CN110461101A - A kind of room temperature sintering method of nano-copper conductive ink - Google Patents

A kind of room temperature sintering method of nano-copper conductive ink Download PDF

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Publication number
CN110461101A
CN110461101A CN201910724096.9A CN201910724096A CN110461101A CN 110461101 A CN110461101 A CN 110461101A CN 201910724096 A CN201910724096 A CN 201910724096A CN 110461101 A CN110461101 A CN 110461101A
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CN
China
Prior art keywords
film
solvent
nano
copper
conductive ink
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CN201910724096.9A
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Chinese (zh)
Inventor
王涛
戴小凤
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Tsinghua University
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Tsinghua University
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Priority to CN201910724096.9A priority Critical patent/CN110461101A/en
Publication of CN110461101A publication Critical patent/CN110461101A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods

Abstract

The invention discloses a kind of room temperature sintering methods of nano-copper conductive ink, belong to conductive ink technology field.Itself the following steps are included: a, with printing machine or film applicator etc. by ink print or be coated in flexible film substrates on；B, the film of step a is soaked in 0.1-30min in the alcoholic solution of 0.1-100v% organic acid, then is cleaned 2-4 times with solvent, is dried up；C, it repeats a and b step carries out repeating printing or coating, reach required printing layer thickness；D, the film of step c is soaked in 0.05-60min in certain density reducing agent solution, then washed with water 2-4 times, dried up.The method of the present invention realizes the sintering in air at room temperature, the resistivity of obtained copper film is low, can be used on a variety of temperature-sensitives and flexible parent metal, and simple process is suitable for large-scale production suitable for cheap nano-copper ink.

Description

A kind of room temperature sintering method of nano-copper conductive ink
Technical field
The present invention relates to conductive ink technology fields, in particular to the room temperature sintering method of nano-copper conductive ink.
Background technique
In recent years, metal nano material as electronic functional material have be easy to flexibly connect, be easy to implement low-temperature sintering, The features such as chemical property is active is increasingly becoming the research hotspot of microelectronic field.Not only waste of material is serious for conventional etch method, system Standby process is complicated, and there is also the problems such as at high cost, environmental pollution is serious.And printed electronics are then printing technology and electronics skill Art is combined together well, is had broad application prospects.The core of the technology is that the preparation and application of functional ink. Wherein, conductive ink is the important class of functional ink, is widely paid close attention to.
In numerous conductive components, the electric conductivity of metal is the most excellent.Wherein, silver is most widely used in conductive ink The material of water, however it is clearly uneconomic to be applied to printed circuit as noble metal.And the electric conductivity of copper and silver are close to simultaneously And price is low, is a kind of ideal alternative materials.But the antioxidative stabilizer of Nanometer Copper is poor, seriously hinders copper conductive ink The application of water.Simultaneously as the stabilizer of nano-material surface can prevent to form conductive path between particle, it is therefore desirable to print Pattern carries out subsequent sintering processes.The oxidation sensitive of limited Nanometer Copper, traditional heat-agglomerating are generally required in high temperature Under the conditions of be aided with reducing atmosphere or reducing agent, prevent oxidation generation.Not only energy consumption is high for this sintering method, complicated for operation, And since higher heating temperature limits the selection of substrate.Especially heatsensitive substrates, such as paper, plastics, fabric etc. Operation temperature is below 150 DEG C.Therefore, researcher is dedicated to developing novel sintering processing, including microwave sintering, laser are burnt Knot, infrared sintering and plasma agglomeration etc..Reduce the destruction to substrate by way of local fast heating.But it is to substrate Protect equipment support that is limited, and needing expensive.
Therefore, realize that the sintering in air is still a big difficulty of nano-copper ink under low temperature.There is document report benefit With the method for realizing room temperature sintering from reuniting effect of nano silver material, technique is greatly simplified, can be adapted for more Substrate.But existing document and patent are all without really realizing that the room temperature of nano-copper ink is sintered.Trial (J few in number MATER CHEM C, 2017,5), do not obtain ideal electric conductivity yet.The present invention will fill up this blank, by simply changing Sintering is learned, the copper film of high conduction performance is obtained.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of methods of room temperature sintering nano-copper conductive ink.This method Using the stabilizer of organic acid soln removing particle surface, connects particle tentatively, reapply reducing solution for particle surface Oxide be reduced to simple substance, realize intergranular welding, solve particle problem of oxidation and conventional high-temperature be sintered bring disadvantage End.It the described method comprises the following steps:
1) it in a solvent by Nanometer Copper dispersion, is configured to the solution that solid content is 5~80w%, is put into ultrasonic cleaning machine Ultrasonic 2h obtains conductive ink；
2) conductive ink made from step 1) is printed using printing machine or film applicator or is coated on flexible film substrates, Form figure or coating；
3) film made from step 2) is soaked in 0.1-30min in the alcohols solvent solution of 0.1-100v% organic acid, It removes the hydrophobic stabilizers on Nanometer Copper surface sufficiently, and the patterned surface printed or coated is made to become hydrophilic from hydrophobicity Property.Alcohols solvent is used again, is cleaned 2~4 times, drying；
4) step 2) is repeated with 3), reaches required printing layer thickness；
5) film obtained by step 4) is soaked in 0.05-60min in the reducing agent aqueous solution of 0.1~40w%, then clear with water It washes 2~4 times, dries up.
Using the square resistance of four-point probe measurement film, film thickness, meter are measured using scanning electron microscope (SEM) Calculate membrane resistivity.
Further, Nanometer Copper described in step 1) includes the nano particle and nano wire that diameter is less than 100nm, surface quilt Partial oxidation.
Further, the solid content of solution described in step 1) is 5~80w%.
Further, solvent described in step 1) includes hydrophilic solvent and hydrophobic solvent.
Further, the hydrophilic solvent includes methanol, ethyl alcohol, isopropanol, ethylene glycol；The hydrophobic solvent includes for oneself Alkane, octane, toluene.
Further, soaking time described in step (3) is 0.1-30min.
Further, organic acid described in step 3) includes formic acid, acetic acid, citric acid；The alcohols solvent includes methanol, second Alcohol, isopropanol.
Further, the volume fraction of organic acid in the solution is 0.1~100v% in step (3).
Further, reducing agent described in step (5) is sodium borohydride, hydrazine hydrate or formaldehyde.
Further, the mass fraction of reducing agent in aqueous solution is 0.1-40w% in step (5).
The beneficial effects of the present invention are: (1) realizes the sintering air at room temperature suitable for cheap nano-copper ink (2) (3) flexible parent metal (4) simple process that can be used for thermal sensitivity, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the change in resistance figure of embodiment 1.
Fig. 2 is the change in resistance figure of embodiment 2.
Fig. 3 is the change in resistance figure of embodiment 3.
Specific embodiment
The present invention is described in detail with attached drawing with reference to embodiments.
Embodiment 1:
(1) diameter 11nm copper nano particles (pressing I&ECR, the preparation of 2018,57 methods) are dispersed in normal octane, are configured to Solid content is the ink of 30w%, is put into ultrasound 2h in ultrasonic cleaning machine, obtains magenta ink.
(2) it takes appropriate ink on polyethylene terephthalate (PET) film, carries out film with preparing device.
(3) film made from step (2) is soaked in 20s in the ethanol solution of 10v% formic acid, using formic acid by particle surface Oleyl amine sufficiently remove so that film surface becomes hydrophily from hydrophobicity.It is cleaned 3 times, is dried up with ethyl alcohol again.
(4) (2) are repeated and (3) step carries out 3 films；
(5) film of step (4) is soaked in 3w%NaBH40.08-3min in aqueous solution, then wash with water 3 times, it dries up.
By the square resistance of four-point probe measurement film, SEM measures film thickness, resistivity such as Fig. 1 of film is calculated It is shown.With NaBH4The extension of solution soaking time, resistivity gradually decrease, and only need 30s can be down to 20.88 μ Ω .cm.Into One step extends the time, and resistivity does not change significantly, and illustrating the sintering condition only needs the immersion of 30s i.e. sinterable complete.
Embodiment 2:
(1) diameter 11nm copper nano particles (pressing I&ECR, the preparation of 2018,57 methods) are dispersed in normal octane, are configured to Solid content is the ink of 30w%, is put into ultrasound 2h in ultrasonic cleaning machine, obtains magenta ink.
(2) it takes appropriate ink on polyethylene terephthalate (PET) film, carries out film with preparing device.
(3) film made from step (2) is soaked in 20s in the methanol solution of 10v% formic acid, using formic acid by particle surface Oleyl amine sufficiently remove so that film surface becomes hydrophily from hydrophobicity.Again with methanol is cleaned 3 times, drying.
(4) (2) are repeated and (3) step carries out 3 films；
(5) film of step (4) is soaked in 0.75w%NaBH41-9min in solution, then wash with water 3 times, it dries up.
By the square resistance of four-point probe measurement film, SEM measures film thickness, resistivity such as Fig. 2 of film is calculated It is shown.Work as 0.75w%NaBH4The soaking time of solution reach 7min i.e. it is sinterable completely, resistivity be 17.35 μ Ω .cm.
Embodiment 3:
1) diameter 11nm copper nano particles (pressing I&ECR, the preparation of 2018,57 methods) are dispersed in normal octane, are configured to Solid content is the ink of 30w%, is put into ultrasound 2h in ultrasonic cleaning machine, obtains magenta ink.
2) it takes appropriate ink on polyethylene terephthalate (PET) film, carries out film with preparing device.
3) film made from step 2) is soaked in 20s in the methanol solution of 10v% acetic acid, using formic acid by particle surface Oleyl amine sufficiently removes, so that film surface becomes hydrophily from hydrophobicity.Again with methanol is cleaned 3 times, drying.
4) it repeats 2) to carry out 3 films with 3) step；
5) film of step 4) is soaked in 0.75w%NaBH44-30min in solution, then wash with water 3 times, it dries up.
By the square resistance of four-point probe measurement film, SEM measures film thickness, resistivity such as Fig. 3 of film is calculated It is shown.Use acetic acid alcoholic solution for the sintering reagent of the first step, effect is poor, 0.75w%NaBH4Solution impregnates 30min ability Resistivity is reduced to 80.29 μ Ω .cm.
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.

Claims (10)

1. a kind of room temperature sintering method of nano-copper conductive ink, which is characterized in that include the following steps:
1) it in a solvent by Nanometer Copper dispersion, is configured to the solution that solid content is 5~80w%, is put into ultrasonic cleaning machine ultrasonic 2h obtains conductive ink；
2) by printing conductive ink made from step 1) or coated on flexible film substrates, figure or coating are formed；
3) film made from step 2) is soaked in 0-30min in the alcohols solvent solution of 0.1-100v% organic acid, makes nanometer The hydrophobic stabilizers on copper surface sufficiently remove, and the patterned surface printed or coated is made to become hydrophily from hydrophobicity；It uses again Alcohols solvent cleans 2~4 times, drying；
4) step 2) is repeated with 3), reaches required printing layer thickness；
5) film obtained by step 4) is soaked in 0.05-60min in the reducing agent aqueous solution of 0.1~40w%, then washes with water 2 ~4 times, drying.
2. the method according to claim 1, wherein Nanometer Copper described in step 1) includes that diameter is less than 100nm Nano particle and nano wire, surface is partially oxidized.
3. the method according to claim 1, wherein the solid content of solution described in step 1) is 5~80w%.
4. the method according to claim 1, wherein solvent described in step 1) includes hydrophilic solvent and hydrophobic Property solvent.
5. according to the method described in claim 4, it is characterized in that, the hydrophilic solvent include methanol, ethyl alcohol, isopropanol, Ethylene glycol；The hydrophobic solvent includes hexane, octane, toluene.
6. the method according to claim 1, wherein soaking time described in step (3) is 0-30min.
7. the method according to claim 1, wherein organic acid described in step 3) includes formic acid, acetic acid, lemon Acid；The alcohols solvent includes methanol, ethyl alcohol, isopropanol.
8. the method according to claim 1, wherein the volume fraction of organic acid in the solution is in step (3) 0.1~100v%.
9. the method according to claim 1, wherein reducing agent described in step (5) is sodium borohydride, hydrazine hydrate Or formaldehyde.
10. the method according to claim 1, wherein the mass fraction of reducing agent in aqueous solution in step (5) For 0.1-40w%.
CN201910724096.9A 2019-08-07 2019-08-07 A kind of room temperature sintering method of nano-copper conductive ink Pending CN110461101A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021132446A1 (en) * 2019-12-27 2021-07-01 花王株式会社 Ink containing fine metal particles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120168684A1 (en) * 2009-03-24 2012-07-05 Yissum Research Development Company of the Hebrew University of Jerusaem, Ltd. Process for sintering nanoparticles at low temperatures
KR20140075500A (en) * 2012-12-11 2014-06-19 삼성정밀화학 주식회사 Metal nanoparticles with enhanced anti-oxidation and method of preparation of the same
KR20150103857A (en) * 2014-03-04 2015-09-14 한국과학기술원 Method for preparing conductive ink and conductive ink prepared by the same
CN109280424A (en) * 2018-09-05 2019-01-29 清华大学 A kind of room temperature sintering method of nano silver coated copper conductive ink

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120168684A1 (en) * 2009-03-24 2012-07-05 Yissum Research Development Company of the Hebrew University of Jerusaem, Ltd. Process for sintering nanoparticles at low temperatures
KR20140075500A (en) * 2012-12-11 2014-06-19 삼성정밀화학 주식회사 Metal nanoparticles with enhanced anti-oxidation and method of preparation of the same
KR20150103857A (en) * 2014-03-04 2015-09-14 한국과학기술원 Method for preparing conductive ink and conductive ink prepared by the same
CN109280424A (en) * 2018-09-05 2019-01-29 清华大学 A kind of room temperature sintering method of nano silver coated copper conductive ink

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021132446A1 (en) * 2019-12-27 2021-07-01 花王株式会社 Ink containing fine metal particles
JP2021107516A (en) * 2019-12-27 2021-07-29 花王株式会社 Metal fine powder-containing ink
US11965105B2 (en) 2019-12-27 2024-04-23 Kao Corporation Ink containing fine metal particles

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