KR102278837B1 - Method of forming pattern - Google Patents

Abstract

(Project) To provide a pattern formation method capable of reducing the number of photolithography steps and enabling formation of a fine pattern.
(Solution) The pattern forming method according to the present invention comprises a step of forming a first coating film having liquid repellency and lyophilizing by irradiating energy on a substrate, and a step of removing the insulating layer in the first region on the substrate and forming a concave pattern in a second region disposed in at least a portion of a region other than the first region on the substrate, wherein the step of removing the insulating layer in the first region comprises irradiating energy of a specific wavelength to The step of removing the first coating film in the first region by contacting the first coating film in the first region with a specific chemical solution, wherein the step of forming the concave pattern in the second region includes a second region by irradiating energy of a specific wavelength and a step of making the surface of the insulating layer in the region lyophilic.

Description

Pattern forming method {METHOD OF FORMING PATTERN}

The present invention relates to a pattern forming method using a hair-philic material.

BACKGROUND ART In electronic devices such as liquid crystal displays, mobile information devices such as mobile phones and tablets, digital cameras, organic EL displays, organic EL lighting, and sensors, in addition to downsizing and thinning, further performance enhancement is demanded. As a method of manufacturing these electronic devices at a lower cost, printed electronics in which wiring is directly printed are attracting attention.

Thin film transistors and electronic circuits using them are manufactured by laminating various thin films such as semiconductors, insulators and conductors on a substrate, and forming predetermined patterns by photolithography as appropriate. The photolithography technique is a technique for transferring a pattern such as a circuit formed of a material that does not pass light on a transparent flat surface called a photomask onto a target substrate using light, and is used for manufacturing semiconductor integrated circuits, etc. It is widely used in the process.

In a manufacturing process using a conventional photolithography technique, a multi-step process such as exposure, development, firing, and peeling is required only by handling a mask pattern formed using a photosensitive organic resin material called a photoresist. Therefore, as the number of photolithography processes increases, the manufacturing cost inevitably rises. In order to improve this problem, it has been attempted to manufacture a thin film transistor by reducing the photolithography process.

Further, in recent years, substrates have been gradually enlarged in area, and in connection therewith, the enlargement of vacuum apparatuses such as CVD apparatuses, increase in apparatus cost, increase in power consumption, etc. become remarkable, and there is a tendency that the manufacturing cost increases. From such a background, a non-vacuum process is attracting attention with the aim of reduction of process cost etc. The advantage that a non-vacuum process leads to reduction of facility investment and operating cost, simplification of maintenance, etc. is mentioned.

Manufacturing of electronic components by the printing method can usually skip a multi-step process including exposure and development, and a vacuum process such as a vapor deposition method, and a significant simplification of the process is expected.

Printing methods, such as inkjet, screen printing, gravure printing, and gravure offset printing, are used as a simple and low-cost process at the point which can form wiring of a desired pattern directly on a board|substrate. However, in forming the wiring of a desired pattern, as a result of the flow of the film-forming material to be used, they spread and spread, and there is a limit in manufacturing wiring having a fine pattern having excellent linearity.

An object of the present invention is to provide a pattern forming method capable of reducing the number of photolithography steps and forming a fine pattern.

The pattern forming method according to the present invention includes a step of forming a first coating film whose liquid repellency is changed by energy irradiation on a substrate, a step of removing the first coating film in a first region on the substrate, and a second coating film on the substrate. a step of forming a concave pattern in a second region disposed in at least a part of the region excluding the first region, wherein the first coating film in the first region is brought into contact with a specific chemical solution to form a first region in the first region The step of removing the coating film is included, and the step of forming the concave pattern in the second region includes a step of lyophilizing the surface of the first coating film in the second region by energy irradiation.

The pattern forming method according to the present invention includes a step of forming a first coating film whose liquid repellency is changed by energy irradiation on a substrate, a step of removing the first coating film in a first region on the substrate, and a second coating film on the substrate. A step of depositing a predetermined material on one region and a step of removing the first coating film in a region other than the first region on the substrate, wherein the step of removing the first coating film includes a first step by irradiating energy of a specific wavelength and a step of removing the first coating film in the first region by bringing the coating film into contact with a specific chemical solution, wherein the step of depositing a predetermined material on the first region includes a solution containing the predetermined material on the first coating film The applying step includes depositing a predetermined material on the first region.

It is possible to provide a pattern forming method capable of reducing the number of photolithography steps and forming a fine pattern.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure explaining the structure of the wiring structure formed by the wiring formation method which concerns on one Embodiment of this invention.
2A is a view for explaining a wiring forming method according to an embodiment of the present invention.
2B is a view for explaining a wiring forming method according to an embodiment of the present invention.
2C is a view for explaining a wiring forming method according to an embodiment of the present invention.
2D is a view for explaining a wiring forming method according to an embodiment of the present invention.
2E is a view for explaining a wiring forming method according to an embodiment of the present invention.
2F is a view for explaining a wiring forming method according to an embodiment of the present invention.
3 is a view for explaining the configuration of a wiring structure formed by a wiring forming method according to a modification of one embodiment of the present invention.
4A is a view for explaining a wiring forming method according to an embodiment of the present invention.
4B is a view for explaining a wiring forming method according to an embodiment of the present invention.
4C is a view for explaining a wiring forming method according to an embodiment of the present invention.
5 is a view for explaining the configuration of a wiring structure formed by a wiring forming method according to an embodiment of the present invention.
6A is a view for explaining a wiring forming method according to an embodiment of the present invention.
6B is a view for explaining a wiring forming method according to an embodiment of the present invention.
6C is a view for explaining a wiring forming method according to an embodiment of the present invention.
6D is a view for explaining a wiring forming method according to an embodiment of the present invention.
7 is a view for explaining the configuration of a wiring structure formed by a wiring forming method according to an embodiment of the present invention.
8A is a view for explaining a wiring forming method according to an embodiment of the present invention.
8B is a view for explaining a wiring forming method according to an embodiment of the present invention.
8C is a view for explaining a wiring forming method according to an embodiment of the present invention.
8D is a view for explaining a wiring forming method according to an embodiment of the present invention.
9 is a view for explaining the configuration of a wiring structure formed by a wiring forming method according to an embodiment of the present invention.

(Form for implementing the invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail, referring drawings. In addition, embodiment shown below is an example of embodiment of this invention, and this invention is limited to these embodiment and is not interpreted. In addition, in the drawings referred to in this embodiment, the same code|symbol or similar code|symbol is attached|subjected to the same part or the part which has the same function, and the description of the repetition may be abbreviate|omitted. In addition, the dimensional ratio of a drawing may differ from an actual ratio for the convenience of description, or a part of a structure may be abbreviate|omitted from drawing.

MEANS TO SOLVE THE PROBLEM The present inventors completed the material of the base film which can form a fine pattern by suppressing wetting, spreading, and spreading of a film-forming ink. From the property of the said material mentioned later, in this specification, the said material is called a hydrophilic material. As a hydrophilic material, a hydrophilic part and a water repellent part can be formed by heat, and a hydrophilic part and a water repellent part can be formed also by irradiation of a radiation. A hydrophilic material capable of forming a hydrophilic portion and a water-repellent portion even by irradiation with radiation is particularly called a radiation-sensitive composition. The radiation-sensitive composition of the present invention comprises a compound having an acid-dissociable group and an acid generator.

When a coating film is formed by coating a solution comprising a radiation-sensitive composition on a substrate, and radiation is irradiated onto the coating film, the acid dissociable group is released and volatilized by the effect of the acid generator. As a result, the film thickness of the radiation-irradiated portion becomes thinner than the film thickness of the non-radiation-irradiated portion, and a concave pattern is formed. At this time, if the acid dissociable group has a fluorine atom or a silicon atom, the obtained coating film and the non-radiation portion exhibit lyophobic properties, but the radiation-irradiated portion becomes lyophilic compared to the radiation unirradiated portion due to disappearance of the acid dissociable group.

Thus, the insulating layer formed by apply|coating the solution which consists of a radiation-sensitive composition to a board|substrate is called a hydrophilic material in this specification.

When a liquid film-forming material is applied on a lipophilic material having a concave pattern formed thereon by irradiating such radiation, the material tends to collect on the concave portion due to the unevenness of the coating film surface due to the difference in the film thickness of the convex portion and the concave portion, Not only the effect of the surface shape of the coating film, but also the lyophilic and lyophobic properties of the surface make it easier to collect the material on the concave portion, thereby making it easy to form a wiring having a more desired shape, specifically, a fine pattern.

By utilizing such a characteristic of the hydrophilic material, the number of photolithography steps can be reduced and a wiring formation method capable of forming a fine pattern can be provided. First, the radiation-sensitive composition used in the wiring forming method according to the present invention will be described below.

First, a radiation-sensitive composition, particularly, a compound of an embodiment of the present invention suitable as a component thereof will be described. Then, a wiring structure according to the present invention and a wiring forming method for forming the same will be described.

<Radiation-sensitive resin composition>

The radiation-sensitive resin composition of the present invention has a characteristic that the irradiated portion changes from liquid repellency to hydrophilicity by energy irradiating the coating film formed on the substrate from the composition.

The radiation-sensitive resin composition (hereinafter, simply referred to as a composition) of the embodiment of the present invention is a polymer having at least one group selected from a group having an acetal bond or a group containing a silicon atom ([A] polymer) and an acid generator as components. The group having an acetal bond is particularly preferably a group containing a fluorine atom.

The composition of the embodiment of the present invention is used in the method for manufacturing a substrate having a lyophilic part and a lyophobic part according to the embodiment of the present invention described above, and a substrate having a lyophilic part and a lyophobic part can be manufactured.

And, in the composition of the embodiment of the present invention, in the polymer having at least one group selected from a group having an acetal bond or a group containing a silicon atom, it is preferable that the group is an acid dissociable group. The composition of the embodiment of the present invention is applied to the steps (1) and (2) and further the step (3) in the method for producing a substrate having a lyophilic portion and a liquid-repellent portion according to the embodiment of the present invention described above; A substrate having a lyophilic part and a lyophobic part can be manufactured.

The composition of the present embodiment contains, in addition to the polymer [A], a solvent, an acid generator (hereinafter, sometimes referred to as [B] acid generator), [C] a compound different from [A], and an auxiliary material for the acid generator In addition, as a sensitizer (hereinafter, may be referred to as [D] sensitizer) as a sensitizer (hereinafter, may be referred to as [E] sensitizer) as a diffusion inhibitor of acid from the acid generator (hereinafter, may be referred to as [E] compound). can do.

Furthermore, the composition of this embodiment can contain the polymeric compound (Hereinafter, it may call [F] polymeric compound) which has an ethylenically unsaturated bond. Furthermore, the composition of this embodiment can contain the radiation-sensitive polymerization initiator (it may call a [G] radical photopolymerization initiator hereafter).

And the composition of embodiment of this invention can contain other arbitrary components, unless the effect of this invention is impaired.

The viscosity (temperature: 20°C, shear rate: 10 sec ⁻¹ ) of the composition of the embodiment of the present invention can be adjusted according to a desired coating method, the film thickness of the coating film to be formed, and the like.

Hereinafter, each component which can be used as a composition of this embodiment is demonstrated.

<[A] Polymer>

[A] A polymer ([A] polymer) having at least one group selected from a group containing an acetal bond or a group containing a silicon atom as a component of the composition of the present embodiment.

First, the polymer which has a group which has an acetal bond is demonstrated. The group having an acetal bond has a group containing at least one structural unit selected from the group consisting of an acetal bond and a hemiacetal ester bond. It is preferable to contain at least 1 sort(s) chosen from the structural unit more specifically represented by a following formula (1a-1) or (1a-2).

(In formulas (1a-1) and (1a-2), R ^1a and R ^2a each independently represent a hydrogen atom or a methyl group, and Rf independently represents an organic group substituted with a fluorine atom. * represents a bond area is indicated.)

A compound containing an acetal bond _{can be obtained by reacting an alcohol with a compound having a group CH 2} =C(R ^1a )-O-, and a compound containing a hemiacetal ester bond is obtained by reacting an _{alcohol with a group CH 2} =C ( It can be obtained by reacting a compound having ^{R 1a )-O-.}

As said Rf, the organic group which has a fluorine atom is mentioned. As said Rf, groups represented by the following formulas (1-1-1) to (1-1-33) are preferable.

[A] The polymer has a structure in which a protecting group derived from a vinyl ether compound represented by the following formula (1D) (hereinafter sometimes referred to as “compound (1D)”) is introduced into the hydroxyl group of a compound having a hydroxyl group as a precursor. It is preferable to have Moreover, the [A] polymer may have a structure in which the protecting group derived from compound (1D) is introduce|transduced into the carboxyl group of the compound which has a carboxyl group which is a precursor.

In the formula (1D), R ⁰ represents a hydrogen atom or a methyl group. In the formula (1D), R ^A is independently a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 4 to 12 carbon atoms. represents a substituted or unsubstituted alicyclic hydrocarbon group of or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom. In said formula (1D), x represents the integer of 0-12.

^{Examples of the alkylene group having 2 to 12 carbon atoms in R A} in the formula (1D) include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and an unde. A silene group, a dodecylene group, etc. are mentioned.

^{Examples of the alkenylene group having 2 to 12 carbon atoms in R A} in the formula (1D) include a vinylene group, an ethene-1,2-diyl group, and a 2-butene-1,4-diyl group.

^{Examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms in R A} in the formula (1D) include a phenylene group, a tolylene group, a mesitylene group, a naphthylene group, and a biphenylene group.

^{Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms in R A} in the formula (1D) include (cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and bicyclohexyl group). can

^{In R A} of the formula (1D), a methylene group, an alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, Examples of the group in which one or more hydrogen atoms are substituted with fluorine atoms include groups in which one or more hydrogen atoms of the groups exemplified above are substituted with fluorine atoms.

^{As R A in} the formula (1D), a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a vinylene group are preferable. Among these groups, a phenylene group is particularly preferable from the viewpoint of developability.

In the formula (1D), R ^B represents a group in which one or more hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms.

In the formula (1D), R ^B is, for example, a group represented by the formulas (1-1-1) to (1-1-33) for Rf, 2,2,2-trifluoro ethyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 1,2,2-trifluorovinyl group, 2,2,2-trifluoroethyl group, above formula 3,3,3-trifluoropropyl group of (1-1-1), 4,4,4-trifluorobutyl group of formula (1-1-2), of formula (1-1-4) 3,3,4,4,4-pentafluorobutyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4 of formula (1-1-8) ,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 1,2,2-trifluorovinyl group, 2 of formula (1-1-29) The ,3,4,5,6-pentafluorophenyl group is preferred.

In said formula (1D), the integer of 0-9 is preferable and, as for x, 0 is more preferable.

As the polymer having a group having an acetal bond, a polymer can be used with reference to the description in WO2014/178279 International Publication No. WO2014/178279.

Next, the group containing a silicon atom is demonstrated.

The group containing a silicon atom is at least 1 group selected from the group represented by following formula (1-1), following formula (1-2), following formula (1-3), and following formula (1-4) have

(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rs independently represent a monovalent organic group having a silicon atom.

In formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a C 1 to C 12 divalent organic group. 20 represents an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which some or all of the hydrogen atoms of these groups are substituted with a substituent, or a monovalent organic group having a silicon atom. In formulas (1-1), (1-2), (1-3) and (1-4), * represents a binding site.)

As a specific example of preferable Rs in said formula (1-1) and said formula (1-2), group represented by each following formula is mentioned. In addition, in each formula, * represents a binding site.

Next, groups represented by the formulas (1-3) and (1-4) will be described.

In the formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, a group in which some or all of the hydrogen atoms of these groups are substituted with a substituent, or a monovalent organic group having a silicon atom.

For R ⁶ , the same groups as the specific examples of preferred Rs in formulas (1-1) and (1-2) can be used.

The group containing such a silicon atom is obtained by reacting the vinyl compound containing a silicon atom with the polymer which has a hydroxyl group similarly to the polymer which has a group which has an acetal bond. The groups described in Japanese Patent Application No. 2014-157156 can be used.

[A] The polymer preferably has a structure in which a protecting group derived from a vinyl ether compound containing a silicon atom is introduced into a hydroxyl group of a compound having a hydroxyl group as a precursor. Moreover, the polymer [A] may have a structure in which the protective group originating in the vinyl ether compound containing a silicon atom is introduce|transduced into the carboxyl group of the compound which has a carboxyl group which is a precursor.

Next, the method for obtaining [A] polymer is demonstrated. [A] Two methods are possible as a method for obtaining a polymer, the method of using a polymer as a compound used as a precursor, and the method of using a monomer as a compound used as a precursor.

In the method of using a polymer as a precursor compound, the precursor polymer contains a hydroxyl group or a carboxyl group in a molecule, and the polymer [A] can be obtained by reacting the compound (1D) with the hydroxyl group of the precursor polymer.

Further, in the method of using a monomer as a precursor compound, the precursor monomer contains a hydroxyl group or a carboxyl group in a molecule, and the compound (1D) is reacted with the hydroxyl group or carboxyl group of the precursor monomer, and then the obtained monomer is polymerized [A] polymer can be obtained by doing this.

[A] As a method of obtaining a polymer, it carries out similarly to the synthesis method of the polymer described in International Publication WO2014/178279 and Japanese Patent Application No. 2014-157156, and a polymer can be obtained. [A] As a preferable example of a polymer, the polymer which has at least 1 selected from the group which consists of structural units represented by following formula (2)-(6) is mentioned.

In formulas (2) to (6), R ³ independently represents a hydrogen atom or a methyl group. R ⁴ is independently a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or a substituted or unsubstituted alicyclic group having 4 to 12 carbon atoms. A hydrocarbon group or a group in which at least one hydrogen atom of these groups is substituted with a fluorine atom. R ⁵ independently represents a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a fluorine atom. m represents 0 or 1. n independently represents the integer of 0-12.

Examples of R ⁴ include the same groups as those exemplified by ^{R A above.}

As the R ^5, there may be mentioned a group and the same group such as exemplified by the R ^B.

As said n, the integer of 0-9 is preferable.

[A] A polymer may be used individually by 1 type, and may mix and use 2 or more types.

The compound used as a precursor of the polymer [A] described above, particularly a compound having a hydroxyl group as a precursor, has a property that the protective group is less likely to be removed by heat, and on the other hand, the protective group can be controlled by radiation exposure. Since it has the property that it can be used, it can be used suitably for obtaining [A] polymer. In addition, the [A] polymer is preferable in combination with the [B] acid generator described later, since more precise control of the removal of the protecting group by irradiation with radiation becomes possible.

The composition of the embodiment of the present invention contains the polymer [A] having the above structure and is used in the method for producing a substrate having a lyophilic portion and a lyophobic portion according to the embodiment of the present invention described above. And, immediately after formation, the coating film formed in the above-mentioned process (1) has said Formula (1-1), said Formula (1-2), said Formula (1-3), and said Formula which [A] polymer has The characteristic derived from the group represented by (1-4) is shown. Specifically, when the composition of the embodiment of the present invention is used, first, in the above-mentioned step (1), a liquid-repellent coating film derived from a fluorine atom or a silicon atom is formed. Next, when the coating film is irradiated with radiation in the above-described step, the above formulas (1-1), (1-2), (1-3) and (1-4) in the exposed portion ) as a group represented by any of those contained therein is decomposed to form a state in which a protecting group for a hydroxyl group or a carboxyl group is removed. As a result, in the coating film using the composition of the embodiment of the present invention, in the portion in which the protecting groups such as hydroxyl groups have been removed by exposure, hydroxyl groups and the like remain, and the liquid repellency resulting from the protecting groups is lost. It is preferable that the phenolic hydroxyl group and carboxyl group which accelerate|stimulate melt|dissolution to an alkali developing solution generate|occur|produce especially, when a protecting group detach|desorbs.

<[B] Acid Generator>

[B] The acid generator is at least a compound that generates an acid upon irradiation with radiation. When the composition of the embodiment of the present invention contains the [B] acid generator, the acid dissociable group can be released from the polymer [A].

[B] Examples of the acid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carbonic acid ester compound. have.

In the composition of this embodiment, [B] acid generator may be used individually or in combination of 2 or more types.

[Oxime sulfonate compound]

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (2A) is preferable.

In the formula (2A), R ²¹ is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or these alkyl groups or alicyclic groups. A group in which some or all of the hydrogen atoms of the formula hydrocarbon group and the aryl group are substituted with a substituent.

^{As the alkyl group represented by R 21} described above, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-2-oxonorbornyl group. The alicyclic group containing a bridge|crosslinking cyclic alicyclic group, etc. are mentioned. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ²¹ may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

^{The aryl group having 6 to 20} carbon atoms represented by R 21 described above is preferably a phenyl group, a naphthyl group, a tolyl group and a xylyl group. The aforementioned aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

Specific examples of these oxime ester compounds include, for example, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluene Sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl)acetonitrile, etc. are mentioned.

Moreover, the oxime ester compound of Unexamined-Japanese-Patent No. 2011-227106 and Unexamined-Japanese-Patent No. 2012-150494 can be used as a photoacid generator.

[Onium salt]

Examples of the onium salt include a diphenyliodonium salt, a triphenylsulfonium salt, a sulfonium salt, a benzothiazonium salt, a tetrahydrothiophenium salt, and a sulfonimide compound.

As the above-mentioned sulfonimide compound, for example, N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide Imide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide , N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(tri Fluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester, etc. are mentioned.

As another photoacid generator, the photoacid generator of Unexamined-Japanese-Patent No. 2011-215503 and International Publication WO2011/087011A1 can be used.

The composition of this embodiment WHEREIN: As content of [B] acid generator, 0.1 mass part - 10 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 1 mass part - 5 mass parts are more preferable. [B] Since the sensitivity of the radiation-sensitive composition can be optimized by making the content of the acid generator into the above range, a concave pattern with high resolution can be formed by passing the above-described steps (1) to (3). .

The said radiation-sensitive resin composition may contain the [C] compound as another component other than said [A] and [B] component. When the said radiation-sensitive resin composition contains the compound [C], etc., it has the effect of segregating [A] polymer on the film|membrane surface more efficiently. By containing this compound [C] in the said radiation-sensitive resin composition, the addition amount of polymer [A] can be made less than before. Hereinafter, the [C] compound will be described in detail.

<[C] compound (compound different from [A] polymer)>

It is preferable that the compound different from the polymer [A] (hereinafter also referred to as the compound [C]) is a compound having low liquid repellency compared to the polymer [A]. [C] The compound may be a low-molecular compound or a high-molecular compound such as a polymer. The liquid repellency changes depending on the difference in the constituent atoms in the compound, the molecular weight, and the chemical species giving the constituent units, and in particular, it changes depending on the presence of a fluorine atom and a silicon atom.

[A] The polymer contains at least one of a fluorine atom or a silicon atom in an acid dissociable group,

[C] The compound is preferably a compound containing neither a fluorine atom nor a silicon atom, or an acid dissociable group which does not contain either a fluorine atom or a silicon atom even when it has an acid dissociable group.

[C] The compound is preferably a polymer from the viewpoint of improving the heat resistance of the obtained film. The [C] compound can improve the heat resistance and solvent resistance of the obtained film|membrane by using together with the [A] polymer. Furthermore, by appropriately changing the mixing ratio of the polymer [A] and the compound [C], the concave shape of the exposed portion can be controlled, for example, while exhibiting the lipophilic function by the polymer [A].

In addition, by appropriately changing the type and mixing ratio of the [A] polymer and the [C] compound, the [A] polymer having a fluorine atom and a silicon atom is the upper part of the film and the [C] compound is the lower part of the film. In some cases, it can be formed.

Such compounds [C] are described below. [C] As the compound, at least one polymer selected from the group consisting of acrylic resins, polyimides and polyimide precursors, polysiloxanes, cyclic olefin resins, polyethers, polycarbonates, polyesters, epoxy resins, phenol resins, and polyamides. It is preferable to be A polymer is demonstrated.

<Acrylic resin>

As an acrylic resin, the polymer obtained by radical polymerization of the unsaturated monomer which has a (meth)acryloyl group is mentioned. It will not specifically limit if it is such an alkali resin. When using for the process which has developability, it is preferable that it is a polymer containing the structural unit which has a carboxyl group.

Moreover, it is preferable that it is resin containing a polymeric group from a viewpoint of film|membrane property improvement, such as heat resistance and solvent resistance of the film|membrane obtained. As such a polymerizable group, an epoxy group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.

Examples of the polymer having such an epoxy group include two or more oxiranyl groups, oxetanyl groups, glycidyl groups, 3,4-epoxycyclohexyl groups, 3,4-epoxytricyclo[5.2.1.0 ^{2.6 in one molecule.} ] The polymer which has a decyl group etc. is mentioned.

It is resin containing the structural unit which has a carboxyl group, and the structural unit which has a polymerizable group.

In that case, it is preferable that the structural unit which has a polymeric group is at least 1 sort(s) of structural unit chosen from the group which consists of a structural unit which has an epoxy group, and a structural unit which has a (meth)acryloyloxy group. By including the said specific structural unit, the cured film which has the outstanding surface hardenability and deep part sclerosis|hardenability can be formed.

An ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (a1)") and other copolymerizable ethylenically unsaturated monomers such as a monomer having an epoxy group (hereinafter referred to as "unsaturated monomer (a2)") and By copolymerizing, the polymer which has an epoxy group and a carboxyl group can be obtained.

Examples of the unsaturated monomer (a1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, a mono[(meth)acryloyloxyalkyl]ester of a polycarboxylic acid, a carboxyl group and a hydroxyl group at both terminals and mono(meth)acrylates of a polymer having , an unsaturated polycyclic compound having a carboxyl group, and anhydrides thereof.

As the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, etc., as the unsaturated dicarboxylic acid, as an anhydride of unsaturated dicarboxylic acid, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc. , for example, the anhydrides of the compounds exemplified as the unsaturated dicarboxylic acids. An unsaturated monomer (a1) can be used individually or in mixture of 2 or more types.

The copolymer of an unsaturated monomer (a1) and an unsaturated monomer (a2) WHEREIN: The copolymerization ratio of the unsaturated monomer (a1) in the said polymer becomes like this. Preferably it is 5-50 mass %, More preferably, it is 10-40 mass %. By copolymerizing the unsaturated monomer (a1) in such a range, a composition excellent in alkali developability and storage stability can be obtained.

Among the unsaturated monomers (a2), as the monomer having an epoxy group, glycidyl (meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) ) acrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate, and the like.

As a specific example of the copolymer of an unsaturated monomer (a1) and an unsaturated monomer (a2), Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-31308, for example. No., Japanese Unexamined Patent Publication No. 10-300922, Japanese Patent Application Laid-Open No. Hei 11-174224, Japanese Unexamined Patent Publication No. Hei 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication No. 2004-101728, Japan The copolymer disclosed in Unexamined-Japanese-Patent No. 4-352101 etc. is mentioned.

Moreover, in this invention, as a polymer which has a (meth)acryloyl group as a polymeric group, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. Hei, for example. As disclosed in Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. Hei 09-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, and Japanese Patent Application Laid-Open No. 2008-181095, a (meth) acryloyl group in the side chain A carboxyl group-containing polymer having a polymerizable unsaturated bond can also be used.

It is preferable that the said acrylic resin has a structural unit containing the group whose alkali developability increases with the acid which generate|occur|produces from an acid generator from a viewpoint of the developability. Examples of the group whose alkali solubility increases by the action of such an acid include a group having a lactone ring, an acid dissociable group, and the like.

As said lactone ring group, for example,

monocyclic lactone ring groups such as butyrolactone ring and valerolactone ring;

and polycyclic lactone cyclic groups such as a norbornane lactone cyclic group and a 5-oxo-4- ^{oxatricyclo[4.3.1.1 3,8]undecane cyclic group.}

As said lactone ring group, it is preferable that the ring-opening reaction rate by an alkali is larger than an unsubstituted norbornane lactone ring group. Here, "the rate of the ring-opening reaction of a lactone ring group by alkali" means the rate of the ring-opening reaction of the lactone ring group in an aqueous solution of pH 10.

The lactone ring group is preferably a monocyclic lactone ring group, a polycyclic lactone ring group substituted with an electron withdrawing group, or a polycyclic lactone ring group containing an oxygen atom or a sulfur atom in a ring other than the lactone ring. Usually, such a lactone ring group has a larger ring-opening reaction rate with an alkali than an unsubstituted norbornane lactone ring group.

Examples of the electron withdrawing group substituting the lactone ring group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorinated hydrocarbon group such as a cyano group and a fluorinated alkyl group. Among these, a fluorine atom, a cyano group, and a fluorinated alkyl group are preferable, and a fluorine atom, a cyano group, a trifluoromethyl group, and a hexafluoroisopropyl group are preferable. Other such groups may include structural units having a lactone ring group described in Japanese Patent Application Laid-Open No. 2006-021023.

Specific examples of the structural unit containing an acid dissociable group are shown below. An "acid dissociable group" is a group which substitutes for the hydrogen atom of a carboxy group, a hydroxyl group, or a sulfo group, and refers to the group which dissociates by the action|action of an acid. By having an acid-dissociable group, the radiation-sensitive resin composition differs in solubility in a developing solution in an exposed part and an unexposed part by the acid generated by exposure, As a result, alkali solubility can be improved.

As said acid dissociable group, the group which has an acetal structure is mentioned. Examples of the group having an acetal structure include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n -butoxyethoxy group, etc. are mentioned. As a monomer which can form the structural unit containing such an acetal structure, 1-alkoxyalkyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 1-alkoxy alkoxystyrene, and tetrahydropyranyloxystyrene are preferable. and 1-alkoxyalkyl (meth)acrylate, etc. are preferable. Moreover, the structural unit represented by following formula (1) is also mentioned.

In said formula (1), R<^1> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y ¹ is a monovalent acid dissociable group.

As said R<^1> , a hydrogen atom and a methyl group are preferable from a copolymerizable viewpoint of a monomer, and a methyl group is more preferable.

Examples of the monovalent acid-dissociable group represented by wherein Y ^1, preferred is represented by formula (Y-1).

In the formula (Y-1), R ^e1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Re2 and ^Re3 are each independently a monovalent chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or reduced water 3 composed of these groups together with the carbon atom to which they are bonded The alicyclic structure of -20 is shown.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. can be heard

Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms represented by ^Re1 , ^Re2 and ^{Re3 include:}

alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and n-pentyl group;

Alkenyl groups, such as an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group;

Alkynyl groups, such as an ethynyl group, a propynyl group, a butynyl group, and a pentynyl group, etc. are mentioned.

Among these, an alkyl group is preferable, an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group, an ethyl group, and an i-propyl group are more preferable, and an ethyl group is particularly preferable.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by ^Re1 , ^Re2 and ^{Re3 include:}

monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group;

polycyclic cycloalkyl groups such as norbornyl, adamantyl, tricyclodecyl and tetracyclododecyl;

monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group;

Polycyclic cycloalkenyl groups, such as a norbornenyl group and a tricyclodecenyl group, etc. are mentioned.

Among these, a monocyclic cycloalkyl group and a polycyclic cycloalkyl group are preferable, and a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group are more preferable.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by ^{R e1 include,}

Aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a methylanthryl group;

Aralkyl groups, such as a benzyl group, a phenethyl group, a naphthylmethyl group, and an antholylmethyl group, etc. are mentioned.

As a monomer which can form the structural unit containing such an acid-dissociable group, t-butoxy (meth)acrylate, adamantyl (meth)acrylate, etc. are mentioned. As other specific examples, the compound described in Japanese Patent Application Laid-Open No. 2006-021023 can be applied.

<Polyimide and polyimide precursor>

It is preferable that a polyimide is a polyimide which has alkali-soluble group in the structural unit of a polymer. As alkali-soluble group, a carboxyl group is mentioned, for example. By having an alkali-soluble group, for example, a carboxyl group in a structural unit, alkali developability (alkali solubility) is provided, and scum expression of an exposure part can be suppressed at the time of alkali development. Similarly, a polyimide precursor also has alkali-soluble groups, such as a carboxyl group, and can be equipped with alkali solubility, for example.

Moreover, when polyimide has a fluorine atom in a structural unit, when developing with aqueous alkali solution, since water repellency is provided to the interface of a film|membrane, spreading of an interface, etc. are suppressed, it is preferable. The fluorine atom content in the polyimide is preferably 10 mass % or more in order to sufficiently obtain the effect of preventing the spread of the interface, and more preferably 20 mass % or less from the viewpoint of solubility in aqueous alkali solution.

The polyimide used for the composition of this embodiment is a polyimide obtained by condensing an acid component and an amine component, for example. It is preferable to select tetracarboxylic dianhydride as an acid component, and it is preferable to select diamine as an amine component.

Examples of the tetracarboxylic dianhydride used in the formation of the polyimide include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarbon Acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4- Dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane Dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-( 3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride or acid dianhydride of the structure shown below is preferable. You may use these 2 or more types.

Specific examples of the diamine used for formation of the polyimide include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, m-phenyl Rendiamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene or diamine having the structure shown below is preferable. You may use these 2 or more types.

As such a polyimide and a polyimide precursor, the polymer disclosed by Unexamined-Japanese-Patent No. 2011-133699, Unexamined-Japanese-Patent No. 2009-258634, etc. can also be used, for example. Moreover, the polyimide derivative which has the above-mentioned acid dissociation property in the carboxyl group of polyamic acid which is a polyimide precursor can also be used suitably.

<Polysiloxane>

The polysiloxane is not particularly limited as long as it is a polymer of a compound having a siloxane bond. Usually, this polysiloxane hardens|cures the acid which generate|occur|produced from a photoacid generator, and the base which generate|occur|produced from a photobase generator as a catalyst, for example.

As polysiloxane, it is preferable that it is a hydrolysis-condensation product of the hydrolysable silane compound represented by following formula (2B).

In formula (2B), R ²⁰ is a non-hydrolyzable organic group having 1 to 20 carbon atoms. R ²¹ is an alkyl group having 1 to 4 carbon atoms. q is an integer of 0-3. When R ²⁰ or R ²¹ is plural, these may be the same or different.

Examples ^{of the non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R 20} include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. These may be linear, branched, or cyclic. In addition, a part or all of the hydrogen atoms which these alkyl group, an aryl group, and an aralkyl group have may be substituted by the vinyl group, the (meth)acryloyl group, or the epoxy group.

Examples ^{of the alkyl group having 1 to 4 carbon atoms represented by R 21} include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Although q is an integer of 0-3, Preferably it is an integer of 0-2, More preferably, it is 0 and 1, More preferably, it is 1. When q is the said numerical value, advancing of a hydrolysis and condensation reaction becomes easier, As a result, the speed|rate of hardening reaction becomes large, and the intensity|strength, adhesiveness, etc. of the cured film obtained can be improved.

Among the hydrolysable silane compounds represented by the above formula (2B), a silane compound substituted with four hydrolysable groups and a silane compound substituted with one non-hydrolysable group and three hydrolysable groups are preferable, and one non-hydrolysable group A silane compound substituted with three hydrolysable groups is more preferable. Specific examples of the preferred hydrolyzable silane compound include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, and ethyltrime. Toxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane is mentioned. These hydrolyzable silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

The conditions for hydrolyzing and condensing the hydrolysable silane compound represented by the formula (2B) include hydrolyzing at least a part of the hydrolysable silane compound represented by the formula (2B), converting the hydrolyzable group into a silanol group, and performing a condensation reaction. Although it is not specifically limited as long as it raise|generates, As an example, it can implement as follows.

It is preferable to use water purified by methods, such as a reverse osmosis membrane treatment, an ion exchange treatment, distillation, as water used for hydrolysis-condensation of the hydrolysable silane compound represented by said Formula (2B). By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.

Although it does not specifically limit as a solvent which can be used for hydrolysis-condensation of the hydrolysable silane compound represented by said formula (2B), For example, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl Ether, propylene glycol monoalkyl ether acetate, propionic acid ester, etc. are mentioned.

As polysiloxane, the polysiloxane disclosed by Unexamined-Japanese-Patent No. 2011-28225, Unexamined-Japanese-Patent No. 2006-178436, etc. can also be used, for example.

<Cyclic olefin resin>

It does not restrict|limit especially as cyclic olefin resin, Any resin containing a cyclic olefin moiety may be sufficient, for example, cyclic olefin resin described in International Publication WO2013/054864 can be used.

<Polycarbonate>

It does not restrict|limit especially as a polycarbonate, What is necessary is just a polycarbonate resin containing a fluorene moiety, for example, the polycarbonate described in Unexamined-Japanese-Patent No. 2008-163194 can be used.

<Polyester>

It does not restrict|limit especially as polyester, Polyester which has a urethane bond site|part, and polyester containing a fluorene site|part are especially preferable, For example, Unexamined-Japanese-Patent No. 2010-285505 and Unexamined-Japanese-Patent No. 2011-197450. It can be synthesized by the method described in

<Epoxy resin>

It does not restrict|limit especially as an epoxy resin, What is necessary is just a compound which has an epoxy group, and a specific example is shown below.

Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl bisphenol-type diglycidyl ethers such as cidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether polyglycidyl ethers of polyhydric alcohols such as cidyl ether;

polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; phenol novolak-type epoxy resin;

cresol novolak-type epoxy resin; polyphenol-type epoxy resin; diglycidyl esters of aliphatic long-chain dibasic acids;

glycidyl esters of higher fatty acids; aliphatic polyglycidyl ethers; and epoxidized soybean oil and epoxidized linseed oil.

<Phenolic resin>

As a preferable phenol resin as a resin used for the composition of this embodiment, a phenol resin obtained by polycondensing phenols with aldehydes, such as formalin, by a well-known method is used suitably, and a novolak resin and a resol resin are used. Among these, especially from a viewpoint of control of molecular weight, a novolak resin is especially preferable.

<Polyamide>

As the polyamide, a polyamide soluble in an organic solvent is preferably used, and as such polyamide, for example, a special polyamide resin: PA series (manufactured by T&K TOKA Corporation) or the like can be used.

[C] As a compound, an acrylic resin, a polyimide derivative, and a phenol resin are preferable from a viewpoint of alkali developability.

In the composition of this embodiment, as content of compound [C], 1 mass part - 10,000 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 10 mass parts - 8500 mass parts are more preferable. [C] By making content of a compound agent into the above-mentioned range, the heat resistance, solvent resistance, and light resistance of the film|membrane obtained can be improved.

<[D] sensitizer>

The composition of embodiment of this invention can contain [D] a sensitizer. [D] By further containing a sensitizer, the radiation sensitivity of the composition can be improved more. [D] It is preferable that a sensitizer is a compound used as an electron excited state by absorbing an actinic light or a radiation. The [D] sensitizer, which has become an electron excited state, comes into contact with the [B] acid generator to generate electron transfer, energy transfer, heat generation, etc., and accordingly, the [B] acid generator causes a chemical change and decomposes to an acid create

[D] As a sensitizer, it belongs to the following compounds, and the compound etc. which have an absorption wavelength in the area|region of 350 nm - 450 nm are mentioned.

[D] As a sensitizer, polynuclear aromatics, acridones, styryl, base styryl, coumarins, and xanthone are preferable, and xanthone is more preferable. Among xanthones, diethyl thioxanthone and isopropyl thioxanthone are particularly preferable.

The composition of this embodiment WHEREIN: [D] A sensitizer may be used individually by 1 type, and may mix and use 2 or more types.

Composition of this embodiment WHEREIN: As content of [D] sensitizer, 0.1 mass part - 30 mass parts are preferable with respect to 100 mass parts of [B] acid generators, and 1 mass part - 4 mass parts are more preferable. [D] By setting the content of the sensitizer to the above range, the composition of the present embodiment can optimize the sensitivity as a radiation-sensitive composition, so a high-resolution concave pattern is formed to produce a base material having a lyophilic part and a lyophobic part can do.

<[E] wife>

The composition of the embodiment of the present invention may contain the above-mentioned [A] polymer, [B] acid generator, [C] compound, and [D] sensitizer, in addition to the [E] chemical agent.

The [E] dispersant functions as an acid diffusion inhibitor that prevents diffusion of the acid from the [B] acid generator. [E] As the quenching agent, a photodegradable base that generates a weak acid by sensitizing by exposure can be used. The photodegradable base generates an acid in the exposed part, while in the unexposed part, a high acid trapping function is exhibited by an anion, [B] supplements the acid from the acid generator, and diffuses from the exposed part to the unexposed part inactivate the acid That is, in order to deactivate an acid only in an unexposed part, the contrast of the desorption reaction of a protecting group improves, and resolution can be improved more as a result. As an example of the photodegradable base, there is an onium salt compound that decomposes upon exposure and loses acid diffusion controllability.

The composition of this embodiment WHEREIN: As for [E], you may use individually by 1 type, and may mix and use 2 or more types. In the composition of the present embodiment, the content of [E] is preferably 0.001 parts by mass to 5 parts by mass, more preferably 0.005 parts by mass to 3 parts by mass, with respect to 100 parts by mass of the [B] acid generator. . Since the reactivity of the composition of this embodiment can be optimized by setting it as the above-mentioned range, a high-resolution concave pattern can be formed and the base material which has a lyophilic part and a lyophobic part can be manufactured.

<[F] polymerizable compound>

The composition of the embodiment of the present invention can cure the composition by containing the [F] polymerizable compound.

[F] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. Examples of such a polymerizable compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. ) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di ( Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri( Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol di Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether Poly(meth)acrylate etc. are mentioned. These compounds can be used individually or in combination of 2 or more types.

These compounds and the photoinitiators of Unexamined-Japanese-Patent No. 2013-164471, Unexamined-Japanese-Patent No. 2012-212114, and Unexamined-Japanese-Patent No. 2010-85929 can be used.

The composition of this embodiment WHEREIN: 1 mass part - 9900 mass parts are preferable with respect to 100 mass parts of [A] polymer, as for the usage-amount of [F] polymeric compound, 3 mass parts - 8000 mass parts are more preferable, 5 Mass parts - 5000 mass parts are more preferable. [F] By carrying out the usage-amount of a polymeric compound in the above-mentioned range, the hardness of the coating film obtained from the composition of this embodiment can be raised, and heat resistance can be made more favorable.

<[G] Photoradical polymerization initiator>

[G] The radical photopolymerization initiator is a compound that promotes polymerization of the [F] polymerizable compound upon irradiation with radiation. Therefore, when the composition of the embodiment of the present invention contains a [F] polymerizable compound, it is preferable to use a [G] radical photopolymerization initiator.

A radical photopolymerization initiator is a component which respond|sensitizes a radiation and generate|occur|produces the radical species which can start superposition|polymerization of the compound provided with polymerizability. It becomes possible to start the crosslinking reaction of a polymeric compound, and to improve the heat resistance and solvent resistance of the film|membrane obtained.

As such a radical photopolymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned, for example. These compounds may be used independently, and 2 or more types may be mixed and used for them.

Examples of the O-acyloxime compound include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H- Carbazol-3-yl]-1-(O-acetyloxime) or ethanone-1-[9-ethyl-6-a2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) ) methoxybenzoyl｝-9H-carbazol-3-yl]-1-(O-acetyloxime) is preferred.

Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.

Among the acetophenone compounds, α-aminoketone compounds are preferable, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2 -Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 is preferred desirable.

Moreover, the radical photopolymerization initiator of Unexamined-Japanese-Patent No. 2013-164471, Unexamined-Japanese-Patent No. 2012-212114, and Unexamined-Japanese-Patent No. 2010-85929 can be used.

To [A] content of the photoinitiator illustrated as a radical photoinitiator becomes like this with respect to 100 mass parts of polymers, Preferably they are 1 mass part - 5000 mass parts, More preferably, they are 5 mass parts - 3000 mass parts. By making content of a radical photopolymerization initiator into 1 mass part - 5000 mass parts, even if it is a low exposure amount, the radiation-sensitive resin composition of this embodiment can form the cured film which has high solvent resistance, high hardness, and high adhesiveness.

<solvent>

Alcohols, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol from the viewpoint of being non-reactive with each component and easiness of coating film formation Monoalkyl ether acetates, ketones and esters are preferable, and in particular, 1-octanol, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, etc. are preferable.

<Adhesive preparation>

In the radiation-sensitive resin composition of the present embodiment, inorganic substances serving as substrates, for example, silicon compounds such as silicon, silicon oxide and silicon nitride, glass such as silicates and quartz, and metals such as gold, copper, and aluminum; In order to improve the adhesiveness of an insulating film, it is preferable to use an adhesion aid. As such adhesion aid, a functional silane coupling agent is preferably used. As an example of a functional silane coupling agent, the silane coupling agent etc. which have reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably oxiranyl group), and a thiol group, are mentioned.

Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycan Cydoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyl trime Toxysilane etc. are mentioned. Among these, γ-glycidoxypropylalkyldialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

<Other optional ingredients>

The composition of this embodiment can contain other arbitrary components further, unless the effect of this invention is impaired. Examples of other optional components include surfactants, storage stabilizers, and heat resistance improvers. The composition of this embodiment WHEREIN: Other arbitrary components may be used individually by 1 type, and may mix and use 2 or more types.

The said radiation-sensitive resin composition can be used also for the object for positive pattern formation using an alkali developer, and for the object for negative pattern formation using the developer containing an organic solvent.

<Example of preparation of hair-friendly material>

Synthesis examples of the polymer [A] used for the hair-philic material are shown below.

[Synthesis Example 1]

To a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and propylene 200 parts by mass of glycol monomethyl ether acetate was prepared. Subsequently, 64 parts by mass of 4-hydroxyphenyl methacrylate and 36 parts by mass of methyl methacrylate are added, and the temperature of the solution is raised to 80° C. while slowly stirring in a nitrogen atmosphere, and the temperature is maintained for 4 hours. By superposing|polymerizing, the solution containing the polymer [A-1] which is a copolymer was obtained (solid content concentration=34.7 mass %, Mw=28000, Mw/Mn=2.4). In addition, the solid content concentration means the ratio of the copolymer mass to the total mass of the copolymer solution.

Next, to 10 parts by mass of a solution containing the obtained polymer [A-1], 11 parts by mass of propylene glycol monomethyl ether acetate, 3,3,4,4,5,5,6,6,7,7,8 ,8,8-tridecafluoro-1-vinyloxyoctane 5.3 mass parts was added, and after fully stirring, 0.31 mass parts of trifluoroacetic acid was added and it was made to react at 80 degreeC in nitrogen atmosphere for 9 hours. Then, the reaction solution was cooled to room temperature, 0.43 mass parts of pyridine was added, and reaction was quenched. Reprecipitation purification is performed by dripping the obtained reaction solution into a large excess of methanol, and then, after dissolving in 13 mass parts of propylene glycol monomethyl ether acetate, reprecipitation refinement|purification is performed by dripping into a large excess of hexane, and after drying, white 7.1 mass parts of polymer [A-1] was obtained as a solid copolymer. About the obtained polymer [A-1], ^{it analyzed using <1>} H-NMR, and confirmed that acetalization was advancing (chemical shift: 5.50 ppm, acetal group CH)

100 parts by mass of [A] polymer [A-1] obtained in Synthesis Example 1 above, [B] 2 parts by mass of N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester as an acid generator, [D] 0.5 parts by mass of 2,4-diethylthioxanthone as a sensitizer, and 0.1 parts by mass of 2-phenylbenzoimidazole as [E] as a component were mixed, and Polyflow No95 (Kyoeisha Chemical (Kyoeisha Chemical) A radiation-sensitive composition is prepared by adding 0.1 mass part of manufacture), adding propylene glycol monomethyl ether acetate as a solvent, respectively, and filtering with a Millipore filter with a pore diameter of 0.5 micrometer so that solid content concentration may become 18 mass %. did.

<Pattern structure and pattern formation method>

The pattern formation method using the above-mentioned hydrophilic material and the pattern structure formed by the method are demonstrated. Hereinafter, as a pattern structure, especially a wiring structure is demonstrated.

<First embodiment>

The wiring structure 100 and the wiring formation method according to the present embodiment will be described.

[Wiring structure]

First, the structure of the wiring structure 100 formed by the wiring formation method which concerns on this embodiment is demonstrated, referring drawings.

1 is a view for explaining the configuration of a wiring structure 100 formed by the wiring forming method according to the present embodiment. In this figure, a top view of the wiring structure 100, a cross-sectional view taken along A-A', and a cross-sectional view taken along B-B' are shown from the upper end. In addition, description of the wiring formation method WHEREIN: The same applies to drawings used below.

The wiring structure 100 according to the present embodiment includes at least a substrate 102 , a first coating film 104 , and a wiring 108 .

The substrate 102 has a first surface 102a and a second surface 102b that are opposed to each other. Moreover, the board|substrate 102 has the 1st area|region R1 and the 2nd area|region R2 in planar view. The second region R2 is disposed in at least a part of the region excluding the first region R1 .

In the present embodiment, the first region R1 is disposed along the periphery of the substrate 102 . Further, the first region R1 and the second region R2 are not separated from each other and are in contact with each other.

As a material of the board|substrate 102 which can be used, glass, quartz, silicon|silicone, resin etc. are mentioned, for example. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, polyimide, ring-opened polymer of cyclic olefin (ROMP polymer), and hydrogenated substances thereof.

Moreover, as the board|substrate 102, since it is preferable to use the wiring structure 100 finally obtained by the wiring formation method which concerns on this embodiment as it is for an electronic circuit etc., since it is a point which has been conventionally used for an electronic circuit, the resin board|substrate, glass A substrate or a semiconductor substrate is preferable.

The 1st coating film 104 is arrange|positioned on the 1st surface 102a of the board|substrate 102 in the area|region except the 1st area|region R1. In other words, the region excluding the region where the first coating film 104 is disposed is the first region R1 . In this embodiment, the 1st coating film 104 is arrange|positioned on the 1st surface 102a of the board|substrate 102 in island shape.

As a material of the 1st coating film 104, the hydrophilic material mentioned above is contained as a component. The region where the first coating film 104 is disposed includes the second region R2, and in the second region R2, it has lyophilicity at least on the first surface 102a side surface. In this embodiment, the 1st coating film 104 has lyophilicity in the surface and inside of 2nd area|region R2, and the area|region except 2nd area|region R2 has liquid repellency. Moreover, in the 1st coating film 104, the film thickness of 2nd area|region R2 is thin compared with the film thickness of the area|region except 2nd area|region R2.

The wiring 108 is formed on at least the first coating film 104 in a cross-sectional view. In addition, the wiring 108 is formed in the 2nd area|region R2 on the 1st coating film 104 at least in planar view. Here, the second region R2 is a region having lyophilic properties. The wiring 108 is not formed in a region other than the second region R2 on the first coating film 104 . That is, the wiring 108 is not formed on the first coating film 104 in a region other than the region having lyophilicity. In this embodiment, a part of the wiring 108 further extends to the first region R1 of the substrate 102 and is in contact with the first surface 102a of the substrate 102 .

In this embodiment, a simplified example is used for the layer structure of the first coating film 104 and the wiring 108 and the planar pattern, etc., however, this is for the sake of simplification of explanation and is not limited to this example. , a wide variety of configurations can be employed.

[Wiring Formation Method]

Next, a wiring forming method for forming the wiring structure 100 according to the present embodiment will be described in detail with reference to the drawings.

The wiring formation method using the lipophilic material according to the present embodiment includes the following steps (a) to (c) in this order.

(a) a step of forming a first coating film 104 on the substrate 102;

(b) removing the first coating film 104 of the first region R1 on the substrate 102;

(c) A process of depositing the conductive material 106 in the second region R2 on the substrate 102 .

Hereinafter, each process is demonstrated in detail, referring drawings.

[Process (a)]

Step (a) is a step of forming the first coating film 104 on the substrate 102 . The first coating film 104 has liquid repellency and is lyophilized by irradiating energy of a specific wavelength. The 1st coating film 104 is provided with this property by including the hydrophilic material mentioned above, for example.

FIG. 2A is a diagram for explaining the step of preparing the substrate 102 used in the wiring forming method according to the present embodiment.

As the material of the substrate 102 that can be used, those described in the description of the configuration of the wiring structure 100 can be used, and therefore, detailed description thereof is omitted here.

FIG. 2B is a diagram schematically illustrating a state in which the first coating film 104 is applied on the substrate 102 .

As a coating method of the 1st coating film 104, the application method using a brush or a brush, the dipping method, the spray method, the roll coating method, the rotation coating method (spin coating method), the slit die coating method, the bar coating method, for example , flexographic printing, offset printing, inkjet printing, an appropriate method such as a dispensing method can be employed. Among these coating methods, the slit die coating method or the spin coating method is particularly preferable.

After application, if necessary, pre-baking (PB) may be performed in order to volatilize the solvent in the coating film. As PB temperature, it is 60 degreeC - 140 degreeC normally, and 80 degreeC - 120 degreeC are preferable. As PB time, it is 5 second - 600 second normally, and 10 second - 300 second are preferable.

As a film thickness of the 1st coating film 104 apply|coated at a process (a), 100 nm - 10,000 nm are preferable, and 200 nm - 5,000 nm are more preferable.

In addition, before applying the 1st coating film 104 to the board|substrate 102, you may perform pre-processing, such as washing|cleaning, roughening, and provision of a micro uneven|corrugated surface, if necessary.

[Process (b)]

Step (b) is a step of removing the first coating film 104 in the first region R1 on the substrate 102 . Step (b) includes the following steps (b-1) and (b-2). The step (b-1) is an exposure step, and the first coating film 104 in the first region R1 is irradiated with energy of a specific wavelength. At the same time, the surface of the first coating film 104 in the first region R1 is lyophilized. The step (b-2) is a developing step, and the first coating film 104 in the first region R1 is removed by bringing it into contact with the specific chemical solution. Hereinafter, the specific chemical solution is called a developer.

FIG. 2C is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the first coating film 104 of the first region R1 on the substrate 102 .

In the step (b-1), as shown in FIG. 2C , the first region R1 of the first coating film 104 on the substrate 102 is irradiated with energy of a specific wavelength, and the irradiation unit 104a (first region) is irradiated with energy of a specific wavelength. (R1)) and the first coating film 104 having the unirradiated portion 104b is formed.

According to the step (b-1), the acid dissociable group in the lipophilic material is released and volatilized by the effect of the acid generator. As a result, the film thickness of the irradiated portion 104a (first region R1) becomes thinner than that of the unirradiated portion 104b, and a concave pattern is formed. At this time, if the acid dissociable group has a fluorine atom, the first coating film 104 and the unirradiated portion 104b obtained in the step (a) exhibit liquid repellency, but the irradiated portion 104a (first region R1) is With the disappearance of the acid dissociable group, it becomes lyophilic compared to the unirradiated portion 104b.

Therefore, in the step (a), when a composition containing a compound containing an acid-dissociable group having a fluorine atom is used, the liquid-repellent unirradiated portion is placed on the substrate 102 by the step (b-1) in step (b-1). A first coating film 104 having 104b and an irradiated portion 104a (first region R1) that is a concave pattern more lyophilic than the unirradiated portion 104b is formed.

In a process (b-1), the photomask and metal mask which have a predetermined pattern so that the irradiation part 104a (1st area|region R1) of the same shape as the pattern shape of the 1st coating film 104 to be formed may be formed. , a light-shielding seal or the like 114 may be used to expose the light. As a photomask, multi-gradation masks, such as a binary mask, a halftone mask, and a gray tone mask, can be used. Both the exposure method and the contact exposure method are applicable. Or you may draw and expose a predetermined pattern using a direct drawing type exposure apparatus.

Examples of radiation having energy used for exposure include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (13.5 nm, EUV), X-ray, and γ-ray; and charged particle beams such as electron beams and α-rays. Among these, ultraviolet rays generally used in industry are preferable, particularly radiation having a wavelength of g-line, h-line, and i-line having a wavelength of 300 nm or more, and radiation having a short wavelength of i-line or a short wavelength of 375 nm.

After the step (b-1), a step of heating the first coating film 104 may be included. By heating the 1st coating film 104 obtained in the process (b-1), the recessed part corresponded to the part which was the irradiation part 104a (1st area|region R1), and the convex part corresponded to the part which was the unirradiated part 104b. A first coating film 104 having a negative portion is formed.

A component in which the acid dissociable group generated in the irradiation portion 104a (the first region R1) in the step (b-1) in the step of heating the first coating film 104 is released due to the effect of the acid generator can be further volatilized. As a result, the dent in the concave state in the irradiated portion 104a is further deepened (the film thickness of the concave portion becomes thinner), and the film thickness of the concave portion is thinner than the film thickness of the convex portion by 10% or more. ) can be formed.

In the step (a), when a composition containing a compound containing an acid-dissociable group having a fluorine atom is used, the first coating film 104 is heated to form a liquid-repellent convex portion on the substrate 102 ; The first coating film 104 which has a lyophilic recessed part rather than the said part is formed.

Although the details will be described later, when a liquid film-forming material is applied on such a first coating film 104, since the film thickness difference of the convex portion and the concave portion is large, the concavities and convexities on the surface of the first coating film 104 cause the concave portion to fall. Although the material tends to collect, not only the effect of the surface shape of the first coating film 104 but also the lyophilic and lyophobic properties of the surface make it easier to collect the material on the concave portion, resulting in a more desired shape, specifically, It becomes easy to form wiring which has a fine pattern.

In addition, in the step (a), when a composition containing a compound containing an acid-dissociable group having a fluorine atom is used, the group having a fluorine atom is released by energy irradiation. Since this leaving group is relatively easy to volatilize, in the process of heating the 1st coating film 104, the 1st coating film 104 with a large difference in the film thickness of a convex part and a recessed part can be formed more simply.

As a method of heating the 1st coating film 104, for example, the method of heating the board|substrate 102 to which the 1st coating film 104 was applied using a hot plate, a batch type oven, or a conveyor type oven, a dryer, etc. A method of hot air drying using a vacuum baking method is mentioned.

The heating conditions vary depending on the composition of the hydrophilic material used in the step (a), the thickness of the first coating film 104 obtained in the step (b-1), and the like, but preferably at 60°C to 150°C for 3 minutes. About 30 minutes.

FIG. 2D is a diagram schematically illustrating a state in which the irradiation portion 104a (the first region R1) of the first coating film 104 on the substrate 102 is selectively removed.

In the step (b-2), the irradiated portion 104a (the first region R1 ) formed in the first coating film 104 in the step (b-1) is selectively removed using a developing solution. As a result, a predetermined pattern of the first coating film 104 is formed.

As said developing solution, the developing solution containing an alkali developing solution, an organic solvent, etc. are mentioned, for example. A developing solution can be selected according to the pattern shape to form. When the mask pattern is projected onto the first coating film 104 by exposure, by developing a region having a strong light irradiation intensity with an alkaline aqueous solution, the exposed portion above a predetermined threshold value is dissolved and removed, thereby forming the first coating film 104 . pattern can be formed. That is, the first coating film 104 containing the hydrophilic material can function as a positive resist. On the other hand, when the mask pattern is projected onto the first coating film 104 by exposure, the region having a weak light irradiation intensity is developed with a liquid containing an organic solvent, so that the exposed portion below a predetermined threshold is dissolved and removed, so that the A pattern of the first coating film 104 can be formed. That is, the first coating film 104 containing the lipophilic material can also function as a negative resist. It is also possible to develop by combining these developing solutions according to the desired resolution or pattern shape.

Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1 The alkaline aqueous solution etc. which melt|dissolved at least 1 sort(s) of alkaline compounds, such as 5-diazabicyclo-[4.3.0]-5-nonene, are mentioned.

As an organic solvent contained in the developing solution containing the said organic solvent, 1 type, 2 or more types of the solvent enumerated as a solvent of the above-mentioned radiation-sensitive resin composition, etc. are mentioned, for example. Among these, an alcohol solvent, an ether solvent, an ester solvent, and a ketone solvent are preferable. As the ether-based solvent, an aromatic-containing ether-based solvent is preferable, and anisole is more preferable. As an ester solvent, an acetate ester solvent is preferable, and n-butyl acetate is more preferable. As the ketone solvent, a chain ketone solvent is preferable, and 2-heptanone is more preferable.

As content of the organic solvent in a developing solution, 80 mass % or more is preferable, 90 mass % or more is more preferable, 95 mass % or more is still more preferable, and 99 mass % or more is especially preferable. By setting the content of the organic solvent in the developer within the above range, the contrast between the exposed portion and the unexposed portion can be improved, and as a result, a resist pattern with smaller LWR and CDU can be formed while exhibiting more excellent depth of focus and exposure margin. can do. Moreover, as components other than an organic solvent, water, silicone oil, etc. are mentioned, for example.

An appropriate amount of surfactant can be added to the developer as needed. As the surfactant, for example, an ionic or nonionic fluorine-based and/or silicone-based surfactant can be used.

As a developing method, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method of developing by stopping the developer for a certain period of time by raising the developer to the surface of the substrate by surface tension (puddle method), applying the developer to the surface of the substrate A method of spraying (spray method), a method of continuously drawing out a developer while scanning a developer guiding nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), etc. are mentioned.

After the said development, it is preferable to dry after rinsing using rinsing liquids, such as water and alcohol. Examples of the rinsing method include a method of continuously extracting a rinse liquid on a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a bath filled with a rinse liquid for a certain period of time (dip method), the surface of the substrate The method (spray method) etc. of spraying a rinse liquid is mentioned.

[Process (c)]

Step (c) is a step of depositing the conductive material 106 in the second region R2 on the substrate 102 . Step (c) includes the following steps (c-1) and (c-2). In the step (c-1), the surface of the first coating film 104 in the second region R2 is lyophilized by irradiating energy of a specific wavelength. The process (c-2) deposits the electrically-conductive material 106 in 2nd area|region R2 at least by apply|coating the solution containing the electrically-conductive material 106 on the 1st coating film 104.

FIG. 2E is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the second region R2 of the first coating film 104 .

In the process (c-1), as shown in FIG. 2E, energy of a specific wavelength is irradiated to a part of the pattern of the 1st coating film 104 formed on the board|substrate 102, and the irradiation part 104a (2nd area|region (2) R2)) and a first coating film 104 having an unirradiated portion 104b is formed.

Here, by the same mechanism as in the step (b-1), the acid dissociable group in the lipophilic material desorbs and volatilizes due to the effect of the acid generator. As a result, the film thickness of the irradiated portion 104a (second region R2) becomes thinner than the film thickness of the unirradiated portion 104b, and a concave pattern is formed. At this time, if the acid dissociable group has a fluorine atom, the coating film obtained in step (a) and the unirradiated portion 104b exhibit liquid repellency, but the irradiated portion 104a (the second region R2) is the acid dissociable group. With disappearance, it becomes lyophilic compared to the unirradiated portion 104b.

In the step (c-1) also in the same manner as in the step (b-1), a photomask having a predetermined pattern such that the irradiated portion 104a having the same shape as the pattern shape of the second region R2 to be formed is formed; Exposure can be carried out through a metal mask, a light-shielding seal, or the like 114 . Or you may draw and expose a predetermined pattern using a direct drawing type exposure apparatus.

After the step (c-1), a step of heating the first coating film 104 may be included. As a heating process, the same process as the heating process demonstrated in process (b) can be used. By heating the 1st coating film 104 obtained by the process (c-1), the recessed part corresponded to the part which was the irradiation part 104a (2nd area|region R2), and the convex part corresponded to the part which was the unirradiated part 104b. A first coating film 104 having a negative portion is formed.

FIG. 2F is a diagram schematically illustrating a process of applying a solution containing the conductive material 106 on the first coating film 104 .

In the step (c-2), as shown in FIG. 2F , the conductive material 106 is applied to at least the second region R2 by applying a solution containing the conductive material 106 on the first coating film 104 . to deposit

It does not specifically limit as a method of the said application|coating, For example, the application method using a brush or a brush, the dipping method, the spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method , an appropriate method such as a squeegee method, a flexographic printing method, an offset printing method, an inkjet printing method, and a dispensing method can be employed. Among these, the dipping method, the spray method, the spin coating method, the slit-die coating method, the offset printing method, the inkjet printing, and the dispensing method are especially preferable.

Moreover, the dipping method, the inkjet method, and the dispensing method are preferable from a viewpoint of forming fine and thick wiring which is low resistance and is hard to disconnect.

As for the conductive material 106, since the first coating film 104 has lyophobic convex portions and more lyophilic concave portions (second region R2), when the liquid conductive material 106 is used, , even if any of the methods described above is used, the conductive material 106 splashes on the convex portion and tends to collect in the concave portion, so that the conductive material 106 is deposited along the concave portion.

By the above-described step (c), the wiring 108 is formed. By the above process, the wiring structure 100 shown in FIG. 1 can be formed.

As mentioned above, the wiring formation method which concerns on this embodiment was demonstrated. According to the wiring forming method according to the present embodiment, it is possible to provide a wiring forming method capable of forming a fine pattern by reducing the number of photolithography steps.

In addition, in this embodiment, the wiring formation method which includes the said process (a), process (b), and process (c) in this order was demonstrated. However, the order and number of each of the steps are not limited thereto, and a person skilled in the art can arbitrarily change the order and number of each of the steps according to a desired configuration of the wiring structure. should be interpreted as belonging to the technical scope of

In addition, in this embodiment, as a pattern structure and its formation method, especially the wiring structure and its formation method were demonstrated. However, the present invention is not limited thereto, and if the lipophilic material according to the present embodiment is used, a pattern structure using a variety of other materials can be formed.

That is, in the said process (c), the said predetermined|prescribed material can be deposited on the concave pattern by apply|coating the solution containing a predetermined|prescribed material on the 1st coating film 104. As the predetermined material, a conductive material, an insulating material, a semiconductor material, a luminescent material, or the like can be used.

As a conductive material, the conductive material containing ink described in JP 2011-34750 etc., as a semiconductor material, the conductive polymer solution containing conductive polymers, such as PEDOT-PSS of JP 2007-150240 , As a luminescent material, Japan The material for organic EL light emitting layer formation, etc. described in Unexamined-Japanese-Patent No. 2007-35647, Unexamined-Japanese-Patent No. 2004-39630, etc. are mentioned.

<Modified example>

A wiring structure 150 according to a modification of the present embodiment and a wiring forming method for forming the same will be described.

[Wiring structure]

First, the configuration of the wiring structure 150 formed by the wiring forming method according to a modification of the present embodiment will be described with reference to the drawings.

FIG. 3 is a diagram for explaining the configuration of a wiring structure 150 formed by a wiring forming method according to a modification of the present embodiment. In this figure, a top view of the wiring structure 150, a cross-sectional view taken along A-A', and a cross-sectional view taken along B-B' are shown from the upper end. In addition, description of the wiring formation method WHEREIN: The same applies to drawings used below.

The wiring structure 150 according to the present embodiment is different from the wiring structure 100 according to the first embodiment only in the pattern of the first region R1 .

In the present embodiment, the first region R1 is provided at two locations within the surface of the substrate 102 . The two first regions R1 are separated from each other.

The wiring 108 is in contact with the first surface 102a of the substrate 102 in two first regions R1 separated from each other. In the wiring 108 , each of the two first regions R1 becomes both ends, and is connected via the second region R2 on the first coating film 104 .

[Wiring Formation Method]

Next, a description will be given of a wiring forming method according to a modification of the present embodiment, narrowing down to differences from the above-described wiring forming method.

The wiring forming method according to the present embodiment includes the above steps (a) to (c) in this order.

[Process (a)]

Step (a) is a step of forming the first coating film 104 on the substrate 102 . The first coating film 104 has liquid repellency and is lyophilized by irradiating energy of a specific wavelength. The 1st coating film 104 is provided with this property by including the hydrophilic material mentioned above, for example. Since the process (a) is the same as the above-mentioned process (a) using FIGS. 2A and 2B, description is abbreviate|omitted.

[Process (b)]

Step (b) is a step of removing the first coating film 104 in the first region R1 on the substrate 102 . Step (b) includes the following steps (b-1) and (b-2). The step (b-1) is an exposure step, and the first coating film 104 in the first region R1 is irradiated with energy of a specific wavelength. At the same time, the surface of the first coating film 104 in the first region R1 is lyophilized. The step (b-2) is a developing step, and the first coating film 104 in the first region R1 is removed by bringing it into contact with the specific chemical solution. The specific chemical solution includes the developer described above.

FIG. 4A is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the first coating film 104 on the substrate 102 .

In the step (b-1), as shown in FIG. 4A , energy of a specific wavelength is irradiated to the first region R1 of the first coating film 104 on the substrate 102 , and the irradiation unit 104a (first region) is irradiated with energy of a specific wavelength. (R1)) and the first coating film 104 having the unirradiated portion 104b is formed.

In the present embodiment, the first region R1 is provided at two locations within the surface of the substrate 102 . The two first regions R1 are separated from each other.

FIG. 4B is a diagram schematically illustrating a state in which the irradiation portion 104a (the first region R1) of the first coating film 104 on the substrate 102 is selectively removed.

In the step (b-2), the irradiated portion 104a (the first region R1 ) formed in the first coating film 104 in the step (b-1) is selectively removed using a developing solution. As a result, a predetermined pattern of the first coating film 104 is formed. In this embodiment, openings are formed in two places of the first coating film 104 .

[Process (c)]

Step (c) is a step of depositing the conductive material 106 in the second region R2 on the substrate 102 . Step (c) includes the following steps (c-1) and (c-2). In the step (c-1), the surface of the first coating film 104 in the second region R2 is lyophilized by irradiating energy of a specific wavelength. The process (c-2) deposits the electrically-conductive material 106 in 2nd area|region R2 at least by apply|coating the solution containing the electrically-conductive material 106 on the 1st coating film 104.

FIG. 4C is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the second region R2 of the first coating film 104 .

In step (c-1), as shown in FIG. 4C, energy of a specific wavelength is irradiated to a part of the pattern image of the 1st coating film 104 formed on the board|substrate 102, and the irradiation part 104a (2nd area|region (2nd area|region) R2)) and a first coating film 104 having an unirradiated portion 104b is formed.

In the process (c-2), similarly to FIG. 2F , the conductive material 106 is deposited on at least the second region R2 by applying a solution containing the conductive material 106 on the first coating film 104 . do.

As for the conductive material 106, since the first coating film 104 has lyophobic convex portions and more lyophilic concave portions (second region R2), when the liquid conductive material 106 is used, , whichever method described above is used, the conductive material 106 splashes on the convex portion and tends to collect in the concave portion, so that the conductive material 106 is deposited along the concave portion.

By the above-described step (c), the wiring 108 is formed. Through the above steps, the wiring structure 150 shown in FIG. 3 can be formed.

As mentioned above, the wiring formation method which concerns on the modification of this embodiment was demonstrated. According to the wiring forming method according to the modification of the present embodiment, the number of photolithography steps can be reduced and a wiring forming method capable of forming a fine pattern can be provided.

<Modification 2>

As another modification, in the hydrophilic material used in the present embodiment, a modification of adjusting the content of the compound [C] described above will be described. In the configuration of the wiring structure according to the present embodiment, when the irradiated portion 104a is lyophilized by irradiating the first coating film 104 with energy of a specific wavelength, it is not lyophilized even to the inside of the first coating film 104, It is sufficient to lyophilize only the vicinity of the surface of the first coating film 104 .

Then, as demonstrated below, the 1st coating film 104 which segregated the hydrophilic material efficiently on the surface can be formed by adjusting the compound [C] appropriately.

The [C] compound can improve the heat resistance and solvent resistance of the obtained film|membrane by using together with the [A] polymer. Furthermore, by appropriately changing the mixing ratio of the polymer [A] and the polymer [A], the concave shape of the exposed portion can be controlled, for example, while exhibiting the lipophilic function by the polymer [A].

In addition, by appropriately changing the type and mixing ratio of the [A] polymer and [C] compound, the [A] polymer having a fluorine atom and a silicon atom is the upper part of the film and the [C] compound is the lower part of the layer separation membrane. formation becomes possible.

Details are described below.

Synthesis examples of the compound [C] are shown below.

[Synthesis Example 2]

7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were charged to a flask provided with a cooling tube and a stirrer. Next, 5 parts by mass of methacrylic acid, 40 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate After introducing part and 3 parts by mass of α-methylstyrene dimer to replace with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70°C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the polymer [C-1] as a copolymer. The polystyrene conversion mass average molecular weight (Mw) of the polymer [C-1] was 9000. In addition, the solid content concentration of the polymer solution obtained here was 31.3 mass %.

5 parts by mass of the polymer [A-1] obtained in Synthesis Example 1, 95 parts by mass of the polymer [C-1] obtained in Synthesis Example 2, [B] N-hydroxynaphthalimide-tri as an acid generator 2 parts by mass of fluoromethanesulfonic acid ester, 0.5 parts by mass of 2-isopropylthioxanthone as a sensitizer [D], and 0.1 parts by mass of 2-phenylbenzoimidazole as an agent for [E] are mixed, and adhesion aid 2 parts by mass of γ-glycidoxypropyltrialkoxysilane was added as a solvent, and propylene glycol monomethyl ether acetate and 1-octanol were added in a ratio of 90:10 as solvents so that the solid content concentration was 18% by mass. Then, the radiation-sensitive composition was prepared by filtering with a Millipore filter with a pore diameter of 0.5 micrometer.

By adjusting the lipophilic material containing the [C] compound as described above, it is possible to efficiently segregate the lipophilic material on the surface of the first coating film 104 .

As mentioned above, the wiring formation method which concerns on the modification of this embodiment was demonstrated. According to the wiring formation method which concerns on the modification of this embodiment, the quantity of the hydrophilic material to be used can be reduced, and the amount of outgas by deprotection can be reduced.

<Second embodiment>

The wiring structure 200 and the wiring formation method according to the present embodiment will be described.

[Wiring structure]

First, the configuration of the wiring structure 200 formed by the wiring forming method according to the present embodiment will be described with reference to the drawings.

5 is a diagram for explaining the configuration of the wiring structure 200 formed by the wiring forming method according to the present embodiment. In this figure, a top view of the wiring structure 200, a cross-sectional view taken along A-A', and a cross-sectional view taken along B-B' are shown from the upper end. In addition, description of the wiring formation method WHEREIN: The same applies to drawings used below.

The wiring structure 200 according to the present embodiment includes at least a substrate 102 and a wiring 108 .

The substrate 102 has a first surface 102a and a second surface 102b that are opposed to each other. Moreover, the board|substrate 102 has the 1st area|region R1 and the 2nd area|region R2 in planar view. The second region R2 corresponds to a region excluding the first region R1. Although described later, the second region R2 is a region in which the conductive material 106 is deposited to form the wiring 108 .

As the material of the substrate 102 that can be used, those described in the description of the configuration of the wiring structure 100 can be used, and therefore, detailed description thereof is omitted here.

The wiring 108 is formed in the second region R2 and is not formed in the first region R1 .

In this embodiment, a simplified example is used for the layer structure of the first coating film 104 and the wiring 108 and the planar pattern, etc., however, this is for the sake of simplification of explanation and is not limited to this example. , a wide variety of configurations can be employed.

[Wiring Formation Method]

Next, a wiring forming method for forming the wiring structure 200 according to the present embodiment will be described in detail with reference to the drawings.

The wiring forming method using the lipophilic material according to the present embodiment includes the following steps (a) to (d) in this order.

(a) a step of forming a first coating film 104 containing a hydrophilic material on the substrate 102;

(b) removing the first coating film 104 of the second region R2 on the substrate 102;

(c) depositing the conductive material 106 in the second region R2 on the substrate 102;

(d) A step of removing the first coating film 104 in the first region R1 on the substrate 102 .

Hereinafter, each process is demonstrated in detail, referring drawings.

[Process (a)]

A process (a) is a process of forming the 1st coating film 104 containing a hydrophilic material on the board|substrate 102. Since the process (a) is the same as the above-mentioned process (a) using FIGS. 2A and 2B, description is abbreviate|omitted.

[Process (b)]

Step (b) is a step of removing the first coating film 104 in the second region R2 on the substrate 102 . Step (b) includes the following steps (b-1) and (b-2). The step (b-1) is an exposure step, and the first coating film 104 in the second region R2 is irradiated with energy of a specific wavelength. At the same time, the surface of the first coating film 104 in the second region R2 is lyophilized. The step (b-2) is a developing step, and the first coating film 104 in the second region R2 is removed by bringing it into contact with the specific chemical solution. The specific chemical solution includes the developer described above.

FIG. 6A is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the second region R2 of the first coating film 104 .

In the step (b-1), as shown in FIG. 6A , the second region R2 of the first coating film 104 formed on the substrate 102 is irradiated with energy of a specific wavelength, and the irradiated portion 104a (first A first coating film 104 having two regions R2) and an unirradiated portion 104b is formed.

6B is a diagram schematically illustrating a state in which the irradiation portion 104a (the second region R2) of the first coating film 104 on the substrate 102 is selectively removed.

In the step (b-2), the irradiated portion 104a (the second region R2) formed in the first coating film 104 in the step (b-1) is selectively removed using a developing solution. Thereby, the opening which has the pattern of the predetermined|prescribed 1st coating film 104 is formed.

[Process (c)]

Step (c) is a step of depositing the conductive material 106 in the second region R2 on the substrate 102 .

In the step (c), the conductive material 106 is deposited on the second region R2 by applying a solution containing the conductive material 106 to the first surface 102a side of the substrate 102, and the wiring ( 108) is formed.

FIG. 6C is a diagram schematically illustrating a state in which the wiring 108 is formed in the second region R2 on the substrate 102 .

Since the conductive material 106 has a liquid-repellent first coating film 104 and more lyophilic openings (second region R2), when using the liquid conductive material 106, any of the above methods Even if , the conductive material 106 is splashed in the first coating film 104 and tends to collect in the opening, so that the conductive material 106 is deposited along the opening.

[Process (d)]

The step (d) is a step of removing the first coating film 104 in the first region R1 on the substrate 102 . The step (d) includes the following steps (d-1) and (d-2). The step (d-1) is an exposure step, and energy of a specific wavelength is irradiated. At the same time, the surface of the first coating film 104 in the first region R1 is lyophilized. Here, energy of a specific wavelength is irradiated to the entire surface of the substrate 102 . The step (d-2) is a developing step, and the first coating film 104 in the first region R1 is removed by bringing it into contact with the specific chemical solution. The specific chemical solution includes the developer described above.

FIG. 6D is a diagram schematically illustrating a state in which the first coating film 104 in the first region R1 on the substrate 102 is lyophilized. In this state, all of the first coating film 104 applied in the step (a) is removed by immersion in the developer.

By the above process, the wiring structure 200 shown in FIG. 5 can be manufactured.

As mentioned above, the wiring formation method which concerns on this embodiment was demonstrated. According to the wiring forming method according to the present embodiment, it is possible to provide a wiring forming method capable of forming a fine pattern by reducing the number of photolithography steps.

<Third embodiment>

The wiring structure 300 and the wiring formation method according to the present embodiment will be described.

[Wiring structure]

First, the configuration of the wiring structure 300 formed by the wiring forming method according to the present embodiment will be described with reference to the drawings.

7 is a view for explaining the configuration of the wiring structure 300 formed by the wiring forming method according to the present embodiment. In this figure, a top view of the wiring structure 300, a cross-sectional view taken along A-A', and a cross-sectional view taken along B-B' are shown from the upper end. In addition, description of the wiring formation method WHEREIN: The same applies to drawings used below.

The wiring structure 300 according to the present embodiment is different from the wiring structure 100 according to the first embodiment only in the pattern of the wiring 108 .

In the present embodiment, the pattern of the wiring 108 is formed not only on the island-shaped first coating film 104 but also outside the first coating film 104 . In addition, in the following description, the area|region except the area|region where the island-shaped 1st coating film 104 on the board|substrate is arrange|positioned is called 1st area|region R1.

In this embodiment, a simplified example is used for the layer structure of the first coating film 104 and the wiring 108 and the planar pattern, etc., however, this is for the sake of simplification of explanation and is not limited to this example. , a wide variety of configurations can be employed.

[Wiring Formation Method]

Next, the wiring forming method for forming the wiring structure 300 according to the present embodiment will be described narrowly to differences from the above wiring forming method.

The wiring forming method using the lipophilic material according to the present embodiment includes the following steps (a) to (d) in this order.

(a) a step of forming a first coating film 104 on the substrate 102;

(b) removing the first coating film 104 of the third region R3 on the substrate 102;

(c) depositing the conductive material 106 in the second region R2 and the third region R3 on the substrate 102;

(d) A step of removing the first coating film 104 in the first region R1 on the substrate 102 .

[Process (a)]

Step (a) is a step of forming the first coating film 104 on the substrate 102 . The first coating film 104 has liquid repellency and is lyophilized by irradiating energy of a specific wavelength. Since the process (a) is the same as the above-mentioned process (a) using FIGS. 2A and 2B, the description is omitted.

[Process (b)]

Step (b) is a step of removing the first coating film 104 in the third region R3 on the substrate 102 . Step (b) includes the following steps (b-1) and (b-2). The step (b-1) is an exposure step, and the first coating film 104 in the third region R3 is irradiated with energy of a specific wavelength. At the same time, the surface of the first coating film 104 in the third region R3 is lyophilized. The step (b-2) is a developing step, and the first coating film 104 in the third region R3 is removed by bringing it into contact with the specific chemical solution. The specific chemical solution includes the developer described above.

FIG. 8A is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the first coating film 104 on the substrate 102 .

In the step (b-1), as shown in FIG. 8A , energy of a specific wavelength is irradiated to the third region R3 of the first coating film 104 on the substrate 102 , and the irradiation unit 104a (the third region) is irradiated with energy. (R3)) and the first coating film 104 having the unirradiated portion 104b is formed.

In the present embodiment, the third region R3 is formed at two locations within the surface of the substrate 102 . The two third regions R3 have a groove-like shape and are separated from each other.

FIG. 8B is a diagram schematically illustrating a process of selectively removing the irradiation portion 104a (third region R3) of the first coating film 104 on the substrate 102 .

In the step (b-2), the irradiated portion 104a (the third region R3) formed in the first coating film 104 in the step (b-1) is selectively removed using a developer. Thereby, the pattern of the predetermined 1st coating film 104 is formed. In this embodiment, groove-shaped openings are formed in two places of the first coating film 104 .

[Process (c)]

Step (c) is a step of depositing the conductive material 106 in the second region R2 and the third region R3 on the substrate 102 . Step (c) includes the following steps (c-1) and (c-2). In the step (c-1), the surface of the first coating film 104 in the second region R2 is lyophilized by irradiating energy of a specific wavelength. In the step (c-2), the conductive material 106 is applied to at least the second region R2 and the third region R3 by applying a solution containing the conductive material 106 on the first coating film 104 . to deposit

FIG. 8C is a diagram schematically illustrating a process of irradiating energy of a specific wavelength to the second region R2 of the first coating film 104 .

In step (c-1), as shown in FIG. 8C, energy of a specific wavelength is irradiated to a part of the pattern of the 1st coating film 104 formed on the board|substrate 102, and the irradiation part 104a (2nd area|region (2nd area|region) R2)) and a first coating film 104 having an unirradiated portion 104b is formed.

In the step (c-2), at least in the second region R2 and the third region R3 by applying a solution containing the conductive material 106 on the first coating film 104 similarly to FIG. 2F . A conductive material 106 is deposited.

As for the conductive material 106, since the first coating film 104 has lyophobic convex portions and more lyophilic concave portions (second region R2), when the liquid conductive material 106 is used, , whichever method described above is used, the conductive material 106 splashes on the convex portion and tends to collect in the concave portion, so that the conductive material 106 is deposited along the concave portion.

[Process (d)]

The step (d) is a step of removing the first coating film 104 in the first region R1 on the substrate 102 . The step (d) includes the following steps (d-1) and (d-2). The step (d-1) is an exposure step, and the first coating film 104 in the first region R1 is irradiated with energy of a specific wavelength. At the same time, the surface of the first coating film 104 in the first region R1 is lyophilized. The process (d-2) is a developing process, and it is made to contact the said specific chemical|medical solution, and the 1st coating film of 1st area|region R1 is removed. The specific chemical solution includes the developer described above.

By the step (d) described above, the first coating film in the first region R1 is removed. By the above process, the wiring structure 300 shown in FIG. 7 can be manufactured.

As mentioned above, the wiring formation method which concerns on this embodiment was demonstrated. According to the wiring forming method according to the present embodiment, it is possible to provide a wiring forming method capable of forming a fine pattern by reducing the number of photolithography steps.

<Fourth embodiment>

The wiring structure 400 and the wiring formation method according to the present embodiment will be described.

[Wiring structure]

First, the configuration of the wiring structure 400 formed by the wiring forming method according to the present embodiment will be described with reference to the drawings.

9 is a view for explaining the configuration of the wiring structure 400 formed by the wiring forming method according to the present embodiment. In this figure, a top view of the wiring structure 400, a cross-sectional view taken along A-A', and a cross-sectional view taken along B-B' are shown from the upper end.

The wiring structure 400 according to the present embodiment includes a substrate 102 , a first coating film 104 , a first wiring 108a , and a second wiring 108b .

The wiring structure 400 according to the present embodiment has a configuration in which the wiring structure 150 according to the modification of the first embodiment and the wiring structure 200 according to the second embodiment are combined.

That is, the configuration of the substrate 102 and the portion along the first wiring 108a of the wiring structure 400 according to the present embodiment coincides with the configuration of the wiring structure 200 according to the second embodiment. Then, if the wiring structure 150 according to the modified example of the first embodiment is laminated on the configuration of the wiring structure 200 according to the second embodiment, the first coating film 104 and the configuration of the part along the wiring are laminated. , corresponds to the configuration of the wiring structure 400 according to the present embodiment.

In the wiring structure 400 according to the present embodiment, the first wiring 108a and the second wiring 108b are connected. That is, by combining the wiring structure according to the embodiment of the present invention, a wiring structure having a plurality of layers of wiring can be formed.

[Wiring Formation Method]

Next, a wiring forming method for forming the wiring structure 400 according to the present embodiment will be described in detail with reference to the drawings.

The wiring formation method using the lipophilic material according to the present embodiment includes the following steps (a) to (g) in this order.

(a) a step of forming a first coating film 104 containing a hydrophilic material on the substrate 102;

(b) removing the first coating film 104 of the second region R2 on the substrate 102;

(c) depositing the conductive material 106 in the second region R2 on the substrate 102;

(d) removing the first coating film 104 of the first region R1 on the substrate 102;

(e) forming a first coating film 104 containing a hydrophilic material on the substrate 102;

(f) removing the first coating film 104 of the third region R3 on the substrate 102;

(g) A process of depositing the conductive material 106 in the fourth region R4 on the substrate 102 .

Here, the above steps (a) to (d) correspond to the wiring forming method according to the second embodiment as it is. In the above steps (e) to (g), if the "third area" and "fourth area" are replaced with "first area" and "second area", respectively, the modified example of the first embodiment Corresponds to the wiring formation method according to The detailed description of each of the above steps is omitted because the above description may be referred to.

As mentioned above, the wiring formation method which concerns on this embodiment was demonstrated. According to the wiring forming method according to the present embodiment, it is possible to provide a wiring forming method capable of forming a fine pattern by reducing the number of photolithography steps.

As mentioned above, the wiring formation method by preferred embodiment of this invention was demonstrated. However, these are merely examples, and the technical scope of the present invention is not limited thereto. In fact, those skilled in the art will be able to make various changes without departing from the gist of the present invention as claimed in the appended claims. Accordingly, it should be construed that these changes also fall within the technical scope of the present invention.

[Contact angle]

On an alkali free glass substrate, after apply|coating a radiation-sensitive composition with a spinner, respectively, the 0.5 micrometer-thick coating film was formed by prebaking for 2 minutes on a 90 degreeC hotplate. Next, the obtained coating film was irradiated with a high-pressure mercury lamp via a quartz mask (contact) (exposure machine: MA-1400 manufactured by Dainippon Kagen) at an exposure amount of 250 mJ/cm 2 . Thereafter, by baking at 110° C. for 5 minutes using a hot plate, a film patterned by the lyophilic portion and the liquid-repellent portion in which the energy irradiated portion became the lyophilic portion and the lyophilic portion other than the energy irradiated portion became the liquid-repellent portion was formed.

In the formed lipophilic patterning film, using a contact angle meter (CA-X manufactured by Kyowa Chemicals Co., Ltd.), the coating film surface of the energy irradiated portion corresponding to the lyophilic portion and the coated film surface of the energy unirradiated portion corresponding to the lyophilic portion were respectively of , the contact angle of tetradecane was measured. It was confirmed that the contact angle difference with respect to tetradecane was 30 degrees or more in the energy irradiated part and the energy non-irradiated part.

100, 150, 200, 300, 400: wiring structure
102: substrate
102a: first side
102b: second side
104: first coating film
104a: investigation unit
104b: Uninvestigated Department
106: conductive material
108: wiring
108a: first wiring
108b: second wiring
114: photo mask
R1: first region
R2: second region
R3: third region
R4: fourth region

Claims (13)

A step of forming a first coating film whose water repellency is changed by energy irradiation on a substrate;
removing the first coating film in a first region on the substrate;
forming a concave pattern in a second region disposed on at least a portion of an area other than the first area on the substrate;
The step of removing the first coating film in the first region comprises:
After irradiating energy of a specific wavelength to the first coating film in the first region, the first coating film in the first region is brought into contact with a specific chemical to remove the first coating film in the first region process, including
The step of forming the concave pattern in the second region,
and a step of hydrophilizing the surface of the first coating film in the second region by irradiating it with energy. According to claim 1,
A pattern forming method wherein the difference in contact angle with respect to tetradecane in the energy-irradiated portion and the energy-unirradiated portion is 30° or more in the change in water repellency due to the energy irradiation. According to claim 1,
Further comprising the step of depositing a predetermined material on the concave pattern,
The step of depositing the predetermined material on the concave pattern includes a step of depositing the predetermined material on at least the concave pattern by applying a solution containing the predetermined material on the first coating film. A pattern forming method comprising. 4. The method of claim 3,
The step of removing the first coating film in the first region comprises:
A pattern forming method, characterized in that it is performed before depositing the predetermined material on the second region. 5. The method of claim 4,
The first region and the second region are in contact with each other. delete delete delete According to claim 1,
The said specific chemical|medical solution is an alkali developing solution, The pattern formation method characterized by the above-mentioned. 10. The method according to any one of claims 1 to 5 and 9,
The step of forming the first coating film is formed with a hydrophilic material containing an acid generator and a polymer having an acid dissociable group,
The energy of the specific wavelength generates an acid from the acid generator, and the acid dissociates the acid-dissociable group by the acid. 10. The method according to any one of claims 1 to 5 and 9,
In the step of forming the first coating film, an acid generator, a polymer having an acid dissociable group, and a hydrophilic material containing a compound not having an acid dissociable group further include an acid dissociable group on the surface of the first coating film. A pattern forming method, characterized in that segregation of a polymer having 11. The method of claim 10,
The method for forming a pattern, wherein the acid dissociable group is an acid dissociable group containing at least one atom selected from a fluorine atom and a silicon atom. delete

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