KR101199969B1 - silver organo-sol ink for forming conductive patterns - Google Patents

Abstract

The present invention relates to a silver organo sol ink for the formation of a conductive line pattern, comprising a conductive line pattern formation comprising an effective amount of the aromatic carboxylic acid is defined by the following formula 1 and the remaining amount of the solvent dissolving the aromatic carboxylic acid silver Solution to provide an organo sol ink.

Wherein R1, R2, R3, R4 and R5 are each COO-Ag +, hydrogen, a hydroxy group or an alkyl group having 1 to 9 carbon atoms, the same or different.

According to the present invention, it is possible to obtain a high silver content and complete solution of a silver organo sol ink which can be used not only in the display field such as PDP, but also in various fields such as solar cells and RFids. By using ink, a conductive film having a good microstructure of low electrical resistance can be obtained by metallization.

Silver, organosol, metallization, inkjet

Description

Silver organo-sol ink for forming conductive patterns

1 is an infrared spectroscopy graph of silver powder, TEA and silver ink prepared in Example 1,

2 is a photograph showing a contact angle with a substrate to which silver ink prepared in Example 1 of the present invention is applied;

Figure 3 is a SEM image (a) of two scales of a sample each baked in Example 3 of the present invention and then heat treated at 550 ° C. for 10 minutes, and baked in Example 4 and then heat treated at 550 ° C. for 10 minutes. SEM picture (b) of two scales of one sample, SEM picture (c) of two scales of sample baked in Example 5 and then heat treated at 550 ° C. for 10 minutes.

Patent literature

turn Country of origin Applicant
(inventor) Name of invention Application date
(Public, Notice, Registration Number) Characteristics of the technology One) United States of America Engelhard
(Pascalin New Yen) metallized substrates and process for producing 1986,9,10
(Registration No.4808274) Metal carboxylates, alkoholates, mercaptide, amino + carboxylates, acyl + carboxylates, alkoxides 2) United States of America (Michael, Firmstone) Seed layer compositions containing organogold and organosilver compounds 1990,4,27
(Registration No.5059242) Thio, polythio, carboxylate crosslinking of metals and hydrocarbons 3) United States of America Degussa
( Lotze ; Marion) Gold (I) mercaptocarboxylic acid esters, method of their preparation and use 1993,4,5
(Registration No. 5312480) Gold (I) mercaptocarboxylic acid ester used for gold decoration of ceramic 4) International application Parelec , Inc.
( Kydd ; Paul H. party) Material and method for printing high conductivity electrical conductors and other components on thin film transistor arrays International application
1997, 9, 12
(International Publication WO98-37133) Metal powder + MOD (or RMO or reactive organic material); MOD is an organic substance bonded to metal through heteroatoms (O, N, S, P, As. Se, etc.) 5) United States of America Kovio , Inc
( Rockenberger  ; Joerg ) Nanoparticle synthesis and the formation of inks therefrom 2002,8,9
(Registration No. 6878184) MOD (or metal powder + RMO) is reduced to aldehyde to produce nanoparticles, producing ink [using particle form or MOD] 6) Korea Hyeeun Comtec
(Kwang Kwang-Chun party) Organic silver composition and method for manufacturing the same, ink prepared therefrom and method for forming conductive wiring using the ink 2003,03,28
(Publication 2004-84570) 5-40% by weight silver oxide + 10-20% by weight (lactam, lactone or carbonate) + 20-85% by amine

Literature other than patents

turn writer The title of the literature Archive
Date Characteristics of the technology One) Teng, KF, and Vest, RW
Liquid Ink Jet Printi
ng with MOD Inks for Hybrid Microcircuits
IEEE Transactions on Components,
Hybrids and Mamufacturing Technology, 12 (4), 545-549, 1987
As MOD material, it is described as a material connected to carbon through hetero elements (O, N, P, S) on metal, and specifically, silver neodecanoate and Au amine 2-ethylhexoate are used. Dielectric ink and resistance using other metal components Ink also mentioned 2) Lea Yancey
Direct Write Metallizations with Organometallic Inks
2000,8,18
Berkeley Undergraduate Thesis (hfa) Ag (COD), (hfa) Cu (BTMS),
(hfa) Cu (VTMS), sprayed on heated glass substrates or inkjet printed and annealed to investigate resistance


3) C. Curtis,
Metallizations  by Direct-Write Inkjet  Printing
To be presented at the NCPV Program Review Meeting
Lakewood, colorado
14-17 October 2001
(hfa) Ag (COD) 4) Alex Martinson
Synthesis of Single Phase SrCu2 O2
from Liquid Precursors

Peer-Reviewed science Journal
2004, 3, 3 Optical semiconductor used as copper formate and strontium acetate (MOD) SrCu2O2 solar cell annealed using high temperature 5) Kevin Cheng, *
Ink-Jet Printing, Self-Assembled Polyelectrolytes, and
Electroless Plating:
Macromol. Rapid Commun. 2005, 26, 247-264
Using PEM technology, polymer electrolyte PAA and PAH can be laminated, and Na2PdCl4 used as plating catalyst can be metallized at room temperature by conducting non-plating in copper plating bath after pattern formation with ink jet.

The present invention relates to a solution type silver organo sol ink for forming a conductive line pattern.

Pattern forming technology applied to semiconductor and display is largely applied to thin film forming technology such as CVD, PVD, and sputtering. Subtractive, which is manufactured by developing and etching pattern with lithography after forming film, screen printing method and Additives (pattern forming by a contact printing method such as screen printing) mainly applied to the same thick film forming technology can be divided into addition and subtraction methods using them in combination. Formation of the pattern by additive method is an economical manufacturing method because it can greatly shorten the material and the process, but the thick film forming technology such as screen printing is less accurate and therefore the technical field was different.

Attempts have been made to apply additive methods to patterns (for example, color filters in LCDs) formed by conventional thin film forming techniques. In particular, the pattern formation by ink jet printing corresponds to additive method, and if the precision can be achieved, it is very advantageous in terms of environmental and manufacturing cost reduction because it can shorten the process and prevent the waste of materials to obtain economical efficiency. The technology is attracting attention in the near future.

Since Vest, RW has tested the feasibility of inks using MOD materials (IEEE Transactions on Components, Hybrids and Mamufacturing Technology, 12 (4), 545-549, 1987). Kid's International Publication WO98-37133 is characterized by using a composite composition of MOD material and particulate metal for ink jet printing. Kovio, Inc U. S. Patent 6878184 does not use MOD ink, but uses MOD and a reducing agent (for example, aldehyde) to form ink on nanoparticles. Many attempts have been made to use such fine metal powders, especially suspension inks containing silver powder, to form conductive line patterns in an inkjet manner.

However, metal powder suspension inks must use additives to maintain the suspension and these additives adversely affect the physical properties of the formed pattern. In addition, the behavior of the suspension is different from the general inks, so the development of inkjet printer systems including inkjet nozzles is necessary. In this regard, inks in solution containing organo sol inks or metallo-organic decompositon ( MOD ) can be used without significant improvement in conventional inkjet printing apparatus. In addition, since the solution ink can lower the metallization temperature, there is a possibility that the solution ink can be applied to a flexible substrate such as plastic.

Korean Patent Publication No. 2004-84570 of Hye Eun Comtec discloses 5-40 wt% silver oxide + 10-20 wt% (lactam, lactone or carbonate) + 20-85 wt% amine as a composition of MOD ink for ink jet ink. However, the composition is closer to the suspension than the silver solution as shown in the dark color of the embodiment, and in order to maintain this suspension, a large amount of additives must be used and management of the ink jet nozzle has a problem.

An object of the present invention is to provide a silver organo sol ink capable of forming a conductive line pattern having good physical properties.

It is also an object of the present invention to provide a silver organo sol ink for forming a conductive line pattern that can be applied to conventional printing methods including ink jet printing equipment.

According to the present invention, a solution silver organosol ink for forming a conductive line pattern comprising an effective amount of an aromatic carboxylic acid defined by the following formula 1 and a residual amount of a solvent dissolving the aromatic carboxylic acid silver is provided.

Wherein R1, R2, R3, R4 and R5 are each COO-Ag +, hydrogen, a hydroxy group or an alkyl group having 1 to 9 carbon atoms, the same or different. Here, organo sol means that silver is combined with an organic material and is in a solution state.

The organic solvent preferably consists of a reactive organic solvent that forms a chelating agent or a complex with silver and a polar or nonpolar diluent for viscosity adjustment. The reactive organic solvent forming the chelating agent or the complex with silver is, for example, an organic solvent having a substituted or unsubstituted ketone group, mercapto group, carboxyl group, aniline group or sulfite group. The aromatic carboxylic acid silver is generally 5 to 70% by weight.

As one preferred embodiment of the present invention, the aromatic carboxylic acid defined by the following Formula 1a is 10-50% by weight; 10 to 60% by weight of a reactive organic solvent selected from the group consisting of amines substituted with at least one hydroxyethyl group and linear or branched aliphatic thiols having 2 to 16 carbon atoms; And a silver organo sol ink for forming a conductive line pattern comprising a residual amount of polar or nonpolar diluent solvent.

Wherein R1, R2, R3, R4 and R5 are each hydrogen, a hydroxy group or the same or different alkyl group having 1 to 9 carbon atoms. As a compound of said Formula 1a, it is silver benzoic acid, for example.

As another preferable embodiment of this invention, Aromatic carboxylic acid defined by following formula 1b is 10-50 weight%; 10 to 60% by weight of a reactive organic solvent selected from the group consisting of amines substituted with at least one hydroxyethyl group and linear or branched aliphatic thiols having 2 to 16 carbon atoms; And a silver organo sol ink for forming a conductive line pattern consisting of a residual amount of polar or nonpolar diluent solvent.

Wherein R _{1 ,} R _{2 ,} R _{3 ,} R ₄ and R ₅ One of which is COO ^_ Ag ⁺ and the others are each hydrogen, a hydroxy group or the same or different alkyl groups having 1 to 9 carbon atoms. Preferably, R ₃ is COO ^_ Ag ⁺ and the remaining R _{1 ,} R _{2 ,} R ₄ and R ₅ are each hydrogen, a hydroxy group or an alkyl group having the same or different carbon atoms of 1 to 9, respectively. For example, the compound of Formula 1b is silver terephthalic acid. When the compound of Formula 1b has two or more COO ^_ Ag ⁺ has the advantage of increasing the content of silver per mole.

As another preferable embodiment of this invention, Aromatic carboxylic acid defined by following formula (1c) is 10-50 weight%; 10 to 60% by weight of a reactive organic solvent selected from the group consisting of amines substituted with at least one hydroxyethyl group and linear or branched aliphatic thiols having 2 to 16 carbon atoms; And a silver organo sol ink for forming a conductive line pattern comprising a residual amount of polar or nonpolar diluent solvent.

Wherein at least two of R1, R2, R3, R4 and R5 is COO ^_ Ag + and the others are each hydrogen, a hydroxy group or the same or different alkyl groups having 1 to 9 carbon atoms. Preferably wherein R2 and R4 is COO ^_ Ag +, and the remaining R1, R3 and R5 are each hydrogen, a hydroxy group or the same or different alkyl groups having 1 to 9 carbon atoms. For example, the compound of formula 1c is trimesic acid silver. The content of silver is much higher than the compounds of formulas 1a and 1b.

Such silver organo sol inks may include small amounts of additives such as surfactants and mucoadhesive agents. In addition, the silver organo sol ink of the present invention may include a nonconductive polymeric or glassy material as the matrix or flux material of the silver conductor. The silver organo sol ink of the present invention can be used in various fields requiring conductive line patterns such as solar cells and RFids as well as display fields such as PDPs.

The aromatic carboxylic acid silver defined by Equation 1 has an advantage of being able to be reduced to a relatively high concentration of metallic silver even when a small amount of precursor is used as 47% or more of the specific gravity of silver per unit mole.

The amount of the aromatic series carboxylic acid silver defined by the above formula 1 is preferably 5 to 70% by weight. If it is 5 wt% or less, the silver concentration is low, and if it is 70 wt% or more, there may be a problem in making a solution. The amount of the aromatic carboxylic acid silver defined by Formula 1 is preferably 10 to 50% by weight, most preferably 20 to 40% by weight. The aromatic series carboxylic acid silver defined by Formula 1 may preferably be prepared by reacting a silver solution such as silver nitrate with an aromatic series carboxylic acid alkali metal salt corresponding to Formula 1. The aromatic carboxylic acid alkali metal salt is easily prepared by reacting alkali with an aromatic carboxylic acid.

The organic solvent preferably consists of a reactive organic solvent that forms a chelating agent or a complex with silver and a polar or nonpolar diluent for viscosity adjustment. The reactive organic solvent forming the chelating agent or the complex with silver is, for example, an organic solvent having a substituted or unsubstituted ketone group, mercapto group, carboxyl group, aniline group or sulfite group. The reactive organic solvent is most preferably monoethanolamine, diethanolamine or triethanolamine. The reactive organic solvent is preferably monoethanolamine, diethanolamine or triethanolamine. The reactive organic solvent is presumed to increase the solubility in the solvent by forming a complex by the chelate or the coordination bond with the aromatic series carboxylic acid silver defined by the formula (1 ). The organo sol ink of the present invention is a completely solution ink which is basically transparent and may be slightly colored. When liquefied by an amine solvent such as ethanolamine, it has a viscosity of about 10,000 cPs ~ 100,000 cPs depending on the content of solids. Depending on the purpose the user can adjust the viscosity using either polar or nonpolar solvents. Silver organo sol, which is solutioned with one or more amines substituted with ethanol, can be diluted using a polar or nonpolar solvent depending on the nature of the substrate. The nonpolar diluent is an aliphatic or aromatic hydrocarbon. The polar solvent is substituted or unsubstituted monovalent to trivalent saturated or unsaturated aliphatic alcohol or water having 1 to 12 carbon atoms. Examples of such diluent solvents are 2-methoxyethanol, 1,2-hexanediol, benzene, toluene, xylene, dimethylcarbitol, kerosene, ethanol, methanol 2-propanol, chloroform and ethylene glycol. For example, a solvent such as ethylene glycol or water may be used for the substrate having a hydrophilic group, and it is well dispersed in a lower alcohol such as ethanol when printing on a substrate of a metal oxide film having a hydrophobic group.

Such a solution ink may be used to form a conductive line pattern of a flat panel display such as a plasma display panel (PDP) by conventional ink jet printing, thereby greatly reducing their production process. In particular, the metallized silver organosol ink of the present invention is stable at relatively high temperatures, for example at temperatures of 450-600 ° C., more specifically at temperatures of 480-580 ° C., whereby conductive line patterns are formed to form sutures or partition walls. It is suitable for use in PDPs that undergo a variety of high temperature treatments.

Hereinafter, the present invention will be described in detail by examples. These examples are intended to illustrate the invention and should not be construed as limiting the protection scope of the invention.

Example 1

50 mmol benzoic acid is dissociated in 50 mL methanol. To this stirred solution is slowly added 50 mL of water with 50 mmol of NaOH dissociated to form sodium benzoate salt. When 50 mL of water in which 50 mmol of silver nitrate is dissociated is slowly added thereto, white precipitate is formed quickly. The resulting precipitate is sufficiently washed with water to remove unreacted silver nitrate and sodium hydroxide, filtered, and then unreacted benzoic acid is removed using a sufficient amount of methanol to terminate the reaction. Since the produced pure white benzoic acid silver intermediate is a light sensitive material, it is easily oxidized in visible light such as a fluorescent lamp, and thus is completely dried under light blocking (or yellow light). In order to liquefy the powder, 0.07 mol of silver benzoic acid (molecular weight: about 228 g / mol) was dissolved in 0.14 mol of triethanolamine, and the viscosity was adjusted using 40 mL of ethanol. The viscosity of the resulting solution was confirmed to have 15 cPs at 25 ° C. with a Brookfield Viscometer. As measured by UV spectrophotometer, the characteristic peak observed in the silver solution was confirmed at about 428.5 nm. In the infrared spectroscopy analysis, silver benzoic acid was analyzed for silver powder and solution, and the solution band was observed at 1000 and 1300 cm ^-1 , which are the characteristic peaks of silver.

The contact angle measured to confirm the patterning of the solution was found to be about 40 degrees on the glass substrate. Conductivity was measured by heat treatment at 150 ° C. for 10 minutes by bar coating method and measuring electrical resistance (5.5 × 10 ⁻⁶ Ω · cm). In order to measure the remaining solid content, the solution weight immediately after coating and the film weight after heat treatment at 500 ° C. were measured, and the content of solid content was found to be about 0.5804 g and 0.3656 g, respectively, about 63 wt%. The electrical resistance was 2.505 x 10 < ^-6 >

Example 2

50 mmol benzoic acid is dissociated in 50 mL methanol. To this stirred solution is slowly added 50 mL of water with 50 mmol of NaOH dissociated to form sodium benzoate. To this solution is added 50 mL of silver nitrate dissociated in 50 mL of water, which quickly forms a white precipitate. At this time, the precipitate forms silver benzoate due to the ionization tendency of Na + and Ag + added in the solution. do. The precipitate is washed well with water, filtered, washed again with methanol and dried at 50 ° C. to produce silver benzoate.

0.07 mol of the silver benzoic acid is completely dissolved with 0.84 mol of octanethiol, and then xylene is added to maintain the viscosity of 13 to 15 cps. Stir well for 30 minutes in succession. The silver solution prepared was bar-coated on a glass substrate, dried at room temperature, heated at 150 ° C. for 10 minutes, and then heated up again and heat-treated at 500 ° C. for 10 minutes. After the heat treatment, the weight of the remaining solid content was determined as the final silver content, and the thickness of the film was measured to measure the volume resistance using a surface resistance measuring device. Accurate addition amounts and measurements are listed in Table A.

Example 3

50 mmol benzoic acid is dissociated in 50 mL methanol. To this stirred solution is slowly added 50 mL of water with 50 mmol of NaOH dissociated to form sodium benzoate. To this solution is added 50 mL of silver nitrate dissociated in 50 mL of water, which quickly forms a white precipitate. At this time, the precipitate forms silver benzoate due to the ionization tendency of Na + and Ag + added in the solution. do. The precipitate is washed well with water, filtered, washed again with methanol and dried at 50 ° C. to produce silver benzoate.

0.21 mol of silver benzoic acid was completely dissolved in 0.42 mol of EA (ethanol amine), and then ethanol was added to maintain a viscosity of 15 cps. Stir well for 30 minutes in succession. The silver solution prepared was bar-coated on a glass substrate, dried at room temperature, heated at 150 ° C. for 10 minutes, and then heated up again and heat-treated at 550 ° C. for 10 minutes. After the heat treatment, the weight of the remaining solid content was determined as the final silver content, and the thickness of the film was measured to measure the volume resistance using a surface resistance measuring device. Accurate addition amounts and measurements are listed in Table A.

Example 4

Terephthalic acid was used instead of benzoic acid and the same procedure as in Example 2 was carried out. Accurate addition amounts and measurements are listed in Table A.

Example 5

Trimethic acid was used instead of benzoic acid and the same procedure as in Example 2 was carried out. Accurate addition amounts and measurements are listed in Table A.

Table a

Precursor Reactive Organic Solvents Solvent resistance
(10 ^-6 Ω? Cm)
Example input
(mol) persons input
(mol) persons input
(ml) or (g) Ag 1 0.07 TEA 0.14 xylene 40 (ml) 2.505 2. Ag 1 0.07 OT 0.14 EtOH 40 (ml) 2.75 Ag 1 0.21 EA 0.42 EtOH 58 (g) 9.9 4.Ag 2 0.21 EA 0.84 EtOH 186 (g) 2.7 5. Ag 3 0.21 EA 1.26 EtOH 150 (g) 1.1

Ag 1; COOAg is 1 Ag 2; COOAg is two Ag 3; 3 COOAg

According to the present invention, silver organosol inks with high silver content and complete solution can be obtained, and these solution inks are used to form conductive line patterns in flat panel displays such as PDPs by conventional inkjet printing to produce them. The process can be dramatically reduced.

Claims (18)

To a solution property to the conductor pattern formation comprising the aromatic carboxylic acid and the solvent for dissolving the aromatic carboxylic acid is defined by formula 1 are organo-sol ink

Wherein R1, R2, R3, R4 and R5 are each COO-Ag +, hydrogen, a hydroxy group or an alkyl group having 1 to 9 carbon atoms, the same or different. The silver organo sol ink for forming a conductive line pattern according to claim 1, wherein the solvent comprises a reactive organic solvent forming a chelating agent or a complex with silver and a polar or nonpolar diluent for viscosity adjustment. delete The silver organo sol ink of claim 2, wherein the reactive organic solvent is an organic solvent having a ketone group, a mercapto group, a carboxyl group, or a sulfite group. The silver organo sol ink of claim 4, wherein the aromatic carboxylic acid silver is 5-70% by weight of the total ink. delete The silver organo sol ink according to claim 4, wherein the aromatic carboxylic acid silver is benzoic acid silver. delete delete The silver organo sol ink according to claim 4, wherein the compound of formula 1 is silver phthalate. delete delete The silver organo sol ink according to claim 4, wherein the compound of formula 1 is trimesic acid silver. The ink according to any one of claims 1, 2, 4, 5, 7, 7, 10, and 13, wherein the ink is used for forming a conductive line pattern by ink jet printing. Organo sol ink. The silver organo sol ink according to claim 14, wherein the amount of the aromatic carboxylic acid silver defined by Formula 1 is 20 to 40% by weight of the total ink. The silver organo sol ink of claim 15, wherein the reactive organic solvent is ethanolamine or triethanolamine. The silver organosol ink according to claim 16, wherein the nonpolar diluent solvent is benzene, toluene or xylene and the polar diluent solvent is monovalent to trivalent saturated or unsaturated aliphatic alcohol or water having 1 to 12 carbon atoms. delete

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