was used to observe morphology of a copper film, and surface of a copper film was observed using a laser confocal test system in an XploRAPLUS Raman spectrometer, Japan Horiba, Inc.
Example 1
A particle-free conductive copper ink capable of being heated in air is prepared from copper acetate, ethylenediamine, isopropanol and polyethylene glycol; wherein, the copper acetate accounts for 35 percent, the ethylenediamine accounts for 20 percent, the isopropanol accounts for 43 percent and the polyethylene glycol accounts for 2 percent;
a preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving ethylenediamine in isopropanol and polyethylene glycol, and uniformly mixing for 15min to obtain a mixed solution;
(2) and adding copper acetate into the mixed solution, stirring for 2h at 25 ℃ until the copper acetate is completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in air is blue, does not contain any solid particles, and has the ink viscosity of 12mPa & s, the contact angle of 20 degrees and the surface tension of 35 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: printing particle-free conductive copper ink capable of being heated in air on a polyethylene naphthalate (PEN) substrate in an ink-jet mode, and sintering in air, wherein the sintering conditions are as follows: heating to 200 deg.C, and heat treating for 2min to obtain conductive copper wire adhered on PEN substrate with resistivity of 10 μ Ω cm.
The XRD pattern of the prepared conductive copper film is shown in figure 1, the diffraction peak of the conductive copper film is compared with the JCPDS standard card, and the data result is well matched.
Example 2
A particle-free conductive copper ink capable of being heated in air is prepared from copper formate, 1, 4-butanediamine, ethylene glycol and glycerol; wherein, the copper formate accounts for 20 percent, the 1, 4-butanediamine accounts for 60 percent, the ethylene glycol accounts for 15 percent and the glycerol accounts for 5 percent;
a preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving 1, 4-butanediamine in ethylene glycol and glycerol, and uniformly mixing for 30min to obtain a mixed solution;
(2) and adding copper formate into the mixed solution, stirring for 10 hours at 25 ℃ until the copper formate is completely dissolved, and filtering by using a microporous filter membrane with the aperture of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in air is blue, does not contain any solid particles, has the ink viscosity of 600mPa & s, has a contact angle of 55 degrees on a quartz piece substrate and has the surface tension of 52 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: coating particle-free conductive copper ink capable of being heated in air on a quartz plate substrate in a rotating mode, and sintering in air, wherein the sintering conditions are as follows: heating to 300 deg.C, and heat treating for 5min to obtain conductive copper film adhered on quartz substrate with resistivity of 4.1 μ Ω cm.
The SEM topography of the prepared conductive copper film is shown in figure 2, and the SEM topography is shown in figure 2, so that particles are tightly connected to form a coherent conductive channel and are relatively compact.
Example 3
A particle-free conductive copper ink capable of being heated in air is prepared from copper propionate, copper succinate, diethanolamine, dodecanol and polyacrylic acid; wherein, the copper propionate accounts for 15 percent, the copper succinate accounts for 22 percent, the diethanolamine accounts for 30 percent, the dodecanol accounts for 28 percent and the polyacrylic acid accounts for 5 percent;
a preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving diethanol amine in dodecyl alcohol and polypropylene alcohol, and uniformly mixing for 30min to obtain a mixed solution;
(2) and adding copper propionate and copper succinate into the mixed solution, stirring for 12h at 25 ℃ until the copper propionate and the copper succinate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in air is blue, does not contain any solid particles, has the ink viscosity of 290mPa & s, the contact angle on a monocrystalline silicon substrate of 40 degrees and the surface tension of 55 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: coating a particle-free conductive copper ink scraper which can be heated in the air on a monocrystalline silicon substrate, and sintering in the air, wherein the sintering conditions are as follows: heating to 250 deg.C, and heat treating for 1min to obtain conductive copper film adhered on the monocrystalline silicon substrate and having resistivity of 21 μ Ω cm.
The prepared copper film adhered on the substrate is torn by a 3M adhesive tape or a 600M adhesive tape, the copper film does not fall off, the copper film generated on the flexible substrate cannot be damaged after being bent for 200 times, and the resistivity ratio R/R0Is 2.
The obtained conductive copper film has Cu 2p XPS pattern shown in FIG. 3, and no Cu is observed2+The position of the peak is determined,and Cu 2p2/3Corresponding to 932eV, is elemental copper.
Example 4
A particle-free conductive copper ink capable of being heated in air is prepared from copper benzoate, propylene diamine, methanol, water, pentanediol, polyethylene glycol and polyvinylpyrrolidone; the copper benzoate-propylene copolymer comprises, by mass, 25% of copper benzoate, 17% of propylene diamine, 13% of methanol, 16% of water, 19% of pentanediol, 3% of polyethylene glycol and 7% of polyvinylpyrrolidone.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink which can be heated in the air, dissolving propylene diamine in methanol, water, pentanediol, polyethylene glycol and polyvinylpyrrolidone, and uniformly mixing for 20min to obtain a mixed solution;
(2) and adding copper benzoate into the mixed solution, stirring for 6h at 25 ℃ until the copper benzoate is completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, does not contain any solid particles, has the ink viscosity of 15mPa & s, the contact angle on a glass substrate of 15 degrees and the surface tension of 31 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: spraying particle-free conductive copper ink capable of being heated in air on a glass substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 190 deg.C, and heat treating for 15min to obtain conductive copper film adhered on the glass substrate with resistivity of 26 μ Ω cm.
The SEM topography of the prepared copper film is shown in figure 4, the film is relatively flat, and continuous conductive channels are formed among copper particles.
Example 5
A particle-free conductive copper ink capable of being heated in air is prepared from copper formate, copper acetate, ethylenediamine, ethanol and ethylene glycol; wherein, the copper formate is 12%, the copper acetate is 13%, the ethylenediamine is 47%, the ethanol is 14%, and the ethylene glycol is 14% by weight.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving ethylenediamine in ethanol and ethylene glycol, and uniformly mixing for 20min to obtain a mixed solution;
(2) and adding copper formate and copper acetate into the mixed solution, stirring for 0.5h at 25 ℃ until the copper formate and the copper acetate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, does not contain any solid particles, has the ink viscosity of 5mPa & s, the contact angle on a PET substrate of 22 DEG and the surface tension of 28 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: flatly printing particle-free conductive copper ink capable of being heated in air on a PET substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 130 deg.C, and heat treating for 8min to obtain conductive copper film adhered on PET substrate with resistivity of 46 μ Ω cm.
Example 6
A particle-free conductive copper ink capable of being heated in air is prepared from copper nitrate, copper acetate, triethylene tetramine, heptanol and span 80; wherein, the copper nitrate accounts for 27 percent, the copper acetate accounts for 11 percent, the triethylene tetramine accounts for 31 percent, the heptanol accounts for 24 percent and the span 80 accounts for 7 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving triethylene tetramine in heptanol and span 80, and uniformly mixing for 20min to obtain a mixed solution;
(2) and adding copper nitrate and copper acetate into the mixed solution, stirring for 2 hours at 25 ℃ until the copper nitrate and the copper acetate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 8mPa & s, the contact angle on a Polyimide (PI) substrate of 29 degrees and the surface tension of 35 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: coating a particle-free conductive copper ink wire rod which can be heated in the air on a PI substrate, and sintering in the air, wherein the sintering conditions are as follows: heating to 270 ℃, and carrying out heat treatment for 2min to obtain the conductive copper film adhered on the PI substrate, wherein the resistivity of the conductive copper film is 22 mu omega cm.
Example 7
A particle-free conductive copper ink capable of being heated in air is prepared from copper oxide, oleylamine, octanediol, butenol, span 80 and polyethylene glycol; wherein, the copper oxide accounts for 30 percent, the oleylamine accounts for 32 percent, the octanediol accounts for 21 percent, the butenol accounts for 13 percent, the span 80 accounts for 1 percent, and the polyethylene glycol accounts for 3 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink which can be heated in the air, dissolving oleylamine in octanediol, butenol, span 80 and polyethylene glycol, and uniformly mixing for 30min to obtain a mixed solution;
(2) adding copper oxide into the mixed solution, stirring for 11h at 25 ℃ until the copper oxide is completely dissolved, and filtering by using a microporous filter membrane with the aperture of 450nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in air is blue, has no solid particles, has the ink viscosity of 12mPa & s, the contact angle of 49 ℃ on a monocrystalline silicon substrate and the surface tension of 42 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: coating a particle-free conductive copper ink which can be heated in air on a monocrystalline silicon substrate in water immersion mode, and sintering in air, wherein the sintering conditions are as follows: heating to 350 deg.C, and heat treating for 15min to obtain conductive copper film adhered on the monocrystalline silicon substrate, wherein the resistivity of the conductive copper film is 15 μ Ω cm.
Example 8
A particle-free conductive copper ink capable of being heated in air is prepared from copper malonate, aniline, triethanolamine, decanol, glycerol and acacia; wherein, the components and the mass percentage thereof are that the copper malonate is 35 percent, the aniline is 9 percent, the triethanolamine is 21 percent, the sunflower alcohol is 10 percent, the glycerol is 19 percent and the Arabic gum is 6 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving aniline and triethanolamine in sunflower alcohol, glycerol and Arabic gum, and uniformly mixing for 30min to obtain a mixed solution;
(2) and adding copper malonate into the mixed solution, stirring for 6h at 25 ℃ until the copper malonate is completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 1000mPa & s, has a contact angle of 65 ℃ on an alumina ceramic plate substrate and has the surface tension of 60 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: printing particle-free conductive copper ink which can be heated in the air on an alumina ceramic chip substrate by silk screen, and sintering in the air, wherein the sintering conditions are as follows: heating to 330 deg.C, and heat treating for 5min to obtain conductive copper wire adhered on the aluminum oxide ceramic substrate with resistivity of 4.1 μ Ω cm.
Example 9
A particle-free conductive copper ink capable of being heated in air is prepared from copper stearate, tetraacetylethylenediamine, hexylamine, ethylene glycol, butanol, polypropylene alcohol and ethyl cellulose; wherein, the copper stearate accounts for 73 percent, the tetraacetylethylenediamine accounts for 2 percent, the hexylamine accounts for 13 percent, the ethylene glycol accounts for 5 percent, the butanol accounts for 5 percent, the polypropylene alcohol accounts for 1 percent, and the ethyl cellulose accounts for 1 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink which can be heated in the air, dissolving tetraacetylethylenediamine and hexylamine in ethylene glycol, butanol, polyvinyl alcohol and ethyl cellulose, and uniformly mixing for 30min to obtain a mixed solution;
(2) and adding copper stearate into the mixed solution, stirring for 9 hours at 25 ℃ until the copper stearate is completely dissolved, and filtering by using a microporous filter membrane with the aperture of 450nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, does not contain any solid particles, has the ink viscosity of 70mPa & s, the contact angle on a glass substrate of 43 degrees and the surface tension of 38 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: gravure printing particle-free conductive copper ink which can be heated in air on a glass substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 270 deg.C, and heat treating for 1min to obtain conductive copper wire adhered on the glass substrate with resistivity of 56.7 μ Ω cm.
Example 10
A particle-free conductive copper ink capable of being heated in air is prepared from copper cyclobutylformate, tetraethylenepentamine, octanol, butanol and Tween 80; wherein, the copper cyclobutylformate is 30 percent, the tetraethylenepentamine is 18 percent, the octanol is 26 percent, the butanol is 19 percent, and the tween 80 is 7 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component ratio of the particle-free conductive copper ink capable of being heated in the air, dissolving tetraethylenepentamine in octanol, butanol and tween 80, and uniformly mixing for 20min to obtain a mixed solution;
(2) and adding the copper cyclobutylformate into the mixed solution, stirring for 3 hours at 25 ℃ until the copper cyclobutylformate is completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 117mPa & s, has a contact angle of 48 degrees on a silicon nitride ceramic plate substrate, and has the surface tension of 41 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: flexibly printing particle-free conductive copper ink capable of being heated in air on a silicon nitride ceramic chip substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 340 ℃, and carrying out heat treatment for 3min to obtain the conductive copper wire bonded on the silicon nitride ceramic wafer substrate, wherein the resistivity of the conductive copper wire is 16.1 mu omega cm.
Example 11
A particle-free conductive copper ink capable of being heated in air is prepared from copper oxalate, tert-butylamine, cyclohexanediamine, ethylene glycol, methanol and ammonium polyacrylate; wherein, the copper oxalate accounts for 22 percent, the tert-butylamine accounts for 10 percent, the cyclohexanediamine accounts for 16 percent, the glycol accounts for 12 percent, the methanol accounts for 39 percent, and the ammonium polyacrylate accounts for 1 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving tert-butylamine and cyclohexanediamine in ethylene glycol, methanol and ammonium polyacrylate, and uniformly mixing for 15min to obtain a mixed solution;
(2) adding copper oxalate into the mixed solution, stirring for 2h at 25 ℃ until the copper oxalate is completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in air is blue, has no solid particles, has the ink viscosity of 18mPa & s, the contact angle on a polyether sulfone resin (PES) substrate of 29 degrees and the surface tension of 31 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: printing particle-free conductive copper ink capable of being heated in air on a PES substrate in an ink-jet mode, and sintering in air, wherein the sintering conditions are as follows: heating to 160 deg.C, and heat treating for 6min to obtain conductive copper wire adhered on PES substrate with resistivity of 18.6 μ Ω cm.
Example 12
A particle-free conductive copper ink capable of being heated in air is prepared from copper oxalate, copper propionate, isopropylamine, pentaethylenehexamine, butanediol and ammonium polymethacrylate; wherein, the components and the mass percentage thereof are that copper oxalate is 10%, copper propionate is 13%, isopropylamine is 26%, pentaethylenehexamine is 14%, butanediol is 35%, and ammonium polymethacrylate is 2%.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving isopropylamine and pentaethylenehexamine in butanediol and ammonium polymethacrylate, and uniformly mixing for 15min to obtain a mixed solution;
(2) and adding copper oxalate and copper propionate into the mixed solution, stirring for 5 hours at 25 ℃ until the copper oxalate and the copper propionate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 220nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 35mPa & s, the contact angle on a PI substrate of 33 degrees and the surface tension of 37 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: gravure printing particle-free conductive copper ink capable of being heated in air on a PI substrate, and sintering in air under the following conditions: heating to 350 ℃, and carrying out heat treatment for 15min to obtain the conductive copper wire adhered on the PI substrate, wherein the resistivity of the prepared conductive copper wire is 31.3 mu omega cm.
Example 13
A particle-free conductive copper ink capable of being heated in air is prepared from copper nitrate, copper malonate, tert-butylamine, butanediamine, ethanol, ethylene glycol and hydroxymethyl cellulose; wherein, the copper nitrate accounts for 20 percent, the copper malonate accounts for 23 percent, the tert-butylamine accounts for 16 percent, the butanediamine accounts for 11 percent, the ethanol accounts for 20 percent, the ethylene glycol accounts for 6 percent, and the hydroxymethyl cellulose accounts for 4 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving tert-butylamine and butanediamine in ethanol, ethylene glycol and hydroxymethyl cellulose, and uniformly mixing for 10min to obtain a mixed solution;
(2) and adding copper nitrate and copper malonate into the mixed solution, stirring for 4 hours at 25 ℃ until the copper nitrate and the copper malonate are completely dissolved, and filtering by using a microporous filter membrane with the aperture of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, does not contain any solid particles, has the ink viscosity of 40mPa & s, the contact angle on a quartz piece substrate of 38 degrees and the surface tension of 29 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: gravure printing particle-free conductive copper ink which can be heated in air on a quartz plate substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 230 deg.C, and heat treating for 5min to obtain conductive copper wire with resistivity of 23.8 μ Ω cm.
Example 14
A particle-free conductive copper ink capable of being heated in air is prepared from copper formate, cyclopentyl copper formate, aniline, butylamine, water, isopropanol and polyethylene glycol; wherein, the copper formate is 18 percent, the cyclopentyl copper formate is 5 percent, the aniline is 6 percent, the butylamine is 28 percent, the water is 10 percent, the isopropanol is 26 percent and the polyethylene glycol is 7 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving aniline and butylamine in water, isopropanol and polyethylene glycol, and uniformly mixing for 10min to obtain a mixed solution;
(2) and adding copper formate and cyclopentyl copper formate into the mixed solution, stirring for 8 hours at 25 ℃ until the copper formate and the cyclopentyl copper formate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, does not contain any solid particles, has the ink viscosity of 94mPa & s, has a contact angle of 34 degrees on a quartz piece substrate, and has the surface tension of 60 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: letterpress printing particle-free conductive copper ink which can be heated in the air on a quartz plate substrate, and sintering in the air, wherein the sintering conditions are as follows: heating to 200 deg.C, and heat treating for 3min to obtain conductive copper film adhered on quartz substrate with resistivity of 38.5 μ Ω cm.
Example 15
A particle-free conductive copper ink capable of being heated in air is prepared from copper formate, copper acetate, butanediamine, nonanol and polyvinyl alcohol; wherein, the copper formate is 34 percent, the copper acetate is 6 percent, the butanediamine is 30 percent, the nonanol is 28 percent and the polyvinyl alcohol is 2 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving butanediamine in nonanol and polyvinyl alcohol, and uniformly mixing for 15min to obtain a mixed solution;
(2) and adding copper formate and copper acetate into the mixed solution, stirring for 5 hours at 25 ℃ until the copper formate and the copper acetate are completely dissolved, and filtering by using a microporous filter membrane with the aperture of 450nm to prepare the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 31mPa & s, the contact angle on a photographic paper substrate of 31 degrees and the surface tension of 38 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: coating a particle-free conductive copper ink rod which can be heated in air on a photographic paper substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 220 deg.C, and heat treating for 6min to obtain conductive copper film adhered on the photographic paper substrate, wherein the resistivity of the conductive copper film is 7.8 μ Ω · cm.
Example 16
A particle-free conductive copper ink capable of being heated in air is prepared from copper formate, copper acetate, butanediamine, nonanol and polyvinyl alcohol; wherein, the copper formate is 34 percent, the copper acetate is 6 percent, the butanediamine is 30 percent, the nonanol is 28 percent and the polyvinyl alcohol is 2 percent.
A preparation method of particle-free conductive copper ink capable of being heated in air comprises the following steps:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink capable of being heated in the air, dissolving butanediamine in nonanol and polyvinyl alcohol, and uniformly mixing for 25min to obtain a mixed solution;
(2) and adding copper formate and copper acetate into the mixed solution, stirring for 0.5h at 25 ℃ until the copper formate and the copper acetate are completely dissolved, and filtering by using a microporous filter membrane with the pore diameter of 450nm to obtain the particle-free conductive copper ink capable of being heated in the air.
The prepared particle-free conductive copper ink capable of being heated in the air is blue, has no solid particles, has the ink viscosity of 1mPa & s, the contact angle on a photographic paper substrate of 15 degrees and the surface tension of 20 mN/m.
The use method of the particle-free conductive copper ink capable of being heated in air comprises the following steps: printing the particle-free conductive copper ink which can be heated in the air on a photographic paper substrate in an ink-jet manner, and sintering in the air, wherein the sintering conditions are as follows: heating to 170 deg.C, and heat treating for 6min to obtain copper film with resistivity of 7.8 μ Ω cm.
Claims (8)
1. The particle-free conductive copper ink capable of being heated in the air is characterized by being prepared from a copper precursor, a complexing agent and a solvent; wherein, the copper precursor comprises the following components in percentage by mass: 20-25%, complexing agent: 47-60%, solvent: 20-28%;
the copper precursor is one or a mixture of more of aliphatic carboxylic acid copper, aromatic carboxylic acid copper or alicyclic carboxylic acid copper which does not contain hydroxyl;
the complexing agent is one of aliphatic diamine with 2-6N atoms;
the solvent is one or a mixture of more of alcohol compounds; the alcohol compound is an alcohol compound containing 1-3 hydroxyl functional groups and having 1-12 carbon atoms.
2. The particle-free conductive copper ink heatable in air according to claim 1 wherein the particle-free conductive copper ink heatable in air is blue, free of any solid particles, has an ink viscosity of 1 to 1000mPa · s, a contact angle of 15 to 65 °, and a surface tension of 20 to 60 mN/m.
3. The method of making an air-heatable, particle-free conductive copper ink as recited in claim 1, comprising the steps of:
(1) weighing the components according to the component proportion of the particle-free conductive copper ink which can be heated in the air, adding a complexing agent into a solvent, and uniformly mixing to obtain a mixed solution;
(2) and adding a copper precursor into the mixed solution, stirring until the copper precursor is completely dissolved, and filtering by using a microporous filter membrane to obtain the particle-free conductive copper ink capable of being heated in the air.
4. The method for preparing particle-free conductive copper ink capable of being heated in air according to claim 3, wherein in the step (1), the mixing is uniform, and the mixing time is 15-30 min.
5. The method for preparing particle-free conductive copper ink capable of being heated in air according to claim 3, wherein in the step (2), the stirring is carried out at room temperature for 0.5-12 h; the pore diameter of the microporous filter membrane is 220nm or 450 nm.
6. The method of using the particle-free conductive copper ink capable of being heated in air as claimed in claim 1, wherein the method of using the particle-free conductive copper ink capable of being heated in air is as follows: printing or coating a particle-free conductive copper ink which can be heated in air on a substrate, and sintering in air, wherein the sintering conditions are as follows: heating to 130-350 ℃, and carrying out heat treatment for 1-15 min to obtain the copper film adhered on the substrate or the copper wire adhered on the substrate.
7. The method of using the particle-free conductive copper ink capable of being heated in air according to claim 6, wherein the resistivity of the copper film or the copper wire is 4.1 to 56.7 μ Ω' cm; the prepared copper film adhered on the substrate is glued by 3M and 600MAfter the tape is torn, no copper film falls off, the copper film generated by the flexible substrate cannot be damaged after being bent for 200 times, and the resistivity ratio is 1<R/R0<2.5; wherein R is a bent resistor, R0Is an unbent resistor.
8. The method for using the particle-free conductive copper ink capable of being heated in air according to claim 6, wherein in the using method, the substrate is one of polyethylene terephthalate, polyether sulfone resin, polyethylene naphthalate, polyimide, glass, monocrystalline silicon, quartz plate, ceramic plate or photographic paper.
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