KR100760252B1 - Positive photoresist composition for far ultraviolet rays exposure - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist composition for exposure to far ultraviolet rays, which has excellent storage stability over time and solves the problem of developing defects during development.

The present invention is a compound which generates an acid by irradiation of actinic radiation or radiation, a polymer having a repeating unit of a specific structure and a repeating unit of a specific structure having an alicyclic ring in the main chain, and having a group which is decomposed by the action of an acid. And a mixed solvent comprising at least one member selected from the group consisting of butyl acetate and propylene glycol monoalkyl ether carboxylate, and at least one member selected from the group consisting of ethyl lactate and propylene glycol monoalkyl ether. It consists of a positive photoresist composition for ultraviolet exposure.

Description

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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for ultra-violet exposure for use in ultra-microlithography processes such as the production of ultra-LSI and high-capacity microchips, and other photographic processes. More specifically, the present invention relates to a positive photoresist composition for ultraviolet exposure capable of forming a very precise and refined pattern by using an ultraviolet ray region including an excimer laser light, particularly a light having a wavelength of 250 nm or less.

In recent years, integrated circuits have increased their degree of integration even more, and in the manufacture of semiconductor substrates such as ultra-LSI, processing of ultrafine patterns having a line width of 1/2 micron or less is required. In order to meet this need, the wavelength of the exposure apparatus used in photolithography has become even shorter, and now, the use of excimer laser light (XeCl, KrF, ArF, etc.), which is a short wavelength in far ultraviolet rays, has been considered.

Chemical amplification resists are used for pattern formation in lithography in this wavelength region.

In general, chemically amplified resists can be roughly classified into three types, namely two-component, 2.5-component, and three-component systems. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin that is decomposed by the action of an acid and retains in the molecule a group (also referred to as an acid-decomposable group) that increases solubility in an alkaline developer of the resin. The 2.5 component system contains a low molecular compound further having an acid-decomposable group in such a two component system. A three component system contains a photo-acid generator, alkali-soluble resin, and the said low molecular weight compound.

The chemically amplified resist is suitable for ultraviolet or far-infrared ray photoresist, but it is necessary to correspond to the required performance in use.

As photoresist compositions for ArF light sources, resins in which alicyclic hydrocarbon sites have been introduced to impart dry etching resistance have been proposed. However, since the system becomes very hydrophobic as a detriment of introduction of alicyclic hydrocarbon sites, it is widely used in conventional resist developing solutions. The development in the tetramethylammonium hydroxide (TMAH) aqueous solution which has been used has become difficult, or the phenomenon in which the resist peels from a board | substrate during development is seen.

In response to such a resist hydrophobicity, a response such as mixing an organic solvent such as isopropyl alcohol in a developer has been examined, and although the end result is obtained, problems such as the expansion of the resist film and the complicated process are necessary. It cannot be said that it has been solved. In the approach of improving the resist, many measures have been taken to supplement hydrophobic and various alicyclic hydrocarbon sites by introducing hydrophilic groups.

Japanese Patent Laid-Open No. 10-10739 discloses an energy sensitive resist material 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. 11-202491 discloses a radiation-sensitive resin composition containing a polymer containing a norbornene derivative and an androstane-17-carboxylic acid ester compound.

Resin containing an acid-decomposable group used for the photoresist for far-ultraviolet exposure generally contains an aliphatic cyclic hydrocarbon group in a molecule | numerator simultaneously. For this reason, resin became hydrophobic and there existed a problem resulting from it. Although various such means for improving the above have been examined in various ways, the technique is still insufficient (particularly with respect to developability), and improvement is required.

In other words, there is still room for improvement in the technology in which the above-mentioned ultraviolet light and short wavelength light source, for example, an ArF excimer laser (193 nm) are used as the exposure light source. Specifically, there was room for improvement in the storage stability of the resist liquid. For example, when the chemically amplified photoresist is stored in a liquid state, compatibility between the resin and the photoacid generator is deteriorated, particles are generated in the liquid, and resist performance is degraded. Was still present (deterioration of the storage stability of the resist solution).

 Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in the microphotographic manufacturing process using far ultraviolet light, in particular, ArF excimer laser light, and specifically, a positive photoresist composition for far ultraviolet light having excellent storage stability. Is to provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the constituent material of a resist composition with a positive chemical amplification system, it came to know that the objective of this invention is achieved by using 2 or more types of specific acid-decomposable resins, and came to this invention.

That is, the said object is achieved by the following structure.

(1) at least one compound selected from the group consisting of (A) a compound which generates an acid by irradiation with actinic rays or radiation, and (B) a repeating unit represented by the following general formula (Ia) and general formula (Ib); It is a resin which has a repeating unit represented by the following general formula (II), and has a group (acid-decomposable group) decomposed by the action of an acid, and the content rate (mol%) of an acid-decomposable group-containing repeating unit among all repeating units. 2 or more types of this other resin are contained, The positive photoresist composition for far ultraviolet exposures characterized by the above-mentioned.

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 optionally substituted alkyl group or an alkoxy group Or a cyclic hydrocarbon group or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. 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, haloalkyl group, cycloalkyl group or 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 an atomic group for forming an alicyclic structure which contains two bonded carbon atoms (C-C) and may have a substituent.

(2) In the above (1), the resin (B) contains two kinds of resins having a difference in the content rate of the acid-decomposable group-containing repeating unit in the total repeating unit of 5 to 30 mol%. Positive photoresist composition for exposure.

(3) In the above (1) or (2), Z in General Formula (II) contains two carbon atoms (CC) bonded to each other to form a bridged alicyclic structure which may have a substituent. A positive photoresist composition for far ultraviolet exposure, characterized by displaying an atomic group for

(4) The positive photoresist composition for far ultraviolet exposure according to (1) or (2), 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 has the same meaning 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.

(5) The positive photoresist composition for far ultraviolet exposure according to any one of (1) to (4), which contains a nitrogen-containing basic compound.

(6) The above-mentioned (5), wherein the nitrogen-containing basic compound is 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimines A positive photoresist composition for far ultraviolet light exposure, characterized in that the compound is at least one compound selected from the group consisting of didines, tertiary morpholines, and hindered amines having a suppressed piperidine skeleton.

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

(A) A compound which generates 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 of actinic light or radiation.

As a compound which decomposes | dissolves by irradiation of actinic light or radiation used for this invention, and produces | generates an acid, it is used for the photoinitiator of photocationic polymerization, the photoinitiator of photoradical polymerization, the photochromic agent of pigments, a photochromic agent, a microresist, etc. Acids are generated by known light (ultraviolet rays of 400-200 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. Compounds and mixtures thereof may be appropriately selected 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, SISchlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal et al, Polymer, 21,423 ( Diazonium salts described in US Pat. No. 4,069,055, US Pat. No. 4,069,056, Re27,992, JP-A 3-140140, etc., DCNecker et al, Macromolecules, 17,2468 (1984), CSWen et al. Teh, Proc.conf.Rad.Curing ASIA, p.478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivello et al, Macromorecules, 10 (6), 1307 (1977) ), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Patent No. 339,049, US Patent No. 410,201, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, and the like. Ium salts, JVCrivello et al, Polymer J. 17,73 (1985), JVCrivello et al, J. Org . Chem. 43,3055 (1978), WRWatt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivello et al, Polymer Bull., 14, 279 (1985), JVCrivello et al, Macromorecules, 14 (5), 1141 (1981), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17,2877 (1979), European Patent 370,693, 161,811, 410,201, 339,049 , 233,567, 297,443, 297,442, US Patent 3,902,114, 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patent 2,904,626, 3,604,580, 3,604,581 Sulfonium salts described in Japanese Patent Application Laid-Open No. 7-28237, 8-27102, etc., JVCrivello et al, Macromorecules , 10 (6), 1307 (1977), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, Onium salts such as selenium salts described in 1047 (1979) and the like, arsnium salts described in CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo, Oct (1988), US Patent No. 3,905,815, Special Publications 46-4605, 48-36281, 55-32070, 60-239736, 61-16 Organic halogen compounds described in 9835, Japanese Patent Application Laid-Open No. 61-169837, Japanese Patent Application Laid-Open No. 62-58241, Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, and the like. Rad. Curing, 13 (4), 26 (1986), TPGill et al, Inorg. Chem., 19,3007 (1980), D. Astruc, Acc, Chem. Res., 19 (12), 377 (1896) , Organometallic / organic halides described in Japanese Patent Application Laid-Open No. 2-161445 et al., S. Hayase et al, J. Polymer Sci., 25,753 (1987), E. Reichmanis et al, J. Polymer Sci., Polymer Chem. Ed. 23, 1 (1985), QQZhu et al, J. Photochem., 36,85, 39,317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem. Soc., 371 (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 Technology, 11 (4), 191 (1985), HM Houlihan et al, Macromorecules, 21, 2001 (1988), PM Collins et al, J. Chem. Soc., Chem. Comm., 532 (1972), S. Hayase et al, Macromorecules, 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 No. 0290,750, 046,083, 156,535, 271,851, 0,388,343, US Patent No. 3,901,710 , M.TUNOOKA et al, Polymer Preprints Japan, 35 (8), G.Berner, O-nitrobenzyl-type protecting groups described in 4,181,531, JP-A 60-198538, JP-A 53-133022, etc. 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, 84515, 044,115, 618,564, 0,101,122, US Patent 4,371,605, 4,431,774, WO 64-18143, WO 2-245756, WO 3-3- Compounds that are photodegraded to generate sulfonic acid, such as iminosulfonates described in 140109 and the like, disulfone compounds described in Japanese Patent Application Laid-Open Nos. 61-166544, JP-A 2-71270, JP-A 3-103854, and 3- It is listed in 103856, 4-210960 Dia joke toseol may be a phone, a dia Jody sulfone compound.

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, MEWoodhouse et al, J. Am. Chem. Soc., 104,5586 (1982), SP Pappas et al, J. Imaging Sci., 30 (5), 218 (1986), S. Kodo et al, Makromol. Chem., Rapid Commun., 9,625 (1988), Y. Yamada et al, Makromol. Chem. , 152,153,163 (1972), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), US Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Application No. 63-26653, Japanese Patent Application Publication No. 63-26653 The compounds described in 55-164824, Japanese Patent Laid-Open No. 62-69263, Japanese Patent Laid-Open No. 63-146038, Japanese Patent Laid-Open No. 63-163452, Japanese Patent Laid-Open No. 62-153853, Japanese Patent Laid-Open No. 63-146029 and the like can be used.

VNRPillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetra hedron Lett., (47), 4555 (1971), DHR Barton et al, J. Chem. Soc., (C ), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712, and the like, may also be used compounds which generate an acid by light.

Among the compounds which decompose upon irradiation with actinic light or radiation to 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, or -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds are mentioned in detail, it is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by the 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 aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, 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 hydroxy group and a halogen atom. 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, condensed naphthalene-1-sulfonic acid anion, such as Although polynuclear aromatic sulfonic acid anion, anthraquinone sulfonic acid anion, 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) and (PAG4) are known and are described, for example, in JWKnapczyk et al, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok et al, J. Org. Chem., 35, 2532 (1970), E. Goethas et al, Bull. Soc. Chem. Belg., 73, 546 (1964), HMLeicester, J. Ame. Chem. Soc., 51, 3587 (1929). ), JVCrivello et al., J. Polym. Chem. Ed., 18,2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Application Laid-Open No. 53-101331, and the like.

(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 the irradiation of such 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). Is used in the range of 0.01 to 20% by weight, more preferably 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 ( Baking margins are particularly narrow.

Next, (B) a group having at least one of the repeating units represented by the general formulas (Ia) and (Ib) and a repeating unit represented by the general formula (II), and decomposed by the action of an acid. The polymer (henceforth "resin which concerns on this invention") to hold is demonstrated.

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 , an alkyl group, an alkoxy group or a cyclic hydrocarbon group which may be substituted, or the above-Y group is represented. Here, R <_5> represents the alkyl group which may have a substituent, a cyclic hydrocarbon group, or the said -Y group. 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 It is a linear or branched alkyl group, More preferably, they are 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 in said R <_1> , R <_2> , R <_5> , and R <_6> , a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2-methyl- 2-adamantyl group, a norbornyl group, a boroyl group , Isoboroyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and the like.

As said 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 in R ₄ include trifluoromethyl group, nanofluorobutyl 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> .

As other substituents, such as an alkyl group, a cyclic hydrocarbon group, and an alkoxy group, 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, fluorine atom, bromine 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.

As the divalent linking group of A in the general formulas (Ia) and (Ib), 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, and a urethane group There are one or a combination of two or more groups selected from the group consisting of babies and the like.

In said A, group represented by a following formula is mentioned as an alkylene group and a substituted alkylene group.

[C (R ₂ ) (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 both 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 is 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 structural unit represented by the general formula (Ib) include the following [I'-1] to [I'-7], but the present invention is not limited thereto.

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 an atomic group for forming an alicyclic structure containing two carbon atoms bonded thereto and which 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, Most preferable is a methyl group, an ethyl group, and a propyl group , Isopropyl group, n-butyl group, isobutyl group, sec-butyl, t-butyl group.

Examples of other substituents in the alkyl groups of R ₁₁ and R ₁₂ include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the halogen atom include 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, 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 these, an alicyclic over bridge forming a repeating unit of an alicyclic hydrocarbon that spans the bridge. Atom groups for forming the 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 bridged alicyclic hydrocarbon, (5), (6), (7), (9), (10), (13), (14), (15), (23), There are (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 alicyclic hydrocarbons spanning the bridges, the repeating units represented by the general formula (II-A) or (II-B) are more preferable.

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 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 resin according to the present invention, the acid-decomposable group may be included in the above -C (= O) -XAR ₁ , -C (= O) -XAR ₂ , or may be included as a substituent of Z in General Formula (II).

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, 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, a fluorine atom, a bromine atom and an 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, and propyl Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

As said cyclic hydrocarbon group in said R <_13> -R <_16> , there exist a cyclic alkyl group and a bridged 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 ring having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

Examples of the alkoxy group in R ₁₇ include one having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

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 fluorine atom, a bromine 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 Or a combination of two or more groups selected from the group consisting of a sulfonamide group, a urethane group, and a urea group.

As said alkylene group and substituted alkylene group in said A, the thing similar to the thing of the bivalent coupling group of A in the said General formula (Ia) is mentioned.

In the resin of the present invention, the group decomposed by the action of an acid is a repeating unit represented by formula (Ia), a repeating unit represented by formula (Ib), a repeating unit represented by formula (II), and It may be contained in one or more repeating units of the repeating unit of the copolymerization component.

In the above general formula (II-A) or (II-B), various substituents of R ₁₃ to R ₁₆ form an atomic group to a bridged alicyclic structure for forming an alicyclic structure in the general formula (II). It is made of a substituent of the atomic group Z.

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

Resin which concerns on this invention is a unit of at least any one of the repeating unit represented by general formula (Ia) and general formula (Ib), and general formula (II) (General formula (II-A), (II-B) In addition to containing one or more repeating units, each of which is characterized in that, the dry etching resistance, the standard developer aptitude, the substrate adhesion, the resist profile, and the general requirements of the resist, such as resolution, heat resistance, sensitivity, etc. It may be a copolymer containing repeating units of various monomers for the purpose of.

As a preferable copolymerization component, the repeating unit represented by the following general formula (IV ') and (V') is mentioned.

Wherein Z represents an oxygen atom, -NH-, -N (-R ₅₀ )-, -N (-OSO ₂ -R ₅₀ )-, and R _{50 is} also the same (substituted) alkyl group 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] However, it is not limited to these specific examples.

Although the resin of this invention may be copolymerized within the range in which the effect of this invention is effectively acquired, and the following monomers give the repeating unit which comprises this resin, it is not limited to the following monomer.

Thereby, the performance required for the said resin, especially (1) solubility to a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film loss (hydrophilicity, alkali solubility) Selection), (5) adhesion to the unexposed portion of the substrate, and (6) fine adjustment of dry etching resistance.

As such a copolymerization monomer, the addition polymerizable unsaturated bond chosen from acrylic acid ester, methacrylic acid ester, acrylamide, methacrylic acid amide, aryl compound, vinyl ether, vinyl ester, etc. is used, for example. The compound etc. which hold one are mentioned.

Specifically, for example, acrylate esters, which include alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (e.g. methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cycloacrylate Hexyl, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimetholol Propane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

Methacrylic acid esters, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate) Acrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, crawlbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate Acrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate , Tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example acrylamide, N-alkyl acrylamide, (alkyl group having 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 (The alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.) N-hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide, etc .;

Methacrylamides, for example methacrylamide, N-alkyl methacrylamide (as alkyl group having 1 to 10 carbon atoms, for example methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, Cyclohexyl group and the like), N, N-dialkyl methacrylamide (alkyl groups include ethyl group, propyl group, butyl group and the like), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (e.g. allyl acetate, allyl capronate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearic acid, allyl benzoate, allyl acetate, allyl lactate, etc.), aryl Oxyethanol and the like;

Vinyl ethers, for example alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, crawlethyl 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, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl crawl acetate, vinyl dicro acetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetate acetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconic acid (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.);

Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the resin according to the present invention, a repeating unit represented by General Formula (Ia) and / or General Formula (Ib), and General Formula (II) (General Formula (II-A) or (II-B)) are also included. The content of the repeating unit represented by) can be appropriately set in consideration of dry etching resistance, sensitivity of the desired resist, prevention of cracking of the pattern, substrate adhesion, resist profile, resolution, heat resistance, etc., which are requirements of general resists. In general, in the resin according to the present invention, 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) are each total monomer repeating units of the resin. 25 mol% or more is suitable, Preferably it is 30 mol% or more, More preferably, it is 35 mol% or more.

In the resin according to the present invention, the content in the resin of the repeating unit (General Formula (IV ′) or (V ′)) derived from the above-mentioned preferred copolymer monomer can also be appropriately set depending on the desired resist performance. It is preferable that it is 99 mol% or less 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), More preferably, it is 90 mol% Hereinafter, more preferably, 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 a repeating unit represented by general formula (Ia) and / or general formula (Ib). And 99 mol% or less is preferable with respect to the total mole number which totaled the repeating unit represented by General formula (II), 90 mol% or less is more preferable, 80 mol% or less is more preferable. If the amount of the repeating unit based on the monomer of this other copolymerization component exceeds 99 mol%, it is not preferable because the effect of the present invention is not sufficiently expressed.

And as resin (B), it is preferable to contain 2 types of resin whose difference of content of an acid-decomposable group containing repeating unit in all the repeating units is 5-30 mol%.

If the difference in content is less than 5 mol% or exceeds 30 mol% in the total repeating units of the acid-decomposable group-containing repeating units in the two or more resins, the storage stability and sensitivity of the resist composition tend to deteriorate, which is not preferable. .

In addition, when 3 or more types of resin (B) is contained, the difference of the resin with the most content and the least resin among all the repeating units of an acid-decomposable group containing repeating unit should just be 5-30 mol%. More preferably, this difference is 6-25 mol%, More preferably, it is 7-20 mol%.

In addition, in the resin which concerns on this invention, the group decomposed by the action of an acid is a repeating unit represented by general formula (Ia) and / or general formula (Ib), the repeating unit represented by general formula (II), and a copolymerization component. Although it may be contained in any of the repeating units based on the monomer, the content of the repeating unit containing a group which decomposes by the action of an acid is suitable for 10 to 80 mol% of all the repeating units of the resin. Preferably it is 12-75 mol%, More preferably, it is 15-70 mol%.

The resin having the highest acid-decomposable group content preferably has a range of content of an acid-decomposable group-containing repeating unit in the resin, preferably 12 to 90 mol%, more preferably 15 to 85 mol%, even more preferably 18 to 80 mol. It is chosen from what is%. Further, the resin having the least content of the acid-decomposable group has a range of content of the acid-decomposable group-containing repeating unit in the resin, preferably 5 to 70 mol%, more preferably 8 to 65 mol%, even more preferably It is chosen from 10-60 mol%.

The resin according to the present invention is a copolymer obtained by copolymerizing a monomer corresponding to a 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 by ring-opening-esterifying with an alcohols under basic or acidic conditions, or hydrolyzing and converting a post-generation carboxylic acid moiety to a desired substituent.

The weight average molecular weight of resin which concerns on this invention 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, it is not preferable because deterioration of heat resistance or dry etching resistance is observed, and if it exceeds 200,000, developability is deteriorated or the film formation is deteriorated because the viscosity is very high. do.

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

It is preferable to melt | dissolve 3-25% of solid content, such as said (A) photoacid generator and (B) resin, as said solid content concentration, More preferably, it is 5 to 22%, More preferably, it is 7 to 20% to be.

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

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

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 resistance 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 Application Laid-Open No. 62-36663, Japanese Patent Application No. 61-226746, Japanese Patent Application No. 61-226745, Japanese Patent Application No. 62-170950, Japanese Patent Application No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165 As Unexamined-Japanese-Patent No. 8-62834, surfactant of Unexamined-Japanese-Patent No. 9-54432 and 9-5988 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 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430 and 431 (manufactured by Sumimoto 3M Company), Megafac F171, F173, F176, F189, and R08 (Dainipone Ink) Company), and fluorine-based surfactants or silicone-based surfactants such as Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass, Inc.). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicone 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.

As said other surfactant, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol in detail Polyoxyethylene alkylallyl ethers such as ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan mono Sorbitan fatty acid esters such as oleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, poly Oxyethylene Sorbitan Trioleate, Polyjade And the like can be mentioned 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, and preferably 1 part by weight or less per 100 parts by weight of solids 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 are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Here, R ²⁵¹ and R ²⁵² may be bonded to 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.)

More 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 atoms or alkyls. A compound having an amino 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-trilpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine , 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine , N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 2 Agents such as 4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, and cyclohexyl morpholinoethylthiourea (CHMETU) Tertiary morpholine derivatives, including the inhibited amines described in Japanese Patent Application Laid-Open No. 11-52575 (for example, those described in the above publication), and the like, but are not limited to these.

Particularly preferred embodiments are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2 .2] tertiary moles such as octane, 4-dimethylaminopyridine, hexanemethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines and CHMETU Suppressed amines, such as porin and bis (1,2,2,6,6-pentamethyl-4- piperidyl) sebagate, 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) sebagate is preferred.

Such 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 photosensitive resin composition. If it is less than 0.001 weight%, the addition effect of the said nitrogen-containing basic compound is not acquired. On the other hand, when it 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 of the present invention may further 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.

The positive resist composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and is apply | coated on a support body. 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 the above, preferred solvents include 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether Le, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, tetrahydrofuran and the like.

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 No. 7-69611 with a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorber, or a maleic anhydride disclosed in US Pat. No. 5294680 A reaction product of a copolymer with a diamine type light absorber, the resin binder described in Japanese Patent Laid-Open No. 6-118631, and a metholol melamine-based thermal crosslinking agent; the carboxylic acid group described in Japanese Patent Laid-Open No. 6-118656, an epoxy group and a light absorber An acrylic resin antireflection film retained therein, comprising a methirolmelamine of JP-A-8-87115 and a benzophenone-based light absorber, and adding a low molecular light absorber to the polyvinyl alcohol resin of JP-A-8-179509 Can be.

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

The resist liquid is applied to a substrate (e.g., silicon / silicon dioxide coating) used for the manufacture of the precision integrated circuit device (on the substrate on which the anti-reflection film is provided, if necessary), or by a suitable coating method such as a spinner or a coater. After coating, a favorable resist pattern can be obtained by exposing through a predetermined mask, baking and developing. Here, light of 150-250 nm wavelength is preferable as exposure light. 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.

Moreover, alcohol and surfactant 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 this Example.

Synthesis Example (1) Synthesis of Resin (1-A)

By the reaction of the tetracyclo dodecene derivative (1-1) obtained by reaction of the acrylic acid ester of 3-oxo-1,1-dimethylbutanol, and cyclopentadiene diene, and an acrylonitrile and cyclopentadiene diene The mixture of the molar ratio 4/1/5 of the obtained tetracyclo dodecene derivative (1-2) maleic anhydride was put into a separate flask, and it heated at 80 degreeC under nitrogen stream. When the reaction temperature was stabilized, 2.5 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 12 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then charged into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain resin (1-A) as a target product.

When the molecular weight analysis by GPC of the obtained resin (1-A) was tested, it was 10400 (weight average) in polystyrene conversion. In the NMR spectrum, the ratio of the (1-1) and (1-2) units and the maleic anhydride repeating unit in the resin (1) was (1-1) / (1-2) / maleic anhydride = 38/12/50 Therefore, it was confirmed that the ratio of the acid-decomposable repeating unit was 38%.

Resins (1-B) to (12-C) were synthesized in the same manner as in Synthesis Example (1-A). In the structure of synthesize | combined resin (1-A)-(12-C), each repeating unit which A-C contains is the same, and the content rate is another resin.

The structure of the said resin (1)-(12) is shown below.

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

Examples 1-12, Comparative Examples 1-12                     

1.4 g of the resin (total amount) shown in Table 2 synthesized in the synthesis example,

0.18 g of photoacid generator (PAG4-36),

10 mg of organic basic compound (amine),

Surfactant (addition amount is 1% by weight relative to the total solids of the composition) is blended as shown in Table 2, dissolved in propylene glycol monoethyl ether acetate at a ratio of 14% by weight of solids, respectively, and then filtered through a 0.1 μm microfilter. Thus, the positive photoresist composition solutions of Examples 1 to 12 were prepared.

In addition, as a surfactant

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

With amines,

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

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

3 represents trin-butylamine.

Evaluation test

The obtained positive photoresist composition solution was applied onto a silicon wafer using a spin coder, dried at 140 ° C. for 90 seconds to prepare a positive photoresist film having a thickness of about 0.5 μm, and exposed to it by an ArF excimer laser (193 nm). .

The post-exposure heat treatment was performed at 140 ° C. for 90 seconds, developed in a 2.38% aqueous tetramethylammonium hydroxide solution, washed with distilled water to obtain a resist pattern profile.

On this, the storage stability of the resist composition was evaluated.

Sensitivity (relative sensitivity initial value)

The relative exposure amount was expressed as sensitivity, with the minimum exposure amount capable of resolving a pattern of 0.15 mu m as sensitivity, and the sensitivity of No. 1 being 1.

[Storage Stability of Resist Composition]

(Sensitivity change rate) The crude liquid solution was stored at 40 ° C. for 15 hours and again stored at 4 ° C. for 15 days, and then the sensitivity was evaluated and the rate of change in sensitivity before storage was measured by the following formula. In addition, the said sensitivity was defined as the exposure amount which reproduces the pattern of 0.15 micrometer of line widths.

{(Exposure amount before preservation)-(exposure amount after preservation)} / (exposure amount before preservation) × 100

(Initial value of particles and the number of increase) The number of particles immediately after the preparation of the prepared resist liquid is the initial value of the particles, and the initial value and the number of particles in the liquid after storing the resist solution at 30 ° C. for one month. By measuring the number of particles increased before and after the storage over time.

The evaluation results are shown in Table 2.                     

As can be clearly seen from the results in Table 2, the positive ultraviolet exposure positive of the present invention includes a resin (Examples 1 to 12) in which a repeating unit to be contained is the same and a resin having a different content of an acid-decomposable group is mixed. The photoresist composition is at a satisfactory level with respect to sensitivity and storage stability as compared with the case of only one type of resin (Comparative Examples 1 to 12).

That is, although the content of the acid-decomposable group-containing repeating units in the resins shown in Comparative Examples 1 to 12 and the resins obtained by mixing the two types of resins of Examples 1 to 12, the average content of the acid-decomposable group-containing repeating units is almost the same. The case where two kinds of resins are mixed shows that the sensitivity and the storage stability are excellent. As mentioned above, the positive photoresist composition for far ultraviolet exposure of this invention is suitable for lithography using far ultraviolet rays including ArF excimer laser exposure.

The positive photoresist composition for far ultraviolet exposure of the present invention is particularly preferably applied to light in an ultraviolet wavelength range in the range of 170 nm to 20 nm, and is excellent in storage stability.

Claims (6)

(A) a compound which generates an acid by irradiation of actinic light or radiation, (B) at least one member selected from the group consisting of repeating units represented by the following general formulas (Ia) and (Ib) and repeating units represented by the following general formulas (II); Resin having a group (acid-decomposable group) to decompose by, and (C) contains a nitrogen-containing basic compound, Said (B) resin contains 2 or more types of resin from which the content rate (mol%) of an acid-decomposable group containing repeating unit is contained in all the repeating units, The positive photoresist composition for ultraviolet exposures characterized by the above-mentioned.

In formula (Ia): R ₁ and R ₂ are each an alkyl group, an alkoxy group or a cyclic hydrocarbon group which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group and acyloxy group, hydrogen atom , Cyano group, hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , or -Y group shown below. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. Here, R ₅ represents an alkyl group, a cyclic hydrocarbon group or the following -Y group which may have a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. A represents a single bond or a divalent linking group. -Y group;

(In the -Y group, R ₂₁ to R ₃₀ each independently represent an alkyl group or a hydrogen atom which may have a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group). A and b indicate 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, haloalkyl group, cycloalkyl group or camphor residue. In formula (II): R ₁₁ and R ₁₂ are each independently an alkyl group, a hydrogen atom, a cyano group, or a halogen atom which may have a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group Is displayed. Z represents an atomic group for forming an alicyclic structure containing two carbon atoms bonded thereto and which may have a substituent. Here, the substituent is an alkyl group or a cyclic hydrocarbon group which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, hydrogen atom, halogen atom, 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 [X, A have the same meaning as described above. R ₁₇ is an alkoxy group which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, -COOH, -COOR ₅ , -CN, hydroxyl group, -CO -NH-R ₆ , -CO-NH-SO ₂ -R ₆ (wherein R ₅ , R ₆ have the same meaning as described above) or the above -Y group.]. The positive photoresist for far ultraviolet exposure according to claim 1, wherein the resin (B) contains two kinds of resins having a difference of 5 to 30 mol% of the content of the acid-decomposable group-containing repeating units in the total repeating units. Composition. The compound of claim 1 or 2, wherein in formula (II), Z represents an atomic group for forming a bridged alicyclic structure containing two carbon atoms (CC) bonded thereto and having a substituent. Here, the substituent is an alkyl group or a cyclic hydrocarbon group, a hydrogen atom, a halogen atom, which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, Cyano group, -COOH, -COOR ₅ (R ₅ means the same as described above), group decomposed by the action of acid, -C (= O) -XAR ₁₇ [X, A means the same as described above, respectively being. R ₁₇ is an alkoxy group which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, -COOH, -COOR ₅ , -CN, hydroxyl group, -CO -NH-R ₆ , -CO-NH-SO ₂ -R ₆ (wherein R ₅ , R ₆ are the same as described above) or the -Y group.] Is selected from the group consisting of Positive photoresist composition for far ultraviolet exposure. The positive photoresist composition for ultraviolet exposure according to claim 1 or 2, 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 an alkyl group or a cyclic hydrocarbon group, a hydrogen atom or a halogen atom which may have a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group , Cyano group, -COOH, -COOR ₅ (R ₅ has the same meaning as described above), a group which decomposes by the action of an acid, or -C (= O) -XAR ₁₇ . 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 an alkoxy group which may have a substituent selected from the group consisting of hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, -COOH, -COOR ₅ , -CN, hydroxyl 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. delete The method according to claim 1 or 2, The nitrogen-containing basic compound is 1,5-diazabicyclo [4. 3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 1 selected from 4,4-dimethylimidazolines, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines, and inhibited amines having an inhibited piperidine backbone A positive photoresist composition for far ultraviolet light exposure, characterized in that the compound is at least one compound.