KR20010088353A - Positive-working photosensitive composition - Google Patents

Abstract

PURPOSE: To provide a positive photosensitive composition excellent in developability (particularly reduction of residue on development and development defects) and excellent also in sensitivity, resolving power and the shape of pattern profile. CONSTITUTION: The positive photosensitive composition contains a compound which generates an acid when irradiated with active light or radiation, a resin which is decomposed by the action of the acid to increase its solubility in an alkali developing solution and an N,N-dialkylcarboxylic acid amide.

Description

Positive photosensitive composition {POSITIVE-WORKING PHOTOSENSITIVE COMPOSITION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to positive photosensitive compositions used in semiconductor manufacturing processes such as ICs, in the production of circuit boards such as liquid crystals, thermal recording heads, and other photographic manufacturing processes.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to positive photosensitive compositions used in semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal recording heads, and other photographic manufacturing processes. More specifically, the present invention relates to a positive photosensitive composition which is preferable in the case of using an ultraviolet ray or the like of 250 nm or less as an exposure light source.

When a resist consisting of a conventional novolak and a naphthoquinone diazide compound is used for pattern formation in lithography using ultraviolet light or excimer laser light, novolak and naphthoquinone diazide are strongly absorbed in the extra-violet region, and thus It is difficult to reach the bottom of the resist, and only a pattern corresponding to taper with low sensitivity can be obtained.

One method for solving such a problem is a chemical amplification resist composition described in US Pat. No. 4,491,628, EP 249,139, and the like.

The chemically amplified positive resist composition generates an acid in the exposed portion by radiation such as ultraviolet light, and changes the solubility of the active radiation in the developer and the non-irradiated developer by the reaction using the acid as a catalyst to form a pattern on the substrate. It is a pattern forming material formed in.

For example, a combination of a compound which generates an acid by photolysis with an acetal or O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), or a combination with an orthoester or an amide acetal compound (Japanese Patent Japanese Patent Application Laid-Open No. 51-120714), a combination with a polymer having an acetal or ketal group in its main chain (Japanese Patent Publication No. 53-133429), and a combination with an enol ether compound (Japanese Patent Publication No. 55-12995 Japanese Patent Application Laid-Open No. 56-17345), a combination with an N-acyliminocarbonate compound (Japanese Patent Publication No. 55-126236), a combination with a polymer having an orthoester group in the main chain (Japanese Patent Publication No. 56-17345), Combination with tertiary alkyl ester compounds (Japanese Patent Application Laid-Open No. 60-3625), Combination with Cyryl ester compounds (Japanese Patent Publication No. 60-10247), and Combination with Cyryl Ether Compound (Japan) Korean Patent Publication No. 60-37549, East 60-1214 46 each publication). In principle, they exhibit high photosensitivity because the quantum yield is over one.

Similarly, as a system which decomposes by heating in the presence of an acid and alkali-solubilizes, for example, Unexamined-Japanese-Patent No. 59-45439, 60-3625, 62-229242, 63-27829, 63-278 36240, 63-250642, Japanese Patent Laid-Open No. 5-181279, and Polym. Eng. Sce., Vol. 23, p. 1012 (1983); ACS. Sym. 242, p. 11 (1984); Semiconductor World, 1987, November, 91; Macromolecules, 21, 1475 (1988); Esters or carbonic acids of compounds which generate acids upon exposure described in SPIE, vol. 920, p. 42 (1988) and tertiary or secondary carbons (e.g., t-butyl, 2-cyclohexenyl) Combination system with an ester compound, combination system with an acetal compound described in Japanese Patent Laid-Open Nos. 4-219757, 5-249682, 6-65332, etc., and Japanese Patent Laid-Open No. 4-211258 And combinations thereof with t-butyl ether compounds described in the publications of No. 6-65333 and the like.

Such a system is mainly absorbed less in the 248nm region, and since the resin containing poly (hydroxystyrene) as a basic skeleton is used as a main component, when KrF excimer laser is used as an exposure light source, a high sensitivity, high resolution, and a good pattern are formed. In addition, it can be a good system compared with the conventional naphthoquinone diazide / novolak resin system.

However, in the case of using another short wavelength light source such as ArF excimer laser (193 nm) as the exposure light source, the chemical amplification system was sufficient because the compound having an aromatic group was largely absorbed in the 193 nm region.

In addition, as a polymer absorbed less in the 193 nm wavelength range, it is preferred to use poly (meth) acrylate in J. Vac. Sci. Although described in Technol, B9, 3357 (1991), this polymer has a problem in that the resistance to wet etching generally performed in the semiconductor manufacturing process is lower than that of conventional phenol resins having aromatic groups.

On the other hand, it is found that the polymer having an alicyclic hydrocarbon group exhibits the same wet etching resistance as the aromatic group and is less absorbed in the 193 nm region. Reported in SPIE, 1672, 66 (1992), the use of the same polymer has recently reached an aggressive stage. Specifically, Japanese Patent Application Laid-Open Nos. 4-39665, 5-80515, 5-265212, 5-297591, 5-346668, 6-289615, 6-324494, The polymer described in Unexamined-Japanese-Patent No. 7-49568, 7-185046, 7-191463, 7-199467, 7-234511, 7-252324, etc. are mentioned.

Since these polymers possess alicyclic hydrocarbons having extremely high hydrophobicity, they have problems in developability (developing residues and development defects, etc.).

Accordingly, an object of the present invention is to solve the problem of the performance improvement technique inherent in the ultra-fine photo production process using ultraviolet light, in particular, ArF excimer laser light, and is excellent in developability (development of development residues and development defects). Reduction) and the positive photosensitive composition which is excellent also in the shape of a sensitivity, a resolution, and a pattern profile.

This invention consists of the positive photosensitive composition of the following structure, by which the said objective of this invention is achieved.

(1) A compound that generates an acid by irradiation with (A) actinic radiation or radiation, and (B) a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure and is decomposed by the action of an acid to increase its solubility in an alkaline developer. And (C) a positive photosensitive composition containing N, N-dialkylcarboxylic acid amide.

(2) In the above (1), (D) further contains a low molecular weight dissolution inhibiting compound having a group that can be decomposed by the acid, the molecular weight is 3000 or less, the dissolution rate in the alkaline developer is increased by the action of the acid. Positive photosensitive composition.

(3) The positive photosensitive composition as described in the above (1) or (2), wherein the (B) resin further has a lactone structure.

(4) a compound which generates an acid by (A) irradiation with actinic light or radiation, (C) a N, N-dialkylcarboxylic acid amide, (D) a group that can be decomposed by an acid, A positive photosensitive composition containing a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, and (E) a resin which is insoluble in water and soluble in an alkaline developer due to its action.

(5) The positive photosensitive composition as described in any one of said (1)-(4) which further contains (F) nitrogen-containing basic compound.

(6) The positive photosensitive composition as described in any one of said (1)-(5) which further contains (G) fluorine type and / or silicone type surfactant.

(7) The item according to any one of (1) to (6), wherein (C) N, N-dialkylcarboxylic acid amide is at least one of N, N-dimethylacetamide and N, N-dimethylformamide. One positive photosensitive composition.

(8) The positive photosensitive composition as described in any one of said (1)-(7) whose irradiation light is far ultraviolet light with a wavelength of 220 nm or less.

<< (A) acid generator >>

First, the compound (photoacid generator) which generate | occur | produces an acid by irradiation of (A) actinic light or a radiation is demonstrated.

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. Compounds which generate acid by known light (ultraviolet rays from 400 to 200 nm, far ultraviolet rays, in particular g-rays, h-rays, i-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, molecular rays or ion beams, and Mixtures of these 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, SI Schlesinger, Photogr. Sci. Eng. , Diazonium salts described in TS Bal et al., Polymer , 21, 423 (1980), et al., US Pat. Nos. 4,069,055, 4,069,056 and Re27,992, Japanese Patent Application Laid-Open. Ammonium salts described in 3-140140 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, US Patent No. 339,049 and US Patent No. 410, 201, Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, JV Crivello et al. 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), EP 370,693, EP 161,811, EP 410,201, EP 339,049, EP 233,567, EP 297,443, EP 297,442, EP 3,902,114, EP 4,933,377, EP 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. And selenium salts and CS Wen et al., Teh, Proc. Conf. Rad. Curing ASIA , p. 478, Tokyo, Oct. Onium salts such as arzonium 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., J. Chem. Commun. , 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichmanis 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 incorporating the compound into the main chain or the side chain of the polymer, such as 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, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263 The compounds described in 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.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, and arzonium salts, organic halogen compounds, organometallic / organohalides, and o-nitrobenzyl protecting groups Examples of the photoacid generator, iminosulfonate, and the like, include a compound that is photolyzed to generate sulfonic acid, a disulfone compound, a diazoketo sulfone, and a diazo disulfone compound.

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 compounds which generate an acid by 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, or -C (Y) ₃ . Y represents a chlorine atom or a fluorine atom.

(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 aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 18 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 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 -, the number of the optionally substituted alkanesulfonic acid, a perfluoroalkyl alkanoic acid, optionally substituted benzene sulfonic acid, naphthalene sulfonic acid, anthracene sulfonic acid, camphor sulfonic acid, etc., but It is not limited to this. Alkanesulfonic acid, perfluoro alkanesulfonic acid, alkyl substituted benzene sulfonic acid, pentafluorobenzene sulfonic acid are preferable.

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 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.

(4) Diazodisulfone derivatives represented by the following general formula (PAG7).

Here, R represents a linear, branched, or cyclic alkyl group or an aryl group which may be substituted.

Specific examples include compounds shown below, but are not limited thereto.

In the present invention, the compound represented by the general formula (PAG-3) or (PAG-4) or (PGA-7) is most preferred in terms of sensitivity and resolution.

The amount of the compound which is decomposed by irradiation of actinic light or radiation to generate an acid is generally used in the range of 0.001 to 40% by weight relative to the total composition (excluding the solvent) of the positive photosensitive composition of the present invention. Preferably 0.01 to 20% by weight, more preferably used in the range of 0.01 to 5% by weight. When the amount of the compound that is decomposed by irradiation with actinic radiation or radiation to generate an acid is less than 0.01% by weight, the sensitivity is lowered, or when the amount is more than 40% by weight, the light absorption of the resist is excessively increased and the profile is deteriorated. Process (especially baking) margins become narrow and undesirable.

<< Resin whose solubility to alkaline developing solution increases by the action of (B) acid >>

In the present invention, the resin (hereinafter referred to as "acid-decomposable resin") whose solubility in an alkaline developer is increased by the action of (B) acid has a group which is decomposed by the action of acid.

A group decomposed by the action of an acid (hereinafter referred to as an "acid decomposable group") is, for example, a group that is hydrolyzed by an action of an acid to form an acid, and a carbon cation is desorbed by the action of an acid to The group which forms is mentioned. Preferably they are the group represented by the following general formula (x), (y), the acid-decomposable group containing a lactone structure, and the acid-decomposable group containing an alicyclic structure. This improves the stability over time.

Here, Ra, Rb, and Rc each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent. Provided that at least one of Ra, Rb and Rc in formula (x) is a group other than a hydrogen atom. Rd represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. In addition, two groups of Ra, Rb and Rc of formula (x) or two groups of Ra, Rb and Rd of formula (y) may combine to form a ring structure of 3 to 8 carbon atoms. You may form the ring structure which consists of heteroatoms in these. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, and a 2-tetrahydropyranyl group.

Za and Zb each independently represent an oxygen atom or a sulfur atom.

The alkyl group of Ra to Rd preferably has 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group which may have a substituent There is a personal thing. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may preferably have a substituent. The alkenyl group preferably has 2 to 6 carbon atoms such as vinyl group, propenyl group, aryl group, butenyl group, pentenyl group, hexenyl group and cyclohexenyl group which may have a substituent.

In addition, the other substituent of each substituent described above is preferably a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, propyl group, n- Alkyl groups, such as butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group, alkoxy, such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group Alkoxycarbonyl groups such as groups, methoxycarbonyl groups and ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, acyloxy groups such as acetoxy groups and butyryloxy groups and carboxyl groups.

Hereinafter, although the specific example of the repeating unit which has an acid-decomposable group is shown, the content of this invention is not limited to this.

Among the above, (c1), (c7) and (c11) are particularly excellent in acid decomposability.

In the present invention, the acid-decomposable resin contains a monocyclic or polycyclic alicyclic hydrocarbon structure. It is also preferable to include a lactone structure.

Here, it is preferable to have a lactone structure in the side chain of resin, and the repeating unit (a1)-(a20) which has a lactone structure in the side chain shown below can be illustrated specifically ,. Any of the alicyclic hydrocarbon structures and lactone structures herein may be provided with acid decomposability, but may not necessarily be provided.

The acid-decomposable group which may contain an alicyclic hydrocarbon group may be linked to an acid-decomposable structure, may be decomposed by the action of an acid, and the alicyclic hydrocarbon group may be desorbed, or the alicyclic hydrocarbon group may be represented by the above formula (x) or (y). The group may be bonded directly or through a linking group.

In the case where the monocyclic or polycyclic alicyclic hydrocarbon group is held in the side chain of the resin, it is preferable that the resin main chain and the alicyclic hydrocarbon group are connected to a tertiary ester group.

Among the above (a1) to (a20), for example, (a1), (a12), (a15) and the like are generally preferred since acid degradability is confirmed.

In the monocyclic or polycyclic alicyclic hydrocarbon structure contained in the acid-decomposable resin, examples of the monocyclic type include groups having an alicyclic skeleton having 3 or more carbon atoms, preferably 3 to 8 carbon atoms, and an alicyclic skeleton. There are cyclic hydrocarbon backbones such as cyclopropane, cyclobutane, cyclopentane and cyclohexane. Examples of the polycyclic type include those having an alicyclic skeleton having 5 or more carbon atoms, preferably 7 to 25 carbon atoms. For example, there are alicyclic cyclic hydrocarbon skeletons such as cyclo, tricyclo and tetracyclo. More specifically, the following structure is mentioned.

As the repeating unit having such a monocyclic or polycyclic alicyclic hydrocarbon skeleton, there are preferably structural units represented by the following general formulas (II) to (V).

Formulas (II) to (IV) will be described, and then Formula (V) will be described.

In formulas (II) to (IV), the substituents connected to the main chain of the repeating unit, that is, R ¹¹ , R ¹² , R ¹⁴ to R ¹⁶ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ¹¹ , R ¹² and R ¹⁴ to R ¹⁶ may be the same as or different from each other.

Examples of the alkyl group represented by R ¹¹ , R ¹² , R ¹⁴ to R ¹⁶ include a carbon group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group and sec-butyl group.

As said haloalkyl group, the group by which the halogen atom is substituted by one part or all part of a C1-C4 alkyl group is mentioned. Here, the halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom. Specific examples of the haloalkyl group include fluoromethyl group, chloromethyl group, bromomethyl group, fluoroethyl group, chloroethyl group, bromoethyl group and the like.

You may further have substituents other than such an alkyl group, a haloalkyl group, and a halogen atom.

Substituent R ¹³ represents a cyano group, -CO-OR ²³ or -CO-NR ²³ R ²⁴ .

R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group, or an acid-decomposable group. As such a group, the compound which has the same repeat structural unit as the above is preferable, for example. In R ²³ , the alkyl group, cycloalkyl group, and alkenyl group may further have a substituent.

In addition, said R <^24> , R <^25> represents a hydrogen atom or an alkyl group, a cycloalkyl group, or an alkenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent. R ²⁴ and R ²⁵ may be the same as or different from each other. It may combine with each other and may form a ring with a nitrogen atom. As a ring structure in this case, a 5-8 membered ring is preferable, and a pyrrolidine, a piperidine, a piperazine skeleton etc. are specifically, mentioned.

The alkyl group represented by R ²³ to R ²⁶ is preferably an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, Octyl group and the like. As a cycloalkyl group, a C3-C8 cycloalkyl group is preferable, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc. are specifically, mentioned. As an alkenyl group, a C2-C6 alkenyl group is preferable, and a vinyl group, a propenyl group, an aryl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, etc. are mentioned specifically ,. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent.

In the formulas (II) to (IV), of the substituents formed in the form of X ₁ -A, X ₂ -A or X ₃ -A, X ₁ to X ₃ represent a single bond or a divalent group. Examples of the divalent group include an alkylene group, an alkenylene group, a cycloalkylene group, -O-, -SO _2- , -O-CO-R ^26- , -CO-OR ^27- , and -CO-NR ^28- . R ²⁹ etc. are mentioned. X ₁ to X ₃ may be the same as or different from each other.

The alkylene group, the alkenylene group, and the cycloalkylene group in X ₁ to X ₃ may each include a divalent group having the same carbon skeleton as the alkyl group, alkenyl group, cycloalkyl group represented by R ¹¹ , R ¹² , and R ¹⁴ to R ¹⁶ . .

In the above -O-CO-R ^26- , -CO-OR ^27- , and -CO-NR ²⁸ -R ²⁹ -of X ₁ to X ₃ , R ²⁶ and R ²⁷ each represent a single bond or a divalent group. .

As a bivalent group, an alkylene group, an alkenylene group, and a cycloalkylene group is mentioned, for example. The alkylene group, the alkenylene group, and the cycloalkylene group in this case also include a divalent group having the same carbon skeleton as the alkyl group, alkenyl group, cycloalkyl represented by R ¹¹ , R ¹² , R ¹⁴ to R ¹⁶ . Such groups may be combined with ether groups, ester groups, amide groups, urethane groups or ureide groups to form divalent groups as a whole. The three of R ²⁶ , R ²⁷ and R ²⁹ may be the same as or different from each other.

Substituent R <^28> of -CO-NR <^28> -R <^29> -in X <_1> -X <_3> shows a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group similarly to said R <^23> -R <^25> . Such alkyl group, cycloalkyl group, and alkenyl group may have a substituent. R ²⁸ may be the same as or different from any one of R ²⁴ and R ²⁵ . Specific examples of the alkyl group, cycloalkyl group, alkenyl group and the like represented by R ²⁸ are the same as those of the alkyl group, cycloalkyl group and alkenyl group represented by R ²³ to R ²⁵ , respectively.

Substituent A, which is directly bonded to the main chain of the repeating unit via X ₁ or the like, represents a monocyclic or polycyclic cyclic hydrocarbon group. Examples of the monocyclic cyclic hydrocarbon group represented by A include groups having 3 or more carbon atoms, and preferably an alicyclic skeleton having 3 to 8 carbon atoms. For example, cyclic hydrocarbon backbones, such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, are mentioned. Examples of the polycyclic cyclic hydrocarbon group include groups having 5 or more carbon atoms, preferably 7 to 25 carbon alicyclic skeletons. For example, there are alicyclic cyclic hydrocarbon skeletons such as cyclo, tricyclo and tetracyclo. Such a monocyclic or polycyclic cyclic hydrocarbon skeleton may further have a substituent to increase the carbon number.

As a preferable substituent of a polycyclic alicyclic group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amide group, a sulfonamide group, and the alkyl group of the said R <^23> can be used as it is. Halogen atoms are fluorine, chlorine, bromine or iodine. Examples of the substituent further include an alkoxy group, alkoxycarbonyl group, acyl group, acyloxy group, and carboxyl group. Examples of the alkoxy group include alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group. Examples of the acyl group include formyl group, acetyl group and benzoyl group. Examples of the acyloxy group include acetoxy group and butyryloxy group.

Representative structural examples of the polycyclic or monocyclic alicyclic moiety, ie, A, among the polycyclic or monocyclic hydrocarbon groups include those shown below.

Next, General Formula (V) will be described.

In said general formula (V), n is 0 or 1.

Xa and Xb represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Ya and Yb represent a hydrogen atom, a hydroxyl group, or a group represented by -COOXc. Here, Xc represents a hydrogen atom or an alkyl group as one aspect. As this alkyl group, a C1-C8 alkyl group, Preferably, a C1-C4 alkyl group is mentioned, Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, tert- butyl group etc. are mentioned, for example. Can be. Such an alkyl group may have a hydroxyl group, a halogen or a cyano group substituted with some or all of the hydrogen atoms.

In another embodiment of Xc, a group representing an acid-decomposable group in the entirety of -COOXc is represented. Specifically, group represented by said formula (x), (y) is mentioned. In addition, the group containing an acid-decomposable lactone structure, and the prayer containing an acid-decomposable alicyclic structure are mentioned.

Although the specific example of the repeating structural unit represented by general formula (II)-(V) is shown below, this invention is not limited to this.

Among these embodiments, for example, (b1), (b2), (b5), (b9), (b47), (b48), (b49), (b50), (b54), (b58), (b60) ) And the like are generally preferred because of their acid degradability. Especially, (b1), (b47), (b48), and (b49) which the amanthyl group connected with the resin main chain by the acid-decomposable structure are preferable. Use of these improves wet etching resistance and resolution.

The acid-decomposable resin may further include a carboxyl group.

The carboxyl group may be included in each repeating structural unit described above, but may be included in a repeating structural unit different from these.

In addition, they may be included in a plurality of positions among these structural units.

In the acid-decomposable resin contained in the positive photosensitive composition of the present invention, the content of all repeating structural units having the carboxyl group is adjusted by the performance such as alkali developability, substrate adhesion, and sensitivity, but the total repeating structural unit of the acid-decomposable resin It is preferably 0 to 60 mol%, more preferably 0 to 40 wt%, most preferably 0 to 20 wt%.

Although the specific example of the repeating structural unit which has a carboxyl group is shown below, this invention is not limited to this.

In order to improve the performance of the acid-decomposable resin, other polymerizable monomers may be further copolymerized within the range of not significantly impairing the permeability and the wet etching resistance of 220 nm or less of the resin.

The copolymer monomer which can be used has what is shown below.

For example, addition-polymerizable unsaturation selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylic acid amides, aryl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, and the like The compound etc. which have one bond are mentioned.

Specifically, they are acrylic esters, for example, alkyl (preferably having 1 to 10 carbon atoms in an alkyl group) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, Amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-diethylhydroxypropyl acrylate, 5-hydroxypentyl Acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, perfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl Acrylate, methoxyethoxyethyl acrylate;

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) Latex, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate Acrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate Acrylate, perfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like), aryl methacrylate (for example, phenyl methacrylate, naphthyl methacrylate, etc.), methoxyethoxy Butyl methacrylate;

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 group, heptyl group, octyl group , Cyclohexyl group, benzyl group, hydroxyethyl group and the like), N-arylacrylamide, N, N-dialkylacrylamide (as alkyl group having 1 to 10 carbon atoms, for example methyl group, ethyl group, butyl Groups, isobutyl group, ethylhexyl group, cyclohexyl group, and the like), N-arylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide, and the like. ;

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-aryl-methacrylate, N, N-dialkylmethacrylamide (alkyl groups include ethyl group, propyl group and butyl group), N-hydroxyethyl-N-methyl Methacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;

Aryl compounds such as aryl esters (e.g., aryl acetate, caprylic acid, aryl caprylate, aryl laurate, aryl palmitic acid, aryl stearate, aryl benzoate, aryl acetic acid, aryl lactate, etc.), Aryloxyethanol and the like;

Crotonic acid esters such as alkyl crotonate (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); Dialkyl itaconic acid (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.);

Dialkyl esters of maleic acid or fumaric acid (for example, dimethyl maleate, dibutyl maleate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleylonitrile and the like.

Of these, methoxyethoxyethyl methacrylate and methoxyethoxyethyl acrylate are particularly preferable.

As for content of the repeating structural unit derived from the other polymerizable monomer in (B) acid-decomposable resin, 50 mol% or less is preferable with respect to all the repeating structural units, More preferably, it is 30 mol% or less.

From the viewpoint of ensuring permeability to actinic rays or radiation, it is preferable that the (B) acid-decomposable resin does not contain an aromatic ring. When the permeability to radiation is reduced by introduction of an aromatic ring, it is difficult for exposure light to reach a resist film bottom part, and it becomes a pattern profile called a taper.

In the (B) acid-decomposable resin, the content of the repeating structural unit having an acid-decomposable group is adjusted by the balance of wet etching resistance, alkali developability, etc., but it is preferable to contain 20 mol% or more of the total repeating units, more Preferably it is 30 mol% or more, Most preferably, it is 40 mol% or more.

The content of the structural unit having the cyclic hydrocarbon group (preferably a repeating structural unit represented by formulas (II) to (IV)) is adjusted by the balance of wet etching resistance, alkali developability, etc. It is preferable to contain 20 mol% or more with respect to a unit. As for the content, it is more preferable that it is 30-80 mol%, 35-70 mol% is still more preferable, The range of 40-60 mol% is the most preferable.

The content of the repeating structural unit having a lactone structure in the acid-decomposable resin (B) is adjusted by the balance of wet etching resistance, alkali developability, etc., but is preferably 20 mol% or more based on the total repeating structural units. Do. It is more preferable that the content is 30-80 mol%, 35-70 mol% is still more preferable, 40-60 mol% is the most preferable.

In the present invention, the content ratio of the resin whose solubility in the alkaline developer is increased by the action of the acid (B) with respect to the whole composition or solid content except the solvent is preferably 20 to 99.8% by weight, preferably 50 to 99.5% by weight. .

The weight average molecular weight of the acid-decomposable resin (B) is preferably in the range of 1000 to 100000 in polystyrene conversion value measured by the GPC method, more preferably 2000 to 50000, most preferably 3000 to 30000. Moreover, as for dispersion degree, 1.0-5.0 are preferable, More preferably, it is 1.0-3.0.

<< (C) N, N-dialkylcarboxylic acid amide >>

As N, N-dialkylcarboxylic acid amide, there is a compound represented by the following general formula (C).

Ra-CON (Rb) (Rc) general formula (C)

Here, Rb and Rc each independently represent an alkyl group. Ra represents a hydrogen atom, a straight chain, a branched alkyl group or an alicyclic group. The alkyl group of Rb, Rc and the linear or branched alkyl group of Ra are preferably a lower alkyl group having 1 to 4 carbon atoms, and include methyl group, ethyl group, propyl, isopropyl, butyl, isobutyl, t-butyl and the like. Examples of the alicyclic group for Ra include groups such as "monocyclic or polycyclic cyclic hydrocarbon group" in A in General Formulas (II) to (IV) described in the above acid-decomposable resins. Rb and Rc may combine with each other to form a ring. The ring may contain an oxygen atom, a sulfur atom, or a nitrogen atom. Specific examples of the ring include carboxylic acid amides of a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, (C) component includes N, N-di-lower alkylcarboxylic acid amide (when Rb and Rc are lower alkyl groups), in particular, N, N-dimethylformamide and N, N- Dimethylacetamide is preferred.

In addition, in view of improving wet etching resistance, it is preferable that Ra represents an alicyclic group, for example, N, N-dimethyl-1-ademantancarboxylic acid amide, N, N-dimethylcholate amide, N, N, N-dialkylcarboxylic acid amide which has monocyclic or polycyclic cyclic hydrocarbon group in carboxylic acid skeleton, such as N-dimethylcyclohexane carboxylic acid amide, is mentioned.

This (C) N, N-dialkylcarboxylic acid amide can be used individually by 1 type or in combination of 2 or more types.

In addition, the compounding quantity is used in 0.1-50 weight% with respect to the photoacid generator (A), Preferably it is used in the range of 1-20 weight%. If the amount is less than 0.1% by weight, there is a concern that the above effect may not be sufficiently exhibited. If the amount exceeds 5% by weight, the effect does not improve with the amount, and the sensitivity may deteriorate.

<< (D) acid-decomposable dissolution inhibiting compound >>

The positive photosensitive composition of the present invention has a group which is decomposed by the action of the acid (D) to increase the solubility in the alkaline developer, and has a molecular weight of 3000 or less dissolution inhibiting low molecular compound (hereinafter referred to as an "acid-decomposable dissolution inhibiting compound"). It is preferable to contain.

Particularly, in order not to lower the permeability of 220 nm or less, (D) an acid-decomposable dissolution inhibiting compound, such as a cholic acid derivative including an acid-decomposable group described in Preciding of SPIE, 2724, 355 (1996), contains an acid-decomposable group. Alicyclic or aliphatic compounds are preferred. The acid-decomposable group and the alicyclic structure include those described in the acid-decomposable resin.

(D) The addition amount of the acid-decomposable dissolution inhibiting compound is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solids of the whole composition of the positive photosensitive composition.

Although the specific example of the (D) acid-decomposable dissolution inhibiting compound is shown below, it is not limited to this.

<(F) nitrogen-containing basic compound >>

It is preferable that the photosensitive composition of this invention contains (F) nitrogen-containing basic compound, in order to reduce the performance change by time-lapse from exposure to post-heating.

As a preferable structure, the structure represented by following formula (A)-(E) is mentioned.

Where R²⁵⁰, R²⁵¹And R²⁵²May be the same or different and is 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, wherein R²⁵¹And R²⁵²May combine with each other to form a ring.

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

Specifically preferred are substituted or unsubstituted guanidines, 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 Razin, 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.

Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4- Dimethylaminopyridine, 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-aminomorpholine, 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, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylaniline, Although N-cyclohexyl-N'- morpholino ethylthio urea etc. are mentioned, It is not limited to these.

These nitrogen-containing basic compounds may be used alone or in combination of two or more thereof. The usage-amount of (F) nitrogen-containing basic compound is 0.001-10 weight% normally, Preferably it is 0.01-5 weight% based on solid content 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.

<< (G) fluorine type and / or silicone type surfactant >>

It is preferable that the positive photosensitive resin composition of this invention contains any 1 type, or 2 or more types of fluorine type and / or silicone type surfactant (surfactant which contains both a fluorine type surfactant and a silicone type surfactant, and a fluorine atom and a silicon atom).

Since the positive photosensitive composition of the present invention contains the above-mentioned (G) surfactant, it is not only excellent in sensitivity, resolution, substrate adhesion, and wet etching resistance when using an exposure light source of 250 nm or less, particularly 220 nm or less, but also in particular in developing defects and scum. This little resist pattern is obtained.

As these surfactants, for example, Japanese Patent Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, and Japanese Patent Laid-Open No. 7-230165 Although the surfactant of the 9-54432 and 9-5988 is mentioned as 8-62834, 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 & Chemicals Co., Ltd.), and 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.) and Torosol S-366 (manufactured by Toro Chemical Co., Ltd.) may also be used as the silicone surfactant.

The blending amount of the surfactant is preferably 0.0001% by weight to 2% by weight, more preferably 0.001% by weight to 1% by weight based on the total amount of the positive photosensitive composition.

<< (E) alkali-soluble resin >>

The positive photoresist composition of the present invention may contain a resin which is insoluble in water (E) which does not contain an acid-decomposable group, and which is soluble in an alkaline developer, thereby improving the sensitivity.

In the present invention, novolak resins having a molecular weight of about 1000 to 20000 and polyhydroxystyrene derivatives having a molecular weight of about 3000 to 50000 can be used as such resins, but in order to increase absorption for light of 250 nm or less, It is preferable to use by hydrogenation or in the quantity of 30 weight% or less of the total resin amount.

Moreover, the resin containing a carboxyl group as an alkali-soluble group can also be used. In order to improve wet etching resistance in resin containing a carboxyl group, it is preferable to have a monocyclic or polycyclic alicyclic hydrocarbon group. Specifically, (meth) acrylic acid ester resin of the alicyclic hydrocarbon group which contains a carboxyl group in the copolymer or the terminal of the methacrylic acid ester which has an alicyclic hydrocarbon structure which does not show acid decomposability, or a (meth) acrylic acid is mentioned. .

`` Other substances ''

The positive photosensitive composition of this invention can contain a compound which accelerates solubility to dyes, a plasticizer, surfactant other than the said (D) component, a photosensitizer, and a developing solution as needed.

The dissolution promoting compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1000 or less, having two or more phenolic OH groups or one or more carboxyl groups. In the case of having a carboxyl group, an alicyclic or aliphatic compound is preferable for the same reasons as described above.

The preferred amount of such dissolution promoting compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin which is decomposed by the action of the acid (B) and increases the solubility in the alkaline developer. It is unfavorable at the addition amount exceeding 50 weight% that a developing residue worsens and a new fault which a pattern deform | transforms at the time of image development arises.

Such phenolic compounds having a molecular weight of 1000 or less can be easily understood by those skilled in the art, for example, with reference to the methods described in JP-A 4-122938, 2-28531, US Pat. No. 4,916,210, and European Patent No. 219294. Can be synthesized.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having an steroid structure such as cholic acid, deoxycholic acid, and tricolic acid, ademantancarboxylic acid derivatives, ademantandicarboxylic acid, and cyclohexanecarba. Acid, cyclohexanedicarboxylic acid, etc. are mentioned, but it is not limited to these.

"How to use"

The photosensitive composition of this invention consists of melt | dissolving the said component in a predetermined solvent in the mixed state. It is applied to a predetermined support and used. The solvent used here is ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-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. These solvents can be used individually or in combination of 2 or more types.

Among the above, single or two kinds of 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate and ethyl ethoxypropionate are mixed and used at a ratio of 1/9 to 9/1. It is preferable.

In this invention, surfactant other than the said (D) fluorine type and / or silicone type surfactant can be added. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether Polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, Polyoxyethylene Sorbitan Tristea Sites such as polyoxyethylene, and the like sorbitan fatty acid non-ionic surfactants such as esters.

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

The positive photosensitive composition dissolved in the solvent is applied on a predetermined substrate as follows.

That is, the photosensitive composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of the precision integrated circuit device by a suitable coating method such as a spinner or a coater. After application, a predetermined mask is passed through By exposing and baking and developing, a favorable resist pattern can be obtained, In this case, preferable exposure light is far ultraviolet rays having a wavelength of 150 nm or less, more preferably 220 nm or less, specifically, KrF excimer laser (248 nm) and ArF. Excimer laser (193 nm), F ₂ excimer laser (15 7 nm), X-rays, electron beams and the like.

In the developing process, the developer is used as follows. As a developing solution of the photosensitive composition, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, 1st amines, such as ethylamine and n-propylamine, diethylamine, and di-n- Second amines such as butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions, such as cyclic amines, such as a quaternary ammonium salt, a pyrrole, and piperidine, can be used.

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

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example.

<Synthesis example of resin>

[Synthesis of Resin P1 (a1) / (b1) = 50/50]

To 7.0 g of N, N-dimethylacetamide heated to 60 ° C. under nitrogen stream, 5.0 g of 2-methyl-2-adamantane methacrylate, 4.23 g of mebaronic lactone methacrylate, and a polymerization initiator 2,2′- The solution which melt | dissolved 0.534 g of azobis (2, 4- dimethyl vareronitrile) (light pure chemicals; V-65) in 30.0 g of N, N- dimethylacetamide was dripped over 4 hours. After reacting at 60 ° C. for 2 hours, 0.267 g of V-65 was added and the mixture was further reacted for 2 hours. The reaction solution was poured into 1000 ml of ion-exchanged water, and the precipitated powder was collected. This was dissolved in THF, poured into 1500 ml of hexane, and the powder obtained was dried to obtain Resin (I-1).

The weight average molecular weight of obtained resin was 5500, and dispersion degree (Mw / Mn) was 1.9. In addition, a weight average molecular weight and dispersion degree are polystyrene conversion values measured by the DSC method.

(Synthesis of Resin (P2) to Resin (P12))

Resin (P2)-resin (P12) shown in Table 1 were synthesize | combined in order by the substantially the same method. The molecular weight and dispersion degree of such resin are shown in Table 1.

<Resist adjustment>

EXAMPLES 1-14

The raw material shown in Table 2 was dissolved in propylene glycol monomethyl ether acetate, the solution of 15% of solid content concentration was adjusted, and this was filtered with the 0.1 micrometer Teflon filter, and the photosensitive composition was produced. The prepared composition was evaluated by the following method, and the results are shown in Table 3.

(Explanation of Table 2)

TPSTF; Triphenylsulfonium triplate

TPSPFB; Triphenylsulfoniumperfluorobutanesulfonate

TPSPFOS; Triphenylsulfonium perfluorooctanesulfonate

TBDPIPFBS; Bis (4-t-butylphenyl) iodonium perfluorobutanesulfonate

DMAc; N, N-dimethylacetamide

DMF; N, N-dimethylformamide

AdCAM; N, N-dimethyl-1-ademethane carboxylic acid amide

CAM; N, N-dimethylcholate

CHCAM; N, N-dimethylcyclohexanecarboxylic acid amide

DBN; 1,5-diazabicyclo [4.3.0] -5-nonene

DIA; 2,6-diisopropylaniline

TPI; 2,4,5-triphenylimidazole

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; Toroidol S-366 (product of Toroy Chemical Corporation) (fluorine system)

<Image evaluation method>

(1) Evaluation of phenomena

The photosensitive resin composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate with a spin coater, heated and dried on a hot plate at 120 ° C. for 90 seconds to form a resist film of 0.50 μm. This resist film was exposed to ArF excimer laser light through a mask, and heated on a hot plate at 110 ° C. for 90 seconds immediately after the exposure. Then, the solution was developed at 23 ° C. for 60 seconds in an aqueous solution of tetramethylammonium hydroxide at a concentration of 2.38 wt%, washed with pure water for 30 seconds, and dried. The development defect function of the sample in which the contact hole pattern thus obtained was formed was measured with KLA 2112 (KLA Tencol Co., Ltd. product) (Threshold12, Pixcel Size = 0.39).

(2) Evaluation of sensitivity, resolution, pattern profile, developing residue

The anti-reflective film DUV-42, manufactured by Flow Science, was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater at 600 Hz, dried on a hot plate at 100 ° C. for 90 seconds, and dried by heating at 190 ° C. for 240 seconds. . Then, each photosensitive resin composition was applied with a spin coater and dried at 120 ° C. for 90 seconds to form a resist film of 0.50 μm. The resist film was exposed to an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) through a mask, and heated on a hot plate at 120 캜 for 90 seconds immediately after the exposure. Then, the solution was developed at 23 ° C. for 60 seconds in a 2.38% aqueous tetramethylammonium hydroxide solution, washed with pure water for 30 seconds, and dried to obtain a resist line pattern.

Sensitivity represents the exposure amount which reproduces the mask pattern of 0.20 micrometer.

The resolution represents the limit resolution at an exposure amount that reproduces a mask pattern of 0.20 mu m.

As for the pattern profile, the pattern shape by the scanning electron microscope was observed.

The developing residue was observed with the microscope and the following three stages of evaluation were performed.

O: No development residue

(Triangle | delta): A pattern is formed but a developing residue is confirmed.

X: The part in which the image development residue does not develop to the very bottom exists

The following facts become clear from the results shown in Table 3.

The compositions of Examples 1 to 14 are excellent in sensitivity and resolution, have no development residue, are not only defective in development, but also form an excellent pattern profile.

On the other hand, in the compositions of Comparative Examples 1 to 3, in which N, N-dialkylcarboxylic acid amide was not blended, the shape of the pattern profile was excellent as in Example, and the sensitivity was the same, but the development residue and development defect were It was not good compared with the composition.

The positive photosensitive composition of the present invention is excellent in sensitivity and resolution, there are few developing residues, and development defects can be formed as well as excellent pattern profiles.

Therefore, the positive photosensitive composition of the present invention is preferably used in ultra-microphotographic production processes using ultraviolet light, in particular ArF excimer laser light.

Claims (8)

(A) a compound which generates an acid by irradiation with actinic light or radiation, (B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to increase solubility in an alkaline developer, and ( C) A positive photosensitive composition containing N, N-dialkylcarboxylic acid amide. (D) It further contains a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group which can be decomposed by an acid, and the dissolution rate in an alkali developer is increased by the action of an acid. Positive photosensitive composition. The positive photosensitive composition as claimed in claim 1 or 2, wherein the resin (B) further has a lactone structure. (A) a compound which generates an acid by irradiation of actinic radiation or radiation, (C) a N, N-dialkylcarboxylic acid amide, (D) a group which can be decomposed by an acid, and by the action of an acid A positive photosensitive composition comprising a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, and an resin insoluble in water and soluble in an alkaline developer, wherein the dissolution rate in the alkaline developer is increased. The positive photosensitive composition according to any one of claims 1 to 4, further comprising (F) a nitrogen-containing basic compound. The positive photosensitive composition according to any one of claims 1 to 5, further comprising (G) a fluorine-based and / or silicone-based surfactant. The method according to any one of claims 1 to 6, wherein (C) N, N-dialkylcarboxylic acid amide is at least one of N, N-dimethylacetamide and N, N-dimethylformamide. Positive photosensitive composition. The positive photosensitive composition according to any one of claims 1 to 7, wherein the irradiation light is ultraviolet light having a wavelength of 220 nm or less.