JP2010163382A - Method for producing cyclic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method by which a calixresorcinarene compound having a carboxy group can be produced by a small number of reaction steps. <P>SOLUTION: The method for producing the cyclic compound represented by general formula (3) includes a step for subjecting an aldehyde compound represented by formula (1) to a condensation reaction with an aromatic compound represented by formula (2) in the presence of an acid catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a cyclic compound useful as a radiation-sensitive compound or a precursor thereof. The present invention also relates to a photoresist composition used in the electrical / electronic field such as a semiconductor and the optical field, and more particularly to a photoresist composition for ultrafine processing.

  Lithography using extreme ultraviolet light (hereinafter sometimes referred to as EUVL) or electron beam is useful as a high-productivity, high-resolution microfabrication method in the manufacture of semiconductors and the like. There is a demand for photoresists with high sensitivity and high resolution. It is indispensable to improve the sensitivity of the photoresist from the viewpoint of the productivity and resolution of the desired fine pattern.

  As a photoresist used in the ultrafine processing by EUVL, for example, a method using a chemically amplified positive photoresist having a higher concentration of photoacid generator than other resist compounds has been proposed (for example, Patent Document 1). However, the photoresists of the examples are considered to be limited in processing up to 100 nm exemplified in the case of using an electron beam from the viewpoint of line edge roughness. This is presumed to be mainly due to the large three-dimensional shape of the polymer compound aggregate or each polymer compound molecule used as the base material, which affects the production line width and the surface roughness. .

The inventor has already proposed a calix resorcinarene compound as a photoresist material with high sensitivity and high resolution (see Patent Documents 2 and 3). Patent Document 4 discloses a calix resorcinarene compound. However, some of these compounds are considered to be insufficiently soluble, and the use of the compound is not described for use as a photoresist base material. Only the use as an agent is described.
On the other hand, in the current semiconductor manufacturing process, since the photoresist base material is used after being dissolved in a solvent, high solubility in a coating solvent is required. Therefore, the present inventors have also proposed a calix resorcinarene compound having improved coating solvent solubility (see Patent Document 5).

JP 2002-055557 A JP 2004-191913 A Japanese Patent Laying-Open No. 2005-075757 US Pat. No. 6,093,517 JP 2007-197389 A

In addition to the above-mentioned compounds, the present inventors have found a calix resorcinarene compound for use in a photoresist base material having improved solubility in a coating solvent, resist pattern strength, and adhesion to a substrate (Japanese Patent Application). 2008-158769).
However, in this method for producing a precursor compound of calix resorcinarene compound, it was necessary to obtain a product in two steps from the raw material. In the production method described above, when a calix resorcinalene compound having a carboxyl group is synthesized, the carboxyl group of the raw material compound needs to be used as a protective group such as an ester group in advance. For this reason, the yield of the final compound was low in consideration of the step of using a carboxyl group as a protecting group and the step of deprotecting after the reaction. Moreover, there existed problems, such as complication of the refinement | purification process accompanying the coloring of a target object or the production | generation of a by-product.
The objective of this invention is providing the manufacturing method which can obtain the calix resorcinalene compound which has a carboxyl group by a fewer process.

According to the present invention, the following method for producing a cyclic compound and the like are provided.
1. A method for producing a cyclic compound represented by the following formula (3), comprising a step of subjecting an aldehyde compound represented by the following formula (1) and an aromatic compound represented by the following formula (2) to a condensation reaction under an acid catalyst.
[Wherein, R is a group represented by the following formula (4) or (5).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms. Group, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, alkoxyalkyloxy group, siloxy group, or a divalent group thereof (substituted or unsubstituted alkyleneoxy group, substituted or unsubstituted aryleneoxy group) A group having a structure in which a group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group in which these groups are bonded to an ester bond, a carbonate ester bond, or an ether bond) It is.
R ² is hydrogen, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. An aromatic hydrocarbon group or an aromatic group having 6 to 10 carbon atoms.
A plurality of R, R ¹ and R ² in the formula (1) and the formula (2) may be the same or different.
(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or one or more alkylene groups and 1 It is a group in which at least one of the above ether bond groups and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms is combined. In the case of having a substituent, the substituent is bromine, fluorine, nitrile group, carbon number 1 -10 alkyl groups.
R ³ and R ⁴ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x represents an integer of 1 to 5, y represents 0 to 3, and z represents an integer of 0 to 4. A plurality of R ³ , R ⁴ , Ar, A ¹ , x, y and z may be the same or different. ]]
2. 2. The production method according to 1, wherein the acid catalyst is a catalyst having Lewis acidity.
3. 3. The production method according to 2, wherein the Lewis acid catalyst is a Lewis acid composition containing boron trifluoride or a Lewis acid compound having tin or aluminum as a central metal.
4). The cyclic compound manufactured by the manufacturing method in any one of said 1-3, and / or the following formula (1) manufactured using the cyclic compound manufactured by the manufacturing method in any one of Claims 1-3 as a raw material ( A photoresist composition containing a cyclic compound represented by 3 ′) and a solvent.
[Wherein, R represents a group represented by the following formula (4 ′) or (5 ′).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms. Group, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, alkoxyalkyloxy group, siloxy group, or a divalent group thereof (substituted or unsubstituted alkyleneoxy group, substituted or unsubstituted aryleneoxy group) A group having a structure in which a group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group in which these groups are bonded to an ester bond, a carbonate ester bond, or an ether bond) It is.
R ² is hydrogen, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. Group hydrocarbon group or aromatic group having 6 to 10 carbon atoms.
A plurality of R, R ¹ and R ² in the formula (3 ′) may be the same or different.
(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or one or more alkylene groups and 1 It is a group obtained by combining at least one of the above ether bonds and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, a carbon number of 1 to 10 alkyl groups.
R ³ and R ⁴ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
R ⁵ is an acid dissociable, dissolution inhibiting group.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x represents an integer of 1 to 5, y represents 0 to 3, and z represents an integer of 0 to 4. A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , x, y, and z may be the same or different. ]]
5). The thin film containing the cyclic compound manufactured with the manufacturing method in any one of said 1-3.
6). 5. A microfabrication method using the photoresist composition as described in 4 above.
7). A semiconductor device manufactured by the microfabrication method described in 6 above.

  By the production method of the present invention, a cyclic compound useful as a photoresist base material or a precursor compound thereof can be produced in a small number of steps.

2 is a ¹ H-NMR spectrum of the compound (A) synthesized in Example 1. FIG. 2 is a ¹ H-NMR spectrum of a compound (B) synthesized in Comparative Example 1. 2 is a ¹ H-NMR spectrum of a compound (A) synthesized in Comparative Example 1.

The production method of the cyclic compound of the present invention (the following formula (3)) comprises a step of subjecting an aldehyde compound represented by the following formula (1) and an aromatic compound represented by the following formula (2) to a condensation reaction under an acid catalyst. It is characterized by including.

  In the aldehyde compound represented by the formula (1), R is a group represented by the following formula (4) or (5).

In the formula, Ar is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or one or more alkylene groups and one or more And a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, nitrile group, 1 to 10 carbon atoms. It is an alkyl group.
For example, phenylene group, methylphenylene group, dimethylphenylene group, trimethylphenylene group, tetramethylphenylene group, naphthylene group, biphenylene group, and oxydiphenylene group are preferable.
Of these, a phenylene group, a biphenylene group, and an oxydiphenylene group are preferable.

A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
As the alkylene group, those having 1 to 4 carbon atoms such as a methylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a butylene group are preferable.
The group in which one or more alkylene groups and one or more ether bonds are combined is preferably an oxymethylene group, an oxydimethylmethylene group, an oxyethylene group, an oxypropylene group, or an oxybutylene group.
A ¹ is preferably a single bond or an oxymethylene group (—O—CH ₂ —).

R ³ and R ⁴ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.

As the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable.
As the branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group, and the like are preferable.
As the cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, diamantyl group, and the like are preferable.
As the aromatic group having 6 to 12 carbon atoms, a phenyl group, a naphthyl group, and the like are preferable.

x represents an integer of 1 to 5, y represents 0 to 3, and z represents an integer of 0 to 4.
In addition, when there are a plurality of R ³ , R ⁴ , Ar, A ¹ , x, y, and z in formula (3) and formula (4), they may be the same or different.

As R, the following groups are preferable.

  As the aldehyde compound represented by the formula (1), an industrially commercially available one may be used, or a compound that becomes a synthesis precursor of the aldehyde compound represented by the formula (1) may be formylated. Further, it can be synthesized by introducing a formyl group by oxidation, reduction or the like, or by performing a known substituent introduction reaction, substituent conversion reaction, skeleton conversion reaction or the like on an aldehyde compound as a synthesis precursor.

In the aromatic compound represented by the above formula (2), R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkyloxy group, a siloxy group, or a divalent group (substituted or unsubstituted). A substituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or an ester bond (—CO ₂ —) with these groups, This is a group having a structure in which a carbonic acid ester bond (—CO ₃ —) or an ether bond is bonded).

As the linear alkoxy group having 1 to 20 carbon atoms, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, and the like are preferable.
As the branched alkoxy group having 3 to 12 carbon atoms, a t-butoxy group, an iso-propoxy group, an iso-butoxy group, a 2-ethylhexoxy group, and the like are preferable.
The cyclic alkoxy group having 3 to 20 carbon atoms is preferably a cyclohexoxy group, a norbornyloxy group, an adamantyloxy group, a biadamantyloxy group, a diamantyloxy group, or the like.
The aryloxy group having 6 to 10 carbon atoms is preferably a phenoxy group or a naphthoxy group.
As the alkoxyalkyloxy group, a methoxymethoxy group, an ethoxymethoxy group, an adamantyloxymethoxy group and the like are preferable.
As the siloxy group, a trimethylsiloxy group, a t-butyldimethylsiloxy group and the like are preferable.
Each of the above groups may have a substituent. Specifically, alkyl groups such as methyl group and ethyl group, ketone groups, ester groups, alkoxy groups, nitrile groups, nitro groups, hydroxyl groups and the like Can be mentioned.

R ² is hydrogen, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having a branch having 3 to 12 carbon atoms, or a group having 3 to 20 carbon atoms. It is a cyclic aliphatic hydrocarbon group or an aromatic group having 6 to 10 carbon atoms.
Specific examples of each of the above groups are the same as R ³ and R ⁴ described above.
Preferably R ² is hydrogen.

Two R ¹ and ^two R ² in the formula (2) may be the same or different.

Specific examples of the compound of the formula (2) are resorcinol, pyrogallol, phenol having R ¹ at the 3-position, and 1,3-dihydroxybenzene having R ¹ at the 2-position.

  As the aromatic compound represented by the formula (2), an industrially commercially available one may be used, and a compound that becomes a synthesis precursor of the aromatic compound represented by the formula (2) is oxidized. It can be synthesized by introducing a hydroxyl group by hydrolysis, etc., or performing other known substituent introduction reaction, substituent conversion reaction, skeleton conversion reaction and the like.

In the present invention, the compounds of the above formulas (1) and (2) are reacted under an acid catalyst.
As the acid catalyst, a catalyst having Lewis acidity is preferable. Here, “having Lewis acidity” means that a chemical species having a low-energy vacant orbital has a property of accepting an electron pair, and has no proton donating ability in the broad definition of an acid (that is, It means that the chemical species (not Bronsted acid) has acidity to express.
Examples of such catalysts include Lewis acidic compositions containing trifluoroboron, tin tetrachloride, dilauryl tin dichloride, dibutyl tin dichloride, aluminum chloride, aluminum bromide, trialkylaluminum, trialkoxyaluminum, tetra In addition to titanium chloride and iron chloride, metal-substituted heteropolyacids, metal triflates and the like can be mentioned.
Preferred catalysts include Lewis acidic compositions containing trifluoroboron or Lewis acidic compounds having tin or aluminum as the central metal.
Particularly preferable catalysts include boron trifluoride / ether adduct, tin tetrachloride, dilauryl tin dichloride, dibutyl tin dichloride, aluminum chloride, and aluminum bromide. If these are used, the yield of the obtained cyclic compound can be improved.

  The addition amount of the acid catalyst is preferably 0.1 equivalents to 10 equivalents with respect to the aldehyde compound represented by the above formula (1). If it is less than 0.1 equivalent, there is a possibility that sufficient productivity cannot be obtained because the reaction rate is slow. On the other hand, when it exceeds 10 equivalents, generation of impurities or coloring due to the progress of side reactions may be observed.

  The reaction is preferably performed in a solvent. The solvent may be appropriately selected according to the compounds of the above formula (1) and formula (2) to be used. For example, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, carbon tetrachloride, chlorobenzene, n-hexane, n-heptane, benzene, toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Pyrrolidone, acetonitrile, etc. can be used.

After completion of the reaction, the cyclic compound represented by the above formula (3) is obtained by purification if necessary. Note that a plurality of R, R ¹ and R ² in the formula (3) may be the same or different.
In the conventional production method, when a calix resorcinalene compound having a carboxyl group, as represented by the formula (3), is synthesized, the carboxyl group of the raw material compound needs to be a protective group such as an ester group in advance. there were. For this reason, the yield of the final compound was low in consideration of the step of using a carboxyl group as a protecting group and the step of deprotecting after the reaction. Moreover, there existed problems, such as complication of the refinement | purification process accompanying the coloring of a target object or the production | generation of a by-product.
On the other hand, in the production method of the present invention, it is not necessary to protect the carboxyl group of the raw material compound, that is, the aldehyde compound of the above formula (1). Therefore, a calix resorcinarene compound having a carboxyl group can be produced without a protection step.

  In the cyclic compound obtained by the production method of the present invention, R has a carboxyl group. For example, by using this cyclic compound as a precursor and introducing an acid dissociable, dissolution inhibiting group or the like into the carboxyl group of the precursor, a compound suitable as a material for a photoresist composition can be obtained.

Specifically, a cyclic compound represented by the following formula (3 ′) is obtained.

Wherein, ^{R 1} and ^{R 2} each represent the same as ^{R 1} and ^{R 2} in the formula (2).
R is a group represented by the following formula (4 ′) or (5 ′).

In the formula, each group except R ⁵ represents the same group as in the above formulas (4) and (5).
R ⁵ is an acid dissociable, dissolution inhibiting group. Since the acid dissociable, dissolution inhibiting group has high reactivity with EUVL and electron beam, it is excellent in terms of sensitivity and etching resistance. Therefore, it can be suitably used as a photoresist base material for ultrafine processing.
As the acid dissociable, dissolution inhibiting group, a group represented by any of the following formulas (I) to (IV) is preferable.

  In the formulas (I) to (IV), α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms. , A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.

  β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure. Preferably, a tertiary carbon contained in a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure is bonded to an oxygen atom.

  γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms. The alkoxy group substituted by a group having an aromatic structure, a monocyclic aliphatic structure or a polycyclic aliphatic structure is preferably a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a polycyclic aliphatic structure. The tertiary carbon contained in the group to be bonded to the oxygen atom.

  δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.

As the acid dissociable, dissolution inhibiting group, a group selected from the following formulas (6) to (37) is particularly preferable.

  The cyclic compound into which the acid dissociable dissolution inhibiting group is introduced is obtained by converting the compound having an acid dissociable dissolution inhibiting group into the cyclic compound (precursor) represented by the above formula (3) by an esterification reaction or an etherification reaction. , Can be synthesized by introduction by acetalization reaction or the like.

  The cyclic compound represented by the above formula (3) and / or the cyclic compound represented by the above formula (3 ′) obtained by the production method of the present invention can be suitably used as a photoresist material.

The photoresist composition of the present invention is a cyclic compound represented by the above formula (3 ′) produced using the cyclic compound represented by the above formula (3) and / or the cyclic compound produced by the production method of the present invention as a raw material. And a solvent. These cyclic compounds are used as a substrate.
The compounding amount of the cyclic compound is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the entire composition excluding the solvent. When a cyclic compound is used as a photoresist base material, it may be used alone or in combination of two or more, as long as the effects of the present invention are not impaired.

  Examples of the solvent used in the photoresist composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycols such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Monoalkyl ethers; methyl lactate, ethyl lactate (E Lactic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Other esters such as methyl ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; tetrahydrofuran, dioxane Examples thereof include cyclic ethers such as lactones and lactones such as γ-butyrolactone, but are not particularly limited. These solvents can be used alone or in combination of two or more.

  The components other than the solvent in the composition, that is, the amount of the photoresist solid content, is preferably set to an amount suitable for forming a desired film thickness of the photoresist layer. Specifically, it is generally 0.1 to 50% by weight of the total weight of the photoresist composition, but it can be defined according to the type of base material and solvent used, or the desired film thickness of the photoresist layer. . The solvent is preferably blended in an amount of 50 to 99.9% by weight in the entire composition.

  The photoresist composition of the present invention does not require an additive particularly when the substrate molecule contains a chromophore active against EUVL and / or an electron beam and exhibits the ability as a photoresist alone. When it is necessary to enhance the performance (sensitivity) as a photoresist, a photoacid generator (PAG) or the like is generally included as a chromophore as necessary.

The photoacid generator is not particularly limited, and those proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. There are various known acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

  Of these photoacid generators, compounds that generate an organic sulfonic acid by the action of actinic rays or radiation are particularly preferred.

  The blending amount of PAG is 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight in the total composition excluding the solvent.

  In the present invention, an acid diffusion control agent (quencher) having an action of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. May be blended in the photoresist composition. By using such an acid diffusion controller, the storage stability of the photoresist composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent.

  Examples of such an acid diffusion controller include electron beam radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds such as cyclic amines, basic sulfonium compounds, and basic iodonium compounds. The acid diffusion controller can be used alone or in combination of two or more.

  The blending amount of the quencher is 0 to 40% by weight, preferably 0.01 to 15% by weight in the total composition excluding the solvent.

  In the present invention, if desired, further miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving coating properties, dissolution control agents, sensitizers, plasticizers. Stabilizers, colorants, antihalation agents, dyes, pigments, and the like can be appropriately added and contained.

  The dissolution control agent is a component having an action of reducing the solubility of the cyclic compound in an alkaline developer so as to moderate the dissolution rate during development. The dissolution control agent can be used alone or in combination of two or more. The blending amount of the dissolution control agent is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and more preferably 0 to 30% by weight based on the total weight of the solid component. Is more preferable.

  The sensitizer is a component that absorbs the energy of the irradiated radiation and transmits the energy to the acid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. is there. These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, even more preferably 0 to 10% by weight based on the total weight of the solid component.

  The surfactant is a component having an action of improving the coating property and striation of the photoresist composition of the present invention, the developing property as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, nonionic surfactants are preferred. Nonionic surfactants have better affinity with the solvent used in the photoresist composition and are more effective. The blending amount of the surfactant is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and still more preferably 0 to 0.1% by weight based on the total weight of the solid components.

  Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid.

  An organic carboxylic acid or phosphorus oxo acid or a derivative thereof is added as an optional component for the purpose of preventing sensitivity deterioration when an acid diffusion control agent is added and improving the resist pattern shape, retention stability, etc. be able to. In particular, phosphonic acid is preferred. These compounds can be used in combination with an acid diffusion controller or may be used alone.

  In order to form a resist pattern, first, the photoresist composition of the present invention is applied on a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum, by coating means such as spin coating, cast coating, roll coating, etc. Then, a resist film is formed by coating.

  If necessary, a surface treatment agent may be applied in advance on the substrate. Examples of the surface treatment agent include a silane coupling agent such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group), an anchor coating agent or a base agent (polyvinyl acetal, acrylic resin, vinyl acetate). Based resins, epoxy resins, urethane resins, etc.), and coating agents obtained by mixing these base agents and inorganic fine particles.

  If necessary, a protective film may be formed on the resist film in order to prevent an amine or the like floating in the atmosphere from entering. By forming a protective film, the acid generated in the resist film due to radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity. Can be prevented from decreasing. As the material for the protective film, a water-soluble and acidic polymer is preferable. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  In order to obtain a high-precision fine pattern and to reduce outgas during exposure, it is preferable to heat before irradiation (before exposure). The heating temperature varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The exposure conditions and the like are appropriately selected according to the composition of the photoresist composition. In the present invention, in order to stably form a high-precision fine pattern, it is preferable to heat after irradiation (after exposure). The post-exposure heating temperature (PEB) varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, a predetermined resist pattern can be formed by developing the exposed resist film with an alkaline developer. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution of preferably 1 to 10% by weight, more preferably 1 to 5% by weight, in which one or more compounds are dissolved is used. An appropriate amount of an alcohol such as methanol, ethanol, isopropyl alcohol, or the above-mentioned surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by weight of isopropyl alcohol. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  When a cyclic compound having an acid dissociable, dissolution inhibiting group is used as a photoresist base material, the resist film is exposed to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, thereby generating an acid. When the dissociable dissolution inhibiting group is eliminated or the structure is changed, the dissociable dissolution inhibiting group is dissolved in the alkaline developer. On the other hand, it is preferable that the unexposed portion of the pattern is not dissolved in the alkaline developer.

  The non-solubility in the alkali developer cannot be generally defined because the preferred non-solubility differs depending on the development conditions such as the size of the pattern to be formed and the type of the alkali developer to be used. When an aqueous methylammonium hydroxide solution is used as an alkaline developer, the insolubility expressed by the developer dissolution rate of a thin film made of a photoresist substrate is preferably less than 1 nanometer / second, preferably 0.5 nanometer / second. Less than a second is particularly preferred.

  In some cases, post-baking may be performed after the alkali development, or an organic or inorganic antireflection film may be provided between the resist film and the substrate.

  After forming the resist pattern, the pattern wiring board is obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas, wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. After the resist pattern is formed, a plating process such as copper plating, solder plating, nickel plating, or gold plating can be performed.

  The residual resist pattern after etching can be peeled off with an aqueous solution that is stronger than an organic solvent or an alkaline developer. Examples of the organic solvent include PGMEA, PGME, EL, acetone, tetrahydrofuran, and the like. Examples of the strong alkaline aqueous solution include 1 to 20% by weight sodium hydroxide aqueous solution and 1 to 20% by weight potassium hydroxide aqueous solution. Is mentioned. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  After forming a resist pattern using the photoresist composition of the present invention, a wiring substrate can be formed by a method in which a metal is vacuum-deposited and then the resist pattern is eluted with a solution, that is, a lift-off method.

  A semiconductor device can be produced by a microfabrication method using the photoresist composition of the present invention. This semiconductor device can be provided in various devices such as an electric product (electronic device) such as a television receiver, a mobile phone, and a computer, a display, and a computer controlled car.

  The cyclic compound obtained by the production method of the present invention can produce various molded products (thin films, films, thin plates, fibers, etc. formed on a substrate such as a silicon wafer) by a known molding method.

Molding methods include injection molding, injection compression molding, extrusion molding, blow molding, pressure molding, transfer molding, spin coating, spray coating, casting, vapor deposition, thermal CVD, plasma Examples thereof include a CVD method and a plasma polymerization method, and these molding methods can be appropriately selected according to the form and performance of a desired product.
Moreover, a thin film is obtained by the above method using a cyclic compound, and the obtained thin film is cured by heat, ultraviolet rays, deep ultraviolet rays, vacuum ultraviolet rays, extreme ultraviolet rays, electron beams, plasma, X-rays, etc. (cycloaddition reaction) You may let them.

When the cyclic compound is formed into a thin film by a spin coating method or the like, a paint in which the compound is dissolved in an organic solvent can be used.
Examples of organic solvents include chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, dichloroethane, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide, dimethyl sulfoxide. (DMSO), anisole, acetophenone, benzonitrile, nitrobenzene, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran (THF), cyclohexanone, methyl ethyl ketone, acetone and the like.

The concentration of the cyclic compound in the paint may be appropriately adjusted in consideration of the viscosity of the paint and the thin film forming method.
The thickness of the thin film is not particularly limited, but generally a thickness of about 10 nm to 10 μm is preferably used. The film thickness of the thin film can be measured with an ellipsometer, a reflective optical film thickness meter, or the like, or with a stylus film thickness meter or AFM.

  The thin film of the present invention is used as a photoresist thin film, optical thin films for various optical information processing devices such as optical lenses, optical fibers, optical waveguides, photonic crystals, interlayer insulating films for semiconductors, protective films for semiconductors, etc. It is useful as a thin film for ULSI devices, a liquid crystal display, a liquid crystal projector, a plasma display, an EL display, an LED display and other thin film for image display devices, a CMOS image sensor, a CCD image sensor, and the like. Furthermore, these thin films are provided for semiconductor devices such as CPU, DRAM, flash memory, electronic circuit devices for information processing, electronic circuit devices such as high-frequency communication electronic circuit devices, image display devices, optical information processing devices, and optical communication devices. It can also be used in a member such as a surface protective film and a heat-resistant film.

Example 1
Under a nitrogen stream, in a round bottom flask with a capacity of 200 ml, 50.0 g (402.8 mmol) of 3-methoxyphenol (Tokyo Chemical Industry Co., Ltd.), 4-formylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 60. 5 g (402.8 mmol) and 500 ml of dehydrated dichloromethane were added and immersed in an ice-water bath and cooled to 5 ° C. or lower. To this mixture, 60.8 ml (483.6 mmol) of boron trifluoride ether adduct (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 15 ° C., and then the temperature was raised to room temperature. Warmed and continued stirring for 8 hours. The reaction solution was cooled in an ice water bath, quenched slowly by dropwise addition of water, and the precipitated solid was filtered off. Further, the precipitate separated by filtration is washed with water until it becomes neutral, then dissolved in N-methyl-2-pyrrolidone, reprecipitated with ethyl acetate, and the precipitated solid is separated by filtration to obtain a cyclic compound (A [Yield 94.4 g (Yield 91%)].
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (A).

Example 2
Under a nitrogen stream, 2.0 g (16.11 mmol) of 3-methoxyphenol, 2.41 g (16.11 mmol) of 4-formylbenzoic acid and 50 ml of chloroform were added to a 100 ml flask and cooled to -78 ° C. . To this, 11.68 ml (99.8 mmol) of tin tetrachloride was added dropwise, then the temperature was naturally raised to room temperature, further heated to 50 ° C., and allowed to react for 8 hours. The reaction mixture was poured into ice-cold water, and 500 ml of 1N hydrochloric acid was added and stirred. The reaction mixture was filtered, and the collected filtrate was washed with water and then dried under reduced pressure. The cyclic compound (A) was obtained by reprecipitation using N-methyl-2-pyrrolidone and ethyl acetate [yield 3.38 g (yield 82%)].
As a result of ¹ H-NMR measurement, a spectrum similar to that shown in FIG. 1 was obtained, and it was confirmed that the obtained compound had the structure of the above formula (A).

Example 3
A cyclic compound (A) was obtained in the same manner as in Example 2 except that 13.3 g (99.8 mmol) of aluminum chloride was used instead of tin tetrachloride in Example 2. [Yield 2.91 g (Yield 70%)].
As a result of ¹ H-NMR measurement, a spectrum similar to that shown in FIG. 1 was obtained, and it was confirmed that the obtained compound had the structure of the above formula (A).

Comparative Example 1
Under a nitrogen stream, 10.0 g (81 mmol) of 3-methoxyphenol, 13.2 g (80.6 mmol) of methyl 4-formylbenzoate and 100 ml of dehydrated dichloromethane were added to a round bottom flask having a capacity of 200 ml, and -78 Cooled to ° C. To this mixture, 30.8 ml (250 mmol) of boron trifluoride-ether adduct was added dropwise, and then the temperature was raised to room temperature and stirring was continued for 8 hours. The reaction solution was cooled to −78 ° C., and the precipitated solid was washed with 80 ml of dichloromethane, 200 ml of water and ethanol to obtain a cyclic compound (B) as an intermediate [yield 20.5 g (yield 94%). ].
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (B).

Under a nitrogen stream, 0.8 g (0.74 mmol) of the obtained intermediate cyclic compound (B), 0.74 g (18.5 mmol) of sodium hydroxide and 10 ml of water were added and heated at 90 ° C. for 5 hours. After stirring, the mixture was allowed to cool. The reaction solution was acidified by adding dilute hydrochloric acid solution, and the deposited precipitate was filtered and washed with water to obtain a cyclic compound (A) as a solid [yield 0.68 g (yield 90%)].
As a result of ¹ H-NMR measurement (FIG. 2), it was confirmed that the structure was represented by the following formula (A).
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (A).

  In Comparative Example 1, two steps of reaction are required from the starting material to obtain the target cyclic compound (A), and the operation is complicated. Further, the overall yield of the two-stage reaction was 85%, which was lower than that of Example 1. Although the yield was high as compared with Examples 2 and 3, the obtained solid of the cyclic compound (A) was colored yellowish brown and was not suitable.

The method for producing a cyclic compound of the present invention can produce a photoresist substrate or a precursor thereof with few reaction steps.
The photoresist composition of the present invention is suitably used in the electrical / electronic field and the optical field of semiconductor devices and the like.

Claims (7)

A method for producing a cyclic compound represented by the following formula (3), comprising a step of subjecting an aldehyde compound represented by the following formula (1) and an aromatic compound represented by the following formula (2) to a condensation reaction under an acid catalyst.
[Wherein, R is a group represented by the following formula (4) or (5).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms. Group, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, alkoxyalkyloxy group, siloxy group, or a divalent group thereof (substituted or unsubstituted alkyleneoxy group, substituted or unsubstituted aryleneoxy group) A group having a structure in which a group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group in which these groups are bonded to an ester bond, a carbonate ester bond, or an ether bond) It is.
R ² is hydrogen, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. An aromatic hydrocarbon group or an aromatic group having 6 to 10 carbon atoms.
A plurality of R, R ¹ and R ² in the formula (1) and the formula (2) may be the same or different.
(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or one or more alkylene groups and 1 It is a group in which at least one of the above ether bond groups and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms is combined. In the case of having a substituent, the substituent is bromine, fluorine, nitrile group, carbon number 1 -10 alkyl groups.
R ³ and R ⁴ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x represents an integer of 1 to 5, y represents 0 to 3, and z represents an integer of 0 to 4. A plurality of R ³ , R ⁴ , Ar, A ¹ , x, y and z may be the same or different. ]]   The production method according to claim 1, wherein the acid catalyst is a catalyst having Lewis acidity.   The manufacturing method according to claim 2, wherein the catalyst having Lewis acidity is a Lewis acid composition containing boron trifluoride or a Lewis acid compound having tin or aluminum as a central metal. The following formula manufactured using the cyclic compound manufactured with the manufacturing method in any one of Claims 1-3 and / or the cyclic compound manufactured with the manufacturing method in any one of Claims 1-3 as a raw material. A photoresist composition comprising a cyclic compound represented by (3 ′) and a solvent.
[Wherein, R represents a group represented by the following formula (4 ′) or (5 ′).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms. Group, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, alkoxyalkyloxy group, siloxy group, or a divalent group thereof (substituted or unsubstituted alkyleneoxy group, substituted or unsubstituted aryleneoxy group) A group having a structure in which a group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group in which these groups are bonded to an ester bond, a carbonate ester bond, or an ether bond) It is.
R ² is hydrogen, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. Group hydrocarbon group or aromatic group having 6 to 10 carbon atoms.
A plurality of R, R ¹ and R ² in the formula (3 ′) may be the same or different.
(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or one or more alkylene groups and 1 It is a group obtained by combining at least one of the above ether bonds and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, a carbon number of 1 to 10 alkyl groups.
R ³ and R ⁴ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
R ⁵ is an acid dissociable, dissolution inhibiting group.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x represents an integer of 1 to 5, y represents 0 to 3, and z represents an integer of 0 to 4. A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , x, y, and z may be the same or different. ]]   The thin film containing the cyclic compound manufactured with the manufacturing method in any one of Claims 1-3.   A fine processing method using the photoresist composition according to claim 4. A semiconductor device manufactured by the microfabrication method according to claim 6.