KR20040042389A - Method for forming a pattern of High conductive metal by organometallic compounds - Google Patents

Abstract

PURPOSE: A method for forming a high conductive metal line using an organic metal compound is provided to be capable of directly forming a conductive metal line pattern of high purity by simple processes. CONSTITUTION: A composition containing an organic metal compound and a predetermined pattern are formed on a substrate. At this time, the predetermined pattern is formed by using electromagnetic wave or heat. A line pattern made of metal or metal oxide is obtained by carrying out oxidation or reduction, or heat treatment on the resultant structure under nitrogen or hydrogen gas atmosphere. A high conductive metal pattern is obtained by growing grains of the metal of the line pattern. Preferably, a displacement from the metal pattern to another high conductive metal is additionally carried out.

Description

Method for forming a pattern of high conductive metal by organometallic compounds

The present invention relates to a method of forming a pattern of high conductivity metal using an organometallic compound, and more specifically, i) a predetermined pattern is formed on a substrate using a composition containing an organometallic compound and electromagnetic waves or heat. And then oxidizing or reducing it, or heating in a hydrogen or nitrogen atmosphere to obtain a wiring pattern made of a metal or metal oxide, ii) using the pattern as a nucleating agent to grow crystals of a high conductivity metal to form a high conductivity metal. And a step of obtaining, if necessary, i) replacing the high conductivity metal pattern with another high conductivity metal.

BACKGROUND In electronic devices such as integrated circuits and liquid crystal display devices, metal wiring patterns to be formed on substrates are becoming finer as the integration degree increases and the device size becomes smaller. In order to form a fine pattern of metal wiring on a substrate, photolithography is mainly used using photoresist (see FIG. 1). In the photolithography process, chemical vapor deposition is performed. Deposition process: CVD process, plasma deposition, or electroplating, etc. First, a metal material layer is formed on a substrate, and then a photoresist is applied on the metal layer, and the photoresist is applied under a photomask. After exposure and development, a metal layer including a patterned photoresist layer is obtained, and then the metal layer is etched by a method such as reactive ion etching to form a fine pattern metal wiring on the substrate. Currently, metals used as wiring materials are limited to metals having low cost and good process characteristics such as Al, Cr, and Mo, in consideration of ease of process and conductivity. However, as electronic devices become larger and more integrated, the length of the entire wiring becomes longer, but the width of the wiring becomes relatively narrower. As a result, the display quality deteriorates due to an increase in resistance and signal delay in the metal wiring. In particular, the problem is an absolute obstacle in the development of high-definition, large-area TFT-LCD.

As a solution to this problem, the use of Al-alloys, for example AlNd, which have a low resistivity, is now disclosed, but Al-alloys not only increase their resistivity with the addition of dissimilar metals, but also with n + a-Si and ITO. Due to the high contact resistance, it can be used only as a multilayer structure of Cr / AlNd / Cr, resulting in a complicated process resulting in high production costs and a significant drop in productivity. As a result, a review of the conventional metal wiring material (see Table 1) has been made, and as a result, it has a lower specific resistance than the Al-alloy material currently used and has good contact properties on the amorphous silicon layer. Process development for Cu and Ag materials as materials is of great interest:

characteristic Ag Cu Au Pure Al AlNd Thin Film Resistivity (μΩ㎝) 2.1 2.3 2.4 (bulk) 3.1 Gate 4.5S / D 7.0 n + a-Si contact ○ × × × × ITO contact ○ ○ ○ × × Wet Etch Castle Need to develop etchant Need to develop etchant Need to develop etchant ○ ○ Dry Etch Sex ○ × × ○ △ Chemical resistance (corrosion resistance) × × ○ △ △ Thermal resistance × △ ○ × ○ Adhesion with Lower Film ×× × △ ○ ○ Target price ○ ○ ×× ○ ×

However, in the case of the copper (Cu) metal and silver (Ag) metal, there is no metal organic compound suitable for the chemical vapor deposition method which is widely used in forming a fine pattern, and there is no appropriate etchant in the photolithography process using a photoresist. In general, it is difficult to apply a photolithography process using a photoresist because there is a problem in that the adhesion to the lower substrate material is not good and easily peels off during the subsequent processing. Furthermore, the photolithography process using a photoresist is inherently required for high temperature and high vacuum, and has a large number of complex processes including pattern formation processes such as photosensitive resin coating, exposure, and development, and subsequent processes such as etching and peeling of the resist layer. There is.

Meanwhile, a method of forming a metal pattern without a photolithography process using a photoresist is also disclosed. For example, Japanese Patent Laid-Open No. 62-263973 discloses a method of forming a metal pattern by directly irradiating an electron beam to an organometallic compound thin film layer. The method is advantageous because there is no separate process such as etching and peeling, but there is a problem in mass productivity due to a long time for irradiating an electron beam.

As another example, US Pat. No. 5,064,685 discloses a method of obtaining a metal pattern through thermal decomposition by applying a metal organic ink to a substrate and then heating with a laser. In this case, high temperature treatment of the substrate can be avoided. There is no problem in mass productivity because the time for forming the metal pattern of the entire substrate is too long.

On the other hand, U.S. Patent No. 5,534,312 discloses coordination of a photoreactive organic compound on a metal to coat a synthesized organometallic coordination compound on a substrate, and then the film is placed under vacuum or a specific gas atmosphere and irradiated with electromagnetic waves in a predetermined region. Disclosed is a method of directly obtaining a metal pattern by inducing a photo-chemical reaction to convert a metal coordination compound in an exposed area into a new metal material adherent to a substrate and developing the same. At this time, the organic metal coordination compound is a metal coordination compound having at least one ligand in alkali or alkaline earth metal, transition metal, Al, actinium-based metal, etc., the ligand includes at least one azide group, preferably acetylacetonate, Dialkyldithiocarbamate, carboxylate, pyridine, amine, diamine, arsine, diarcin, phosphine, diphosphine, arene, or alkoxy ligand, alkyl ligand, and aryl ligand. After applying the synthesized organometallic compound on the substrate and passing the light through the patterned mask, the light directly reacts with the organometallic compound to decompose and decompose the organic ligands in the metal, the remaining metals around A metal oxide film pattern is formed by reaction with a metal atom or oxygen in the atmosphere. However, the method does not disclose the formation of a wiring of a metal or a metal oxide made of Ag or Cu, which is attracting attention as a next generation high-conductivity wiring material, and in the wiring of other metals, most of the ligands are desorbed by photoreaction. To form metals or metal oxides to contaminate ligands on metal wires

(ligand contamination) may remain, making it difficult to apply to the actual process. Furthermore, in order to improve the electrical conductivity of the formed oxide film, the hydrogen / nitrogen mixed gas must be flowed, and a high cost is required since a reduction reaction and surface heat treatment are performed for 30 hours to 30 hours at a high temperature of 200 ° C. or higher. Since the steric hindrance is constituted by a relatively large ligand, the space of the ligand decomposed by light irradiation is large, thus increasing the shrinkage of the metal film thickness. As a result, when the metal pattern is formed according to the above method, the shrinkage of the metal film reaches 75 to 90%, causing cracking and cracking of the metal film.

Therefore, in the art, a method of forming a metal wiring pattern made of Ag or Cu, which is attracting attention as a highly conductive metal pattern material for high integration and size of an electronic device, without undergoing a microphotographic etching process using a photoresist, There is a need for forming a metal pattern of Ag or Cu of high purity in a short time without requiring high temperature or high vacuum during the process.

The present inventors have made diligent efforts to solve the problems of the prior art. As a result, the organic metal coordination compound is applied to light or thermal energy under relatively mild conditions, oxidized or reduced to form a pattern made of metal or metal oxide, By using this as a nuclei for crystal growth, by growing a crystal of a high conductivity metal such as Cu or Ag by plating or the like, it was confirmed that a wiring pattern of a highly conductive metal can be obtained at low cost and high efficiency. The present invention has been led.

In conclusion, the present invention relates to a method for directly forming a high purity conductive metal wiring pattern directly on a substrate under relatively mild conditions.

1 is a schematic diagram schematically showing a metal wiring forming method using a photoresist according to the prior art.

Figure 2 is a schematic diagram showing a case of forming a wiring of copper or silver metal using an organometallic compound according to the present invention, which is not subjected to a substitution reaction.

3 is a schematic diagram schematically showing a case of forming a wire of a silver metal using an organometallic compound according to the present invention and undergoing a substitution reaction.

The present invention relates to a method of forming a pattern of a high conductivity metal using an organometallic compound, and more specifically, (i) after forming a predetermined pattern using the composition containing the organometallic compound, and electromagnetic waves or heat on the substrate Or oxidizing or reducing it, or heating under a nitrogen or hydrogen atmosphere to obtain a wiring pattern made of a metal or metal oxide, ii) growing a crystal of a high conducting metal by using the pattern as a nucleating agent. And a step of obtaining a pattern, and further, if necessary, i) replacing the conductive metal pattern with another high conductivity metal.

Hereinafter, the present invention will be described in detail by dividing step by step.

Step (i)

In order to form the high conductivity metal wiring pattern according to the present invention, first, a composition including an organometallic compound on a substrate, and a predetermined pattern are formed using electromagnetic waves or heat, and then oxidized or reduced, or nitrogen or Heating in a hydrogen atmosphere yields a wiring pattern made of metal or metal oxide.

The material of the substrate used in forming the metal pattern according to the present invention is not particularly limited. For example, a substrate made of an inorganic material such as silicon or glass, as well as a substrate made of an organic material such as plastic and a composite of an inorganic material and an organic material. It is also possible to use a substrate made of.

The composition containing the organometallic compound used in the present invention is a soft lithography or whether the pattern forming method is a photo-chemical reaction

It depends on whether or not soft lithography is used. First, the case of photo-chemical reaction will be described.

(A) Using photo-chemical reactions:

In the case of using a photo-chemical reaction, a composition containing a specific organometallic compound is applied on a substrate, and after exposure and development, it is oxidized or reduced, or heated in a nitrogen or hydrogen atmosphere to form a wiring pattern made of a metal or metal oxide. do.

A composition comprising an organometallic compound is prepared by a) dissolving an organometallic compound represented by Formula 1 in b) an organic solvent:

M _m L _n X _p

(Wherein

M is a transition metal, lanthanide or main group metal;

L is a ligand;

X is 1 to trivalent anion;

m is an integer from 1 to 10, and when m is 2 or more, each M may be the same or different from each other;

n is an integer from 0 to 60, and when n is 2 or more, each L may be the same or different from each other, and when there are two or more metals, n may also act as a ligand connecting the metal and the metal;

p is an integer of 0 to 60, and when p is 2 or more, each X may be the same or different from each other, where n and p are not simultaneously 0).

The number of ligands in the organometallic compound varies depending on the type of metal and its oxidation number, and it is possible to bond up to 0 to 6 per metal. In addition, the number of the anions can also be bonded to 0 to 6 per metal.

The metal M constituting the organometallic compound is preferably a post-transition metal belonging to Groups 9 to 12, more preferably a metal selected from the group consisting of Co, Ag, Au, Cu, Pd, Ni and Pt.

L is a ligand bound to a metal, and is an organic compound containing a main atom such as N, P, As, O, S, Se, Te, preferably a compound containing the main atom and consisting of 20 carbons or less . Specifically, acetylacetonate, acetate, β-ketoiminate, β-diiminate, β-ketoester, dialkyldithiocarbamate, carboxylate, oxaleto, halogen, hydrogen, hydroxy, cyano, nitro , Anionic ligands, pyridine, amines, diamines, arsines, diarsines, phosphates, exemplified by nitrates, nitroxyls, azides, carbonates, thiocyanatos, isothiocyanatos, alkoxy or derivatives thereof Fin, diphosphine, arene, carbonyl, imidazolylidene, ethylene, acetylene, water, thiocarbonyl, thioether or derivatives of the above compounds can be used.

X acts as an anion to match the electrical neutrality of the metal compound, and may or may not be coordinated with the metal atom. Specifically, halogen, hydroxy, cyano (CN ^-), nitro (NO ₂ ^-), nitrate (NO ₃ ^-), nitroxyl, azide (N ₃ ^-), thio when isocyanato, isothiocyanato when Arne Ito, tetraalkylborate (BR ₄ ⁻ , where R is Me, Et or Ph), tetrahaloborate (BX ₄ ⁻ , wherein X is F or Br), hexafluorophosphate (PF ₆ ⁻ ), triflate (CF ₃ SO ₃ ^- may be an anion of the like), sulfate (SO ₄ ^2-) and carbonate (CO ₃ ^{2-) -),} tosylate (Ts.

The type of organic solvent used to prepare the composition including the organometallic compound is not particularly limited, but may be acetonitrile, propionitrile, pentanenitrile, or hexanenitrile.

nitrile solvents such as (hexanenitrile), heptanenitrile, and isobutylnitrile; Hexane, heptane, octane, dodecane

aliphatic hydrocarbon solvents such as dodecane; Anisole, mesitylene

aromatic hydrocarbon solvents such as mesylene and xylene; Methyl Isobutyl Ketone

ketone solvents such as (methyl isobutyl ketone), 1-methyl-2-pyrrolidinone (1-methyl-2-pyrrolidinone), cyclohexanone and acetone; Tetrahydrofuran

(tetrahydrofuran), diisobutyl ether, isopropyl ether

ether solvents such as (isopropyl ether); Acetate solvents such as ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate; Isopropyl Alcohol

alcohol solvents such as isopropyl alcohol, butyl alcohol, hexyl alcohol, and octyl alcohol; Preference is given to using inorganic solvents or mixtures of these solvents.

The composition including the organometallic coordination compound is coated on the target substrate, and exposed and developed to form a wiring pattern made of a metal compound directly on the substrate.

Coating method of the composition is spin coating (spin coating), roll coating

(roll coating), deep coating, thermal evaporation, spray coating

spray coating, flow coating, or screen printing may be used, but is not limited thereto. Preferably spin coating is used.

The light source used for such electromagnetic irradiation is not limited, but it is most preferable to use ultraviolet (UV) light.

When exposing the coated composition, the organometallic compound in the composition is decomposed, so that a difference in solubility occurs between the exposed part and the non-exposed part.

.

In the above reaction scheme, the compound of the exposed portion is separated from the ligand bound to the metal atom by electromagnetic radiation, so that the other metal compound becomes more unstable and accelerates decomposition, depending on the metal or the exposure atmosphere. To metal oxides. The photochemical reaction mechanism of organometallic compounds differs depending on the metal and the ligand, but generally a) metal to ligand charge transfer, b) ligand to metal transfer. ligand to metal charge transfer, c) the diorbital-diobital excitation state, and d) the intermolecular charge transfer, resulting in unstable bonds between metals and ligands. Decomposition occurs.

An important feature of the present invention is that since the pattern of the metal or metal oxide obtained by the pattern forming process only needs to serve as a nucleating agent in a subsequent step, the organometallic compound is completely decomposed by light as in the prior art, The exposure is not necessary until it is a pure metal or metal oxide, but only until the time when the exposed part does not dissolve in the solvent. Therefore, it is further advantageous in that the exposure time can be shortened, and the shortening of the exposure time has an advantage in that the production efficiency is greatly increased in that it means an increase in productivity.

After the exposure step, it is possible to obtain a metal or metal oxide pattern consisting of only the exposed portions by removing the non-exposed portions using a developing solvent. The developing solvent is a solvent used in the preparation of the composition, a mixed solvent in which two or more solvents of the composition are mixed for controlling the dissolution rate, or an inorganic solvent commonly used in a semiconductor process, for example, tetramethylammonium hydroxide ( TMAH) can be used, and in order to obtain a clean pattern, it is also possible to use said developing solvent alternately.

The exposure and development process may be performed in a vacuum atmosphere or air, oxygen, hydrogen, nitrogen, argon or a mixed gas atmosphere according to circumstances, and may be performed at a temperature in a range in which no thermal decomposition of an organometallic compound occurs at room temperature or .

The obtained pattern can be converted into a desired metal or metal oxide by oxidation or reduction, or by heating at high temperature in a nitrogen and hydrogen gas atmosphere. At this time, in order to obtain a purer metal, it is preferable to proceed with a reduction reaction.

As the reducing agent, an organic or inorganic reducing agent may be used. Preferably, hydrazines are used as the organic reducing agent; Silanes; Amines or derivatives thereof are used, and metal hydrides such as NaBH ₄ and LiAlH ₄ are used as the inorganic reducing agent. These organic and inorganic reducing agents can be dissolved in a solvent or used by themselves, and can react with the substrate in the form of gas phase or liquid phase reaction.

As the oxidizing agent, organic or inorganic oxidizing agents can be used.

The method according to the present invention further comprises annealing the pattern formed after the oxidation or reduction reaction at a temperature in the range of 30 to 1000 ° C., preferably 50 to 300 ° C. for 1 minute to 1 hour, and the substrate of the metal pattern. Can increase the adhesion.

In particular, in relation to heat treatment, the conventional method in which high temperature heat treatment is necessary has a problem in that the conventional method cannot be used when the substrate is plastic due to thermal modification of the substrate, but in the case of the method according to the present invention, the metal compound already formed Since the wiring pattern is used only as the nucleating agent, the heat treatment needs to be performed only to increase the adhesive ability, so that the heat treatment temperature can be adjusted according to the properties of the substrate, so that a substrate having a wider material range can be used.

In order to facilitate understanding of the present invention, a method of obtaining a silver metal wiring pattern according to the present invention will be described as an example.

The silver (Ag) salt is reacted with an organic ligand such as alkylamine to obtain an organic silver compound having good solubility, which is dissolved in a nitrile or alcohol solvent, spin coated onto a substrate, and then exposed to light by a photo-reduction reaction. Most of the organic ligands are desorbed. This is developed to remove the non-exposed portions to form a desired pattern on the substrate. The pattern is reduced with an organic reducing agent to obtain a relatively pure silver (Ag) pattern.

(B) Using soft lithography:

In the method according to the present invention, as a step (iii), not only the pattern formed by photo-chemical reaction, but also the pattern formed using soft lithography can be used as crystal nuclei in a subsequent step. "Soft lithography" here refers to microcontact printing

(microcontact printing), microtransfer printing, micro molding in capillary (MIMIC), and solvent-assistance micromolding. The transfer of a pattern of organic compounds or organic materials onto a substrate using an elastomeric stamp or mold. Soft lithography forms a self-assembled monolayer of certain compounds on a substrate by contact printing and also forms microstructures in the material by embossing and replica molding. do.

In the present invention, elastomeric PDMS having a fine pattern

(Polydimethylsilane) is used as a mold or a stamp, and as an organic compound, an organometallic compound solution containing a metal such as palladium, silver, or platinum is injected into the mold or coated on a stamp, and then, it is applied to a predetermined substrate. The pattern is obtained by transferring.

After the pattern is formed, the organic component may be volatilized by applying ultraviolet rays or heat, or converted to a desired metal or metal oxide by heating at a high temperature in a nitrogen and hydrogen gas atmosphere.

In addition to the above, a pattern can be formed by a direct printing method.

(Ii) step:

Since the metal pattern obtained in step (iii) is not exposed to harsh conditions such as high temperature heat treatment, the crystallization degree or density is not high enough to be used as a metal wiring in an electronic device, so that the formed metal pattern is nucleated in this step. By performing plating by zero, crystals of a highly conductive metal are grown to obtain a metal pattern of a denser structure.

The plating method used in the present invention is an electroless plating or an electrolytic plating method, and the highly conductive metal used in the present invention is copper (Cu) or silver (Ag).

In the case of using electroless plating as a copper metal crystal growth method to form a highly conductive copper wiring, 1) copper salt, 2) reducing agent, 3) complexing agent, 4) pH adjusting agent, 5) pH buffer, and 6) improving agent It is formed by dipping a substrate having the pattern in a plating solution including a.

1) The copper salt serves to supply copper ions to the substrate, and examples of the copper salt include chloride, nitrate, sulfate, and cyanide compounds of copper. Preferably copper sulfate is used. 2) The reducing agent serves to reduce metal ions on the substrate, specific examples of the reducing agent include a polysaccharide compound such as NaBH ₄ , KBH ₄ , NaH ₂ PO ₂ , hydrazine, formalin or glucose. Preferably it is a polysaccharide compound such as formalin or glucose. 3) The complexing agent prevents hydroxide precipitation in the alkaline solution and controls free metal ion concentration to prevent decomposition of metal salts and to control the plating rate. Specific examples of the complexing agent include ammonia solution and acetic acid. Chelating agents such as guanic acid, tartarate and EDTA, or organic amine compounds. Preferably it is a chelating agent, such as EDTA. 4) The pH adjusting agent serves to adjust the pH of the plating solution, and is an acid or a base compound. 5) pH buffering agent suppresses the pH variation of plating solution and refers to various organic acid and weakly acidic inorganic compounds. 6) Enhancer Compound refers to a compound that can improve coating and planarization properties, and specific examples thereof include general surfactants and adsorbent materials capable of adsorbing components that interfere with crystal growth.

In order to form a highly conductive copper wiring, when the electroplating method is used as a copper metal crystal growth method, a plating composition comprising 1) copper salt, 2) complexing agent, 3) pH adjusting agent, 4) pH buffer, and 5) improving agent It is formed by immersing the substrate having the pattern.

The role and specific examples of the components contained in the plating solution composition are as described above.

In order to form a highly conductive silver (Ag) wiring, a metal crystal is grown by electroless plating or electrolytic plating using the metal pattern as a nucleating agent.

In the case of forming a high conductivity silver (Ag) wiring by electroless plating, a plating composition comprising 1) silver salt, 2) reducing agent, 3) complexing agent, 4) pH adjusting agent, 5) pH buffer and 6) improving agent It is formed by immersing the substrate on which the metal pattern is formed.

1) The silver salt supplies silver ions to the metal wiring, and specific examples of the silver salt include chloride of silver, nitrate of silver and cyanate of silver. Preferably a silver nitrate compound is used. The role and specific examples of other components contained in the plating solution composition are as described above.

In the case of using the electroplating method as the metal crystal growth method for the formation of silver (Ag) wiring of high conductivity, plating including 1) silver salt, 2) complexing agent, 3) pH adjusting agent, 4) pH buffer and 5) improving agent It forms by immersing the board | substrate which has the said pattern in the composition.

The role and specific examples of the components contained in the plating solution composition are as described above.

The first stage

When the pattern made of copper metal is obtained in step (ii), a wiring pattern made of silver metal may be obtained by further substituting the copper metal with silver metal as necessary.

The metal wiring made of silver (Ag) may be manufactured by plating silver metal directly in the step (ii), but there may be a problem in adhesiveness depending on the pattern formation method or the property of the substrate in step (iii). The metal pattern made of silver metal is preferably manufactured by forming a metal wiring pattern made of copper having better adhesion characteristics, and then converting the metal pattern made of silver through a substitution reaction in the step (iii).

The formation of the wiring of the silver metal by the substitution method is caused by a redox reaction between copper and silver. The Cu wiring board formed above is deposited in a suitable silver (Ag) salt solution, and one Cu atom is dissolved in the solution in an ionic state. This is accomplished by allowing two Ag atoms to deposit in the wiring instead of exiting.

Silver salt solutions for the substitution reaction include 1) silver salts, 2) reducing agents, 3) inhibitors, 4) surfactants, 5) pH buffers, 6) Cu complexation.

In the above, 1) the silver salt serves to supply silver ions, and specific examples thereof include chlorides of silver, nitrates of silver or cyanates of silver, and preferably silver nitrate compounds. 2) The reducing agent serves to reduce the metal ion, specific examples thereof include polysaccharide compounds such as NaBH ₄ , KBH ₄ , NaH ₂ PO ₂ , hydrazine, formalin and glucose, preferably formalin and glucose, etc. 3) The inhibitor acts to deposit silver uniformly and prevents metal ions in solution from being oxidized or reduced by external light. Specific examples thereof include thiourea, carbon disulfide, and general phenolic antioxidants, and preferably phenolic antioxidants are used. 4) The surfactant serves to prevent the electromigration of the metal ions of the formed silver wiring and to prevent discoloration. Specific examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, and polyhydric alcohol. . 5) The pH buffering agent suppresses the pH variation of the plating solution and uses ammonia water or sodium thiosulfate. 6) The Cu coordination compound does not directly affect the substitution reaction, but serves to prevent reprecipitation of dissolved Cu ions.

EXAMPLE

Hereinafter, the configuration and effects of the present invention will be described in more detail with specific examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

Preparation Example of Photosensitive Organometallic Coordination Compound:

1) Synthesis of Ag (NH ₂ Pr) _n (NO ₂ ) mixture (n = 1, 2, 3 and 4)

In synthesizing all the compounds using a Schlenk technique or a Glove box technique was carried out in a nitrogen atmosphere excluding moisture or oxygen atmosphere. In a 50 mL round Schlenk flask, 3.4 g (20.0 mmol) of AgNO ₂ was dissolved in 15 mL of acetonitrile (CH ₃ CN), followed by droplets using a syringe of propylamine (1.2 g; 20.3 mmol). Added. After the reaction was stirred at room temperature for about 1 hour, the mixture was filtered using a 0.2 m membrane filter, blocked with light, and all solvent was removed over 3 to 4 hours under reduced pressure to obtain a colorless oil. ^{The 1} H-NMR spectral results are as follows:

¹ H-NMR (CD ₃ CN, ppm): 2.68 [t, 2H, N-CH ₂ )], 1.49 [m, 2H, CH ₂ CH ₃ ], 0.90 [t, 3H, CH ₂ CH ₃ ]

Example 1: Wiring Formation and Electroless Plating

(Iii) step:

The compound synthesized in Preparation Example 1 was dissolved in a nitrile or alcohol solvent, respectively, to prepare a solution of an organic metal coordination compound, and the solution was spin-coated on a glass substrate, respectively. Using Oriel's UV-exposure as a light source, a wide band of ultraviolet light is exposed through a photomask while varying the output to form a pattern, and then the same solvent as the solvent is used. By developing to obtain a pattern. The substrate with the pattern was immersed in an alcohol solution of 0.1 mol% of hydrazine for about 30 seconds to effect a reduction reaction.

(Ii) step:

The obtained metal wiring was immersed for 5 minutes at 35 ° C. in an electroless copper (Cu) plating solution as shown in (A) composition of Table 2 to grow a crystal of copper metal on the metal wiring obtained in step (iii). Copper wiring of the same pattern was obtained.

(Iii) step:

On the other hand, the copper wiring was immersed in the substituted silver salt solution of Table 2 (b) at 40 ° C. for 30 seconds to replace copper with silver to obtain a wiring made of silver.

(A) Copper plating solution (B) Substituted silver salt solution Copper sulfate 3.5 g Tin salt 8.5 g Formalin (37%) 22 ml Thiono urine 1 g Ammonia 40 g Water 1 l 4 g silver nitrate 45 g glucose 45 g tin salt 4 g polyvinyl alcohol 1.5 g ethanol 100 ml water 1 l

The physical properties of the obtained copper wiring and silver wiring are as shown in Table 3. The thickness was measured by Dektak's alpha step, the resistivity was measured by a 4 point probe, and the reflectivity was measured by reflectance compared to Si wafer in a 700 nm wavelength light source.

Example 2

Cis-dichlorobis (triphenyl-phosphine) platinum (II) purchased from Aldrich was thermally deposited and coated on the LCD substrate. This was exposed to ultraviolet rays through a mask to form a pattern, and then developed using acetone to obtain a metal wiring of a predetermined pattern on the LCD substrate. The metal wiring of the predetermined pattern was immersed in an alcohol solution of 0.1 mol% of hydrazine for about 30 seconds to undergo a reduction reaction to obtain a platinum wiring of the predetermined pattern.

On the platinum wiring, a silver film was grown in the same manner as in Example 1 to obtain a silver metallic wiring having high conductivity. The physical properties of the obtained copper wiring and silver wiring are shown in Table 3.

Example 3

Step (iii):

After preparing an isopropanol solution containing palladium (II) acetate (5% by weight), it was capillary injected into poly (dimethyl siloxane: PDMS) having a fine pattern of capillary shape. Heated to a volatilized organic coordination compound to obtain a palladium metal interconnect.

The obtained pattern was immersed in an alcohol solution of 0.1 mol% of hydrazine for about 30 seconds to cause a reduction reaction.

(Ii) step:

By plating in the same manner as in Example 1 using the silver plating solution of Table 2 (b), a silver film was grown on the wiring surface to obtain a metal wiring pattern containing silver metal. The physical properties of the obtained copper wiring and silver wiring are shown in Table 3.

Example Cu thickness Cu resistivity (μohm-cm) Ag thickness Ag resistivity (μohm-cm) Example 1 1865 4.5 2226 4.2 Example 2 1517 4.9 1932 4.7 Example 3 1680 5.9 2090 4.4

As can be seen from Table 3, in the case of the copper wiring or silver wiring obtained by the method according to the present invention, the conductivity was very excellent and the desired metal thickness was obtained.

According to the present invention, a pure high conductivity metal wiring can be easily manufactured in a simple process without the need for high temperature or high vacuum, and thus it is applicable to the metal wiring formation of highly integrated and enlarged electronic devices.

Claims (11)

Iii) forming a predetermined pattern using a composition containing an organometallic compound on the substrate, and electromagnetic waves or heat, and then oxidizing or reducing it, or heating in a nitrogen or hydrogen atmosphere to form a wiring pattern composed of a metal or metal oxide. Obtaining, ii) obtaining a pattern made of a high conductivity metal by growing a crystal of the conductive metal using the pattern as a nucleating agent. The method of claim 1, further comprising: i) replacing the conductive metal pattern with another high conductivity metal. The method according to claim 1 or 2, wherein the pattern formation in step (i) is carried out by applying a composition containing an organometallic compound of the following formula on a substrate, exposing it in a vacuum, an inert gas atmosphere or air, and developing A method of forming a wiring of a highly conductive metal, wherein the wiring pattern is formed of a metal or a metal oxide by oxidizing or reducing the same, or performing heat treatment under a nitrogen or hydrogen atmosphere: [Formula 1] M _m L _n X _p (Wherein M is a transition metal, lanthanide or main group metal; L is a ligand; X is 1 to trivalent anion; m is an integer from 1 to 10, wherein when M is 2 or more, each M may be the same or different from each other; n is an integer from 0 to 60, and when n is 2 or more, each L may be the same or different from each other, and when there are two or more metals, n may also act as a ligand connecting the metal and the metal; p is an integer of 0 to 60, and when p is 2 or more, each X may be the same or different from each other, where n and p are not simultaneously 0). The metal M constituting the organometallic compound is a metal selected from the group consisting of Co, Ag, Au, Cu, Pd, Ni and Pt; L is a ligand bound to a metal, and is a compound consisting of up to 20 carbons containing major atoms such as N, P, As, O, S, Se, Te; X is a non-coordinating or coordinated to the metal atom, halogen, hydroxy, cyano (CN ^-), nitro (NO ₂ ^-), nitrate (NO ₃ ^-), nitroxyl, azide (N ₃ ^-), thio Cyanato, isothiocyanato, tetraalkylborate (BR ₄ ⁻ , wherein R is Me, Et or Ph), tetrahaloborate (BX ₄ ⁻ , wherein X is F or Br), hexafluorophosphate (PF ₆ ^-), triflate (CF ₃ SO ₃ ^-), tosylate (Ts ^-), sulfate (SO ₄ ^2-) and a carbonate or 1, selected from the group consisting of (CO ₃ ^2-) A method for forming a wiring of a high conductivity metal, which is an organometallic compound which is two or more anions. The method of claim 3, wherein in the oxidation reaction, an organic or inorganic oxidant is used, and in the reduction reaction, hydrazines; Silanes; Using organic reducing agents of amines or derivatives thereof, or metal hydrides A method for forming wiring of a high conductivity metal, characterized by using an inorganic reducing agent of (metal hydride). The method of claim 3, wherein the pattern formed after the oxidation or reduction reaction is annealed at 30 to 1000 ° C. for 1 minute to 1 hour. The method according to claim 1 or 2, wherein the pattern formation in step (iii) uses an elastomeric PDMS (polydimethylsilane) as a mold or a stamp and contains a metal of palladium, silver, or platinum. After organometallic compound solution is injected into the mold or applied to the stamp, it is transferred to a predetermined substrate to form a pattern, and then the organic component is volatilized by applying ultraviolet rays or heat, or heated at a high temperature under nitrogen and hydrogen gas atmosphere to obtain a desired pattern. A wiring formation method of a high conductivity metal, characterized in that the wiring pattern is formed by converting the metal or metal oxide. The radioactive cell of claim 1 or 2, wherein the metal crystal growth of (ii) comprises 1) a metal salt, 2) reducing agent, 3) complexing agent, 4) pH adjusting agent, 5) pH buffer, and 6) improving agent. A high-conductivity metal wiring formation method using a plating solution. The electrolytic solution according to claim 1 or 2, wherein the metal crystal growth of (ii) comprises an electroplating solution consisting of 1) a metal salt, 2) a complexing agent, 3) a pH adjusting agent, 4) a pH buffer, and 5) an improving agent. And a high-conductivity metal wiring formation method. The process of claim 2 wherein the substitution with another metal is carried out using a composition comprising 1) a metal salt, 2) reducing agent, 3) inhibitor, 4) surfactant, 5) pH buffer, 6) metal coordination compound. A wiring formation method of a high conductivity metal, characterized in that the step of performing. A liquid crystal display device having the high conductivity metal wiring formed by the above-mentioned 1 or 2.