KR101402010B1 - Method for fabricating the conductive fine patterns using metal nano-ink for direct laser patterning - Google Patents
Method for fabricating the conductive fine patterns using metal nano-ink for direct laser patterning Download PDFInfo
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- KR101402010B1 KR101402010B1 KR1020120139390A KR20120139390A KR101402010B1 KR 101402010 B1 KR101402010 B1 KR 101402010B1 KR 1020120139390 A KR1020120139390 A KR 1020120139390A KR 20120139390 A KR20120139390 A KR 20120139390A KR 101402010 B1 KR101402010 B1 KR 101402010B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/0006—Working by laser beam, e.g. welding, cutting or boring taking account of the properties of the material involved
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/32—Bonding taking account of the properties of the material involved
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/34—Laser welding for purposes other than joining
- B23K26/342—Build-up welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/359—Working by laser beam, e.g. welding, cutting or boring for surface treatment by providing a line or line pattern, e.g. a dotted break initiation line
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/34—Coated articles, e.g. plated or painted; Surface treated articles
- B23K2101/35—Surface treated articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
- B23K2103/56—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26 semiconducting
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0257—Nanoparticles
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
Abstract
Description
The present invention relates to a metal ink for a laser patterning process capable of producing fine nano-sized particles whose surface oxide film formation is controlled and a method for producing a metal conductive fine pattern using the same.
The present invention also relates to a method for producing a metal conductive fine pattern having excellent conductivity.
The present invention also relates to a highly conductive metal nano ink composition for laser patterning which improves the adhesion of the metal nanoparticles on a substrate and does not affect the physical properties of the conductive metal nanoparticles, and a metal conductive fine pattern produced therefrom.
The development of metallic nano ink for laser patterns containing metal nanoparticles can be carried out by a single printing process such as screen printing, inkjet printing, gravure offset printing and reverse offset printing, without using a complicated process of photolithography It is advantageous in that the process can be simplified by printing on various substrates through the process. In addition, the manufacturing cost can be drastically reduced due to the simplification of the process, and the wiring width can be miniaturized, making it possible to manufacture a highly integrated and highly efficient printed circuit.
As a method of manufacturing metal nanoparticles for laser patterning by a conventional physical method, it is practically impossible to make nano-sized metal particles having oxidation stability. As a polar solvent, for example, it is dispersed in deionized water or the like, It is more difficult to provide a dispersion of the metal nano-particles.
These metal nanoparticles are generally synthesized by a wet reduction method, and the surface oxide film is easily formed on the metal particles during the synthesis, resulting in deterioration of the conductivity in terms of conductivity.
Korean Patent Laid-Open Publication No. 2000-0018196 (Patent Document 1) discloses a method for preparing metal nanoparticles having oxidative stability against a conventional polar solvent, wherein metal ions are reacted with a reducing agent in the presence of a surfactant solution and an antioxidant And a wet reduction method for producing metal nanoparticles by reducing metal ions has been disclosed. In this method, a small nano-sized reactor is prepared by using a surfactant, and the particle size is controlled by a reduction reaction using a reducing agent. The particle size is easily controlled and stable. However, There is a problem that resistance is increased when wiring and metal film are formed due to the surfactant and antioxidant used to ensure dispersion stability.
There is still room for improvement of the disadvantage that the metal oxide is formed on the surface of the produced nanoparticles and the conductivity of the metal is damaged.
Further, when the resulting nanoparticles are firmly adhered to the substrate, the use of a binder in the formation of the wiring and the metal film may increase resistance and insufficient conductivity.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems described above, and it is an object of the present invention to simplify the process of synthesizing metal nanoparticles for laser patterning and to synthesize metal nanoparticles completely controlled in formation of a surface oxide film causing deterioration in conductivity in terms of conductivity, And it is an object of the present invention to produce an inexpensive conductive fine pattern having excellent conductivity by effectively removing the capping molecules introduced to suppress oxide film formation.
It is also an object of the present invention to provide an ink composition for a laser patterning process having improved stability of an ink containing metal nanoparticles and a metal conductive fine pattern produced using the ink composition.
Another object of the present invention is to provide an ink composition for a laser patterning process in which the metal nanoparticles are stably fixed on a substrate without sacrificing conductivity, and a metal conductive fine pattern produced therefrom.
In order to accomplish the above object, the present invention provides a method of manufacturing a conductive ink composition for laser patterning, comprising: synthesizing metal nanoparticles for laser patterning, the formation of a surface oxide film being controlled and having better conductivity; Wherein the metal-based ink composition is a metal-based ink.
The present invention also relates to a method of manufacturing a laser-patterning process, comprising the steps of: synthesizing metal nano-particles for laser-patterning process whose surface oxide film formation is controlled; preparing a conductive ink composition for laser- And a step of irradiating the substrate coated with the ink composition with a laser to form a fine pattern. The present invention also provides a method of manufacturing a metal conductive fine pattern using the laser.
Hereinafter, the production method of the present invention will be described in detail as follows.
First, in the step of manufacturing the ink for laser patterning, the present invention is a method for producing an ink for a laser patterning process, comprising heating and stirring a solution containing a metal precursor, an organic acid compound, an organic amine compound and a reducing agent simultaneously to form a solution containing a metal nano- To prepare a metal nano ink preliminary composition for a laser patterning process.
The present invention also provides means for producing a conductive metal nano ink composition for a laser patterning process having better conductivity characteristics by heating to produce nanoparticles in an inert atmosphere in the step of preparing the metal nano ink pre-composition. In the above, the inert atmosphere means an atmosphere of inert gas such as nitrogen or argon, which is generally understood in the field, but is not limited to the above.
In addition, the present invention can produce a conductive metal nano ink composition for laser patterning by dispersing the prepared metal nano ink pre-composition in a non-aqueous solvent.
The present invention also relates to an ink for imparting a function of tightly adjusting metal nanoparticles on a substrate without impairing conductivity, including compounds of the following structural formulas in the production of the metal nano ink preliminary composition, and a metal by a laser pattern process manufactured therefrom Thereby providing a conductive fine pattern. When one or more kinds of compounds selected from the following compounds are included, it is preferable that the resolution is further increased upon laser irradiation. In the present invention, the following compounds may be added together with the metal precursor, or may be added when the resulting metal nanoparticles described below are dispersed in a nonaqueous solvent.
[Chemical Formula 1]
[XR 1 ] n [R 2 ] 4-n Si
(In Formula 1, X is an amine group (-NH 2) or a thiol group (-SH), R 1 is (C 0 -C 17) alkyl group, R 2 is (C 1 -C 17) alkyl or (C 1 -C 5 ) alkoxy group, and n is an integer of 1 to 3.)
(2)
[R 1 ] - [R 2 ] -SH
(In the
Next, a method of manufacturing a metal conductive fine pattern by laser irradiation according to the present invention will be described.
Applying a conductive metal nano ink composition for laser patterning of the above aspects to an insulating substrate; And a step of irradiating an insulating substrate coated with the conductive metal nano ink composition with a laser to form a metal conductive fine pattern, the metal conductive fine pattern having a good conductivity.
In the present invention, the metal precursor may be selected from the group consisting of metals such as copper, nickel, cobalt and aluminum, and alloys thereof, though not particularly limited. Examples of the metal precursor include copper, nickel And inorganic salts composed of nitrates, sulfates, acetates, phosphates, silicates, and hydrochlorides of metal components such as cobalt and alloys thereof, and the like.
In the present invention, the organic acid compound is not particularly limited, but may be at least one organic acid compound of straight chain, branched or cyclic having 6 to 30 carbon atoms, and may be one or more selected from saturated or unsaturated acids. Examples of the organic acid include oleic acid, lysine oleic acid, stearic acid, hyrodoxystearic acid, linoleic acid, amino decanoic acid, hydroxydecanoic acid, lauric acid, decenoic acid, undecenoic acid, Hydroxycarboxylic acid, hydroxycarboxylic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid,
The content of the organic acid compound according to the present invention is not particularly limited, but the molar ratio of the metal precursor to the organic acid compound is preferably in the range of 1: 0.2 to 4 in terms of the properties required in the present invention.
In the present invention, the organic amine compound has at least one form of straight chain, branched or cyclic having 6 to 30 carbon atoms, and may be one or two or more selected from saturated and unsaturated amines. Examples of the organic amine compound include hexylamine, heptylamine, octylamine, dodecylamine, 2-ethylhexylamine, 1,3-dimethyl-n-butylamine and 1-aminotridecane, but are not limited thereto In the present invention, the content of the organic amine compound is not particularly limited, but if the molar ratio of the organic amine compound to the metal precursor is 1: 0.2 or more, there is no problem in the generation of the particle size or the stability of the ink. The organic amine compound may also be used in excess, surprisingly, even when used in excess, it has been found that the organic amine compound acts as a solvent and does not affect particle size control, particle reduction and ink stability. For example, it may be used at a molar ratio of 30 mol or more and 50 mol or more per mol of the metal precursor, but is not limited thereto.
The reducing agent may be one or more selected from a hydrazine-based, hydride-based, borohydride-based, sodium phosphate-based, and ascorbic acid.
More specifically, the reducing agent may be one or more hydrazine-based reducing agents selected from hydrazine, hydrazine anhydride, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate and phenylhydrazine.
The reducing agent is not particularly limited as long as it can reduce the metal precursor to metal particles. For example, the reducing agent / metal precursor molar ratio may be in the range of 1 to 100 to obtain the desired effect of the present invention.
The reducing agent may be added to the synthesis solution prior to the heating and stirring steps and may be added after the heating and stirring steps. In the present invention, the heating step is not limited so long as reduction can be smoothly performed. For example, it is preferable to conduct the heating at 100 to 350 ° C., preferably 150 to 300 ° C., to improve the conductivity.
The non-aqueous solvent used for dispersing the metal nano ink pre-composition prepared in the present invention is not particularly limited, but includes, for example, alcohols having 6 to 30 carbon atoms, amines, toluene, xylene, chloroform, dichloromethane, tetradecane, But are not limited to, one or more selected from the group consisting of decene, chlorobenzene, dichlorobenzene, chlorobenzoic acid, and dipropylene glycol propyl ether.
The amount of the non-aqueous solvent to be used can be variously adjusted depending on the viscosity of the ink and the application field thereof, so that the present invention is not limited thereto.
Although the reason for the simultaneous introduction of a metal precursor, an organic acid compound, and an organic amine compound is not clear in the present invention, the particle size of the metal precursor is reduced to improve the stability of the ink and to suppress the generation of a metal oxide film, To achieve the unexpected effect of. Although such an effect is not clear, it is considered that when the metal precursor is reduced by simultaneously introducing the acid component and the amine component, the metal precursor acts on the metal surface to protect the surface to inhibit the formation of metal oxides. The effect of decreasing the particle due to the simultaneous introduction is remarkably exhibited in the present invention.
Further, the present invention can achieve an unexpected effect of increasing the conductivity when heating in an oxygen-free atmosphere in the step of preparing metal nanoparticles. In the case of providing the metal nanoparticles in the oxygen-free atmosphere as described above, the metal oxide film is already suppressed in the atmosphere of oxygen or the like using the constitution of the present invention, but even the fine generation of the metal oxide film is controlled, do.
In the present invention, the coating may be carried out by a coating or printing method, and the coating may be selected from dip coating, spin coating and casting, and the printing may be performed by ink jet printing, electrostatic hydraulic printing, micro contact printing, imprinting, Printing, reverse offset printing, gravure offset printing and screen printing.
In order to form a fine pattern applied in the present invention, a fine pattern can be produced by sintering by irradiating a laser.
The conditions of the laser irradiation in the present invention include a laser irradiation method (continuous irradiation, pulse irradiation), laser intensity, laser wavelength, irradiation time, irradiation atmosphere (general atmosphere, inert, hydrogen reduction atmosphere).
The conductive ink composition for forming a laser pattern may include 1 to 20 parts by weight of a dispersant based on 100 parts by weight of the metal nanoparticles.
The dispersant may be selected from one or more of an anionic compound, a nonionic compound, a cationic compound, a positive-working compound, a polymeric water-based dispersant, a polymeric non-aqueous dispersant, and a polymeric cationic dispersant.
Also, the metal conductive fine pattern produced by the manufacturing method according to the present invention is included in the scope of the present invention.
The metal conductive fine pattern produced by the laser patterning process according to the present invention is a simple and efficient process because the metal precursor, the organic acid and the organic amine compound are simultaneously added and reduced by the reducing agent.
INDUSTRIAL APPLICABILITY The present invention suppresses the formation of a metal oxide film on the surface at the time of producing metal nanoparticles for laser patterning, and therefore, high conductivity can be obtained. That is, the present invention has excellent electric conductivity because it has not only a process efficiency but also a surface oxide film which causes deterioration in characteristics in terms of conductivity in nanoparticle synthesis.
In addition, the present invention can further manufacture metal nanoparticles for laser patterning, which have better conductivity when metal nanoparticles are prepared in a non-oxygen atmosphere.
In addition, the present invention can achieve stable effects of ink by manufacturing stable laser patterning nanoparticles.
In addition, it will be possible to manufacture low-cost, conductive fine patterns that can replace conventional noble metal nanoparticle-based conductive ink, and its application will be further expanded.
1 is a graph showing XRD of the copper nanoparticles prepared in Preparation Example 2,
2 is a graph showing XPS of the copper nanoparticles prepared in Production Example 2,
3 is a SEM photograph of the nickel nanoparticles prepared in Production Example 6
4 is XRD data of the nickel particles produced in Production Example 6. Fig.
5 is an SEM photograph of the fine pattern of Example 1. Fig.
Hereinafter, the production method of the present invention will be described in detail.
First, an aspect of the present invention relates to a method of manufacturing a metal nanoparticle for a laser patterning process, And preparing a conductive ink composition for a laser patterning process using the metal nanoparticles.
According to another aspect of the present invention, there is also provided a method of fabricating a semiconductor device, comprising: synthesizing metal nanoparticles by controlling formation of a surface oxide film and reducing by heating in an inert atmosphere; And preparing a conductive ink composition for a laser patterning process using the metal nanoparticles.
Another aspect of the present invention provides a highly conductive metal nano ink composition for a laser patterning process in which formation of a surface oxide film is suppressed by simultaneously introducing a metal precursor, an organic acid compound, and an organic amine compound to reduce a metal precursor by a reducing agent.
According to another aspect of the present invention, there is provided a method for producing a conductive metal nano ink for laser patterning, which further improves conductivity by heating simultaneously in the inert atmosphere when a metal precursor, an organic acid compound and an organic amine compound are simultaneously charged and the metal precursor is heated and reduced by a reducing agent Lt; / RTI >
The present invention also relates to an ink for imparting a function of tightly adjusting metal nanoparticles on a substrate without damaging the conductivity by mixing or mixing the compounds of the following structural formulas in the production of the metal nano ink composition and a laser sintering inspection ). ≪ / RTI > In the present invention, the following compounds may be added together with the metal precursor, or may be added when the resulting metal nanoparticles described below are dispersed in a nonaqueous solvent. In the present invention, the content of the following compounds is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.3 part by weight based on 100 parts by weight of the metal precursor.
[Chemical Formula 1]
[XR 1 ] n [R 2 ] 4-n Si
(In Formula 1, X is an amine group (-NH 2) or a thiol group (-SH), R 1 is (C 0 -C 17) alkyl group, R 2 is (C 1 -C 17) alkyl or (C 1 -C 5 ) alkoxy group, and n is an integer of 1 to 3.)
(2)
[R 1 ] - [R 2 ] -SH
(In the
The present invention further includes a step of dispersing the synthesized metal nanoparticle solution in a non-aqueous solvent in the step of preparing the conductive nano ink composition, wherein the metal nano ink composition for laser patterning produced by the aspects of the present invention includes ≪ / RTI >
The present invention also provides a method of manufacturing a metal conductive fine pattern patterned by a laser, the method comprising the step of applying a highly conductive metal nano ink composition for a laser patterning process in which the non-aqueous solvent is dispersed on a substrate.
In another aspect of the present invention, there is provided a method for manufacturing a metal conductive fine pattern, comprising the steps of: applying the above-mentioned highly conductive metal nano ink composition to a substrate; and irradiating the substrate with a laser to sinter to form a fine pattern.
Specifically, the highly conductive metal nano ink composition for laser patterning of the present invention comprises
a) synthesizing metal nanoparticles whose surface oxide film formation is controlled by heating and stirring a solution containing a metal precursor, an organic acid compound, an organic amine compound and a reducing agent;
and b) dispersing the metal nanoparticles produced in step a) in a non-aqueous solvent to prepare a conductive ink composition for a laser patterning process.
The present invention also encompasses that the step a) is a step of heating in an inert atmosphere.
The method of manufacturing a metal conductive fine pattern by the laser patterning process of the present invention
a) synthesizing metal nanoparticles whose surface oxide film formation is controlled by heating and stirring a solution containing a metal precursor, an organic acid compound, an organic amine compound and a reducing agent;
b) dispersing the metal nanoparticles produced in step a) in a non-aqueous solvent to prepare a conductive ink composition;
c) applying the conductive ink composition to an insulating substrate; And
d) sintering the insulating substrate coated with the ink composition with a laser to form a metal conductive fine pattern;
And a method for manufacturing the metal conductive fine pattern.
Hereinafter, each step of the method for producing a highly conductive metal nano ink composition for a laser pattern and the method for producing a metal conductive fine pattern according to the present invention will be described in detail.
The step a) is a step of synthesizing metal nanoparticles, and a step of synthesizing metal nanoparticles whose surface oxide film formation is controlled by heating and stirring a solution containing a metal precursor, an acid, an amine and a reducing agent, Metal ions of the metal precursor are reduced to form metal nanoparticles. In this case, metal nanoparticles in the form of capsules in which acid and amine are capped on the surface of the metal nanoparticles are formed, and the metal nanoparticles can be prevented from being transformed into metal oxides even when they are left in the air.
The present invention enables the reduction reaction at 100 DEG C or higher by adding the reducing agent. In the case where an organic acid compound or an organic amine compound is not contained at the same time as in the present invention, a metal oxide is generated on the surface and the conductivity is inevitably lowered. However, according to the present invention, such a problem can be eliminated.
Further, it has been found that the present invention can achieve the effect of obtaining metal particles having excellent conductivity even when the metal nano-particles are heated and reduced in an inert atmosphere.
In the step a), the metal precursor may be selected from one or more selected from the group consisting of copper, nickel, cobalt and alloys thereof.
More specifically, one or more inorganic salts selected from nitrates, sulfates, acetates, phosphates, silicates and hydrochlorides of metals selected from the group consisting of copper, nickel, cobalt and their alloys may be used.
In the step a), the acid has at least one form of straight chain, branched or cyclic having 6 to 30 carbon atoms, and may be one or two or more selected from saturated or unsaturated acids.
More concretely, there can be mentioned oleic acid, lysine oleic acid, stearic acid, hyadroxystearic acid, linoleic acid, aminodecanoic acid, hydroxydecanoic acid, lauric acid, decenoic acid, undecenoic acid, palmitoleic acid, hexyldecano Hydroxycarboxylic acid, hydroxycarboxylic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid,
The metal conductive fine pattern according to the present invention is characterized in that the molar ratio of the metal precursor to the acid is 1: 0.2-4.
If the molar ratio of the acid to the precursor is less than 0.2, the capping may not be performed completely and oxidation may occur on a part of the metal that is not capped. If the mole ratio is more than 4, They may become entangled and may not be recovered in the form of capped particles.
In step a), the amine has at least one form of straight chain, branched or cyclic having 6 to 30 carbon atoms, and one or more of saturated and unsaturated amines can be selected.
More specifically, it may be selected from hexylamine, heptylamine, octylamine, dodecylamine, 2-ethylhexylamine, 1,3-dimethyl-n-butylamine and 1-aminotridecane. The content of the amine is preferably 0.2 mol or more, preferably 1 to 50 mol, more preferably 5 to 50 mol, per mol of the metal precursor, and in the case of the upper limit, the organic amine compound may act as a non-aqueous solvent and is therefore not limited .
In the step a), the hydrazine-based reducing agent may be one or two or more selected from hydrazine, hydrazine anhydride, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate and phenylhydrazine. In addition, other hydrides; Borohydride systems including tetrabutylammonium borohydride, tetramethylammonium borohydride, tetraethylammonium borohydride, and sodium borohydride; Sodium phosphate system; And ascorbic acid; One or more of them can be selected and used. Among them, the hydrazine-based reducing agent is most preferable because of its strong reducing power.
In the step a), the metal nanoparticle synthesis step for laser patterning is not limited but is performed at a temperature of 100 to 350 ° C, more preferably 140 to 300 ° C, and more preferably 150 to 250 ° C, in consideration of reduction efficiency Is suitable.
The present invention enables a reduction reaction at 100 ° C or higher.
In addition, since the reduction reaction can be performed at a high temperature of 100 ° C or higher, the production rate and yield of metal nanoparticles can be increased. Also, the hydrazine-based reducing agent is generally better because it has a better reducing power compared to other reducing agents due to its excellent reducing power.
In the synthesis of the metal nanoparticles of step a), the composition ratio of the first solution will be described in detail. The composition ratio is not particularly limited, but when considering the capping efficiency of the metal nanoparticles, the acid is 0.2 to 4 moles, the amine is 0.2 or more, preferably 0.2 to 50, more preferably 5 to 20 moles per mole of the metal precursor ≪ / RTI >
The reducing agent may include a reducing agent / metal precursor molar ratio of 1 to 100. If the molar ratio is less than 1, metal ions of the metal precursor are not completely reduced. If the molar ratio is more than 100, excess metal ions may not be added to the metal precursor and the reduction rate may not be affected.
The metal nanoparticles containing the metal nanoparticles may be obtained only by separation methods such as washing and recovery using a centrifugal separation method.
The metal conductive ink according to the present invention is a simple and simple process in which a metal precursor, an organic acid compound, an organic amine compound and a reducing agent are added at once to perform a reaction. The metal conductive ink is generated by capping the metal oxide nanoparticles or capping only organic acids with metal nanoparticles It is possible to synthesize metal nanoparticles for laser patterning process in which the surface oxide film is completely controlled by a technique for suppressing the generation of an oxide film.
At this time, the reducing agent may be partially added in advance in the synthesis of the metal nanoparticles according to the present invention to promote the reduction of the metal ion of the metal precursor. In this case, especially, the hydrazine-based reducing agent is present in the solution before the reaction to remove the oxygen which causes the oxidation of the metal nanoparticles, thereby further suppressing the formation of the surface oxide film.
Further, the present invention can achieve an unexpected effect of increasing conductivity when heating in an incombustible atmosphere in the step a) of producing metal nanoparticles. In the case of providing the metal nanoparticles in the inert atmosphere in this manner, the metal oxide film is already suppressed to such an extent that the metal oxide film can not be detected in the oxygen atmosphere using the constitution of the present invention, but even the fine generation of the metal oxide film is controlled, .
Next, step b) will be described.
b) is a step of preparing a conductive ink composition for laser patterning using the metal nanoparticles prepared in the step a) and a non-aqueous solvent.
In this case, the nonaqueous solvent is not particularly limited, but is preferably an alkane, amine, toluene, xylene, chloroform, dichloromethane, tetradecane, octadecene, chlorobenzene, dichlorobenzene, chlorobenzoic acid, Propylene glycol propyl ether, and the like. Such a conductive ink composition is not particularly limited, but may be prepared by dispersing by a method such as stirring and milling.
The conductive ink composition may further contain a dispersant if necessary.
The dispersant may be at least one selected from the group consisting of fatty acid salts (soaps), alpha -sulfo fatty acid ester salts (MES), alkylbenzenesulfonic acid salts (ABS), linear (straight chain) alkylbenzenesulfonic acid salts (LAS), alkylsulfuric acid salts Low molecular weight anionic compounds such as salts (AES) and alkylsulfuric triethanol; Low molecular weight non-ionic compounds such as fatty acid ethanol amides, polyoxyalkylene alkyl ethers (AE), polyoxyalkylene alkyl phenyl ethers (APE), sorbitol and sorbitan; Low molecular weight cationic compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chlorides and alkylpyridinium chlorides; Low molecular weight positive-working compounds such as alkylcarboxybetaine, sulfobetaine and lecithin; Polymeric dispersants such as formalin condensates of naphthalene sulfonic acid salts, polystyrene sulfonic acid salts, polyacrylic acid salts, copolymer salts of vinyl compounds and carboxylic acid monomers, carboxymethylcellulose, and polyvinyl alcohol; Polymeric non-aqueous dispersing agents such as polyacrylic acid partial alkyl esters and polyalkylene polyamines; And polymeric cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers; and the like.
Specifically, EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA4080, EFKA7462, EFKA4020, EFKA4050, EFKA4055, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782, EFKA8503 (EFKA ADDITIVES BV products), TEXAPHOR-UV21, TEXAPHOR-UV61 (Cognis Japan or wrong to manufactured products), DisperBYK101, DisperBYK102, DisperBYK106, DisperBYK108, DisperBYK111, DisperBYK116, DisperBYK130, DisperBYK140, DisperBYK142, DisperBYK145, DisperBYK161, DisperBYK162 , DisperBYK163, DisperBYK164, DisperBYK166, DisperBYK167, DisperBYK168, DisperBYK170, DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070, DisperBYK2155, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322 , BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK380N, BYK410, BYK425, and BYK430 (manufactured by Big Chemical Japan Co., ), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL, ftergent 212P, 245P, 245P, 245P, 250P, 251, 710FM, 730FM, 730LL, 730L, 730LS, 750MT, 750M, and more. MEGAFACE F-477, Megapack 480SF, and Megapack F-482 (manufactured by DIC Corporation) can be exemplified, but the present invention is not limited thereto.
The dispersant may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the metal nanoparticles. When the content of the dispersant is used within the above range, it is possible to prevent a sufficient dispersion effect and a lowering effect of conductivity.
Next, step c) will be described.
The step c) is a step of applying the conductive ink composition for a laser patterning process prepared in the step b) on an insulating substrate.
By modifying the surface of the substrate prior to step c), the coating or printing may be more effective. Such a method may employ a surface modification method such as UV irradiation or electron beam irradiation.
The coating of step c) may be carried out by a coating or printing method, and the coating may be selected from dip coating, spin coating and casting, and the printing may be carried out by inkjet printing, electrostatic hydraulic printing, microcontact printing, imprinting, Gravure printing, reverse offset printing, gravure offset printing, and screen printing.
The coating thickness is not particularly limited, but it is preferable that the thickness after heat treatment is 0.1 to 50 탆.
In the present invention, the substrate is made of silica, a silica-coated substrate on a
Finally, pattern formation by laser irradiation in step d) will be described.
In the step d), a metal conductive fine pattern is formed by selectively irradiating the metal nanoparticle thin film with a laser to induce sintering between the particles and washing the laser non-irradiated portion with a solvent. At this time, the irradiation method of laser can be both continuous irradiation and pulse irradiation. The frequency of the pulse laser is preferably 1 to 500 kHz. In addition, the laser intensity is preferably 0.01 - 1 W, more preferably 0.1 - 0.4 W. The laser wavelength is preferably 300 to 1500 nm. The irradiation speed is preferably from 1 to 100 mm / s, and the irradiation atmosphere is preferably atmospheric, inert, or hydrogen reduction atmosphere.
The metal conductive fine patterns produced by the above-described manufacturing method described so far are included in the scope of the present invention.
Further, a flexible circuit board including the metal conductive fine pattern is included in the scope of the present invention.
Hereinafter, the present invention will be described by way of examples for the purpose of illustrating the present invention. However, the present invention is not limited to the following production examples and examples.
[Preparation Example 1] (Method for producing nanoparticles and thin films with inhibited oxide film)
73.63 g of octylamine, 3.52 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 0.2. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. The copper nanoparticles obtained were found to be copper particles free of copper oxides as a result of XRD measurement. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant (DisperBYK130) were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
The presence and the conductivity of the conductive thin film thus formed were measured. As a result, in the synthesis of metal nanoparticles, it is possible to express 6 × 10 3 (S / cm) of excellent conductivity by simultaneous addition of acid and amine together with addition of reducing agent. As a result of XRD and XPS analysis, . ≪ / RTI >
[Production Example 2]
73.63 g of octylamine, 25.1 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 1.42. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The copper nanoparticles thus synthesized were washed and recovered by centrifugation, and copper nanoparticles of about 80 nm finally obtained were dispersed in toluene to prepare a conductive ink composition. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant (DisperBYK130) were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
As a result of measuring the presence and the conductivity of the conductive thin film, the conductivity was 6 × 10 3 (S / cm). 1, which is an XRD graph of the copper nanoparticles prepared according to the preparation example of the present invention, it can be confirmed that no oxide film is formed. However, in the production of conductive thin films, even a slight amount of oxide film not detected by XRD analysis may result in increasing the resistivity of the conductive thin film. Therefore, XPS analysis was performed for more accurate analysis. As a result, as a result of XPS analysis in FIG. 2, no peaks due to Cu-O chemical bonding were observed at all, and peaks having symmetry due to Cu-Cu chemical bonding were observed. As a result, .
[Production Example 3]
73.63 g of octylamine, 70.3 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 4. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant (DisperBYK130) were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
As a result of examining the presence or absence of an oxide film of the conductive thin film thus produced, an oxide film was not formed as in the preparation example 2, and the conductivity was also excellent at 6 × 10 3 (S / cm).
[Production Example 4]
73.63 g of octylamine, 3.52 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 0.2. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant (DisperBYK130) were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat treated on an insulating substrate using a casting method and then coated to a thickness of 2 탆 and then heat treated at 250 캜 and 5% H2 atmosphere to prepare a conductive thin film.
As a result of examining the existence of the oxide film of the conductive thin film thus produced, an oxide film was not formed and the conductivity was 3 × 10 5 (S / cm) as in the case of the preparation example 2. Especially, in the hydrogen atmosphere, the increase of the conductivity showed very good conductivity characteristics even when the firing was performed at a lower temperature as compared with the inert gas atmosphere, and it was found that the firing in the hydrogen atmosphere was more effective.
[Production Example 5]
73.63 g of octylamine, 3.52 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 0.2. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. The copper nanoparticles obtained were found to be copper particles free of copper oxides as a result of XRD measurement. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant (DisperBYK130) and 0.1 part by weight of amino-octyltrimethylsilane were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to obtain a copper conductive ink A composition was prepared. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
As a result of examining the presence or absence of an oxide film of the conductive thin film thus produced, an oxide film was not formed as in the preparation example 2, and the conductivity was also excellent at 6 × 10 3 (S / cm).
[Production Example 6]
71.84 g of oleamine, 4.23 g of oleic acid, 29 g of phenylhydrazine and 5 g of nickel acetoacetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 0.73. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to the synthesis temperature of 240 ° C. to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugation. The resulting nickel particles produced pure nickel metal particles without nickel oxide formation (see FIGS. 3 to 4) and also exhibited very good conductivity characteristics of 1.2 x 10 5 (S / cm) after heat treatment in a 5% H2 atmosphere .
[Comparative Production Example 1]
73.63 g of octylamine, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The copper nanoparticles thus synthesized were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. The size of the copper nanoparticles produced was as large as about 180 nm. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
It was found by analyzing the existence of the oxide film of the conductive thin film thus produced, and it was found that the conductivity was also very low as 4 × 10 2 (S / cm).
[Comparative Production Example 2]
70.3 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 4. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered by centrifugal separation, and finally the copper nanoparticles obtained were dispersed in toluene to prepare a conductive ink composition. 20 parts by weight of copper nanoparticles and 1 part by weight of a polymer non-aqueous dispersant were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase. The prepared ink composition was heat - treated on an insulating substrate using a casting method and then coated to a thickness of 2 쨉 m and then heat treated in an Ar atmosphere at 250 캜 to prepare a conductive thin film.
It can be seen from the analysis that there is an oxide film of the conductive thin film thus produced, and it is found that the conductivity is very low as 7 × 10 2 (S / cm).
[Example 1]
(Laser patterning using copper nanoparticles whose oxide film formation is controlled)
73.63 g of octylamine, 25.1 g of oleic acid, 87.4 g of phenylhydrazine and 10.38 g of copper acetate were added to prepare a synthesis solution. The molar ratio of oleic acid / copper acetate is 1.42. Nitrogen gas was used to make an inert atmosphere, and then the temperature was raised to 150 캜, which is the synthesis temperature, to induce the reduction reaction of copper ions to synthesize copper nanoparticles. The synthesized copper nanoparticles were washed and recovered using a centrifugal method, and finally the copper nanoparticles obtained were dispersed in propylene glycol propyl ether to prepare a conductive ink composition. 4 parts by weight of copper nanoparticles and 1 part by weight of polymeric non-aqueous dispersant (DisperBYK130) were added to 100 parts by weight of toluene, followed by ball milling and ultrasonic irradiation to prepare a copper conductive ink composition having a uniform dispersed phase.
In order to coat the prepared ink composition on a glass substrate, the glass substrate was subjected to UV treatment and spin coating was performed at 1500-4000 rpm to prepare a thin film. To induce sintering between particles through laser irradiation, a pulse laser (frequency: 100 kHz) having a wavelength of 1070 nm and an average power of 0.2 W was irradiated at a scanning rate of 30 mm / The area was washed with toluene to prepare a conductive copper micropattern.
FIG. 5 shows a surface SEM image of a micro-conductive pattern formed with a thin film-based laser irradiation and selective cleaning formed using a copper ink composition, and it was possible to produce highly detailed fine pattern with high resolution. That is, to check that the case where the surface oxide film formed on the control copper nanoparticles synthesized according to the present invention a fine conductive pattern having a line width of 20 ㎛ and formed very easily with a resolution of 4 × 10 5 S / cm High conductivity.
[Comparative Example 1]
(Laser patterning using copper nanoparticles having a surface oxide film formed thereon)
A solution containing 60 parts by weight of CuO nanoparticles (Nanophase Technologies Corp.), 13 parts by weight of polyvinylpyrrolidone (molecular weight: 10,000) and 27 parts by weight of ethyleneglycol was prepared and then subjected to ball milling and ultrasonic irradiation to prepare a conductive ink The viscosity of the composition was adjusted by adding secondary distilled water having a weight of 23 parts by weight based on 100 parts by weight of the ink composition. In order to coat the prepared ink composition on a glass substrate, a UV treatment was performed, and a thin film was prepared by spin coating at 1500-4000 rpm. In order to induce sintering of particles and partial reduction of CuO by laser irradiation, a pulse laser (frequency: 100 kHz) having a wavelength of 1070 nm and an average power of 0.2 W was irradiated at 30 mm / And a conductive microcrystalline conductive pattern was prepared by washing the unexposed area with secondary distilled water.
In the case of the micro-conductive pattern based on the CuO ink prepared, the partial reduction reaction occurs after the laser irradiation, so that the formation of the oxide film is not completely controlled, and the fine pattern formed by this is 3 × 10 4 S / cm, Which is lower than that of the conductive pattern prepared with the nanoparticle ink.
Claims (10)
2) heating the solution to synthesize metal nanoparticles;
3) dispersing the metal nanoparticles in a dispersant to prepare a conductive ink composition;
4) applying the conductive ink composition to a substrate;
5) firing the substrate coated with the conductive ink composition by laser irradiation to form a metal conductive fine pattern;
≪ / RTI > wherein the metal conductive fine pattern is formed by laser fine patterning.
Wherein the metal precursor is one or two or more selected from the group consisting of copper, nickel, cobalt, and alloys thereof.
Wherein the acid has at least one form of straight chain, branched or cyclic carbon atoms having 6 to 30 carbon atoms, and the acid is one or two or more selected from saturated or unsaturated acids.
Wherein the molar ratio of the metal precursor to the acid is 1: 0.2-4.
Wherein the amine has at least one of linear, branched or cyclic carbon atoms having 6 to 30 carbon atoms and is one or two or more selected from saturated and unsaturated amines.
Wherein the reducing agent is at least one selected from the group consisting of hydrazine, hydride, borohydride, sodium phosphate, and ascorbic acid.
Wherein the metal nanoparticle synthesis step in step 2) is performed at 100 to 240 ° C.
Wherein the conductive ink composition of step 3) comprises 1 to 20 parts by weight of a dispersant per 100 parts by weight of the metal nanoparticles.
Wherein the firing by the laser irradiation is performed in an active atmosphere by laser fine patterning.
Wherein the conductive ink composition contains 0.001 to 1 part by weight of one or two or more compounds selected from the group consisting of formulas (1) and (2), based on 100 parts by weight of the metal precursor, to form a metal conductive fine pattern.
[Chemical Formula 1]
[XR 1 ] n [R 2 ] 4-n Si
(In Formula 1, X is an amine group (-NH 2) or a thiol group (-SH), R 1 is (C 0 -C 17) alkyl group, R 2 is (C 1 -C 17) alkyl or (C 1 -C 5 ) alkoxy group, and n is an integer of 1 to 3.)
(2)
[R 1 ] - [R 2 ] -SH
(In the formula 2, R 1 is CH 3, CF 3, C 6 H 5, C 6 H 4 F, C 6 F 5, R 2 is (CH 2) n, (CF 2) n, (C 6 H 4 ) n , and n is an integer from 1 to 17.)
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| PCT/KR2013/011109 WO2014088291A1 (en) | 2012-12-04 | 2013-12-03 | Method for forming fine conductive pattern using metal nanoink for laser patterning process |
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| KR101798277B1 (en) | 2014-09-17 | 2017-11-15 | 주식회사 엘지화학 | Method for manufacturing conductive copper thin-film pattern using flat-type oxidized copper nano material |
| JP2018085437A (en) * | 2016-11-24 | 2018-05-31 | 株式会社村田製作所 | Method for manufacturing electronic component and electronic component |
| KR20200068209A (en) * | 2018-12-05 | 2020-06-15 | 한양대학교 에리카산학협력단 | Manufacturing method of engraved pattern and nano metal coated layer produced by the method |
| KR20200100331A (en) * | 2019-02-18 | 2020-08-26 | (주)디엔에프 | a method for manufacturing conductive thin film |
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| JP2007321216A (en) | 2006-06-02 | 2007-12-13 | Nippon Shokubai Co Ltd | Method for producing metallic nanoparticles, metallic nanoparticles, dispersion of metallic nanoparticles, and electron device |
| JP2009024193A (en) * | 2007-07-17 | 2009-02-05 | Nippon Shokubai Co Ltd | Method for producing metallic nanoparticle, metallic nanoparticle, dispersion of metallic nanoparticle, and metallic coating film |
| KR20100080120A (en) * | 2008-12-31 | 2010-07-08 | 한국생산기술연구원 | Sintering method of printed circuit by laser writing |
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| KR101798277B1 (en) | 2014-09-17 | 2017-11-15 | 주식회사 엘지화학 | Method for manufacturing conductive copper thin-film pattern using flat-type oxidized copper nano material |
| JP2018085437A (en) * | 2016-11-24 | 2018-05-31 | 株式会社村田製作所 | Method for manufacturing electronic component and electronic component |
| KR20200068209A (en) * | 2018-12-05 | 2020-06-15 | 한양대학교 에리카산학협력단 | Manufacturing method of engraved pattern and nano metal coated layer produced by the method |
| KR102125148B1 (en) * | 2018-12-05 | 2020-06-19 | 한양대학교 에리카산학협력단 | Manufacturing method of engraved pattern and nano metal coated layer produced by the method |
| KR20200100331A (en) * | 2019-02-18 | 2020-08-26 | (주)디엔에프 | a method for manufacturing conductive thin film |
| KR102171531B1 (en) | 2019-02-18 | 2020-10-29 | (주)디엔에프 | a method for manufacturing conductive thin film |
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