KR20110091452A - Silver treatment agent, silver treatment method, and conductive pattern forming method - Google Patents

Abstract

PURPOSE: Silver-treatment agent, a method of treating silver and a method of forming a pattern of a conductor are provided to prevent treatment agent from excessively permeating a silver layer in halogenation since imidazole, 1-, 2- or 4-C, or N atom contains one of imidazole compound with 1~4 Cs of alkyl substituent and 1,2-dialkylimidazole. CONSTITUTION: A method of forming a pattern of a conductor comprises next steps. An etching resist layer is formed on a substrate with a silver layer so that a part of the silver layer is exposed. Silver-treatment agent comprises one of imidazole compound with 1~4 Cs of alkyl substituent and 1,2-dialkylimidazole in imidazole, 1-, 2- or 4-C, or N atom. The silver-treatment agent makes contact with the silver layer exposed from the etching resist of the substrate to change the silver layer to silver halide. Removing agent comprising at least one of complexing agent and acid makes contact with the silver halide to remove the silver halide from the substrate to form a pattern of a conductor.

Description

Silver processing agent, the processing method of silver, and the formation method of a conductor pattern {SILVER TREATMENT AGENT, SILVER TREATMENT METHOD, AND CONDUCTIVE PATTERN FORMING METHOD}

The present invention is a silver treating agent, a method for treating silver and a method of forming a conductor pattern, specifically, in order to form a conductor pattern of silver on a substrate such as a glass substrate, It relates to a forming method.

As electrode materials, such as a flat panel display and a touch panel, such as a liquid crystal panel and an organic EL panel, metals, such as aluminum and silver, are laminated | stacked on a transparent conductive film, and the electrode which formed the conductor pattern by patterning this metal is used a lot. .

As a material metal for conductors, the use of silver which has the outstanding characteristic as an electrode wiring material with a high light reflectivity and a low resistivity is increasing recently compared with the aluminum used conventionally.

As a method of patterning silver on such a glass substrate, the method by wet etching by etching liquid is known.

Patterning by etching is applied by, for example, applying a resist on a layer of a silver thin film, and exposing through a photomask for performing a desired pattern exposure on the resist to develop a pattern of an etching resist. Thereafter, etching is performed by bringing the thin film layer of silver into contact with the etching liquid using the etching resist as a mask, and then the etching resist is removed to form a conductor pattern.

As an etching liquid of silver used for formation of such a conductor pattern, the acidic etching liquid which mixed phosphoric acid, nitric acid, and acetic acid is generally used (patent document 1-patent document 3).

However, the acidic etching solution mixed with phosphoric acid, nitric acid and acetic acid is etched using nitrogen oxide (NOx) produced by decomposition of nitric acid due to contact with silver as an oxidant, so it is necessary to safely treat NOx which is a hazardous substance. There is a processing cost.

Moreover, since etching is performed by the oxidation action of NOx, the place where NOx is generated is etched intensively and it is difficult to etch uniformly.

In particular, the side surface (pattern side surface) of the pattern exposed from the etching resist has a problem that the linearity of the pattern side and the smoothness of the side deteriorate when the NOx remains partially etched unevenly and viewed from the top surface.

If the linearity and smoothness of the pattern side are bad, a problem arises when inspecting the substrate. That is, in the conventional inspection, the width of the pattern is optically recognized and inspected from the upper side of the substrate after the formation of the conductor pattern. However, if there is a deviation in the pattern width as described above, there is a possibility that the pattern cannot be recognized normally and may be misrecognized.

Japanese Patent Application Laid-Open No. 2005-29869 Japanese Laid-Open Patent Publication No. 2003-55780 Japanese Laid-Open Patent Publication No. 2003-49285

In view of the above-mentioned conventional problems, the present invention is capable of safely treating silver, and in the case of forming a conductor pattern of silver, the silver having a shape according to a desired pattern and having a good shape on the pattern side. It is a subject to provide a processing agent, a processing method of silver, and a formation method of a conductor pattern.

The silver treatment agent of the present invention is an imidazole compound having a halogen ion, a copper and / or iron ion, an imidazole, an alkyl substituent having 1 to 4 carbon atoms at a carbon number 1 or 2, or a nitrogen atom, and 1 And at least one compound selected from the group consisting of, 2-dialkylimidazole.

In addition, the silver treatment agent of the present invention comprises the imidazole, an imidazole compound having 1 to 4 carbon atoms or an alkyl substituent having 1 to 4 carbon atoms in a nitrogen atom, and 1,2-dialkylimidazole. It is preferable that 0.001 mass% or more and 10 mass% or less are contained in the at least 1 sort (s) of compound chosen from the group.

The method for treating silver of the present invention includes an imidazole compound having a halogen ion, a copper and / or iron ion, an imidazole, a carbon number 1, 2 or 4 carbon, or an alkyl substituent having 1 to 4 carbon atoms in a nitrogen atom; Halogenation process which changes the said silver layer to halogenated silver by making the said silver of the base material which has a silver layer contact the silver processing agent containing at least 1 sort (s) of compound selected from the group which consists of 1,2-dialkylimidazole. It is characterized by performing.

The method of forming a conductor pattern of the present invention includes a resist forming step of forming an etching resist layer on a substrate having a silver layer so that a part of the silver layer is exposed; Imidazole compounds having 1 to 4 carbon atoms or halogenated ions, copper and / or iron ions, imidazoles, carbons 1, 2 or 4, or nitrogen atoms and 1,2-dialkylimides A halogenation step of bringing a silver treating agent including at least one compound selected from the group consisting of sol into silver halide by contacting the silver layer exposed from the etching resist of the base material; Performing a removal step of contacting the silver halide with a removal liquid containing at least one selected from a complexing agent and an acid to remove the silver halide from the substrate to form a conductor pattern. Doing.

Moreover, it is preferable that the formation method of the conductor pattern of this invention performs the resist peeling process which peels the said etching resist layer after the said removal process.

In addition, although the silver processing agent of the said invention is liquid which processes silver, this "silver" includes not only pure silver but also silver alloy.

By treating the silver layer on a base material with the silver treatment agent of this invention, it is easy to change silver into silver halide. In addition, the silver treatment agent of the present invention includes an imidazole, an imidazole compound having 1 to 4 carbon atoms or an alkyl substituent having 1 to 4 carbon atoms at a nitrogen atom, and 1,2-dialkylimidazole Since it contains at least 1 type of compound chosen from the above, it can suppress that a process liquid penetrates into a silver layer more than necessary in halogenation. Therefore, only the place where the treatment liquid is in contact can be halogenated.

And if the said compound is added in the density | concentration of 0.01 mass% or more and 10 mass% or less in a processing agent, it can suppress excess penetration to a silver layer more effectively.

Further, in the method of forming the conductor pattern of the present invention, when the silver of a portion which is not covered with the resist of the substrate by the silver treating agent is changed to silver halide, the treating agent penetrates from the side of the etching resist to the bottom of the etching resist. Instead, it can be changed to silver halide only where the treatment agent is contacted.

Therefore, the silver layer can be halogenated in the shape exposed by the resist, and then the variation in the pattern side of the conductor pattern formed by removing the silver halide with the removal liquid can be reduced.

Therefore, the conductor pattern with a favorable shape of the pattern side with little error detection at the time of optical inspection can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of this invention is described.

The silver treatment agent of this embodiment is a liquid containing the component of following (a)-(c).

(a) halogen ions

(b) copper and / or iron ions

(c) at least one member selected from the group consisting of imidazole, carbon number 1, 2 or 4, or an imidazole compound having an alkyl substituent having 1 to 4 carbon atoms at a nitrogen atom and 1,2-dialkylimidazole; compound.

The halogen ion of (a) component is contained in the silver treating agent of this embodiment as a component which couple | bonds with halogen and halogenates.

Examples of the halogen include chlorine, bromine, fluorine and iodine. Among them, chlorine and bromine may be eroded (fluorine) or colored (iodine) when the glass substrate is used as the substrate. It is preferable because there is no.

Although halogen exists as an ion in a liquid, it is preferable to add as a halogen compound.

Examples of the halogen compound include sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, sodium fluoride, potassium fluoride, ammonium fluoride and the like.

In addition, examples of the halogen compound may be in the form of acids such as hydrochloric acid and hydrobromic acid, or in the form of metal salts such as copper chloride, zinc chloride, iron chloride, tin chloride, copper bromide, zinc bromide, iron bromide, and tin bromide. In addition, there are other compounds capable of dissociating halogen ions in solution.

Moreover, halogen ion can also use 2 or more types together.

As a halogen ion concentration, the preferable addition amount of the said halogen is 0.01 mass% or more and saturation concentration, It is preferable that they are 0.1 mass% or more and 5 mass% or less, It is more preferable that they are 0.2 mass% or more and 1.0 mass% or less.

If the halogen ion concentration is within the above-mentioned range, halogenation can be performed quickly.

Copper and / or iron ions of the component (b) are included in the silver treatment agent of the present embodiment as a catalyst component for promoting the bonding of silver and halogen.

Copper and / or iron ions are preferably added in the etching solution as a copper salt or iron salt, for example, cuprous chloride, cupric chloride, ferrous chloride, ferric chloride, copper sulfate, iron sulfate, or the like. It is preferable to add as a metal compound of.

And when using the compound containing halogen, such as copper chloride and iron chloride, in the said metal compound, it can be used together as a supply source of the halogen ion of the said (a) component.

If the preferable addition amount of copper and / or iron ion of the said (b) component is added as 0.001 mass% or more as copper ion concentration or iron ion concentration, or the total concentration of copper ion and iron ion, it can exhibit a function as a catalyst. have.

As said (c) component, it is selected from the group which consists of imidazole, carbon number 1, 2, or 4, or an imidazole compound which has a C1-C4 alkyl substituent in a nitrogen atom, and 1,2-dialkylimidazole. At least 1 type is contained in the silver processing agent of this embodiment.

By adding these components, it is possible to suppress excessive penetration of the treating agent into silver, and therefore only silver in the contacted portion can be halogenated.

As said imidazole compound which has a C1-C4 alkyl substituent in carbon number 1, 2, or 4, or a nitrogen atom in the said (c) component, 1-butylimidazole, 2-methylimidazole, 4 -Propylimidazole, 1,2-diethylimidazole, etc. are mentioned.

Especially as said (c) component, imidazole is suitable because it is excellent in the inhibitory effect of liquid penetration, and since it is easy to obtain, it is suitable.

Moreover, you may use together 2 or more of the said (c) components.

The addition amount of the said (c) component is 0.001 mass% or more and 10 mass% or less, More preferably, it is 0.01 mass% or more and 3 mass% or less, Especially preferably, the ranges are 0.1 mass% or more and 1.0 mass% or less.

When (c) component is added within the above-mentioned range, the effect which suppresses excessive penetration of a liquid can be acquired, and the rate of halogenation does not fall extremely.

The range of preferable pH of the silver treatment agent of this embodiment is pH12 or less, It is more preferable that it is pH3 or more and pH11 or less.

If the pH is 12 or less, the rate of halogenation is not extremely reduced. If it is pH3 or more, it can suppress that halogenation rate becomes too high and it becomes difficult to control the liquid of a processing agent.

In order to adjust the silver treating agent of this embodiment to the range of pH mentioned above, in addition to the said (a)-(c) component, acid, such as acetic acid, sodium hydroxide, ammonia, etc. can also be added as a pH adjuster, or the said You may adjust to the said preferable pH range by adjusting the addition amount of (a)-(c) component.

And, for example, in the case of adding hydrochloric acid such as hydrochloric acid, it may also have a function of adjusting the source and pH of the halogen ions of the component (a).

The silver processing agent of this embodiment can be easily prepared by dissolving each component mentioned above in solvent, such as water. When using water as a solvent, it is preferable that it is water from which the ionic substance and the impurity was removed, for example, ion-exchange water, pure water, ultrapure water, etc. are preferable.

In addition, the silver treatment agent of this embodiment may be mix | blended so that each component mentioned above may be made into predetermined | prescribed density | concentration at the time of use, or you may prepare a concentrated liquid, and dilute and use just before use.

Next, the removal liquid which also removes the halogenated silver using the silver treatment agent of this embodiment is demonstrated.

The removal liquid is a solution containing a complexing agent and / or an acid.

As said complexing agent, a thiosulfate, a cyan compound, an ammonium salt, an amine compound, the amino compound containing an amino acid, etc. are mentioned, Specifically, Thiosulfate, such as sodium thiosulfate and potassium thiosulfate, potassium cyanide, sodium cyanide, etc. are mentioned. Cyan compound; ammonia; Ammonia salts such as ammonium chloride, ammonium acetate, ammonium borate, ammonium bromide, ammonium carbonate, ammonium formate, ammonium bicarbonate, ammonium nitrate, ammonium oxalate, ammonium sulfate, ammonium thiocyanate and tetramethylammonium; Alkanolamines such as methylamine, ethylamine, dimethylamine, urea, monoethanolamine, diethanolamine and triethanolamine; Amine compounds such as piperidine, pyridine and ethylenediamine; Amino acids such as alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tyrosine, valine, and theanine.

Among the complexing agents, alkanolamines such as thiosulfate, monoethanolamine, diethanolamine, and triethanolamine, urea and alanine are suitable because they have low odor and easy availability of raw materials.

Although the addition amount of a complexing agent changes with kinds of complexing agents to be used, it is preferable to add in 0.1 mass% or more and saturation concentration in 0.5 mass% or more and 10 weight% or less.

In this range, the silver halide can be quickly and sufficiently dissolved and removed.

Examples of the acid include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as acetic acid, formic acid, citric acid and oxalic acid. Preferably, sulfuric acid, acetic acid, citric acid and oxalic acid are particularly suitable from the viewpoint of solubility of silver halides. .

However, when an acid that generates nitrous oxide, such as nitric acid, is added as an acid, it is difficult to uniformly remove silver halides by oxidation by nitrous oxide. Therefore, an acid having no risk of nitrous oxide is used. It is preferable.

In addition, in the case of using a halogenated acid such as hydrochloric acid, there is a possibility that a halogenation reaction of a non-halogenated silver portion occurs and uniform removal cannot be performed.

Although the addition amount of an acid changes with kinds of acid to be used, it is preferable to add at the density | concentration of 0.5 mass% or more to 30 mass% to 0.1 mass% or more and saturation concentration.

Within this range, the silver halide can be quickly dissolved and removed.

Either one of the said complexing agent and an acid may be added to the removal liquid of this embodiment, and 2 or more may be used together.

The removal liquid of this embodiment can be easily prepared by dissolving the said complexing agent or the said acid in solvents, such as water. When water is used as the solvent, water from which ionic substances and impurities have been removed is preferable, for example, ion-exchanged water, pure water, ultrapure water, and the like.

In addition, you may dilute the removal liquid of this embodiment immediately before use with a solvent, such as said water, so that it may become a predetermined density | concentration when using the said complexing agent or the said acid.

Next, the method of forming a conductor pattern of silver on a glass substrate using the silver processing agent of this embodiment is demonstrated.

The formation method of the conductor pattern of this embodiment is used, for example in order to form a conductor pattern on the glass substrate for liquid crystal display panels in which the silver layer by the thin film of silver is formed into a film by the sputter | spatter on a glass substrate.

The said glass substrate is a board | substrate for liquid crystal display panels, for example, and the board | substrate with which thickness of about 10 mm-500 nm is normally deposited on the upper surface of a board | substrate is common.

On the upper surface of the silver layer of such a glass substrate, a resist pattern is formed with a photosensitive dry film etc., and the part which is not coat | covered with the said resist is processed by the said silver treatment agent, and halogenation is performed.

As a method of bringing the said silver treating agent into contact with the silver surface of the said board | substrate, well-known methods, such as the spraying process by a spray or the immersion process which immerses a board | substrate in liquid, can be employ | adopted.

When spraying by spraying, the thickness varies depending on the thickness of the silver thin film. In general, it is preferable to treat the liquid at a temperature of 20 to 40 ° C, a spray pressure of 0.01 to 0.2 MPa, and a spray time of about 20 to 120 seconds.

In the case of the immersion treatment, it is preferable to immerse about 20 to 300 second immersion time in the 1st liquid of 20-40 degreeC of liquid temperature.

After performing the above-mentioned process, it is preferable to wash the board | substrate and to perform a removal process with the said removal liquid.

As a method of making a removal liquid contact silver, well-known methods, such as the spraying process by spray or the immersion process which immerses a board | substrate in liquid, can be employ | adopted.

When spraying by spraying, the treatment is preferably performed at a liquid temperature of 20 to 40 ° C, a spray pressure of 0.01 to 0.2 MPa, and a spray time of about 5 to 30 seconds.

In the case of the immersion treatment, it is preferable to immerse about 10 to 120 second immersion time in the liquid of 20-40 degreeC of liquid temperature.

After the above-mentioned removal treatment, a silver conductor pattern is formed by peeling the resist with a known resist stripping solution such as an alkaline solution.

At this time, the pattern side of a conductor pattern does not have a deviation and can form the pattern which has favorable linearity in a linear part.

This is because since the silver treatment agent can halogenate the silver layer in the shape exposed by the resist, the conductor pattern formed by removing the silver halide with the removal liquid becomes smaller in the pattern side variation.

Therefore, in the present embodiment, a conductor pattern with less error detection can be obtained when optically inspecting the pattern width.

[Example]

Hereinafter, the silver processing agent, the processing method, and the pattern formation method which concern on this invention are demonstrated to an Example and a comparative example as an example. In addition, this invention is limited to the following Example and is not interpreted.

(Test board)

A 10 cm x 10 cm test substrate was prepared on which a 200 nm thick silver deposition film was formed on a float glass substrate (Asahi Glass Co., Ltd.) having a thickness of 2 mm.

The photosensitive dry film (SUNFORT ^™ AQ1558) was laminated on the silver deposition film of this test substrate, and the etching resist pattern was formed by the photolithographic method. At this time, the etching resist pattern was 15 micrometers in thickness, pitch 60 micrometers, and line / space = 30 micrometers / 30 micrometers.

Using the said test board | substrate, the Example and the comparative example were performed on condition of the following.

(Silver treatment agent and removal liquid)

Each liquid of the composition shown in Table 1 and Table 2 was prepared.

And after mixing each composition, it adjusted to each pH shown in Table 1 and Table 2 using a pH adjuster (90% acetic acid and 24% sodium hydroxide).

TABLE 1

TABLE 2

(Silver processing condition)

The silver treatment process uses the spray treatment machine (use nozzle: VT-9020, Inc. make the silver treatment agent shown in Table 1 and Table 2), and the conditions of spray pressure 0.1 MPa and the processing temperature of 25 degreeC It was performed by spray treatment at.

About the processing time, it observed with the metal microscope and made time required for each liquid the time required until the silver thin film between resist patterns became halogenated and became completely white.

(Removal processing condition)

The removal treatment process was performed on the following conditions after each test board | substrate after the said silver treatment process was washed with water and dried.

Each removal liquid was spray-processed to the test board | substrate on the conditions of spray pressure of 0.1 Mpa, and processing temperature of 25 degreeC using the spray processing machine (use nozzle: VP-9020 by the company make).

The treatment time was performed until the white halide was completely removed by visual observation.

(Resist stripping)

The test substrate after the removal treatment was washed with water and dried, and then the resist was peeled off by immersion treatment in an aqueous 3% sodium hydroxide solution.

(Linearity evaluation)

Linearity was measured by image measurement with an optical microscope.

The image of the pattern top part was image | photographed with the optical microscope from the test substrate upper surface, and image measurement was performed. At the time of this image measurement, the pattern width was measured by 10 points at 5 micrometer intervals, and the standard deviation was made into linearity (micrometer).

That is, the smaller this numerical value is, the more the pattern width is not varied, indicating that the linearity of the pattern side is good.

The results are shown in Table 1 and Table 2.

From the above result, in the Example, the conductor pattern which is good linearity compared with the comparative example is formed.

Claims (5)

Imidazole compounds having 1 to 4 carbon atoms or halogenated ions, copper and / or iron ions, imidazoles, carbons 1, 2 or 4, or nitrogen atoms and 1,2-dialkylimides A silver treating agent comprising at least one compound selected from the group consisting of sol. The method of claim 1,
At least one compound selected from the group consisting of the imidazole, carbon number 1, 2 or 4, or an imidazole compound having an alkyl substituent having 1 to 4 carbon atoms at a nitrogen atom and 1,2-dialkylimidazole Silver treatment agent contained in 0.001 mass% or more and 10 mass% or less. Imidazole compounds having 1 to 4 carbon atoms or halogenated ions, copper and / or iron ions, imidazoles, carbons 1, 2 or 4, or nitrogen atoms and 1,2-dialkylimides A silver treatment method comprising performing a halogenation step of bringing a silver treating agent containing at least one compound selected from the group consisting of sol into contact with the silver of a substrate having a silver layer to change the silver layer to silver halide. A resist forming step of forming an etching resist layer on a substrate having a silver layer so that a part of the silver layer is exposed;
Imidazole compounds having 1 to 4 carbon atoms or halogenated ions, copper and / or iron ions, imidazoles, carbons 1, 2 or 4, or nitrogen atoms and 1,2-dialkylimides A halogenation step of bringing a silver treating agent comprising at least one compound selected from the group consisting of sol into silver halide by contacting the silver layer exposed from the etching resist of the substrate; And
A removal step of forming a conductor pattern by contacting the silver halide with a removal liquid containing at least one selected from a complexing agent and an acid to remove the silver halide from the substrate.
The formation method of a conductor pattern which carries out. The method of claim 4, wherein
The formation method of the conductor pattern which performs the resist peeling process which peels the said etching resist layer after the said removal process.