WO2012032790A1

WO2012032790A1 - Composition having acid-labile dissolution inhibiting group

Info

Publication number: WO2012032790A1
Application number: PCT/JP2011/005092
Authority: WO
Inventors: 英昭塩谷; 柏村　孝; 宏寿石井; 貴紀大和田
Original assignee: 出光興産株式会社
Priority date: 2010-09-10
Filing date: 2011-09-09
Publication date: 2012-03-15
Also published as: JPWO2012032790A1

Abstract

A composition comprising a compound represented by formula (I) and a compound represented by formula (II). In the formulae, R and R' independently represent a substituted or unsubstituted linear aliphatic hydrocarbon group or the like having 1-20 carbon atoms, or any one group selected from groups represented by formulae (1)-(3); R¹ and R^1' independently represent a hydroxy group, a substituted or unsubstituted linear alkoxy group or the like having 1-20 carbon atoms, or any one group selected from groups represented by formulae (1)-(3); and R² and R^2' independently represent a group represented by R¹ _, or the like; wherein two groups in at least one combination selected from the combination of R and R', the combination of R¹ and R^1' and the combination of R² and R^2' are different from each other.

Description

Composition having acid dissociable, dissolution inhibiting group

The present invention relates to a composition, a fine processing method using the composition, a semiconductor device obtained by the processing method, and a device including the semiconductor device.

Lithography using extreme ultraviolet light (Extreme Ultra Violet, EUV) or electron beam is useful as a high-productivity, high-resolution microfabrication method in the manufacture of semiconductors, etc., and develops high-sensitivity, high-resolution photoresists for use in it. It is requested to do. It is indispensable to improve the sensitivity of the photoresist used in these lithography from the viewpoint of the productivity and resolution of the desired fine pattern.

Examples of the photoresist used in ultrafine processing with extreme ultraviolet light include chemically amplified polyhydroxystyrene-based photoresists used in ultrafine processing with a known KrF laser. It is known that this resist can be finely processed up to about 50 nm. However, with this resist, the most important line edge roughness can be achieved even if high sensitivity and low resist outgas can be achieved to a certain extent by creating a pattern of 50 nm or less, which is the greatest merit of ultra-fine processing using extreme ultraviolet light. Since it cannot be reduced, it cannot be said that the original performance of extreme ultraviolet light has been sufficiently brought out. Against this background, it has been demanded to develop a higher performance photoresist.

In order to solve this problem, the inventors of the present invention have developed a resist compound (Patent Document 1).
However, a resist composition with higher sensitivity has been demanded.

International Publication No. 2009/075307 Pamphlet

An object of the present invention is to provide a resist composition with higher performance.

According to the present invention, the following compositions and the like are provided.
1. A composition comprising a compound of formula (I) and a compound of formula (II).

[Wherein, R and R ′ are each hydrogen, a substituted or unsubstituted straight-chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, substituted or unsubstituted lactone rings having 4 to 20 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 carbon atoms, and the like It is either a group in which two or more of the groups are combined, or a group represented by the following formulas (1) to (3).
R ¹ and R ^{1 ′} are each hydrogen, hydroxyl group, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 3 to 12 carbon atoms, substituted or unsubstituted A cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 10 carbon atoms, an alkoxyalkyloxy group, a siloxy group, and these groups and a divalent group (where a divalent group is A substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, an ester bond group, a carbonate ester bond group, an ether bond group, or a combination of two or more of these groups A substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 3 An aliphatic hydrocarbon group having 12 branches, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 aromatic groups, alkoxyalkyl groups, carboxy groups, silyl groups, and these groups and divalent groups (wherein the divalent groups are substituted or unsubstituted alkylene groups, substituted or unsubstituted arylenes) A group, a substituted or unsubstituted silylene group, an ester bond group, a carbonate ester bond group, an ether bond group, or a group formed by bonding two or more of these groups), an acid dissociable, dissolution inhibiting group, Or any one of groups represented by the following formulas (1) to (3).
R ² and R ^{2 ′} are each a group represented by R ¹ .
R and R ', ^{R 1} and R ^1', and at least one of ^{R 2} and R ^{2 'are} different from each other.

(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond) Or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, nitrile group or alkyl having 1 to 10 carbon atoms It is a group.
R ³ represents hydrogen, a hydroxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted, Unsubstituted cycloaliphatic group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted An alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms, an alkoxyalkyl group, a carboxy group, a silyl group, and these groups and a divalent group (where, The divalent group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond group, a carbonate bond group, an ether bond group, or A group formed by bonding two or more of these groups) or an acid dissociable, dissolution inhibiting group.
R ⁴ and R ⁵ are each hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted Alternatively, it is an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group obtained by combining two or more of these groups.
A ¹ is a group combining two or more selected from an alkylene group, an ether bond and an alkylene group, or a group combining one or more alkylene groups and one or more ether bonds. x represents an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , Ar, and A ¹ may be the same or different. ]]
2. R is any one of the groups represented by formulas (1) to (3), or R ¹ is hydrogen, a hydroxyl group, a substituted or unsubstituted linear aliphatic carbon atom having 1 to 20 carbon atoms, respectively. Hydrogen group, substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 10 aromatic groups, substituted or unsubstituted linear alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 3 to 12 carbon atoms, substituted or unsubstituted 3 to 20 carbon atoms A cyclic alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, and a divalent group thereof (wherein the divalent group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted group) Or leave A substituted silylene group, an ester bond group, a carbonate ester bond group, an ether bond group, or a group formed by bonding two or more of these groups), or an acid dissociable, dissolution inhibiting group, 2. The composition according to ¹ , wherein one or more of R ¹ is an acid dissociable, dissolution inhibiting group.
3. R is any of the groups represented by the above formulas (1) to (3), and one of two R ¹ existing on the same aromatic ring is a hydroxyl group, and the other is OR ″. R ″ is hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having a branch having 3 to 12 carbon atoms, or a group having 3 to 20 carbon atoms. 2. The composition according to 1, which is a cyclic aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing oxygen.
4). R ′ is any one of the groups represented by the above formulas (1) to (3), and one of two R ^{1 ′} existing on the same aromatic ring is a hydroxyl group and the other is OR R '' is hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having a branch having 3 to 12 carbon atoms, or 3 to 3 carbon atoms. 4. The composition according to 3, which is a 20 cycloaliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing oxygen.
5. 5. The composition according to any one of 1 to 4, which satisfies the following formula (A).
0.01 ≦ t × 100 / (s + t) ≦ 90 (A)
(S is the total weight of the compound of formula (I) in the composition, and t is the total weight of the compound of formula (II) in the composition.)
6). 6. The composition according to any one of 1 to 5, wherein R ³ is any one of the following formulas (I) to (IV):

(In the above formulas (I) to (IV),
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
β is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group, a group formed by bonding a substituted or unsubstituted bicyclic aliphatic group to oxygen, or A linear group having 1 to 10 carbon atoms and a group selected from a quaternary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group and a substituted or unsubstituted bicyclic aliphatic group A group formed by combining an aliphatic hydrocarbon group is a group formed by bonding with oxygen.
γ is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group or a substituted or unsubstituted bicyclic aliphatic group bonded to oxygen, or A straight chain having 1 to 10 carbon atoms and a group selected from a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group and a substituted or unsubstituted bicyclic aliphatic group A group formed by combining a group of aliphatic hydrocarbon groups is a group formed by bonding with oxygen.
δ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms. )
7. 6. The composition according to any one of 1 to 5, wherein R ³ is a group selected from the following formulas (6) to (42).

(Wherein, r represents any one of the substituents represented by the above formulas (6) to (34) and (38) to (42)).
8). The compound of the formula (I) and the compound of the formula (II) each contain a plurality of R ^{3 s} , all R ³ contained in the compound of the formula (I) do not contain a polar structure at the end, and the formula 8. The composition according to any one of 1 to 7, wherein at least two of R ³ contained in the compound of (II) contain a polar structure at the end.
9. 9. The composition according to 8, wherein at least two ends of R ³ contained in the compound of the formula (II) are a lactone ring having 3 to 20 carbon atoms or a carbocyclic ketone having 3 to 20 carbon atoms.
10. R ³ contained in the formula (I) is a group selected from the following formulas (8) to (11), (16), (17) and (20) to (25),
The composition according to 9, wherein R ³ contained in the formula (II) is a group selected from the following formulas (18), (19), (26) to (29), (43) and (44): .

11. A microfabrication method using the composition according to any one of 11.1 to 10.
A semiconductor device manufactured by the microfabrication method described in 12.11.
A device comprising the semiconductor device according to 13.12.

According to the present invention, a higher-performance resist composition can be provided.

FIG. 3 is a graph showing the measurement result of ¹ H-NMR of cyclic compound P-1 of Production Example 1. FIG. 4 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound P-2 of Production Example 2. FIG. 4 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound A-1 of Production Example 3. FIG. 6 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound A-2 of Production Example 4. FIG. 6 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound A-3 in Production Example 5. FIG. 6 is a graph showing the ¹ H-NMR measurement result of cyclic compound A-6 of Production Example 8. FIG. 10 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound A-7 of Production Example 9. FIG. 3 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound P-3 of Production Example 10. FIG. 6 is a graph showing the results of ¹ H-NMR measurement of cyclic compound A-8 in Production Example 11. FIG. 6 is a diagram showing the measurement result of ¹ H-NMR of cyclic compound A-9 in Production Example 12. FIG. 6 is a graph showing the ¹ H-NMR measurement result of cyclic compound A-10 of Production Example 13. FIG. 6 is a graph showing the ¹ H-NMR measurement result of cyclic compound A-11 of Production Example 14. FIG. 6 is a graph showing the ¹ H-NMR measurement result of cyclic compound A-12 of Production Example 15. It is a photograph which shows the line drawn using the photoresist solution of Example 2, Example 15, and Comparative Example 2. FIG.

The composition of the present invention comprises a compound of formula (I) and a compound of formula (II).

In the formula, R and R ′ are each hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms. Substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, substituted or unsubstituted lactone rings having 4 to 20 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 carbon atoms, and these groups Among these groups, or groups represented by the following formulas (1) to (3).
Here, the aromatic group is a group containing a benzene ring.

“Group combining two or more types” means a group in which two or more types are single-bonded or a group in which two or more types are condensed to form a ring. For example, the following groups include an unsubstituted straight-chain aliphatic hydrocarbon group having 1 carbon atom, an unsubstituted aliphatic hydrocarbon group having 4 carbon atoms, and an unsubstituted cycloaliphatic group having 6 carbon atoms. It is a group in which a hydrocarbon group and an unsubstituted aromatic group having 10 carbon atoms are combined.

R and R ′ are each preferably a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms or a group represented by the following formulas (1) to (3), more preferably in the following formula (2). The group represented.

In the above, the substituent when substituted is a monovalent group containing a hetero element capable of bonding to carbon. Specific examples include halogen groups such as fluorine, chlorine and bromine, halogen-containing hydrocarbon groups such as trifluoromethyl group, pentafluorophenyl group and trifluoromethylphenyl group, carbonyl-containing groups such as acetyl group and benzoyl group, methoxy group And groups containing an ether bond such as ethoxy group, silicon-containing groups such as trimethylsilyl group and trimethoxysilyl group, and nitrogen-containing groups such as diethylamino group.

R ¹ and R ^{1 ′} are each hydrogen, hydroxyl group, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 3 to 12 carbon atoms, substituted or unsubstituted A cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxyl group, an alkoxyalkyloxy group, a siloxy group, a divalent group (substituted or unsubstituted alkyleneoxy group) Substituted or unsubstituted aryleneoxy group, substituted or unsubstituted silyleneoxy group, ester bond group (—CO ₂ —), carbonate bond group (—CO ₃ —), ether bond (—O—) group, or A group formed by combining two or more of these groups), a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted group. Substituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, substituted Or an unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a carboxy group, a silyl group, and these groups and a divalent group (substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, substituted Or an unsubstituted silylene group, an ester bond group, a carbonate ester bond group, an ether bond group, or a group formed by bonding two or more of these groups), an acid dissociable, dissolution inhibiting group, or the following formula (1 ) To (3).

Substituted or unsubstituted alkyleneoxy group, substituted or unsubstituted aryleneoxy group, substituted or unsubstituted silyleneoxy group, ester bond group (—CO ₂ —), carbonate bond group (—CO ₃ —), ether bond The (—O—) group or a divalent group formed by bonding two or more of these groups is preferably a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or An unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or an ester bond (—CO ₂ —), a carbonate ester bond (—CO ₃ —) or an ether bond (—O—) of these groups Is a group formed by bonding.

A substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond group, a carbonate bond group, an ether bond group, or a group formed by bonding two or more of these groups. The divalent group is preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group formed by bonding two or more of these groups, or these groups 1 This is a group combining at least one selected from an ester bond, a carbonate ester bond and an ether bond.

R ¹ and R ^{1 ′} are each preferably a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 4 carbon atoms, or a group represented by the following formulas (1) to (3). It is.
Preferably, at least two of the eight R ¹ included in the formula (I) are hydroxyl groups, and at least two of the eight R ^{1 ′} included in the formula (II) are hydroxyl groups.
Preferably, at least four of the eight R ¹ included in the formula (I) are hydroxyl groups, and at least four of the eight R ^{1 ′} included in the formula (II) are hydroxyl groups.
Preferably, among bonded to two and the R ¹ on each benzene ring, at least one of R ¹ is a hydroxyl group, and among bond to have two R ^{1 'to} each benzene ring, at least one of R ^{1 '} Is a hydroxyl group.

More preferably, one R ¹ and R ^{1 ′} of the benzene ring is a hydroxyl group, and the other R ¹ and R ^{1 ′} is a linear or branched alkoxy group having 1 to 4 carbon atoms. That is, of the two R ¹ bonded to each benzene ring, at least one R ¹ is a hydroxyl group and the other R ¹ is a linear or branched alkoxy group having 1 to 4 carbon atoms, and each Of the two R ^{1 ′} bonded to the benzene ring, at least one R ^{1 ′} is a hydroxyl group and the other R ^{1 ′} is a linear or branched alkoxy group having 1 to 4 carbon atoms.

R ² and R ^{2 ′} are each a group represented by R ¹ . R ² and R ^{2 ′} are preferably hydrogen.

R and R ', ^{R 1} and R ^1', and at least one of ^{R 2} and R ^{2 'are} different from each other. Preferably R and R ′ are different.

In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond. Or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms. It is. Here, the “group in which two or more substituents are combined” means a group in which two or more substituents are single-bonded.
Ar is preferably a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and more preferably a phenylene group.

R ³ represents hydrogen, a hydroxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted, Unsubstituted cycloaliphatic group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted A branched C3-C12 alkoxy group, a substituted or unsubstituted C3-C20 cyclic alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, a divalent group (substituted or unsubstituted). substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond group (-COO-), carbonate bond group _(-CO 3 -), ether formation Group (-O-), or these groups more bonds to become group) bonded group, or an acid dissociable, dissolution inhibiting group.

Here, the cyclic aliphatic group includes a cyclic ether and a lactone ring in addition to the cyclic aliphatic hydrocarbon group.

R ³ is preferably a substituted or unsubstituted cyclic aliphatic group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an unsubstituted alkylene group, an ester bond, and an ether bond. A group having a combination of one or more selected from the above, or an acid dissociable, dissolution inhibiting group.

R ⁴ and R ⁵ are each hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted Alternatively, they are an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group formed by combining two or more of these groups. R ⁴ and R ⁵ are preferably hydrogen or an alkyl group.

A ¹ is a group in which two or more selected from an alkylene group, an ether bond and an alkylene group are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined. A ¹ is preferably a single bond or an oxymethylene group (—O—CH ₂ —), and more preferably a single bond.

X is 1 to 5, preferably 1. y is 0 to 3, preferably 0 or 1. z is 0 to 4, preferably 0 or 1. Preferably x = 1, y = 1 and z = 0, or x = 1, y = 0 and z = 0.

A plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , Ar, and A ¹ may be the same or different.

In the compound of the formula (I), preferably R is any one of the groups of the above formulas (1) to (3), or R ¹ is any group represented by the above R ³ and a plurality of R ¹ or more of 1 is an acid dissociable, dissolution inhibiting group.

In the compound of formula (I), preferably R is any one of the groups represented by the above formulas (1) to (3), and two R ¹ existing on the same aromatic ring, One is a hydroxyl group and the other is a group represented by OR ″, and R ″ has hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a branch having 3 to 12 carbon atoms. An aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing oxygen.

In this case, more preferably, in the compound of the formula (II), R ′ is any one of the groups represented by the above formulas (1) to (3) and two Rs existing on the same aromatic ring. ^{1 ′} , one is a hydroxyl group and the other is a group represented by OR ″, R ″ is hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, or 3 to 12 carbon atoms. A branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing oxygen.

In the compound of the formula (I), at least two of the plurality of R ¹ are hydroxyl groups, and at least one of the plurality of R and the plurality of R ¹ is any one of the groups of the above formulas (1) to (3). In the compound of formula (II), at least two of the plurality of R ^{1 ′} are hydroxyl groups, and at least two of the plurality of R ′ and the plurality of R ^{1 ′} are represented by the above formulas (1) to (3 In the case of any of the groups of the formula (I), the plurality of R ³ contained in the compound of the formula (I) all do not contain a polar structure at the end, and the plurality of R ³ contained in the compound of the formula (II) At least two of R ³ preferably contain a polar structure at the end.
More preferably, in the above case, the plurality of R ³ contained in the compound of the formula (I) all do not contain a polar structure at the end, and the plurality of R ³ contained in the compound of the formula (II) are All preferably contain polar structures at the ends.

Here, “having a polar structure at the end” means that R ³ is “a hydroxyl group, a substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms containing a polar structure, a substituent containing a polar structure” An aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted cyclic aliphatic group having 3 to 20 carbon atoms containing a polar structure, and a substituted aromatic group having 6 to 10 carbon atoms containing a polar structure A substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms, Alkoxyalkyl group, carboxy group, and these groups and divalent groups (substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, substituted or unsubstituted silylene group, ester bond group, carbonate bond group , An ether bond group, or a group formed by bonding two or more of these groups). Here, “containing a polar structure” means containing an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). Examples thereof include a carbonyl group, an ether bond, an ester bond, an amino group, an amide group, and a halogen group.

By setting it as the above, there exists the following effect, when this application composition is used as a resist composition.
-By making all of R ³ (of the compound of formula (I)) "not containing a polar structure at the end", dissolution of the non-irradiated region is prevented and deterioration of the roughness value is prevented.
-By making at least two of R ³ (of the compound of formula (II)) "contain polar structures at the ends", R ³ of the compound of formula (II) and formula (I hydroxyl group of a compound of) (R ¹⁾ is hydrogen bonded, improves film strength, results also the value of the roughness (LWR) as drops (= development line is clean).

More preferably, among R ³ constituting R ′, the atom located most outside and the atoms constituting the polar structure (oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom) , Bromine atom, iodine atom)) and the most distant atom is 6 cm or less.

More preferably, the terminal of R ³ constitutes a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms (such as a carbocyclic ketone) substituted with a carbonyl group (the leftmost terminal in the above figure) or its ring. This is a group (lactone ring or the like) in which a part of carbon atoms to be replaced with oxygen atoms (the rightmost terminal in the above figure).

R ³ is preferably any one of the following formulas (I) to (IV).

In the above formulas (I) to (IV), α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted aliphatic group having 3 to 10 carbon atoms. It is a hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
α is preferably a substituted or unsubstituted straight-chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably methylene.

β is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group, a group formed by bonding a substituted or unsubstituted bicyclic aliphatic group to oxygen, or these A group formed by combining oxygen and a straight-chain aliphatic hydrocarbon group having 1 to 10 carbon atoms is a group formed by bonding with oxygen.
When β is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted monocyclic aliphatic group, preferably a tertiary carbon contained in these groups is bonded to an oxygen atom. When β is a group containing a benzene ring, the benzylic carbon is preferably bonded to an oxygen atom.

γ is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group or a substituted or unsubstituted bicyclic aliphatic group bonded to oxygen, or A group formed by combining a group selected from these and a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms is a group formed by bonding with oxygen.
γ is preferably a group in which a tertiary aliphatic structure, a monocyclic aliphatic structure or a polycyclic aliphatic structure is bonded to oxygen.

δ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.

In the above formulas (I) to (IV), the aliphatic hydrocarbon group (α) is preferably alkylene.
α and δ are preferably linear or branched aliphatic hydrocarbon groups. The α-δ linear or branched aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms, and most preferably a methylene group.

Examples of β, γ tertiary aliphatic groups include t-butyl, t-amyl and the like. The aromatic group is a group containing a benzene ring (the benzene ring may be condensed with cycloalkyl or cyclic ether), and examples thereof include phenyl, naphthyl, tetrahydronaphthyl, indanyl, chromanyl and the like. Examples of monocyclic aliphatic groups include cyclopentyl and cyclohexyl. Examples of the bicyclic aliphatic group include norbornyl, adamantyl, biadamantyl, diamantyl and the like. In addition, the monocyclic or polycyclic aliphatic group includes cyclic ethers, lactones of oxyacids such as groups (28), (29), (43), and (44) described later.

The substituents for β and γ are preferably alkyl, alkoxy, carboxy, and carbonyl. When the substituent is carbonyl, it is included in the ring, for example, as described later (18), (19), (26), (27) and the like.
The number of carbon atoms of the substituent alkyl, alkylene or alkoxy is preferably 1 to 4.

Although not limited to the following, specific examples of R ³ include groups represented by the following formulas (6) to (42).

(Wherein, r represents any one of the substituents represented by the above formulas (6) to (34) and (38) to (42)).
Preferred structures for R ³ are (8), (10), (19), (20), (28), and (43).

The cyclic compound used in the present invention can be obtained by, for example, a calix by a condensation cyclization reaction between an aldehyde compound having a corresponding structure and an aromatic compound having both a solubility adjusting group and a hydroxyl group in the presence of an acid catalyst by a known method. A resorcinalene derivative (precursor) is synthesized, and a compound corresponding to a group such as R ³ is introduced into the precursor by an esterification reaction, an etherification reaction, an acetalization reaction, or the like. Specific examples will be described in the embodiments described later.

The composition of the present invention is preferably a photoresist composition comprising a compound of formula (I) and a compound of formula (II) as a photoresist substrate, and the two photoresist substrates are mixed as described above. As a result, the heat resistance, sensitivity, and resolution of the photoresist composition can be improved.

In the compound of the formula (I) and the compound of the formula (II), preferably, R and R ′ are each a group represented by the formula (2), R ² and R ^{2 ′} are hydrogen, and the same aromatic ring Of the two R ¹ and R ^{1 ′} present above, one is a hydroxyl group and the other is the same linear or branched alkoxy group having 1 to 4 carbon atoms. R and R ′ are more preferably groups of formula (2) and x = 1, y = 1 and z = 0, respectively, and the compound of formula (I) and the compound of formula (II) are different in R ³ .

Further, at this time, all of the plurality of R ³ contained in the compound of the formula (I) do not contain a polar structure at the end, and at least two of the plurality of R ³ contained in the compound of the formula (II) are terminal. The part preferably contains a polar structure. More preferably, the plurality of R ³ contained in the compound of the formula (I) do not contain any polar structure at the end, and the plurality of R ³ contained in the compound of the formula (II) all contain the polar structure at the end. It is preferable to contain. Here, “having a polar structure at the end” is as described above.

The composition of the present invention preferably satisfies the following formula (A), more preferably the following formula (B), still more preferably the following formula (C), and most preferably the following formula (D).
0.01 ≦ t × 100 / (s + t) ≦ 90 (A)
0.05 ≦ t × 100 / (s + t) ≦ 70 (B)
0.1 ≦ t × 100 / (s + t) ≦ 50 (C)
1 ≦ t × 100 / (s + t) ≦ 40 (D)
s is the total weight of the compound of formula (I) in the composition, and t is the total weight of the compound of formula (II) in the composition.

The total content of the compound of the formula (I) and the compound of the formula (II) in the composition of the present invention is preferably 50 to 99.9% by weight in the total composition excluding the solvent, more preferably 75 to 95% by weight.

Examples of the solvent used in the composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycol monoalkyls such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Ethers; lactic acid such as methyl lactate and ethyl lactate (EL) Stealth; Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Other esters such as ethyl 3-ethoxypropionate; 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 And lactones such as γ-butyrolactone are not particularly limited. These solvents can be used alone or in combination of two or more.

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

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

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

Among these photoacid generators, a compound that generates an organic sulfonic acid by the action of actinic rays or radiation is particularly preferable.

The blending amount of the PAG is 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight in the total composition excluding the solvent.

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

Examples of such acid diffusion control agents include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Isopropano Alkyl alcohol amines such as amine, di-n-octanolamine, tri-n-octanolamine; 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5 Electron beam-decomposable basic compounds such as nitrogen-containing basic compounds such as cyclic amines such as nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, basic sulfonium compounds and basic iodonium compounds Is mentioned. The acid diffusion controller can be used alone or in combination of two or more.

The blending amount of the quencher is 0 to 40% by weight, preferably 0.01 to 15% by weight, based on the total composition excluding the solvent.
In the present invention, if desired, further miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving coating properties, dissolution control agents, sensitizers, plasticizers. Stabilizers, colorants, antihalation agents, dyes, pigments, and the like can be appropriately added and contained.

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

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

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

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

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

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

When a cyclic compound having an acid dissociable, dissolution inhibiting group is used as a photoresist base material, the resist film is exposed to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, thereby generating an acid. When the dissociable dissolution inhibiting group is eliminated or the structure is changed, the dissociable dissolution inhibiting group is dissolved in the alkaline developer. On the other hand, it is preferable that the unexposed portion of the pattern is not dissolved in the alkaline developer. That is, the acid dissociable, dissolution inhibiting group is an alkali developer that undergoes elimination or changes in structure by reacting with an acid (proton) generated from the photoacid generator within the resist film by radiation such as KrF excimer laser. It is a substituent having a function of becoming a substituent that contributes to dissolution in the aqueous solution.

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

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

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

It is also possible to form a wiring board by a method in which a resist pattern is formed using the composition of the present invention, a metal is vacuum-deposited, and then the resist pattern is eluted with a solution, that is, a lift-off method.

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

Production Example 1 (Cyclic Compound P-1)

Under a nitrogen stream, in a 200 ml round bottom flask, 50.0 g of 3-methoxyphenol (402.8 mmol, Tokyo Kasei), 60.5 g of 4-formylbenzoic acid (402.8 mmol, Tokyo Kasei), and dehydration Dichloromethane (Kanto Chemical) (500 ml) was added and immersed in an ice-water bath and cooled to 5 ° C. or lower. To this mixture, 60.8 ml of boron trifluoride diethyl ether adduct (483.6 mmol, Hiroshima Wako) was added dropwise so that the internal temperature did not exceed 15 ° C., then the temperature was raised to room temperature and 8 hours. Stir. The reaction solution was cooled in an ice water bath, quenched slowly by dropwise addition of water, and the precipitated solid was filtered off. The precipitate separated by filtration was washed with water until neutral, then dissolved in N-methyl-2-pyrrolidone (Hiroshima Wako), reprecipitated with ethyl acetate, and the precipitated solid was separated by filtration to obtain a cyclic compound ( P-1) (94.4 g, 91%) was obtained.
The structure of the cyclic compound (P-1) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 2 (Cyclic Compound P-2)

A 1-liter flask equipped with a dropping funnel was charged with resorcinol 100 g (0.91 mol, Hiroshima Wako) and benzaldehyde 96.4 g (0.91 mmol, Hiroshima Wako), followed by nitrogen substitution, and then 2-propanol 490 Milliliter was added and stirred with a mechanical stirrer to obtain a uniform solution.

Next, after the flask was cooled to 5 ° C. in an ice bath, a 2-propanol solution of concentrated hydrochloric acid (concentrated hydrochloric acid / 2-propanol = 40 ml / 40 ml) was stirred and the internal temperature did not exceed 15 ° C. The solution was slowly dropped through a dropping funnel. After completion of the dropping, the reactor was removed from the ice bath, stirred at room temperature for 40 minutes, and then heated and stirred in an oil bath heated to 65 ° C. for 2 hours. After the reaction, it was cooled to room temperature.

950 ml of ion-exchanged water was added to the reaction solution and stirred for 30 minutes, and then the crude product solid was filtered off. The solid was washed with ion-exchanged water until the filtrate became neutral and dried in vacuo at 80 ° C. for 8 hours to obtain a crude product solid (144.9 g, yield 81%).

A mixture of this crude product solid (144.9 g) and N, N-dimethylformamide (2.0 liters) was heated to 65 ° C. to make a homogeneous solution, allowed to stand still for 12 hours, and the precipitated solid was filtered off. . The precipitated solid was washed with N, N-dimethylformamide (30 ml) cooled in an ice bath and then washed with water. The washed precipitated solid was collected by filtration and vacuum dried at 80 ° C. for 8 hours to recover a recrystallized product. The obtained compound was confirmed to be a cyclic compound (P-2) by ¹ H-NMR (FIG. 2) (76.3 g, 53% as a recrystallization recovery rate, 42% yield based on charge).

Production Example 3 (Cyclic Compound A-1)

To a 200 ml two-necked flask, the cyclic compound (P-1) (1.00 g, 1.00 mmol) prepared in Production Example 1 was added to form a nitrogen atmosphere, and then anhydrous N-methyl-2-pyrrolidone ( 40 ml, Hiroshima Wako) was further added and stirred at room temperature. Ethyl adamantyl bromoacetate (1 ml) diluted with triethylamine (0.7 ml, 5.00 mmol, Aldrich) and anhydrous N-methyl-2-pyrrolidone (1 ml) (1 .50 g, 5.00 mmol), and 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol, Hiroshima Wako) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. Ion exchange water and a small amount of salt were added to the solution obtained by concentrating the obtained organic layer, and then the precipitate was filtered off to obtain a cyclic compound (A-1) (yield 93%).

The structure of the cyclic compound (1) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG. The target product had four protecting groups, and the purity of the target product was 93% in liquid chromatography (area% when measuring wavelength 280 nm).

Production Example 4 (Cyclic Compound A-2)

To a 200 ml two-necked flask, the cyclic compound (P-1) (1.00 g, 1.00 mmol) prepared in Production Example 1 was added to form a nitrogen atmosphere, and then anhydrous N-methyl-2-pyrrolidone ( 40 ml) and stirred at room temperature, methyl adamantyl bromoacetate (1.43 g, 5.50 ml) diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml). 00 mmol) and 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. Ion exchange water and a small amount of salt were added to the solution obtained by concentrating the obtained organic layer, and then the precipitate was filtered off to obtain a cyclic compound (A-2) (yield 94%).

The structure of the cyclic compound (A-2) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG. The target product had four protecting groups, and the purity of the target product was 93% in liquid chromatography (area% when measuring wavelength 280 nm).

Production Example 5 (Cyclic Compound A-3)

In a three-necked flask (capacity: 1 liter) sufficiently dried and substituted with nitrogen gas, the cyclic compound (P-1) (10.0 g, 10 mmol) prepared in Production Example 1 and dimethylformamide (344 ml) were sealed. It was dissolved by heating to 40 ° C. The mixture was allowed to cool to room temperature, cooled to 0 ° C., triethylamine (10.4 g, 103 mmol) was added and stirred for 10 minutes, and adamantyloxymethylene chloride (10.9 g, 54 mmol) was added. After warming to room temperature and stirring for 21 hours, the reaction was stopped by adding a saturated ammonium chloride solution. Subsequently, the reaction solution was extracted with ethyl acetate and washed with pure water and saturated brine. The obtained solution was concentrated and reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain a cyclic compound (A-3) (10.5 g, yield 62%).

The structure of the cyclic compound (A-3) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG. The target product had four protecting groups, and the purity of the target product was 94% in liquid chromatography (area% when measuring wavelength 280 nm).

Production Example 6 (Cyclic Compound A-4)

A cyclic compound (A-4) was obtained in the same manner as in Production Example 3 except that 6-methoxyindenyl bromoacetate was used instead of ethyl adamantyl bromoacetate (yield: 81%).

The structure of the cyclic compound (A-4) was confirmed by ¹ H-NMR. The results are shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent weight DMSO: ppm): 1.925-2.033 (4H, m), 2.433-2.494 (4H, m), 2.680-2. 733 (4H, m), 2.830-2.905 (4H, m), 3.464-3.3.586 (12H, m), 3.632 (12H, d), 4.845 (8H, s), 5.204 (2H, t), 5.640 (4H, s), 6.126 (4H, s), 6.216 (2H, t), 6.326 (2H, s), 6. 510 (2H, s), 6.658-6.724 (8H, m), 7.849 (8H, s), 7.156 (4H, s), 7.478-7.569 (8H, m) , 9.032 (2H, s), 9.185 (2H, s)
The target product had four protecting groups, and the purity of the target product was 93% in liquid chromatography (area% when measuring wavelength 280 nm).

Production Example 7 (Cyclic Compound A-5)

A cyclic compound (A-5) was obtained in the same manner as in Production Example 3 except that 5-acetoxyindenyl bromoacetate was used instead of ethyl adamantyl bromoacetate (yield: 85%).

The target product had four protecting groups, and the purity of the target product was 93% in liquid chromatography (area% at wavelength 280 nm measurement).
¹ H-NMR (internal standard tetramethylsilane: solvent (heavy DMSO: ppm): 1.976-2.106 (4H, m), 2.268 (12H, s), 2.434-2.520 (4H M), 2.800-2.838 (4H, m), 2.934-2.992 (4H, m), 3.479-3.620 (12H, m), 4.853 (8H, s) ), 5.231 (2H, t), 5.658 (4H, s), 6.175 (4H, s), 6.237 (2H, t), 6.341 (2H, s), 6.528 (2H, s), 6.680-6.744 (8H, m), 6.944 (4H, d), 7.041 (4H, s), 7.369 (4H, d), 7.497- 7.593 (8H, m), 9.019 (2H, s)

Production Example 8 (Cyclic Compound A-6)

In a 100 ml flask, a cyclic compound of formula (P-2) (2.0 g, 2.5 mmol), NMP (23 ml), sodium carbonate (3.0 g, 28.2 mmol) prepared in the raw material synthesis 2 was added. ) Was enclosed and replaced with nitrogen.
Next, methyl adamantyl bromoacetate (6.6 g, 23.2 mmol) was added, and the mixture was heated for 24 hours with stirring in an oil bath at 65 ° C. under a nitrogen atmosphere. The reaction solution was allowed to cool, and ethyl acetate was added to the filtrate obtained by filtration to obtain a homogeneous solution, which was then washed with a 0.5 M acetic acid aqueous solution in a separatory funnel. Further, the ethyl acetate solution was washed with ion exchange water until the aqueous layer became neutral, and the ethyl acetate solution was treated with anhydrous magnesium sulfate to remove moisture. After filtration, the filtrate was concentrated with a rotary evaporator under reduced pressure, and the concentrate was poured into hexane to obtain a solid. The solid was filtered off and dried under vacuum at 50 ° C. for 8 hours to obtain a cyclic compound represented by the cyclic compound (A-6).

^The structure was confirmed by ¹ H-NMR (FIG. 6), the substitution isomer contained in LC / MS was identified, and the average introduction rate of acid dissociable, dissolution inhibiting groups was calculated by LC (average introduction) Rate 64%, 1.5 g). In liquid chromatography, the purity of the target product was 93% (area% when measuring wavelength 280 nm).

Production Example 9 (Cyclic Compound A-7)

Synthesis was performed in the same manner as in Production Example 5 except that 5-oxoadamantyloxymethylene chloride was used instead of adamantyloxymethylene chloride (yield 85.2%). The target product had four protecting groups, the structure was confirmed by ¹ H-NMR (FIG. 7), and the purity of the target product was 94% by liquid chromatography (at the wavelength of 280 nm measurement). area%).

Production Example 10 (Cyclic Compound P-3)

In Production Example 1, instead of 50.0 g (402.8 mmol) of 3-methoxyphenol and 60.5 g (402.8 mmol) of 4-formylbenzoic acid, 10 g (72.38 mmol) of 3-ethoxyphenol, 4- A cyclic compound (P-3) was obtained in the same manner as described above except that 10.86 g (72.38 mmol) of formylbenzoic acid was used (yield 18.0 g, yield 92%). The structure of the cyclic compound (P-3) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 11 (Cyclic Compound A-8)

The same operation as in Production Example 3 was carried out except that 10 g (9.250 mmol) of the cyclic compound (P-3) was used instead of the cyclic compound (P-1) to obtain the cyclic compound (A-8). (Yield 18 g, yield 99%). The structure of the cyclic compound (A-8) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 12 (Cyclic Compound A-9)

The same operation as in Production Example 4 was carried out except that 10 g (9.250 mmol) of the cyclic compound (P-3) was used instead of the cyclic compound (P-1) to obtain the cyclic compound (A-9). (Yield 16 g, yield 90.7%). The structure of the cyclic compound (A-9) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 13 (Cyclic Compound A-10)

The same operation as in Production Example 5 was carried out except that 10 g (9.250 mmol) of the cyclic compound (P-3) was used instead of the cyclic compound (P-1) to obtain the cyclic compound (A-10). (Yield 16 g, yield 99%). The structure of the cyclic compound (A-10) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 14 (Cyclic Compound A-11)

A cyclic compound (A-11) was obtained in the same manner as in Production Example 5 except that norbornyllactone oxymethylene chloride (10.9 g, 54 mmol) was used instead of adamantyloxymethylene chloride (yield). 15.8 g, yield 88.1%). The target product had four protecting groups, and the structure was confirmed by ¹ H-NMR. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 15 (Cyclic Compound A-12)

The same procedure as in Production Example 5 was performed, except that 2-chloromethoxy-4-oxa-5-homoadamantan-5-one (12.4 g, 54 mmol) was used instead of adamantyloxymethylene chloride. Compound (A-12) was obtained (yield: 85.2%). The target product had four protecting groups, and the structure was confirmed by ¹ H-NMR. The measurement result of ¹ H-NMR is shown in FIG.

Example 1
The above compounds were mixed and dissolved in the compositions and blending amounts shown in Table 1 to prepare a photoresist composition. In Table 1, compounds (I) and (II) indicate the type of compound in the upper part and the blending amount (parts by weight) in the lower part.

Triphenylsulfonium nonafluorobutanesulfonate (manufactured by ALDRICH) as PAG, 1,4-diazabicyclo [2.2.2] octane (manufactured by Junsei Chemical Co., Ltd.) as quencher, propylene glycol monomethyl ether (Hiroshima Wako Co., Ltd.) as solvent 1) and propylene glycol monomethyl ether acetate (manufactured by Keiyo Chemie Co., Ltd.) 1: 1 were used in a weight ratio shown in Table 1, respectively.

Evaluation Example 1 (Resolution / Sensitivity)
The photoresist solutions of all Examples and Comparative Examples were each spin-coated on a silicon wafer subjected to hexamethyldisilazane treatment (OAP manufactured by Tokyo Ohka Kogyo Co., Ltd.) and heated at 130 ° C. for 90 seconds to form a thin film.
Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), baked at 100 ° C. for 60 seconds, and then a 2.38 wt% tetrabutylammonium hydroxide aqueous solution (Tokyo, Japan). The film was developed with NMD-3) manufactured by Okaka Co., Ltd. for 60 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream.
Table 2 shows the results of resolution (half pitch) and sensitivity (necessary electron beam dose) when a line / space pattern having a size of 1/1 was obtained from the observation results obtained with a scanning electron microscope.

Examples using the composition of the present invention have higher sensitivity and fine resolution than the comparative examples.

Example 2
In the same manner as in Example 1, the above compounds were mixed and dissolved in the compositions and blending amounts shown in Table 3 to prepare a photoresist composition. In Table 3, compounds (I) and (II) indicate the type of compound in the upper part and the blending amount (parts by weight) in the lower part.

Evaluation example 2 (resolution / sensitivity)
Evaluation was performed in the same manner as in Evaluation Example 1 except that the heating temperature after spin coating the photoresist solution on the silicon wafer was 110 ° C. The results are shown in Table 4.

Evaluation Example 3 (Line Edge Roughness)
A photograph of a line drawn using the photoresist solutions of Examples 2, 15 and Comparative Example 2 obtained in Evaluation Examples 1 and 2 is shown in FIG. LER (LER is a 30 nm line & space pattern manufactured by the method of Evaluation Examples 1 and 2 using a scanning electron microscope (SEM) S-4800 manufactured by Hitachi High-Technology Corporation, SEM photograph. As for image data obtained as above, the fluctuation of the edge of the resist pattern (roughness) is measured at 10 nm intervals by taking 10 lines of 1.5 μm in the lateral direction of the line pattern using SuMMIT, an image analysis software made by EUV Technology. 3σ (where σ is a standard deviation) is calculated from (1), the smaller the value, the closer the resist pattern line is to a straight line. As in Example 15, the composition in which the outermost substituent group is nonpolar (I) and the outermost substituent group (II) is used in combination has a line of It can be seen that the line edge roughness is reduced near the straight line.

In addition to the above, the LER of Example 1 is 7.9, the LER of Example 2 is 7.8, the LER of Example 11 is 5.5, the LER of Example 12 is 5.3, and the LER of Example 14 is 6.2, LER of Example 16 was 5.9, LER of Example 17 was 5.9, LER of Example 18 was 5.4, and LER of Example 19 was 5.0.

The composition of the present invention can be used in the electric / electronic field and the optical field such as semiconductor devices.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The entire contents of the documents described in this specification are incorporated herein by reference.

Claims

A composition comprising a compound of formula (I) and a compound of formula (II).

[Wherein, R and R ′ are each hydrogen, a substituted or unsubstituted straight-chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, substituted or unsubstituted lactone rings having 4 to 20 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 12 carbon atoms, and the like It is either a group in which two or more of the groups are combined, or a group represented by the following formulas (1) to (3).
R 1 and R 1 ′ are each hydrogen, hydroxyl group, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 3 to 12 carbon atoms, substituted or unsubstituted A cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 10 carbon atoms, an alkoxyalkyloxy group, a siloxy group, and these groups and a divalent group (where a divalent group is A substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, an ester bond group, a carbonate ester bond group, an ether bond group, or a combination of two or more of these groups A substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 3 An aliphatic hydrocarbon group having 12 branches, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 aromatic groups, alkoxyalkyl groups, carboxy groups, silyl groups, and these groups and divalent groups (wherein the divalent groups are substituted or unsubstituted alkylene groups, substituted or unsubstituted arylenes) A group, a substituted or unsubstituted silylene group, an ester bond group, a carbonate ester bond group, an ether bond group, or a group formed by bonding two or more of these groups), an acid dissociable, dissolution inhibiting group, Or any one of groups represented by the following formulas (1) to (3).
R 2 and R 2 ′ are each a group represented by R 1 .
R and R ', R 1 and R 1', and at least one of R 2 and R 2 'are different from each other.

(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond) Or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and in the case of having a substituent, the substituent is bromine, fluorine, nitrile group or alkyl having 1 to 10 carbon atoms It is a group.
R 3 represents hydrogen, a hydroxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted, Unsubstituted cycloaliphatic group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted An alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic alkoxy group having 3 to 20 carbon atoms, an alkoxyalkyl group, a carboxy group, a silyl group, and these groups and a divalent group (where, The divalent group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond group, a carbonate bond group, an ether bond group, or A group formed by bonding two or more of these groups) or an acid dissociable, dissolution inhibiting group.
R 4 and R 5 are each hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted Alternatively, it is an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group obtained by combining two or more of these groups.
A 1 is a group combining two or more selected from an alkylene group, an ether bond and an alkylene group, or a group combining one or more alkylene groups and one or more ether bonds. x represents an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 1 ′ , R 2 ′ , R 3 ′ , Ar, and A 1 may be the same or different. ]]
R is any one of the groups represented by formulas (1) to (3), or R 1 is hydrogen, a hydroxyl group, a substituted or unsubstituted linear aliphatic carbon atom having 1 to 20 carbon atoms, respectively. Hydrogen group, substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 10 aromatic groups, substituted or unsubstituted linear alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 3 to 12 carbon atoms, substituted or unsubstituted 3 to 20 carbon atoms A cyclic alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, and a divalent group thereof (wherein the divalent group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted group) Or nothing A substituted silylene group, an ester bond group, a carbonate ester bond group, an ether bond group, or a group formed by bonding two or more of these groups), or an acid dissociable, dissolution inhibiting group, The composition according to claim 1 , wherein one or more of R 1 is an acid dissociable, dissolution inhibiting group.
R is any of the groups represented by the above formulas (1) to (3), and one of two R 1 existing on the same aromatic ring is a hydroxyl group, and the other is OR ″. R ″ is hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having a branch having 3 to 12 carbon atoms, or a group having 3 to 20 carbon atoms. 2. The composition according to claim 1, which is a cyclic aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing oxygen.
R ′ is any one of the groups represented by the above formulas (1) to (3), and one of two R 1 ′ existing on the same aromatic ring is a hydroxyl group and the other is OR R '' is hydrogen, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having a branch having 3 to 12 carbon atoms, or 3 to 3 carbon atoms. The composition according to claim 3, which is a group containing 20 cycloaliphatic hydrocarbon groups, an aromatic group having 6 to 10 carbon atoms, or oxygen.
The composition according to any one of claims 1 to 4, which satisfies the following formula (A):
0.01 ≦ t × 100 / (s + t) ≦ 90 (A)
(S is the total weight of the compound of formula (I) in the composition, and t is the total weight of the compound of formula (II) in the composition.)
The composition according to any one of claims 1 to 5, wherein R 3 is any one of the following formulas (I) to (IV):

(In the above formulas (I) to (IV),
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
β is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group, a group formed by bonding a substituted or unsubstituted bicyclic aliphatic group to oxygen, or A linear group having 1 to 10 carbon atoms and a group selected from a quaternary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group and a substituted or unsubstituted bicyclic aliphatic group A group formed by combining an aliphatic hydrocarbon group is a group formed by bonding with oxygen.
γ is a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group or a substituted or unsubstituted bicyclic aliphatic group bonded to oxygen, or A straight chain having 1 to 10 carbon atoms and a group selected from a tertiary aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted monocyclic aliphatic group and a substituted or unsubstituted bicyclic aliphatic group A group formed by combining a group of aliphatic hydrocarbon groups is a group formed by bonding with oxygen.
δ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted lactone ring having 4 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms. )
The composition according to any one of claims 1 to 5, wherein R 3 is a group selected from the following formulas (6) to (42).

(Wherein, r represents any one of the substituents represented by the above formulas (6) to (34) and (38) to (42)).
The compound of the formula (I) and the compound of the formula (II) each contain a plurality of R 3 s , all R 3 contained in the compound of the formula (I) do not contain a polar structure at the end, and the formula The composition according to any one of claims 1 to 7, wherein at least two of R 3 contained in the compound of (II) contain a polar structure at the end.
9. The composition according to claim 8, wherein at least two ends of R 3 contained in the compound of the formula (II) are a lactone ring having 3 to 20 carbon atoms or a carbocyclic ketone having 3 to 20 carbon atoms. .
R 3 contained in the formula (I) is a group selected from the following formulas (8) to (11), (16), (17) and (20) to (25),
The R 3 contained in the formula (II) is a group selected from the following formulas (18), (19), (26) to (29), (43) and (44), respectively. Composition.
A fine processing method using the composition according to any one of claims 1 to 10.
A semiconductor device manufactured by the microfabrication method according to claim 11.
An apparatus comprising the semiconductor device according to claim 12.