JP2000292925A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the occurrence of development defects and a scum by incorporating a compound which generates an acid when irradiated with active light or the like, a polymer having specified repeating units and a group which is decomposed by the action of the acid and a compound which is decomposed by the action of the acid to generate sulfonic acid. SOLUTION: The positive type photoresist composition contains a compound which generates an acid when irradiated with active light or the like, a polymer having repeating units of one of formulae Ia and Ib, repeating units of formula II and a group which is decomposed by the action of the acid and a compound which is decomposed by the action of the acid to generate sulfonic acid. In the formula Ia, R1 and R2 are each H, cyano, hydroxyl or the like, X is O, S, -NH- or the like and A is a single bond or a divalent combining group. In the formula Ib, Z2 is -O- or the like. In the formula II, R11 and R12 are each H, cyano, halogen or alkyl which may have a substituent and Z1 is an atomic group containing combined two carbon atoms (C-C) for forming an alicyclic structure which may have a substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for deep ultraviolet exposure used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity microchip and other photofabrication processes. It is. More specifically, the present invention relates to a positive photoresist composition for deep ultraviolet exposure which can form a high-definition pattern by using light having a wavelength of not more than 250 nm, particularly a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol with a developing solution have been studied. Although some results have been obtained, concerns about the swelling of the resist film and the process become complicated. This does not necessarily mean that the problem has been solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in the main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed.

A resin containing an acid-decomposable group used for a photoresist for exposure to far ultraviolet rays generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. For this reason, the resin becomes hydrophobic, and there is a problem caused by the hydrophobicity. Various means for improving the above have been studied, but the above techniques still have many unsatisfactory points (especially in terms of developability), and improvements are desired.

On the other hand, JP-A-8-248561 discloses a photoreactive composition comprising a photoacid generator and an acid multiplying agent which newly generates an acid by the acid generated from the photoacid generator. ing. SPIE., Vol. 3049., 76-8
2p. Discloses a chemically amplified resist for 193 nm lithography containing an acid generator, a partially protected alicyclic polymer and an acid multiplying agent.

[0008] However, the above-mentioned deep ultraviolet light and short wavelength light source, for example, an ArF excimer laser (193 nm)
However, there is still room for improvement in the developability of the technology using as an exposure light source. Specifically, there are problems such as generation of development defects and generation of scum (development residue). Further, there is still room for improvement in the problem of line width reproducibility that the line width fluctuates for each pattern formation.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. Specifically, it is an object of the present invention to provide a positive photoresist composition which solves the problems of development defects and scum during development. It is a further object of the present invention to provide a positive photoresist composition for deep ultraviolet exposure which has excellent line width reproducibility.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, and as a result, by using a specific acid-decomposable resin and a specific additive, the present invention has been developed. Knowing that the object of the invention is achieved, the present invention has been achieved. That is, the above object is achieved by the following constitutions.

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) at least one of the repeating units represented by the following general formulas (Ia) and (Ib); A polymer having a repeating unit represented by the formula (II) and having a group decomposable by the action of an acid; and (C) a compound capable of decomposing by the action of an acid to generate a sulfonic acid. A positive photoresist composition for deep ultraviolet exposure.

[0012]

Embedded image

In the formula (Ia): R ₁ and R ₂ are each independently
Hydrogen atom, cyano group, hydroxyl group, -COOH, -COOR
₅ represents a _{-CO-NH-R 6, -CO} -NH-SO 2 -R 6, which may be substituted, an alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NH
Represents SO ₂ NH—. Here, R ₅ represents an optionally substituted alkyl group, cyclic hydrocarbon group or the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. A —Y group;

[0014]

Embedded image

(In the —Y group, R _{21 to} R ₃₀ are each independently
Represents a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2. In formula (Ib): Z ₂ represents —O— or —N (R ₃ ) —. Here, R ₃ is a hydrogen atom, a hydroxyl group or —OSO ₂ —R
Represents ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z ₁ represents an atomic group for forming an alicyclic structure which may have a substituent and includes two bonded carbon atoms (C—C).

(2) Z ₁ in the general formula (II) is:
The above-mentioned (1), which represents an atomic group for forming a bridged alicyclic structure which contains two bonded carbon atoms (C-C) and may have a substituent. A positive photoresist composition for deep ultraviolet exposure.

(3) The positive type for deep ultraviolet exposure according to the above (1), wherein the general formula (II) is the following general formula (II-A) or general formula (II-B). Photoresist composition.

[0018]

Embedded image

In the formulas (II-A) and (II-B): R _{13 to} R ₁₆
Is independently a hydrogen atom, a halogen atom, a cyano group,
—COOH, —COOR ₅ (R ₅ is as defined above), a group decomposed by the action of an acid, —C (＝ O) —X
-AR ₁₇ , or an alkyl group or a cyclic hydrocarbon group which may have a substituent. Further, at least two members out of R _{13 to} R ₁₆ may combine to form a ring. n represents 0 or 1. Here, X and A are as defined above. R ₁₇ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO
—NH—R ₆ , —CO—NH—SO ₂ —R ₆ (R ₅ , R
₆ each has the same meaning as described above) or the above-mentioned -Y group.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (A) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator) The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, and a photochromic Agents or known light used for microresist or the like (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line,
KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a molecular beam, or a compound capable of generating an acid by an ion beam, and a mixture thereof can be appropriately selected and used.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
No. 9,056, Re 27,992, ammonium salts described in JP-A-3-140140, DC Necker et al., Macromolecules, 1,
7,2468 (1984), CSwen et al, Teh, Proc.Conf.Rad.Curin
g ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCriv
ello etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693, 161,811, 4
No. 10,201, No. 339,049, No. 233,567, No. 297,443,
No. 297,442, U.S. Pat.Nos. 3,902,114 and 4,933,377,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581,
Sulfonium salts described in JP-A-7-28237 and JP-A-8-27102, JVCrivello et al., Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Nos., Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc, A
cc.Chem.Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Te
trahedron Lett., (24) 2205 (1973), DHR Barton etal,
J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem. So
C., PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahedro
n Lett., (17), 1445 (1975), JWWalkeretal J. Am. Chem. So
c., 110,7170 (1988), SCBusman et al, J.Imaging Techno
l., 11 (4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PM Collinsetal, J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichman et al., J. Electrochem. Soc., Soli
d State Sci.Technol., 130 (6), FMHoulihan et al, Macr
omolcules, 21, 2001 (1988), EP 0290,750, 0
No. 46,083, No. 156,535, No. 271,851, No. 0,388,343,
U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-19
No. 8538, JP-A-53-133022, etc., a photoacid generator having a 0-nitrobenzyl-type protecting group, M. TUNOOKA etal, Pol
ymer Preprints Japan, 35 (8), G. Berner et al., J. Rad. Cur
ing, 13 (4), WJMijs etal, CoatingTechnol., 55 (697), 4
5 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 044,115
No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A 2-2457
No. 56, iminosulfone described in JP-A-3-140109 and the like
Compounds that generate sulfonic acid upon photolysis, such as those disclosed in JP-A-61-166544, JP-A-2-71270, JP-A-3-103854,
Examples thereof include diazoketosulfone and diazodisulfone compounds described in JP-A-3-103856 and JP-A-210960.

A group that generates an acid by the light;
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sci.,
30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rapid
Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Chem., 1
52,153,163 (1972), JVCrivello etal, J. PolymerSci.,
Polymer Chem.Ed., 17,3845 (1979), U.S. Pat.
No. 7, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55
-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-14602
Compounds described in No. 9 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (19
80), A. Abad et al, Tetrahedron Lett., (47) 4555 (197
1), DHR Barton et al, J. Chem. Soc., (C), 329 (197
0), compounds which generate an acid by light described in US Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0025]

Embedded image

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0031]

Embedded image

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0034] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0052]

Embedded image

Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.1% based on the total weight of the resist composition (excluding the coating solvent).
It is used in the range of 001 to 40% by weight, preferably 0.1 to 40% by weight.
It is used in the range of 01 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

(C) Compound which decomposes under the action of acid to generate sulfonic acid (hereinafter also referred to as sulfonic acid generating compound) In the present invention, the sulfonic acid generating compound is stable when no acid is present. Decomposes by the action of an acid generated from the photoacid generator upon exposure to produce sulfonic acid. Here, the acid generated from the sulfonic acid-generating compound preferably has a high acid strength. Specifically, the dissociation constant (pKa) of the acid is preferably 3 or less, more preferably 2 or less. As the acid generated from the sulfonic acid generating compound, a sulfonic acid having an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group is preferable. As the sulfonic acid generating compound, compounds represented by the following general formulas (1) to (5) are preferable.

[0062]

Embedded image

In the above general formulas (1) to (5): R
Represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group. R ₀ represents a group constituting a group which is decomposed by the action of an acid at —COOR ₀ . R ₁ is an alkyl group,
Represents a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group. R ₂ represents an alkyl group or an aralkyl group. R ₃ represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group. R ₄ ,
R ₅ each independently represents an alkyl group, and R ₄ and R ₅ may combine with each other to form a ring. R ₆ represents a hydrogen atom or an alkyl group. R ₇ represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group. R
₈ represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group. R ₉ represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group. However, R ₉ may combine with R ₇ to form a ring. R
₁₀ represents an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group. R ₁₁ represents an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyl group. R ₁₀ and R ₁₁ may combine with each other to form a ring.

In the above formulas (1) to (5), examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. And an octyl group. Examples of the cyclic alkyl group include a cyclic alkyl group having 4 to 10 carbon atoms. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and a boronyl group. Groups, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, and the like.

The aryl group includes an aryl group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group and a tolyl group. Examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms, and specific examples include a benzyl group, a phenethyl group, and a naphthylethyl group. Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group.

The aryloxy group may have 6 to 14 carbon atoms.
And an aryloxy group, specifically, a phenoxy group, a naphthoxy group, and the like. Examples of the alkenyloxy group include an alkenyloxy group having 2 to 8 carbon atoms, and specific examples include a vinyloxy group and an allyloxy group.

Each of the above substituents may further have a substituent. Examples of the substituent include the following. That is, halogen atoms such as Cl, Br, and F,
-CN group, -OH group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an acylamino group such as an acetylamino group,
Benzyl group, aralkyl group such as phenethyl group, allyloxyalkyl group such as phenoxyethyl group, having 2 to 2 carbon atoms
Examples thereof include five alkoxycarbonyl groups and acyloxy groups having 2 to 5 carbon atoms. Moreover, the range of the substituent is not limited to these.

The ring formed by combining R ₄ and R ₅ includes a 1,3-dioxolane ring, a 1,3-dioxane ring and the like. Examples of the ring formed by combining R ₇ and R ₉ with each other include a cyclopentyl ring and a cyclohexyl ring. Examples of the ring formed by combining R ₁₀ and R ₁₁ with each other include a 3-oxocyclohexenyl ring and a 3-oxoindenyl ring, which may contain an oxygen atom in the ring. Examples of the acid-decomposable group include a t-butyl group as Ro,
tertiary alkyl groups such as t-amyl group, isobornyl group, 1
-An ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-alkoxyethyl group such as a 1-cyclohexyloxyethyl group, a 1-methoxymethyl group,
And those representing an alkoxymethyl group such as -ethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl group, a 3-oxocyclohexyl group, and the like.

Preferred examples of each of the above R, R ₀ , R _{1 to} R ₁₁ include the following. R: methyl, ethyl, propyl, butyl, octyl, trifluoromethyl, nonafluorobutyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, phenyl, pentafluorophenyl Group, methoxyphenyl group, toluyl group, mesityl group,
Fluorophenyl group, naphthyl group, cyclohexyl group,
Camphor group R ₀ ; t-butyl group, methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group R ₁ ; methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, Phenyl, naphthyl, benzyl, phenethyl, methoxy, ethoxy, propoxy, phenoxy, naphthoxy R ₂ ; methyl, ethyl, propyl, butyl, benzyl R ₃ ; methyl, ethyl group, propyl group, cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a benzyl group, phenethyl group, naphthylmethyl group R _4, R _5; a methyl group, an ethyl group, a propyl group, an ethylene bonded to each other R ₆ ; hydrogen atom, methyl group, ethyl group

R ₇ , R ₉ ; hydrogen, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, R ₈ : methyl, ethyl, isopropyl, t-butyl, neopentyl, cyclohexyl, phenyl, benzyl R ₁₀ ; methyl, ethyl, propyl Group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy group, vinyloxy group, methylvinyloxy group, May be bonded to each other to contain an oxygen atom, Seo cyclohexenyl ring, those forming a 3-Okisoindeniru ring R _11; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, A phenyl group, a naphthyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group, an allyl group, a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring which may be bonded to each other to contain an oxygen atom; Specific examples of the compounds represented by the formulas (1) to (5) will be illustrated, but the content of the present invention is not limited thereto.

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

In the present invention, the compound represented by the above general formula (4) is particularly preferred as the sulfonic acid generating compound. In the present invention, the addition amount of the sulfonic acid-generating compound in the composition is based on the total solid content of the composition.
The content is preferably 0.01 to 10% by weight, more preferably 0.1 to 10% by weight.
0.5 to 5% by weight.

(B) having at least one of the repeating units represented by the general formulas (Ia) and (Ib) and the repeating unit represented by the general formula (II),
A polymer having a group that is decomposed by the action of an acid (hereinafter, abbreviated as “resin of the present invention”) will be described.

In the above formula (Ia), R ₁ , R
₂ is each independently a hydrogen atom, a cyano group, a hydroxyl group, -C
_{OOH, -COOR 5, -CO-NH} -R 6, -CO-
NH-SO ₂ -R _6, which may be substituted, an alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the -
Represents a Y group. Wherein, R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or the -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. In the above-mentioned -Y group, R ₂₁ to
R ₃₀ each independently represents a hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 or 2. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A represents a single bond or a divalent linking group.

In the formula (Ib), Z ₂ represents —O— or —N (R ₃ ) —. Here, R ₃ represents a hydrogen atom, a hydroxyl group, or —OSO ₂ —R ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The above R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₂₁
As the alkyl group for R _{30 to} R _{30, a} linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the cyclic hydrocarbon group for R ₁ , R ₂ , R ₅ , and R ₆ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, and an isobornyl group. ,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. Examples of the alkoxy group in R ₁ and R ₂ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the haloalkyl group for R ₄ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of further substituents of the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

The divalent linking group represented by A in the general formulas (Ia) and (Ib) includes an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group,
Examples thereof include a single group selected from the group consisting of an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups. Examples of the alkylene group and substituted alkylene group in A include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

Specific examples of the repeating unit represented by the above general formula (Ia) include the following [I-1] to [I-65], but the present invention is not limited to these specific examples. Absent.

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

The following [I'-1] to [I'-7] are specific examples of the repeating unit represented by the general formula (Ib), but the present invention is limited to these specific examples. Not something.

[0091]

Embedded image

[0092]

Embedded image

In the above general formula (II), R ₁₁ , R
Each ₁₂ independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z ₁ represents an atomic group for forming an alicyclic structure which may have a substituent and includes two bonded carbon atoms (C—C).

Examples of the halogen atom for R ₁₁ and R ₁₂ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. The alkyl group for R ₁₁ and R ₁₂ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group.

Examples of further substituents on the alkyl groups R ₁₁ and R ₁₂ include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. And formyl group as acyl group,
An acetyl group and the like can be mentioned, and an acyloxy group can be an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z ₁ is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent on the resin. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferred. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0097]

Embedded image

[0098]

Embedded image

Preferred skeletons of the bridged alicyclic hydrocarbon include (5), (6), (7) and
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R _{13 to} R ₁₆ in the general formula (II-A) or (II-B). Among the repeating units having a bridged alicyclic hydrocarbon, a repeating unit represented by the above general formula (II-A) or (II-B) is more preferable. In the above general formula (II-A) or (II-B), R ₁₃
To R ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (where R ₅ may have a substituent, an alkyl group, a cyclic hydrocarbon group, or the above general formula ( represents the same group -Y as in I)), group decomposable by the action of an acid, -C (= O) -X- a-R 17, or optionally substituted alkyl group or cyclic hydrocarbon Represents a hydrogen group. n represents 0 or 1. X is an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂
Represents NH-. R ₁₇ is, -COOH, -COOR _5, -
CN, hydroxyl, optionally substituted alkoxy _{group, -CO-NH-R 6,} -CO-NH-SO 2 -R 6
(R ₅ and R ₆ are as defined above) or the above-mentioned general formula (I
a) represents a -Y group. A represents a single bond or a divalent linking group.

In the resin according to the present invention, the acid-decomposable group
Is -C (= O) -XA-R ₁, -C (= O)-
XAR_TwoOr Z in the general formula (II)₁
May be included as a substituent. The structure of the acid-decomposable group
-C (= O) -X₁-R₀It is represented by Where R
₀Are tertiary alkyl groups such as t-butyl group and t-amyl group.
Kill group, isobornyl group, 1-ethoxyethyl group, 1-
Butoxyethyl group, 1-isobutoxyethyl group, 1-si
1-alkoxyethyl such as chlorohexyloxyethyl group
Group, 1-methoxymethyl group, 1-ethoxymethyl group, etc.
Alkoxymethyl group, tetrahydropyranyl group, tetra
Hydrofuranyl group, trialkylsilyl ester group, 3
-Oxocyclohexyl ester group, 2-methyl-2-
Adamantyl group, mevalonic lactone residue, 2- (γ
-Butyrolactonyloxycarbonyl) -2-propyl
And the like. X₁Is synonymous with X above
You.

Examples of the halogen atom in R _{13 to} R ₁₆ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R _{13 to} R ₁₆ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

The cyclic hydrocarbon group represented by R _{13 to} R ₁₆ is, for example, a cyclic alkyl group or a bridged hydrocarbon group, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl. Group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two of the above R _{13 to} R ₁₆ includes cyclopentene, cyclohexene, cycloheptane, cyclooctane and the like having 5 to 1 carbon atoms.
And 2 rings.

As the alkoxy group for R ₁₇ ,
Examples thereof include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group of A include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, and a carbonyl group, similarly to the divalent linking group of A in formula (Ia). , An ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified. As the alkylene group and the substituted alkylene group in the above A, 2 of A in the general formula (Ia)
Examples are the same as those of the valent linking group.

In the resin according to the present invention, the group decomposed by the action of an acid is a repeating unit represented by the general formula (Ia), a repeating unit represented by the general formula (Ib), or a group represented by the general formula (II) It can be contained in at least one of the repeating units represented and the repeating units of the copolymer component described below.

The formula (II-A) or (II
The various substituents of R _{13 to} R ₁₆ in —B) may be an atomic group for forming an alicyclic structure in the above general formula (II) or an atomic group Z for forming a bridged alicyclic structure. It also serves as a substituent.

The formula (II-A) or the formula (II
-B) As specific examples of the repeating unit represented by the following [II]
-1] to [II-166], but the present invention is not limited to these specific examples.

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

The resin according to the present invention comprises at least one of the repeating units represented by the general formula (Ia) and the general formula (Ib), and the resin represented by the general formula (II) (general formula (II-
A) and one or more kinds of repeating units represented by general formula (II-B)), in addition to dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resist For the purpose of adjusting the resolving power, heat resistance, sensitivity and the like, which are the general requirements of the above, copolymers containing repeating units of various monomers can be prepared. Preferred copolymerization components are those represented by the following general formula (IV)
') And (V').

[0129]

Embedded image

Here, in the formula, Z is an oxygen atom, -NH-,-
_{N (-R 50) -, -} N (-OSO 2 R 50) - represents, R
₅₀ also has the same meaning as the above (substituted) alkyl group and (substituted) cyclic hydrocarbon group. The general formulas (IV ′) and (V
') The following [IV'
-9] to [IV'-16], [V'-9] to [V'-1]
6], but is not limited to these specific examples.

[0131]

Embedded image

[0132]

Embedded image

The resin according to the present invention may be further copolymerized with the following monomers so as to give a repeating unit constituting the resin within a range where the effects of the present invention can be effectively obtained. However, it is not limited to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance can be finely adjusted. Examples of such a comonomer include acrylates, methacrylates,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl) Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the resin according to the present invention, the compound represented by the general formula (I)
a) and / or a repeating unit represented by the general formula (Ib) and a repeating unit represented by the general formula (II) (including the general formulas (II-A) and (II-B)) The amount should be appropriately set in consideration of the desired dry etching resistance of the resist, sensitivity, prevention of pattern cracking, substrate adhesion, resist profile, and resolution, heat resistance, etc. which are necessary requirements of general resists. Can be. In general, the resin represented by the general formula (I)
a) and / or the content of the repeating unit represented by the general formula (Ib) and the repeating unit represented by the general formula (II) is 25 mol% in the total monomer repeating units of the resin.
The above is suitable, preferably at least 30 mol%, more preferably at least 35 mol%.

Further, in the resin according to the present invention, the content of the repeating unit (general formula (IV ′) or general formula (V ′)) derived from the above-mentioned preferable comonomer in the resin is also desired. Although it can be appropriately set according to the performance of the dist, in general, the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) and the repeating unit represented by the general formula (II) 99 for the total number of moles
It is preferably at most 90 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%. In addition, the content of the repeating unit based on the monomer of the further copolymerization component in the resin can also be appropriately set according to the desired dist performance, but generally, the general formula (Ia) and the general formula (Ia) /
Alternatively, it is preferably 99 mol% or less, more preferably 90 mol%, based on the total number of moles of the repeating unit represented by the general formula (Ib) and the repeating unit represented by the general formula (II).
Mol% or less, more preferably 80 mol% or less.
When the amount of the repeating unit based on the monomer of the further copolymer component exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, so that it is not preferable.

In the resin according to the present invention, the group decomposed by the action of an acid is represented by a repeating unit represented by the general formula (Ia) and / or the general formula (Ib) or a general formula (II) May be contained in any of the repeating units based on the monomer of the copolymer component, but the content of the repeating unit containing a group that is decomposed by the action of an acid may be contained in the total repeating units of the resin. The amount is suitably from 8 to 60 mol%, preferably from 10 to 55 mol%, and more preferably from 12 to 50 mol%.

The resin according to the present invention is obtained by copolymerizing a monomer corresponding to the repeating unit represented by the general formula (II) and maleic anhydride with a monomer of the copolymer component when the copolymer component is used. Polymerized, copolymerized in the presence of a polymerization catalyst, and a repeating unit derived from maleic anhydride of the obtained copolymer is subjected to ring-opening esterification with an alcohol under basic or acidic conditions, or is hydrolyzed, It can also be synthesized by a method of converting the carboxylic acid moiety generated thereafter into a desired substituent.

The weight average molecular weight of the resin according to the present invention is G
It is preferably from 1,000 to 200,000 in terms of polystyrene according to the PC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. When the weight average molecular weight exceeds 200,000, the developability is deteriorated and the viscosity becomes extremely high, so that the film forming property is deteriorated. And so on, which produces very unfavorable results.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of the resin according to the present invention in the entire composition is preferably 40 to 99.99% by weight, more preferably in the total resist solids. Is 50 to 99.97% by weight.

The positive photoresist composition for deep ultraviolet exposure according to the present invention comprises at least one surfactant selected from the group consisting of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. It is preferable to contain an agent. The positive photoresist composition for deep ultraviolet exposure according to the present invention contains the acid-decomposable resin and the surfactant, so that when using an exposure light source of 250 nm or less, particularly 220 nm or less, development defects and scum are reduced. Not only a resist pattern can be obtained, but also line width reproducibility is excellent. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745
No., JP-A-62-170950, JP-A-63-34540, JP-A-7-2
No. 30165, JP-A-8-62834, JP-A-9-54432, JP-A-9
No. -5988, and the following commercially available surfactants can be used as they are. As a commercially available surfactant that can be used, for example, F-top EF30
1, EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC430, 431
(Manufactured by Sumitomo 3M Limited), Mega Fuck F171, F173, F1
76, F189, R08 (Dainippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and the like. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a surfactant other than the above, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like can be contained.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Among the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran.

Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The positive photoresist composition for deep ultraviolet exposure according to the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.4 to 1.5 μm. After applying the above composition on a substrate (eg, silicon / silicon dioxide coating) such as used in the manufacture of precision integrated circuit devices by a suitable coating method such as a spinner or a coater,
By exposing through a predetermined mask, baking and developing, a good resist pattern can be obtained.
Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less.
Specifically, a KrF excimer laser (248 nm),
Examples include an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), an X-ray, an electron beam, and the like, and an ArF excimer laser (193 nm) is particularly preferable.

Examples of the developer for the positive photoresist composition for deep ultraviolet exposure according to the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0156]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example 1 (Photoacid Generator PAG4-36) 50 g of diphenyl sulfoxide was added to 800 m of mesitylene.
L, and 200 g of aluminum chloride was added thereto, followed by stirring at 80 ° C. for 24 hours. After the completion of the reaction, the reaction solution was slowly poured into 2 L of ice. 400 mL of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C. for 10 minutes. The reaction solution was cooled to room temperature, washed with ethyl acetate, and filtered. A solution prepared by dissolving 200 g of ammonium iodide in 400 mL of distilled water was added to the filtrate. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate, dried, and treated with sulfonium iodide 72.
g was obtained. 50 g of the obtained sulfonium iodide was dissolved in 300 mL of methanol, and 31 g of silver oxide was added thereto, followed by stirring for 4 hours. After the reaction solution was filtered, salt exchange was performed with potassium nanofluorobutanesulfonate to recover 40 g of the desired product (PAG4-36).

Synthesis Example 2 (Synthesis Example of Resins (1) to (6)) <Synthesis of Resin (1)> By reacting methacrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadientadiene. An obtained equimolar mixture of the tetracyclododecene derivative (1-1) having the following structure and maleic anhydride is dissolved in tetrahydrofuran, and the solid content is 50%.
Was prepared. This was charged into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 5 mol% of a radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a large amount of hexane to precipitate a white powder. The precipitated powder was taken out by filtration and dried to obtain the intended resin (1).

[0159]

Embedded image

When an attempt was made to analyze the molecular weight of the obtained resin (1) by GPC, it was 6,800 (weight average) in terms of polystyrene. From the NMR spectrum, it was found that the molar ratio of the repeating unit of tetracyclododecene and the repeating unit of maleic anhydride in the resin (1) was 50/50. Resins (2) to (6) were synthesized in the same manner as above. The structures of the synthesized resins (1) to (6) are described below.

[0161]

Embedded image

[0162]

Embedded image

Table 1 shows the molar ratio and the weight average molecular weight of each repeating unit of the resins (2) to (6).

[0164]

[Table 1]

Synthesis Example 4 (Synthesis of Sulfonic Acid Generating Compound) Compound (1-1) 32 g of t-butyl acetoacetate was dissolved in tetrahydrofuran and cooled to 0 ° C. under a nitrogen stream. Next, 1.2 equivalents of sodium hydride were added, and methyl iodide 4 was added.
0 g was added dropwise. After completion of the dropwise addition, the reaction solution was heated to room temperature and stirred for 3 hours. After completion of the reaction, the reaction solution was poured into distilled water, and the target product was extracted with ethyl acetate and concentrated.
17 g of the obtained compound and a 37% formalin aqueous solution 13
g, 6 mL of dioxane, and stirred.
While controlling the temperature to -20 ° C, 7 g of potassium carbonate was slowly added. After the completion of the addition of potassium carbonate, the mixture was stirred for 8 hours while maintaining the reaction temperature. After completion of the reaction, aqueous sodium bicarbonate was added dropwise to the reaction solution, and a mixture containing the desired product was extracted with ethyl acetate. The obtained mixture was purified by silica gel column chromatography, and 20 g of the desired product (methylol) was recovered. Finally, 2-naphthalenesulfonyl chloride 8
g and 6 g of the methylol compound obtained above were dissolved in THF, cooled to 0 ° C. under a nitrogen stream, and 5 g of pyridine was added dropwise. After dropping,
The reaction solution was warmed to room temperature and stirred for 10 hours. After completion of the reaction, the reaction solution was neutralized and extracted with ethyl acetate / water, and the organic layer was purified by silica gel column chromatography to obtain 8 g of the target compound (1-1).

Compound (1-6) Compound (1-6) was synthesized in the same manner as described above except that pentafluorobenzenesulfonyl chloride was used instead of naphthalene sulfonyl chloride.

Compound (2-3) Ethyl acetoacetate was converted to a cyclic ketal using ethylene glycol according to a conventional method, and then reduced with lithium hydride to obtain a ketal of acetoethanol. This and camphorsulfonyl chloride in TH
It was dissolved in F, cooled to 0 ° C. under a nitrogen stream, excess pyridine was added dropwise, and after completion of the addition, the reaction solution was heated to room temperature and stirred for 10 hours. After completion of the reaction, the reaction solution was neutralized and extracted with ethyl acetate / water, and the organic layer was purified by silica gel column chromatography to obtain the desired compound (2-3).

Compound (3-2) Phenylcyclohexene is oxidized in the presence of osmium oxide to synthesize cisdiol, which is then dissolved in 2-naphthalenesulfonyl chloride and THF, cooled to 0 ° C. under a stream of nitrogen, and excess pyridine is added dropwise. . After completion of the dropwise addition, the reaction solution was heated to room temperature and stirred for 10 hours. After completion of the reaction, the reaction solution was neutralized, extracted with ethyl acetate / water, and the organic layer was purified by silica gel column chromatography to obtain the desired compound (3).
-2) was obtained.

Compound (4-1) Dimedone and 1.2 equivalents of naphthalenesulfonyl chloridepyridine were dissolved in acetonitrile, and the mixture was dissolved at 0 ° C. in a nitrogen stream.
And 2 equivalents of pyridine were added dropwise. After the addition was completed, the reaction solution was heated to room temperature and stirred for 8 hours. After completion of the reaction, the reaction solution was neutralized and extracted with ethyl acetate / water, and the organic layer was purified by silica gel column chromatography to obtain the desired compound (4-1).

Compound (4-3) Compound (4-3) was synthesized in the same manner as in the synthesis of compound (4-1), except that Meldrum's acid was used in place of dimedone.

Compound (5-2) Journal of Photopolymer Science and Technologies V
Compound (5-2) was synthesized according to the method described in ol. 11 No3 (1998) p505-6.

Example 1.4 g of the resin shown in Table 2 synthesized in the above synthesis example, 0.18 g of a photoacid generator,
10 mg of 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), a surfactant (addition amount is 1% by weight based on the total solid content of the composition), and a sulfonic acid generating compound (addition amount) Is 2% by weight based on the total solid content of the composition), and each compound shown in Table 2 is blended.
After being dissolved in propylene glycol monoethyl ether acetate at a ratio of 4% by weight, the solution was filtered through a 0.1 μm microfilter to prepare positive photoresist composition solutions of Examples 1 to 10.

In Table 2, PAG-1 represents triphenylsulfonium triflate, and PAG-2 represents (PAG4-36) synthesized above. The resin R1 used in the comparative example in Table 2 has the following structure.

[0174]

Embedded image

Examples of the surfactant include W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonylphenyl ether.

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer by using a spin coater, dried at 140 ° C. for 90 seconds, and about 0.5 μm
Was prepared and exposed to an ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 140 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile.

[Number of development defects]: Bare S of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the i-substrate, and dried at 140 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
Nik through a test mask with a duty ratio = 1: 3)
After exposure with an on-stepper NSR-1505EX, post-exposure heating was performed at 140 ° C. for 90 seconds. Subsequently, after paddle development with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, 30% with pure water.
Washed with water for 2 seconds and spin dried. The sample thus obtained was used for KLA-2112 manufactured by KLA-Tencor Corporation.
The number of development defects was measured by a machine, and the obtained primary data value was defined as the number of development defects.

[Generation of development residue (scum)] Line width 0.2
Evaluation was made based on the residual state of the development residue in the resist pattern of 2 μm. A case where no residue was observed was evaluated as ○, and a case where a considerable amount was observed was evaluated as ×.

[Line width reproducibility] Line width reproducibility (line width variation rate)
Is represented by the rate of change with respect to the target line width. That is, as described above, a resist pattern profile having a target line width of 0.20 μm is repeatedly formed five times, and their actual measured line widths are measured with a scanning electron microscope. The fluctuation rate was calculated, and the total of the line width fluctuation rates for five times was evaluated as the line width reproducibility. Line width fluctuation rate = | actual measured line width−target line width | × 100 / target line width The evaluation results are shown in Table 2.

[0180]

[Table 2]

As is clear from the results shown in Table 2, the comparative example has problems in terms of the number of development defects and generation of scum. On the other hand, the positive photoresist composition for deep ultraviolet exposure according to the present invention has a satisfactory level of prevention of development defects and scum. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure. Further, the resist composition of the present invention containing a specific surfactant is excellent not only in development defects but also in line width reproducibility.

[0182]

The positive photoresist composition for deep ultraviolet exposure according to the present invention is suitably applied particularly to light in the far ultraviolet wavelength region in the range of 170 nm to 220 nm to prevent development defects and scum. And a good resist pattern profile is obtained, and the line width reproducibility is also excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 5/42 5/42 C08L 35/00 C08L 35/00 45/00 45 / 00 G03F 7/004 501 G03F 7/004 501 H01L 21/027 H01L 21/30 502R (72) Inventor Toshiaki Ao 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. AA00 AA04 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CC20 FA01 FA03 FA12 FA17 4J002 BH021 BK001 EQ016 EU186 EU216 EV216 EV247 EV296 EW176 EY006 EZ006 FD206 FD207 GP03 4J100 AJ10P AK32P AM43P AM45P AM47P BA11Q BA02P BA11Q BA02P BA11Q BA02P BA34P BA34Q BA35Q BA40P BA40Q BA51P BA56Q BA58P BA58Q BA59P BB01Q BB18P BC04P BC08P BC08Q BC09P BC09Q BC12P BC1 2Q BC53P BC53Q CA04 CA05 JA38

Claims (3)

[Claims] 1. A compound which generates an acid upon irradiation with actinic rays or radiation, (B) at least one of the repeating units represented by the following general formulas (Ia) and (Ib), and A polymer having a repeating unit represented by (II) and having a group that decomposes under the action of an acid;
And (C) a positive photoresist composition for deep ultraviolet exposure, comprising a compound which is decomposed by the action of an acid to generate a sulfonic acid. Embedded image In the formula (Ia): R ₁ and R ₂ each independently represent a hydrogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ₅ , or —CO—
_{NH-R 6, -CO-NH} -SO 2 -R 6, which may be substituted, an alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂ NH-
Represents Here, R ₅ may have a substituent,
Represents an alkyl group, a cyclic hydrocarbon group or the following -Y group. R
₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. —Y group; (In the —Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.) In the formula (Ib) : Z ₂ is, -O- or -N (R ₃₎ - represents a. Here, R ₃ is a hydrogen atom, a hydroxyl group or —OSO ₂ —R
Represents ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z ₁ represents an atomic group for forming an alicyclic structure which may have a substituent and includes two bonded carbon atoms (C—C). 2. A compound according to claim 1, wherein Z ₁ in the general formula (II) contains two bonded carbon atoms (CC) and forms a bridged alicyclic structure which may have a substituent. The positive photoresist composition for deep ultraviolet exposure according to claim 1, wherein the positive photoresist composition represents an atomic group represented by the formula: 3. The compound represented by the general formula (II)
The positive photoresist composition for deep ultraviolet exposure according to claim 1, wherein the composition is A) or the general formula (II-B). Embedded image In the formulas (II-A) and (II-B), R _{13 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH,
—COOR ₅ (R ₅ is as defined above), a group decomposed by the action of an acid, —C (＝ O) —XA—R ₁₇ ,
Or an alkyl group or a cyclic hydrocarbon group which may have a substituent. Further, at least two members out of R _{13 to} R ₁₆ may combine to form a ring. n represents 0 or 1. Here, X and A are as defined above. R
_17, -COOH, -COOR _5, -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-
R ₆ , —CO—NH—SO ₂ —R ₆ (R ₅ and R ₆ each have the same meaning as described above), or the above-mentioned —Y group.