KR20110101344A - Method for fabricating the printed conductive-pattern well-adhesive to a glass/ceramic substrate using self-assembled molecules - Google Patents

Abstract

The present invention comprises the steps of a) preparing a self-aligned molecular precursor solution; b) coating the precursor solution on glass and ceramic substrates; And c) printing a conductive nano ink on the coated substrate; relates to a fine conductive pattern manufacturing method comprising a.
The method of manufacturing a fine conductive pattern according to the present invention can improve the adhesion between the pattern and the substrate by solving low adhesion, which is a problem of the fine conductive pattern manufactured by a conventional general printing process.

Description

Method for fabricating the printed conductive-pattern well-adhesive to a glass / ceramic substrate using self-assembled molecules}

The present invention relates to a method of manufacturing a printed fine conductive pattern having excellent adhesion by coating a self-aligned molecular layer on a substrate.

BACKGROUND OF THE INVENTION In the field of display, a technique of manufacturing a fine conductive pattern on glass and ceramic substrates for driving device manufacturing has generally used conventional optical transfer method. However, due to limitations in process cost reduction and large-area processes, research on the manufacture of fine conductive patterns through printing processes has been actively conducted.

However, the manufacture of the fine conductive pattern through the printing process has caused a problem that the adhesion between the glass and ceramic substrate and the pattern is an important application in the printing process. Accordingly, there is a need for a new approach for manufacturing a conductive pattern having excellent adhesion on glass and ceramic substrates through a printing process.

The conventional method is generally a method of producing a fine pattern having excellent adhesion by adding glass frit and a polymer in a conductive ink. However, the additives contained have a limitation in reducing the conductivity of the fine pattern by disturbing the flow of electrons. Another method, surface modification by plasma treatment, has limitations in terms of process convenience and cost efficiency. Therefore, there is an urgent need for research and development of a new approach that can improve adhesion without lowering the conductivity of the fine pattern.

An object of the present invention is to improve adhesion by self-aligning a molecule capable of chemically bonding with a conductive metal on the substrate during a printing process of a conductive fine pattern having excellent adhesion on glass and ceramic substrates.

The present invention comprises the steps of a) preparing a self-aligned molecular precursor solution; and b) coating the precursor solution on glass and ceramic substrates; And c) printing a conductive nano ink on the coated substrate; relates to a fine conductive pattern manufacturing method comprising a.

The self-aligned molecule of a) includes a silane compound of the following [Formula 1].

[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 a (C ₁ -C ₁₇ ) alkyl group, R ₂ is a (C ₁ -C ₂ ) alkyl group or (C ₁ -C ₂ ) alkoxy group, n is an integer of 1 to 3.)

The self-aligned molecule precursor solution of a) comprises mixing 2-5% by volume of the self-aligned molecule in a solvent.

The solvent is water, ethanol, methanol, isopropyl alcohol, acetone, toluene, hexane, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cell Rhosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloro Ethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, heptane, octane, cyclohexane, benzene, xylene, propanol, butanol, t-butanol, cyclohexanone, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, 2-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethylosolve acetate, methyl cellosolve acetate, butyl acetate, γ-butyl lactone, N-methyl Raleigh include money, dimethyl formamide, tetramethyl sulfone, ethylene glycol acetate, at least one selected from ethyl acetate, ethyl lactate, cyclohexanone and the group consisting of rice.

The method for coating the self-aligned molecular precursor solution of b) includes a method of depositing the substrate by immersing the substrate in the prepared self-aligned molecular precursor solution for a predetermined time, and a method of evaporating the self-aligned molecule itself and condensing it on glass and ceramic substrates. .

The conductive nano ink of c) includes metal particles and metal precursors.

The printing method of c) includes ink-jet printing, micro-contact printing, imprinting, gravure printing, gravure-offset printing, Flexography printing and screen printing.

Hereinafter, the present invention will be described in more detail.

The adhesion between the glass and ceramic substrates and the printed metal micropatterns in the printing process is determined by the bonding force between the organic substrate and the metal particles contained in the ink. Therefore, metal-based conductive micropatterns are self-aligned between a glass- and ceramic substrate and a metal-based conductive micropattern by simultaneously aligning molecules having a functional group for chemical bonding with glass and ceramic substrates and a functional group for chemical bonding with metal particles. Can improve the adhesion of the.

Accordingly, in the present invention, in preparing a conductive fine pattern using a printing process on glass and ceramic substrates, a self-aligned molecular precursor solution is prepared to improve adhesion between the substrate and the pattern, and then the precursor solution is formed on the glass and ceramic substrates. Coating on.

The self-aligning molecule includes a silane compound of the following [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 a (C ₁ -C ₁₇ ) alkyl group, R ₂ is a (C ₁ -C ₂ ) alkyl group or (C _1- C ₂ ) alkoxy group, n is an integer of 1-3. The alkoxy group is a functional group that allows self-aligned molecules to be coated on the glass and ceramic substrates through chemical bonding with hydroxyl groups present on the glass and ceramic substrate surfaces, and the amine group or thiol group is capable of chemical bonding with metal particles. It is a functional group that can contribute to the improvement of adhesion through.

Formula 1 of the present invention includes aminoethyltrimethoxysilane, aminoethyldimethoxymethylsilane, aminopropyltrimethoxysilane, aminopropyldimethoxymethylsilane, aminopropyltriethoxysilane (APTES), aminopropyldiethoxymethylsilane, aminopropyldimethoxyethylsilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane (MPTES), mercaptopropyldiimethoxysilane, (17-aminoheptadecyl silane compound selected from 1).

The self-aligned molecular precursor solution mixes 2-5% by volume of the self-aligned molecule in a solvent. When the content of the self-aligned molecules is less than 2% by volume, the surface density of the self-aligned molecules coated on the substrate is low, and when the content of the self-aligned molecules is more than 5% by volume, the reaction between the self-aligned molecules occurs more actively than the coating and adhesion to the organic substrate. For this reason, it is impossible to improve the adhesion between the substrate and the pattern.

In addition, the self-aligned molecule precursor solution may be added with water to promote the hydration reaction of the alkoxy group of the self-aligned molecule. The addition of water preferably has a molar ratio of self-aligned molecules and water of 0.1 to 3. When the molar ratio is less than 0.1, since the hydration reaction does not occur sufficiently, the reaction with the hydroxyl groups on the glass and ceramic substrates is not easily performed. The reaction between them is promoted, making it difficult to form a uniform self-aligned molecular layer on glass and ceramic substrates. In addition, acids may be added to further promote the hydration reaction. The acid includes at least one selected from hydrochloric acid, nitric acid, sulfuric acid, boric acid, acetic acid, and is preferably added to water at a concentration of 0.01 to 10 M. If the acid concentration is less than 0.01M, the effect as a reaction catalyst is not seen, and if it is more than 10M, the adhesion between the substrate and the pattern is lowered.

When the self-aligned molecules are coated by heating, the self-aligned molecules are preferably coated at a temperature of about the boiling point of the self-aligned molecules.

A conductive nano ink is printed on the coated substrate to prepare a fine conductive pattern. The conductive nano ink may include metal particles and metal precursors, and when the water-based ink is used, the self-aligned molecular solution may be lowered to an appropriate interfacial energy of the ink and the adhesion enhancing layer of the substrate formed by coating the self-aligned molecular solution.

The metal particles include silver, copper, gold, chromium, aluminum, tungsten, nickel, zinc, iron, molybdenum, lead and alloys thereof.

It is preferable that the particle diameter of the said metal particle is 100 nm or less, and it is more preferable that it is 0.1 nm or more and 50 nm or less.

When the conductive micropattern is formed on the glass and ceramic substrates coated with the self-aligned molecules according to the present invention by using a printing process, the conductive micropattern having excellent adhesion may be manufactured without causing a decrease in conductivity due to additives. In addition, compared to the existing methods and processes, the present invention is more environmentally friendly, easier for large-area processes, and lower cost mass production due to a single process because the present invention coats onto glass and ceramic substrates by a simple solution process and evaporation method. Has an advantageous advantage.

1 is the actual injection shape of the silver nano ink
2 is a result of the adhesion test of the fine silver pattern printed on the glass substrate
3 and 4 are images of the fine silver pattern formed after the heat treatment
5 is the resistivity of the fine silver pattern printed on the glass substrate

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

Example 1

The glass substrate was immersed in a solution mixed with sulfuric acid and hydrogen peroxide at a weight ratio of 4: 6, and then ultrasonically washed for 3 minutes, followed by further washing with distilled water, acetone, isopropyl alcohol, methanol, and distilled water. The washed glass substrate is dried using nitrogen gas. Next, Aminopropyltriethoxysilane (APTES) solution is prepared. The solution is stirred by adding 2% by volume of ethanol and distilled water to a solvent mixed in a volume ratio of 95: 5 and then immersing the glass substrate. After immersion for 30 minutes, water-based silver nano ink was inkjet printed onto the glass substrate coated with the immersion. The aqueous silver nano ink was prepared by dispersing 25 wt% of silver nanoparticles in distilled water, and the size of the silver nanoparticles was 20 nm. Jetting was performed using a nozzle having a diameter of 30 μm, and the volume of jetted droplets was 4.8 pL. (Fig. 1)

[Example 2]

The glass substrate was immersed in a solution mixed with sulfuric acid and hydrogen peroxide at a weight ratio of 4: 6, and then ultrasonically washed for 3 minutes, followed by further washing with distilled water, acetone, isopropyl alcohol, methanol, and distilled water. The washed glass substrate is dried using nitrogen gas. Next, a Mercaptopropyltriethoxysilane (MPTES) solution is prepared. The solution is stirred by adding 2% by volume of distilled water containing ethanol and 1M acetic acid to a solvent mixed in a volume ratio of 95: 5, and then immersed the glass substrate. After immersion for 30 minutes, water-based silver nano ink was inkjet printed onto the glass substrate coated with the immersion. The aqueous silver nano ink was prepared by dispersing 25 wt% of silver nanoparticles in distilled water, and the size of the nanoparticles having a finer line width was 20 nm. Jetting was performed using a nozzle having a diameter of 30 μm, and the volume of jetted droplets was 4.8 pL.

Comparative Example 1

The glass substrate was immersed in a solution mixed with sulfuric acid and hydrogen peroxide at a weight ratio of 4: 6, and then ultrasonically washed for 3 minutes, followed by further washing with distilled water, acetone, isopropyl alcohol, methanol, and distilled water. The washed glass substrate is dried using nitrogen gas. Water-based silver nano ink was inkjet printed on the dried glass substrate. The aqueous silver nano ink was prepared by dispersing 25 wt% of silver nanoparticles in distilled water, and the size of the silver nanoparticles was 20 nm. Jetting was performed using a nozzle having a diameter of 30 μm, and the volume of jetted droplets was 4.8 pL.

evaluation

2 is a result of the adhesion test of the fine silver pattern printed by the method according to Examples 1, 2 and Comparative Example 1. Heat treatment at 200 ° C. is needed to develop conductivity of the printed fine silver pattern. However, in Comparative Example 1, after the heat treatment at 200 ℃, it was confirmed that all the patterns were removed after the adhesion test. On the other hand, in the case of Example 1 it can be confirmed that even after the heat treatment process at 200 ~ 300 ℃ has a good adhesion, the reduction of adhesion due to the thermal decomposition of APTES deposited on the glass substrate surface was observed at 350 ℃ or more . In the case of Example 2, it showed excellent adhesion at a temperature of 150 ° C. or less, but after the heat treatment at 200 ° C., the chemical bond with the metal was broken, thereby decreasing the adhesion. 3 and 4 is an image of the conductive silver fine pattern formed after the heat treatment at 200 ℃ after printing by the method according to Example 1. 5, the silver fine pattern printed on the glass substrate according to Example 1 exhibited a specific resistance of 3.5 μ 비 · cm after heat treatment at 200 to 300 ° C.

Claims (9)

a) preparing a self-aligned molecular precursor solution;
b) coating the precursor solution on glass and ceramic substrates; And
c) printing a conductive nano ink on the coated substrate. The method of claim 1,
The self-aligning molecule of a) is a method of producing a fine conductive pattern comprising a silane compound of the formula [1].
[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 a (C ₁ -C ₁₇ ) alkylene group, R ₂ is a (C ₁ -C ₂ ) alkyl group or (C ₁ -C ₂ ) alkoxy group, n is an integer of 1 to 3.) The method of claim 1,
The self-aligned molecule precursor solution of a) comprises mixing 2 to 5% by volume of the self-aligned molecule in a solvent. The method of claim 1,
The coating method of b) includes a method of depositing a substrate by immersing a substrate in a solution of a self-aligned molecule precursor for a predetermined time, or a method of manufacturing a fine conductive pattern, by evaporating the self-aligned molecule itself and condensing it on glass and ceramic substrates. The method of claim 1,
The conductive nano ink of c) is a method for producing a fine conductive pattern comprising a metal particle and a metal precursor. The method of claim 1,
The printing method of c) includes ink-jet printing, micro-contact printing, imprinting, gravure printing, gravure-offset printing, Method for producing a fine conductive pattern including flexography printing and screen printing. The method of claim 3, wherein
The solvent is water, ethanol, methanol, isopropyl alcohol, acetone, toluene, hexane, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cell Rhosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloro Ethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, heptane, octane, cyclohexane, benzene, xylene, propanol, butanol, t-butanol, cyclohexanone, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, 2-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethylosolve acetate, methyl cellosolve acetate, butyl acetate, γ-butyl lactone, N-methyl Pyrrolidone, dimethyl formamide, tetramethyl sulfone, ethylene glycol acetate, ethyl ether acetate, a fine conductive pattern manufacturing method that includes at least one member selected from ethyl lactate, cyclohexanone and the group consisting of rice. The method of claim 3, wherein
The self-aligned molecular precursor solution is a method of producing a fine conductive pattern is a mole ratio of self-aligned molecules: water of 0.1 to 3. The method of claim 3, wherein
The self-aligned molecular precursor solution further comprises at least one acid selected from hydrochloric acid, nitric acid, sulfuric acid, boric acid, acetic acid.

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