KR102021424B1 - Composition for forming copper film, method for forming copper film, the copper film, wiring board, and electronic device - Google Patents

Abstract

(Problem) Provided is a composition for forming a copper film which can easily form a low resistance copper film, and a copper film forming method using the same, to provide a copper film, a wiring board, and a touch panel.
(Measures) The composition for copper film formation used for formation of a copper film is at least 1 sort (s) of copper compound chosen from the group which consists of (A) organic acid copper, copper hydroxide, and copper oxide, (B) halogen compound, and (C) It is prepared by containing a reducing agent. A coating film is formed on a board | substrate using this composition for copper film formation, it heats at 200 degrees C or less, a copper film is formed on a board | substrate, and a wiring board is manufactured. Moreover, using the composition for copper film formation, a coating film is formed on the transparent substrate 22 in which the 1st detection electrode 23, the 2nd detection electrode 24, etc. were formed, and the coating film is heated and the lead-out wiring 31 ), And the touch panel 21 is manufactured.

Description

Copper film forming composition, copper film forming method, copper film, wiring board and electronic device {COMPOSITION FOR FORMING COPPER FILM, METHOD FOR FORMING COPPER FILM, THE COPPER FILM, WIRING BOARD, AND ELECTRONIC DEVICE}

The present invention relates to a composition for forming a copper film, a method for forming a copper film, a copper film, a wiring board, and an electronic device.

Wiring boards are also called printed wiring boards and the like, and have become major components for fixing and wiring electronic components in the field of electronic devices. In this wiring board, a patterned metal film is formed on the board and constitutes a wiring, an electrode, a terminal, and the like. In the field of electronic devices, like a printed wiring board, a patterned metal film is formed on a board | substrate, and it uses as a wiring etc., and there exist a touch panel, a liquid crystal display element, an organic EL element, etc.

In manufacturing a wiring board, as a method of forming a pattern such as a wiring which is a metal film on the substrate, for example, a method using a photolithography technique is known. In this method, a homogeneous flat metal film is first formed on a substrate. As a metal film formation method, the plating method is used suitably. Moreover, the vapor deposition method, sputtering method, etc. can also be utilized. Then, a resist liquid is applied on the formed metal film to form a resist layer. Next, the resist layer is irradiated with ultraviolet rays using a photomask, and then developed to pattern the resist layer. Subsequently, the metal film which is not covered by the resist layer is etched and removed, and the remaining resist part is peeled off to obtain a patterned metal film. The method using the photolithography technique can also make the line width of the wiring pattern formed into a submicron order, and becomes the effective method of forming the pattern of a metal film.

In the method using such a photolithography technique, although the plating method is suitably used for formation of the metal film patterned as mentioned above, in the plating method, formation of the seed layer by a sputtering method and plating process are usually required. Since the sputtering method needs to be performed in a vacuum, the apparatus and the operational limitation are large. In addition, the process requires a long time and the production efficiency is low. In the plating treatment, the waste liquid treatment of the plating liquid becomes a big problem in the environment.

Similarly, even when a vapor deposition method, a sputtering method, or the like is used for the formation of the metal film, since the metal film must be formed in a vacuum, the device and the operational constraints are large, and a long time is required for processing, and the metal film can be efficiently formed. Can't.

Therefore, there is a need for a metal film forming technology that can be easily formed with a low resistance metal film in a short time due to few restrictions on the device and the environment. The metal film forming technique is a technique capable of forming a uniform flat metal film on the substrate, and preferably a patterned metal film.

In recent years, the technique which draws the patterned metal film directly using the dispersion obtained by disperse | distributing metal microparticles | fine-particles to an organic solvent etc. is attracting attention. For example, a desired pattern is formed by inkjet printing or screen printing using a dispersion of metal fine particles. When the average particle diameter of the metal fine particles is about several nm to about 10 nm, the melting point is lower than that of the bulk metal, and fusion of the particles occurs by relatively low temperature heating at about 300 ° C. The above-described technique is a technique of utilizing this phenomenon to obtain a patterned metal film by sintering metal fine particles at a relatively low temperature.

As a dispersion composition for forming such a metal film, what contains silver nanoparticles etc. which are noble metal microparticles | fine-particles etc. in a metal microparticle is known.

Moreover, the method of using metal salt etc. as a raw material of metal instead of a metal microparticle is attracting attention as a technique of forming a new metal film. For example, a method of preparing a composition by combining a readily available copper salt and a reducing agent, and forming a copper film using the composition is known.

Specifically, in the techniques disclosed in Patent Literature 1 and Patent Literature 2, production of fine-grained copper particles is realized by combining copper formate and an amine as raw materials. Then, the prepared particulate copper particles are dispersed to prepare an ink. Subsequently, an ink containing the particulate copper particles is applied, and the coating film is baked at 300 ° C. under an argon atmosphere to form a line-shaped copper wiring.

Moreover, in patent document 3, copper film formation is implement | achieved by the composition which combined the copper salt and amine. In patent document 4, copper film formation is implement | achieved by the composition which combined copper formate and an amine. In patent document 5, it implements by the composition which combined copper formate and alkanolamine.

And in patent document 6 and patent document 7, copper film formation is implement | achieved by the composition containing a noble metal microparticle, a copper salt, a reducing agent, and a monoamine.

Japanese Laid-Open Patent Publication No. 2008-13466 Japanese Laid-Open Patent Publication No. 2008-31104 Japanese Laid-Open Patent Publication No. 2004-162110 Japanese Laid-Open Patent Publication 2005-2471 Japanese Laid-Open Patent Publication No. 2010-242118 Japanese Laid-Open Patent Publication No. 2011-34749 Japanese Laid-Open Patent Publication No. 2011-34750

As mentioned above, for example, in order to be suitable for providing a wiring board, the metal film formation technique which can form a low resistance metal film easily in a short time is calculated | required. The metal film forming technique is a technique capable of forming a uniform metal film on one surface of the substrate, and is also a technique capable of directly forming a metal film patterned into a desired shape. Therefore, as mentioned above, examination is actively performed about the composition containing metal microparticles | fine-particles, a metal salt, etc. However, each technique has a problem to be solved.

Specifically, in the technique of forming a metal film using a composition containing metal fine particles, it was difficult to fuse the metal fine particles completely by simple sintering at low temperature. Therefore, in the metal film obtained after sintering, there existed a problem that electrical resistance characteristic, ie, low resistance, when compared with a bulk metal was not implementable.

In addition, in the case of the technique using the dispersion composition containing the above-mentioned silver nanoparticles, etc., there exists a problem that silver is easy to produce electromigration. In addition, silver is a precious metal and becomes expensive material compared with copper etc. which are easy to obtain. Therefore, there is a problem that the silver nanoparticles themselves are expensive and cause high cost of the metal film forming process. Electromigration is a phenomenon in which a metal component (for example, a metal such as silver used for wiring or an electrode) moves across or inside a nonmetallic medium (for example, an insulator, in particular, a substrate, etc.) under the influence of an electric field. to be.

Therefore, as mentioned above, the technique of forming a metal film using a metal salt etc. as a raw material instead of a metal fine particle attracts attention. In particular, the technique of using copper compounds, such as a copper salt, which is easy to obtain and has little concern of electromigration as a raw material is expected. However, the method using such an easy-to-use copper salt as a raw material was also not easy to form a low resistance copper film by simple heating at low temperature.

For example, although the formation of the copper wiring using copper formate and an amine is described in the above-mentioned patent document 1 and patent document 2, it is not described how much low resistance the formed copper wiring implement | achieves.

In addition, although the formation of the copper film by the composition which combined copper salt and an amine is described in patent document 3 mentioned above, it is not described whether the copper film formed is low resistance. Similarly, in patent document 4, although formation of the copper film by the composition which combined copper formate and an amine is described, it does not describe whether the copper film formed is low resistance.

Further, in Patent Document 6 and Patent Document 7, a combination of noble metal fine particles and a copper salt is realized, and the formation of a copper film is further realized by a composition containing a reducing agent and a monoamine, but expensive noble metal fine particles or noble metal compounds are essential components. This results in an increase in raw material cost, and a copper film cannot be easily formed with high productivity.

In addition, in the technique of the dispersion composition using the above-mentioned metal fine particles, or the technique of the composition using a metal salt, after forming these coating films, heating in a non-oxidizing atmosphere using a reducing gas such as hydrogen gas is required, for example. There were many cases. Therefore, in many cases, metal films, such as a copper film, cannot be formed simply by high productivity.

As described above, for example, in order to be suitable for providing a wiring board, the metal film forming technology is required to be simple and to reduce the resistance of the metal film to be formed. .

Therefore, the metal film formation method which can form the low-resistance metal film easily by the low temperature heating by using a reducing atmosphere using reducing gas, such as hydrogen gas, is calculated | required. That is, it is possible to use the raw material of copper compounds, such as a copper salt, which is easy to obtain, and it becomes unnecessary in the reducing atmosphere using reducing gas, such as hydrogen gas at the time of heating, and forms a low resistance copper film easily at low temperature. There is a demand for a method of forming a copper film.

And the composition for copper film formation suitable for this copper film formation method is calculated | required.

This invention is made | formed based on the above knowledge. That is, an object of the present invention is to provide a composition for forming a copper film which can easily form a low resistance copper film.

Moreover, the objective of this invention is providing the copper film formation method which can form a low resistance copper film easily using the above-mentioned composition for copper film formation.

An object of the present invention is to provide a wiring board having the copper film while providing a low resistance copper film using the above-described copper film forming method.

And an object of this invention is to provide the electronic device provided with the touchscreen which has the low resistance copper film formed using the copper film formation method mentioned above.

Other objects and advantages of the present invention will become apparent from the following description.

The first aspect of the present invention,

(A) at least one copper compound selected from the group consisting of organic acid copper, copper hydroxide and copper oxide,

(B) a halogen compound, and

(C) reducing agent

It relates to a composition for forming a copper film comprising a.

In the 1st aspect of this invention, the copper compound of (A) component is copper formate, copper acetate, copper propionate, copper butyrate, copper valeric acid, caproic acid copper, lactic acid copper, malic acid, copper citrate, copper benzoate, It is preferable that it is at least 1 sort (s) chosen from the group which consists of copper phthalate, copper salicylate, copper cinnamic acid, copper oxalate, copper malonate, copper succinate, copper hydroxide and copper oxide, and those hydrates.

In the first aspect of the present invention, the halogen compound of component (B) is lithium, sodium, potassium, rubidium, cesium, calcium, magnesium, strontium, barium, radium, chromium, manganese, iron, cobalt, nickel, copper, At least one selected from the group consisting of halides of at least one metal selected from the group consisting of zinc, ruthenium, rhodium, palladium, silver, gold and platinum, hydrogen halides, ammonium halides and halide hydrochloride salts of amines It is preferable that it is 1 type.

It is preferable that the reducing agent of (C) component is at least 1 sort (s) chosen from the group which consists of an amine, reducible carboxylic acid, its salt, its ester, polyhydric alcohol, and an aldehyde.

In the 1st aspect of this invention, it is preferable that content of the halogen containing compound of (B) component is 0.00001 mass%-20 mass% of all components.

In the first aspect of the present invention, the amine compound of the component (C) is preferably alkylamines, alkoxyalkylamines or alkanolamines, and particularly preferably a primary amine having a hydrocarbon group having 3 to 12 carbon atoms.

The 2nd aspect of this invention is a process of forming the coating film of the composition for copper film formation of the 1st aspect of this invention on a board | substrate,

(2) It is related with the copper film formation method characterized by having the process of heating the coating film.

The 3rd aspect of this invention is formed by the copper film formation method of the 2nd aspect of this invention, It is related with the copper film characterized by the above-mentioned.

In the 3rd aspect of this invention, it is preferable to have a halogen atom.

In the 3rd aspect of this invention, it is preferable that the content rate of the halogen atom when the copper atom in a film | membrane is set to 100 is 0.001-10.

The 4th aspect of this invention has a copper film of the 3rd aspect of this invention, It is related with the wiring board characterized by the above-mentioned.

The 5th aspect of this invention is related with the electronic device characterized by including the touch panel which has the copper film of the 3rd aspect of this invention.

According to the 1st aspect of this invention, the composition for copper film formation which can form a low resistance copper film easily is provided.

According to the 2nd aspect of this invention, the copper film formation method which can form a low resistance copper film easily is provided.

According to the 3rd aspect of this invention, it forms simply and a copper film of low resistance is provided.

According to the 4th aspect of this invention, the wiring board which is formed easily and has a low resistance copper film is provided.

According to the 5th aspect of this invention, the electronic device provided with the touch panel which is simply formed and has a low resistance copper film is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a top view which shows the touch panel of embodiment of this invention.
FIG. 2 is a cross-sectional view taken along line BB ′ of FIG. 1.

(Form to carry out invention)

In the present invention, as a raw material of the copper film, using a copper compound such as readily available organic acid copper, copper hydroxide and copper oxide, a composition for forming a copper film together with a halogen compound and a reducing agent for reducing the copper film formation To prepare. And the composition for copper film formation is apply | coated on a board | substrate, for example, a coating film is formed, and this coating film is heated and a copper film is formed.

At this time, the composition for copper film formation of this invention can form a flat plate-shaped metal film on a board | substrate, and combines with a suitable coating method, and the patterned copper film which becomes wiring, an electrode, a terminal, etc. directly on a board | substrate It is also possible to form. Therefore, in the present invention, the "copper film" is a concept including a patterned copper film together with a flat film made of copper. That is, patterns, such as a copper wiring and a copper electrode, are also contained in the "copper film" of this invention. Similarly, the "film" may be used as a concept including a pattern.

In addition, in this invention, a "wiring board | substrate" is not limited only to the wiring board known as a so-called printed wiring board mentioned above. In the present invention, the "wiring substrate" includes a substrate on which a patterned metal film is formed on the substrate and constitutes wiring, electrodes, terminals, and the like. For example, in the present invention, the "wiring substrate" is a substrate for constituting a touch panel, a liquid crystal display element, an organic EL element, etc., in addition to the above-described printed wiring board, and a patterned metal film is formed on the substrate, The board | substrate which comprises wiring, an electrode, a terminal, etc. is contained.

In addition, in this invention, the electrically conductive member called electroconductivity called wiring, an electrode, a terminal, etc. which a wiring board has are hereafter generically called wiring.

Hereinafter, the composition for copper film formation of embodiment of this invention is demonstrated in detail. Then, the copper film formation method of embodiment of this invention using the preparation of the composition for copper film formation of embodiment of this invention, and the composition for copper film formation of embodiment of this invention is demonstrated.

<Composition for Copper Film Formation>

The composition for copper film formation of embodiment of this invention is a composition containing at least 1 sort (s) chosen from the group which consists of organic acid copper, copper hydroxide, and copper oxide as a copper compound, and also contains a halogen compound and a reducing agent, and is reduced It is a composition for forming a reactive copper film. In addition, the composition for copper film formation of this embodiment can contain a solvent further. In addition, the composition for copper film formation of this embodiment can contain other arbitrary components other than a metal fine particle further. And the composition for copper film formation of this embodiment can form the coating film patterned by various well-known coating methods, and this coating film can be heated and can form a copper film.

Under the present circumstances, the composition for copper film formation of embodiment of this invention has the composition mentioned above, and after apply | coating on a suitable board | substrate to form a coating film, it is convenient, for example, in non-oxidizing atmosphere, such as nitrogen gas, or under air | atmosphere. By heating in the same oxidizing atmosphere, the copper film of embodiment of this invention can be formed on a board | substrate. And as temperature of heating, it is possible to set it as 200 degrees C or less which becomes low temperature compared with the prior art.

Therefore, in the composition for copper film formation of embodiment of this invention, it is not necessary to form especially in the reducing atmosphere using reducing gas, such as hydrogen gas, and is excellent in resistance characteristics by comparatively low temperature heating in a simple and safe state. A copper film can be formed.

Hereinafter, each component of the composition for copper film formation of this embodiment is demonstrated.

[Copper Compound]

The copper compound contained in the composition for copper film formation of embodiment of this invention is at least 1 sort (s) of copper compound chosen from the group which consists of organic acid copper, copper hydroxide, and copper oxide.

As organic acid copper which can be contained in the composition for copper film formation of this embodiment, copper formate, copper acetate, copper propionate, copper butyrate, copper valeric acid, caproic acid copper, lactic acid copper, malic acid, copper citrate, copper benzoate, copper phthalate Copper salicylate, copper cinnamic acid, copper oxalate, copper malonic acid, copper succinate, copper hydroxide and copper oxide, and hydrates thereof.

Further, the copper hydroxide as possible contained in the composition for a copper film formed according to one embodiment of the invention, the compounds mainly composed of _{Cu (OH) 2, 1~2CuCO 3} · can be represented by Cu (OH) _2. Copper hydroxide is heated to become copper oxide, and the copper oxide is reduced to form metallic copper, that is, a copper film. Copper hydroxide is easy to obtain, and a commercial item can be used, for example. However, in embodiment of this invention, it does not specifically limit about the obtaining method of copper hydroxide.

In addition, the copper oxide contained in the copper film-forming composition of the present embodiment is an oxide of a divalent copper oxide represented by the one or CuO of monovalent copper into Cu ₂ O appears. Copper oxide is reduced to form metallic copper, that is, a copper film. Copper oxide is easy to obtain, and a commercial item can be used, for example. However, in embodiment of this invention, it does not specifically limit about the acquisition method etc. of copper oxide.

Copper compounds, such as organic acid copper, copper hydroxide, and copper oxide shown above, are easy to obtain and can use a commercial item, for example. However, in embodiment of this invention, it does not specifically limit about the acquisition method etc. of a copper compound.

In addition, it does not specifically limit about the purity of copper compounds, such as organic acid copper, copper hydroxide, and copper oxide. However, if it is low purity, when forming a copper film as an electroconductive low resistance film | membrane, there exists a possibility that electroconductivity may fall. Therefore, 90% or more is preferable and, as for the purity of a copper compound, 95% or more is more preferable.

As content of the copper compound in the composition for copper film formation of this embodiment, 1 mass%-70 mass% are preferable with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains, and 5 mass % -50 mass% is more preferable. By making content of a copper compound into 1 mass%-70 mass%, the copper film which has the outstanding electroconductivity can be formed. By making content of a copper compound into 5 mass%-50 mass%, the copper film of a lower resistance value can be formed.

[Halogen Compound]

The halogen-containing compound contained in the composition for copper film formation of this embodiment is a component which shows the effect of reducing the resistance value of the copper film formed, and copper film formation of this embodiment which forms a low resistance copper film easily at low temperature. It becomes the characteristic component of the composition for. Regarding the action of the halogen-containing compound, when the copper compound contained in the composition for forming a copper film of the present embodiment is reduced to form metallic copper, it can be considered to promote fusion of the copper fine particles and to help form a dense copper film. have.

Examples of the halogen compound include halides of hydrogen halides, metal halides, ammonium halides, and amines.

Specific examples of the hydrogen halide include hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydrogen iodide.

As metal halides, lithium, sodium, potassium, rubidium, cesium, calcium, magnesium, strontium, barium, radium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, gold and platinum Halides may be mentioned.

Examples of the ammonium halides include halides of quaternary ammonium cations.

As a halogenated hydrochloride of amines, the halogenated hydrochloride of ammonia, an organic monoamine compound, an organic diamine compound, and an organic triamine compound can be mentioned.

More specifically, the following compounds are mentioned as a metal halide compound contained in the composition for copper film formation of this embodiment.

Examples of the metal halide include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, calcium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, radium fluoride, chromium fluoride, manganese fluoride, ferrous fluoride, Ferric fluoride, cobalt fluoride, nickel fluoride, cuprous fluoride, cupric fluoride, zinc fluoride, ruthenium fluoride, rhodium fluoride, palladium fluoride, silver fluoride, gold fluoride, platinum fluoride, lithium chloride, sodium chloride, potassium chloride , Rubidium chloride, cesium chloride, calcium chloride, magnesium chloride, strontium chloride, barium chloride, radium chloride, chromium chloride, manganese chloride, ferrous chloride, ferric chloride, cobalt chloride, nickel chloride, cuprous chloride, chloride Cuprous chloride, zinc chloride, ruthenium chloride, rhodium chloride, palladium chloride, silver chloride, gold chloride, platinum chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, calcium bromide, helium bromide Nesium, strontium bromide, barium bromide, radium bromide, chromium bromide, manganese bromide, ferrous bromide, ferric bromide, cobalt bromide, nickel bromide, cuprous bromide, cupric bromide, zinc bromide, ruthenium bromide, brominated Rhodium, palladium bromide, silver bromide, gold bromide, platinum bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, calcium iodide, magnesium iodide, strontium iodide, barium iodide, chromium iodide, manganese iodide, manganese iodide Ferrous iodide, ferric iodide, cobalt iodide, nickel iodide, cuprous iodide, cuprous iodide, zinc iodide, ruthenium iodide, rhodium iodide, palladium iodide, silver iodide, gold iodide, platinum iodide, etc. have.

The metal halide mentioned above may be anhydride or hydrate.

As a halogenated quaternary ammonium salt, the following compounds are mentioned specifically ,.

For example, tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, chloride Tetrapropylammonium, tetrapropylammonium bromide, tetrapropylammonium iodide, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-sec fluoride -Butylammonium, tetra-sec-butylammonium chloride, tetra-sec-butylammonium bromide, tetra-sec-butylammonium iodide, tetra-t-butylammonium fluoride, tetra-t-butylammonium chloride, tetra-t-butyl bromide Ammonium, iodide tetra-t-butylammonium, etc. are mentioned.

Specific examples of the halogenated hydrochloride of ammonia include the following compounds.

For example, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, etc. are mentioned.

Specific examples of the halogenated hydrochloride of the monoamine compound include the following compounds.

For example, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine , n-octylamine, 2-ethylhexylamine, 2-ethylhexylpropylamine, 3-ethoxypropylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n- Hydrofluoric acid salts such as tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzylamine, aminoacetoaldehyde diethyl acetal, hydrochloride, bromide hydrochloride, and iodide hydrochloride. have.

Specific examples of the halogenated hydrochloride of the diamine compound include the following compounds.

For example, ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N-ethylethylenediamine, N, N'-diethyl Ethylenediamine, 1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N'-dimethyl-1,4-butanediamine, 1,5-pentane Hydrofluoric acid salts, hydrochloride, hydrogen bromide, such as diamine, N, N'-dimethyl-1,5-pentanediamine, 1,6-hexanediamine, N, N'-dimethyl-1,6-hexanediamine, and isophoronediamine Acid salts, hydroiodic acid salts and the like.

Specific examples of the halogenated hydrochloride of the triamine compound include the following compounds.

For example, hydrogen fluorides such as diethylenetriamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N- (aminoethyl) piperazine, and N- (aminopropyl) piperazine Acid salts, hydrochlorides, hydrobromide salts, hydroiodic salts and the like.

Among these, chlorine-containing compounds which are particularly effective for promoting the formation of a copper film are preferable, and hydrochloric acid, metal chlorides and hydrates thereof, and hydrochlorides of amines are more preferable. Specifically, hydrochloric acid, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, nickel chloride, cuprous chloride, cupric chloride, ferric chloride, ferric chloride, cobalt chloride, tetramethylammonium chloride, chloride Tetraethylammonium chloride, tetra-n-butylammonium chloride, n-propylamine hydrochloride, n-hexylamine hydrochloride, n-heptylamine hydrochloride, n-octylamine hydrochloride, 2-ethylhexylamine hydrochloride, aminoacetoaldehyde diethylacetal hydrochloride This is preferred.

It is preferable to use these halogen compounds in combination of 1 type, or 2 or more types chosen from the group which consists of a halogen compound mentioned above. In addition, a halogen-containing compound can use a commercial item, and there is no restriction | limiting in particular about the acquisition method.

The purity of the halogen-containing compound contained in the composition for forming a copper film of the present embodiment is not particularly limited. However, if it is low purity, when forming a copper film as a conductive thin film, there exists a possibility that electroconductivity may fall. Therefore, the purity of the halogen-containing compound is preferably 90% or more, and more preferably 95% or more.

As content of the halogen containing compound in the composition for copper film formation of this embodiment, it is 0.00001 mass%-20 mass% with respect to 100 mass% of all the components contained in the composition for copper film formation of this embodiment, Preferably 0.00005 mass%-10 mass%, More preferably, they are 0.0001 mass%-5 mass%. By making content of a halogen containing compound into the above-mentioned range, the low resistance copper film which has the outstanding electroconductivity can be formed.

[reducing agent]

The reducing agent contained in the composition for copper film formation of this embodiment is a component which produces the reduction for copper film formation.

Examples of the reducing agent include an amine compound, a reducing carbonic acid, a salt of the reducing carbonic acid, an ester of the reducing carbonic acid, a polyhydric alcohol, and an aldehyde.

The amine compound which the composition for copper film formation of this embodiment contains is following General formula (1), following General formula (2), following General formula (3), ethylenediamine, N-methylethylenediamine, N, N ' -Dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N-ethylethylenediamine, N, N'-diethylethylenediamine, 1,3-propanediamine, N, N'-dimethyl- 1,3-propanediamine, 1,4-butanediamine, N, N'-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N'-dimethyl-1,5-pentanediamine, 1 Diamine compounds such as, 6-hexanediamine, N, N'-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ', N ", N" -pentamethyldiethylene It is an amine compound represented by at least 1 general formula among triamine compounds, such as triamine, N- (aminoethyl) piperazine, and N- (aminopropyl) piperazine.

In said general formula (1), R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C18 alkyl group, a C3-C18 alicyclic hydrocarbon group, or a C6-C18 aromatic hydrocarbon group. R <^3> represents a single bond, a methylene group, a C2-C12 alkylene group, or a phenylene group. R <^4> represents a hydrogen atom, a C1-C36 alkyl group, or a C3-C18 alicyclic hydrocarbon group.

As a specific example of R <^1> , R <^2> and R <^4> which is group which the amine represented by the said General formula (1) has, as a linear alkyl group besides a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, cyclohexyl group, benzyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, tetradecyl group, A pentadecyl group, a hexadecyl group, a tridecyl group, etc. are mentioned, As a cycloaliphatic hydrocarbon group, a cyclohexyl group and a cyclopentyl group are mentioned.

In said general formula (2), R <^5> and R <^6> respectively independently represents a hydrogen atom, a C1-C18 alkyl group, or a C3-C18 alicyclic hydrocarbon group. R <^7> represents a methylene group, a C2-C12 alkylene group, or a phenylene group. R <^8> represents a C1-C18 alkyl group or a C3-C18 alicyclic hydrocarbon group.

As an example of R <^5> and R <^6> which is group which the amine represented by the said General formula (2) contains, as a linear alkyl group besides a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neo Pentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, As an alicyclic hydrocarbon group, a cyclohexyl group is mentioned. And cyclopentyl group.

And as an example of R <^8> which is group which the amine represented by the said General formula (2) contains, as a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group , Decyl group, undecyl group, dodecyl group, stearyl group and the like, and are branched, and isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, tert- Pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,3-dimethyl A butyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, As an alicyclic hydrocarbon group, a cyclohexyl group and a cyclopentyl group are mentioned. Can be.

In said general formula (3), R <^9> and R <^10> respectively independently represents a hydrogen atom, a C1-C18 alkyl group, or a C3-C18 alicyclic hydrocarbon group. R <^11> represents a methylene group, a C2-C12 alkylene group, or a phenylene group. R ¹² and R ¹³ each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

Examples of the groups R ⁹ and R ¹⁰ included in the amine represented by the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, In addition to an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc., 2, 2- dimethoxy ethyl group is mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert- butyl group, Isopentyl, neopentyl, tert-pentyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,1,2-trimethylpropyl, 1,2,2 -Trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, and an alicyclic hydrocarbon group is mentioned. Examples of the cyclohexyl group include cyclohexyl group and cyclopentyl group.

In addition, the formula group containing an amine represented by (3) As examples of R ¹² and R ^13, an alkyl group of a straight chain, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, hexyl group, heptyl group, octyl group And 2,2-dimethoxyethyl groups, in addition to nonyl, decyl, undecyl and dodecyl groups, and are branched, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group and isopene. Methyl, neopentyl, tert-pentyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,1,2-trimethylpropyl, 1,2,2-trimethyl Propyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, As an alicyclic hydrocarbon group, A cyclohexyl group and a cyclopentyl group are mentioned.

As a preferable amine compound which the composition for copper film formation of this embodiment contains, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decyl Amine, undecylamine, dodecylamine, stearylamine, isopropylamine, sec-butylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, tert-pentylamine, 1-ethylpropylamine , 1,1-dimethylpropylamine, 1,2-dimethylpropylamine, 1,1,2-trimethylpropylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylbutylamine, neopentylamine, 1 , 5-dimethylhexylamine, 2-ethylhexylamine, 4-heptylamine, 2-heptylamine, cyclohexylamine, cyclopentylamine, benzylamine, 2-ethylhexylamine, n-tridecylamine, n-tetradecyl An amine, n-pentadecylamine, n-hexadecylamine, etc. are mentioned.

Moreover, as another preferable amine compound which the composition for copper film formation of this embodiment contains, for example, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, Ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, isopropoxypropylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine , Butoxypropylamine, (ethylhexyloxy) propylamine, isobutoxypropylamine, butoxybutylamine, oxybis (ethylamine), aminoacetoaldehyde diethyl acetal, and the like.

And it is more preferable that the amine compound which the composition for copper film formation of this embodiment contains is a primary amine which has a C4-C12 hydrocarbon group.

As a more preferable amine compound which the composition for copper film formation of this embodiment contains, for example, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodec Silamine, stearylamine, sec-butylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, tert-pentylamine, 1-ethylpropylamine, 1,1-dimethylpropylamine, 1, 2-dimethylpropylamine, 1,1,2-trimethylpropylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylbutylamine, neopentylamine, 1,5-dimethylhexylamine, 2-ethylhexyl Amine, 4-heptylamine, 2-heptylamine, cyclohexylamine, cyclopentylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, (ethylhexyloxy) propylamine, isobu Oxypropylamine, butoxybutylamine, oxybis (ethylamine), aminoacetoaldehyde diethyla There may be mentioned, such as deionized.

In addition, the reducing carbonic acid which can be contained in the composition for copper film formation of this embodiment is the carbonic acid which can have reducibility with respect to organic acid copper, copper hydroxide, and copper oxide. The reducing carbonic acid is not particularly limited as long as it can show reducibility with respect to organic acid copper, copper hydroxide and copper oxide, but for example, formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, and Citric acid and the like.

Moreover, as a polyhydric alcohol, diols are mentioned, for example, More specifically, ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2, 3-butanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 3,4-hexanediol, 3,4-heptanediol, 3,4-octanediol, 3,4- Nonanediol, 3,4-decanediol, 4,5-octanediol, 4,5-nonanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino-1,2 -Propanediol, 3-N, N-diethylamino-1,2-propanediol, 3-N, N-di-n-propylamino-1,2-propanediol, 3-N, N-di-i -Propylamino-1,2-propanediol, 3-N, N-di-n-butylamino-1,2-propanediol, 3-N, N-di-i-butylamino-1,2-propanediol And 3-N, N-di-t-butylamino-1,2-propanediol.

Examples of the polyhydric alcohols include diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, and the like, in addition to the diols described above. Glycerin is mentioned as an especially preferable polyhydric alcohol.

As aldehydes, paraaldehyde, para-tolualdehyde, glyoxylic acid, n-pentanal, i-pentanal, t-pentanal, n-hexanal, n-heptanal, cyclohexanecarboaldehyde, n Octanal, 2-ethylhexanal, n-nonanal, glutaraldehyde, cinnamic aldehyde, perylaldehyde, 2,6-dimethylbenzaldehyde, para-acetoxybenzaldehyde, 4-pyridinecarboxyaldehyde, benzaldehyde, 4 -Methylbenzaldehyde, adialdehyde, fimelaldehyde, submeraldehyde, azelaaldehyde, sebacaldehyde, isophthalaldehyde, terephthalaldehyde and the like.

In the composition for copper film formation of this embodiment, it is preferable to use combining the 1 type selected from the group which consists of a reducing agent demonstrated above, or 2 or more types compatible with each other. It does not specifically limit about the acquisition method etc. of these reducing agents. About what can obtain a commercial item among the reducing agents, use of a commercial item is possible.

The purity of the reducing agent is not particularly limited, but considering the use of the copper film-forming composition of the present embodiment in the field of electronic materials, 95% or more is preferable, and 99% or more is further reduced to reduce impurities. desirable.

As content of the reducing agent in the composition for copper film formation of this embodiment, 10 mass%-99 mass% are preferable with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains, 20 Mass%-90 mass% are more preferable. By making content of a reducing agent into 10 mass%-99 mass%, the copper film which has the outstanding electroconductivity can be formed. By making content of a reducing agent into 20 mass%-90 mass%, the copper film of a lower resistance value can be formed.

[solvent]

In the composition for copper film formation of this embodiment, it is possible to add a solvent as a component. By adding a solvent and containing it in the composition for copper film formation, viscosity adjustment of the composition for copper film formation corresponding to the coating method becomes easy, and it becomes possible to form a stable copper film of uniform physical properties.

As a solvent to add, it is a thing which can melt | dissolve or disperse each component in the composition for copper film formation, and if it does not participate in the reduction reaction of organic acid copper, copper hydroxide, and copper oxide, it will not specifically limit. For example, 1 type of liquid chosen from water, alcohols, ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons, or 2 or more types of liquids compatible are mentioned.

Specific examples of the solvent include alcohols such as methanol, ethanol, n-propyl alcohol (1-propanol), i-propyl alcohol, n-butyl alcohol (1-butanol), i-butyl alcohol, sec-butyl alcohol, Pentanol, hexanol, heptanol, octanol, nonyl alcohol, decanol, cyclohexanol, benzyl alcohol, terpineol, dihydroterpineol and the like.

Examples of the ethers include hexyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and propylene glycol monomethyl ether. , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di (Poly) alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like Can be mentioned.

As ester, methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, (gamma) -butyrolactone, etc. are mentioned, for example.

As aliphatic hydrocarbons, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, tetradecane, cyclohexane, decalin Etc. can be mentioned.

As aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene, etc. are mentioned, for example.

Among these organic solvents, ethers are preferable from the viewpoint of easy adjustment of the viscosity of the composition for forming a copper film.

The solvent contained in the composition for copper film formation of this embodiment is an arbitrary component, The content is the range of 0 mass%-95 mass% with respect to 100 mass% of all the components of the copper film formation composition of this embodiment, It is preferable that it is the range of 0 mass%-70 mass%, and it is more preferable that it is the range which is 0 mass%-50 mass%.

[Metal Fine Particles and Other Optional Components]

In addition to the above-mentioned copper compound, a halogen compound, and a reducing agent, the composition for copper film formation of this embodiment can contain metal microparticles, unless the effect of this invention is impaired. In addition, the composition for copper film formation of this embodiment can contain formic acid and / or ammonium formate as another arbitrary component, unless the effect of this invention is impaired, and also a dispersing agent and antioxidant It is possible to contain a density | concentration regulator, a surface tension regulator, a viscosity regulator, and a coating film formation auxiliary agent.

Although it does not specifically limit as a metal fine particle which can be contained in the composition for copper film formation of this embodiment, For example, at least 1 chosen from the group which consists of gold, silver, copper, platinum, ruthenium, rhodium, osmium, and palladium. It is preferable to contain metal species of species. These metal species may be single or an alloy with other metals. When these metal species are a single substance, as a preferable metal microparticle, at least 1 type, or 2 or more types selected from the group which consists of a gold fine particle, silver fine particle, copper fine particle, platinum fine particle, ruthenium fine particle, rhodium fine particle, osmium fine particle, and palladium fine particle is do.

Among these, it is preferable to contain at least 1 sort (s) of metal species chosen from the group which consists of silver, copper, and palladium from cost viewpoint, the availability, and the catalytic ability at the time of forming a copper film. Although metal microparticles other than these may be used, metal microparticles | fine-particles are oxidized by copper ion during copper film formation, a catalyst capability does not fall or express, and there exists a possibility that the reduction precipitation rate from a copper compound to metal copper may fall. Therefore, it is more preferable to use the metal microparticle mentioned above.

In the composition for copper film formation of this embodiment, it is preferable that the average particle diameter of a metal microparticle is a range of 0.005 micrometer-5 micrometers. When the particle diameter of the metal fine particles is less than 0.005 µm, the activity of the metal surface becomes very high, and there is a possibility that the metal reaction is dissolved in addition to generating an oxidation reaction. Moreover, when it exceeds 5 micrometers, metal fine particles may settle in the case of long-term storage. Therefore, it is preferable that the average particle diameter of a metal fine particle exists in the above-mentioned range.

In embodiment of this invention, as a measuring method of the particle diameter of a metal microparticle, the measuring method applied to a general microparticle can be used. For example, a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), etc. can be used suitably. The value of an average particle diameter is observed using the microscope mentioned above, and selects three places where particle diameters are comparatively uniform among the observed visual field, and image | photographs at the magnification most suitable for particle size measurement. From each obtained photograph, 100 particles which are considered to exist most are selected, the diameter is measured by a measuring instrument such as a ruler, the particle diameter is calculated by excluding a measurement magnification, and these values can be obtained by arithmetic average. have. In addition, about standard deviation, it can obtain | require by the particle diameter and number of individual metal microparticles | fine-particles at the time of the above-mentioned observation. And the variation coefficient can be calculated by the following formula based on the above-mentioned average particle diameter and its standard deviation.

Coefficient of variation = (standard deviation / volume average particle diameter) x 100 (%)

In the composition for forming a copper film of the present embodiment, the metal fine particles may be commercially available or may be synthesized by a known method, and are not particularly limited. As a known synthesis method, for example, a gas phase method (dry method) for performing a synthetic reaction by a physical method such as a sputtering method or a vapor deposition method in a gas, or reducing a metal compound solution in the presence of a surface protective agent to precipitate metal fine particles, etc. The liquid phase method (wet method) and the like are generally known.

Although the purity of metal fine particles is not specifically limited in the composition for copper film formation of this invention, when it is low purity, when it sets as a conductive thin film, since it may adversely affect electroconductivity, 95% or more is preferable, 99 % Or more is more preferable.

Although content of the metal microparticles | fine-particles in the composition for copper film formation of this embodiment does not have a restriction | limiting in particular, It is arbitrary components and 0 mass with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains. It is preferable that it is the range of% -50 mass%, and it is more preferable to set it as the range of 0 mass%-20 mass%. By making content of a metal fine particle into the above-mentioned range, although the improvement of the reduction precipitation rate from the above-mentioned copper compound to metal copper can be anticipated, when content of metal fine particles is added so that it exceeds 50 mass%, it is a thing of desired resistance characteristic. There is a possibility that a copper film cannot be formed.

Next, the composition for copper film formation of this embodiment contains formic acid and / or ammonium formate (henceforth a formic acid etc.) as other arbitrary components, unless the effect of this invention is impaired. can do. These formic acid etc. have the effect of promoting a reduction reaction in forming a copper film with the copper film formation composition of this embodiment, and can promote the formation of a copper film of desired resistance characteristics.

The formic acid and ammonium formate which can be contained in the composition for copper film formation of this embodiment can use a commercial item, and the acquisition method etc. are not specifically limited.

The purity of formic acid and ammonium formate contained in the composition for forming a copper film of the present embodiment is not particularly limited. However, if it is low purity, when forming a copper film as a conductive thin film, there exists a possibility that electroconductivity may fall. Therefore, 95% or more is preferable and, as for the purity of formic acid and ammonium formate, 99% or more is more preferable.

Although content, such as formic acid, in the composition for copper film formation of this embodiment does not have a restriction | limiting in particular, They are arbitrary components and with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains, It is preferable that it is the range of 0 mass%-50 mass%, and it is more preferable to set it as the range of 0 mass%-20 mass%. Even if content of other arbitrary components is added so that it exceeds 50 mass%, the effect similar to content is not acquired. Moreover, the formation amount of the metal copper per unit weight of the composition for copper film formation falls, and there exists a possibility that the copper film of a desired characteristic may not be formed with high manufacturing efficiency.

In addition, the composition for copper film formation of this embodiment can also contain components other than formic acid etc. which were mentioned above as other arbitrary components, unless the effect of this invention is impaired. About other arbitrary components other than formic acid etc. which can be contained in the composition for copper film formation of this embodiment, if it is equipped with desired characteristic and does not inhibit the formation reaction of the copper film by the above-mentioned copper compound, It is not limiting. For example, it is also possible to select from the organic solvent which each component mentioned above melt | dissolves and does not react, and to contain as other arbitrary components. And by adding this organic solvent, the composition for copper film formation can be prepared so that it may become desired density | concentration, surface tension, and a viscosity.

Although content of other arbitrary components other than formic acid etc. in the composition for copper film formation of this embodiment does not have a restriction | limiting in particular, They are arbitrary components and of all the components which the composition for copper film formation of this embodiment contains. It is preferable that it is the range of 0 mass%-50 mass% with respect to 100 mass%, and it is more preferable to set it as the range of 0 mass%-20 mass%. Even if content of other arbitrary components is added so that it exceeds 50 mass%, the effect by the other arbitrary components which correspond to content is not acquired. Moreover, the formation amount of the metal copper per unit weight of the composition for copper film formation falls, and there exists a possibility that the copper film of a desired characteristic may not be formed with high manufacturing efficiency.

<Preparation of the composition for forming a copper film>

[Method of Preparation]

The composition for copper film formation of this embodiment can be conveniently prepared and manufactured by mixing the above-mentioned copper compound, a halogen compound, and a reducing agent. The order of mixing is not particularly limited.

In preparation of the composition for copper film formation of this embodiment, it is possible to add a solvent as mentioned above. Addition of a solvent can be performed, for example after mixing the above-mentioned copper compound, a halogen compound, and a reducing agent. The solvent to be added is not particularly limited as long as it dissolves or disperses a copper compound, a halogen compound and a reducing agent as described above.

In preparation of the composition for copper film formation of this embodiment, in addition to the above-mentioned metal microparticles | fine-particles, formic acid, a dispersing agent, antioxidant, a concentration regulator, a surface tension regulator, a viscosity regulator, etc. which were mentioned above are added as other arbitrary components. Can be. Metal microparticles | fine-particles and other arbitrary components can be added, for example after mixing the above-mentioned copper compound, a halogen compound, and a reducing agent. And other arbitrary components, such as a dispersing agent, antioxidant, a concentration regulator, a surface tension regulator, and a viscosity regulator, are used with essential components, such as a copper compound mentioned above, and the component which the composition for copper film formation of this embodiment desires It can be adjusted to have concentration, surface tension, viscosity, and the like.

[Mixing method]

Although it does not specifically limit as a mixing method in preparation of the composition for copper film formation of this embodiment, For example, stirring by a stirring blade, stirring by a stirrer and a stirrer, stirring by a scourer, ultrasonic homogenizer The method using the analyzer, the bead mill, the paint shaker, the stirring defoaming apparatus, etc. are mentioned. As mixing conditions, for example, in the case of stirring by a stirring blade, the rotation speed of a stirring blade is a range of 1 rpm-4000 rpm normally, Preferably it is the range of 10 rpm-2000 rpm.

<Copper film forming method and copper film>

The composition for copper film formation of embodiment of this invention demonstrated above is apply | coated on a suitable suitable board | substrate, and forms the coating film of the composition for copper film formation of this embodiment. And the coating film of the composition for copper film formation of this embodiment is heated, and a copper film is formed on a board | substrate. That is, the copper film formation method of embodiment of this invention forms the copper film of embodiment of this invention using the composition for copper film formation of embodiment of this invention. As a result, the wiring board of embodiment of this invention can be manufactured using the copper film of embodiment of this invention.

Under the present circumstances, the copper film formation method of embodiment of this invention uses the composition for copper film formation of this embodiment, under the non-oxidizing atmosphere using inert gas, such as nitrogen gas, helium gas, and argon gas, and in oxidizing atmosphere. A copper film can be formed by heating. That is, the copper film formation method of embodiment of this invention does not need to form the reducing atmosphere using reducing gas, such as hydrogen gas, in particular, It is easy to carry out heating for copper film formation in a safe state, and forms a copper film. can do.

In the copper film formation method of embodiment of this invention, the copper compound contained in this composition is reduced, and metal copper is formed by heating the coating film of the composition for copper film formation of this embodiment apply | coated on the board | substrate. At the same time, the organic substances contained in the coating film are removed by decomposition and volatilization. Under the present circumstances, the halogen containing compound contained in the composition for copper film formation of this embodiment accelerates | stimulates a copper film formation reaction.

And it is preferable that the copper film of embodiment of this invention formed contains halogen (halogen atom) with a copper component, and is comprised. In the copper film of this embodiment, the content rate of the halogen atom when the copper atom in a film | membrane is set to 100 is 0.001-10, Preferably it is 0.002-8, More preferably, it is 0.003-5. The copper film of this embodiment contains a halogen atom in such a ratio. And the copper film of this embodiment can exhibit the outstanding resistance characteristic.

Therefore, the copper film formation method of embodiment of this invention is a process of (1) forming the coating film of the composition for copper film formation of embodiment of this invention which is a composition containing a copper compound, a halogen compound, and a reducing agent on a board | substrate. And (2) It is preferable to comprise including the process of heating the coating film on the board | substrate.

Hereinafter, the copper film formation method of embodiment of this invention is demonstrated in detail.

[Board]

In the copper film formation method of embodiment of this invention, a well-known thing can be used as a board | substrate which forms the coating film of the composition for copper film formation of this embodiment, It does not specifically limit.

As a material which comprises a board | substrate, resin, paper, a metal, glass, etc. are mentioned, for example, More specifically, a low density polyethylene resin, a high density polyethylene resin, and ABS resin (acrylonitrile butadiene styrene copolymerization synthetic resin) ), Acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate), polyacetal resin, cellulose derivatives Resin substrate, non-coated printing paper, micro-coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper (heavy use Paper substrates such as matte kraft paper, matte kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coat ball, chip ball corrugated paper, etc. There may be mentioned a plate, iron plate, an aluminum metal substrate of the plate or the like, soda glass, borosilicate glass, silica glass, a glass substrate such as quartz glass, alumina, sapphire, zirconia, titania, yttrium oxide, ITO (indium tin oxide) or the like.

[Application method]

As a coating method of the composition for copper film formation of this embodiment in the copper film formation method of embodiment of this invention, printing methods, such as inkjet printing, gravure printing, flexographic printing, (silk) screen printing, and convex printing, etc. And coating methods such as spin coating, spray coating, bar coating, casting, dip coating, and roll coating. As an application amount which apply | coats the composition for copper film formation of this embodiment to a board | substrate, it can adjust suitably according to the film thickness of a desired copper film.

The composition for copper film formation of this embodiment can be applied by the application | coating method mentioned above. Therefore, the copper film formation method of embodiment of this invention can form the flat film-like coating film on a board | substrate using the composition for copper film formation of this embodiment, and can form the copper film of this embodiment. Do. Moreover, by combining with a suitable coating method, it is also possible to form the coating film patterned in a desired shape, and to form the patterned copper film which becomes wiring, an electrode, a terminal, etc. directly on a board | substrate. In addition, coating film formation and subsequent copper film formation by direct drawing using inkjet printing, gravure printing, gravure offset printing, reverse offset printing, flexographic printing, (silk) screen printing, convex printing, and the like It is also possible to do this. As a result, the wiring board of embodiment of this invention can be manufactured using the patterned copper film of embodiment of this invention formed on a suitable board | substrate.

In addition, in that case, the composition for copper film formation of this embodiment adjusts the kind and quantity with respect to an amine compound, a solvent, etc., and responds to the application | coating method chosen, and is suitable for the coating method to be used, and the composition for copper film formation It is preferable to adjust the viscosity of.

[Heating condition]

In the copper film formation method of embodiment of this invention, the heating for forming a copper film from the composition for copper film formation of this embodiment requires specially under reducing atmosphere using reducing gas, such as hydrogen gas, as mentioned above. I do not do it. That is, in the copper film formation method of embodiment of this invention, the heating for forming a copper film can be performed, for example in non-oxidizing atmosphere using nitrogen gas, argon gas, and helium gas, and in oxidizing atmosphere, such as air | atmosphere. have. That is, the copper film formation method of this embodiment can heat the coating film of the composition for copper film formation of this embodiment formed on the board | substrate in a non-oxidizing atmosphere, and can form a copper film on the board | substrate.

Moreover, the copper film formation method of this embodiment heats the coating film of the composition for copper film formation of this embodiment formed on the board | substrate under reducing atmosphere using reducing gas, such as hydrogen gas, and forms a copper film on the board | substrate. It is also possible.

In the copper film formation method of this embodiment, heating temperature should just be a temperature at which the copper compound of the composition for copper film formation of this embodiment is reduced, and an organic substance decomposes and volatilizes, and is not specifically limited. For example, the range of 50 degreeC-300 degreeC is preferable, and, as for heating temperature, the range of 50 degreeC-200 degreeC is more preferable. If heating temperature is less than 50 degreeC, reduction of a copper compound may not fully advance, and residual | survival of an organic substance may become remarkable, and when it exceeds 300 degreeC, there exists a possibility that the board | substrate which consists of organic materials may become unavailable. If it is 200 degrees C or less, a desired board | substrate can be selected and used from the group of the various board | substrates mentioned above including the board | substrate which consists of organic materials.

However, when heating temperature is 200 degrees C or less, in the prior art, the fall of the characteristic of the copper film by what is called a lack of heating is concerned. However, the copper film formation method of this embodiment forms the copper film using the composition for copper film formation of this embodiment, and even the heating film of 200 degrees C or less, the copper film of a desired characteristic, especially the outstanding outstanding A copper film of resistance characteristics can be formed. Therefore, as for the copper film formation method of embodiment of this invention from a viewpoint of simplicity, it is preferable that heating temperature is 200 degrees C or less as mentioned above.

In addition, what is necessary is just to select heating time suitably, considering the kind of each component, such as a copper compound and a reducing agent, and the electroconductivity (resistance value) of a desired copper film, and are not specifically limited. And when the comparatively low heating temperature of about 200 degreeC or less is selected, it is preferable to make heating time into about 10 to 120 minutes.

As mentioned above, the copper film formation method of embodiment of this invention does not require a non-oxidative atmosphere using reducing gas, such as hydrogen gas, using the composition for copper film formation of this embodiment in particular, For example, a low-resistance copper film can be easily formed by low-temperature heating in an inert atmosphere and in an oxidizing atmosphere by using an inert gas such as nitrogen gas, helium gas, and argon gas. And the wiring board of embodiment of this invention can be provided using the copper film of embodiment of this invention on the obtained board | substrate.

<Electronic device>

The copper film formation method of embodiment of this invention mentioned above forms the copper film of embodiment of this invention using the composition for copper film formation of embodiment of this invention. And the electronic device of embodiment of this invention using it as a wiring can be provided using the copper film of embodiment of this invention.

As an electronic device of this invention, a touch panel, a liquid crystal display element, an organic electroluminescent element, etc. are mentioned, for example. Moreover, the electronic device with a touch panel provided with a touch panel is mentioned as an input device.

EMBODIMENT OF THE INVENTION Hereinafter, the touchscreen of embodiment of this invention illustrated as an electronic device of embodiment of this invention is demonstrated.

Touch panel

The touch panel of embodiment of this invention is a touch panel which has a light-transmitting insulating film formed so that the detection electrode and the detection wiring for drawing it out may be covered, for example. This touch panel can be, for example, a capacitive touch panel.

In addition, in the touch panel of embodiment of this invention, it is also possible to set it as the structure which does not form the insulating film mentioned above.

1 is a plan view illustrating a touch panel of an embodiment of the present invention.

FIG. 2 is a cross-sectional view taken along the line BB ′ of FIG. 1.

As shown in FIG. 1, the touch panel 21 of this embodiment extends to the surface of the transparent substrate 22 in the Y direction orthogonal to the X detection direction and the 1st detection electrode 23 extending in the X direction. It has the 2nd detection electrode 24 made.

The transparent substrate 22 can be a glass substrate. The transparent substrate 22 may also be a resin substrate, in which case a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, a polyether sulfone film, a polycarbonate film, a polyacryl film , A polyvinyl chloride film, a polyimide film, a ring-opening polymer film of a cyclic olefin, and a film made of hydrogenated substance thereof. As thickness of the transparent substrate 22, in the case of a glass substrate, it can be 0.1 mm-3 mm. In the case of a resin substrate, it can be 10 micrometers-3000 micrometers.

The 1st detection electrode 23 and the 2nd detection electrode 24 are each arranged in multiple numbers. And the 1st detection electrode 23 and the 2nd detection electrode 24 are arrange | positioned in matrix form in the operation area | region of the touch panel 21. FIG. The 1st detection electrode 23 is used in order to detect the coordinate of the Y direction of the touch position by an operator. The second detection electrode 24 is used to detect coordinates in the X direction of the touch position by the operator. The first detection electrode 23 and the second detection electrode 24 are formed on the same layer of the same surface of the transparent substrate 22. In addition, the number of the 1st detection electrode 23 and the 2nd detection electrode 24 is not limited to the example of FIG. 1, It is preferable to determine according to the magnitude | size of an operation area and the detection precision of the touch position required. . In other words, the touch panel 21 can be configured by using a greater number or a smaller number of the first detection electrodes 23 and the second detection electrodes 24.

As shown in FIG. 1, the 1st detection electrode 23 and the 2nd detection electrode 24 are each comprised from the some electrode pad 30 of ridge shape. The first detection electrode 23 and the second detection electrode 24 are spaced apart from the electrode pad 30 of the second detection electrode 24 in which the electrode pad 30 of the first detection electrode 23 is adjacent thereto. Is arranged to. At this time, the gap between these electrode pads 30 becomes very small enough to ensure insulation.

And the 1st detection electrode 23 and the 2nd detection electrode 24 are arrange | positioned so that the part which cross | intersects each other can be made as small as possible. And the electrode pad 30 which comprises the 1st detection electrode 23 and the 2nd detection electrode 24 is arrange | positioned in the whole operation area | region of the touch panel 21. FIG.

As shown in FIG. 1, although the electrode pad 30 can be formed in a rhomboid shape, it is not limited to such a shape, For example, it can be made into polygonal shapes, such as a hexagon.

The first detection electrode 23 and the second detection electrode 24 are transparent so as not to reduce the visibility of a display such as a liquid crystal display element (not shown) disposed under the touch panel 21, respectively. It is preferable that it is an electrode. Here, a transparent electrode is an electrode provided with high permeability with respect to visible light. As the first detection electrode 23 and the second detection electrode 24, an electrode made of a transparent conductive material such as an electrode made of ITO or an electrode made of indium oxide and zinc oxide can be used. When the 1st detection electrode 23 and the 2nd detection electrode 24 consist of ITO, respectively, it is preferable to make those thickness into 10 nm-100 nm so that sufficient electroconductivity can be ensured.

Formation of the 1st detection electrode 23 and the 2nd detection electrode 24 can be performed using a well-known method, For example, the film | membrane which consists of transparent conductive materials, such as ITO, is formed into a film by sputtering method etc., and is formed. By photolithography or the like.

As shown to FIG. 1 and FIG. 2, the 1st detection electrode 23 and the 2nd detection electrode 24 are formed on the same surface of the transparent substrate 22, and comprise the same layer. Therefore, the 1st detection electrode 23 and the 2nd detection electrode 24 cross | intersect in several place in the operation area | region, and the intersection part 28 is formed.

In the touch panel 21 of the present embodiment, as shown in FIG. 2, one of the first detection electrodes 23 and the second detection electrodes 24 does not contact the other at the intersection portion 28. To be segmented. That is, in the intersection part 28, although the 1st detection electrode 23 is connected, the 2nd detection electrode 24 extended in the left-right direction of FIG. 2 is divided and formed. And the bridge electrode 32 is formed in order to electrically connect the broken part of the 2nd detection electrode 24. FIG. An interlayer insulating film 29 made of an insulating material is formed between the bridge electrode 32 and the first detection electrode 23.

As shown in FIG. 2, the interlayer insulating film 29 formed on the first detection electrode 23 at the intersection portion 28 is formed of a material having excellent light transmittance. The interlayer insulating film 29 can be formed by applying a printing method using polysiloxane, an acrylic resin, an acrylic monomer, or the like, patterning if necessary, and then heating and curing it. In the case of using polysiloxane, the interlayer insulating film 29 is an inorganic insulating layer made of silicon oxide (SiO ₂ ). In addition, when acrylic resin and an acryl monomer are used, the interlayer insulation film 29 becomes an organic insulation layer which consists of resins. In the case where SiO ₂ is used for the interlayer insulating film 29, for example, a SiO ₂ film is formed only on the first detection electrode 23 in the intersection portion 28 by a sputtering method using a mask to form an interlayer insulating film. (29) can also be comprised.

The bridge electrode 32 is formed in the upper layer of the interlayer insulation film 29. As described above, the bridge electrode 32 functions to electrically connect the second detection electrodes 24 disconnected from the intersections 28. The bridge electrode 32 is preferably formed of a material excellent in light transmittance such as ITO. By forming the bridge electrode 32, the second detection electrode 24 can be electrically connected in the Y direction.

As shown in FIG. 2, the first detection electrode 23 and the second detection electrode 24 have a shape in which a plurality of ridge electrode pads 30 are arranged vertically or horizontally as described above. In the 1st detection electrode 23, the connection part located in the cross | intersection part 28 is considered to have a shape narrower than the ridge electrode pad 30 of the 1st detection electrode 23. As shown in FIG. The bridge electrode 32 is also narrower in width than the ridge electrode pad 30 and is formed in a single shape.

Terminals (not shown) are formed at the ends of the first detection electrode 23 and the second detection electrode 24 of the touch panel 21, respectively, and lead wires 31 are drawn out from the terminals. The lead-out wiring 31 can be a metal wiring using the copper film of embodiment mentioned above of this invention. Similarly, a terminal can also be formed using the copper film of embodiment of this invention.

That is, the lead-out wiring 31 etc. of the touch panel 21 can be formed in accordance with the copper film formation method of above-mentioned embodiment of this invention using the composition for copper film formation of embodiment mentioned above. have.

For example, the coating film of the composition for copper film formation of this embodiment is made into the 1st detection electrode 23, the 2nd detection electrode 24, etc. by the coating method illustrated by the copper film formation method of embodiment of this invention. It forms on the formed transparent substrate 22, and forms a wiring pattern. For example, a coating film is formed by direct drawing using the inkjet printing method, the gravure printing method, the gravure offset printing method, the reverse offset printing method, the flexographic printing method, the (silk) screen printing method, the convex plate printing, and the like. Patterns can be formed.

As described above, for example, the lead-out wiring 31 and the like are heated and cured in a non-oxidizing atmosphere in an inert atmosphere using an inert gas such as nitrogen gas, helium gas, and argon gas, and in an oxidizing atmosphere using the atmosphere. Can be formed.

In addition, the heat-hardening of a coating film can also be performed by baking in a reducing atmosphere using reducing gas, such as hydrogen gas, as mentioned above.

The lead-out wiring 31 uses an external connection terminal (not shown) at an end thereof to detect the position of voltage application or touch operation to the first detection electrode 23 and the second detection electrode 24. Electrically connected to a control circuit (not shown).

As shown in FIG. 1 and FIG. 2, on the surface of the transparent substrate 22 on which the first detection electrode 23 and the second detection electrode 24 are arranged, the first detection electrode 23 and the second detection electrode ( The light-transmitting insulating film 25 is arrange | positioned so that 24 may be covered.

The insulating film 25 is patterned and formed to cover and protect the first detection electrode 23 and the second detection electrode 24 in the operation region of the touch panel 21. In addition, the insulating film 25 is patterned and formed so that the connection terminal (not shown) of the edge part of the lead wiring 31 drawn out from the 1st detection electrode 23 and the 2nd detection electrode 24 may be exposed.

A radiation sensitive resin composition can be used for formation of the insulating film 25, and can be arrange | positioned on the 1st detection electrode 23 and the 2nd detection electrode 24 by predetermined patterning.

The touch panel 21 is provided with, for example, an adhesive layer (not shown) made of, for example, an acrylic transparent adhesive, on the formation surface of the first detection electrode 23 and the second detection electrode 24 of the transparent substrate 22. It is possible to form the cover film (not shown) which consists of transparent resin using this.

The touch panel 21 having the above-described configuration measures capacitance in an operating region in which the first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix shape, and touch operation of an operator's finger or the like is performed. The contact position of a finger etc. can be detected from the change of the electrostatic capacitance which arises when there exists. And it is possible to mount on a display, such as a liquid crystal display element or organic electroluminescent element, and to use suitably as an input device of the display of an electronic device.

Therefore, the lead-out wiring can be comprised using the copper film of embodiment of this invention formed according to the copper film formation method of embodiment of this invention mentioned above using the composition for copper film formation of embodiment of this invention. . And a touch panel can be comprised using the lead-out wiring which consists of the copper film of embodiment of this invention, The electronic device of embodiment of this invention, such as a liquid crystal display element and organic electroluminescent element provided with this touch panel, Can provide.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described more concretely based on an Example. However, the present invention is not limited at all by these examples.

<Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a and Comparative Examples 1b to 4b>

In Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a and Comparative Examples 1b to 4b, Examples 1a to 35a, Examples 1b to 38b, and Comparative Examples 1a to 4a and Comparative Examples were compared. The copper film formation composition of Examples 1b-4b was prepared, and the copper film of Examples 1a-35a, Examples 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b was formed using it. And as evaluation of these copper films, resistance characteristics (volume resistance value) were evaluated, and halogen content (halogen content ratio) was further evaluated.

[Preparation of Composition for Copper Film Formation]

The copper compound, the halogen compound, the reducing agent, the solvent added, and other arbitrary components of the kind and addition amount which are shown in Table 1 and Table 2, respectively, are mixed as needed, and the rotation speed is 200 rpm and 60 minutes at room temperature using a stirrer. It stirred and prepared the composition for copper film formation. In addition, "-" in the column of each table | surface shows that the corresponding component was not used.

About the copper compound, a halogen compound, a reducing agent, a solvent, and other arbitrary components which were used for preparation of each copper film formation composition of Examples 1a-35a, Examples 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b All used the commercial item.

[Formation of Copper Film]

Using the composition for copper film formation of Examples 1a-35a, Examples 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b, on the alkali free glass substrate of the square shape of 150 mm in length and 150 mm in width. The coating was carried out using a bar coater, and patterned into a rectangular shape having a length of 50 mm and a width of 100 mm to form a coating film having a film thickness of 50 µm. Next, using the hot plate, the glass substrate in which the above-mentioned coating film was formed was heat-processed for 10 minutes in the non-oxidizing atmosphere using nitrogen gas under the atmosphere of heating. Table 1 and Table 2 collectively show the atmosphere of heating and the temperature of heating as baking conditions. Unless otherwise specified, heating conditions are 200 degreeC and 90 minutes in oxidative atmosphere using air | atmosphere.

And the copper film of Examples 1a-35a, Example 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b was obtained as a thin film patterned in the said shape whose film thickness is about 0.1 micrometer-about 20 micrometers.

[evaluation]

(Measurement of Volume Resistance)

Examples 1a to 35a and Examples respectively formed by the above-described method for forming a copper film using the compositions for forming a copper film of Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a, and Comparative Examples 1b to 4b. Using the copper films of Examples 1b to 38b, Comparative Examples 1a to 4a, and Comparative Examples 1b to 4b, their specific resistance values (volume resistance values) were used using a four probe resistance measuring instrument (trade name: Model sigma-5, manufactured by NPS). Measured by. The measurement result is put together in Table 1 and Table 2, and is shown.

As shown in Table 1 and Table 2, the volume resistivity value of each copper film of Examples 1a-35a obtained with the composition for copper film formation of Examples 1a-35a is the copper of the comparative examples 1a-4a which are compared objects. It is lower than the volume resistivity value of the copper film of Comparative Examples 1a-4a obtained with the film forming composition. In addition, the volume resistance value of each copper film of Examples 1b-38b obtained by the composition for copper film formation of Examples 1b-38b is the comparison obtained by the composition for copper film formation of Comparative Examples 1b-4b which becomes a comparison object. It is lower than the volume resistivity value of the copper film of Examples 1b-4b. It turned out that the composition for copper film formation of Examples 1a-35a and Examples 1b-38b containing a halogen compound with a copper compound and a reducing agent can form a low resistance copper film. That is, as shown in the evaluation results of the copper films of Examples 1a to 35a and Examples 1b to 38b, it was found that the inclusion of the halogen compound in the composition for forming a copper film is effective for reducing the resistance of the formed copper film. And it turned out that the volume resistivity value of the copper film formed can be reduced remarkably by carrying out content of a halogen compound in the range of 0.00001 mass%-20 mass%.

(Measurement of Halogen Content Ratio)

Examples 1a to 35a and Examples formed by the above-described copper film forming method using the compositions for forming a copper film of Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a, and Comparative Examples 1b to 4b. The content rate of a halogen atom was measured using each copper film of 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b.

Measuring method, secondary ion mass analysis (SIMS): In to a method of using a (trade name PHI ADEPT1010, foil, are prepared wave director), a primary ion species: Cs ^+, primary accelerating voltage: 5.0kV, detection zone: On the conditions of 42 micrometers x 42 micrometers, the copper film of Examples 1a-35a, Examples 1b-38b, Comparative Examples 1a-4a, and Comparative Examples 1b-4b was measured. In each of the copper films of Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a, and Comparative Examples 1b to 4b, commercially available high-purity copper (purity 99.9999%) was quantified as a reference sample, The content rate of the halogen atom at the time of making copper atom 100 was evaluated. The measurement result is put together in Table 1 and Table 2, and is shown. In addition, the notation of "ND" shown in a table | surface shows that a halogen atom was not detected.

As shown in Table 1 and Table 2, each copper film of Examples 1a to 35a, Examples 1b to 38b, Comparative Examples 1a to 4a and Comparative Examples 1b to 4b having a low volume resistance value contains a halogen atom, When the content rate of the halogen atom made the copper atom in a film | membrane 100, it turned out that it is 0.001-10.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, It can variously deform and implement in the range which does not deviate from the summary of this invention.

The composition for copper film formation of this invention can be used suitably as a composition for formation of the conductive pattern of the circuit board in the field of electronics. And the copper film of this invention and the copper film formation method of this invention can be used for manufacture of electronic components etc. in the field of electronics. For example, the copper film of this invention and the copper film formation method of this invention can be used for manufacture of a wiring, a circuit board, an antenna, a sensor, a calculation element, and a display element. Moreover, the composition for copper film formation of this invention can be used suitably for various printing, such as inkjet printing, screen printing, flexographic printing, gravure offset printing, reverse offset printing, as a conductive ink.

21: touch panel
22: transparent substrate
23: first detection electrode
24: second detection electrode
25: insulating film
28: intersection
29: interlayer insulation film
30: electrode pad
31: outgoing wiring
32: bridge electrode

Claims (11)

(A) at least one copper compound selected from the group consisting of organic acid copper, copper hydroxide and copper oxide,
(B) a halogen compound, and
(C) reducing agent
Including,
Content of the halogen compound of (B) component is 0.00001 mass%-20 mass% of all components, The composition for copper film formation characterized by the above-mentioned. The method of claim 1,
Copper compound of (A) component is copper formate, copper acetate, copper propionate, copper butyrate, copper valeric acid, caproic acid copper, lactic acid copper, copper malic acid, copper citrate, copper benzoate, copper phthalate, copper salicylate, copper cinnamic acid And at least one member selected from the group consisting of copper oxalate, copper malonic acid, copper succinate, copper hydroxide and copper oxide, and hydrates thereof. The method of claim 1,
Halogen compounds of the component (B) are lithium, sodium, potassium, rubidium, cesium, calcium, magnesium, strontium, barium, radium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver , At least one metal selected from the group consisting of at least one metal selected from the group consisting of gold and platinum, hydrogen halides, ammonium halides, and halide hydrochloride salts of amines; Composition. The method of claim 1,
The reducing agent of component (C) is at least one member selected from the group consisting of amines, reducing carbonic acids and salts thereof, esters thereof, polyhydric alcohols, and aldehydes. delete (1) forming a coating film of the composition for forming a copper film according to any one of claims 1 to 4 on a substrate;
(2) heating the coating film
The copper film formation method characterized by having. It is formed by the copper film formation method of Claim 6, The copper film characterized by the above-mentioned. The method of claim 7, wherein
A copper film containing a halogen atom. The method of claim 8,
The copper film in which the content rate of the halogen atom at the time of making 100 copper atoms in a film | membrane is 0.001-10. It has a copper film of Claim 8, The wiring board characterized by the above-mentioned. An electronic device comprising the touch panel having the copper film according to claim 8.

Images