JP2017097060A - Photosensitive resin composition and production method of photosensitive resin pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition from which improvement in various characteristics (sensitivity, pattern profile, resolution, film remaining property and the like) in the formation of a pattern can be further achieved.SOLUTION: A photosensitive resin composition showing changes in the solubility with a developer by exposure is provided, which comprises a metal resin composite material (A) that is a composite of metal particles (a1) and a phenolic resin (a2) and has a metal atom-oxygen atom-carbon atom bond. The photosensitive resin composition preferably comprises the metal resin composite material (A) and a photosensitive material (B), or comprises the metal resin composite material (A) and a photoacid generator (C) and a crosslinking agent (D).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition and a method for producing a photosensitive resin pattern.

In the manufacture of semiconductor elements, liquid crystal display panels, and the like, photolithography technology is used when manufacturing integrated circuits. In the photolithography technique, a photosensitive resin composition is used to draw a pattern having a predetermined shape on a substrate.
The photosensitive resin composition is classified as a positive type when the exposed portion forms a photosensitive resin film that is soluble in a developer, and when the exposed portion forms a photosensitive resin film that is insoluble in a developer. Classified as negative.
For example, a photosensitive resin film is formed on a wafer using a photosensitive resin composition, the photosensitive resin film is exposed with an exposure device through a photomask, and developed with a developer. A photosensitive resin film (photosensitive resin pattern) having a pattern shape is manufactured. Next, unnecessary portions of the wafer are removed by etching using the photosensitive resin pattern as a mask. Thereafter, the photosensitive resin film remaining on the wafer is removed, and a circuit having a pattern shape is manufactured.

As the photosensitive resin composition, one containing an alkali-soluble resin and a photosensitive material is generally used.
For example, a novolac-type phenol resin obtained by reacting phenols and aldehydes containing metacresol, para-cresol and 2,5-xylenol in the presence of an acid catalyst under specific temperature conditions, a naphthoquinone diazide derivative, A photosensitive resin composition containing a solvent has been proposed (see Patent Document 1).
In the invention of Patent Document 1, various properties (sensitivity, pattern shape, resolution, residual film properties, etc.) are improved by controlling the monomer composition and ortho-conversion rate when synthesizing the phenol resin. It has been.

JP 2013-254193 A

In recent years, semiconductor devices, liquid crystal display panels, and the like are increasingly required to be downsized and highly functional. In connection with this, the technical level requested | required with respect to the various characteristics of the photosensitive resin composition has become high compared with the past.
The present invention has been made in view of the above circumstances, and provides a photosensitive resin composition capable of further improving various characteristics (sensitivity, pattern shape, resolution, residual film property, etc.) in pattern formation. To do.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the photosensitive resin composition according to the first aspect of the present invention is a composite of a metal particle (a1) and a phenol resin (a2) in a photosensitive resin composition whose solubility in a developer changes upon exposure. And a metal resin composite material (A) having a metal atom-oxygen atom-carbon atom bond.

  Preferably, in addition to the metal resin composite material (A), it is further selected from the group consisting of a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound, and a naphthoquinonediazide compound. And a photosensitive resin composition containing at least one photosensitive material (B).

  Preferably, in addition to the metal resin composite material (A), a photosensitive resin composition further containing a photoacid generator (C) and a crosslinking agent (D) can be mentioned.

The metal constituting the metal particles (a1) is preferably at least one selected from the group consisting of silver, copper, tin, nickel, iron, zinc, manganese and aluminum.
The proportion of the metal particles (a1) in the component (A) is preferably 1 to 85% by mass.

  According to a second aspect of the present invention, there is provided a method for producing a photosensitive resin pattern, comprising: applying a photosensitive resin composition according to the first aspect on a support to form a photosensitive resin film; and And a step of exposing the resin film and a step of developing the exposed photosensitive resin film to form a photosensitive resin pattern.

According to the photosensitive resin composition of the present invention, various characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) can be further improved in pattern formation.
According to the method for producing a photosensitive resin pattern of the present invention, a pattern with improved various characteristics can be formed.

It is a figure which shows Ag3d narrow scan spectrum measured about the metal resin composite material (A-1). It is a figure which shows Ag3d narrow scan spectrum measured about the sample which cleaned Ag foil with Ar ion. It is a figure which shows the image which observed the surface of the metal resin composite material (A-1) with the transmission electron microscope (TEM).

(Photosensitive resin composition)
In the photosensitive resin composition of the present embodiment, the solubility in a developer changes upon exposure.
When the photosensitive resin film formed using the photosensitive resin composition of the present embodiment is exposed, the exposed portion of the photosensitive resin film changes in solubility in the developer, and the non-exposed portion of the photosensitive resin film is The solubility in the developer does not change. That is, a difference in solubility in the developer occurs between the exposed portion and the non-exposed portion of the photosensitive resin film. Thus, when the exposed photosensitive resin film is developed, a pattern-shaped photosensitive resin film (photosensitive resin pattern) is formed.
In the case of a positive photosensitive resin composition, the exposed portion of the photosensitive resin film is dissolved and removed in the developer, and the non-exposed portion of the photosensitive resin film remains to form a photosensitive resin pattern.
In the case of a negative photosensitive resin composition, the non-exposed portion of the photosensitive resin film is dissolved and removed in the developer, and the exposed portion of the photosensitive resin film remains to form a photosensitive resin pattern.

The photosensitive resin composition of this embodiment is a composite of metal particles (a1) and a phenol resin (a2), and contains a metal resin composite material (A) having a metal atom-oxygen atom-carbon atom bond. . Hereinafter, the metal resin composite material (A) is also referred to as component (A), the metal particles (a1) as component (a1), and the phenol resin (a2) as component (a2).
Since the photosensitive resin composition contains the component (A), various characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) are further improved when an integrated circuit is manufactured.

For example, the photosensitive resin composition containing the component (A) includes the component (A), a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound, and naphtho. Preferred examples include a photosensitive resin composition (first embodiment) containing at least one photosensitive material (B) selected from the group consisting of quinonediazide compounds.
Moreover, as a photosensitive resin composition containing this (A) component, the photosensitive resin composition (A) containing the said (A) component, a photo-acid generator (C), and a crosslinking agent (D) ( The second embodiment) is preferable.

<First Embodiment>
The photosensitive resin composition according to the first embodiment includes the metal resin composite material (A), a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound, and a naphthoquinonediazide compound. And at least one photosensitive material (B) selected from the group consisting of (hereinafter also referred to as “component (B)”).

≪Metal resin composite material (A) ≫
The component (A) in the first embodiment is a composite of metal particles (a1) and a phenol resin (a2), which is a metal resin composite material having a metal atom-oxygen atom-carbon atom bond.

-Regarding the metal particles (a1) The lower limit of the average particle size of the particle group of the component (a1) is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm, because etching resistance and the like are more likely to be increased. That's it.
The upper limit of the average particle diameter of the particle group of the component (a1) is preferably 1 μm or less, more preferably 600 nm or less, and even more preferably 300 nm or less because dispersibility in the component (a2) is easy to improve. .
The average particle size of the particle group of the component (a1) is obtained by observing the surface of the component (A) with a transmission electron microscope (TEM) and measuring the particle size of 100 arbitrarily selected metal particles. It is determined by calculating the value.

Examples of the metal constituting the component (a1) include gold (Au), platinum (Pt), palladium (Pd), silver (Ag), copper (Cu), tin (Sn), nickel (Ni), cobalt ( Co), iron (Fe), chromium (Cr), zinc (Zn), manganese (Mn), aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), scandium (Sc), vanadium ( V), gallium (Ga), strontium (Sr), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), cadmium (Cd), barium (Ba), lanthanum (La), cerium ( Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), tellurium Um (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Examples include rhenium (Re), osmium (Os), and iridium (Ir).
Among these, gold, platinum, palladium, silver, copper, tin, nickel, cobalt, iron, chromium, zinc, manganese, and aluminum are preferable because the effects of the present invention are easily obtained.
(A1) The metal which comprises a component may be 1 type individual, and 2 or more types may be sufficient as it.
The metal constituting the component (a1) is more preferably at least one selected from the group consisting of silver, copper, tin, nickel, iron, zinc, manganese and aluminum.

  The metal constituting the component (a1) is usually mostly “zero-valent” metal atoms, but may contain metal ions having a cationic property. Various properties (sensitivity, pattern shape, resolution, residual film property, etc.) are further enhanced by the interaction between the metal ions and the component (a2).

In the component (A), the component (a1) may be used alone or in combination of two or more.
The proportion of the component (a1) in the component (A) is preferably 1 to 85% by mass with respect to the total amount (100% by mass) of the entire component (A).
The lower limit of the ratio of the component (a1) is preferably 1% by mass or more, more preferably 3% by mass with respect to the total amount (100% by mass) of the entire component (A) because the effect derived from the metal particles is further increased. % Or more, more preferably 5 mass% or more.
The upper limit of the ratio of the component (a1) is preferably 85% by mass or less, more preferably based on the total amount of the component (A) (100% by mass) because the specific gravity of the component (A) as a whole is easily suppressed. Is 75% by mass or less, more preferably 65% by mass or less.

-About phenol resin (a2) As a (a2) component, a novolak type phenol resin, a resol type phenol resin, an aryl alkylene type phenol resin etc. are mentioned, for example.

.. About novolac type phenol resin As the novolac type phenol resin, for example, those obtained by reacting phenols and aldehydes under an acidic catalyst are used.

Examples of the phenols used for the production of the novolak type phenol resin include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5- Xylenols such as xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; trimethylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol; o-ethyl Ethylphenols such as phenol, m-ethylphenol, p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol, p-tert-butylphenol; resorcin, catechol, hydroquinone, pyrogallol, phloroglucin, alkyl resorsi Alkyl polyhydric phenols such as alkylcatechol and alkylhydroquinone (all alkyl groups preferably have 1 to 4 carbon atoms); p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, Examples include p-octylphenol, p-nonylphenol, p-cumylphenol, bisphenol A, bisphenol F, resorcinol, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and derivatives thereof. .
Phenols may be used alone or in combination of two or more.

Examples of aldehydes used for the production of novolak type phenol resins include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde; benzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4- Aromatic aldehydes such as hydroxybenzaldehyde can be used.
Examples of the formaldehyde source include formalin (aqueous solution), paraformaldehyde, hemiformal with alcohols, trioxane and the like.
Aldehydes may be used alone or in combination of two or more.

Examples of the acidic catalyst include organic carboxylic acids such as oxalic acid and acetic acid; organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid and methanesulfonic acid; 1-hydroxyethylidene-1,1′-diphosphonic acid, 2- Organic phosphonic acids such as phosphonobutane-1,2,4-tricarboxylic acid; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
An acidic catalyst may be used individually by 1 type, and may use 2 or more types together.

  When synthesizing a novolac-type phenol resin, the reaction molar ratio of phenols and aldehydes is preferably 0.3 to 1.7 moles, more preferably 0.8 to aldehydes per mole of phenols. 5 to 1.5 mol.

.. Resol type phenol resin As the resol type phenol resin, for example, a resin obtained by reacting phenols and aldehydes in the presence of an alkali catalyst is used.

Examples of the phenols used in the production of the resol-type phenol resin include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5- Xylenols such as xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; trimethylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol; o-ethyl Ethylphenols such as phenol, m-ethylphenol and p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol; p-tert-amylphenol, p-octylphenol, p-nonylphenol and p-cumyl Alkylphenols such as enol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol; monovalent phenol substitutes such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol; 1 -Monovalent phenols such as naphthol and 2-naphthol; polyhydric phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene Have an aldehyde group such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde Phenols; or derivatives thereof.
Phenols may be used alone or in combination of two or more.

Examples of aldehydes used in the production of resol type phenol resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples include benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde and the like.
Among these aldehydes, formaldehyde and paraformaldehyde are preferable because they are excellent in reactivity and inexpensive.
Aldehydes may be used alone or in combination of two or more.

Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkaline earth metal oxides or hydroxides such as calcium, magnesium, and barium; sodium carbonate, ammonia Water; amines such as triethylamine and hexamethylenetetramine; and divalent metal salts such as magnesium acetate and zinc acetate.
An alkali catalyst may be used individually by 1 type, and may use 2 or more types together.

  When synthesizing a resol-type phenol resin, the reaction molar ratio of phenols to aldehydes is preferably 0.8 to 2.5 moles, more preferably 1. 0 to 2.3 moles.

-About aryl alkylene type phenol resin An aryl alkylene type phenol resin means the phenol resin which has a repeating unit containing one or more aryl alkylene groups.
Examples of such aryl alkylene type phenol resins include xylylene type phenol resins and biphenyl dimethylene type phenol resins.
The aryl alkylene type phenol resin is produced by a known production method.

The metal resin composite material (A) has a metal atom-oxygen atom-carbon atom bond.
The oxygen atom which forms this bond is not limited to the phenolic hydroxyl group which (a2) component (phenol resin) has, but may be an oxygen atom derived from a functional group other than this. Thus, the oxygen atom derived from various functional groups and the component (a1) (metal particle) interact with each other, so that a metal atom-oxygen atom-carbon atom bond is easily formed.

Among the components (a2), a phenol resin having an aliphatic alcohol group in the molecule, a phenol resin having an ether group in the molecule, a phenol resin having a ketone group in the molecule, and a formyl group (—CHO) in the molecule. A phenol resin, a phenol resin having a carboxy group in the molecule, a phenol resin having an ester group in the molecule, and a phenol resin having a urethane group in the molecule are preferable.
Among these, a phenol resin having a carbonyl moiety (carbonyl group) such as a ketone group, an aldehyde group, a carboxy group, an ester group, or a urethane group in the molecule is more preferable.
By using such a preferable phenol resin, the metal atom in the component (a1) can be bonded not only to the oxygen atom of the phenolic hydroxyl group in the component (a2) but also partially to the oxygen atom of the carbonyl group. Become. Thereby, a metal atom-oxygen atom-carbon atom bond is more easily formed.
In addition, the phenol resin which has a carbonyl group in a molecule | numerator as mentioned above is manufactured by using the phenols which have a corresponding functional group in a molecule | numerator as a raw material.

When a phenol resin having an aldehyde group in the molecule is used, the metal resin composite material as the component (A) can be easily produced.
As will be described later, when the component (A) is produced, a solution of a metal salt and a phenol resin are mixed to bond oxygen atoms and metal atoms in the phenol resin. When a phenol resin having an aldehyde group in the molecule is used as a raw material, the aldehyde group brings about a reducing action on the metal cation constituting the metal salt. In addition, in this case, the metal atom and the oxygen atom in the phenol resin are easily bonded.

  Such a phenol resin having an aldehyde group in the molecule is, for example, hydroxybensaldehyde such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde or the like as a raw material phenols. It is manufactured by using a derivative.

The lower limit of the number average molecular weight (Mn) of the component (a2) is preferably 150 or more, more preferably 200 or more, and still more preferably 250 or more.
The upper limit of the number average molecular weight (Mn) of the component (a2) is preferably 1500 or less, more preferably 1200 or less, and still more preferably 1000 or less.
By setting Mn of the component (a2) within the above preferable range, moderate flexibility as the resin component is easily exhibited.

The lower limit of the weight average molecular weight (Mw) of the component (a2) is preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more.
The upper limit of the weight average molecular weight (Mw) of the component (a2) is preferably 2500 or less, more preferably 2000 or less, and even more preferably 1800 or less.
By setting the Mw of the component (a2) within the preferable range, appropriate flexibility as the resin component is easily exhibited.

  In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin mean values in terms of polystyrene measured by gel permeation chromatography (GPC).

In the component (a2), the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is preferably 2.5 or less, more preferably 2.2 or less, and even more preferably 2.0 or less as the upper limit. .
The lower limit value of Mw / Mn is not particularly limited, and is 1.05 or more, for example.
The effect of the present invention is further enhanced by setting Mw / Mn of the component (a2) within the above preferred range.

In addition, since a chemical reaction is performed when the component (A) is produced, the phenol resin used as a raw material and the phenol resin after the reaction constituting the component (A) have a molecular weight (Mn , Mw, Mw / Mn) may not match.
In producing the component (A), considering the production conditions, the molecular weight of the component (a2) used as a raw material is adjusted so that the post-reaction phenol resin constituting the component (A) is in the range of the above molecular weight and the like. It is preferable to set.

In the component (A), the component (a2) may be used alone or in combination of two or more.
The proportion of the component (a2) in the component (A) is preferably 10 to 99% by mass with respect to the total amount (100% by mass) of the entire component (A).
The lower limit of the proportion of the component (a2) is easy to impart moderate flexibility as a composite material, and it is easy to improve the applicability of the photosensitive resin composition to the support. 10 mass% or more is preferable with respect to the total amount (100 mass%) of the whole, More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more.
The upper limit of the proportion of the component (a2) is preferably 99% by mass or less, more preferably 95% by mass with respect to the total amount (100% by mass) of the entire component (A) because the effect derived from the metal particles is further increased. % Or less, more preferably 90% by mass or less.

In the component (A), the mixing ratio of the component (a1) and the component (a2) is expressed as a mass ratio represented by the component (a2) / component (a1) (hereinafter also simply referred to as “(a2) / (a1)”). 4 to 99 is preferable, 6 to 32 is more preferable, and 9 to 19 is more preferable.
If the mass ratio (a2) / (a1) is equal to or greater than the preferable lower limit of the above range, it is easy to impart moderate flexibility as a composite material, and the applicability of the photosensitive resin composition to the support is easy. Etc., and various characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) are further enhanced if the upper limit of the range is not exceeded.

-About other component (a3) (A) component may contain components (henceforth "(a3) component") other than (a1) component and (a2) component as needed.
Examples of component (a3) include resins other than component (a2); mold release agents such as stearic acid, calcium stearate or polyethylene; flame retardants such as calcium hydroxide; colorants such as carbon black; coupling agents; Etc.

The specific gravity of the component (A) may be appropriately set, the lower limit of the specific gravity, for example 1.25 g / cm ³ or more, more preferably 1.27 g / cm ³ or more, more preferably 1.30g / Cm ³ or more.
The upper limit of the specific gravity of the component (A), for example, is preferably from 16.6 g / cm ^3, more preferably 16.0 g / cm ³ or less, more preferably 15.5 g / cm ³ or less.

The component (A) in the first embodiment has a metal atom-oxygen atom-carbon atom bond. In the component (A), the metal atom (M) on the surface of the metal particles as the component (a1) and the oxygen atom (OC) in the phenol resin as the component (a2) form a bond, The component (a1) is dispersed in the matrix of component a2.
The metal atom (M) and O (oxygen atom) in O—C form a chemical bond (M—O). This is observed by X-ray photoelectron spectroscopy (ESCA) (FIGS. 1 and 2 described later).
Thus, in component (A), component (a1) forms bonds with oxygen atoms in component (a2), so component (a1) is stably dispersed in the matrix of component (a2). obtain. By using the component (A) in the photosensitive resin composition, various characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) are improved in pattern formation.

In the photosensitive resin composition of the first embodiment, the component (A) may be a single type or two or more types.
As for the content rate of (A) component in the photosensitive resin composition of 1st Embodiment, 40-95 mass% is preferable with respect to the total amount (100 mass%) of solid content of a composition, More preferably, it is 60-90. % By mass.

-About the manufacturing method of (A) component The metal resin composite material which is (A) component can be manufactured by the manufacturing method which has the process of mixing the solution of a metal salt, and a phenol resin, for example.
For this phenol resin, the component (a2) described above may be appropriately selected and used.

..Metal salt solution The metal salt solution is prepared by dissolving the above-described metal salt constituting the component (a1) in a solvent.
As such a metal salt, one composed of a combination of a cation (cation) and an anion (anion) of the metal atom constituting the component (a1) described above is used.
This anion includes halogen ions such as chlorine ion, bromine ion and iodine ion; carboxylate ions such as acetate ion, oxalate ion and fumarate ion; p-toluenesulfonate ion, methanesulfonate ion, butanesulfonate ion, benzene Examples thereof include sulfonate ions such as sulfonate ions; sulfate ions; perchlorate ions; carbonate ions; nitrate ions.
For example, when silver is selected as the metal, it is preferable to use silver nitrate having nitrate ions as anions because of its high solubility in a solvent.
When selecting copper as a metal, it is preferable to use copper sulfate and copper nitrate.
When selecting zinc as a metal, it is preferable to use zinc chloride, zinc sulfate, and zinc nitrate.
When calcium is selected as the metal, calcium chloride or calcium nitrate is preferably used.
When iron is selected as the metal, it is preferable to use iron chloride, iron sulfate, or iron nitrate.
When selecting aluminum as a metal, it is preferable to use aluminum nitrate.
When selecting magnesium as a metal, it is preferable to use magnesium chloride, magnesium sulfate, and magnesium nitrate.
In addition, what is necessary is just to select the valence of the metal in a metal salt considering the solubility with respect to a solvent, the ease of a reduction | restoration, etc.

What is necessary is just to select suitably as a solvent at the time of preparing the solution of metal salt according to the characteristic of metal salt, for example, water.
In addition, water can be used other than water, for example, alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, tetrahydrofuran; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; N-methyl-2-pyrrolidone, N An amide solvent such as N-dimethylformamide; dimethyl carbonate or the like can be used.
The solvent of the metal salt solution may be one kind alone, or two or more kinds of mixed solvents.
As a preferable mixed solvent, for example, a combination of water and a solvent other than this may be mentioned.

When preparing a solution of a metal salt, the pH of the solution may be adjusted for the purpose of improving the solubility of the metal salt in a solvent.
In the metal salt solution, the lower limit value of the content ratio of the metal salt is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, with respect to the total mass (100% by mass). The upper limit of the content ratio of the metal salt is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, with respect to the mass (100% by mass) of the entire solution. By setting the content ratio of the metal salt within the preferable range, desired metal particles are stably generated from the metal salt.

[Step of mixing metal salt solution and phenolic resin]
In this step, the metal resin composite material as the component (A) is obtained by mixing the metal salt solution and the phenol resin.
When the metal salt solution and the phenol resin are mixed, a reduction reaction is performed on the metal salt, whereby metal particles are generated from the metal salt (that is, precipitated as zero-valent metal particles).
In this reduction reaction, a known reducing agent may be used, or a reducing functional group resulting from the structure of the phenol resin may be utilized. In this embodiment, the phenol resin which is the component (a2) in the component (A) can function as a reducing agent.

As the reducing agent, known ones can be employed, for example, inorganic or organic reduction such as sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, formaldehyde, hydrazine, ascorbic acid and the like. Agents.
Examples of the reducing agent include resins having a polar group containing nitrogen or oxygen, such as an epoxy resin, a melamine resin, a urea resin, an aniline resin, and an isocyanate resin.

In the reduction reaction, when a reducing functional group resulting from the structure of the phenol resin is utilized, a phenol resin having an aldehyde group in the molecule can be employed as the phenol resin. In this case, the aldehyde group in the phenol resin molecule brings about a reducing action on the metal cation constituting the metal salt, thereby obtaining metal particles.
When using a phenol resin having an aldehyde group in the molecule, the phenol resin is preferably used in an amount of 0.1 times or more, more preferably 0.5 times or more of the phenol relative to the mass of the metal salt. A resin is used, and more preferably, the phenol resin is used in an amount twice or more. The upper limit of the amount of the phenol resin is not particularly limited, and for example, an amount of 100 times or less is used.

In this step, a reducing aid can be used as appropriate in order to promote the reduction reaction. For example, when a phenol resin having an aldehyde group in the molecule and silver nitrate are mixed, as a reducing auxiliary agent, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diphenyl sulfide, ethyl Phenyl sulfide, thiodiethanol, thiodipropanol, thiodibutanol, 1- (2-hydroxyethylthio) -2-propanol, 1- (2-hydroxyethylthio) -2-butanol, 1- (2-hydroxyethylthio) ) -3-butoxy-1-propanol and the like can be used.
In addition, amine compounds and alcohols can also be used as reducing aids.
Examples of the amine compound include ammonia, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropyldiethylamine, diethanolamine, triethanolamine, morpholine, ethylenediamine, and pyridine.
Examples of the alcohols include ethoxyethanol, ethylene glycol, diethylene glycol and the like.

In this step, the metal salt solution and the phenol resin may be mixed while ripening.
The temperature condition at the time of ripening is preferably 30 ° C. or more, more preferably 40 ° C. or more, further preferably 45 ° C. or more as its lower limit, and preferably 100 ° C. or less as its upper limit. Yes, more preferably 90 ° C. or lower, and still more preferably 80 ° C. or lower.

  The time (reaction time) for mixing the metal salt solution and the phenol resin is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 1 hour or more as its lower limit, and its upper limit. Is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 8 hours or less.

≪Specific photosensitive material (B) ≫
The component (B) in the first embodiment is at least one selected from the group consisting of a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound, and a naphthoquinonediazide compound. It is a photosensitive material.

  Examples of the polyhydroxybenzophenone compound include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ', 6-pentahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2 ', 3,4,5-pentahydroxybenzophenone, 2,3', 4,4 ', 5 ', 6-hexahydroxybenzophenone, 2,3,3', 4,4 ', 5'-hexahydroxybenzopheno Etc. The.

  Examples of the bis [(poly) hydroxyphenyl] alkane compound include bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, and 2- (4-hydroxyphenyl) -2. -(4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2 -(2 ', 3', 4'-trihydroxyphenyl) propane, 4,4 '-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3, 3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and the like. It is.

  Examples of the tris (hydroxyphenyl) methane compound include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, and bis (4-hydroxy-2,5). -Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane Bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, or a methyl-substituted product thereof Etc.

Examples of the naphthoquinonediazide compound include a complete ester compound, a partial ester compound, an amidated product, or a polyhydroxybenzophenone compound or a bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethane compound or a methyl-substituted product thereof, and a quinonediazide group-containing sulfonic acid. Examples include partially amidated products.
Examples of the polyhydroxybenzophenone compound include those exemplified above.
Bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethane compounds or methyl-substituted products thereof include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2 -Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl) -4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxy) Loxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl- 2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl)- 4-hydroxy Phenyl methane, and the like.
Examples of the quinonediazide group-containing sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazidesulfonic acid.

In the photosensitive resin composition of the first embodiment, the component (B) may be a single type or two or more types.
Among the components (B), it is more preferable to use a photosensitive material containing a naphthoquinonediazide compound because the effects of the present invention are easily obtained.
As for the content rate of (B) component in the photosensitive resin composition of 1st Embodiment, 1-70 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 5-50 mass parts, More preferably Is 5-40 parts by mass.
When the content ratio of the component (B) is equal to or higher than the preferable lower limit value of the range, an image faithful to the photomask pattern is easily obtained, and when the content ratio is equal to or lower than the preferable upper limit value of the range, the sensitivity is further increased.

≪Other ingredients≫
The photosensitive resin composition of 1st Embodiment may contain components other than (A) component and (B) component as needed.
Examples of the component other than the component (A) and the component (B) include a solvent, a surfactant, an adhesion improver, and a dissolution accelerator.

Examples of the solvent that may be contained in the photosensitive resin composition of the first embodiment include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate Propylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate , Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, acetic acid Examples thereof include esters such as ethyl, butyl acetate, methyl acetoacetate and ethyl acetoacetate.
A solvent may be used individually by 1 type and may use 2 or more types.

  The solid content concentration of the photosensitive resin composition of the first embodiment is preferably 10 to 90% by mass. If the solid content concentration of the photosensitive resin composition is within the above preferred range, the fluidity of the composition becomes better, and a photosensitive resin film having a uniform film thickness is easily formed.

  The preparation method of the photosensitive resin composition of 1st Embodiment is not specifically limited, For example, a dispersion apparatus (a dissolver, a homogenizer, a 3 roll mill etc.) is used, and (A) component and (B) component are needed. A method of dispersing or mixing other components accordingly is mentioned. Moreover, you may further filter the dispersion liquid or mixed liquid obtained by the said method using a mesh filter, a membrane filter, etc. as needed.

When the photosensitive resin film formed using the photosensitive resin composition of the first embodiment described above is exposed through a photomask, the structure changes to the component (B) in the exposed portion of the photosensitive resin film. Occurs, and the solubility in the developer changes. For example, when developing with an alkali developer, the solubility of the exposed portion of the photosensitive resin film in the alkali developer increases. On the other hand, the structure does not change in the non-exposed portion of the photosensitive resin film, and the solubility in the developer does not change. For example, when developed with an alkali developer, low solubility (slightly soluble) in the alkali developer of the non-exposed portion of the photosensitive resin film is maintained.
Thus, the photosensitive resin pattern is formed by the difference in solubility in the developer. In the case of developing with an alkaline developer, the exposed portion of the photosensitive resin film is dissolved and removed in the alkaline developer, and the non-exposed portion of the photosensitive resin film remains to form a photosensitive resin pattern.
According to the photosensitive resin composition of the first embodiment, since the component (A) is employed, various characteristics (sensitivity, pattern shape, resolution) in pattern formation when manufacturing an integrated circuit or the like. , Residual film properties, etc.) can be further improved.

<Second Embodiment>
The photosensitive resin composition of the second embodiment includes the metal resin composite material (A), a photoacid generator (C) (hereinafter also referred to as “component (C)”), and a crosslinking agent (D) ( (Hereinafter also referred to as “component (D)”).

≪Metal resin composite material (A) ≫
As the component (A) in the second embodiment, the same component as the component (A) in the first embodiment can be used.
In the photosensitive resin composition of the second embodiment, the component (A) may be a single type or two or more types.
As for the content rate of (A) component in the photosensitive resin composition of 2nd Embodiment, 40-95 mass% is preferable with respect to the total amount (100 mass%) of solid content of a composition, More preferably, it is 60-90. % By mass.

≪Photoacid generator (C) ≫
The component (C) in the second embodiment is a known photocatalyst polymerization photoinitiator, photoradical polymerization photoinitiator, dye photodecoloring agent, photochromic agent or microresist. A compound capable of generating an acid by the light or a mixture thereof can be used.
Examples of the component (C) include those disclosed in JP-A-5-303196, JP-A-5-80513, and the like.

In the photosensitive resin composition of the second embodiment, the component (C) may be a single type or two or more types.
As for the content rate of (C) component in the photosensitive resin composition of 2nd Embodiment, 0.2-25 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.3-15 mass Parts, more preferably 1 to 5 parts by mass.
When the content ratio of the component (C) is equal to or higher than the preferable lower limit of the above range, high sensitivity is easily achieved, and film loss of the image is suppressed, and a pattern with a favorable shape is easily obtained. . When the amount is not more than the upper limit of the above range, the remaining development is suppressed, or the cross-sectional shape of the image is less likely to be an inverted trapezoid.

≪Crosslinking agent (D) ≫
As the component (D) in the second embodiment, the acid generated from the component (C) is exposed to light to form a crosslinked structure that connects the components (A), and the photosensitive resin film is dissolved in the developer. The compound which can change property is mentioned.
For such component (D), for example, a compound having a methylol group or a substituted methylol group as a formaldehyde precursor, or an alkoxymethylated melamine can be used.
Examples of the alkoxymethylated melamine include methoxymethylated melamine, ethoxymethylated melamine, propoxymethylated melamine, and butoxymethylated melamine.

In the photosensitive resin composition of the second embodiment, the component (D) may be a single type or two or more types.
As for the content rate of (D) component in the photosensitive resin composition of 2nd Embodiment, 1-50 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, 4-45 mass parts is more preferable. Is 10-30 parts by mass.
If the content rate of (D) component is more than the preferable lower limit of the said range, sufficient crosslinked structure can be formed in the exposed part of the photosensitive resin film. When the amount is not more than the preferable upper limit of the above range, a uniform solution is easily obtained when dissolved in a solvent.

In the photosensitive resin composition of the second embodiment, the mixing ratio of the component (C) and the component (D) is appropriately set according to the type of each component, for example, the component (D) / component (C). It is preferable that it is 0.04-250, More preferably, it is 0.1-100, More preferably, it is 1-50 by mass ratio (henceforth "D / C ratio") represented by these.
When the D / C ratio is equal to or higher than the preferable lower limit of the above range, the resolution is increased and a photosensitive resin pattern having a highly rectangular shape is easily formed. If it is less than or equal to the preferable upper limit of the above range, high sensitivity can be easily achieved, and film loss of the image can be suppressed, and a pattern with a good shape can be easily obtained.

≪Other ingredients≫
The photosensitive resin composition of 2nd Embodiment may contain components other than (A) component, (C) component, and (D) component as needed.
Examples of the component other than the component (A), the component (C), and the component (D) include a solvent, a sensitizer, a surfactant, an adhesion improver, and a dissolution accelerator.
As a solvent which the photosensitive resin composition of 2nd Embodiment may contain, the thing similar to the solvent in 1st Embodiment is mentioned.

  The solid content concentration of the photosensitive resin composition of the second embodiment is preferably 20 to 95% by mass. If the solid content concentration of the photosensitive resin composition is within the above preferred range, the fluidity of the composition becomes better, and a photosensitive resin film having a uniform film thickness is easily formed.

  The preparation method of the photosensitive resin composition of 2nd Embodiment is not specifically limited, For example, using a dispersing device (a dissolver, a homogenizer, a 3 roll mill etc.), (A) component and (B) component are needed. A method of dispersing and mixing other components accordingly can be mentioned. Moreover, you may further filter the dispersion liquid or mixed liquid obtained by the said method using a mesh filter, a membrane filter, etc. as needed.

When the photosensitive resin film formed using the photosensitive resin composition of the second embodiment described above is exposed through a photomask, a structural change occurs in the exposed portion of the photosensitive resin film, and a crosslinked structure is formed. And the solubility in the developer changes. For example, when developing with an alkali developer, the solubility of the exposed portion of the photosensitive resin film in the alkali developer is lowered. On the other hand, the structure does not change in the non-exposed portion of the photosensitive resin film, and the solubility in the developer does not change. For example, when developed with an alkali developer, the solubility of the non-exposed portion of the photosensitive resin film in the alkali developer is maintained.
Thus, the photosensitive resin pattern is formed by the difference in solubility in the developer. In the case of developing with an alkali developer, the non-exposed portion of the photosensitive resin film is dissolved and removed in the alkali developer, and the exposed portion of the photosensitive resin film remains to form a photosensitive resin pattern.
According to the photosensitive resin composition of the second embodiment, since the component (A) is employed, various characteristics (sensitivity, pattern shape, resolution) in the formation of a pattern when manufacturing an integrated circuit or the like. Property, residual film property, etc.) can be further improved.

<Other embodiments>
In the photosensitive resin composition of the first embodiment described above, as the photosensitive material, component (B), that is, a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound, and a naphtho compound are used. At least one photosensitive material selected from the group consisting of quinonediazide compounds is used, but the photosensitive material in the photosensitive resin composition according to the present invention is not limited to this, and a developer for developing a photosensitive resin film by exposure. Any material can be used as long as it can change the solubility in the.
By employing the component (B) (specific photosensitive material) as the photosensitive material and using this component (B) in combination with the component (A), the effects of the present invention can be obtained more reliably.

  The photosensitive resin composition of the present embodiment is not limited to those of the first embodiment and the second embodiment described above, but contains at least the component (A) and is dissolved in the developer by exposure. Compositions that vary in nature are included.

(Method for producing photosensitive resin pattern)
The manufacturing method of the photosensitive resin pattern of this embodiment apply | coats the photosensitive resin composition of embodiment mentioned above on a support body, forms the photosensitive resin film, and exposes the said photosensitive resin film. And a step of developing the photosensitive resin film after the exposure to form a photosensitive resin pattern (developing step).

The support is not particularly limited, and examples thereof include a silicon wafer, a metal substrate, a glass substrate, and those obtained by subjecting these substrates to surface treatment.
The temperature condition for forming the photosensitive resin film on the support is preferably 50 to 150 ° C., and the preferred heating time is 30 to 180 seconds.
The film thickness of the photosensitive resin film formed on the support is appropriately set in consideration of the application and the like, and is, for example, 100 to 100,000 nm.

The exposure wavelength is not particularly limited. For example, g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, vacuum ultraviolet (VUV), extreme ultraviolet (EUV), or electron beam (EB) can be selected.

Development is performed using a developer.
As a developing solution, it selects according to the objective, For example, an alkali developing solution may be used and an organic solvent may be used.
As the alkali developer, a 2.38 mass% tetramethylammonium hydroxide aqueous solution is usually used.
Examples of the organic solvent used in the developer include esters, alcohols, ethers, hydrocarbons, and the like.

When the photosensitive resin composition of the first embodiment is used and an alkaline developer is used as the developer, the exposed portion of the photosensitive resin film is dissolved and removed in the alkaline developer, and the non-exposed portion of the photosensitive resin film is removed. It remains to form a photosensitive resin pattern.
When the photosensitive resin composition of the first embodiment is used and an organic solvent is used as the developer, the non-exposed portion of the photosensitive resin film is dissolved and removed in the organic solvent, and the exposed portion of the photosensitive resin film remains. Thus, a photosensitive resin pattern is formed.

When the photosensitive resin composition of the second embodiment is used and an alkali developer is used as the developer, the non-exposed portion of the photosensitive resin film is dissolved and removed in the alkali developer, and the exposed portion of the photosensitive resin film is It remains to form a photosensitive resin pattern.
When the photosensitive resin composition of the second embodiment is used and an organic solvent is used as the developer, the exposed portion of the photosensitive resin film is dissolved and removed in the organic solvent, and the non-exposed portion of the photosensitive resin film remains. Thus, a photosensitive resin pattern is formed.

  According to the method for producing a photosensitive resin pattern of the above-described embodiment, since the photosensitive resin composition according to the present invention is used, various characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) However, a more improved pattern can be formed.

Moreover, the support body can be etched using the formed photosensitive resin pattern as a mask after the developing step in the method for producing the photosensitive resin pattern of the present embodiment. The photosensitive resin pattern formed by the manufacturing method of this embodiment is excellent in etching resistance.
As the etching method, a known method (dry etching, wet etching) can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

<Preparation of photosensitive resin composition>
(Examples 1-8, Comparative Examples 1-8)
A positive photosensitive resin composition and a negative photosensitive resin composition were respectively prepared as follows.

<< Production of Novolac Type Phenolic Resin (a2-1) >>
A four-necked 1 L flask equipped with a stirring blade, thermometer, dropping funnel and condenser was prepared. In this flask, 1000 g of phenol and 10 g of oxalic acid were charged, and a 37% by mass aqueous formaldehyde solution was added under reflux conditions. 690 g was sequentially added and reacted while dehydrating at normal pressure. Thereafter, dehydration and dephenolation were performed under reduced pressure until the free phenol content by gas chromatography became 1% by mass or less, to obtain 1060 g of a novolac type phenol resin (a2-1).

<< Production of Novolac Type Phenolic Resin (a2-2) >>
In the production of the above-mentioned novolak type phenol resin (a2-1), GPC (gel permeation) was used instead of 1000 g of phenol using 689 g of metacresol and 460 g of paracresol (molar ratio: metacresol / paracresol = 60/40). By performing the reaction and the like in the same manner as the production of the novolak type phenol resin (a2-1) until the Mw becomes 5000 as measured by chromatography, 1209 g of the novolak type phenol resin (a2-2) was obtained.

<< Production of Novolac Type Phenolic Resin (a2-3) >>
In the production of the novolak type phenol resin (a2-1), 460 g of metacresol and 689 g of paracresol (molar ratio: metacresol / paracresol = 40/60) were used instead of 1000 g of phenol, and GPC (gel permeation) was used. By performing the reaction and the like in the same manner as the production of the novolak type phenol resin (a2-1) until Mw reaches 5000 as measured by chromatography), 1209 g of the novolak type phenol resin (a2-3) was obtained.

≪Manufacture of novolac type phenolic resin (a2-4) ≫
In the production of the novolak type phenol resin (a2-1), 574 g of metacresol, 345 g of paracresol and 260 g of 3,5-xylenol (molar ratio: metacresol / paracresol / 3,5-xylenol) were used instead of 1000 g of phenol. = 50/30/20) and carrying out the reaction and the like in the same manner as the production of the novolak type phenol resin (a2-1) until the Mw becomes 5000 as measured by GPC (gel permeation chromatography). , 1239 g of a novolac type phenol resin (a2-4) was obtained.

≪Manufacture of metal resin composite material (A-1) ≫
A four-necked 1 L flask equipped with a stirring blade, thermometer, dropping funnel and condenser was prepared. In this flask, 30.0 g of the novolac phenol resin (a2-1) obtained above and 300 g of water were added. On the other hand, an aqueous solution of sodium hydroxide in which 4.6 g (0.11 mol) of sodium hydroxide was dissolved, 6.0 g (0.05 mol) of thiodiethanol, and 31.6 g (0.03 mol) of 1N silver nitrate I was charged. Next, stirring was performed to dissolve them uniformly. Next, the temperature was raised until the internal temperature reached 50 ° C., and the reaction was carried out for 2 hours while maintaining the temperature from the time when the internal temperature reached 50 ° C.
After the reaction, it was confirmed that the internal temperature of the flask had dropped to 30 ° C. or lower, and 0.5 g of acetic acid was added dropwise from the dropping funnel to adjust the reaction system from neutral to weakly acidic with pH = 5 as the limit. As a result, the metal resin composite material (A-1) was deposited.
Finally, what was deposited in the flask was collected and dried to obtain 33 g of a metal resin composite material (A-1).

The obtained metal resin composite material (A-1) is added to tetrahydrofuran, and the molecular weight of the portion of the metal resin composite material (A-1) that is soluble in tetrahydrofuran is measured by GPC (gel permeation chromatography). , Number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn were determined. The results are shown below.
Number average molecular weight (Mn) 1000, weight average molecular weight (Mw) 3000, Mw / Mn 3.0

About metal resin composite material (A-1), the spectrum measurement was performed with the X-ray photoelectron spectroscopy analyzer (Escalab-220iXL, the product made by Thermo Fisher Scientific Co., Ltd.). The measurement conditions at this time were set as follows.
・ Irradiated X-ray: Monochrome AlKα
・ Detection depth: about 5nm
・ X-ray spot diameter: about 1mm

FIG. 1 is a diagram showing an Ag3d narrow scan spectrum measured for the metal resin composite material (A-1).
FIG. 2 is a diagram showing an Ag3d narrow scan spectrum measured for a sample obtained by cleaning an Ag foil with Ar ions.
In the spectrum shown in FIG. 1, the peak position of Ag3d5 was 368.9 eV. On the other hand, in the spectrum shown in FIG. 2, the peak position of Ag3d5 was 368.3 eV, and a difference of 0.6 eV was observed in the peak position between the two.
Usually, the peak of Ag alone appears at 368.1 to 368.3 eV, whereas in a compound in which an Ag atom and an O atom interact, such as silver acetate, this peak is 368.3. It is known to appear at 368.9 eV (Source: Handbook ofX-ray Photoelectron Spectroscopy (Physical Electronics)).
From this, it can be confirmed that the metal resin composite material (A-1) has an Ag—O—C bond in its structure.

FIG. 3 is a view showing an image obtained by observing the surface of the metal resin composite material (A-1) with a transmission electron microscope (TEM).
From the image shown in FIG. 3, in the metal resin composite material 10, it can be confirmed that the silver particles 1 of the order of several tens of nm are uniformly dispersed in the matrix 2 of the novolac type phenol resin.

≪Manufacture of metal resin composite material (A-2) ≫
In the production of the metal resin composite material (A-1), the metal resin composite material (A-) was used except that the novolac type phenol resin (a2-2) was used instead of the novolac type phenol resin (a2-1). A metal resin composite material (A-2) was obtained by performing a reaction and the like in the same manner as in the production of 1).

≪Manufacture of metal resin composite material (A-3) ≫
In the production of the metal resin composite material (A-1), the metal resin composite material (A-) was used except that the novolac type phenol resin (a2-3) was used instead of the novolac type phenol resin (a2-1). A metal resin composite material (A-3) was obtained by performing a reaction and the like in the same manner as in the production of 1).

≪Manufacture of metal resin composite material (A-4) ≫
In the production of the metal resin composite material (A-1), the metal resin composite material (A-) was used except that the novolac type phenol resin (a2-4) was used instead of the novolac type phenol resin (a2-1). A metal resin composite material (A-4) was obtained by carrying out the reaction in the same manner as in the production of 1).

(Examples 1-4, Comparative Examples 1-4: Preparation of positive photosensitive resin composition)
Any 100 parts by mass of metal resin composite materials (A-1) to (A-4) or novolak type phenol resins (a2-1) to (a2-4), and naphthoquinone-1,2-diazide-5-sulfone A mixture was obtained by mixing 20 parts by mass of 2,3,4-trihydroxybenzophenone ester of acid.
Next, this mixture was dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate to obtain a solution (p).
Thereafter, this solution (p) was filtered using a membrane filter having a pore size of 1.0 μm to prepare positive photosensitive resin compositions of respective examples.

(Examples 5-8, Comparative Examples 5-8: Preparation of negative photosensitive resin composition)
It was prepared according to the preparation method described in JP-A-5-80513.
100 parts by mass of any of the metal resin composite materials (A-1) to (A-4) or the novolak type phenol resins (a2-1) to (a2-4), and diphenyliodonium / PF6 salt as a photoacid generator 3 parts by mass, 25 parts by mass of Nicarac (registered trademark; manufactured by Sanwa Chemical Co., Ltd., MW-30) having methylol melamine as a main component as a crosslinking agent, and 0.3 parts by mass of anthracene as a sensitizer A solution (n) was obtained by dissolving in 330 parts by mass of propylene glycol monomethyl ether acetate.
Thereafter, this solution (n) was filtered using a membrane filter having a pore diameter of 1.0 μm to prepare negative photosensitive resin compositions of respective examples.

<Evaluation about photosensitive resin composition>
The sensitivity, resolution, residual film property, and etching resistance of the photosensitive resin composition of each example were evaluated as follows.

≪Manufacture of photosensitive resin pattern (1) ≫
The photosensitive resin composition of each example was applied onto a hexamethyldisilazane-treated silicon wafer with a spin coater so that the film thickness when dried was 1.5 μm, and 100 ° C. at 110 ° C. on a hot plate. It was dried for 2 seconds to form a photosensitive resin film.
Then, repeated test chart mask on a silicon wafer with a photosensitive resin film is formed, ultraviolet rays were irradiated respectively by changing the amount of irradiation and ^{20mJ / cm 2, 40mJ / cm} 2, 60mJ / cm 2.
Next, the photosensitive resin film after the ultraviolet irradiation was developed with a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) for 60 seconds to form a line-and-space-shaped photosensitive resin pattern.

[Evaluation of sensitivity]
The shape of the photosensitive resin pattern obtained in the production (1) of the photosensitive resin pattern was observed with a scanning electron microscope, and the sensitivity was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.
Evaluation criteria (circle): An ultraviolet-ray irradiation amount is less than 20 mJ / cm < ² > and an image (photosensitive resin pattern) can be formed.
△: The dose of ultraviolet rays is less than 20 mJ / cm ² or more 40 mJ / cm ^2, an image (photosensitive resin pattern) can be formed.
X: An image (photosensitive resin pattern) cannot be formed even when the irradiation amount of ultraviolet rays is 40 mJ / cm ² or more.
The sensitivity of the photosensitive resin composition is preferably evaluated as “◯” or “Δ” in the production of the photosensitive resin pattern. When the sensitivity is “x”, the sensitivity is too slow to make pattern formation difficult.

[Evaluation of resolution]
The rectangularity in the line-and-space-shaped photosensitive resin pattern formed in the production (1) of the photosensitive resin pattern was measured as follows.
The cross section of the resolved resist line having the smallest width is observed with an electron microscope, and the ratio (b / a) of the width (a) at the bottom of the resist line to the width (b) at the top of the resist line. Was determined as the rectangularity of the photosensitive resin pattern. The results are shown in Tables 1 and 2.
The closer the ratio (b / a) is to 1, the higher the degree of rectangularity and the better the resolution.

[Evaluation of remaining film properties]
The photosensitive resin composition of each example was applied onto a hexamethyldisilazane-treated silicon wafer with a spin coater so that the film thickness when dried was 1.5 μm, and 100 ° C. at 110 ° C. on a hot plate. The film was dried for 2 seconds to form a photosensitive resin film (film thickness: 1.5 μm).
Next, the silicon wafer on which the photosensitive resin film was formed was immersed in a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) for 60 seconds, washed with water, and 100 ° C. at 110 ° C. on a hot plate. Dry for 2 seconds. The film thickness of the photosensitive resin film after development, washing and drying was measured.
And the remaining film rate was computed from the following formula. The results are shown in Tables 1 and 2.
Residual film ratio (%) = photosensitive resin film thickness after development / washing / drying / photosensitive resin film thickness before development (1.5 μm) × 100
The larger the remaining film ratio, the better the remaining film property.

[Evaluation of etching resistance]
After forming the photosensitive resin pattern, dry etching and wet etching were performed by the methods shown below, and etching resistance was evaluated.

≪Manufacture of photosensitive resin pattern (2) ≫
The photosensitive resin composition of each example was applied onto a hexamethyldisilazane-treated silicon wafer with a spin coater so that the film thickness when dried was 1.5 μm, and 100 ° C. at 110 ° C. on a hot plate. It was dried for 2 seconds to form a photosensitive resin film.
Next, using the reduced projection exposure apparatus, the formed photosensitive resin film was exposed through a test chart mask.
Next, the exposed photosensitive resin film was developed for 60 seconds using a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) to obtain a photosensitive resin pattern.

- to dry etching process resulting photosensitive resin pattern, a reactive ion etching apparatus, the gas composition _{C 2 F 6: CHF 3:} He = 15: 25: 100 and (volume ratio), 80W, 100W , 120 W, and dry etching was performed for 3 minutes each.
And the photosensitive resin pattern surface after dry etching was observed, and the following evaluation criteria evaluated the dry etching tolerance. The results are shown in Tables 1 and 2.
Evaluation criteria ○: No change on the surface of the photosensitive resin pattern.
(Triangle | delta): A part of photosensitive resin pattern surface was cloudy.
X: The whole photosensitive resin pattern surface was cloudy.

· Wet etching silicon wafers photosensitive resin pattern was formed, it was immersed for 60 seconds in BHF solution _{(NH 4 F / HF / H} 2 O) is a wet etching solution.
And the peeling condition of the pattern from a silicon wafer was observed with the electron microscope, and the following evaluation criteria evaluated the wet etching tolerance. The results are shown in Tables 1 and 2.
Evaluation criteria ○: No peeling of the pattern from the silicon wafer.
Δ: A part of the pattern was peeled off from the silicon wafer.
X: No pattern remained on the silicon wafer (the entire pattern was peeled off).

  From the results shown in Tables 1 and 2, the photosensitive resin compositions of Examples 1 to 8 to which the present invention was applied differed in pattern formation as compared with the corresponding photosensitive resin compositions of Comparative Examples 1 to 8, respectively. It can be confirmed that the characteristics (sensitivity, pattern shape, resolution, remaining film property, etc.) of the film are improved.

1 silver particles,
2 matrix,
10 Metal resin composite material

Claims (6)

In the photosensitive resin composition whose solubility in the developer changes by exposure,
The photosensitive resin composition containing the metal resin composite material (A) which is a composite of a metal particle (a1) and a phenol resin (a2) and has a metal atom-oxygen atom-carbon atom bond.   Furthermore, it contains at least one photosensitive material (B) selected from the group consisting of a polyhydroxybenzophenone compound, a bis [(poly) hydroxyphenyl] alkane compound, a tris (hydroxyphenyl) methane compound and a naphthoquinonediazide compound. Item 2. A photosensitive resin composition according to Item 1.   Furthermore, the photosensitive resin composition of Claim 1 containing a photo-acid generator (C) and a crosslinking agent (D).   The metal constituting the metal particles (a1) is at least one selected from the group consisting of silver, copper, tin, nickel, iron, zinc, manganese, and aluminum. The photosensitive resin composition as described in 2.   The photosensitive resin composition as described in any one of Claims 1-4 whose ratio of the said metal particle (a1) to the said (A) component is 1-85 mass%. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a support to form a photosensitive resin film;
Exposing the photosensitive resin film;
Developing the photosensitive resin film after the exposure to form a photosensitive resin pattern; and
The manufacturing method of the photosensitive resin pattern which has these.