JP4614056B2 - Resist compound and radiation-sensitive composition - Google Patents

Description

  The present invention relates to a resist compound represented by a specific chemical structural formula, which is useful as an acid amplification type non-polymer resist material. Moreover, this invention relates to the radiation sensitive composition containing this compound and an acid generator. The compound of the present invention is used as a radiation-sensitive material sensitive to ultraviolet rays, far-ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, and X-rays, for masks used in the manufacture of LSIs and VLSIs in the electronics field.

  Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a line width is obtained by irradiating a resist thin film prepared by applying a polyhydroxystyrene derivative and a solution dissolved in a solvent for dissolving it on a substrate with ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. A line pattern of about 0.08 μm is produced.

  However, conventional polymer resist materials have a large molecular weight of about 10,000 to 100,000, a broad molecular weight distribution, and further entanglement between polymer chains, so that fine processing advances in lithography using polymer resist materials. Then, roughness is generated on the pattern surface, and it becomes difficult to control the pattern dimension, resulting in a decrease in yield and deterioration in transistor characteristics. Therefore, there is a limit to miniaturization with a line width of 0.06 μm or less in conventional lithography using a polymer resist material. Therefore, in order to produce a finer pattern, a material having a small molecular weight distribution and a narrow molecular weight distribution is disclosed.

  Examples of non-polymer resist materials are (1) positive and negative resists derived from fullerene, (2) positive and negative resists derived from calixarene, and (3) derived from starburst compounds. A positive resist, (4) a positive resist derived from a dendrimer, (5) a positive resist derived from a dendrimer / calixarene, and (6) a positive resist derived from a highly branched starburst compound, And (7) a positive resist derived from a starburst compound having an ester bond with trimesic acid as the central skeleton.

  About (1), although etching resistance is good, applicability | paintability and a sensitivity have not reached the practical use level (refer patent documents 1-5). About (2), although it is excellent in etching tolerance, since a solubility with respect to a developing solution is bad, a satisfactory pattern is not obtained (refer patent documents 6-8). Regarding (3), the image may be distorted during heat treatment after exposure due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and it cannot be said that it is practical (see Non-Patent Document 1). . Regarding (5), the manufacturing process is complicated and the raw material is expensive, so it cannot be said that it is practical. (See Patent Documents 12 to 13.) Regarding (6), the manufacturing process is complicated, the raw materials are expensive, and a metal catalyst which is hated by semiconductor factories is used, so it cannot be said that it is practical. Regarding (7), since the heat resistance is low, the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so it cannot be said that it is practical (see Patent Document 14). .

Moreover, the example which uses a low molecular compound as an additive of the photosensitive resin composition is disclosed. Photosensitive resin composition comprising a photoactive compound having a hydrophobic group selected from a hydrocarbon group and a heterocyclic group, a linking group, and a hydrophilic group protected by a protecting group removable by light irradiation (Patent Literature) 15), a resist composition comprising a low-molecular dissolution inhibiting compound having a structure in which two or more triphenylmethane structures are non-conjugatedly linked to a portion other than a group that can be decomposed by the action of an acid (see Patent Document 16). ), A resist resin composition containing a photoactive compound having a fluorene structure (see Patent Document 17) is exemplified, but a composition containing the compound of the present invention described below as a main component is disclosed. Not. Moreover, since both are resist compositions containing a resin, the line edge roughness of the pattern to be formed is large and cannot be said to be sufficient. Further, when the disclosed resist compound is used as a main component, the propylene glycol mono-monohydride generally used in semiconductor factories, having high crystallinity and poor film formability, not having heat resistance to withstand semiconductor processes. It was difficult to use as a single component due to any problems such as poor solubility in safety solvents such as ethyl ether acetate and ethyl lactate and poor substrate adhesion.
JP-A-7-134413 JP 9-211182 A JP-A-10-282649 Japanese Patent Application Laid-Open No. 11-143074 Japanese Patent Laid-Open No. 11-258996 JP-A-11-72916 JP-A-11-322656 JP-A-9-236919 JP 2000-305270 A JP 2002-99088 A JP 2002-99089 A JP 2002-49152 A JP 2003-183227 A Japanese Patent Laid-Open No. 2002-328466 JP 2002-363123 A JP 2001-312055 A JP 2004-137262 A Proceedings of SPIE vol. 3999 (2000) P1202-1206.

  An object of the present invention is to provide a compound and a radiation-sensitive composition that are sensitive to radiation such as excimer laser light such as KrF, extreme ultraviolet light (EUV), electron beam, and X-ray. Another object of the present invention is to provide a high-sensitivity, high-resolution, high heat resistance, high etching resistance and solvent-soluble non-polymeric radiation-sensitive composition without using a metal catalyst and with a simple production process. There is to do.

As a result of intensive studies, the present inventors have found that a compound represented by a specific chemical structural formula and a composition containing the compound solve the above problems.
That is, the present invention is a radiation-sensitive composition containing 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the following a) and b):
a) of a polyphenol compound (A) obtained from a condensation reaction between an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups , Having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group,
b) Molecular weight of 300-3000
A radiation-sensitive composition comprising a compound (B) satisfying the above condition, wherein the sum of the compound (B) and the dissolution accelerator is 50 to 99.999% by weight based on the total weight of the solid component Is.
Furthermore, this invention relates to the compound shown by Formula (1).

(In the formula (1),
R ¹ each independently represents a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, And an acid dissociable functional group selected from the group consisting of alkoxycarbonyl groups;
R ² each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, or an aryloyloxy group. And represents a substituent selected from the group consisting of a cyano group and a nitro group;
R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and R ⁵ represents a monovalent substituent having 10 to 18 carbon atoms having a biphenyl structure or a naphthalene structure; or —CR ⁴ R ⁵ - ^{R 4} and ^{R 5} are bonded to, ^-CR 4 ^{R 5} - fluorene structure, acenaphthene structure, a divalent substituent having 10 to 18 carbon atoms having 1 ketoacenaphthene structure or benzophenone structure;
m0 and n0 are each an integer from 0 to 3, m1 and n1 are each an integer from 0 to 3, m2 and n2 are each an integer from 0 to 4, and 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 Satisfy the following conditions: ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, 1 ≦ n0 + n1 ≦ 3;
The carbons of the two benzene rings in the ortho position with respect to —CR ⁴ R ⁵ — are bonded via an oxygen atom or a sulfur atom to form the following formula (2):

(In the formula (2), R ¹ , R ² , R ⁴ and R ⁵ are the same as above;
p0 and q0 are each an integer from 0 to 2, p1 and q1 are each an integer from 0 to 2, p2 and q2 are each an integer from 0 to 3, and 1 ≦ p0 + p1 + p2 ≦ 4, 1 ≦ q0 + q1 + q2 ≦ 4, 1 ≦ p1 + q1 ≦ 4, 1 ≦ p0 + p1 ≦ 2, 1 ≦ q0 + q1 ≦ 2 is satisfied; X is an oxygen atom or a sulfur atom), or a xanthene structure or a thioxanthene structure may be formed.

  The radiation-sensitive compound of the present invention is used as a main component of a non-polymeric radiation-sensitive composition that does not contain a metal catalyst and has high sensitivity, high resolution, high heat resistance, high etching resistance, and solvent solubility. By using the radiation-sensitive composition and the dissolution accelerator, a high-resolution and high-sensitivity pattern can be produced, so that a highly integrated semiconductor element can be produced with high productivity.

Hereinafter, the present invention will be described in detail.
The radiation-sensitive composition of the present invention contains 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent. The following a) and b):
a) of a polyphenol compound (A) obtained from a condensation reaction between an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups , Having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group,
b) Molecular weight of 300-3000
The sum of the compound (B) and the dissolution accelerator is 50 to 99.999% by weight based on the total weight of the solid component.

  The compound (B) (resist compound) preferably includes a conjugated structure involving at least two benzene rings and / or non-bonded electron pairs of heteroatoms. By having the above conjugated structure, it is possible to impart performance such as film forming property, high etching resistance, a low outgas amount during radiation exposure, and high sensitivity due to a sensitizing effect even though it is a low molecular compound. This sensitization effect is considered to be due to the absorption of a part of the energy of radiation such as an electron beam and the efficient transmission of the absorbed energy to the acid generator.

  Examples of the conjugated structure include biphenyl structure, naphthalene structure, fluorene structure, anthracene structure, phenanthrene structure, pyrene structure, benzopyrene structure, acenaphthene structure, acenaphthylene structure, 1-ketoacenaphthene structure, benzophenone structure, xanthene structure, thioxanthene structure, flavone structure , Isoflavone structure, indane structure, indene structure, indacene structure, phenalene structure, biphenylene structure, coronene structure, chrysene structure, trinaphthylene structure, hexaphen structure, hexacene structure, rubicene structure, fluoracene structure, acephenanthrylene structure, perylene structure, picene Structure, pentaphen structure, heptaphen structure, heptacene structure, pyranthrene structure, phenacene structure, naphthacene structure, pentacene structure, aceanthrene Structure, acephenanthrene structure, azulene structure, triphenylene structure, p-terphenyl structure, m-terphenyl structure, 1,3,5-triphenylbenzene structure, 1,2,3-triphenylbenzene structure, 1,2, A 4-triphenylbenzene structure, a phenylnaphthalene structure, a phenylnaphthalene structure, a binaphthalene structure, an ovalen structure, and the like can be given. It is relatively inexpensive to have at least one structure selected from a biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, acenaphthene structure, 1-ketoacenaphthene structure, benzophenone structure, xanthene structure, and thioxanthene structure It is particularly preferable because it can be introduced from various raw materials.

  The compound (B) (resist compound) is preferably at least one compound selected from the group consisting of compounds represented by the following formula (1).

In formula (1), each R ¹ independently represents a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, or a 1-substituted alkoxymethyl. An acid dissociable functional group selected from the group consisting of a group, a cyclic ether group, and an alkoxycarbonyl group.

  Specific examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4 -Methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-butoxycarbonylmethyl group, etc. Can do.

  Specific examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxy. Ethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group and 1,1-diphenyl An ethyl group etc. can be mentioned.

  Examples of the 1-substituted-n-propyl group include a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group.

  Examples of the 1-branched alkyl group include isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, and 1,1-dimethylbutyl group.

  Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, and tri-tert-butylsilyl. Group and triphenylsilyl group.

  Examples of the acyl group include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantyl group, benzoyl group and naphthoyl group. Can do.

  Examples of the 1-substituted alkoxymethyl group include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group and 1 -Adamantyl methoxymethyl group etc. can be mentioned.

  Furthermore, examples of the cyclic ether group include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, and a 4-methoxytetrahydrothiopyranyl group. Can do.

  Furthermore, examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, and a tert-butoxycarbonyl group.

  Among these acid dissociable functional groups, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, tert- A butyl group, a trimethylsilyl group, a tetrahydropyranyl group and a 1-cyclohexylmethoxymethyl group are preferred.

R ² each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, or an aryloyloxy group. And a substituent selected from the group consisting of a cyano group and a nitro group.
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl group, cycloalkyl groups include cyclohexyl group, norbornyl group, adamantyl group and the like, and aryl groups include phenyl group, tolyl group, xylyl group and naphthyl group. The aralkyl group includes a benzyl group, the alkoxy group includes a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, sec An abutene having 1 to 4 carbon atoms such as a butoxy group or a tert-butoxy group; Examples of the aryloxy group include a phenoxy group. Examples of the alkenyl group include an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, and a butenyl group, and an acyl group. Examples thereof include an aliphatic acyl group having 1 to 5 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group and pivaloyl group, and aromatic acyl groups such as benzoyl group and toluoyl group. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, isobutoxycarbonyloxy group, sec-butoxycarbonyloxy group, tert -Butoxyca Examples of the alkoxycarbonyloxy group having 2 to 5 carbon atoms such as a bonyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group valeryloxy group, an isovaleryloxy group, and pivaloyloxy. Group and the like, and the aryloyloxy group includes a benzoyloxy group.

R ² is preferably substituted at the ortho position of the phenolic hydroxyl group. The ortho-position R ² suppresses the crystallinity of the compound (B) and improves the film formability. In addition, since the solubility of the compound (B) in an alkaline developer is suppressed, the acid dissociation protection rate of the resist compound can be reduced, so that solvent solubility and substrate adhesion are improved, and resist sensitivity is further improved. Sometimes. R ² effective for this purpose is preferably a bulky structure and / or an electron donating group, and is an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group, a benzyl group, a cyclohexyl group, a norbornyl group). , An adamantyl group, etc.), an alkoxy group (such as a methoxy group, an ethoxy group, an isopropoxy group, a phenoxy group, etc.). Note that an electron-withdrawing functional group such as halogen may increase the solubility of the compound (B) in an alkaline developer.

R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and R ⁵ represents a monovalent substituent having 10 to 18 carbon atoms having a biphenyl structure or a naphthalene structure.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Examples thereof include straight chain, branched or cyclic alkyl groups such as hexyl group and cyclohexyl group. The aryl group represented by R ⁴ include phenyl groups.

R ⁵ represents the following formula:

(In the above formula, R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; p3 is an integer of 0 to 4; q3 is an integer of 0 to 3; and a condition of 0 ≦ p3 + q3 ≦ 7. Is preferably a monovalent substituent having a biphenyl structure or a naphthalene structure. Examples of the alkyl group having 1 to 6 carbon atoms include the same alkyl groups as exemplified for R ⁴ .

Further, ^-CR 4 ^{R 5} - ^{R 4} and ^{R 5} are bonded to, ^-CR 4 ^{R 5} - is, fluorene structure, acenaphthene structure, divalent having 10 to 18 carbon atoms having 1 ketoacenaphthene structure or benzophenone structure Substituents, preferably the following formula:

(In the above formula, R ³ , p3 and q3 are the same as above; Y is a single bond or a carbonyl group; Z is a methylene group or a carbonyl group)
It is a bivalent substituent represented by these.
m0 and n0 are each an integer from 0 to 3, m1 and n1 are each an integer from 0 to 3, m2 and n2 are each an integer from 0 to 4, and 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5 The conditions of 1 ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, and 1 ≦ n0 + n1 ≦ 3 are satisfied.
In addition, the carbon in the ortho position with respect to —CR ⁴ R ⁵ — of the two benzene rings in the formula (1) is bonded through an oxygen atom or a sulfur atom to form the following formula (2):

(In the formula (2), R ¹ , R ² , R ⁴ and R ⁵ are the same as above;
p0 and q0 are each an integer of 0 to 2;
p1 and q1 are each an integer of 0 to 2;
p2 and q2 are each an integer of 0 to 3;
1 ≦ p0 + p1 + p2 ≦ 4, 1 ≦ q0 + q1 + q2 ≦ 4, 1 ≦ p1 + q1 ≦ 4, 1 ≦ p0 + p1 ≦ 2, 1 ≦ q0 + q1 ≦ 2;
X may be an oxygen atom or a sulfur atom) and may form a xanthene structure or a thioxanthene structure.

  Although the compound of formula (1) is a low molecular compound, it has excellent film-forming properties, heat resistance, dry etching resistance, and low outgas properties, and has high resolution and high resistance to a resist composition containing the compound as a main component. Performance such as sensitivity and low line edge roughness can be added.

  The compound (B) is preferably at least one compound selected from compounds represented by the following formulas (3) and (5) to (12).

(In the formula (3), R ¹ , R ² , R ⁴ , R ⁵ , m2 and n2 are the same as described above, and the carbon in the ortho position relative to —CR ⁴ R ⁵ — of the two benzene rings Bonded through an oxygen atom or sulfur atom, the following formula (4):

(In formula (4), R ¹ , R ² , R ⁴ , R ⁵ , X, p2 and q2 may be the same as those described above), and may form a xanthene structure or a thioxanthene structure).
The compound of formula (3) is further excellent in practicality such as excellent substrate adhesion, solvent solubility, and heat resistance, and the availability of raw materials at a relatively low cost.

(In formula (5), R ^{1 to} R ⁴ , m0 to m2, n0 to n2, p3, and q3 are the same as above).

(In formula (6), R ^{1 to} R ⁴ , m0 to m2, n0 to n2, p3, and q3 are the same as above).

(In formula (7), R ^{1 to} R ³ , Y, m0 to m2, n0 to n2, p3, and q3 are the same as above).

(In formula (8), R ^{1 to} R ³ , Z, m0 to m2, n0 to n2, p3, and q3 are the same as above).

(In formula (9), R ^{1 to} R ⁴ , p0 to p3, and q0 to q3 are the same as above).

(In formula (10), R ^{1 to} R ⁴ , p0 to p3, and q0 to q3 are the same as above).

(In formula (11), R ^{1 to} R ³ , Y, p0 to p3, and q0 to q3 are the same as above).

(In formula (12), R ^{1 to} R ³ , Z, p0 to p3, and q0 to q3 are the same as above).

  The compound (B) is a polyphenol compound (A) obtained by condensing an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms with a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups. And an acid dissociable functional group is introduced into at least one phenolic hydroxyl group of the polyphenol compound (A).

Examples of aromatic ketones or aromatic aldehydes having 5 to 45 carbon atoms include acetophenone, benzophenone, α-acetonaphthone, β-acetonaphthone, 9-fluorenone, acenaphthenone, benzoquinone, naphthoquinone, anthraquinone, acenaphthenequinone, benzoylbiphenyl, benzoyl Naphthalene, acylbiphenyl, acylanthracene, acylphenanthrene, acylphenothiazane, acylpyrene, acylbenzopyrene, acylindacene, acylphenacene, acylacenaphthylene, acylnaphthacene, acylpentacene, acyltriphenylene, acylpyridine, acylimidazole, acylfuran, Acylpyrrole, acylovalene, indanone, tetralone, acylthiazole, acridone, flavone, isoflavone Aromatic ketones such as benzaldehyde, toluylaldehyde, anisaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, anthraldehyde, biphenylaldehyde, formylfluorene, formylbiphenyl, formylanthracene, formylphenanthrene, formylphenothiazane, formylpyrene And aromatic aldehydes such as formylbenzopyrene, formylindacene, formylphenacene, formylacenaphthylene, formylnaphthacene, formylpentacene, formyltriphenylene, formylpyridine, and formylovalene.
In particular, α-acetonaphthone, β-acetonaphthone, 9-fluorenone, acetylanthracene, acetylpyrene, acenaphthenone, acenaphthenequinone, anthraquinone, 1-naphthaldehyde, and 4-biphenylaldehyde are available at low cost and have relatively high reactivity. The polyphenol compound (A) is preferable because it is easy to produce.

Examples of the compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups include phenol, (C _1-6 alkyl) phenol (for example, cresol such as o-cresol, m-cresol, p-cresol and the like). , O-phenylphenol, 2-cyclohexylphenol), dialkylphenols (eg 2,3-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,6-di-tert-butylphenol), Trialkylphenol, alkoxyphenol (for example, anisole such as o-methoxyphenol), arylphenol (for example, phenylphenol such as o- and m-phenylphenol), cycloalkylphenol (for example, 2-cyclohexylphenol), halogenated fluorine, etc. Knols (eg, chlorophenol, dichlorophenol, chlorocresol, bromophenol, dibromophenol), polyhydric phenols (eg, catechol, alkylcatechol, chlorocatechol, resorcinol, alkylresorcinol, hydroquinone, alkylhydroquinone, chlororesorcinol, chloro Hydroquinone, pyrogallol, alkyl pyrogallol, phloroglicinol, 1,2,4-trihydroxyphenol) and the like. You may use the said compound individually or in combination of 2 or more types. The purity is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

Among the compounds containing 1 to 3 phenolic hydroxyl groups, phenol, (C _1-6 alkyl) phenol, such as 2- (C _1-6 alkyl) phenol (o-cresol, o-phenylphenol, 2- Cyclohexylphenol, etc.), catechol, resorcinol, and pyrogallol are preferred from the viewpoint of availability of raw materials. In addition, the use of a phenol having a bulky substituent and / or an electron donating functional group at the ortho position suppresses the crystallinity of the compound (B) and improves the film formability. Further, the solubility of the compound (B) in an alkaline developer can be suppressed, and the introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group can be reduced, so that solvent solubility and substrate adhesion can be improved and resist sensitivity can be improved. Bring improvement. Examples of such phenol include 2- (C _1-6 alkyl) phenol (o-cresol, o-phenylphenol, 2-cyclohexylphenol, 2-t-butylphenol, 2,6-di-t-butylphenol, and the like. ), 2-alkoxyphenol (2-methoxyphenol, 2-isopropoxyphenol, 2-phenoxyphenol, etc.).

The polyphenol compound (A) contains 1 mol to an excess of a compound containing 1 to 3 phenolic hydroxyl groups such as phenol and o-cresol with respect to 1 mol of an aromatic ketone or aromatic aldehyde, an acid catalyst (hydrochloric acid or Sulfuric acid) and thioacetic acid or β-mercaptopropionic acid as a co-catalyst for suppressing by-products, and the reaction is carried out at 60 to 150 ° C. for about 0.5 to 20 hours. After completion of the reaction, methanol or isopropyl is added to the reaction solution. After adding alcohol and heating to 60-80 ° C. and stirring for 0.5-2 hours, an appropriate amount of pure water is added to precipitate the reaction product, cooled to room temperature, filtered, separated and dried. However, there is no particular limitation. The polyphenol compound (A) is produced by isolating the aromatic ketone or aromatic aldehyde as a dihalide with hydrogen halide or halogen gas and then reacting with a compound containing 1 to 3 phenolic hydroxyl groups. You can also
A compound for introducing an acid dissociable functional group such as a tert-butoxycarbonyl group or a tetrahydropyranyl group is added to the polyphenol compound (A), and in the presence of an amine catalyst such as triethylamine or dimethylaminopyridine, or pyridinium tosylate, etc. In the presence of an acid catalyst at normal pressure, 20 to 60 ° C. for 6 to 24 hours, the reaction solution is added to distilled water to precipitate a white solid, washed with distilled water, and silica gel column chromatography as necessary. Although it can manufacture a compound (B) by refine | purifying and drying by a graphic, it does not specifically limit.

  Examples of the compound for introducing the acid dissociable functional group include acid chlorides, acid anhydrides, dicarbonates, alkyl halides, vinyl alkyl ethers, and dihydropyrans having an acid dissociable functional group, but are not particularly limited. .

  In the present invention, the acid dissociable functional group refers to a characteristic group that is cleaved in the presence of an acid to generate a phenolic hydroxyl group. The acid-dissociable functional group preferably has a property of causing a cleavage reaction in a chain in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.

  The acid-dissociable functional group is preferably introduced into 10 to 95% of the total number of phenolic hydroxyl groups in the polyphenol compound (A), and particularly preferably 20 to 80%. By satisfying the above conditions, the solvent solubility, substrate adhesion, and sensitivity of the compound (B) are further improved.

  The molecular weight of the compound (B) is 300 to 3000, preferably 300 to 1500, and more preferably 400 to 1000. Within the above range, the resolution is improved while maintaining the film formability required for the resist.

  Compound (B) is preferably dissolved in propylene glycol monomethyl ether acetate or ethyl lactate at 23 ° C. at 5% by weight or more. By satisfying the above conditions, it is possible to use a safe solvent that can be used in a semiconductor factory.

  The radiation-sensitive composition of the present invention comprises a solid component of 1 to 80% by weight and a solvent of 20 to 99% by weight, preferably a solid component of 1 to 50% by weight and a solvent of 50 to 99% by weight, particularly preferably solid. Contains 5-40% by weight of components and 60-95% by weight of solvent. The total content of the compound (B) and the dissolution accelerator is 50 to 99.999% by weight, preferably 60 to 99% by weight, particularly preferably 80 to 99% by weight, based on the total weight of the solid components. is there. Within this range, high resolution is obtained and line edge roughness is reduced. The blending ratio of the dissolution accelerator is preferably 0 to 80% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight based on the total weight of the solid component. With the above blending ratio, high sensitivity and high resolution can be obtained, and the line edge roughness becomes small.

  Since the radiation-sensitive composition of the present invention contains the compound (B) satisfying the conditions a) and b) as a main component, it has heat resistance that can withstand a semiconductor process, safety such as propylene glycol monomethyl ether acetate or ethyl lactate. It has performances required for resist compositions such as solvent solubility, film formability, silicon substrate adhesion, alkali developability, etching resistance, low outgassing property during exposure, high resolution, and low edge roughness.

  Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol Propylene glycol monoalkyl ether acetates such as monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; Methyl lactate and Ethyl lactate Lactate esters such as (EL); vinegar Aliphatic carboxylic esters such as methyl, ethyl acetate, propyl acetate, butyl acetate; other methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc. Examples include esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane. Not. These solvents can be used alone or in combination of two or more.

In this invention, if an acid generate | occur | produces in a radiation sensitive composition, the generation method of an acid will not be limited. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.
The solid component preferably contains one or more acid generators that generate an acid upon irradiation with radiation selected from extreme ultraviolet (EUV), electron beam, and X-ray. The content of the acid generator is preferably 0.001 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 3 to 20% by weight based on the total weight of the solid component. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained.

  The acid generator is not particularly limited, but is preferably at least one selected from the group consisting of compounds represented by the following formulas (13) to (20).

In formula (13), R ¹³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxyl A group or a halogen atom; X ⁻ is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

  The compound represented by the formula (13) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate. Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nona Fluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate Bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4 -Methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzene Phonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6- Group consisting of trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate It is preferable that it is at least one selected from.

In the formula (14), R ¹⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxyl Represents a group or a halogen atom. X ⁻ is the same as described above.

  The compounds represented by the formula (14) are bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butyl). Phenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4 -T-buchi Phenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium-10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium-p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium-10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4- Difluorobenzenesulfonate, diphenyliodine Ni-hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per Fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium-p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium-10-camphor It is preferably at least one selected from the group consisting of sulfonates.

In formula (15), Q is an alkylene group or an arylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The compound represented by the formula (15) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-e It is preferably at least one selected from the over 2,3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.

In formula (16), R ¹⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (16) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It is at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.

In formula (17), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (17) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α It is preferably at least one selected from the group consisting of-(methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (18), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

In the formulas (19) and (20), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopentyl group, or a cyclohexyl group. A cycloalkyl group having 3 to 6 carbon atoms, such as a cycloalkyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, or an aryl group such as a phenyl group, a toluyl group, and a naphthyl group, preferably carbon An aryl group having 6 to 10 atoms. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, the following formula (21):

, A carbonyl group, an ester group, an amide group or an ether group, Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ¹⁹ and X ²⁰ are each independently the following formula (22):

(In the formula (22), Z ²² each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents an integer of 0 to 3. ).

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Bissulfonyldiazomethanes such as diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3 5-triazine, tris (2,3-dibromopropyl) Halogen-containing triazine derivatives, such as isocyanurate and the like.

When the solubility of the compound (B) in a developer such as an alkali is relatively low, the dissolution accelerator has an action of increasing the solubility of the compound (B) during development by increasing the solubility of the compound (B). It is an ingredient. As such a dissolution accelerator, those that do not chemically change in steps such as baking of the resist film, electron beam irradiation, and development are preferable. Examples of the dissolution accelerator include low molecular weight phenolic compounds. Specific examples include bisphenols, tris (hydroxyphenyl) methane, and tetrakisphenols. Examples of bisphenols include biphenol, bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methanone, methylene bisphenol, ethylidene bisphenol, cyclohexylidene bisphenol, and phenylethylidene bisphenol. Tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenylbenzene) and the like can be mentioned, and tetrakisphenols are 4,4 ′, 4 ″, 4 ′ ″. -(1,2-ethanediylidene) tetrakisphenol, 4,4 ', 4'',4'''-(1,2-phenylenedimethylidyne) tetrakisphenol, calix [4] arene, tetrakis (bicyclohexylidene) Examples include phenol It is. These dissolution promoters can be used alone or in admixture of two or more. The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the compound (B) to be used, but is preferably 0 to 80% by weight, more preferably 20 to 80% based on the total weight of the solid component. % By weight, particularly preferably 30 to 70% by weight.
The low molecular weight phenolic compound is preferably a compound of the following formula (25).

(In formula (25), R ² , R ⁴ , and R ⁵ are the same as defined above,
m3 and n3 are each an integer of 1 to 3;
m4 and n4 are each an integer of 0 to 4;
1 ≦ m3 + m4 ≦ 5, 1 ≦ n3 + n4 ≦ 5;
The carbons in the ortho position with respect to —CR ⁴ R ⁵ — of the two benzene rings are bonded via an oxygen atom or a sulfur atom, and the following formula (26):

(In the formula (26), R ² , R ⁴ , R ⁵ and X are the same as above;
p3 and q3 are each an integer of 1 to 2;
p4 and q4 are each an integer of 0 to 3. )
You may form the xanthene structure or thioxanthene structure represented by these.

  Various additives such as an acid diffusion controller, a dissolution controller, a sensitizer, and a surfactant can be added to the radiation-sensitive composition of the present invention.

  The acid diffusion control agent has a function of controlling an undesired chemical reaction in an unexposed region by controlling a phenomenon in which an acid generated from an acid generator upon irradiation is diffused into a resist film. By using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, the holding time before irradiation of an electron beam or the like, and the pulling time after irradiation of the electron beam. Changes in the line width of the resist pattern due to fluctuations in placement time 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, 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 acid diffusion controller is preferably 0 to 10% by weight, more preferably 0.001 to 5% by weight, particularly preferably 0.001 to 3% by weight, based on the total weight of the solid component. is there. When the compounding amount of the acid diffusion control agent is 0.001% by weight, depending on the process conditions, the resolution, pattern shape, and dimensional fidelity tend to decrease, and further, from electron beam irradiation to post-irradiation heating. If the holding time of the pattern becomes longer, the pattern shape tends to deteriorate in the upper layer portion of the pattern. On the other hand, when the compounding amount of the acid diffusion control agent exceeds 10% by weight, the sensitivity of the resist composition, the developability of the unexposed area, and the like tend to decrease.

  The dissolution control agent is a component having an action of controlling the solubility to moderately reduce the dissolution rate during development when the solubility of the compound (B) in a developing solution such as alkali is relatively high. As such a dissolution control agent, those that do not chemically change in steps such as baking of the resist film, irradiation with radiation, and development are preferable.

  Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents 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 compound (B) to be used, but is preferably 0 to 50% by weight, more preferably 0.1 based on the total weight of the solid component. -20% by weight, particularly preferably 1-10% by weight.

  The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the photoacid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. It is. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. 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 based on the total weight of the solid component, more preferably 0.1 to 20% by weight, and particularly preferably 1 to 10% by weight.

  The surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, preferred surfactants are nonionic surfactants. Nonionic surfactants have better affinity with the solvent used in the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) Each series such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) can be mentioned, but is not particularly limited.

  The blending amount of the surfactant is preferably 0 to 2% by weight based on the total weight of the solid component, more preferably 0.0001 to 1% by weight, and particularly preferably 0.001 to 0.1% by weight. It is. 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.

  In addition to the above-mentioned additives, the radiation-sensitive composition of the present invention is a resin that is insoluble in water and soluble in an alkaline aqueous solution, or is insoluble in water and soluble in an alkaline aqueous solution by the action of an acid, and developed with an alkaline aqueous solution. You may add resin which becomes possible. Examples of the resin that can be added include a phenol resin or a resin in which an acid-dissociable functional group is introduced into a phenol resin; a resin in which an acid-dissociable functional group is introduced into a novolac resin or a novolac resin; a hydrogenated novolac resin or a hydrogenated novolac resin O-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof or o-polyhydroxystyrene, m-polyhydroxystyrene, p- Resins having acid-dissociable functional groups introduced into polyhydroxystyrene and copolymers thereof; resins having acid-dissociable functional groups introduced into alkyl-substituted polyhydroxystyrene or alkyl-substituted polyhydroxystyrene; polyhydroxystyrene or polyhydroxy Styrene has acid dissociable functional groups Incorporated resin; Resin in which part of polyhydroxystyrene is o-alkylated or Resin in which part of polyhydroxystyrene is o-alkylated; Resin having functional group capable of acid dissociation; Styrene-hydroxystyrene Resin having an acid-dissociable functional group introduced into a copolymer or a styrene-hydroxystyrene copolymer; an acid-dissociative functional group into an α-methylstyrene-hydroxystyrene copolymer or an α-methylstyrene-hydroxystyrene copolymer A resin in which an acid-dissociable functional group is introduced into a polyalkyl methacrylate resin or polyalkyl methacrylate, a polyolefin, a polyester, a polyamide, a polyurea, and a polyurethane. However, since the line edge roughness increases with the amount of resin added, a better pattern profile tends to be obtained when it is not added as much as possible.

  The radiation sensitive compound of this invention is obtained by stirring and mixing a compound (B), a solvent, an acid generator, and another additive. There is no particular limitation on the stirring, mixing method and order of addition, and it can be easily produced based on the ordinary knowledge of those skilled in the art.

  In order to form a resist pattern using the radiation-sensitive composition of the present invention, first, a radiation-sensitive composition is spin-coated on a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum. A resist film is formed by coating by a coating means such as spread coating or roll coating.

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

  The thickness of the resist film is not particularly limited, and is preferably 0.01 to 10 μm, more preferably 0.05 to 1 μm, and particularly preferably about 0.08 to 0.5 μm.

  If necessary, a resist protective film may be formed to prevent intrusion of amine or the like floating in the air after the resist film is formed. By forming a resist protective film, the acid generated by 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 decreases. This can be suppressed. The material for the resist protective film is preferably a water-soluble and acidic polymer. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  Next, the resist film is exposed to a desired pattern by radiation such as ultraviolet rays, extreme ultraviolet rays (EUV), and electron beams. In the exposed compound (B), the acid-dissociable functional group is cleaved to become a phenolic hydroxyl group, which changes to a compound soluble in an alkali developer. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. 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 in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used.

  In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

  After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

  Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

  The remaining resist pattern can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include the PGMEA, PGME, and EL, and examples of the strong alkaline aqueous solution include a 1 to 20% by mass sodium hydroxide aqueous solution and a 1 to 20% by mass potassium hydroxide aqueous solution. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  The wiring board obtained using the radiation-sensitive composition of the present invention can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not particularly limited to these examples.
The evaluation method of a compound and a radiation sensitive composition and the evaluation method of a resist pattern are as follows.

I. Evaluation of compound and radiation-sensitive composition (1) Safety solvent solubility test of compound A solubility test of a compound in a safety solvent was conducted at 23 ° C. The case where 5 wt% or more was dissolved in PGMEA or EL was designated as A, the case where 0.1 wt% or more and less than 5 wt% was dissolved was designated as B, and the case where 0.1 wt% or more was not dissolved was designated as C.

(2) Film-formability test of radiation-sensitive composition A 10% by weight PGMEA solution of the compound was spin-coated on a silicon wafer with a spin coater to form a resist film having a thickness of about 0.2 μm, and then a hot plate at 110 ° C. After heating for 3 minutes above, the state of the resist film was observed. The case where whitening or irregularities occurred on the surface was designated as C, the case where partial whitening or irregularities occurred on the surface was designated as B, and the case where surface properties were good was designated as A.

(3) Dissolution inhibition test in alkaline developer The resist film obtained in the above test (2) is immersed in a developer (TMAH 2.38% aqueous solution) for 3 minutes, and when the film state does not change visually, A, The case where film surface roughening or film thickness reduction was recognized was defined as C.

(4) Silicon substrate adhesion A when the resist film formed in the test (2) did not peel from the silicon wafer, and B when the surface treatment agent (silane coupling agent) was not used. When it peeled even if it used the surface treating agent, it evaluated as C.

(5) Alkali developability The developability of the polyphenol compound (A) corresponding to each compound before introduction of an acid-dissociable functional group with respect to an alkali developer was tested.
A 10 wt% PGMEA solution of the polyphenol compound (A) is spin-coated with a spin coater to form a resist film having a film thickness of about 0.2 μm, and then heated on a hot plate at 110 ° C. for 3 minutes, and then a 2.38% aqueous solution of TMAH. Soaked for 10 seconds. A was the case where the resist film was completely dissolved and disappeared, and C was the case where the resist film remained even a little.

II Evaluation of Resist Pattern (1) Preparation of Resist Film The components shown in Table 5 below were blended and filtered through a 0.2 μm Teflon (registered trademark) filter to prepare a radiation sensitive composition. Each radiation-sensitive composition was applied onto a silicon wafer using a spin coater and dried on a hot plate at 110 ° C. for 60 seconds to obtain a resist film having a thickness of about 0.2 μm.

(2) Preparation of resist pattern This resist film was irradiated using an electron beam drawing apparatus (acceleration voltage 50 KeV). After irradiation, each was heated for 60 seconds at the post-exposure heating temperature (PEB) shown in Table 6, immersed in a 2.38% TMAH aqueous solution for 30 seconds, rinsed with distilled water for 30 seconds and dried. The obtained single wire or line and space was observed with a scanning electron microscope.

(3) Evaluation of sensitivity and resolution The resolution was defined as the limit resolution on a single line or line and space, and the minimum dose that could be resolved with the limit resolution was defined as the sensitivity.

Example 1: Synthesis of compound 5-1

(1) Synthesis of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane o-cresol 43.2 g (0.4 mol) (reagent manufactured by Kanto Chemical Co., Inc.) and β-acetonaphthone 17.1 g (0.1 mol) (reagent manufactured by Kanto Chemical Co., Inc.) was mixed and dissolved by heating to about 30 ° C., then 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid, toluene 10 ml was added and reacted with stirring. After confirming that the conversion rate was 100% by gas chromatography, 100 ml of toluene was added, cooled and the precipitated solid was filtered under reduced pressure, then stirred and washed with hot water at 60 ° C., and purified by silica gel column chromatography. 24 g of compound was obtained.

(2) Synthesis of Compound 5-1 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane synthesized as described above and 5 ml of anhydrous acetone, Di-tert-butyl dicarbonate (reagent manufactured by Kanto Chemical Co., Inc.) 2.62 g (12 mmol) was added dropwise to a solution obtained by adding 1.2 mg of dimethylaminopyridine (reagent manufactured by Kanto Chemical Co., Ltd.) over 10 minutes. The mixture was stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally drying under reduced pressure was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 2: Synthesis of compound 5-2

To 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane synthesized in Example 1, 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine were added. To the solution, 1.32 g (6 mmol) of di-tert-butyl dicarbonate was added dropwise over 10 minutes and stirred at 40 ° C. for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 3: Synthesis of compound 5-3

(1) Synthesis of biscatechol compound The same procedure as in Example 1 (1) except that 43.2 g (0.4 mol) of o-cresol was replaced with 44.0 g (0.4 mol) of catechol (a reagent manufactured by Kanto Chemical). Then, 1- (2-naphthyl) -1,1-bis (3,4-dihydroxyphenyl) ethane was obtained.

(2) Synthesis of Compound 5-3 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3,4-dihydroxyphenyl) ethane synthesized as described above was added to 5 ml of anhydrous acetone, dimethylamino To a solution to which 1.2 mg of pyridine was added, 5.28 g (24 mmol) of di-tert-butyl dicarbonate was added dropwise over 10 minutes, and the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally drying under reduced pressure was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 4: Synthesis of compound 5-4

To 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane synthesized in Example 1, 5 ml of anhydrous acetone and pyridinium p-toluenesulfonate (Kanto Chemical) A solution obtained by adding 0.073 g (0.29 mmol) of a reagent manufactured by (Co.) and 0.43 g (6 mmol) of ethyl vinyl ether (a reagent manufactured by Kanto Chemical Co., Ltd.) was stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 5: Synthesis of compound 5-5

1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane synthesized in Example 1 was added to 5 ml of anhydrous acetone and 0.073 g of pyridinium p-toluenesulfonic acid. (0.29 mmol) and a solution obtained by adding 0.76 g (6 mmol) of cyclohexyl vinyl ether were stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 6: Synthesis of compound 5-6

1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane synthesized in Example 1 was added to 5 ml of anhydrous acetone and 0.073 g of pyridinium p-toluenesulfonic acid. (0.29 mmol) and dihydropyran (reagent manufactured by Kanto Chemical Co., Inc.) 0.50 g (6 mmol) were added, and the solution was stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 7: Synthesis of compound 5-7

(1) Synthesis of 1- (2-naphthyl) -1,1-bis (3-cyclohexyl-4-hydroxyphenyl) ethane In Example 1, (1), 43.2 g (0.4 mol) of o-cresol was added. The target compound was obtained in the same manner as in the above except that 53.0 g (0.3 mol) of 2-cyclohexylphenol (reagent manufactured by Honshu Chemical Industry Co., Ltd.) was used.

(2) Synthesis of Compound 5-7 To 2.52 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-cyclohexyl-4-hydroxyphenyl) ethane synthesized as described above, 5 ml of anhydrous acetone, A solution obtained by adding 0.073 g (0.29 mmol) of pyridinium p-toluenesulfonate and 0.43 g (6 mmol) of ethyl vinyl ether was stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 8: Synthesis of compound 5-8

(1) Synthesis of 1- (2-naphthyl) -1,1-bis (4-hydroxyphenyl) ethane In Example 1 (1), 43.2 g (0.4 mol) of o-cresol was added to 37.4 g of phenol. The same process was performed except having replaced with (0.4 mol) (Kanto Chemical reagent), and bisphenol acetonaphthone was obtained.

(2) Synthesis of Compound 5-8 In (2) of Example 1, 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane was 1 The target compound was obtained in the same manner as in the above except that 1.70 g (5 mmol) of-(2-naphthyl) -1,1-bis (4-hydroxyphenyl) ethane was used. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 9: Synthesis of compound 5-9

(1) Synthesis of 1- (1-naphthyl) -1,1-bis (4-hydroxyphenyl) methane In (1) of Example 1, 17.1 g (0.1 mol) of β-acetonaphthone was converted to α-naphthaldehyde. The same steps were performed except that 15.6 g (0.1 mol) (a reagent manufactured by Kanto Chemical Co., Inc.) was used, and 1- (1-naphthyl) -1,1-bis (4-hydroxyphenyl) methane was obtained. It was.

(2) Synthesis of Compound 5-9 In (2) of Example 1, 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane was converted to 1- A target compound was obtained by carrying out the same steps except that 1.63-g (5 mmol) of (1-naphthyl) -1,1-bis (4-hydroxyphenyl) methane was used. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 10: Synthesis of compound 6-1

(1) Synthesis of 1- (4′-biphenyl) -1,1-bis (4-hydroxyphenyl) methane In (1) of Example 1, 17.1 g (0.1 mol) of β-acetonaphthone was converted to 4′- It replaces with 18.2 g (0.1 mol) of biphenyl aldehyde (Mitsubishi Gas Chemical Co., Ltd.), and is the same except that 43.2 g (0.4 mol) of o-cresol is replaced with 37.4 g (0.4 mmol) of phenol. The process was performed to obtain biphenylaldehyde.

(2) Synthesis of Compound 6-1 In Example 6, 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane was converted to the above 1- ( The same process was carried out except that 1.76 g (5 mmol) of 4′-biphenyl) -1,1-bis (4-hydroxyphenyl) methane was used to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 11: Synthesis of compound 7-1

4.80 g (22 mmol) of di-tert-butyl dicarbonate and 2.4 g of triethylamine were slowly added to a solution obtained by adding 5 ml of dimethylacetamide (DMAc) to 1.91 g (5 mmol) of biscatechol fluorene (produced by Osaka Gas Chemical Co., Ltd.). The solution was added dropwise and stirred at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, white powder was obtained. Finally, vacuum drying was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 12: Synthesis of compound 7-2

Di-tert-butyl dicarbonate (3.27 g, 15 mmol) and triethylamine (2.4 g) were slowly added to a solution obtained by adding 5 ml of dimethylacetamide (DMAc) to 1.91 g (5 mmol) of biscatechol fluorene (produced by Osaka Gas Chemical Co., Ltd.). The solution was added dropwise and stirred at 60 ° C. for 7 hours. The reaction solution was separated and purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4), and the target compound was obtained after drying under reduced pressure. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 13: Synthesis of compound 7-3

(1) Synthesis of 9,9-bis (3,4,5-trihydroxyphenyl) fluorene 50.4 g (0.4 mol) of pyrogallol (reagent manufactured by Kanto Chemical Co., Inc.) and 18.0 g of 9-fluorenone (0. 1 mol) (a reagent manufactured by Kanto Chemical Co., Inc.) was mixed and heated to about 60 ° C. to dissolve, and then 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid and 10 ml of toluene were added and reacted while stirring. . After confirming that the conversion of 9-fluorenone reached 100%, 100 ml of toluene was added, and the solid precipitated was cooled and filtered under reduced pressure, then stirred and washed with hot water at 60 ° C., recrystallized, and 4. 30 g was obtained.

(2) Synthesis of Compound 7-3 9.03 g (0.25 mmol) of 9,9-bis (3,4,5-trihydroxyphenyl) fluorene synthesized as described above, 5 ml of anhydrous acetone, and dimethylaminopyridine. To the solution with 2 mg added, 0.39 g (1.8 mmol) of di-tert-butyl dicarbonate was added dropwise over 30 minutes and stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. Finally, vacuum drying was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 14: Synthesis of compound 7-4

A solution obtained by adding 5 ml of anhydrous acetone, 0.073 g (0.29 mmol) of pyridinium p-toluenesulfonate, and 0.50 g (6 mmol) of dihydropyran to 1.75 g (5 mmol) of bisphenolfluorene (produced by Osaka Gas Chemical Co., Ltd.) Stir at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 15: Synthesis of Compound 7-5

10,10-bis (4-hydroxyphenyl) -9-anthrone (manufactured by Honshu Chemical Industry Co., Ltd.) 1.89 g (5 mmol), anhydrous acetone 20 ml, pyridinium p-toluenesulfonate 0.073 g (0.29 mmol), dihydropyran The solution to which 0.50 g (6 mmol) was added was stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 16: Synthesis of compound 8-1

(1) Synthesis of 1,1-bis (4-hydroxyphenyl) acenaphthene After mixing 43.2 g (0.4 mol) of phenol and 16.8 g (0.1 mol) of acenaphthenone and heating to about 30 ° C. to dissolve Then, 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid and 10 ml of toluene were added and reacted while stirring. After confirming that the conversion rate was 100% by gas chromatography, 100 ml of toluene was added, cooled and the precipitated solid was filtered under reduced pressure, then stirred and washed with hot water at 60 ° C., and recrystallized to obtain the desired product. It was.

(2) Synthesis of Compound 8-1 1,1-bis (4-hydroxyphenyl) acenaphthene 1.69 g (5 mmol) obtained above was added to 10 ml of anhydrous acetone and 0.073 g (0.29 mmol) of pyridinium p-toluenesulfonic acid. ), And a solution obtained by adding 0.50 g (6 mmol) of dihydropyran was stirred at room temperature for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 17: Synthesis of compound 8-2

(1) Synthesis of 1,1-bis (4-hydroxyphenyl) acenaphthen-2-one In (1) of Example 16, 16.8 g (0.1 mol) of acenaphthenone was converted to acenaphthenequinone (manufactured by Kanto Chemical). The same process was performed except having replaced with 16.2 g "(0.1 mol), and 1,1-bis (4-hydroxyphenyl) acenaphthen-2-one was obtained.

(2) Synthesis of Compound 8-2 In (2) of Example 16, 1.69 g (5 mmol) of 1,1-bis (4-hydroxyphenyl) acenaphthene was converted to 1,1-bis (4-hydroxyphenyl) acenaphthene- The same compound was obtained except that the 2-one was replaced with 1.83 g (5 mmol) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 18: Synthesis of compound 8-3

(1) Synthesis of 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) acenaphthene In Example 16, (1), 43.2 g (0.4 mol) of phenol was replaced with 53.0 g (0. The same process was performed except having replaced with 3 mol) to obtain 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) acenaphthene.

(2) Synthesis of Compound 8-3 In Example 4, 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane was converted to 1,1-bis. A target compound was obtained by carrying out the same steps except that 2.51-g (5 mmol) of (3-cyclohexyl-4-hydroxyphenyl) acenaphthene was used. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 19: Synthesis of Compound 8-4

To a solution obtained by adding 1.76 g (5 mmol) of 1,1-bis (4-hydroxyphenyl) acenaphthen-2-one obtained in (1) of Example 17 to 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine. -Tert-butyl dicarbonate 2.64g (12mmol) was dripped over 10 minutes, and it stirred at 40 degreeC for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally drying under reduced pressure was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 20: Synthesis of Compound 8-5

The same process as Example 18 was carried out except that 53.0 g (0.3 mol) of 2-cyclohexylphenol was replaced with 51.0 g (0.3 mol) of 2-phenylphenol to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 21: Synthesis of compound 9-1

The same process as in Example 6 was carried out except that 43.2 g (0.4 mol) of o-cresol was replaced with 44.0 g (0.4 mol) of resorcinol to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 22: Synthesis of compound 10-1.

(1) Synthesis of 2,8-dihydroxy-5- (4-biphenyl) xanthene In (1) of Example 10, phenol 37.4 g (0.4 mmol) was replaced with resorcinol 44.0 g (0.4 mol). The same process was performed except that 2,8-dihydroxy-5- (4-biphenyl) xanthene was obtained. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

(2) Synthesis of Compound 10-1 In Example 19, 1.76 g (5 mmol) of 1,1-bis (4-hydroxyphenyl) acenaphthen-2-one was converted to 2,8-dihydroxy-5- (4-biphenyl). The same process was performed except having replaced with 1.83 g (5 mmol) of xanthene, and the target compound was obtained. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 23: Synthesis of Compound 10-2

The same process as in Example 10 was carried out except that 37.4 g (0.4 mmol) of phenol was replaced with 44.0 g (0.4 mol) of resorcinol to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 24 Synthesis of Compound 11-1

Example 1 (wherein 43.2 g (0.4 mol) of o-cresol was replaced with 44.0 g (0.4 mol) of resorcinol, 17.1 g (0.1 mol) of β-acetonaphthone was replaced with 18.0 g of 9-fluorene ( The target compound was obtained in the same manner except that the amount was changed to 0.1 mol), and the structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement.

Example 25: Synthesis of compound 11-2

In Example 22, the same process was performed except that 18.2 g (0.1 mol) of biphenylaldehyde was replaced with 18.0 g (0.1 mol) of 9-fluorenone (a reagent manufactured by Kanto Chemical Co., Inc.) to obtain the target compound. It was. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 26: Synthesis of compound 11-3

In Example 4, 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane was obtained in 2,8-dihydroxy-5 obtained in Example 24. The same compound was obtained except that 1.82 g (5 mmol) of-(9,9-fluorenyl) xanthene was used. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 27: Synthesis of Compound 12-1

The same process as in Example 26 was carried out except that 18.0 g (0.1 mol) of 9-fluorenone was replaced with 16.8 g (0.1 mol) of acenaphthenone to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 28 Synthesis of Mixture 13-1

To a solution of 1.75 g (5 mmol) of bisphenolfluorene and 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine, 1.20 g (5.5 mmol) of di-tert-butyl dicarbonate was added dropwise over 10 minutes. Stir for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the desired mixture. The introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group was 55% as confirmed by ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 29: Synthesis of Mixture 13-2

Di-tert-butyl dicarbonate (3.27 g, 15 mmol) was added dropwise to a solution of biscatecholfluorene (1.91 g, 5 mmol) and anhydrous acetone (5 ml) and dimethylaminopyridine (1.2 mg) over 10 minutes. Stir for hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the desired mixture. The introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group was 75% as confirmed by ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Example 30: Synthesis of Mixture 13-3

A solution prepared by adding 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine to 0.103 g (0.25 mmol) of 9,9-bis (3,4,5-trihydroxyphenyl) fluorene synthesized in (1) of Example 13 Di-tert-butyl dicarbonate 0.26 g (1.2 mmol) was added dropwise to the mixture over 30 minutes, and the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. Finally, vacuum drying was performed to obtain the target mixture. When confirmed by elemental analysis and ¹ H-NMR measurement, the rate of introduction of the acid-dissociable functional group into the phenolic hydroxyl group was 80%. The analysis results are shown in Tables 1 and 2.

Example 31: Synthesis of Mixture 13-4

To a solution of 1.84 g (5 mmol) of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane added with 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine, di-tert- 1.20 g (9.5 mmol) of butyl dicarbonate was added dropwise over 10 minutes, and the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the desired mixture. ^When confirmed by ¹ H-NMR measurement, the introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group was 95%. The analysis results are shown in Tables 1 and 2.

Example 32: Synthesis of Mixture 13-5

Di-tert-butyl dicarbonate (3.27 g, 19 mmol) was added dropwise to a solution of biscatecholfluorene (1.91 g, 5 mmol) and anhydrous acetone (5 ml) and dimethylaminopyridine (1.2 mg) over 10 minutes. Stir for hours. The reaction solution was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain the desired mixture. ^When confirmed by ¹ H-NMR measurement, the introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group was 95%. The analysis results are shown in Tables 1 and 2.

Comparative Example 1: Synthesis of Compound 14-1

Bisphenol A (reagent manufactured by Kanto Chemical Co., Inc.) 1.14 g (5 mmol) in a solution of 5 ml of anhydrous acetone and 1.2 mg of dimethylaminopyridine was added 2.62 g (12 mmol) of di-tert-butyl dicarbonate over 10 minutes. And then stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally drying under reduced pressure was performed to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Comparative Example 2: Synthesis of Compound 14-2

The same process as in Comparative Example 1 was carried out except that 1.14 g (5 mmol) of bisphenol A was replaced with 1.34 g (5 mmol) of bisphenol Z (reagent manufactured by Kanto Chemical Co., Inc.) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Comparative Example 3: Synthesis of Compound 14-3

In Comparative Example 1, 1.14 g (5 mmol) of bisphenol A was replaced with 1.46 g (5 mmol) of tris (4-hydroxyphenyl) methane (manufactured by Honshu Chemical Industry), and 2.62 g (12 mmol) of di-tert-butyl dicarbonate. ) Was replaced with 3.93 g (16 mmol) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Comparative Example 4: Synthesis of Compound 14-4

In Comparative Example 1, 1.14 g (5 mmol) of bisphenol A was replaced with 1.77 g (5 mmol) of tris (4-hydroxyphenyl) benzene (aldrich reagent), and 2.62 g (12 mmol) of di-tert-butyl dicarbonate. ) Was replaced with 3.93 g (16 mmol) to obtain the target compound. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Comparative Example 5
In Comparative Example 1, 1.14 g (5 mmol) of bisphenol A was replaced with 0.74 g (5 mmol) of polyhydroxystyrene weight average molecular weight 8000 (aldrich reagent) (hereinafter abbreviated as “PHS-1”), and di-tert -The target compound (henceforth "PHS-2") was obtained by performing the same process except having replaced 2.62 g (12 mmol) of butyl dicarbonate with 0.37 g (1.5 mmol). As a result of measurement by ¹ H-NMR, the introduction rate of the acid-dissociable functional group into the phenolic hydroxyl group was 30%.

Examples 33 to 64 and Comparative Examples 5 to 9: Performance of compounds and radiation-sensitive compositions The performance of the compounds and compositions obtained in Examples 1 to 32 and Comparative Examples 1 to 4 was tested. Tables 3 and 4 show the test results.

Example 65
50 mol% of compound 5-6 and 50 mol% of 1- (2-naphthyl) -1,1-bis (3-methyl-4-hydroxyphenyl) ethane (14-5) as an intermediate product thereof were mixed. A test was performed on the mixture (the ratio of the number of substituents OR ¹ to the total number of substituents OR ¹ and substituents OH was 25%). Tables 3 and 4 show the test results.

Example 66
40 mol% of compound 5-7 and 60 mol% of 1- (2-naphthyl) -1,1-bis (3-cyclohexyl-4-hydroxyphenyl) ethane (14-6) as an intermediate product thereof were mixed. A test was performed on the mixture (the ratio of the number of substituents OR ¹ to the total number of substituents OR ¹ and OH is 20%). Tables 3 and 4 show the test results.

Comparative Example 9
Compound 14-5 was tested. Tables 3 and 4 show the test results.

Examples 67 to 88 and Comparative Examples 10 to 16: Evaluation of resist pattern and dry etching resistance Using the compounds obtained in Examples 1 to 32, the components shown in Table 5 were blended and 0.2 μm Teflon (registered) A radiation sensitive composition was prepared by filtration through a filter. Resist patterns were prepared and the resolution and sensitivity were evaluated. The results are shown in Table 6. In each of the resist samples of Examples 67 to 88, a good pattern with very little edge roughness was obtained. Further, the amount of outgas generated during exposure was small.
Etching of 70 sccm, 50 W, and 20 Pa using tetrafluoromethane as an etching gas on a gallium arsenide wafer substrate with respect to a resist film having a film thickness of 100 nm obtained using the compositions of Examples 72 and 86 as the radiation sensitive composition Under the conditions, dry etching is performed with an RIE etching apparatus at an etching time of 30 seconds, 60 seconds, 90 seconds, and 120 seconds, and the film thickness is measured using a film thickness meter, and each of the approximate linear straight line slopes is measured. The etching rate of the sample was determined. As a result, the resist film obtained using the composition of Example 72: 8.8 nm / min, the resist film obtained using the composition of Example 86: 20 nm / min, and high etching resistance was confirmed. .

PAG-1: Diphenyltolylsulfonium nanofluorobutanesulfonate PAG-2: Triphenylsulfonium trifluoromethanesulfonate Q-1: Trioctylamine Q-2: Diazabicyclooctane S-1: PGMEA
S-2: EL

Claims (6)

A radiation-sensitive composition comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, wherein a) and b) below:
a) A polyphenol compound (A) obtained from a condensation reaction of an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups Having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group,
b) Molecular weight of 300-3000
Includes conditions are satisfied compound (B), Ri 50 to 99.999 wt% der based on the total weight of the compound (B) and sum the solid component of solution promoters, the compound (B) is a compound represented by the following formula (5) - (12) at least one compound selected from the compounds represented by, and the dissolution enhancer is a radiation-sensitive composition with a compound der wherein Rukoto represented by the following formula (25) .
(In the formulas (5) to (12),
Each R ¹ independently represents a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, And an acid dissociable functional group selected from the group consisting of alkoxycarbonyl groups;
R ² each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, or an aryloyloxy group. And represents a substituent selected from the group consisting of a cyano group and a nitro group;
R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group;
m0 and n0 are each an integer from 0 to 3, m1 and n1 are each an integer from 0 to 3, m2 and n2 are each an integer from 0 to 4, and 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 Satisfy the following conditions: ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, 1 ≦ n0 + n1 ≦ 3;
p0 and q0 are each an integer from 0 to 2, p1 and q1 are each an integer from 0 to 2, p2 and q2 are each an integer from 0 to 3; and 1 ≦ p0 + p1 + p2 ≦ 4, 1 ≦ q0 + q1 + q2 ≦ 4, 1 ≦ p1 + q1 ≦ 4, 1 ≦ p0 + p1 ≦ 2, 1 ≦ q0 + q1 ≦ 2 is satisfied;
p3 is an integer of 0 to 4; q3 is an integer of 0 to 3; the condition 0 ≦ p3 + q3 ≦ 7 is satisfied;
Y is a single bond or a carbonyl group; Z is a methylene group or a carbonyl group)
(In the formula ^{(25), R 2, R} 4 are as defined above, ^{R 5} represents a monovalent substituent having 10 to 18 carbon atoms having a biphenyl structure or naphthalene structure; or, ^-CR 4 R ^5- R ⁴ and R ⁵ are bonded, and -CR ⁴ R ⁵ -is a C10-18 divalent substituent having a fluorene structure, an acenaphthene structure, a 1-ketoacenaphthene structure or a benzophenone structure;
m3 and n3 are each an integer of 1 to 3;
m4 and n4 are each an integer of 0 to 4;
1 ≦ m3 + is a m4 ≦ 5,1 ≦ n3 + n4 ≦ 5. ) 2. The radiation-sensitive composition according to claim 1 , wherein the solid component further contains one or more acid generators that generate an acid upon irradiation with radiation selected from extreme ultraviolet rays, electron beams, and X-rays. Composition. The radiation-sensitive composition according to claim 1 or 2, wherein the compound (B) is a compound having an acid-dissociable functional group introduced into 10 to 95% of the total number of phenolic hydroxyl groups in the polyphenol compound (A). The radiation-sensitive composition according to any one of claims 1 to 3 , wherein the compound (B) is a compound that dissolves in propylene glycol monomethyl ether acetate or ethyl lactate at 23% by weight at 5% by weight or more. The radiation sensitive composition according to any one of claims 1 to 4, wherein a mixing ratio of the dissolution accelerator is 20 to 80% by weight based on the total weight of the solid component. The radiation sensitive composition according to any one of claims 1 to 5, wherein the compound (B) is selected from the following compound group.