JPH08202038A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE: To provide a positive photosensitive composition capable of easily and suitably preventing acid diffusion and deactivation owing to time lapse from exposure to heat treatment and improving dissolution hindering action and developability and stabilizing good profiles and high resolution. CONSTITUTION: The positive photosensitive composition contains an alkali- soluble resin, and a compound to be allowed to generate an acid, and a block copolymer of a polymer segment (A) comprising an acid decomposable disolution-hindering compound having an acid-decomposable group and increasable in solubility in an alkaline developing solution by action of the acid and having a molecular weight of <=3000, and a polymer component containing F atoms and/or Si atoms in an amount of >=50mol%, and another polymer segment (B) containing these components of (A) in an amount of <=20wt.% or not.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive composition used in semiconductor manufacturing processes such as lithographic printing plates and ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. It is about.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. In the manufacture of semiconductor substrates such as ultra LSIs, it has become necessary to process ultrafine patterns having line widths of half micron or less. In order to achieve this required resolving power, the wavelength used in the exposure apparatus used for photolithography has become shorter and shorter, and far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. When a conventional resist composed of novolak and naphthoquinonediazide compound is used for pattern formation of lithography using far-ultraviolet light or excimer laser light, novolak and naphthoquinonediazide are strongly absorbed in the far-ultraviolet region, so that light reaches the bottom of the resist. It is hard to reach, and only a pattern with low sensitivity and taper can be obtained.

One of means for solving such a problem is
It is a chemically amplified resist composition described in US Pat. No. 4,491,628 and European Patent 249,139. A chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction dissolves the active radiation irradiation area and non-irradiation area in the developing solution. It is a pattern-forming material that changes properties and forms a pattern on a substrate.

As such an example, a combination of a compound capable of generating an acid by photolysis with an acetal or O, N-acetal compound (JP-A-48-89003) or an orthoester or amide acetal compound ( JP-A-51-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1).
No. 33429), a combination with an enol ether compound (JP-A-55-12995), and a combination with an N-acyliminocarbonate compound (JP-A-55-126236).
No.), a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625),
Combination with silyl ester compound (JP-A-60-102)
47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121446).
Etc. can be mentioned. Since these have a quantum yield of more than 1 in principle, they exhibit high photosensitivity.

Similarly, as a system which is stable at room temperature over time but decomposes by heating in the presence of an acid to solubilize with an alkali, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym.Eng.Sce., 23, 101
2 (1983); ACS.Sym.242, 11 (1984); Semicond
uctor World 1987, November issue, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988), etc.
Mention may be made of systems of secondary or primary carbon (eg t-butyl, 2-cyclohexenyl) in combination with ester or carbonate compounds. These systems also have high sensitivity and, compared to the naphthoquinone diazide / novolak resin system, Deep-UV
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The above-mentioned positive chemically amplified resist is a three-component composition comprising an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (a photo-acid generator), and a dissolution inhibiting compound for an alkali-soluble resin having an acid-decomposable group. The system can be roughly classified into a two-component system comprising a resin having a group which is decomposed by a reaction with an acid to be alkali-soluble and a photo-acid generator. In these two-component or three-component positive chemically amplified resists, an acid from a photo-acid generator is interposed by exposure, heat treatment is performed, and development is performed to obtain a resist pattern. Here, as the standing time from exposure to heat treatment (PEB treatment) becomes longer, the generated acid diffuses,
Further, there is a problem that the basic impurities in the atmosphere deactivate the acid on the surface of the resist, thereby changing the sensitivity and the profile and line width of the resist pattern after development.

As a means for solving these problems, a technique of adding a low molecular weight amine to a chemical amplification system is disclosed in JP-A-63-14.
9640, JP-A-5-232706, and JP-A 5-2
49662, JP-A-5-127369, W
O-94 / 1805 and the like. In these techniques, the low-molecular amine easily moves in the resist film, and the resist solution is applied, dried, and exposed to PE.
Since the low molecular weight amine volatilizes and diffuses during the process such as B treatment, the effect of adding the amine is insufficient. On the other hand, in Japanese Patent Laid-Open No. 4-75062,
It has been reported that the inclusion of a tertiary amine in the base polymer can prevent the acid generated by exposure from diffusing and improve the dimensional accuracy of the resist pattern.
However, the amount of the tertiary amine needs to be finely adjusted according to the amount of acid generated. When the tertiary amine is introduced into the base polymer as in the above technique, it is practically difficult to finely adjust the amount of amine in the polymer corresponding to the amount of acid generated. Further, when the above-mentioned base polymer containing a tertiary amine is used, the effect of the base polymer itself becomes insufficient, and a part of the non-image area is eluted during development, or it may be a cause of development residue (scum) in the image area. There was something to do.

Further, WO 92/05474 and European Patent No. 0476840 (A) propose to prevent an acid from being deactivated by a basic substance from the outside by providing an overcoat layer. In this case, since a new layer is provided, the number of steps is increased, which causes a cost increase. Furthermore, it is generally not easy to uniformly coat the overcoat layer and obtain stable performance.
Even if the overcoat layer could be applied uniformly, the development characteristics would be impaired due to changes in solubility in the developing solution, and the resist pattern and profile would change.

[0009]

Therefore, the object of the present invention is to easily and appropriately prevent the diffusion or deactivation of the acid with the passage of time from the exposure to the heat treatment, and improve the dissolution inhibiting effect and the developability. And to provide a positive photosensitive composition having a stable and good profile and high resolution.

[0010]

Means for Solving the Problems As a result of intensive studies made by the present inventors while paying attention to the above various characteristics, the object of the present invention is to obtain the following in a three-component or two-component positive chemical amplification system. The inventors have reached the present invention by finding out what is achieved by using a resin containing a fluorine atom and / or a silicon atom. That is, the present invention includes (a) a resin insoluble in water and soluble in an alkaline aqueous solution, (b) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (c) a group decomposable by an acid, 50% by weight of a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, and (d) a fluorine atom and / or a silicon atom-containing polymer component, the solubility of which in a developing solution is increased by the action of an acid. A polymer segment (A) contained above and a polymer segment (B) containing no or even 20% by weight or less of the polymer component, containing a block-bonded copolymer. It is a positive photosensitive composition.

The present invention also relates to (1) a compound which generates an acid upon irradiation with actinic rays or radiation, and (2) a resin having a group which decomposes by the action of an acid to increase the solubility in an alkaline developing solution. And (3) a polymer segment (A) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, and a polymer segment containing no or even 20% by weight of the polymer component. A positive-type photosensitive composition, characterized in that it contains a copolymer in which the united segment (B) is bonded with a block.

As described above, in the chemically amplified resists of the three-component type and the two-component type, the block copolymer containing a fluorine atom and / or a silicon atom is contained so that the resist is present inside the resist composition. The above-mentioned copolymer becomes unevenly distributed in the outermost surface layer portion of the resist during the coating and drying process. Due to the action of the polymer unevenly distributed on the resist surface, deactivation of the acid due to a basic substance from the outside can be prevented. As a result, it is possible to prevent excessive acid diffusion and acid deactivation on the resist surface portion, and to obtain a positive photosensitive composition having stable and good profile and resolution. Further, in the present invention, as in the conventional case,
Even if an overcoat layer, which is a new layer, is not provided on the resist surface, invasion of a basic substance from the outside can be prevented, so that no new process is added and the cost does not increase. Further, even if the overcoat layer, which is a new layer, is not provided, the same or higher effect can be obtained, and when the new layer is provided, it is difficult to apply it uniformly and obtain stable performance. In the present invention, since the block copolymer containing a fluorine atom and / or a silicon atom is automatically localized in the surface layer portion as described above, such a problem does not occur at all.

Furthermore, since a substance such as basic nitrogen is not introduced into the main component (base polymer etc.) of the three-component system or the two-component system, the interaction between the base polymer (alkali-soluble resin) and the dissolution inhibitor is As a result, the dissolution inhibiting agent maintains the dissolution inhibiting effect of the non-image area during development, and the dissolution of the non-image area can be prevented. On the other hand, it is possible to prevent undeveloped residue in the image area and obtain a positive photosensitive composition having a good profile and high resolution.

The compounds used in the present invention will be described in detail below. (I) A polymer segment (A) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, and 20 or not containing the polymer component.
A copolymer in which the polymer segment (B) is contained in a weight percentage of less than or equal to a block (hereinafter referred to as resin [P]) The polymer component containing a fluorine atom and / or a silicon atom is a resin [P]. It may be incorporated into the polymer main chain or it may be contained as a substituent of the polymer side chain.

Examples of the polymer component containing a fluorine atom include -C _h F _{2h + 1} (h represents an integer of 1 to 18). _{- (CF 2) j CF 2} H (j is an integer of 1~17), - CFH ₂

[0016]

Embedded image

Monovalent organic residues such as --CF _2- , --CFH
-,

[0018]

Embedded image

And the like divalent organic residues and the like. Examples of the substituent containing a silicon atom include, for example,

[0020]

Embedded image

Examples thereof include monovalent or divalent organic residues. However, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and may be an optionally substituted hydrocarbon group or —O.
R ₆ group (R ₆ has the same meaning as the hydrocarbon group of R _{1 to} R ₅ ) is represented.

The hydrocarbon group represented by R _{1 to} R ₅ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group). , Dodecyl group, hexadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2,2,2-
Trifluoroethyl group, 2-cyanoethyl group, 3,3
3-trifluoropropyl group, 2-methoxyethyl group,
3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, etc., and an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, , 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl. Group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) , Carbon number 5
To 8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic groups having 6 to 12 carbon atoms (eg, Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , A bromophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, a dodecyloylamidophenyl group and the like).

In the --OR ₆ group, R ₆ is the above R _{1 to} R.
It has the same meaning as the hydrocarbon group of ₅ . Further, the fluorine atom- and silicon atom-containing organic residue may be constituted in combination, and in that case, they may be directly bonded or may be bonded via another linking group. .

Specifically, as a group to be linked, a divalent organic residue is used.
A group, which is -O-, -S-, -N (R₁)-,-SO
-, -SO₂-, -COO-, -OCO-, -CONH
CO-, NHCONH-, -CON (R₁)-,-SO₂
N (R₁)-, Etc. may be interposed.
A divalent aliphatic group or a divalent aromatic group, or
Organic residue composed of a combination of these divalent residues
Is mentioned. Where R ₁Is as described above.

As the divalent aliphatic group, for example,

[0026]

[Chemical 4]

(E ₁ and e ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, methyl group). Group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.).
Is -O -, - S- or -NR ₂₀ - represents, R ₂₀ represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br).

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like. Next, specific examples of the repeating unit having the above-mentioned polymer component containing a fluorine atom and / or a silicon atom are shown below. However, the scope of the present invention is not limited to these.

[0030] However -R _f denotes the following represents a substituent. _{1) -C n F 2n + 1} 2) -CH 2 C n F
_{2n + 1 3) -CH 2 CH} 2 C n F 2n + 1 4) -CH 2 (CF 2) m
_{CFHCF 3 5) -CH 2 CH 2} (CF 2) m CFHCF 3 6) -CH 2 CH 2 (CF 2) m CFHCF 2 H 7) -CH 2 (CF 2) m CFHCF 3 8) -CH (CF 3 ) ₂

[0031]

Embedded image

However, n: integer of 1-18, m: integer of 1-18, integer of 1: 1-5 b represents a hydrogen atom or a methyl group.

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[0035]

Embedded image

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

Embedded image

[0042]

[Chemical 15]

[0043]

Embedded image

[0044]

[Chemical 17]

In the resin [P] used in the present invention,
In the block (A) containing the fluorine atom and / or silicon atom-containing polymer component, the polymer component contains at least 50% by weight, preferably 70% by weight, of the total amount of the entire block (A). , And more preferably 80% by weight or more.

In the other block (B) formed by combining with the block (A), the fluorine atom and / or silicon atom-containing polymer component is 20% by weight of the total amount of the block (B).
It is below, preferably 0% by weight. The weight ratio of the block (A) to the block (B) is 1 to 95: 5 to 9
9 (weight ratio), preferably 5 to 90 to 10 to 95
(Weight ratio).

In the block (A) or the block (B), components that may be contained in addition to the fluorine atom and / or silicon atom-containing polymer component include acrylic acid esters, methacrylic acid esters, acrylamides,
Examples thereof include homopolymers or copolymers of allyl compounds, vinyl ethers, crotonic acid esters, styrenes and the like.

Preferred embodiments of the resin [P] used in the present invention will be described below. That is, in the resin [P], any polymer may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of a block. For example, an AB type block, an ABA type block, a B-type block A-
Examples thereof include B type blocks, graft type blocks and star type blocks. The weight average molecular weight of the resin [P] is 2 × 10 ³ to 1 × 10 ⁶ , preferably 5 × 10 ³ to
It is 5 × 10 ⁵ . The weight average molecular weight of the block (A) and the block (B) is preferably at least 1 × 10 ³ or more.

These various block copolymers [P] can be synthesized by a conventionally known polymerization method. For example, WJBurlant, ASHoffman “Block and Graft poly
"mers" (1960, Renhald), RJ Ceresa, "Block
and Graft Polymers ”(1962, Butterworths),
DCAllport, WHJames “Block Copolymers” (197
2 years, Applied Sci), A.Noshay, JFMcGvath “Block
Copolymers ”(1977, Academic press], G. Huvt
rez, DJ Wilson, G.Riess, NATO ASI Sev. Sev E.19
85, 149, V. Percea, Applied. Polymer Sci. 28
5, 95 (1985) and the like, and are described in reviews.

For example, organometallic compounds (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides,
For the ionic polymerization reaction using alkylaluminum halides as a polymerization initiator, see TE Hogeu-Esch, J. Smid,
“Receuet Advances in Anionic Polymerization” (1
987, Elsevier New York) Yoshio Okamoto, Polymer, 3
8, 912 (1989), Mitsuo Sawamoto, Polymer, 38, 1
018 (1989), Tadashi Narita, Polymer, 37, 252
(1988), BC Anderson, et al, Macromolecules.
14, 1601 (1981), S. Aoshima, T. Higashimu
ra, Macromolecules 22, 1009 (1989) and the like.

Regarding the ionic polymerization reaction with hydrogen iodide / iodine system, etc., T. Higashimura et al, Macromol.
Chem., Macromol. Symp., 13/14, 457 (198
8), Toshibu Higashimura, Mitsuo Sawamoto, Transactions on Polymers 46,189
(1989) and the like. For group transfer polymerization reaction, see DYSogah et al, Macromolecules 2
0, 1473 (1987), OWWebster, DYSogah,
High Polymer, 36, 808 (1987), MTReetg, et a
l, Angew Chem. Int. Ed. Engl. 25, 9108 (19
86) Described in JP-A-63-97609.

Regarding the living polymerization reaction using the metalloporphyrin complex, T. Yasuda, T. Aida, S. Inoue, Ma.
cromolecules, 17, 2217 (1984), M. Kuroki,
T. Aida, S. Inoue, J. Ann. Chem. Soc. 109, 473
7 (1987), M. Kuroki et al, Macromolecules, 2
1, 3115 (1988), M. Kuroki, I. Inoue, Synthetic Organic Chemistry, 47, 1017 (1989) and the like.

Further, regarding ring-opening polymerization reaction of cyclic compounds, S. Kobayashi, T. Saegusa, “Ring Opening Polym
erization ”(1984, Applied Science Publisher)
s, Ltd), W. Seeliger et al. Angew. Chem. Int .Eng
l. 5, 875 (1966), S. Kobayashi et al, Pol.
y, Bull. 13, 447 (1985), Y. Chujo et al, M
acromolecules, 22, 1074 (1989) and the like.

Furthermore, regarding the photoliving polymerization reaction using a dithiocarbalite compound, a xanthate compound or the like as an initiator, Takayuki Otsu, Polymer, 37, 248.
(1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap.
37, 3508 (1988), JP-A-64-111,
Japanese Unexamined Patent Publication No. 64-26619, M. Niwa, Macromolecules,
189, 2187 (1988) and the like.

On the other hand, by radical polymerization reaction using a polymer containing an azo group or a peroxide group as an initiator,
A method of synthesizing a block copolymer is described in Akira Ueda et al., Polymers, 33, 931 (1976), Akira Ueda, Osaka City Research Institute Report 84, (1989), O. Nuyken et al, Ma.
cromol. Chem., Rapid. Commun. 9, 671 (198)
8), Yasuo Moriya et al., Reinforced plastic, 29, 907
(19), Ryohei Oda, Science and Industry 61, 43 (19
87) and the like.

Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned textbooks and reviews, further, Fumio Ide,
"Graft Polymerization and Its Applications" (1977, Polymer Society), edited by The Society of Polymer Science, "Polymer Alloy" (1981)
Year, Tokyo Kagaku Dojin) etc. For example, polymer chains, polymerization initiator, chemical actinic rays (radiation, electron beam, etc.)
A method of grafting by mechanochemical reaction in mechanical application, a method of grafting by chemical bonding (so-called interpolymer reaction) using macromolecules and functional groups of macromolecules, or macromonomer There is known a method of performing a polymerization reaction and grafting using the same.

Specific examples of the grafting method using a polymer include T. Shiota et al, J. Appl. Polym. Sc.
i.13, 2447 (1969), WHBuck, Rubber Che
mistryand Technology, 50, 109 (1976), Takeshi Endo, Tsutomu Yokozawa, Japan Adhesive Society Journal, 24, 323 (198)
8), Takeshi Endo, ibid, 25, 409 (1989) and the like.

As a method of polymerizing and grafting using a macromonomer, specifically, P. Dreyfuss &
RPQuirk, Encycl. Polym. Sci. Eng. 7, 551 (1
987), PFRempp, E.Franta, Adv. Polym. Sci., 5
8, 1 (1984), V. Percec, Appl. Poly. Sci., 2
85, 95 (1984), R. Asami, M. Takari, Macromo.
l. Chem. Suppl., 12, 163 (1985), P. Remp
p., et al, Macromol. Chem. Suppl., 8, 3 (198
4), Yusuke Kawakami, Chemical Industry, 38, 56 (1987),
Yuya Yamashita, Kobunshi, 31,988 (1982), Shiro Kobayashi, Kobunshi, 30,625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18,536 (1982), Koichi Ito,
Polymer Processing, 35, 262 (1986), Takashi Higashi, Takashi Tsuda, Functional Materials, 1987, No. 10, 5, edited by Yuya Yamashita, "Chemistry and Industry of Macromonomers" (1989,
IPC Corporation, edited by Takeshi Endo, "Molecular Design of New Functional Polymers" Chapter 4 (1991, CMC Corporation, Y.Yamashita et al.Polym. Bull. 5, 36)
1 (1981) and the like.

The synthesis method of the star type block copolymer is as follows:
For example, MT Reetz, Angew. Chem. Int. Ed. Engl. 27,
1373 (1988), M. Sgwarc. “Carbanions, Livin.
g Polymers and Electron Transfer Processes ”(19
1968, Wiley. New York) B. Gordon et al, Polym. Bu
ll., 349 (1984), RBBates et al, J. Or.
g. Chem. 44, 3800 (1979), Y. Sogah, AC
S.Polym. Repr. 1988, No.2, 3, JWMays, Polym. B
ul. 23, 247 (1990), IMKhan. et al, Macr.
omolecules, 21, 2684 (1988), A. Morikaw
a, Macromolecules, 24, 3469 (1991), Akira Ueda, Susumu Nagai, Polymer, 39, 202 (1990), T.
Otsu, Polym. Bull. 11, 135 (1984) and the like.

The synthesis method of the block copolymer (P) of the present invention is not limited to these methods. The amount of the resin (P) added to the photosensitive composition (excluding the coating solvent) is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, based on the total solid content. .

(II) Resin insoluble in water and soluble in aqueous alkali solution (hereinafter, also referred to as alkali-soluble resin) (Compound of the invention (a)) Examples of the alkali-soluble resin used in the invention include novolac resin and hydrogen. Novolak resin, acetone-
Pyrogallol resin, o-polyhydroxystyrene, m-
Polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m /
p-Hydroxystyrene Copolymer, Partial O-Alkyl Compound for Polyhydroxystyrene Hydroxyl Group (eg,
5 to 30 mol% O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O
-2-tetrahydropyranyl compound, O- (t-butoxycarbonyl) methyl compound, etc.) or O-acyl compound (for example, 5 to 30 mol% o-acetyl compound, O-
(T-butoxy) carbonyl compound, etc., styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof. However, the present invention is not limited to these. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene,
It is a partially O-alkylated or O-acylated product of polyhydroxystyrene, a styrene-hydroxystyrene copolymer, and an α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by addition-condensing an aldehyde with a predetermined monomer as a main component in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2 -Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, alkoxyphenols such as p-butoxyphenol, 2-methyl-4-isopropyl Feno Bis-alkylphenols etc., m
-Hydroxy aromatic compounds such as chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. It is not something that will be done.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-.
Phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
Although p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, formaldehyde is used among them. Is preferred. These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. Particularly preferred is 2,000-20,
The range is 000. The weight average molecular weight of the polyhydroxystyrene other than the novolac resin, its derivative, and the copolymer is 2000 or more, preferably 5000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25000 or more is preferable. here,
The weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography. Two or more of these alkali-soluble resins in the present invention may be mixed and used. The amount of alkali-soluble resin used is
5 based on the total weight of the photosensitive composition (excluding solvent)
It is 0 to 97% by weight, preferably 60 to 90% by weight.

(III) Compound that Generates Acid by Irradiation with Actinic Rays or Radiation (Compound of the Invention (b)) As the compound used in the invention, which decomposes by irradiation with actinic ray or radiation to generate acid , A photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a compound that generates an acid by known light used for micro resist and the like. The mixture can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., diazonium salts, U.S. Pat.No. 4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Ammonium salt, DC Necker et al, Macrom
olecules, 17,2468 (1984), CSWen et al, Teh, Proc.Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Phosphonium salts described in 4,069,055, 4,069,056, etc., JV Crivello et al, Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
4,143, U.S. Pat.No. 339,049, No. 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, JVCrivello et al, Polymer J. 17,73 (1985),
JVCrivello et al. J. Org. Chem., 43, 3055 (1978), WR
Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22,1789
(1984), JVCrivello et al, Polymer Bull., 14,279 (198
5), JVCrivello et al, Macromorecules, 14 (5), 1141 (19
81), JVCrivello et al., J. Polymer Sci., Polymer Chem.
Ed., 17,2877 (1979), European Patent No. 370,693, and 3,902,1
No. 14 233,567, 297,443, 297,442, U.S. Pat.Nos. 4,933,377, 161,811, 410,201, 339,0
No. 49, No. 4,760,013, No. 4,734,444, No. 2,833,827
Patent No. 2,904,626, No. 3,604,580, No. 3,604,
Sulfonium salts described in No. 581, JVCrivello et al, M
acromorecules, 10 (6), 1307 (1977), JVCrivello etal,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) and other selenonium salts, CSWen et al, Teh, Proc.Conf.R.
ad.Curing ASIA, p478 Tokyo, Oct (1988) etc. onium salts such as arsonium salts, U.S. Patent No. 3,905,815,
JP-B-46-4605, JP-A-48-36281, JP-A-55-32070
JP-A-60-239736, JP-A-61-169835, JP-A-61
-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, organic halogen compounds described in K. Meier et al., J. Rad.Curing, 13 (4), 26 (1
986), TPGill et al., Inorg. Chem., 19,3007 (1980), D.
Astruc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-161
Organic metal / organic halides described in No. 445, S. Hayas
e et al, J. Polymer Sci., 25,753 (1987), E. Reichmanis e
tal, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q.
Q.Zhu 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., 3571 (1965), PMCollins et al, J.Ch
em.SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Tetr
ahedron Lett., (17), 1445 (1975), JWWalker et al J. Am.
Chem.Soc., 110, 7170 (1988), SCBusman et al, J. Imaging
Technol., 11 (4), 191 (1985), HM Houlihan et al, Macorm
olecules, 21,2001 (1988), PMCollins et al, J. Chem. So
c., Chem. Commun., 532 (1972), S. Hayase et al, Macromolec
ules, 18, 1799 (1985), E. Reichmanis et al, J. Electroche
m.Soc., Solid State Sci.Technol., 130 (6), FM Houliha
n et al, Macromolcules, 21, 2001 (1988), European Patent 029
0,750, 046,083, 156,535, 271,851, and
0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
M.TU, a photo-acid generator having an o-nitrobenzyl type protecting group described in JP-A No. 60-198538, JP-A No. 53-133022 and the like.
NOOKA et al, Polymer Preprints Japan, 35 (8), G. Berner
etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating Tec
hnol., 55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer
Preprints, Japan, 37 (3), European Patent 0199,672, 845
No. 15, No. 199,672, No. 044,115, No. 0101,122, U.S. Pat. -140109
No. 61-166544, which is a compound capable of generating a sulfonic acid by photolysis, represented by iminosulfonates described in JP-A No. 61-166544.
And the disulfone compounds described in JP-A No. 1994-242242.

Further, a group generating an acid by these light,
Alternatively, a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al., J. Am. Chem. So.
c., 104,5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S.Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamada et al, Makromol.Che
m., 152,153,163 (1972), JVCrivello et al, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
9,137, Japan Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038.
JP-A-63-163452, JP-A-62-153853, JP-A-6
The compounds described in 3-146029 and the like can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

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

[0070]

Embedded image

In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —CY ₃ . Y ₃ represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0072]

[Chemical 19]

[0073]

Embedded image

[0074]

[Chemical 21]

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

[0076]

[Chemical formula 22]

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

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof. Here, as a preferable substituent, for an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ −, SiF ₆ ²⁻ , ClO ₄ ⁻ ,
Perfluoroalkane sulfonate anions such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anions, condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, sulfonate group-containing dyes, etc. Examples thereof include, but are not limited to:

Also, two of R ³ , R ⁴ , and R ⁵ and A
r ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0082]

[Chemical formula 23]

[0083]

[Chemical formula 24]

[0084]

[Chemical 25]

[0085]

[Chemical formula 26]

[0086]

[Chemical 27]

[0087]

[Chemical 28]

[0088]

[Chemical 29]

[0089]

Embedded image

[0090]

[Chemical 31]

[0091]

Embedded image

[0092]

[Chemical 33]

[0093]

Embedded image

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnap.
czyk 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), U.S. Pat.No. 2,807, 64
It can be synthesized by the method described in No. 8 and No. 4,247,473, JP-A-53-101,331 and the like.

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

[0096]

Embedded image

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0098]

Embedded image

[0099]

Embedded image

[0100]

[Chemical 38]

[0101]

[Chemical Formula 39]

[0102]

[Chemical 40]

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 01 to 40% by weight, preferably 0.0
It is used in the range of 1 to 20% by weight, more preferably 0.1 to 5% by weight.

(IV) Acid-decomposable dissolution inhibiting compound (Compound of the present invention (c)) The acid-decomposable dissolution inhibiting compound used in the present invention is
Having at least two groups capable of being decomposed by an acid in its structure,
It is a compound having at least 8 bond atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. In the present invention, the acid-decomposable dissolution inhibiting compound preferably has at least two groups capable of decomposing with an acid in its structure, and the acid-decomposable group is present at the position where the distance between the acid-decomposable groups is the longest. At least 10 bond atoms excluding
Preferably, at least 11, more preferably at least 12 compounds, or at least three acid-decomposable groups are present, and the bond excluding the acid-decomposable groups is located at the position where the distance between the acid-decomposable groups is the longest. A compound having at least 9, preferably at least 10 and more preferably at least 11 atoms. Also, the preferable upper limit of the number of bonding atoms is 50, and more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more acid-decomposable groups, preferably four or more, and even when it has two acid-decomposable groups, the acid-decomposable groups have each other. When they are separated by a certain distance or more, the dissolution inhibiting property for the alkali-soluble resin is significantly improved. The distance between acid-decomposable groups in the present invention is indicated by the number of via bond atoms excluding acid-decomposable groups. For example, in the following compounds (1) and (2), the distance between acid-decomposable groups is 4 bonding atoms each, and in compound (3), 12 bonding atoms.

[0105]

Embedded image

The acid-decomposable dissolution inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one benzene ring has one acid-decomposable group. It is a compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution-inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000.
It is 0, more preferably 1,000 to 2,500.

[0107] In a preferred embodiment of the present invention may be decomposed by an acid group, i.e. ^{-COO-A 0, -O-B} 0
The group containing a group, -R ⁰ -COO-A ^0, or -Ar
Examples thereof include a group represented by —O—B ⁰ . Where A ⁰ is −
C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ).
(R ^{0 3} ) or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group,
⁰⁶ represents an alkyl group or an aryl group. However, R ⁰¹
At least two of R ⁰³ are groups other than hydrogen atom,
Further, two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher aliphatic or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent or higher divalent aromatic group which may have a monocyclic or polycyclic substituent. Indicates an aromatic group.

Here, the alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four is preferable. Further, a hydroxyl group as a substituent,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group or a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, acyl such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, etc. Groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups.
Examples thereof include alkenyloxy groups such as propenyloxy group, allyloxy group and butenyloxy group, the above aryl groups, aryloxy groups such as phenoxy group, and aryloxycarbonyl groups such as benzoyloxy group.

Preferably, a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a third group
And a tertiary alkyl ether group, a tertiary alkyl ester group, and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

The acid-decomposable dissolution inhibiting compound is preferably JP-A-1-289946 or JP-A-1-2899.
47, JP-A-2-2560, JP-A-3-12895.
No. 9, JP-A-3-158855, JP-A-3-1793.
53, JP-A-3-191351, and JP-A-3-200.
No. 251, JP-A-3-200252, and JP-A-3-20.
No. 0253, JP-A-3-200254, and JP-A-3-2
No. 00255, JP-A-3-259149, and JP-A-3-25949
279958, JP-A-3-279959, JP-A-4
-1650, JP-A-4-1651, JP-A-4-11
260, JP-A-4-12356, JP-A-4-123
57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032.
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
885, Japanese Patent Application Nos. 4-107889 and 4-1521
Compounds protected by bonding some or all of the phenolic OH groups of the polyhydroxy compounds described in the specification such as No. 95 with the groups shown above, —R ⁰ —COO—A ⁰ or B ⁰ groups, included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, and JP-A-3-2002.
51, JP-A-3-200252, and JP-A-3-200.
255, JP-A-3-259149, and JP-A-3-27.
No. 9958, JP-A-4-1650, and JP-A-4-112.
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219.
Those using the polyhydroxy compound described in the specification of No. 5 are mentioned.

More specifically, the formulas [I] to [XV
I] can be mentioned.

[0113]

Embedded image

[0114]

[Chemical 43]

[0115]

[Chemical 44]

[0116]

Embedded image

Here, R ¹ , R ² , R ³ , and R ⁴ may be the same or different and each is a hydrogen atom, —R ⁰ —COO—A ⁰ or B ⁰ group, R ₁ : —CO—, —. COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
-SO _3- , or

[0118]

Embedded image

[0119] Here, G = 2 to 6, provided that at least one alkyl group of R _4, R ₅ when the G = 2, R _4, R _5: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH, -C
N, halogen atom, -R ₆ -COOR ₇ or -R _8,
-OH (R _6, R _8: an alkylene group, R _7: a hydrogen atom, an alkyl group, an aryl group or an aralkyl _{group,), R 2, R 3} , R 9 ~R 12, R 15, R 17 ~R 21, R ₂₅ ~
_{R 27, R 30 ~R 32,} R 37 ~R 42, R 46 ~R 49 and R _51:
The same or different, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group, Alternatively, —N (R ₁₃ ) (R ₁₄ ) (R ₁₃ , R ₁₄ : H, alkyl group, or aryl group), R ₁₆ : single bond, alkylene group, or

[0120]

[Chemical 47]

R ₂₂ and R ₂₄ may be the same or different and each is a single bond, an alkylene group, —O—, —S—, —CO—, or a carboxyl group, R ₂₃ : a hydrogen atom, an alkyl group, an alkoxy group, Acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that hydrogen of the hydroxyl group may be substituted with t-butoxycarbonyl group, R ₂₈ , R ₂₉ : the same or different Also, a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in the present application refers to an alkyl group having 1 to 4 carbon atoms, R _{33 to} R ₃₆ : may be the same or different. , A hydrogen atom or an alkyl group, R _{43 to} R _45, which may be the same or different, are a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an alkyl group. Siloxy group, R ₅₀ : hydrogen atom, t-butoxycarbonyl group, or

[0122]

Embedded image

R ₅₂ and R ₅₃ : hydrogen atom, lower alkyl group, lower haloalkyl group, or aryl group, which may be the same or different, R _{54 to} R ₅₇ : hydrogen atom, which may be the same or different,
Hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group,
An acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that each of the four substituents having the same symbol does not have to be the same group, Y: -CO-, Alternatively, —SO ₂ —, Z, B: single bond, or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group, E: single bond, or oxymethylene group, a to z, a1 to y1: when more than one, the groups in () may be the same or different, a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: 0 or An integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or 1
4 integers, j1, n1, z1, a2, b2, c2, d2: 0 or integers 1 to 3, z1, a
At least one of 2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s ), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, but in the case of general formula [V], (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5 is represented.

[0124]

[Chemical 49]

[0125]

Embedded image

[0126]

[Chemical 51]

[0127]

Embedded image

Specific examples of preferable compound skeletons are shown below.

[0129]

Embedded image

[0130]

[Chemical 54]

[0131]

[Chemical 55]

[0132]

[Chemical 56]

[0133]

[Chemical 57]

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

[Chemical formula 61]

[0138]

Embedded image

[0139]

[Chemical formula 63]

[0140]

[Chemical 64]

[0141]

Embedded image

[0142]

[Chemical formula 66]

[0143]

Embedded image

[0144]

[Chemical 68]

[0145]

[Chemical 69]

[0146]

Embedded image

[0147]

Embedded image

R in compounds (1) to (63) is a hydrogen atom,

[0149]

Embedded image

Is represented. However, at least two, or three depending on the structure, are groups other than hydrogen atom, and each substituent R
Do not have to be the same group.

The amount of the compound used in the present invention (c) added is 3 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the photosensitive composition (excluding the solvent). is there.

The same compounds as described above can be used as the compound that generates an acid by actinic rays or radiation used in the two-component chemically amplified resist of the present invention. Further, as a resin having a group that decomposes with an acid and increases the solubility in an alkaline developing solution, the main chain or side chain of the resin, or both the main chain and the side chain,
It is a resin having an acid-decomposable group. Of these, a resin having a side chain having an acid-decomposable group is more preferable. Preferred groups as an acid-decomposable group are the above-COOA ⁰ ,-
O-B ⁰ group, more preferably -R ⁰ -COO.
A ⁰ or a group represented by —A _r —O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si
(R ⁰¹ ) (R ⁰² ) (R ^{0 3} ) or -C (R ⁰⁴ ).
It represents a (R ⁰⁵ ) -O-R ⁰⁶ group. B ⁰ is A ⁰ or -CO
Represents an —OA ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar have the same meaning as above).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group or a tertiary alkyl ester. Group, a tertiary alkyl carbonate group, and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

[0154] Next, as the matrix resin in the case where the group capable of decomposing by an acid is bonded as a side chain, -OH or -COOH in the side chain, preferably -R ⁰ -COOH or -A _r -OH group It is an alkali-soluble resin that has. For example, the alkali-soluble resin of the present invention (a) can be mentioned.

The alkali dissolution rate of these alkali-soluble resins was 170 as measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
A / second or more is preferable. Especially preferably 330A
/ Sec or more (A is angstrom). Further, an alkali-soluble resin having a high transmittance for far ultraviolet light or excimer laser light is preferable from the viewpoint of achieving a rectangular profile. Preferably, the transmittance at 248 nm with a film thickness of 1 μm is 20 to 80%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Polyhydroxystyrene and copolymers thereof, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, part of polyhydroxystyrene, O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α -Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention is described in European Patent No. 254853 and JP-A No. 2-25.
No. 850, No. 3-223860, No. 4-251259.
As disclosed in US Pat. Can be obtained.

Specific examples of the resin having an acid-decomposable group used in the present invention are shown below, but the present invention is not limited thereto.

[0158]

Embedded image

[0159]

[Chemical 74]

[0160]

[Chemical 75]

The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.5, more preferably 0.05 to 0.40, still more preferably 0.05 to 0.30. B / (B + S)>
A value of 0.5 is not preferable because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because a standing wave may remain on the side wall of the pattern.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film loss is large due to the development of the unexposed area, and if it exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,
The range is 000 to 100,000, and more preferably the range is 8,000 to 50,000. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

Two or more kinds of the resins having an acid-decomposable group in the invention may be mixed and used. The amount of these resins used in the present invention is 40 to 99% by weight, preferably 60 to 95% by weight, based on the total weight of the photosensitive composition (excluding the solvent). Furthermore, in order to adjust the alkali solubility, an alkali-soluble resin having no acid-decomposable group may be mixed.

Similarly, the acid-decomposable low molecular weight dissolution inhibiting compound may be mixed. In this case, the content of the dissolution inhibiting compound is 1 to 45% by weight, preferably 3 to 30% by weight, more preferably 5 to 25% by weight, based on the total weight of the photosensitive composition (excluding the solvent). .

In the photosensitive composition of the present invention, if necessary,
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer can be contained.
Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5.
05 (all manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Furthermore, the photosensitive composition of the present invention is obtained by adding a spectral sensitizer as described below and sensitizing it to a wavelength region longer than deep ultraviolet where the photo-acid generator used does not have absorption. Sensitivity can be imparted to the i or g line. Examples of suitable spectral sensitizers include benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline,
N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3'-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but not limited to these.

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

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, 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 tristearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rate, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorine-based surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

The above photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and then passed through a predetermined mask. A good resist pattern can be obtained by exposing, baking and developing.

The developer for the photosensitive composition of the present invention is as follows:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine. Use an alkaline aqueous solution of triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pyrelidine. be able to. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0171]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. Synthesis Example of Resin [P] 1: [P-1] 80 g of methyl methacrylate, macromonomer FM0725 of dimethylsiloxane (Mw1 × 1 manufactured by Chisso Corporation)
A mixed solution of 20 g of 0 ⁴ ) and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. To this, 1.0 g of azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours, and 0.7 g of AIBN was further added and reacted for 4 hours. Weight average molecular weight of the obtained copolymer (abbreviation: Mw)
Was 5.8 × 10 ⁴ (measured by GPC method)

[0172]

[Chemical 76]

Synthesis Examples 2 to 9 of Resin [P]: [P-2] to
[P-9] Synthesis example of resin [P-1], except that each monomer corresponding to the polymer component shown in Table 1 below was used instead of methyl methacrylate and FM-0725. Each polymer was synthesized in the same manner as in Example 1. M of the obtained polymer
The w was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0174]

[Table 1]

[0175]

[Table 2]

Synthesis Example 10 of Resin [P]: [P-10] 2,2,3,4,4-hexafluorobutylmethacrylate
60 g, macromonomer A of methyl methacrylate
A-6 (manufactured by Toagosei Kagaku Co., Ltd., Mw 1 × 10) ^Four) 40
g and benzotrifluoride 200 g mixed solution with nitrogen gas.
It was warmed to a temperature of 75 ° C. under flow. A.I.B.N. 1.0
g, react for 4 hours, and add 0.5 g of A.I.B.N.
And reacted for 4 hours. The Mw of the obtained copolymer was 6.5.
× 10^FourMet.

[0177]

Embedded image

Synthesis Examples 11 to 22 of Resin [P]: [P-1
1] to [P-22] Instead of the monomers and macromonomers used in the synthesis examples of the resin [P-10], monomers and macros corresponding to the polymer components shown in Table 2 below. Each copolymer was synthesized in the same manner as in Synthesis Example 10 except that a monomer was used.
Mw of the obtained copolymer was 4.5 × 10 ^{4 to} 6.5 × 1.
It was in the range of 0 ⁴ .

[0179]

[Table 3]

[0180]

[Table 4]

[0181]

[Table 5]

Synthesis Example 23 of resin [P]: [P-23] 67 g of methyl methacrylate, 22 methyl acrylate
A mixed solution of g, methacrylic acid 1 g and toluene 200 g was heated to a temperature of 80 ° C. under a nitrogen stream. To this, 10 g of a polymeric azobis initiator [P-I-1] having the following structure was added and reacted for 8 hours. After the reaction, methanol 1.5
Re-flow into liter to collect and dry the resulting precipitate,
A copolymer [P-23] having an Mw of 3 × 10 ⁴ was obtained with a yield of 75 g.

[0183]

Embedded image

[0184]

Embedded image

Synthesis Example 24 of Resin [P]: [P-24] 70 g of methyl methacrylate and tetrahydrofuran 2
Thoroughly degas the mixed solution of 00g under a nitrogen stream, and
Cooled to ° C. 1,1-diphenylbutyllithium 0.
8 g was added and reacted for 12 hours. Furthermore, in this mixed solution,
30 g of the following monomer (M-1) and tetrahydrofuran 6
0 g of the mixed solution was thoroughly degassed under a nitrogen stream and then added, and the mixture was further reacted for 8 hours. After this mixture was heated to 0 ° C., 10 ml of methanol was added and the mixture was reacted for 30 minutes to terminate the polymerization. The resulting polymer solution was stirred at a temperature of 30
The temperature was adjusted to 0 ° C, and 3 ml of a 30% hydrogen chloride ethanol solution was added thereto, followed by stirring for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The Mw of the polymer obtained by collecting the precipitate and drying it under reduced pressure was 6.8 × 10 ⁴ , and the yield was 76 g.

[0186]

Embedded image

Synthesis Example 25 of Resin [P]: [P-25] 52.5 g of methyl methacrylate: 22.5 g of methyl acrylate (tetraphenyl polyfinate) A mixed solution of 0.5 g of aluminum methyl and 200 g of methylene chloride was used as a nitrogen stream. The temperature was set to 30 ° C. below. 300W for this
-Xenon lamp light 25 cm through glass filter
It was irradiated with light from the distance of and reacted for 20 hours. 25 g of the following monomer (M-2) was further added to this mixture, and 1
After irradiation with light for 2 hours, 3 g of methanol was added to the reaction mixture.
Was added and stirred for 30 minutes to stop the reaction. Next, the reaction mixture was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. The obtained polymer had a yield of 78 g and M
It was w7 × 10 ⁴ .

[0188]

[Chemical 81]

Synthesis Example 26 of Resin [P]: [P-26] A mixture of 60 g of methyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to 50 ° C. Warmed. For this, 40
Photopolymerization was carried out by irradiating with a 0 W high pressure mercury lamp from a distance of 10 cm through a glass filter for 6 hours. This was dissolved in 100 g of tetrahydrofuran, and the following monomer (M-
3) After adding 40 g, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours.

The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer has a yield of 73 g.
And the Mw was 4.8 × 10 ⁴ .

[0191]

[Chemical formula 82]

Synthesis Example 27 of Resin [P]: [P-27] Methyl methacrylate 50 g, ethyl methacrylate 2
A mixture of 5 g and 1.0 g of benzylisopulzanate was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization.

This polymer was concentrated with tetrahydrofuran to a concentration of 4
A 0% solution was prepared, to which 125 g of monomer M was added, and the atmosphere was replaced with nitrogen, followed by irradiation with light for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected and dried to obtain a polymer having a yield of 63 g and an Mw of 6 × 10 ⁴ .

[0194]

[Chemical 83]

Synthesis Examples 28 to 34 of Resin [P]: [P-2
8] to [P-34] Each copolymer shown in Table 3 below was synthesized in the same manner as in the synthesis example of the resin [P-26]. The Mw of the obtained polymer is 3.5.
It was in the range of × 10 ^{4 to} 6 × 10 ⁴ .

[0196]

[Table 6]

[0197]

[Table 7]

Synthesis Example 35 of Resin [P]: [P-35] In the synthesis example of Resin [P-26], benzyl N, N-
The reaction was performed in the same manner as in Synthesis Example 26 except that 18 g of an initiator [I-1] having the following structure was used instead of diethyldithiocarbamate to obtain a copolymer having Mw of 4.5 × 10 ⁴ .

[0199]

[Chemical 84]

Synthesis Example 36 of Resin [P]: [P-36] Synthesis Example of Resin [P-27], except that 2.5 g of an initiator having the following structure was used instead of benzyl isopropyl xanthate. Reacts as in Example [P-27], Mw
A 7.2 × 10 ⁴ copolymer was obtained.

[0201]

Embedded image

Synthesis Example 37 of Resin [P]: [P-37] 67 g of methyl methacrylate and 32 g of methyl acrylate
g, acrylic acid 1 g, and an initiator [I-2] 1 having the following structure
A mixed solution of 7.5 g and tetrahydrofuran 150 g was heated to a temperature of 50 ° C. under a nitrogen stream. 400 in this solution
Photopolymerization was performed by irradiating with a W high pressure mercury lamp from a distance of 10 cm through a glass filter for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having a Mw of 4.0 × 10 ^{4 in} a yield of 72 g.

70 g of this polymer, 30 g of monomer (M-2)
A mixed solution of g and tetrahydrofuran (100 g) was irradiated with light under a nitrogen stream at a temperature of 50 ° C. under the same conditions as above for 13 hours. Next, the reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a yield of 78 g and an Mw of 6 g.
A copolymer of × 10 ⁴ was obtained.

[0204]

[Chemical 86]

Synthesis Examples 38 to 48 of Resin [P]: [P-3
8] to [P-48] In the synthesis example 37 of the resin [P], the initiator [I-2] 1
Instead of 7.5 g, the initiator [I] 0.0 shown in Table 4 below was used.
It operated on the same conditions as the synthesis example 37 except having used 31 mol. The yield of each polymer obtained was 70 to 80 g and Mw4.
It was x10 ^{4 to} 6x10 ⁴ .

[0206]

[Table 8]

[0207]

[Table 9]

[0208]

[Table 10]

[0209]

[Table 11]

[Synthesis Example-1 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,3,
20 g of 5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. Add tert to this solution under a nitrogen atmosphere.
-14 g of butoxypotassium was added, and after stirring at room temperature for 10 minutes, 29.2 g of di-tert-butyl dicarbonate was added. The reaction was carried out at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water, dried and the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of a compound example (31: R is all t-BOC group).

[Synthesis Example-2 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,3,
20 g of 5-triisopropylbenzene in diethyl ether
Dissolved in 400 ml. Add to this solution under nitrogen atmosphere 3,4-
Dihydro-2H-pyran (31.6 g) and a catalytic amount of hydrochloric acid were added, and the mixture was reacted for 24 hours under reflux. After the reaction was completed, a small amount of sodium hydroxide was added and the mixture was filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography and dried, and the compound example (31: R was all TH
(P group) was obtained.

[Synthesis Example-3 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
5-triisopropylbenzene 19.2 g (0.040
21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added to a 120 ml solution of N, N-dimethylacetamide (mol. It was stirred. Then, the reaction mixture was added to 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 3/7 (volume ratio)), which was a pale yellow viscous solid. 30 g was obtained. By NMR, this was confirmed to be a compound example (31: R are all —CH ₂ COOC ₄ H ₉ ^t groups).

[Synthesis Example-4 of Dissolution Inhibitor Compound] 1-
[Α-Methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene 42.4 g (0.10 mol) was added to N, N. -Dissolved in 300 ml of dimethylacetamide, added thereto were 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of bromoacetic acid cumyl ester, and then stirred at 120 ° C for 7 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate.The ethyl acetate extract was concentrated and purified in the same manner as in Synthesis Example [3] to give Compound Example (18). : R
Got all _{-CH 2 COOC (CH 3) 2} C 6 H 5 group) 70 g.

[Synthesis Example-5 of Dissolution Inhibitor Compound] α, α,
α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g (0.
020 mol) of N, N-dimethylacetamide 120 m
1 solution, 21.2 g (0.15 mol) of potassium carbonate,
Further, 27.1 g (0.14 mol) of t-butyl bromoacetate
Was added and stirred at 120 ° C. for 7 hours. Then, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), which was a pale yellow powder. 24 g was obtained. By NMR, this compound Example (62: R are all -CH ₂ -COO
-C ₄ H ₉ ^t group) was confirmed.

[Synthesis Example-6 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
20 g (0.042 mol) of 5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran (THF). To this solution was added potassium tert-butoxide (9.3 g, 0.083 mol) under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then di-t-butyl dicarbonate (19.5 g).
(0.087 mol) was added. The reaction was carried out at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-
As a result of fractional purification with hexane = 1/5 (volume ratio), 7 g of a compound example (31: 2 Rs are t-BOC groups, 1 R is a hydrogen atom) was obtained.

[Synthesis Example-7 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
4-Triisopropylbenzene 48.1 g (0.10 mol) was dissolved in dimethylacetamide 300 ml, and potassium carbonate 22.1 g (0.16 mol) and t-butyl bromoacetate 42.9 g (0.22 mol) were dissolved therein. ) Was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and then extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent:
As a result of fractional purification with ethyl acetate / n-hexane = 1/5 (volume ratio), a compound example (31: 2 R is —CH ₂ —
COO-C ₄ H ₉ ^t group, one R is to obtain a hydrogen atom) 10 g.

[Synthesis Example of Novolac Resin] 40 g of m-cresol, 60 g of p-cresol, 49 g of 37% aqueous formalin solution and 0.13 g of oxalic acid were placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react. After that, the temperature is raised to 200 ° C and gradually increased to 5 mm.
The pressure was reduced to Hg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Next, the molten alkali-soluble novolak resin (NOV.3) was returned to room temperature and recovered. The obtained novolak resin (NOV.3) had a weight average molecular weight of 7100 (converted to polystyrene).

In the same manner, the following novolak resins having different monomer compositions were synthesized. NOV. 1 m-cresol / p-cresol = 60/40, Mw = 12,000 NOV. 2 m-cresol / p-cresol = 50/50, Mw = 8,700 NOV. 4 m-cresol / p-cresol / 3,5-xylenol = 25/50/28, Mw = 5,200 NOV. 5 m-cresol / 2,3,5-trimethylphenol = 55/57, Mw = 5,800

The novolak resin (NOV.
3) After completely dissolving 20 g in 60 g of methanol, 30 g of water was gradually added to this while stirring to precipitate a resin component. The upper layer was removed by decantation and the precipitated resin component was recovered, heated to 40 ° C. and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolac resin (NOV.
6) was obtained. The weight average molecular weight was 8000 (polystyrene conversion).

85 g of m-cresol, 1 of p-cresol
5 g and 53 g of a 37% formalin aqueous solution were charged into a three-necked flask and stirred well while heating in an oil bath at 110 ° C.
2.4 g of zinc acetate dihydrate was added, and the mixture was heated with stirring for 5 hours. Next, 100 g of the same cresol mixture and 47 g of a formalin aqueous solution were continuously charged into the same flask, and the mixture was further heated and stirred for 1 hour, then the temperature was lowered to 80 ° C. and 0.2 g of oxalic acid was added. Again, the temperature of the oil bath was kept at 110 ° C., and the reaction was carried out under reflux for 15 hours. Then, the content was poured into water containing 1% hydrochloric acid and the reaction product was extracted with ethyl cellosolve acetate. Then, this was transferred to a vacuum still, the temperature was raised to 200 ° C. and dehydrated, and further 2 to 3 mmHg
Distillation was performed for 2 hours under reduced pressure to remove residual monomers.
The molten polymer was recovered from the flask to obtain the target novolak resin (NOV.7, Mw = 7,500).

Examples 1 to 20 and Comparative Examples 1 and 2 Resists were prepared using the compounds of the present invention shown in the above synthesis examples. The prescription at that time is shown in Table 12 below.

[0222]

[Table 12]

The abbreviations used in Table 12 have the following meanings. <Polymer> (): Molar ratio NOV.1-7 Novolac resin PHS / St p-hydroxystyrene / styrene copolymer (85/15) (weight average molecular weight 25,000) PHS / TBOMS p-hydroxystyrene / t-butoxy Carbonylmethyloxystyrene copolymer (80/20) (weight average molecular weight 35,000) PHS / VP p-Hydroxystyrene / 4-vinylpyridine copolymer (97/3) (weight average molecular weight 18,000) PHS / AcST p- Hydroxystyrene / p-acetoxystyrene (80/20) (weight average molecular weight 12,000) PHS / OHS p-hydroxystyrene / o-hydroxystyrene (80/20) (weight average molecular weight 32,000)

<Dissolution Inhibitor> BTBPP 2,2-bis (t-
Butoxycarbonyloxyphenyl) propane

<Acid-decomposable group in dissolution inhibitor>

[0226]

[Chemical 87]

<Resin> RP-1 Resin having the following structural formula

[0228]

Embedded image

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 12 was dissolved in 9.5 g of propylene glycol monomethyl ether acetate and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied onto a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 60 seconds to obtain a resist film having a thickness of 1.0 μm. The resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). Immediately after the exposure and 1 hour after the exposure, heating was performed on a vacuum adsorption type hot plate at 100 ° C. for 60 seconds, and immediately 2.
It was immersed in a 38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The profiles, sensitivities and resolving powers of the patterns thus obtained on the silicon wafer, which were subjected to heat treatment immediately after exposure and after 1 hour after exposure, were evaluated and compared as follows. The results are shown in Table 13 below.

[Profile] The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist profile was evaluated as follows. ⊚: Very good ∘: Good x: Poor Here, the term “good profile” means a shape (rectangle) having no taper or T-top shape. [Sensitivity] Sensitivity was defined as the exposure dose for reproducing a mask pattern of 0.50 μm. [Resolving power] The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.50 μm.

[0231]

[Table 13]

From the results shown in Table 13, the resist of the present invention is capable of preventing acid diffusion and acid deactivation on the resist surface portion with the passage of time from the exposure to the heat treatment, and the dissolution inhibiting effect of the dissolution inhibiting compound. It can be seen that the positive photosensitive composition has a good profile, high sensitivity, and high resolution. On the other hand, as shown in Table 13, Comparative Example 1 containing no fluorine atom and / or silicon atom-containing resin used in the present invention, or Comparative Example 2 in which the fluorine atom and / or silicon atom containing resin is a random type, It can be seen that the resolution and profile over time are poor as compared with the present invention.

[0233]

The chemical amplification type positive photosensitive composition of the present invention makes it possible to easily and appropriately prevent the acid diffusion and the acid deactivation of the resist surface portion with the passage of time from the exposure to the heat treatment. Moreover, the dissolution inhibiting effect of the dissolution inhibiting compound is maintained, and it is possible to provide a positive photosensitive composition having a stable and favorable profile, high sensitivity, and high resolution.

Front page continued (72) Inventor Eiichi Kato 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Shashin Film Co., Ltd.

Claims (3)

[Claims] 1. An alkali developing method comprising: (a) a resin insoluble in water and soluble in an alkaline aqueous solution; (b) a compound capable of generating an acid upon irradiation with actinic rays or radiation; and (c) a group decomposable by an acid. Solubility in liquid is increased by the action of acid,
A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, and (d) a polymer segment (A) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, and the polymer. A positive photosensitive composition comprising a block-bonded copolymer containing no or no more than 20% by weight of a polymer segment (B). 2. The compound (c) has at least two groups capable of decomposing with an acid (i), and the acid-decomposable group is excluded at the farthest position between the acid-decomposable groups. A compound having 10 or more bond atoms, and (ii) a bond having at least three groups capable of decomposing with an acid and excluding the acid decomposable group at the position where the distance between the acid decomposable groups is the longest. At least 1 selected from compounds having 9 or more atoms
The positive photosensitive composition according to claim 1, wherein the positive photosensitive composition is a seed. 3. A compound (1) which generates an acid upon irradiation with actinic rays or radiation, and (2) which is decomposed by the action of an acid,
A resin having a group that increases the solubility in an alkaline developer and (3) a polymer segment (A) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, and the polymer. 2 with or without ingredients
A positive photosensitive composition, characterized in that it contains a copolymer in which 0% by weight or less of the polymer segment (B) is bound by a block.