JP2000221685A - Positive silicone-containing photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the positive silicone-containing photosensitive composition high in sensitivity and resolution, especially in manufacture of semiconductor devices by incorporating a specified polymer insoluble in water and soluble in alkaline solutions and polymer or the like having the property that the solubility in an alkaline developing solution is increased by action of acids. SOLUTION: The composition contains the polymer insoluble in water but soluble in an aqueous alkaline solution, having a repeating units each represented by formula I or the like, a compound to be allowed to produce an acid by irradiation with activated light beam and the polymer having the property that solubility in the alkaline developing solution and having repeating units each represented by formula II or the like. In formulae I and II, X is a -C(=O)=R or the like; each of R, Ra, Rb, and Rc is an H atom or the like; each of R'-R''''' is a hydroxyl group or the like; Y is an alkyl group or the like; R0 is an aliphatic hydrocarbon group or the like; each of (l)-(n) and (q) is 0 or a positive integer; and (p) is a positive integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive-type silicone-containing photosensitive composition for exposure to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, and synchrotron radiation. More specifically, a positive type silicone-containing photosensitive composition for fine processing, which has a particularly high resolution and sensitivity, a rectangular cross-sectional shape or a wide process tolerance, which is used, for example, when manufacturing a circuit board in a semiconductor manufacturing process such as an IC. About. The positive silicone-containing photosensitive composition of the present invention can be used in the following steps.
For example, on a semiconductor wafer, or on a substrate of glass, ceramics, metal, or the like, an antireflection layer or an organic film is provided thereon, and then applied to a thickness of 0.01 to 3 μm by spin coating or roller coating. You. Thereafter, the film is heated and dried, and a circuit pattern or the like is baked through an exposure mask by irradiation with actinic rays or the like, and is developed to obtain a positive image. Further, the substrate can be processed in a pattern by etching using the positive image as a mask. Typical application fields are semiconductor manufacturing processes such as IC, liquid crystal,
Manufacturing of circuit boards such as thermal heads and other photofabrication processes are also included.

[0002]

2. Description of the Related Art The resolution limit of conventional single-layer resists has become evident with the increasing integration of LSIs. By forming resists in multiple layers instead of single layers, thick and fine high-profile ratio patterns can be formed. Methods of forming have been proposed.
That is, a thick organic polymer film is formed on the first layer, a thin resist material layer is formed on the second layer thereon, and then the second resist material is irradiated with high energy rays and developed. The first organic polymer is anisotropically etched by oxygen plasma etching (O2RIE) using the pattern obtained as a mask to obtain a pattern having a high rectangular shape (phosphorus, solid state technology, No. 24). Vol. 73, page 1981).

In this case, the second resist material layer is made of O2
Since RIE resistance must be high, the use of silicon-containing polymers has been proposed. For example, Pampalone has reported silylated polyolefin sulfines (see American Chemical Society Chicago Meeting Preliminaries, p. 325 (1985)). Have reported polytrimethylsilylbutenylsulfone (Society of Photo-Obtical in Instrumentation Engineering Abstract 631-01 p. 14 (19)
86)). However, since these resist materials have a low silicon content and silicon is introduced into the side chains, the resistance to oxygen plasma is not sufficient,
It did not serve as a mask when etching the first layer of organic polymer. In addition, a non-swelling resist that can be alkali-developed was required for forming a high-resolution pattern.

A number of attempts have been made to develop resists having oxygen plasma resistance and alkali developability, and some of them have been used for g-ray exposure (exposure wavelength: 436 nm). For example, JP-A-1-283555, JP-A-4-36754, JP-A-4-130324, and JP-A-2-29652 can be cited. But,
These are 0.3 μm using KrF excimer laser light or the like.
For the formation of a fine pattern of m or less, there is a problem that a rectangular shape cannot be obtained with a high resolving power because of a large light absorption for exposure light.

In order to reduce the light absorption of the exposure light, many attempts have been made to solve the problem by using a small amount of a photoacid generator and a compound which becomes alkali-soluble by the decomposition of an alkali-insoluble group by the generated acid. Have been. For example,
JP-A-63-218948, JP-A-63-241542, JP-A-4-245248, and JP-A-6-184431.

However, even in such attempts, the state-of-the-art 0.2
When applied to the formation of a fine pattern of not more than μm, even if not exposed, a part of the film was exposed due to the light diffraction phenomenon, so that the film loss after development was so large that a rectangular shape could not be obtained.
In addition, in some cases, since the silicon content in the resist is low, when transferring a pattern to a lower layer in the next oxygen plasma process, a size shift becomes large, and there is a problem that it is difficult to reproduce the size of the mask. .

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a photosensitive composition having high sensitivity and high resolving power especially in the production of semiconductor devices. More specifically, an object of the present invention is to provide a photosensitive composition which has a small light absorption in the Deep-UV region and can be used for a short wavelength light source. Further, it is another object of the present invention to provide a photosensitive composition which gives a rectangular shape with little film loss after development processing, particularly in a fine pattern of 0.2 μm or less. Further, it is another object of the present invention to provide a photosensitive composition which has a small dimensional shift (dimension fluctuation) when transferring a pattern to a lower layer in an oxygen plasma process and has excellent dimensional reproducibility.

[0008]

Means for Solving the Problems The present inventors have paid careful attention to the above-mentioned characteristics and made intensive studies. As a result, they have completed the present invention. That is, the object of the present invention can be achieved by the following configurations. (1) (a) a polymer having a repeating unit represented by the following general formula [I] and / or [II] and being insoluble in water and soluble in alkali; A compound that generates an acid upon irradiation and (c) a repeating unit containing a group represented by the following general formula [III], general formula (IV) or general formula (V) in the side chain; And a polymer having a property of increasing the solubility in water by the action of an acid.

[0009]

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[In the general formulas [I] and [II], X is -C
It is a group selected from the group consisting of a (） O) —R group, a —CH (OH) —R group and a carboxyl group, and a plurality of Xs in the formula may be the same or different. Here, R represents a hydrogen atom or a hydrocarbon group which may have a substituent.
R ′ to R ′ ″ ″ may be the same or different, and may be a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkenyl group,
It is a group selected from the group consisting of an aralkyl group and a phenyl group. Y is an alkyl group, an alkoxy group or a siloxyl group. R0 represents a hydrogen atom, a halogen atom, or a group selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may have a substituent. l, m, n and q are each 0 or a positive integer, and p is a positive integer.

[0011]

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In the general formulas [III] to (V), Ra, Rb, Rc
Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. s represents an integer of 2 or more.

(2) (a) a polymer having a repeating unit represented by the above general formula [I] and / or [II] and being insoluble in water and soluble in alkali; A compound that generates an acid by irradiation with light or radiation,
(d) a polymer containing a repeating unit containing a polycyclic structure in a side chain thereof, and a polymer having a property of increasing the solubility in an alkali developer by the action of an acid; Composition.

(3) (a) a polymer having a repeating unit represented by the above general formula [I] and / or [II] and being insoluble in water and soluble in alkali; A compound that generates an acid by irradiation with light or radiation,
(e) a repeating unit containing a group represented by the above general formula [III], general formula (IV) or general formula (V) in a side chain, and a repeating unit containing a polycyclic structure in a side chain, A positive-type silicone-containing photosensitive composition comprising a polymer having a property of increasing its solubility in an alkali developer by the action of an acid.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be clarified, but the present invention is not limited thereto. The positive silicone-containing photosensitive composition of the present invention contains a polymer of the component (a), a compound of the component (b), and at least one polymer of the components (c) to (e). The polymer of component (a) is described, for example, in JP-A-1-283555, JP-A-63-241542, or JP-A-4-36.
It can be appropriately synthesized by those skilled in the art with reference to the synthesis method described in JP-A No. 754 or the like. In order to achieve the object of the present invention to a higher degree, the silicon content of the component (a) is preferably high, and specifically, it is preferably 3 to 50% by weight in the polymer of the component (a). , More preferably 5 to 35% by weight. In this regard, among the component (a), a polymer having a repeating unit represented by the general formula [II] as a main structure is more preferable.

Examples of the hydrocarbon group for R include a methyl group, an ethyl group and a butyl group. X is preferably an acetyl group. Examples of the alkyl group of R ′ to R ′ ″ ″ include a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a bromomethyl group, and the like.As the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, Examples include a norbornyl group, an adamantyl group, a p-isopropylcyclohexyl group, and the like, an alkenyl group includes an allyl group, an isopropenyl group, a butenyl group, and the like, and an aralkyl group includes a benzyl group, a phenethyl group, a naphthylethyl group, and the like. And the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group and the like.
R ′ to R ′ ″ ″ are preferably a methyl group, a cyclohexyl group, a methoxy group, and an ethoxy group.

Examples of the alkyl group for Y include a methyl group, an ethyl group, a propyl group, and a chloromethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Examples of the siloxyl group include: Examples include a trimethylsiloxyl group and a triethoxysiloxyl group. Y is preferably, for example, a methyl group, a methoxy group or the like.
Examples of the aliphatic hydrocarbon group of Ro include an alkyl group, an alkoxy group, an alkenyl group, an alkoxycarbonyl group, an acyloxy group, and an acyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples thereof include a butyl group and an octyl group. Examples of the alkoxy group of the alkoxy group or the alkoxycarbonyl group include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. Examples of the acyl group include a formyl group, an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group. Examples of the alkenyl group include an allyl group, an isopropenyl group and a butenyl group.
Asyloxy group, formyloxy group, acetoxy group, propionyloxy group, methacryloyloxy group,
Examples include an acryloyloxy group and a crotonoyloxy group. Examples of the aromatic hydrocarbon group include a phenyl group, a benzyl group, and a phenethyl group. R0 is preferably a hydrogen atom or an alkyl, alkoxy, or acyl group having 1 to 6 carbon atoms. More preferably, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The hydrocarbon group of R, the alkyl group of R ′ to R ″ ″ ″, the cycloalkyl group, the alkenyl group, the aralkyl group and the phenyl group may further have a substituent,
Examples of the substituent in this case include a halogen atom such as Cl, Br, and F, a —CN group, a —OH group, and a C 1 to C 4 group.
Alkyl groups, cycloalkyl groups having 3 to 8 carbon atoms,
Examples thereof include an alkoxy group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms, an acylamino group, a furyl group, a furfuryl group, a pyranyl group, an aralkyl group, an allyloxyalkyl group, and a silyl group. Aralkyl groups include benzyl,
Phenethyl can be exemplified. Examples of the aryloxyalkyl group include phenoxyethyl. As Cyril,
Examples include trimethylsilyl and trimethoxysilyl.
Among these, a halogen atom, a -CN group, an alkoxy group, an alkyl group, a silyl group and the like are preferable in consideration of ease of synthesis.

Regarding l, m, n, p and q, the following conditions are preferable: l / l + m + n + p + q = 0.05-0.95, m / l + m + n + p + q = 0-0.95, n / l + m + n + p + q = 0-0-0. 95, p / l + m + n + p + q = 0.02 to 0.5, q / l + m + n + p + q = 0 to 0.95, more preferably l / l + m + n + p + q = 0.2 to 0.9, m / l + m + n + p + q = 0 to 0.7, n / l + m + n + p + q = 0-0.5, p / l + m + n + p + q = 0.05-0.3, q / l + m + n + p + q = 0-0.7.

The weight average molecular weight of the polymer of component (a) is not particularly limited, but is preferably from 400 to 50,000 from the viewpoint of compatibility with the polymer of component (c), solubility in an organic solvent, and the like. The range is preferably from 10,000 to 10,000, particularly from 1,000 to 8,000.

The component (b) used in the present invention is a compound which decomposes upon irradiation with actinic rays or radiation to generate an acid. Photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decolorants for dyes, photo-discolorants, or compounds that generate an acid by known light used in micro resists and the like, and mixtures thereof Can be appropriately selected and used.

For example, SI Schlesinger, Photogr. Sc
i. Eng., 18, 387 (1974), TS Bal etal, Polymer, 2
1, 423 (1980) and the like diazonium salts, U.S. Pat.
No. 069,055, 4,069,056, Re 27,992, JP-A 3-1
Ammonium salt described in No. 40140, DC Necker eta
l, Macromolecules, 17, 2468 (1984), CS Wen etal,
Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oc
t (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JV Crivello et al, Macromo
recules, 10 (6)., 1307 (1977), Chem. & Eng. News, N
ov. 28, p31 (1988), EP 104,143, U.S. Pat.
Nos. 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514 and the like, iodonium salts described in JV Crive, etc.
llo etal, Polymer J. 17, 73 (1985), JV Crivello e
tal.J. Org.Chem., 43, 3055 (1978), WR Watt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (19
84), JV Crivello etal, Polymer Bull., 14, 279 (1
985), JV Crivello etal, Macromorecules, 14 (5),
1141 (1981), JV Crivello etal, J. Polymer Sci.,
Polymer Chem.Ed., 17, 2877 (1979), European Patent No. 370,6
No. 93, No. 161,811, No. 410, 201, No. 339,049, No. 23
No. 3,567, No. 297,443, No. 297,442, U.S. Pat.
3,377, 3,902,114, 4,760,013, 4,734,44
No. 4, No. 2,833,827, German Patent No. 2,904,626, No. 3,60
No. 4,580, 3,604,581, etc., sulfonium salts described in J.
V. Crivello etal, Macromorecules, 10 (6), 1307 (197
7), JV Crivello etal, J. Polymer Sci., Polymer C
Selenonium salts described in hem. Ed., 17, 1047 (1979) and the like,
CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA,
Onium salts such as arsonium salts described in p478 Tokyo, Oct (1988), etc., U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Organic halide compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13 (4), 26 (198
6), TP Gill et al., Inorg. Chem., 19, 3007 (198
0), D. Astruc, Acc. Chem. Res., 19 (12), 377 (189
6), organometallics / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci., 25, 753 (1
987), E. Reichmanis et al., J. PholymerSci., Polymer
Chem. Ed., 23, 1 (1985), QQ Zhu etal, J. Photoc.
hem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahed
ron Lett., (24) 2205 (1973), DHR Barton etal,
J. Chem Soc., 3571 (1965), PM Collins et al., J. C.
hem. Soc., Perkin I, 1695 (1975), M. Rudinstein eta.
l, Tetrahedron Lett., (17), 1445 (1975), JW Walk
er etal J. Am. Chem. Soc., 110, 7170 (1988), SC B
usman etal, J. Imaging Technol., 11 (4), 191 (198
5), HM Houlihan et al, Macormolecules, 21, 2001
(1988), PM Collins etal, J. Chem. Soc., Chem. Co.
mmun., 532 (1972), S. Hayase etal, Macromole cule
s, 18, 1799 (1985), E. Reichman is etal, J. Electro
chem. Soc., Solid State Sci. Technol., 130 (6), F.
M. Houlihan et al, Macromolcules, 21, 2001 (1988),
European Patent Nos. 0290,750, 046,083, 156,535,
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,710,
No. 4,181,531, JP-A-60-198538, JP-A-53-133022
No., etc., a photoacid generator having an O-nitrobenzyl type protecting group, M. TUNOOKA et al., Polymer Preprints Japan,
35 (8), G. Berner et al, J. Rad. Curing, 13 (4), W.
J. Mijs etal, Coating Technol., 55 (697), 45 (1983),
Akzo, H. Adachi etal, Polymer Preprints, Japan, 37
(3), European Patent Nos. 0199,672, 84515, 044,115,
No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A-2-24575
No. 6, compounds that generate sulfonic acid upon photolysis represented by iminosulfonates and the like described in JP-A-3-140109 and the like, and disulfone compounds described in JP-A-61-166544 and the like. it can.

A group that generates an acid by the light;
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, ME Woodhouse etal, J. Am. Che.
m. Soc., 104, 5586 (1982), SP Pappas etal, J. Im.
aging Sci., 30 (5), 218 (1986), S. Kondo etal, Makro
mol. Chem., Rapid Commun., 9,625 (1988), Y. Yamada
etal, Makromol.Chem., 152, 153, 163 (1972), JV
Crivello etal, J. Polymer Sci., Polymer Chem. Ed.,
17, 3845 (1979), U.S. Patent No. 3,849,137, German Patent No.
3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452,
The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used. VNR Pillai, Syn
thesis, (1), 1 (1980), A. Abad etal, Tetrahedron Let
t., (47) 4555 (1971), DHR Barton et al., J. Chem.
Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712, etc., can also be used to generate a compound which generates an acid by light.

Among them, diazodisulfone compounds, substituted or unsubstituted salts of diaryliodonium or triarylsulfonium, particularly substituted or unsubstituted diazodisulfone compounds, from the viewpoints of acid generation efficiency by exposure, appropriate diffusion of acid, and stability in resist. Unsubstituted aryl sulfonates, camphor sulfonates and the like are preferred.

Hereinafter, the polymers as the components (c) to (e) will be described. The polymer of components (c) and (e) contains a repeating unit having at least one group represented by formulas [III] to [V] in the side chain. General formula (II
In I] to [V], Ra, Rb and Rc each independently represent a hydrogen atom or a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group having 1 to 8 carbon atoms and a hydrocarbon group having 4 to 10 carbon atoms. Examples thereof include a cycloalkyl group and an aralkyl group having 7 to 12 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group and the like. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylethyl group. R above
When a, Rb, and Rc are an alkyl group, a cycloalkyl group, or an aralkyl group, these groups may further have a substituent, and examples of the substituent include the following. That is, halogen atoms such as Cl, Br and F, -CN group, -OH group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, and 1 to 4 carbon atoms.
Alkoxy group, acylamino group such as acetylamino group, benzyl group, aralkyl group such as phenethyl group,
Allyloxyalkyl groups such as a phenoxyethyl group; and silyl groups such as a trimethylsilyl group and a trimethoxysilyl group can be exemplified. Moreover, the range of the substituent is not limited to these.

From the viewpoints of compatibility with the component (a), suitability for a developing solution, and a high degree of attaining the object of the present invention, the general formula [II
Preferably, Ra, Rb, and Rc in I] to [V] are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or a carbon atom having 7 to 7 carbon atoms which may have a substituent. 12 aralkyl groups, more preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, particularly preferably each independently a hydrogen atom, a methyl group, an ethyl group It is. s is preferably an integer of 2 to 6, more preferably 2 to 4, and particularly preferably 2. As the repeating unit containing a group represented by the general formulas (III) to (V) in the side chain, specifically, the following general formula (V
I].

[0027]

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R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen atom,
Represents a cyano group or a —C (＝ O) —Z—R ₄ group. Z is a single bond, -O -, - N (-R 5) - represents a group of the.
R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group. Examples of the substituent of the alkyl group or aralkyl group represented by R _{1 to} R ₅ include the above Ra to R _5.
The same substituents as described in the description of Rc can be used. L
Is a single bond, -C (= O) O-, -C (= O) -N
(R ₆₎ - represents a group of the. R ₆ has the same meaning as R ₅ described above. K represents an alkylene group or an aralkylene group which may have a substituent. Examples of the substituents of these groups include the same substituents as described in the description of Ra to Rc.

T represents 0 or 1. M is a general formula [II
It represents any of the groups represented by I] to [V].
R ₄ preferably has 1 to 1 carbon atoms which may have a substituent.
And 4 is an alkyl group, and a methyl group and an ethyl group are particularly preferable. R ₅ is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group or an ethyl group. R _{1 to} R ₃ are preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a halogen atom, and particularly preferably independently a hydrogen atom or a methyl group.

L is preferably -C (= O) O-,-
C (= O) -NH -, - C-N (CH 3) - is a group represented by, -C (= O) O- is particularly preferable. K is preferably an alkylene group having 1 to 8 carbon atoms which may have a substituent, an aralkylene group having 7 to 12 carbon atoms which may have a substituent, and more preferably A good alkylene group having 1 to 6 carbon atoms. Particularly preferably, K is a methylene group, an ethylene group, a propylene group, -C
H ₂ CH (CH ₃₎ - group, -C (CH _{3) 2} - group, butylene _{group, -CH (CH 3) CH 2} CH 2 - group, -CH ₂ CH (C
H ₃ ) CH ₂ — group, —C (CH ₃ ) ₂ CH ₂ — group, —CH ₂ C
A (CH ₃ ) ₂ — group and a —CH (CH ₃ ) —CH (CH ₃ ) — group.

The polymer of component (d) or (e) contains a repeating unit having a polycyclic structure in the side chain. The repeating unit having a polycyclic structure in the side chain is specifically represented by the following general formula [VII].

[0032]

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In the general formula [VII], R₁₁~ R₁₃Haso
R in general formula [VI]₁~ R _ThreeIs synonymous with L
₁Has the same meaning as L in the general formula [VI]. K₁Is the general formula
It is synonymous with K in [VI]. u is represented by the general formula [VI]
This is synonymous with t. G represents a monovalent polycyclic group. G
Preferably has 5 to 30 carbon atoms which may have a substituent.
Alicyclic polycyclic groups, more preferably a substituent
An alicyclic polycyclic group having 6 to 25 carbon atoms which may have
Specifically, the following structures are exemplified. Note that these
As the substituent of the group, in the general formulas (III) to (V)
The same substituents as described in the description of the substituents of Ra to Rc are listed.
I can do it.

[0034]

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[0035]

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Of the above, G is particularly preferably
(5), (6), (7), (9), (10), (1)
3), (14), (15), (23), (28), (3)
6), (37), (40), (42), and (47). The polycyclic group represented by G can be K ₁ or L ₁ at any position.
Linked to The polymer having a property of increasing the solubility in an alkaline developer used by the present invention due to the action of an acid is preferably a repeating unit containing a group represented by any of the general formulas [III] to [V] in a side chain and / or a polycyclic compound. A repeating unit containing a formula group in a side chain (preferably a general formula [VI] and / or a general formula [VI
A repeating unit having a side chain having another acid-decomposable group for the purpose of further improving acid-decomposability. The repeating unit having another acid-decomposable group in the side chain is specifically represented by the following general formula [VIII].

[0037]

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In the general formula [VIII], R_{twenty one}~ R_{twenty three}Haso
R in general formula [VI]₁~ R_ThreeIs synonymous with R
x represents a group containing an acid-decomposable group, specifically, -C
(= O) -OA or -Ar-OB
You. Here, A is -C (R₃₁) (R₃₂) (R₃₃), -S
i (R₃₁) (R₃₂) (R₃₃), -C (R₃₄) (R₃₅)-
OR₃₆Represents a group. R₃₁~ R₃₅Are the same but different
And may have a hydrogen atom or a substituent.
Alkyl, cycloalkyl, alkenyl, aralkyl
And an aryl group;₃₆May have a substituent
Represents an alkyl group, a cycloalkyl group, or an aryl group.
You. Where R₃₁~ R ₃₃At least two of which are hydrogen atoms
A group other than₃₁~ R₃₃, And R ₃₄~ R₃₆Baby
At least two of the groups may be combined to form a ring
No. As the substituents of these groups, general formulas (III) to
The same substituents as those described in the description of Ra to Rc in [V] are listed.
I can do it.

R _{31 to} R ₃₅ are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, propyl, isopropyl, butyl, t-
A C4-8 cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group and the like), a C2-4 alkenyl group (vinyl group, propenyl group, allyl group and the like), An aralkyl group having 7 to 14 carbon atoms (such as a benzyl group and a phenethyl group); and an aryl group having 6 to 12 carbon atoms (such as a phenyl group, a toluyl group, and a xylyl group).

R ₃₆ is preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 4 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Alkyl groups of formulas 1 to 4 (methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec
-Butyl group, isobutyl group, t-butyl group, etc.), a cycloalkyl group having 5 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, etc.), an aryl group having 6 to 10 carbon atoms (phenyl group, etc.) , A toluyl group, a xylyl group, a t-butylphenyl group, an isopropylphenyl group, etc.). Ar represents a monocyclic or polycyclic divalent or higher valent aromatic group which may have a substituent. Examples of the substituent include the same substituents as those described in the description of Ra to Rc in formulas [III] to [V]. Ar is preferably a phenylene group which may have a substituent. B represents A or —C (＝ O) —OA group. In the polymer (c) in the present invention, the above-mentioned general formulas [III] to
It is preferable that the group represented by [V] and / or the polycyclic group also have an acid-decomposable group.

In the polymer of the component (c) used in the present invention, a repeating unit containing a group represented by the general formulas [III] to [V] in the side chain [preferably, a repeating unit represented by the general formula [VI]] Is preferably 10 to 100 mol%, more preferably 20 to 90 mol%, particularly preferably 25 to 80 mol%. In the polymer of the component (d) used in the present invention, a repeating unit containing a polycyclic group in a side chain (preferably a repeating unit represented by the general formula [VII]) preferably contains 10 to 100 mol%, It is more preferably from 20 to 90 mol%, particularly preferably from 25 to 80 mol%. In the polymer of the component (e) used in the present invention, a repeating unit represented by the general formulas [III] to [V] and a repeating unit containing a polycyclic group in a side chain [preferably the general formula [VI] and the general formula (VII)
Is a total of 10 to 100 mol%.
It is preferably contained, more preferably from 20 to 100 mol%, particularly preferably from 25 to 100 mol%. A repeating unit represented by the general formulas [III] to [V] and a repeating unit containing a polycyclic group in a side chain [preferably a general formula [V
The molar ratio of the repeating unit represented by I] to the repeating unit represented by the general formula [VII] is preferably 15/85 to 85/15, more preferably 20/80 to 80/20, and particularly preferably 25/75. ７５75/25. In the polymer of the components (c) to (e) used in the present invention, the content of the repeating unit having an acid-decomposable group is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and particularly preferably 30 to 100 mol%. １００100 mol%.

In the polymer of the component (c), two types of each of the repeating units represented by the general formulas [III] to [V] (preferably, the repeating units represented by the general formula [VI]) are used. The above may be included. The polymer of the component (d) may contain two or more kinds of each repeating unit of the repeating unit containing the above polycyclic group in the side chain (preferably, the repeating unit represented by the general formula [VII]). . The polymer of the component (e) includes a repeating unit represented by the general formulas [III] to [V] and a repeating unit containing a polycyclic group in a side chain (preferably, the general formulas [VI] and [VII]). ), And two or more kinds of repeating units may be included.

The polymers of the components (c), (d) and (e) used in the present invention each have the general formula [II]
It contains repeating units represented by I] to [V], a repeating unit containing a polycyclic group in the side chain, and both of these repeating units, and in addition to these, improves film properties, adhesion, developability, etc. For the purpose of causing the copolymer to contain another repeating unit, it may be used as a copolymer. Examples of the comonomer corresponding to such a repeating unit include, for example, styrenes, acrylates, methacrylates,
Compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like can be given. Specifically, for example, styrenes (for example, styrene, p-hydroxystyrene, methylstyrene, methoxystyrene, etc.), acrylates, for example, alkyl (alkyl groups preferably having 1 to 10 carbon atoms) acrylate ( For example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2 -Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, Furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.):

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

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

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

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

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

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

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used.

The molar ratio of each repeating unit is determined based on the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion,
It is appropriately set to adjust the resist profile, and further, the resolution, heat resistance, sensitivity, and the like, which are general necessary requirements for the resist. Specific examples of the polymer of component (c), component (d) and component (e) used in the present invention include the following, but are not limited thereto.

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The weight-average molecular weight of each of the acid-decomposable polymers of the components (c), (d) and (e) is not particularly limited, but the compatibility with the polymer of the component (a), the solubility in organic solvents, It is preferably 1,000 to 100,000, and more preferably 3000 to 40,000, from the viewpoint of the balance of the desired performance of the invention. The amount of the component (a) compound used in the present invention is preferably from 10% by weight to 90% by weight, more preferably from 20% by weight to 70% by weight, based on the solid content of the composition of the present invention.

The amount of each of the compounds (c), (d) and (e) used in the present invention is preferably 10% by weight to 90% by weight, and more preferably 30% by weight, based on the solid content of the composition of the present invention. % By weight to 80% by weight is preferred. In the composition of the present invention, the use ratio (weight ratio) of the amount of each of the acid-decomposable polymers of the components (c), (d) and (e) to the amount of the polymer of the component (a) is oxygen-resistant. From the viewpoints of plasma dry etching properties, resolution, sensitivity, developability, and rectangular shape of the developed pattern, 70/30 to 5/95 is preferable, and 60/40 to 20/80 is more preferable.

The compound (b) used in the present invention may be used in an amount of 0.01 to 2% by weight based on the solid content of the composition of the present invention.
0% by weight is preferred, and more preferably 0.1% by weight to 10% by weight.
Is preferred. When the amount of the compound of the component (b) of the present invention is small, the sensitivity becomes low and a high resolution cannot be obtained. On the other hand, if the usage ratio is too large, the dimensional variation of the pattern over time after the pattern exposure increases, which is not desirable.

The positive photosensitive composition of the present invention basically comprises the components (a), (b) and (c) described above.
Although it is composed of the acid-decomposable polymer (e), an alkali-soluble resin may be added in order to further improve film properties, heat resistance and the like. As such an alkali-soluble resin, preferably, a phenolic hydroxyl group, a carboxylic acid group,
It is a polymer having an acidic hydrogen atom having a pKa of 11 or less such as a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamido group, an N-sulfonylurethane group, and an active methylene group. Suitable alkali-soluble polymers include:
Novolak phenol resins, specifically, phenol formaldehyde resin, o-cresol-formaldehyde resin, m-cresol-formaldehyde resin, p-cresol formaldehyde resin, xylenol-formaldehyde resin, or co-condensates thereof, and the like.
Further, as described in JP-A-50-125806, a phenolic resin as described above, together with a phenolic resin such as t-butylphenolformaldehyde resin, having 3 to 3 carbon atoms.
A condensate of phenol or cresol substituted with an alkyl group of 8 and formaldehyde may be used in combination. Also, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol And the like, or a homo- or copolymerized polymer, or a polymer in which these polymers are partially etherified or partially esterified can also be used.

To the composition of the present invention, if necessary, an aromatic polyhydroxy compound described in JP-A-4-122938, JP-A-2-275955, JP-A-4-230754 or the like is added. Is also good. In the composition of the present invention,
It may contain an organic basic compound.

The component (a) in the composition of the present invention,
Solvents for dissolving the polymers (b) and (c) to (e) include ketones such as methyl ethyl ketone and cyclohexanone, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, dioxane and ethylene glycol dimethyl ether. Ethers, methyl cellosolve acetate,
Cellosolve esters such as ethyl cellosolve acetate, fatty acid esters such as butyl acetate, methyl lactate and ethyl lactate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, dimethyl A highly polar solvent such as sulfoxide can be exemplified. These solvents can be used alone or as a mixture of a plurality of solvents.

The positive photoresist composition of the present invention may optionally contain a dye, a plasticizer, an adhesion aid, a surfactant and the like. Specific examples thereof include dyes such as methyl violet, crystal violet, and malachite green, stearic acid, acetal resins, phenoxy resins, alkyd resins, plasticizers such as epoxy resins, and adhesion of hexamethyldisilazane, chloromethylsilane, and the like. There are auxiliary agents and surfactants such as nonylphenoxypoly (ethyleneoxy) ethanol and octylphenoxypoly (ethyleneoxy) ethanol.

In particular, in the case of a dye, a dye containing an alkali-soluble group such as an aromatic hydroxyl group or a carboxylic acid group in the molecule, such as curcumin, is particularly preferably used.

The above positive photoresist composition is applied to a substrate (eg, silicon / silicon dioxide coating), glass, ceramics, metal, or the like used in the manufacture of precision integrated circuit devices by spinner, coater or the like. A good resist can be obtained by applying to a thickness of 0.5 to 3 μm by a suitable coating method, exposing through a predetermined mask, and developing. It is also preferable to add a surfactant having a fluorine substituent, a silicon-containing group, or the like to reduce the surface tension for the purpose of improving the coatability.

As the developer for the positive photoresist composition of the present invention, sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; single amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; triethylamine and methyldiethylamine Tertiary amines such as
It is possible to use aqueous solutions of alkali amines such as alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. it can. Further, an appropriate amount of an alcohol, a surfactant, an aromatic hydroxyl group-containing compound or the like may be added to the aqueous solution of the above alkalis. Among them, it is particularly preferable to use tetramethylammonium hydroxide.

When the photosensitive composition according to the present invention is used as the upper resist of a two-layer resist, the lower organic polymer film is etched by oxygen plasma using the upper resist pattern as a protective mask. It has sufficient resistance to plasma. Although the oxygen plasma resistance of the photosensitive composition of the present invention also depends on the silicon content of the upper resist, the etching apparatus, and the etching conditions, the etching selectivity (the etching rate ratio between the lower layer and the upper resist) is 10 to 100. Can be taken sufficiently large.

In the pattern forming method using the photosensitive composition of the present invention, first, an organic polymer film is formed on a substrate to be processed. The organic polymer film may be any of various known photoresists, for example, FH series or FHi series manufactured by Fujifilm Ohlin Co., Ltd.
Examples are the iR series and the PFI series manufactured by Sumitomo Chemical Co., Ltd. The organic polymer film is formed by dissolving these in an appropriate solvent and applying the resulting solution by a spin coating method, a spray method, or the like. Next, on the first layer of the organic polymer film,
A film of the photosensitive composition of the present invention is formed. This is performed by dissolving the resist material in an appropriate solvent in the same manner as in the first layer, and applying the resulting solution by spin coating, spraying, or the like.

The obtained two-layer resist is then subjected to a pattern forming step. As a first step, first, a second layer,
That is, a pattern forming process is performed on the upper resist composition film. Perform mask alignment as necessary, and irradiate high-energy rays through this mask to make the irradiated portion of the resist composition soluble in an alkaline aqueous solution,
The pattern is formed by developing with an alkaline aqueous solution.

Next, the organic polymer film is etched as a second step. This operation is performed by oxygen plasma etching using the above-described resist composition film pattern as a mask to form a fine pattern having a high aspect ratio. I do. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma ashing used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus or a parallel plate plasma etching apparatus using oxygen as a reactive gas, ie, an etching gas.

Further, the substrate is processed by using the resist pattern as a mask. As a processing method, a dry etching method such as sputter etching, gas plasma etching, or ion beam etching can be used. The etching treatment by the two-layer film resist method including the film of the photosensitive composition of the present invention is completed by the operation of removing the resist film. The removal of the resist film can be performed simply by dissolving the organic polymer material of the first layer. Since this organic polymer material is an arbitrary photoresist and has not been altered (hardened or the like) at all in the photoetching operation, an organic solvent of each known photoresist itself can be used. Alternatively, peeling can be performed by a process such as plasma ashing without using a solvent.

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EXAMPLES The present invention will be described below with reference to examples, but of course, the embodiments of the present invention should not be limited to these examples. (Production Example-1) Synthesis of Component (a) Polymer (Silsesquioxane Polymer) In a 300 ml flask equipped with a stirrer, a thermometer and a dropping funnel, 15 g of anhydrous aluminum chloride and 50 ml of acetyl chloride were placed and stirred. Next, 5 g of polyphenylsilsesquioxane having a molecular weight of 4200 was added to acetyl chloride 5
A solution dissolved in 0 ml was gradually added dropwise. 25 ℃
And proceeded the reaction. Hydrogen chloride was generated with the progress of the reaction. After reacting for 3 hours, the mixture was cooled and the contents were poured into 250 g of ice water. The aluminum chloride was decomposed by stirring well, and 50 g of ethyl ether was added to dissolve the precipitate. After removing the aqueous layer, 100 g of water was added to thoroughly permeate the ether layer. After removal of the aqueous layer, the ether was evaporated and finally dried in a vacuum dryer. The molecular weight of the obtained polymer was 4,500, and elemental analysis showed that it contained 23.2% of silicon elements.

(Production Example 2) Synthesis of Component (a) Polymer << Silsesquioxane Polymer >> The same procedure as in Production Example 1 was carried out except that 5 g of polyphenylmethylsilsesquioxane having a molecular weight of 3,800 was used. A polymer corresponding to component (a) was synthesized. The molecular weight of the obtained polymer was 3,900, and the amount of silicon element was 25.2% by elemental analysis.

(Production Example 3) Synthesis of Component (e) Polymer Synthesis of Polymer Example E-1 2-methyl-2-adamantyl methacrylate and mevalonic methacrylate were charged at a ratio of 50/50.
N, N-dimethylacetamide / tetrahydrofuran =
Dissolved in 5/5 mixed solvent, solution 1 with 20% solids concentration
00 ml was prepared. 3 mol% of Wako Pure Chemical V-65 and 6 mol% of mercaptoethanol were added to this solution,
Under a nitrogen atmosphere, the solution was added dropwise to 10 ml of tetrahydrofuran heated to 60 ° C. over 3 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 3 L of methanol, and the precipitated white powder was recovered. In Polymer Example E-1, the polymer composition ratio determined from C ¹³ NMR was 50/50. The weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) was 7
800. Other polymers were synthesized in the same manner.

(Example 1) 1 g of the silsesquioxane polymer obtained in Production Example-1, 1 g of the polymer of Polymer Specific Example E-1, and triphenylsulfonium-2,4,6-triisopropylphenylsulfonate 0.04 g and 0.005 g of triphenylimidazole were dissolved in 18 g of methoxypropyl acetate, and the resulting solution was subjected to microfiltration with a 0.1 μm-diameter membrane filter to obtain a silicon-containing photosensitive composition. A silicon wafer is coated with FHi-028D resist (resist for i-line manufactured by Fuji Film Orin Co.) using a coater CDS-650 manufactured by Canon Inc., and baked at 90 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.85 μm. Was. Add another 20
After heating at 0 ° C. for 3 minutes, the film thickness became 0.70 μm. The silicon-containing photosensitive composition prepared above was coated thereon and baked at 110 ° C. for 60 seconds to obtain a coating film having a thickness of 0.20 μm.

The wafer obtained in this manner was manufactured by Canon Kr.
F Excimer Laser Stepper FPA-3000EX4
Was exposed while changing the exposure amount and focus. Then, in a clean room at 120 ° C, 90
After heating for 2 seconds, the film was developed with a tetramethylammonium hydroxide developer (2.38%) for 60 seconds, rinsed with distilled water and dried to obtain a pattern (upper layer pattern). Observed with a scanning electron microscope. Further, the wafer having the upper resist pattern was etched (dry-developed) using a parallel plate reactive ion etching apparatus manufactured by ULVAC to form a pattern in the lower layer. Etching gas is oxygen, pressure is 20 mTorr, applied power is 100 m
The W / cm ² etching time was 15 minutes. The results were evaluated with a scanning electron microscope.

The sensitivity, the resolving power, the depth of focus, the dimensional variation and the like were evaluated by the following methods. Sensitivity: The sensitivity was evaluated based on the exposure when a 0.18 μm line / space of the mask was reproduced in the upper layer pattern. Resolving power: At the exposure amount when the 0.18 μm line / space of the above mask was reproduced, evaluation was made at the minimum dimension at which the line / space was separated and resolved in the lower layer. Depth of focus was determined by performing stepwise out-of-focus exposure at the time of exposure, and evaluating the range of change in focus at which a 0.18 μm line could be resolved in the lower layer. Pattern dimensional fluctuation (shift)
Shows the dimensional difference between the size of the pattern of interest of the upper resist formed by exposure and wet development and the size after pattern formation of the lower layer by further dry development.

As a result, the sensitivity was 22 mJ / cm
² , line / space of 0.14 μm (resolution) was resolved. In addition, the film reduction of the 0.18 μm line is 1.
The line was very small, 5%, and the cross-sectional shape of the line was a trapezoid close to a rectangle. A vertical pattern having a width of 0.18 μm was formed with a thickness of 0.8 μm and a depth of focus of 1.2 μm.
Also, the dimensional shift of 0.18 μm was very small, 0.005 μm.

(Example 2) In place of 1 g of the silsesquioxane polymer in Example 1, 1 g of the silsesquioxane polymer obtained in Production Example 2 was used.
E-26 (weight average molecular weight: 6800) was used in place of -1. Except for these, the procedure of Example 1 was repeated to prepare a photosensitive composition. Next, exposure and development were performed in the same manner as in Example 1, and evaluation was performed. A 0.13 μm line / space was resolved at a sensitivity of 36 mJ / cm ² . Further, the film reduction of the 0.18 μm line was as extremely small as 2.5%, and the cross-sectional shape was a trapezoidal shape close to a rectangle. After etching in the same manner as in Example 1, the depth of focus of 0.18 μm was very small, 1.0 μm, and the dimensional shift was very small, 0.007 μm.

(Examples 3 to 20 and Comparative Examples 1 and 2) The components (b) and (c) to (e) described in Table 1 were replaced with the components (b) and (e) of Example 1. Example 1
Each photosensitive composition was prepared in the same manner as described above, exposed and developed and etched in the same manner as in Example 1, and observed with a scanning electron microscope, and evaluated in the same manner as described above. Table 2 shows the results.

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[Table 2]

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According to the present invention, a photosensitive composition having high sensitivity and high resolving power can be provided, particularly in the production of semiconductor devices, and more specifically, has a small light absorption in the Deep P-UV region and is compatible with a short wavelength light source. The photosensitive composition which can be provided can be provided. Furthermore, a photosensitive composition that gives a rectangular shape with less film loss after development processing, particularly in a fine pattern of 0.2 μm or less, can be provided. Further, a photosensitive composition excellent in dimensional reproducibility with a small dimensional shift (dimension fluctuation) when transferring a pattern to a lower layer in an oxygen plasma process can be obtained. Therefore, it is most suitably used for mass production of semiconductor substrates having ultrafine circuits.

Claims (3)

[Claims] (1) (a) The following general formula [I] and / or [II]
Having a repeating unit represented by, a polymer that is insoluble in water and soluble in alkali, (b) a compound that generates an acid by irradiation with actinic rays or radiation, and (c) a side chain having the following general formula: [III] containing a polymer having a repeating unit containing a group represented by the general formula (IV) or (V) and having a property of increasing the solubility in an alkaline developer by the action of an acid. A positive-type silicone-containing photosensitive composition, comprising: Embedded image [In the general formulas [I] and [II], X is -C (= O) -R
A group selected from the group consisting of a group, a —CH (OH) —R group and a carboxyl group, wherein a plurality of Xs in the formula may be the same or different. Here, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. R '~
R '''''' may be the same or different and may be a hydroxyl group or an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aralkyl group and a phenyl group It is a group selected from the group.
Y is an alkyl group, an alkoxy group or a siloxyl group. R0 represents a hydrogen atom, a halogen atom, or a group selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may have a substituent. l, m, n and q are
Each represents 0 or a positive integer, and p represents a positive integer. Embedded image In the general formulas [III] to (V), Ra, Rb and Rc each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent. s represents an integer of 2 or more. (A) a polymer having a repeating unit represented by the general formula [I] and / or [II] according to claim 1 and being insoluble in water and soluble in alkali; b) a compound that generates an acid upon irradiation with actinic rays or radiation, and (d) a repeating unit containing a polycyclic structure in a side chain, the solubility of which in an alkaline developer is increased by the action of an acid. A positive-type silicone-containing photosensitive composition comprising a polymer. (A) a polymer having a repeating unit represented by the general formula [I] and / or [II] according to claim 1 and being insoluble in water and soluble in alkali; b) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (e) a side chain having the general formula [III] or the general formula according to claim 1
(IV) or a repeating unit containing a group represented by the general formula (V) and a repeating unit containing a polycyclic structure in a side chain, and the solubility in an alkaline developer is increased by the action of an acid. A positive-working silicone-containing photosensitive composition, characterized in that the composition comprises: