KR100737253B1 - Positive-working photoresist compositon for far ultraviolet rays exposure - Google Patents

Abstract

An object of the present invention is to provide a positive photoresist composition for far ultraviolet exposure, which has high resolution and has good halftone retardation shift mask suitability (side lobe resistance).

The present invention provides (A) a compound which generates an acid by irradiation with actinic rays or radiation, (B-1) at least one selected from the group of repeating units represented by the first specific structure and the second specific structure; A polymer having a repeating unit having a third specific structure and having a group decomposed by the action of an acid,

(B-2) A positive photoresist composition for far ultraviolet exposure, comprising a polymer having a repeating unit having a fourth specific structure and having a group decomposed by the action of an acid.

Description

Positive photoresist composition for far ultraviolet exposure {POSITIVE-WORKING PHOTORESIST COMPOSITON FOR FAR ULTRAVIOLET RAYS EXPOSURE}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to positive photoresist compositions for microfabrication, such as semiconductor devices, which are sensitive to far ultraviolet rays. More particularly, half-tone retardation shift mask compatibility (side lobe resistance) is good and resist performance is high. It relates to a positive photoresist composition for excellent ultraviolet exposure.

The positive photoresist is applied on a substrate such as a semiconductor wafer, glass, ceramic or metal by a spin coating method or a roller coating method with a thickness of 0.5 to 2 탆. Then, it is heated and dried, and the circuit pattern or the like is baked by exposure to ultraviolet rays or the like through an exposure mask, and then developed by performing post-exposure baking as necessary to form a positive image. In addition, this positive image can be etched with a mask, and pattern processing can be performed on a substrate. Typical applications include semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

Conventionally, in order to increase the resolution and to obtain a good pattern reproducibility, the use of a resist having a high contrast (γ value) is advantageous, and the technical development of a resist composition meeting this purpose has been performed. There are many publications that disclose such techniques. In particular, regarding the resin which is the main part of the positive photoresist, a number of patent applications have been filed regarding the monomer composition, molecular weight distribution, synthesis method, and the like, and a certain result has been obtained. Moreover, about the photosensitive material which is another main component, the compound of many structures effective for high contrast is disclosed. By designing a positive photoresist using such a technique, it is also possible to develop an ultra high resolution resist capable of resolving a pattern having the same dimension as the wavelength of light.

However, integrated circuits are increasing their density increasingly, and in the manufacture of semiconductor substrates such as ultra-LSI, the processing of ultra-fine patterns consisting of line widths of 0.5 mu m or less is required.

On the other hand, various attempts have been made to increase the resolution by super resolution techniques such as exposure technique or mask technique. In the super resolution technology, various super resolution technologies have been studied on the light source surface, the mask surface, the copper surface, and the upper surface, respectively. On the light source surface, it is a technique which raises the resolution by making into a shape different from the conventional circular shape, ie, the conventional illumination method. On the surface of the mask, a technique of obtaining a high resolution by controlling a phase using a phase shift mask, that is, providing a phase difference to light passing through the mask and using the interference preferably has been reported (for example, Ito Tokuhisa). ; Stepper optics (1) to (4), phototechnical contact, Vol. 27, No. 12,762 (1988), Vol. 28, No. 1, 59 (1990), Vol. 28, No. 2, 108 (1990) , Vol. 28, No. 3,165 (1990), Japanese Patent Laid-Open No. 58-173744, Japanese Patent No. 62-50811, Japanese Patent No. 62-67514, Japanese Patent Publication No. 1-147458, Japanese Patent Publication 1-283925 , Disclosed in 2-211451, etc.)

Further, as described in Japanese Patent Application Laid-open No. Hei 8-15851, although the resist exposure method using a halftone system phase shift mask has been particularly noted as a practical technique for improving the spatial image and contrast of the projected image, the resist In addition to the main peak, so-called sub-peaks are generated in the light intensity distribution of the exposure light reaching to, and it is easy to be exposed to the portion of the resist which should not be originally exposed. In particular, the higher the coherence degree (σ), the more sub-peaks are generated. do. When such a sub peak occurs, unevenness caused by the sub peak is formed in the resist after exposure and development, which is undesirable.

In such a projection optical system of optical lithography, various miniaturization studies have been conducted, and active research has also been actively conducted on combining various super-resolution techniques (for example, halftone phase shift masks and annular illumination: CN Ahnetal; SPIE, Vol. 2440, 222 (1995), T. Ogawa et al; SPIE, Vol. 2726, 34 (1996).

However, in the case where the super-resolution technique is applied, resolution in the conventional positive photoresist is deteriorated, exposure margin, exposure latitude is insufficient, irregularities (film reduction) occur, and resist performance is deteriorated. It is reported so far. For example, C.L. Lin reports that the deformation illumination method deteriorates the density dependence of the pattern due to the effect of optical proximity (SPIE, vol. 2726, 437 (1996)), and N. Samarakone et al. And IBHur et al. In the case of forming a contact hole pattern using a mask, it is pointed out that the periphery of the hole pattern is likely to be uneven due to the influence of side lobe light (SPIE, Vol, 2440, 61 (1995), SPIE, Vol. 2440). , 278 (1995). In order to reduce the influence of the side lobe light, studies have been conducted such as the surface treatment of the positive resist with alkali after exposure (T. Yasuzato et al; SPIE, Vol. 2440, 804 (1995)), but the process becomes complicated. There is a problem.

Japanese Patent Laid-Open No. 10-10739 discloses an energy sensitive resist comprising a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in a main chain, a maleic anhydride, and a monomer having a carboxyl group. Japanese Patent Laid-Open No. 10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in a main chain and a radiation-sensitive acid generator. Japanese Patent Laid-Open No. 11-109632 describes the use of a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group as a radiation photosensitive material.

Japanese Patent Application Laid-open No. Hei 9-73173 and No. 9-90637. 10-161313 discloses a resist material using an alkali soluble group protected by a structure containing an alicyclic group, and an acid-sensitive compound comprising a structural unit which is desorbed by an acid to make the alkali soluble group. have.

However, even when such a resist material was used, resistance by side lobe light in the case of forming a contact hole pattern using a halftone type phase difference shift mask was insufficient.

In the case of using the super-resolution technique as described above, resolution may be improved, but other resist performances may decrease. Therefore, in the case of using a super resolution technique, for example, it is hardly known that a positive photoresist material may be designed as described above, respectively. Accordingly, an object of the present invention is to provide a positive photoresist composition for far ultraviolet exposure, which has high resolution and has good halftone retardation shift mask suitability (side lobe resistance).

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the constituent material of the resist composition of positive chemical amplification system, it confirmed that the objective of this invention is achieved by using a specific acid-decomposable resin together, and completed this invention. That is, the said object is achieved with the following structures.

(1) (A) a compound which generates an acid by irradiation of actinic light or radiation,
(B-1) 1 or more types selected from the group of the repeating unit represented by the following general formula (Ia) and general formula (Ib), and the repeating unit represented by the following general formula (II), and the action of an acid A polymer having a group decomposed by, and
(B-2) A positive photoresist composition for far ultraviolet exposure, comprising a polymer having a repeating unit represented by the following general formula (pA) and having a group decomposed by the action of an acid.

In formula (Ia):

R ₁ and R ₂ are each independently a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , an alkyl group which may be substituted, An alkoxy group, a cyclic hydrocarbon group, or the following -Y group is represented.
X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. Here, R <_5> represents the alkyl group, cyclic hydrocarbon group, or the following -Y group which may have a substituent. 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 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.

In 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 represents the atomic group for forming the alicyclic structure which may contain 2 carbon atoms (CC) couple | bonded and may have a substituent.

(Wherein R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is a single bond, an alkylene group) , A substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups.

Ra represents the group in any one of following formula (pI)-(pVI).

Wherein R ₁₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary to form an alicyclic hydrocarbon group together with carbon atoms R ₁₁₂ to R ₁₁₆ each independently represent a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R ₁₁₂ to R ₁₁₄ , or any one of R ₁₁₅ and R ₁₁₆ R ₁₁₇ to R ₁₂₁ each independently represent a hydrogen atom, 1 to 4 carbon atoms, a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₁₇ to R ₁₂₁ is And an alicyclic hydrocarbon group, and any one of R ₁₁₉ and R ₁₂₁ represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, and R ₁₂₂ to R ₁₂₅ are each independently 1 to 4 straight or branched alkyl groups or supports And represent a hydrocarbon group, provided that at least one of R ₁₂₂ ~ R ₁₂₅ represents an alicyclic hydrocarbon group.)

(2) In the above (1), Z in the general formula (II) comprises an atomic group for forming a cyclic bridged alicyclic structure which may include two carbon atoms (CC) bonded and may have a substituent. The positive photoresist composition for far ultraviolet exposure which is shown.

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

In formulas (II-A) and (II-B):

R ₁₃ to R ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (R ₅ means the same as described above), a group decomposed by the action of an acid, -C (= O ) -XAR ₁₇ or an alkyl or cyclic hydrocarbon group which may have a substituent. In addition, two or more of R ₁₃ to R ₁₆ may be bonded to each other to form a ring. n represents 0 or 1. Here, X and A have the same meanings as described above, respectively. R ₁₇ is -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 , R ₆ are respectively The same meaning as described above) or the -Y group.

Hereinafter, the compound used for this invention is demonstrated in detail.

(A) A compound which generates an acid by irradiation of actinic light or radiation (photoacid generator)

The photoacid generator used in the present invention is a compound that generates an acid by irradiation with actinic light or radiation.

Compounds that decompose upon irradiation of actinic rays or radiation used in the present invention to generate an acid include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photopigmentants for pigments, photochromic agents, microresists, and the like. Acid is generated by known light (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g rays, h rays, i rays, KrF excimer laser light), ArF excimer laser light, electron beams, X rays, molecular rays or ion beams. The compound and mixtures of these can be selected suitably and used.

In addition, as a compound which generates an acid by irradiation of actinic light or radiation used in the present invention, for example, SI Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), TS Bal et al., Polymer , 21, 423 (1980), etc., diazonium salts, U.S. Patent Nos. 4,069,055, 4,069,056 and Re27,992, Japanese Patent Laid-Open No. 3 Ammonium salts described in -140140 et al., DC Necker et al., Macromolecules , 17, 2468 (1984), CS Wen et al., Teh, Proc. Conf. Rad. Phosphonium salts described in Curing ASIA , p. 478, Tokyo, Oct. (1988), US Pat. Nos. 4, 069, 055 and 4,069,056, JV Crivello et al., Macromolecules , 10 (6) 1307 (1977) , Chem. & Eng. News , Nov. 28, p. 31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, and U.S. Patent Nos. 410, 201, Japanese Patent Application Laid-Open No. 2-150848, 2-296514, JV Crivello et al., Polymer J. , 17, 73 (1985), JV Crivello et al., J. Org. Chem. , 43, 3055 (1978), WR Watt et al., J. Polymer Sci., Polymer Chem. Ed. , 22, 1789 (1984), JV Crivello et al., Polymer Bull. , 14, 279 (1985), JV Crivello et al., Macromolecules , 14 (5), 1141 (1981), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 2877 (1979), European Patents 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, 297,442, U.S. Patent 3,902,114, 4,933,377, 4,760,013 Sulfonium salts described in US Pat. Nos. 4,734,444 and 2,833,827, German Patents 2,904,626, 3,604,580, and 3,604,581, Japanese Patent Application Laid-Open Nos. 7-28237, 8-27102, etc. , Macromolecules , 10 (6), 1307 (1977), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 1047 (1979) et al., CS Wen et al., Teh, Proc. Conf. Rad. Curing ASIA , p. 478, Tokyo, Oct. Onium salts such as arsonium salts described in (1988) and the like; U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60-239736, Japanese Patent Publication Japanese Patent Application Publication No. 61-169835, Japanese Patent Publication No. 61-169837, Japanese Patent Publication No. 62-58241, Japanese Patent Publication No. 62-212401, Japanese Patent Publication No. 63-70243, Japanese Patent Publication Organic halogen compounds described in 63-298339 and the like; K. Meier et al., J. Rad. Curing , 13 (4), 26 (1986), TP Gill et al., Inorg. Chem. , 19, 3007 (1980), D. Astruc, Acc, Chem. Res. , Organometallic / organic halides described in (19), 377 (1896), Japanese Patent Laid-Open No. 2-161445; S. Hayase et al., J. Polymer Sci. , 25, 753 (1987), E. Reichmanis et al., J. Polymer Sci., Polymer Chem. Ed. , 23, 1 (1985), QQ Zhu et al., J. Photochem. , 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett. , (24) 2205 (1973), DH R Barton et al., J. Chem. Soc. , 3571 (1965), PM Collins et al J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), JW Walker et al., J. Am. Chem. Soc. , 110, 7170 (1988), SC Busman et al., J. Imaging Technol. , 11 (4), 191 (1985), HM Houlihan et al., Macromolecules , 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Chem. Commun. , 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichman et al., J. Eletrochem. Soc., Solid State Sci. Technol. , 130 (6), FM Houlihan et al., Macromolecules , 21, 2001 (1988), European Patent Nos. 0,290,750, 046,083, 156,535, 271,851, and 0,388,343, US Patent 3,901,710 and Photoacid generators having o-nitrobenzyl-type protecting groups described in Japanese Patent Application Laid-Open No. 4,181,531, Japanese Patent Application Laid-Open No. 60-198538, Japanese Patent Application Laid-Open No. 53-133022, and the like; M. TUNOOKA et al., Polymer Preprints Japan , 35 (8), G. Berner et al., J. Rad. Curing , 13 (4), WJ Mijs et al., Coating Technol. , 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan , 37 (3), European Patent Nos. 0,199,672, 84,515, 044,115, 618,564 and 0,101,122 Iminosulfonates described in US Patent Nos. 4,371,605 and 4,431,774, Japanese Patent Publication No. 64-18143, Japanese Patent Publication No. 2-245756, Japanese Patent Publication No. Hei 3-140109, and the like. Compounds which are photolyzed to produce sulfonic acid, disulfone compounds disclosed in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application Laid-Open No. 2-71270, Japanese Patent Application Laid-Open No. 3-103854, Japanese Patent No. 3-103856, The diazo keto sulfone and the diazo disulfone compound as described in 4-210960 etc. are mentioned.

In addition, groups which generate an acid by such light or a compound in which the compound is introduced into the main chain or the side chain of the polymer, for example, M. E. Woodhouse et al, J. Am. Chem. Soc., 104, 5586 (1982), S. P. Pappas et al, J. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al, Makromol. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al, Makromol. Chem., 152, 153, 163 (1972), J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), US Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Publication No. 63-26653, 55-164824, 62-69263, 63-146038, The compound described in the 63-163452, 62-153853, 63-146029, etc. can be used.

See also V. N. R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetra hedron Lett., (47), 4555 (1971), D. H. R. Barton et al, J. Chem. Soc., (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 and the like can also be used to generate an acid by the light.

Among the compounds which decompose upon irradiation with actinic light or radiation and generate an acid, those which are used particularly effectively will be described below.

(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds are specifically mentioned, It is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by general formula (PAG4).

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

R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group. Preferred are C6-C14 aryl groups, C1-C8 alkyl groups, and substituted derivatives thereof. Preferred substituents for the aryl group include 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 hydroxyl group and a halogen atom, and the substituents for the alkyl group include an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group. to be.

Z ^- is shown to mate the anion, for example BF ₄ ^-, AsF ₆ ^{-. _{PF 6 -, SbF 6 -,}} SiF 6 2-, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, a pentafluoro-benzenesulfonic acid anion, naphthalene-1-sulfonic acid anion such as condensed polynuclear aromatic sulfonic acid Although an anion, anthraquinone sulfonic acid anion, a sulfonic acid group containing dye, etc. are mentioned, It is not limited to this.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Although the compound shown below as a detailed example is not limited to this.

The onium salts represented by the formulas (PAG3), (PAG4) are known and are described, for example, in JW Knapczyk et al., J. Am. Chem. Soc. , 91, 145 (1969), AL Maycok et al., J. Org. Chem. , 35, 2532 (1970), E. Goethas et al., Bull. Soc. Chem. Belg. , 73, 546 (1964), HM Leicester, J. Ame. Chem. Soc. 51, 3587 (1929), JV Crivello et al., J. Polym. Chem. Ed. , 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, and Japanese Patent Application Publication No. 53-101331.

(3) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formulas, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group, an aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is a detailed example, it is not limited to this.

The amount of the compound which is decomposed by irradiation of actinic rays or radiation to generate an acid is generally used in the range of 0.001 to 40% by weight based on the total weight of the resist composition (excluding the coating solvent). Preferably 0.01 to 20% by weight, more preferably used in the range of 0.1 to 5% by weight. When the amount of the compound that is decomposed by actinic radiation or radiation to generate an acid is less than 0.001% by weight, the sensitivity is lowered. When the amount of the compound that is added is more than 40% by weight, the light absorption of the resist is too high, and the profile is deteriorated or the process ( Especially baking process) margin becomes narrow and it is unpreferable.

Next, (B-1) one or more of the repeating units represented by the general formulas (Ia) and (Ib) and the repeating unit represented by the general formula (II), and the action of the acid A polymer having a group decomposed by (hereinafter, simply referred to as polymer (B-1)) will be described.

In the general formula (Ia), R ₁ and R ₂ are each individually a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , the alkyl group, the alkoxy group or the cyclic hydrocarbon group which may be substituted, or the said -Y group is represented. Here, R <_5> represents the alkyl group, cyclic hydrocarbon group, or the said -Y group which may have a substituent. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

In the -Y group, R ₂₁ to R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 or 2.

X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-.

A represents a single bond or a divalent linking group.

In Formula (Ib), Z ₂ represents -O- or -N (R ₃ )-, wherein R ₃ represents a hydrogen atom, a hydroxyl group or -OSO ₂ -R ₄ . R ₄ represents an alkyl group, haloalkyl group, cycloalkyl group or camphor residue.

As said alkyl group in said R <_1> , R <_2> , R <_4> , R <_5> , R <_6> -R <_21> -R <_30> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is C1-C6 Linear or branched alkyl groups, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or t-butyl.

As said cyclic hydrocarbon group in said R <_1> , R <_2> , R <_5> , R <_6> , a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2-methyl- 2-adamantyl group, a norbornyl group, a boro And a vinyl group, isoboroyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and the like.

As an alkoxy group in said R <_1> , R <_2> , C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned.

Examples of the haloalkyl group for R ₄ include trifluoromethyl group, nonafluorobutyl group, pentadecafluorooctyl group, trichloromethyl group and the like. A cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned as a cycloalkyl group in said R <_4> .

Examples of other substituents for the alkyl group, cyclic hydrocarbon group and alkoxy group include hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group and acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, acyl group include formyl group and acetyl group, and acyloxy group include acetoxy group and the like. Can be mentioned.

Examples of the divalent linking group of A in General Formulas (Ia) and (Ib) include an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, There is a single or a combination of two or more groups selected from the group consisting of urea groups.

Examples of the alkylene group and substituted alkylene group in the A group include groups represented by the following formulas.

-[C (R _a ) (R _b )] _r-

In formula, R _<a> , R <_b> represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and these may be same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, an alkoxy group, etc. are mentioned. 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. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned. r represents the integer of 1-10.

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

Specific examples of the repeating unit represented by General Formula (Ib) include the following [I'-1] to [I'-7], but the present invention is not limited to these specific examples.

In the general 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 represents the atomic group for forming the alicyclic structure which may contain 2 carbon atoms (CC) couple | bonded and may have a substituent.

Examples of the halogen atom in R ₁₁ and R ₁₂ include a chlorine atom, bromine atom, fluorine atom and iodine atom.

As said alkyl group in said R <_11> , R <_12> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl, t-butyl group.

As another substituent of the alkyl group in said R <_11> , R <_12> , a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, etc. are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. A formyl group, an acetyl group, etc. are mentioned. And as an acyloxy group, an acetoxy group etc. are mentioned.

The atomic group for forming the alicyclic structure of Z is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and among them, a pedestrian alicyclic group forming a repeating unit of an aliphatic alicyclic hydrocarbon. Atom groups for forming the formula structure are preferred.

As a skeleton of the alicyclic hydrocarbon formed, what is represented by the following structure is mentioned.

As the skeleton of the preferred cyclic alicyclic hydrocarbon, (5), (6), (7), (9), (10), (13), (14), (15) and (23) in the above structure. , (28), (36), (37), (42), and (47).

The skeleton of the alicyclic hydrocarbon may have a substituent. As such a substituent, R <_13> -R <_16> in the said general formula (II-A) or (II-B) is mentioned.

Among the repeating units having the above-mentioned alicyclic hydrocarbons, the repeating units represented by the general formula (II-A) or (II-B) are more preferable, thereby improving the pattern resolution of contact hole patterns and the like. You can.

In formula (II-A) or (II-B), each of R ₁₃ to R ₁₆ is a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (even if R ₅ has a substituent) A good alkyl group, a cyclic hydrocarbon group or the same -Y group as in the general formula (I)), a group decomposed by the action of an acid, -C (= O) -XAR ₁₇ , or an alkyl group which may have a substituent Or a cyclic hydrocarbon group. n represents 0 or 1. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , or -NHSO ₂ NH-. R ₁₇ is -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 , R ₆ is The same meaning as the above) or -Y group of the general formula (Ia). A represents a single bond or a divalent linking group.

In the polymer (B-1), the acid-decomposable group may be included in the above -C (= O) -X-AR ₁ , -C (= O) -XAR ₂ , and included as a substituent of Z in general formula (II). You may be.

The structure of the acid-decomposable group is represented by -C (= 0) -X ₁ -R ₀ .

In formula, R <_0> is tertiary alkyl groups, such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. Alkoxymethyl groups, such as 1-alkoxyethyl group, 1-methoxymethyl group, 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, and 3-oxocyclohexyl ester group , 2-methyl-2-adamantyl group, mevalonic lactone residue, 2- (γ-butyrolactyl ylcarbonyl) -2-propyl group, and the like. X ₁ has the same meaning as X.

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

As said alkyl group in said R <_13> -R <_16> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

As said cyclic hydrocarbon group in said R <_13> -R <_16> , it is a cyclic alkyl group and a piercing hydrocarbon, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and 2-methyl- 2-adamantyl group And norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and the like.

Examples of the ring formed by bonding two or more of R ₁₃ to R ₁₆ to each other include a C 5-12 ring such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

As an alkoxy group in said R <_17> , C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned.

Examples of other substituents in the 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 a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and acyl group include formyl group and acetyl group, and acyloxy group includes acetoxy group. .

As the divalent linking group of A, similarly to the divalent linking group of A in General Formula (Ia), a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide Group, sulfonamide group, urethane group, and urea group are selected from the group consisting of single or two or more groups.

Examples of the alkylene group and substituted alkylene group for A include the same as those for the divalent linking group of A in General Formula (Ia).

In the polymer (B-1), the group decomposed by the action of an acid is a repeating unit represented by general formula (Ia), a repeating unit represented by general formula (Ib), a repeating unit represented by general formula (II), and It may be contained in one or more repeating structural units of the repeating units of the following copolymerization component.

The various substituents of R ₁₃ to R ₁₆ in the general formula (II-A) or (II-B) form an atomic group or a pedophilic alicyclic structure for forming an alicyclic structure in the general formula (II). It consists of a substituent of the atomic group Z to make.

Specific examples of the repeating unit represented by General Formula (II-A) or (II-B) include the following [II-1] to [II-166], but the present invention is not limited thereto.

The polymer (B-1) is formula (IV '), (V) for the purpose of controlling dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general requirements of resist. It may preferably include a repeating unit represented by ').

Wherein Z represents an oxygen atom, -NH-, -N (-R ₅₀ )-, -N (-OSO ₂ R ₅₀ )-, and R _{50 is} also a (substituted) alkyl group having the same meaning as described above, ( Substituted) means a cyclic hydrocarbon group.

As specific examples of the repeating unit represented by the general formulas (IV ') and (V'), the following [IV'-9] to [IV'-16], [V'-9] to [V'-16] Although these are mentioned, It is not limited to these specific examples.

Next, a polymer (B-2) having a repeating unit represented by the general formula (pA) and having a group decomposed by the action of an acid (hereinafter simply referred to as polymer (B-2)) will be described. do.

In the general formulas (pI) to (pVI), the alkyl group represented by R ₁₁₂ to R ₁₂₅ represents a straight or branched alkyl group having 1 to 4 carbon atoms, which may be either substituted or unsubstituted. As this alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group etc. are mentioned, for example.

In addition, other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group And nitro groups.

The alicyclic hydrocarbon group or the alicyclic hydrocarbon group formed by Z and a carbon atom in R ₁₁₁ to R ₁₂₅ may be monocyclic or polycyclic. Specifically, the group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. Such alicyclic hydrocarbon group may have a substituent.

Below, the structural example of an alicyclic part is shown in an alicyclic hydrocarbon group.

In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noadamantyl group, a decarin residue group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group and a cyclohep A methyl group, a cyclooctyl group, a cyclo decanyl group, and a cyclododecanyl group are mentioned. More preferably, they are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Substituents of such alicyclic hydrocarbon groups include alkyl groups, substituted alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably represents a substituent selected from the group consisting of methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

As mentioned above, although general formula (pI)-(pVI) are demonstrated in detail, it is preferable that Ra is group represented by general formula (pII) among general formula (pI)-(pVI), and this is a halftone phase shift mask. In the case of forming a contact hole pattern by using, a resist composition for far ultraviolet rays having high resolution can be obtained.

Hereinafter, the specific example of the monomer corresponding to the repeating unit represented by general formula (pA) is shown.

In the said resin, you may contain other repeating units other than the repeating unit which holds the carboxylic acid group protected by the structure represented by the said general formula (pI)-(pVI).

Preferable as such other repeating units are repeating units represented by the following general formula (AI).

R has the same meaning as described above. B represents a halogen atom, a cyano group, a group decomposed by the action of an acid, -C (= O) -YAR _C9 or -COOR _C11 .

Y is a divalent bond group selected from oxygen atom, sulfur atom, -NH-, -NHSO _2- , -NHSO ₂ NH-,

R _C9 : -COOH, -COOR _C10 (R _C10 has the same meaning as R _C11 and represents the following lactone structure), -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R _C11 , -CO-NH-SO ₂ -R _C11 or the following lactone structure is represented.

R _C11 : an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent,

A: single or combination of two or more groups selected from the group consisting of a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group Is displayed.

Ra to Re each independently represent a C1-4 straight or branched alkyl group which may have a hydrogen atom or a substituent. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.

The group decomposed by the action of the acid is preferably a group represented by -C (= 0) -X ₁ -R 0. Here, as R0, tertiary alkyl groups, such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. And alkoxymethyl groups such as 1-alkoxyethyl group, 1-methoxymethyl group and 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl group, and 3-oxocyclohexyl group. X ₁ represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , -NHSO ₂ NH-, but an oxygen atom is preferable.

As said alkyl group, a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, a propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group and t-butyl group.

As said cyclic hydrocarbon group, it is a cyclic alkyl group and a piercing hydrocarbon, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a boronyl group, an isoboroyl group, a tricyclo decanyl group, a dicyclopentenyl group And a norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group, etc. are mentioned.

Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Examples of other substituents for the alkyl group, cyclic alkyl 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 alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, but acyl groups include formyl group and acetyl group, and acyloxy group include acetoxy group and the like. Can be mentioned.

Examples of the alkylene group and substituted alkylene group of A in Formulas (AI) and (pA) include the groups shown below.

[C (Rf) (Rg)] r-

Food,

Rf, Rg: represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and the two may be the same or different, and an alkyl group may be a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group. Is preferred, and more preferably a substituent selected from the group consisting of methyl, ethyl, propyl and isopropyl groups. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. 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. r represents the integer of 1-10.

In the above, the halogen atom includes chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

As said B, group represented by an acid-decomposable group and -COOR _C9 (lactone structure) is preferable.

Also in the structure represented by said general formula (pI)-(pVI), general formula (pII) is preferable and an adamantyl group is preferable as an alicyclic group.

It is preferable that a polymer (B-2) further contains the repeating structural unit represented by the following general formula (III-a)-(III-d). By this, problems due to the hydrophobicity of the resist composition can be improved.

R <_1> is synonymous with R of the said general formula (pA) in said Formula (III-a)-(III-d). R ₅ to R ₁₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group which may have a hydrogen atom or a substituent. m represents the integer of 1-10.

X is selected from the group consisting of alkylene groups, cyclic alkylene groups, arylene groups or ether groups, thioether groups, carbonyl groups, ester groups, amide groups, sulfonamide groups, urethane groups, and urea groups which may have a single bond or a substituent A divalent group which is not decomposed by the action of an acid, alone or in combination of two or more of these groups, is represented.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group combining these. R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group in combination thereof. R <_15> represents an alkylene group, an arylene group, or the bivalent group which combined these. R <_14> represents the alkyl group, cyclic alkyl group, aryl group, or aralkyl group which may have a substituent. R <_16> represents the alkyl group, cyclic alkyl group, alkenyl group, aryl group, or aralkyl group which may have a hydrogen atom or a substituent.

A represents either of the functional groups shown below.

In general formula (III-a)-(III-d), the alkyl group of R <_3> -R <_10> , R, R <_12> , R <_14> may be linear or branched, and may have a substituent. As said linear or branched alkyl group, it is preferable that it is C1-C12, More preferably, it is C1-C10, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl The group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group can be mentioned preferably.

The cyclic alkyl group represented by R, R ₁₂ and R ₁₄ has 3 to 30 carbon atoms, and specific examples thereof include cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and tri Cyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclo dodecanyl group, a steroid residue, etc. can be mentioned.

The aryl group for R, R ₁₂ and R ₁₄ has one having 6 to 20 carbon atoms, and may have a substituent. Specifically, there are a phenyl group, tolyl group, and naphthyl group.

Aralkyl groups of R, R ₁₂ and R ₁₄ have one having 7 to 20 carbon atoms, and may have a substituent. Specifically, there are benzyl group, phenethyl group and cumyl group.

The alkenyl group of R ₁₄ includes an alkenyl group having 2 to 6 carbon atoms, and specifically, a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 3- Oxocyclohexenyl group, 3-oxocyclopentenyl group, 3-oxoindenyl group, and the like. Among these, the cyclic alkenyl group may contain an oxygen atom.

The linking group X may be a single group selected from the group consisting of an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group and a urea group which may have a substituent. Or a combination of at least two or more of these groups is a divalent group that does not decompose under the action of an acid.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group or a divalent group in which these are combined.

R ₁₁ represents a single bond, an alkylene group, an arylene group or a divalent group in which these are combined.

R ₁₃ represents an alkylene group, an arylene group or a divalent group in which these are combined.

In X, R _11, R _13, arylene group is there that the carbon number of 6-10 and may further have a substituent. Specifically, there are phenylene group, tolylene group and naphthylene group.

As X cyclic alkylene group, there exist some in which the above-mentioned cyclic alkylene group becomes bivalent.

X, The alkylene group in Z, R ₁₁ and R ₁₃ has the same meaning as A in General Formula (pA).

Although the specific example of the connector X is shown below, it is not limited to this.

Further substituents of the alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group, arylene group include carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxy group , Acetylamide group, alkoxycarbonyl group and acyl group.

Examples of the alkyl group include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropyl group, cyclobutyl group and cyclopentyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. 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. An acetoxy group etc. are mentioned as said acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom.

Hereinafter, although the structure of the side chain in which X was excluded as a specific example of the side chain structure of general formula (III-b) is shown below, this invention is not limited to this.

Hereinafter, although the detailed example of the monomer corresponding to the repeating structural unit represented by general formula (III-c) is shown, this invention is not limited to this.

Hereinafter, although the specific example of the repeating structural unit represented by general formula (III-d) is shown, this invention is not limited to this.

In general formula (III-b), as R <_3> -R <_10> , a hydrogen atom and a methyl group are preferable. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1-6 of m is preferable.

In general formula (III-c), R ₁₁ is preferably a single bond, an alkylene group such as methylene group, ethylene group, propylene group or butylene group, and R ₁₂ is alkyl group having 1 to 10 carbon atoms such as methyl group and ethyl group, cyclo Cyclic alkyl groups, such as a propyl group, a cyclohexyl group, and camphor residue, a naphthyl group, and a naphthyl methyl group are preferable. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond.

In general formula (III-d), as R <_13> , a C1-C4 alkylene group is preferable. R ₁₄ is an alkyl group having 1 to 8 carbon atoms, cyclohexyl group, adamantyl group, norbornyl group, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, neopentyl group and octyl group which may have a substituent; Boronyl group, isoboroyl group, menthyl group, morpholino group, 4-oxocyclohexyl group, phenyl group which may have a substituent, toluyl group, menthyl group, naphthyl group, and camphor residue are preferable. As another substituent of this group, halogen atoms, such as a fluorine atom, a C1-C4 alkoxy group etc. are preferable.

Also in general formula (III-a)-(III-d), the repeating structural unit represented by general formula (III-b) and (III-d) is preferable.

As described above, the polymers (B-1) and (B-2) described above are in addition to the above-mentioned repeating structural unit, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity which are generally necessary characteristics of the resist. It may contain various repeating structural units for the purpose of controlling the back and the like.

Although the repeating structural unit corresponding to the following monomer is mentioned as such a repeating structural unit, It is not limited to these.

This results in performance required for acid-decomposable resins, in particular

(1) solubility in coating solvents,

(2) Film forming property (glass transition point)

(3) alkali developability

(4) Membrane loss (choose hydrophilic, alkali soluble group)

(5) Adhesion to Substrate of Unexposed Part

(6) dry etching resistance

Fine adjustment of the back and the like becomes possible.

As such a monomer, for example, one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. The compound etc. which are held are mentioned.

Specifically, the following monomers can be illustrated.

Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group):

Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxy Propyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylic acid esters (preferably alkyl methacrylate having 1 to 10 carbon atoms in the alkyl group):

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monometha Methacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides:

Acrylamide, N-alkyl acrylamide (The alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, etc. N, N-dialkylacrylamide (as 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-methacrylamide, N-2-acetamideethyl-N-acetylacrylamide, and the like.

Methacrylamides:

Methacrylamide, N-alkyl methacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N , N-dialkyl methacrylamide (the alkyl group includes ethyl group, propyl group, butyl group and the like), N-hydroxyethyl-N-methylmethacrylamide and the like.

Allyl Compounds:

Allyl esters (for example, allyl acetate, allyl capronate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearic acid, allyl benzoate, allyl benzoate, allyl lactate, etc.), allyloxyethanol, and the like.

Vinyl ethers:

Alkyl vinyl ether (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofur Furyl vinyl ether and the like.

Vinyl esters:

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl varate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetate acetate, vinyl lactate, Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Itaconic acid dialkyls:

Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like

Other crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleylonitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound which can copolymerize with the monomer corresponding to the said various repeating structural unit, it may be copolymerized.

In the polymers (B-1) and (B-2), the molar ratio of each repeating structural unit is determined by the dry etching resistance of the resist, the standard developer suitability, the substrate adhesion, the resist profile, or the resolution, heat resistance, It is appropriately set to adjust the sensitivity and the like.

In the polymer (B-1), a repeating unit represented by general formula (Ia) and / or general formula (Ib), and general formula (II) (General formula (II-A) and general formula (II-B) Content of the repeating unit can be appropriately set in consideration of dry etching resistance, sensitivity of the desired resist, prevention of pattern cracking, substrate adhesion, resist profile, or resolution, heat resistance, which is a requirement of a general resist. have. In general, the content of 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) in the polymer (B-1) are the polymers (B-1), respectively. 25 mol% or more of all the monomer repeating units of is suitable, Preferably it is 30 mol% or more, More preferably, it is 35 mol% or more.

In addition, in the polymer (B-1), the content in the resin of the repeating unit (General Formula (IV ′) or General Formula (V ′)) derived from the above preferred copolymerization monomer may be appropriately set depending on the performance of the desired resist. Generally, 99 mol% or less is preferable with respect to the total number of moles which added the repeating unit represented by general formula (Ia) and / or general formula (Ib), and the repeating unit represented by general formula (II), and is more preferable. Preferably it is 90 mol% or less, Most preferably, it is 80 mol% or less.

Moreover, although content in resin of the repeating unit based on the monomer of the said other copolymerization component can also be set suitably according to the performance of a desired resist, it is generally represented by general formula (Ia) and / or general formula (Ib). It is preferably 99 mol% or less, more preferably 90 mol% or less, and most preferably 80 mol% or less based on the total moles of the total number of units and the repeating unit represented by the general formula (II). If the amount of repeating units based on monomers of such other copolymerization components exceeds 99 mol%, the effect of the present invention is not sufficiently expressed, which is not preferable.

In the polymer (B-1), the group decomposed by the action of an acid is a repeating unit represented by the general formula (Ia) and / or the general formula (Ib), a repeating unit represented by the general formula (II), or copolymerization. Although it may contain in any of the repeating units based on the monomer of a component, 8-60 mol% of all the repeating units of resin are suitable for content of the repeating unit containing the group decomposed by the action of an acid, and it is preferable. Preferably it is 10-55 mol%, More preferably, it is 12-50 mol%.

The polymer (B-1) 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 copolymerization component when using a copolymerization component and copolymerizing in the presence of a polymerization catalyst. The repeating unit derived from maleic anhydride of a copolymer can be synthesize | combined also by ring-opening-esterifying with an alcohol, or hydrolyzing under basic or acidic conditions, and converting the carboxylic acid site | part produced after this into a desired substituent. .

The weight average molecular weight of polymer (B-1) is polystyrene conversion value by GPC method, Preferably it is 1,000-200,000. If the weight average molecular weight is less than 1,000, deterioration of heat resistance or dry etching resistance is confirmed, which is not preferable. If the weight average molecular weight is more than 200,000, developability deteriorates or the viscosity becomes very high, resulting in unfavorable film formation. .

In the positive photoresist composition for far ultraviolet exposure of the present invention, the blending amount of the polymer (B-1) in the whole composition is preferably 5 to 98% by weight, more preferably 7 to 95% by weight, of the total resist solids. Preferably it is 10-92 weight%.

On the other hand, as for content of the repeating structural unit containing the alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in a polymer (B-2), 30-70 mol% is preferable in all the repeating structural units, More preferably, it is 35-65 mol%, More preferably, it is 40-60 mol%.

 As for content of the repeating structural unit represented by general formula (III-a)-(III-d) in a polymer (B-2), 0-20 mol% is preferable in all the repeating structural units, More preferably, it is 0- It is 18 mol%, More preferably, it is 0-16 mol%.

 Content of the acid-decomposable group containing repeating structural unit other than the repeating structural unit containing the alkali-soluble group protected by the structure represented by said general formula (pI)-(pVI) in a polymer (B-2) is all the repeating structural units 0-20 mol% is preferable, More preferably, it is 0-18 mol%, More preferably, it is 0-16 mol%.

As for content of the repeating structural unit containing a lactone structure in a polymer (B-2), 20-70 mol% is preferable in all the repeating structural units, More preferably, it is 25-65 mol%, More preferably, it is 30-60 Molar%.

Moreover, although content in resin of the repeating structural unit based on the monomer of the said other copolymerization component can also be set suitably according to the performance of a desired resist, it is generally protected by the structure represented by said general formula (pI)-(pVI). It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total moles of the total number of repeating structural units containing the alkali-soluble group.

The weight average molecular weight of the polymer (B-2) is a polystyrene conversion value by the GPC method, preferably in the range of 3,000 to 100,000, more preferably 4,000 to 70,000, even more preferably 5,000 to 50,000, the larger the heat resistance and the like. While this improves, developability and the like are lowered, the balance is adjusted to a preferred range.

In the positive photoresist composition for far-ultraviolet exposure of the present invention, the blending amount of the polymer (B-2) in the whole composition is preferably 2 to 95% by weight, more preferably 5 to 90% by weight, more preferably in the total resist solids. Is 10 to 80% by weight.

The content of the monomer component of the polymer (B-1) and the polymer (B-2) is 5% or less of the total pattern area of gel permeation chromatography (GPC), preferably 0.01 to 4%, more preferably 0.1 ˜3%. Here, as GPC, Shodex system-11 by Showa Denko Co., Ltd. can be used, for example. By making the content of the monomer contained in an acid-decomposable resin into the said content, the high sensitivity, the outstanding edge roughness, and the pattern profile were obtained with the photoresist composition.

In the positive photoresist composition for far ultraviolet exposure of the present invention, [polymer (B-1) (weight)] / [polymer (B-2) (weight)] is 95/5 in view of the effects of the present invention and etching resistance. -10/90 is preferable, More preferably, it is 95/5-10/90, More preferably, it is 90/10-20/80.

Although the polymers (B-1) and (B-2) used for this invention can be synthesize | combined by a general method (for example, radical polymerization), it is preferable to set it as the said specific monomer amount, and it is preferable to use following (i)-( by synthesizing or recovering using one or more of the means of iv).

(i) A reaction solution containing each monomer and a radical initiator is added dropwise to a reaction solvent or a reaction solution containing a monomer to cause a polymerization reaction.

(ii) A radical initiator is added to the reaction solution containing each monomer over 30 minutes to 8 hours for polymerization reaction.

(iii) After the reaction solution containing each monomer and the radical initiator is heated and polymerized, the radical initiator is added thereto again and heated to polymerize.

(iv) After the completion of the polymerization reaction, the reaction solution is water or alcohol, at least one of alcohol, water / alcohol, water / ether, water / ketone, water / amide, water / ester or lactone, water / nitrile It is put into at least one liquid selected from the group and collected in powder.

In this invention, it is especially preferable that the combination of the means of i) and iii), the combination of ii) and iii), or these and the means of iv) is combined among the said means.

Specific synthesis methods are described below.                     

The dropping method (the method of (i) mentioned above) is added dropwise to the reaction solvent which is added to the reaction solvent at the same time as the initiator, and a part of the reaction solvent or monomer heated to the desired temperature under nitrogen atmosphere is added to the reaction solvent. )

After adding the monomer to react to a reaction solvent, making it uniform, and heating and stirring in nitrogen atmosphere to a desired temperature, and then polymerizing-reacting by adding a radical initiator at predetermined time (method of said (ii)), And

The monomer to be reacted is added to the reaction solvent to make it uniform, heated and stirred under a nitrogen atmosphere to a desired temperature, and then a radical initiator is added in a batch to polymerize, followed by addition of the initiator (in (iii) Method)
These may be mentioned alone or in combination.

Preferred is the dropping method of (i). By selecting the dropping method of (i), although it is not certain about the specific part yet, all the characteristics of the resist which give priority to the resolution and edge roughness which are the effect of this invention improve further.

In this invention, although the reaction temperature in each said reaction can be set suitably according to the kind of initiator, 30 degreeC-180 degreeC is common. Preferably it is 40 degreeC-160 degreeC, More preferably, it is 50 degreeC-140 degreeC.

The dropping time in the case of employing the dropping method of (i) can be set in various ways depending on the reaction temperature, the type of initiator, and the monomer to be reacted, but it is 30 minutes to 8 hours. Preferably it is 45 minutes-6 hours, More preferably, it is 1 hour-5 hours.

In the method of (i), when dropping into a solution containing a monomer, the content of the monomer in the dropping solution is preferably 30 mol% or more relative to the total amount of the monomer in (dropping solution + dropping solution), more Preferably it is 50 mol% or more, More preferably, it is 70 mol% or more.

Initiation time of the initiator in the case of employing the method of (ii) can be set in various ways depending on the reaction temperature, the type of initiator, and the monomer to be reacted, but it is 30 minutes to 8 hours. Preferably it is 45 minutes-6 hours, More preferably, it is 1 hour-5 hours. In the method of (ii), the injection interval of the initiator is preferably 10 minutes to 3 hours, more preferably 20 minutes to 2 hours 30 minutes, and most preferably 30 minutes to 2 hours. Moreover, as for the said input frequency, 2 times-20 times are preferable, 3 times-15 times are more preferable, More preferably, they are 4 times-10 times.

In addition, in the method of (ii) or (iii), after completion of the initiator addition, the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a predetermined time. In addition, in the case of the dropping method of (i), the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a predetermined time after completion of dropping. The heating time varies depending on the reaction temperature and the type of initiator, but generally within 10 hours. Preferably it is within 8 hours, More preferably, it is within 6 hours.

In any case, the method of adding a 2nd initiator after this heating stirring for a certain time is preferable. By using the addition of the initiator, it is not sure to the specific part, but as a result, the sensitivity, resolution and edge roughness are improved. After adding the initiator, the mixture is heated and stirred for a predetermined time. Moreover, you may raise reaction temperature after adding an initiator.

The solvent used in the reaction can be used as long as it is not a solvent such as dissolving the monomer species to be used and inhibiting the polymerization (for example, no polymerization, for example, nitrobenzene, chain transfer, for example, mercapto compound). have. Examples thereof include alcohols, ethers, ketones, amides, esters and lactones, nitriles, and mixtures thereof. Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol. Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane. Acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone are mentioned as ketones. Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. Ester and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone. Examples of the nitriles include acetonitrile, propionitrile and butyronitrile.

Preferred solvents include 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 1,3-dioxane And methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone and acetonitrile.

Mixed solvents include alcohols and ethers, alcohols and ketones, alcohols and amides, alcohols and esters and lactones, ethers, ethers and ketones, ethers and amides, ethers and esters and lactones, Ethers and nitriles, ketones and amides, ketones and esters and lactones, ketones and nitriles, amides and esters and lactones, amides and nitriles, esters and lactones and nitriles have.

Preferred mixed solvent systems include 1-methoxy-2-propanol and tetrahydrofuran, 1-methoxy-2-propanol and 1,4-dioxane, 1-methoxy-2-propanol and 1,3-dioxolane , 1-methoxy-2-propanol and 1,3-dioxane, 1-methoxy-2-propanol and methyl ethyl ketone, 1-methoxy-2-propanol and N, N-dimethylformamide, 1-methoxy Methoxy-2-propanol and N, N-dimethylacetamide, 1-methoxy-2-propanol and γ-butyrolactone, ethylene glycol monomethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether and 1,4-di Oxane, ethylene glycol monomethyl ether, 1,3-dioxolane, ethylene glycol monomethyl ether, 1,3-dioxane, ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol monomethyl ether, N, N-dimethyl Formamide, ethylene glycol monomethyl ether and N, N-dimethylacetamide, ethylene glycol monomethyl ether, γ-butyrolactone, and ethylene glycol mono Tyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, 1,4-dioxane, ethylene glycol monoethyl ether, 1,3-dioxolane, ethylene glycol monoethyl ether, 1,3-dioxane, ethylene glycol mono Ethyl ether, methyl ethyl ketone, ethylene glycol monoethyl ether, N, N-dimethylformamide, ethylene glycol monoethyl ether, N, N-dimethylacetamide, ethylene glycol monoethyl ether, γ-butyrolactone, tetrahydrofuran And 1,4-dioxane, tetrahydrofuran and 1,3-dioxolane, tetrahydrofuran and 1,3-dioxane, tetrahydrofuran and methyl ethyl ketone, tetrahydrofuran and N, N-dimethylformamide Tetrahydrofuran and N, N-dimethylacetamide, tetrahydrofuran and γ-butyrolactone, tetrahydrofuran and acetonitrile, methyl ethyl ketone and N, N-dimethylformamide, methyl ethyl ketone and N, N- Dimethylacetamide, Meth Methyl ethyl ketone and γ-butyrolactone, methyl ethyl ketone and acetonitrile, N, N-dimethylformamide and γ-butyrolactone, N, N-dimethylacetamide and γ-butyrolactone, and N, N-dimethyl Formamide and acetonitrile, N, N-dimethylacetamide and acetonitrile, γ-butyrolactone and acetonitrile.

The amount of the reaction solvent varies depending on the target molecular weight, the monomer used, and the type of initiator used, but in consideration of the solution of the monomer and the solvent, the monomer concentration is generally 12% by weight to 30% by weight, preferably 14% by weight 28 weight%, More preferably, they are 16 weight%-26 weight%.

In addition, there exist some shown below as a radical initiator which can be used for the polymerization reaction in this invention.

As a radical initiator, what is generally used, such as a peroxide or an azo initiator, can be used. Preferred are azo initiators. Azo initiators include 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azo Bis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane -1-carbonitrile), 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-2-propenylpropionamimi Di)) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2-methyl-N -[1-1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, dimethyl-2,2'-azobis (2-methylpropionate), 4,4'-azobis (4 Cyano valeric acid) and 2,2'-azobis (2- (hydroxymethyl) propionitrile).

Preferred radical initiators include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile ), 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanobarer) Acid), 2,2'-azobis (2-hydroxymethyl) propionitrile).

In the present invention, the polymer (resin) obtained after the polymerization reaction as described above is preferably recovered by the reprecipitation method. That is, after completion | finish of superposition | polymerization, a reaction liquid is thrown into a reprecipitating liquid and collects target resin as powder.

Examples of the reprecipitation liquid include water, alcohols, ethers, ketones, amides, esters, lactones, and nitriles alone and mixtures thereof. Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol and 1-methoxy-2-propanol. Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. . Examples of the esters and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone. Examples of nitriles include acetonitrile, propionitrile and butyronitrile.

Examples of the mixed liquid system include alcohol mixed liquid systems, water / alcohols, water / ethers, water / ketones, water / amides, water / esters, lactones, and water / nitrile.

Specifically, methanol and ethanol, methanol and propanol, methanol and isopropanol, methanol and butanol, ethylene glycol and ethanol, ethylene glycol and propanol, ethylene glycol and isopropanol, ethylene glycol and butanol, and 1-methoxy-2-propanol And ethanol, 1-methoxy-2-propanol and propanol, 1-methoxy-2-propanol and isopropanol, 1-methoxy-2-propanol and butanol, water and methanol, water and ethanol, water and propanol, water and Isopropanol, water and butanol, water and ethylene glycol, water and propylene glycol, water and 1-methoxy-2-propanol, water and tetrahydrofuran, water and acetone, water and methyl ethyl ketone, water and N, N-dimethyl Formamide, water and N, N-dimethylacetamide, water and γ-butyrolactone, water and acetonitrile. The mixing ratio of the mixed liquid system is 20/1 to 1/120.

Preferred reprecipitates are at least one of water and alcohols, at least one liquid selected from the group of water / alcohols, water / ethers, water / ketones, water / amides, water / esters or lactones, water / nitriles to be.

More preferred reprecipitates include water, methanol, isopropanol, water and methanol, water and ethanol, water and propanol, water and isopropanol, water and butanol, water and ethylene glycol, water and propylene glycol, water and 1-methoxy-2- Propanol, water and tetrahydrofuran, water and acetone, water and methyl ethyl ketone, water and N, N-dimethylformamide, water and N, N-dimethylacetamide, water and γ-butyrolactone, water and acetonitrile to be. Particularly preferred are methanol and isopropanol, water and methanol, water and ethanol, water and propanol, water and isopropanol, water and ethylene glycol, water and 1-methoxy-2-propanol, water and tetrahydrofuran, water and acetone, Water and methyl ethyl ketone, water and acetonitrile.

Reprecipitation with hydrocarbon solvents represented by hexane or heptanes described in Japanese Patent Application Laid-Open Nos. 9-73173, 10-207069, and 10-274852 is extremely dangerous. However, this is not preferable because of difficulty in workability.

In addition, repeating the reprecipitation as described in, for example, Japanese Patent Application Laid-open No. Hei 10-301285 unnecessarily increases the waste liquid, does not improve the working efficiency and worsens the edge roughness. In the present invention, the number of reprecipitations is preferably one to three times, and preferably one time.

The amount of the reprecipitation liquid is appropriately set depending on the amount of solvent used in the polymerization, the type and the type of the reprecipitation liquid, but is 3 to 100 times the volume of the polymerization solution. Preferably it is 4 times-50 times, More preferably, it is 5 times-30 times. When this amount is small, it becomes difficult to separate from the powder to collect | recover, and work efficiency will worsen. In many cases, on the contrary, the waste liquid increases, which is not preferable in terms of cost.

The positive photoresist composition for far ultraviolet exposure of the present invention is dissolved in a solvent and coated on a support. As a solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Ethyl 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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Among these, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl ethoxypropionate are mixed individually or two types by the ratio of 1/9-9/1. It is preferable to use.

It is preferable to melt | dissolve solid content, such as said (A) photoacid generator, a polymer (B-1), and a polymer (B-2), in solid content concentration in the said solvent, 3 to 25%, More preferably, it is 5 to 22% Most preferably, it is 7-20%.

It is preferable that the positive photoresist composition for far-ultraviolet exposure of this invention contains a fluorine type and / or a silicon type surfactant.

The fluorine-based and / or silicon-based surfactants are at least one of fluorine-based surfactants, silicon-based surfactants, and surfactants containing both fluorine and silicon atoms.

Since the positive photoresist composition for far-ultraviolet exposure of the present invention contains the acid-decomposable resin and the surfactant, it is excellent in sensitivity, resolution, substrate adhesion, and dry etching when using an exposure light source of 250 nm or less, especially 220 nm or less. A resist pattern with little development defect and scum is obtained.

As these surfactants, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japan The interface described in Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, and Japanese Patent Laid-Open No. 9-54432 and Japanese Patent Laid-Open No. 9-5988. Although an active agent is mentioned, the following commercially available surfactant can also be used as it is.

Commercially available surfactants that can be used include, for example, Eftop EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430, 431 (manufactured by Sumimoto 3M Company), Megafac F171, F173, F176, F189, R08 (Dainipone Ink & Chemical Company), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Company), Troysol S-366 (Troy Chemicals), etc. Can be mentioned. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-based surfactant.

The compounding quantity of surfactant is 0.01 weight%-2 weight% generally based on solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%.
Such surfactant can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl. Polyoxyethylene alkylallyl ethers such as phenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, Polyoxyethylene Sorbitan Trioleate, Paul Oxy, and the like sorbitan tristearate, etc., polyoxyethylene sorbitan fatty acid non-ionic surfactants such as esters.

The compounding quantity of such surfactant is generally 2 parts by weight or less, preferably 1 part by weight or less per 100 parts by weight of the solid content in the composition of the present invention.

These surfactants may be added alone, or may be added in combination.

Preferred organobasic compounds that can be used in the present invention are compounds which are more basic than phenol. Among these, a nitrogen-containing basic compound is preferable.

Where R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aminoalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms, or a substituted or unsubstituted aryl of 6 to 20 carbon atoms. And R ²⁵¹ and R ²⁵² may combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

Further, preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, particularly preferably compounds containing both substituted or unsubstituted amino groups and ring structures containing nitrogen-containing atoms, or It is a compound which has an alkylamino group. Preferred detailed examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted imidazole, substituted or substituted Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted pipepe Razine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferable substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group.

Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethyl Aminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6 -Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4 -Amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) -pyrrolidine, pyrazole, 3 -Amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyri Midine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomol Lean, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexyl morpholinoethylthiourea (CHMETU), etc. Tertiary morpholine derivatives, hindered amines (for example, those described in the above publications) described in Japanese Patent Application Laid-Open No. 11-52575, and the like, but are not limited to these.

Particularly preferred embodiments are 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] -7-undecene 1,4-diazabicyclo [2.2 .2] tertiary moles such as octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines and CHMETU Hindered amines, such as porins and bis (1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, etc. are mentioned. By using these, the roughness dependency becomes excellent.

Among these, 1, 5- diazabicyclo [4.3.0] nona-5-ene and 1, 8- diazabicyclo [5. 4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl 4-piperidyl) sebacate is preferred.

These nitrogen-containing basic compounds may be used alone or in combination of two or more thereof. The usage-amount of a nitrogen-containing basic compound is generally 0.001-10 weight%, Preferably it is 0.01-5 weight% with respect to solid content of the whole composition of the positive photoresist composition for far ultraviolet exposure. If the amount of use is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound is not obtained. On the other hand, when the usage-amount exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

The positive photoresist composition for far ultraviolet exposure of the present invention may contain an acid decomposable dissolution inhibiting compound, a dye, a plasticizer, a sensitizer and a compound for promoting solubility in a developing solution, if necessary.

Such a positive resist composition of the present invention is applied onto a substrate to form a thin film. As for the film thickness of this thin film, 0.2-1.2 micrometers is preferable. In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, etc., and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. for film formation. As the organic antireflection film, for example, a condensation product of a diphenylamine derivative described in JP-A-7-69611 with a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorber, or U.S. Patent No. 5294680 The reactant of the maleic anhydride copolymer described above and the diamine light absorber, the resin binder described in Japanese Patent Application Laid-open No. Hei 6-118631, and the methylolmelamine-based thermal crosslinking agent; the carbohydrate described in Japanese Patent Application Laid-open No. Hei 6-118656 An acrylic resin antireflection film having an acid group, an epoxy group and a light absorber in the same molecule, comprising a methylolmelamine and a benzophenone light absorber described in JP-A-8-87115, JP-A-8-179509 The thing which added the low molecular weight absorber to the polyvinyl alcohol resin of Claim is mentioned.

In addition, as an organic antireflection film, DUV-30 series or DUV-40 series manufactured by Blue War Science Co., Ltd., AC-2 or AC-3 manufactured by Seafrey Inc. may be used.

By applying a suitable coating method such as a spinner or coater on the substrate (e.g. silicon / silicon dioxide coating) used for the manufacture of the precision integrated circuit device (on the substrate on which the antireflection film is formed, if necessary) After application | coating, a favorable resist pattern can be obtained by exposing through a predetermined | prescribed mask, baking, and developing. Here, preferable as exposure light is light of 150-250 nm wavelength. Specifically, there are KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, and the like.

As a developing solution, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 1st amines, such as ethylamine and n-propylamine, diethylamine, di-n-butylamine, etc. Tertiary ammonium salts such as secondary amines, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide, Alkaline aqueous solutions, such as cyclic amines, such as a pyrrole and a piperidine, can be used.

Furthermore, alcohols and surfactants can be added to the alkaline aqueous solution in an appropriate amount.
(Example)

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

Synthesis of Polymer (B-1) (Resins (1) to (12))

A mixture of an equimolar mixture of tetracyclododecene derivative (1-1) and maleic anhydride obtained by the reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol and cyclopentadiene diene is dissolved in tetrahydrofuran, and the solid content is 50 % Solution was prepared. This was put into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stable, 5 mol% of a radical initiator V-60 manufactured by Hwagwang Pure Chemical Co., Ltd. was added to initiate 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 white powder. The precipitated powder was collected by filtration and dried to obtain Resin (1) as a target product.

When the molecular weight analysis by GPC of the obtained resin (1) was tested, it was 6300 (weight average) in polystyrene conversion value. In addition, the NMR spectrum confirmed that the molar ratio of the tetracyclododecene repeating unit of the resin (1) to the maleic anhydride repeating unit was 50/50.

Resins (2) to (12) were synthesized in the same manner as above. The structures of the synthesized resins (1) to (12) are shown below.

In addition, the molar ratio and the weight average molecular weight of each repeating unit of the resins (2) to (12) are shown in Table 1.                     

Synthesis of Polymer (B-2) (Resins (1) to (8))

2-Methyl-2-adamantyl methacrylate and mechatronic lactone methacrylate are added at a ratio of 50/50, and dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5 to obtain a solid content concentration. 100 ml of 20% solution was prepared. 1 mol% of V-65 manufactured by Hwagwang Pure Chemical Co., Ltd. and 2 mol% of mercaptoethanol were added to this solution, which was then added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. over 2 hours under a nitrogen atmosphere. It was. After completion of the dropwise addition, the reaction solution was heated for 3 hours, 1 mol% of V-65 was further added, and stirred for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and crystallized and precipitated white powder was recovered from a mixed solution of 2 L of isopropanol / 1 L of distilled water.

Polymer composition ratio determined from C ¹³ NMR was 54/46. In addition, the weight average molecular weight converted into standard polystyrene measured by GPC method was 13700.

In the same operation as in Synthesis Example, polymers (2) to (8) having a molecular weight were synthesized.

The molar ratio and weight average molecular weight of each repeating unit of the resins (2) to (8) are shown in Table 2.                     

EXAMPLE

10 g of the polymer (B-1) and the polymer (B-2) obtained in the above synthesis example were added (the weight ratio of the polymer (B-1) and the polymer (B-2) is represented by (%) in Table 3), 0.18 g of a photoacid generator, 10 mg of an organic basic compound, and a surfactant (addition amount in an amount of 1% by weight based on the total solids of the composition) are blended as shown in Table 3, and mixed in the ratio of 14% by weight of solids, respectively, in Table 3 After dissolving in a solvent, it filtered with a 0.1 micrometer microfilter, and prepared the positive photoresist composition solution of Examples 1-12.

In Table 3, PAG-1 represents triphenylsulfonium triplate and PAG2 represents (PAG4-36) above. In addition, a resist composition using a polymer (B-1) and a polymer (B-2) alone, and a photoacid generator, an organic basic compound, and a surfactant as shown in Table 3 was used as Comparative Example 1 and Comparative Example 2, respectively. do.

In addition, as a surfactant                     

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W-1: Megafac F176 (product of Dainippon Ink Corporation) (fluorine system)

W-2: Megafac R08 (manufactured by Dainippon Ink, Inc.) (fluorine and silicon)

W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: Polyoxyethylene nonyl phenyl ether

W-5: Troisol S-366 (product of Troy Chemical Co., Ltd.)

As an organic basic compound,

1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN),

2 is bis (1,2,2,6,6-pentamethyl-4-piperidine) sebacate,

3 represents trin-butylamine.

S1: Propylene Glycol Monomethyl Ether Acetate

S2: Propylene Glycol Monomethyl Ether Propionate

S3: ethyl lactate

S4: Propylene Glycol Monomethyl Ether

S5: Butyl Acetate

S6: γ-butyrolactone

S7: ethylene carbonate

S8: Propylene Carbonate

(Evaluation method of side lobe light resistance and resolution by halftone mask exposure)

Each resist film was apply | coated at 0.30 micrometer on the 4-inch Bare Si board | substrate, and it dried for 60 second at 140 degreeC by the vacuum suction type hotplate. Then, it exposed with the ArF stepper made from ISI through the halftone mask (80% of the transmittance | permeability) of a 0.15 micrometer contact hole pattern (Hole Duty = 1: 3). After exposure, heat treatment was performed at 130 DEG C for 60 seconds, followed by a paddle development for 60 seconds with 2.38% TMAH, followed by washing with pure water for 30 seconds to spin-dry to obtain an image. In this case, the optimum exposure amount for reproducing the size of a contact hole (mask) having a diameter of 0.15 mu m on the resist substrate is defined as Etop, and the minimum exposure amount at which side lobe light is transferred onto the resist substrate is defined as Elimit, The ratio Elimit / ETop of was taken as an index of side rope light resistance. In this case, the value of the comparative example 1 was normalized to 1, and the other side lobe light tolerance by the relative evaluation with it was displayed. The larger this value, the better the side rope light resistance, and the smaller this value, the poorer the value.

In addition, the limit resolution (diameter: 占 퐉) when the exposure amount was matched with a contact hole pattern having a diameter of 0.18 탆 was defined as the resolution.

The evaluation results are shown in Table 3.                     

In the results of Table 3, the embodiment of the present invention showed excellent performance in side rope light resistance and resolution. However, the comparative example did not satisfy the above performance, and in particular, the side rope light resistance by halftone mask exposure was insufficient.

By the positive photoresist composition of the present invention, high resolution, good halftone retardation shift mask suitability (side lobe resistance) and excellent resist performance are obtained.

Claims (3)

(A) a compound which generates an acid by irradiation of actinic light or radiation, (B-1) 1 or more types selected from the group of the repeating unit represented by the following general formula (Ia) and general formula (Ib), and the repeating unit represented by the following general formula (II-A) A polymer having a group decomposed by the action of, and (B-2) A positive photoresist composition for far ultraviolet exposure, comprising a polymer having a repeating unit represented by the following general formula (pA) and having a group decomposed by the action of an acid.

In formula (Ia): R ₁ and R ₂ may each independently have a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , and may have a substituent. An alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the following -Y group is represented. X represents an oxygen atom. Here, R <_5> represents the alkyl group, cyclic hydrocarbon group, or the following -Y group which may have a substituent. 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.) Here, the substituent is selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group. In formula (Ib): Z ₂ represents -O-. In formula (II-A): R ₁₃ to R ₁₆ each independently represent a hydrogen atom, -COOH, -COOR ₅ (R ₅ is the same as described above), a group decomposed by the action of an acid, or -C (= O) -XAR ₁₇ Display. n represents 0 or 1. Here, X and A have the same meanings as described above, respectively. R ₁₇ is -COOH, -COOR ₅ , -CN, a hydroxyl group, an alkoxy group which may have a substituent (substituents are hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group or acyloxy group), -CO -NH-R ₆ , -CO-NH-SO ₂ -R ₆ (R ₅ , R ₆ have the same meaning as described above) or the -Y group.

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different, respectively. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Indicates. Ra represents the group in any one of following formula (pI) and (pII).

Wherein R ₁₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary to form an alicyclic hydrocarbon group together with carbon atoms do. R ₁₁₂ to R ₁₁₄ each independently represent a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, except that at least one of R ₁₁₂ to R ₁₁₄ represents an alicyclic hydrocarbon group. delete delete