JPH0812626A - Organocyclic hydrocarbon alcohol - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful for producing dissolution inhibitors or the monomers for producing resins to be suitably used in photosensltive resin compositions to be exposed to far-ultraviolet light. CONSTITUTION:This compound is expressed by formula I (R1 is t- butoxycarbonyl, 2tetrahydropyranyl or 2-tetrahydrofuranyl; R2 is a divalent 7-12C saturated hydrocarbon group having an organocyclic saturated hydrocarbon group), e.g. (2-tetrahydropyranyl)oxymethyl tricyclo[5,2,1,0<2.6>]decanemethanol. A new vinyl group-contg. monomer of formula II (R3 is H or methyl) can be obtained by reaction of the compound of formula I with an equimolar amount of (meth)acryloyl chloride at ice-chilled temperature to 50 deg.C in a dehydrated methylene chloride solvent in the presence of an excess of a base. A compound of formula IV useful as a dissolution inhibitor in the lithography can be obtained by converting a carboxylic acid of formula III (R5 is a mono-tetravalent saturated hydrocarbon group; (k) is 1-4) into the corresponding acid chloride which is then reacted with the compound of formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel vinyl group-containing monomers and their polymers, and more particularly to a polymer having a wavelength of 220.
The present invention relates to a compound suitably used for producing a resin and a dissolution inhibitor suitably used for a photosensitive resin composition that uses far ultraviolet rays of nm or less as exposure light.

[0002]

2. Description of the Related Art In the field of manufacturing various electronic devices such as VLSI, which requires fine processing on the order of submicrons, there is an increasing demand for higher density and higher integration of devices, and fine pattern formation. Requirements for photolithography technology for semiconductors are becoming ever more stringent.

As one of means for achieving finer patterns, it is known to shorten the wavelength of exposure light used when forming a resist pattern. For example, to manufacture a dynamic random access memory (hereinafter, abbreviated as DRAM) having an integration degree of up to 64 Mbits, i.
Line (wavelength = 365 nm) has been used as a light source. Two
56Mbit DRAM (Working dimension is 0.25μm or less) DRAM
KrF with shorter wavelength instead of i-line
The use of an excimer laser (wavelength = 248 nm) as an exposure light source is currently being actively investigated. Furthermore, D with a degree of integration of 1 Gbit (processing size is 0.2 μm or less) or more
For the purpose of manufacturing a RAM, a light source having a shorter wavelength is required, and an excimer laser (KrCl: 222 nm, A
rF: 193nm, F _2:. use of 157nm) have been considered (Takumi Ueno, Iwayanagi Takao, Saburo Nonogaki, Hiroshi Ito, C Grant Wilson (C.Grant Willso
n) Co-author, "Short Wavelength Photoresist Material-Fine Processing for ULSI", Bunshin Publishing, 1988).

However, in view of both the target yield of the mass production process, that is, the time required for the exposure process and the economic efficiency when a new light source is adopted in the production site, batch exposure is possible and the accumulation of conventional techniques. The abundant photolithography is regarded as more promising than electron beam exposure or X-ray exposure. Therefore, for the manufacture of LSIs with a degree of integration of 1 Gbit or more, light with a shorter wavelength, that is, 220 nm
There is an urgent need for the development of photolithography technology using the following short-wavelength light sources.

The photosensitive resin composition for this purpose needs to satisfy the improvement of the cost performance of the laser because the gas as a raw material for laser oscillation has a short life and the laser device itself is expensive. . Therefore, resist materials used for microfabrication are highly required to have high resolution in addition to high resolution corresponding to miniaturization of processing dimensions.
As a method for increasing the sensitivity of a resist, a chemically amplified resist utilizing a photoacid generator as a photosensitive agent is well known. For example, as a typical example, see Japanese Patent Application Laid-Open No. 2-2766.
Japanese Patent Laid-Open Publication No. 0-096 describes a resist composed of a combination of triphenylsulfonium hexafluoroarsenate and poly (p-tert-butoxycarbonyloxy-α-methylstyrene). Chemically amplified resists are currently being studied in detail as resists for KrF excimer lasers [for example, Hiroshito, C.I. Grant
C. Grant Willson, American Chemical Society Symposium Series (American Chemical Soci)
ety Symposium Series), 242
Vol., Pp. 11-23 (1984)]. The characteristic of the chemically amplified resist is that the contained component, a protonic acid generated by a photoacid generator, which is a substance that generates an acid by light irradiation,
The purpose is to move the resist in the resist solid phase by heat treatment after exposure, and to amplify the chemical change of the resist resin or the like by catalytic reaction several hundred times to several thousand times by the acid. In this way, the photosensitivity (reaction per one photon) is significantly higher than that of a conventional resist having a photoreaction efficiency of less than 1.
To change the solubility of resist by chemical amplification, a method that changes the solubility of the resin itself, a dissolution inhibitor (dissolution inhibitor)
A method of changing the solubility of a resin or a method of changing the solubility of a resin and a dissolution inhibitor is known. Currently, most of the resists developed are of the chemical amplification type, and the adoption of the chemical amplification mechanism is indispensable for the development of high-sensitivity materials corresponding to shorter wavelengths of exposure light sources.

[0006]

In the case of lithography in which an excimer laser having a short wavelength of 220 nm or less is used as exposure light, a resist (photosensitive resin composition) for forming a fine pattern cannot be satisfied with conventional materials. Characteristics are required.

That is, regarding the resin component, (1) 220
high transparency to exposure light of nm or less, (2) etching resistance, and as for the photosensitive agent (photoacid generator), (1) 2
It has high transparency to exposure light of 20 nm or less, (2) high photoreactivity (photoacid generating ability) to exposure light, and high transparency to exposure light of 220 nm or less for dissolution inhibitors.

In conventional lithography using KrF excimer laser (248 nm) and exposure light having a longer wavelength than that, the resin component of the photosensitive resin composition is composed of structural units such as novolak resin or poly (p-vinylphenol). A resin having an aromatic ring is used, and the etching resistance of the resin can be maintained by the dry etching resistance of the aromatic ring. However, the light absorption by the aromatic ring is extremely strong for the wavelength of 220 nm or less, and therefore, these conventional resins cannot be directly applied to the short wavelength light of 220 nm or less (ie, most of the exposure light is absorbed on the surface of the resist, Since the exposure light does not reach the substrate, it is not possible to form a fine resist pattern [Sasako et al., "ArF excimer laser lithography (3) -resist evaluation-", Proceedings of the 35th Annual Conference of the Japan Society of Applied Physics, 1p. -K-4
(1989)]. Therefore, a resin material containing no aromatic ring and having etching resistance is desired.

A KrF excimer laser (248 nm)
In conventional lithography using exposure light having a longer wavelength than the above, as a dissolution inhibitor (dissolution inhibitor), for example, naphthalene carboxylic acid-t-butyl ester,
A compound having an aromatic ring such as benzenedicarboxylic acid di-t-butyl ester is mainly used, and a conventional dissolution inhibitor (dissolution inhibitor) is used for the same reason as in the above-mentioned resin.
Cannot be directly applied to short-wavelength light of 220 nm or less.

When an exposure light of 220 nm or less is used, the light transparency of the photosensitive agent (photoacid generator) to the exposure light is also an important issue as in the case of the resin, and it is disclosed in JP-A-2-27660. A conventional photoacid generator having an aromatic ring typified by phenylsulfonium hexafluoroarsenate cannot be used. The inventors have already developed a new photo-acid generator satisfying these requirements (Japanese Patent Application No. 5-17).
No. 4528, Japanese Patent Application No. 5-174532).

As a polymer compound having transparency to 193 nm and resistance to dry etching, a copolymer having an adamantyl methacrylate unit which is an alicyclic polymer [Takechi et al., Journal of Photopolymer.
Science and Technology (Journal
of Photopolymer Science
d Technology, 5 (3), 439-446 (1992), and JP-A-5-2652.
No. 12] or a copolymer of poly (norbornyl methacrylate) and poly (tert-butyl methacrylate) [M. Endor et al., Proceedings of
Proceedings
of IEDM), CA 14-18, San Francisco (1992)].

However, since this resin does not have a residue capable of exhibiting a solubility difference before and after exposure in the adamantane-containing residue unit, for example, a comonomer capable of exhibiting a solubility difference such as tetrahydropyranyl methacrylate For the first time, it can be used as a resin component of a resist by forming a copolymer with the above. However, the comonomer content is required to be about 50 mol%, and the dry etching resistance of the comonomer unit is remarkably low, so that the dry etching resistance effect by the adamantane skeleton is remarkably reduced, and the practicality as a dry etching resistant resin is poor. Further, the copolymer having these alicyclic alkyl groups is generally highly hydrophobic because the alicyclic group and the protective group (polar conversion group) in the polymer compound are hydrophobic. For this reason, the thin film formed by these polymer compounds has poor adhesion to the silicon substrate,
It was difficult to form a uniform coating film with good reproducibility. That is, unlike a novolac resin that has been widely used in conventional resists, since it does not contain a polar site, it has poor adhesion to a silicon substrate. Further, since it has low solubility in an alkaline developing aqueous solution, it has a low sensitivity and further has a drawback that a residue (scum) is likely to appear in the developing solution.

For this reason, a new resist resin material having a high optical transparency to light of 220 nm or less, a high etching resistance, a functional group capable of exhibiting a solubility difference before and after exposure, and an improved substrate adhesion is provided. There is a strong need for a dissolution inhibitor having high light transparency to light of 220 nm or less. Further, the resin and the dissolution inhibitor are required to have material properties excellent in chemical amplification properties. The present invention provides an intermediate compound useful for producing a novel compound that solves these problems.

[0014]

Means for Solving the Problems As a result of intensive studies, the inventors have found that the above technical problem has been solved by the general formula (2) produced by using a novel intermediate compound represented by the general formula (1) disclosed below. ), And a polymer thereof (general formula (3)) (Japanese Patent Application No. 6-9030) and a dissolution inhibitor represented by general formula (4) Is solved by

That is, an alicyclic hydrocarbon residue was introduced for imparting transparency and etching resistance to light having a wavelength shorter than 220 nm, and bonded to the alicyclic hydrocarbon group as a polar group and a polarity conversion site residue. By introducing a hydroxyl group into the resin, the above-mentioned disadvantages could be overcome.

R ₁ —O—R ₂ —OH (1) (In the above formula, R ₁ is a tert-butoxycarbonyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R ₂ is a bridged cyclic saturated group. It represents a saturated hydrocarbon divalent group having 7 to 12 carbon atoms having a hydrocarbon group.)

[0017]

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(In the above formula, R ₁ and R ₂ are the same as above, and R ₃ represents a hydrogen atom or a methyl group.)

[0019]

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(In the above formula, R ₁ , R ₂ and R ₃ are the same as above. R ₄ is an alkylene (saturated hydrocarbon divalent) group having 7 to 12 carbon atoms and having a bridged saturated hydrocarbon group. , R ₅ is a hydrogen atom or a methyl group, x is 0 to 1 (more preferably, 0.4 to 0.8), n is 10 to 500
It represents an integer of (more preferably 10 to 200). )

[0021]

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(In the above formula, R ₁ and R ₂ are the same as above, R ₆ is a monovalent to tetravalent saturated hydrocarbon residue, and k is 1 to 4
Where the valence value and the k value are equal. The present invention provides a novel compound represented by the general formula (1), which is useful for producing the above-mentioned novel compound represented by the general formulas (2) to (4).

R ₂ and R ₄ are alkylene groups having 7 to 12 carbon atoms and having an alicyclic saturated hydrocarbon group (saturated hydrocarbon divalent group), and more specifically, for example, tricyclo [5.2 .1.0 ^2,6 ] decane-4,8-dimethylene group, norbornane-2,6-dimethylene group, tricyclo [5.2.1.0 ^2,6 ] decanediyl group, adamantanediyl group, norbornane-2, 3-diyl group, norbornane-2,3-dimethylene group, norbornane-2,5-
Dimethylene group, bicyclo [2.2.2] octene-2,
It is a saturated bridged cyclic hydrocarbon divalent group such as a 3-dimethylene group. Further, in the general formula (3), R ₂ and R ₄ and R ₃ and R ₅ may be the same or different.

[0024]

[Table 1]

As R ₆ , for example, a monovalent to tetravalent group (more preferably a divalent to tetravalent group) of a linear or branched saturated hydrocarbon having 2 to 20 carbon atoms, or a monocyclic ring having 3 to 14 carbon atoms Monovalent to tetravalent groups of the formula and polycyclic saturated hydrocarbon (more preferably divalent to tetravalent)
A tetravalent group) and a monovalent to tetravalent group (more preferably a divalent to tetravalent group) of a bridged cyclic saturated hydrocarbon having 4 to 13 carbon atoms.

Among the useful intermediates represented by the general formula (1), compounds in which R ₁ is a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group are synthesized, for example, as follows.

That is, HO-R ₂ —OH (5) of the general formula (5) (wherein R ₂ is the same as above) is used in the presence of a small amount of an acid catalyst (eg sulfuric acid) without solvent or in a solvent (dry). A compound of the general formula (1) in which R ₁ is a 2-tetrahydropyranyl group can be synthesized by reacting 3,4-dihydro-2H-pyran in tetrahydrofuran (for example) at room temperature to 80 ° C. for 15 to 24 hours. The compound represented by the general formula (1) wherein R ₁ is a 2-tetrahydrofuranyl group is
It is synthesized in the same manner as above using 2,3-dihydrofuran instead of 3,4-dihydro-2H-pyran.

Examples of the diol compound represented by the general formula (5) include tricyclo [5.2.1.0 ^2,6 ] decane-
4,8-dimethanol, norbornane-2,6-dimethanol, tricyclo [5.2.1.0 ^2,6 ] decanediol, adamantanediol, norbornane-2,3-
Diol, norbornane-2,3-dimethanol, norbornane-2,5-dimethanol, bicyclo [2.2.
2] Octene-2,3-dimethanol, isobornanediol, isobornanedimethanol and the like.

Among the useful intermediates represented by the general formula (1), the compound in which R ₁ is a tert-butoxycarbonyl group is synthesized, for example, as follows.

That is, the hydroxyl group of the diol compound represented by the general formula (5) is determined by a conventional method (JM Freche).
t) et al., Polymer, Vol. 24, No. 8,
For example, di-tert-butyl dicarbonate in a dehydrated tetrahydrofuran solvent in the presence of potassium-tert-butoxide and room temperature
It is synthesized by reacting at 50 ° C. for 3 to 24 hours.

Using the intermediate represented by the general formula (1) produced as described above, a vinyl group-containing monomer represented by the general formula (2) can be produced, for example, as follows.

That is, the intermediate represented by the general formula (1) is
For example, an excess of base (eg, 2
By reacting with an equimolar amount of methacryloyl chloride or acryloyl chloride in an ice-cooled temperature of 50 ° C. for 1 to 20 hours in the presence of at least twice the molar amount (more preferably at least 5 times the molar amount of triethylamine), the compound represented by the general formula (2) is obtained. A vinyl group-containing monomer containing a vinyl group is obtained.

In the synthesis of the polymer represented by the general formula (3) by homopolymerization or copolymerization reaction of the monomer represented by the general formula (2), if the condition that R ₁ is not eliminated is provided. All commonly known polymerization methods can be used. For example, in a tetrahydrofuran solvent, under an inert gas (argon, nitrogen, etc.) atmosphere, a suitable radical initiator (eg, azobisisobutyronitrile, total monomer (one or more) / initiator molar ratio = 10 ~ 200) and 50-70 ° C
It is carried out by heating and stirring for 0.5 to 10 hours.

The average degree of polymerization (n value in the general formula (3)) of the polymer represented by the general formula (3) is from 10 to 500, more preferably from 10 to 200.

The copolymer (x) represented by the general formula (3)
({0.0, 1.0) represents a monomer (a) represented by the general formula (2) wherein R ₁ is the above-mentioned group other than a hydrogen atom, and a general formula (2) wherein R ₁ is a hydrogen atom. By selecting the charge ratio of the monomer (b) represented by the formula and other polymerization conditions, a copolymer having an arbitrary x value can be obtained. In this case, the monomer and (a), the monomer having a different R ₂ groups (in the general formula (3) represented as R ₄₎ and R ₂ groups in the monomer (a) (b) By copolymerizing and
A copolymer represented by the general formula (3) in which R ₂ and R ₄ are not the same is obtained. Further, a copolymer having different R ₃ and R ₅ can be obtained by the same method.

The polymer represented by the general formula (3) is 220
Residues which are highly transparent in the deep ultraviolet region of nm or less and have an acid-labile group can be contained at any ratio.

ArF excimer laser light (193) of a thin film (thickness = 1.0 μm) of the polymer represented by the general formula (3)
nm) was as high as 65 to 75%, which was confirmed to be practical.

Further, in the general formula (3) (R ₁ is a hydrogen atom, R
₃ is a methyl group and R ₂ is tricyclo [5.2.1.
( ^2,6 ] decanedimethylene group), the etching rate in CF ₄ gas reactive ion etching of the polymer thin film was about 180 A / min, which was comparable to that of the poly (p-vinylphenol) thin film. It was confirmed that the polymer represented by the general formula (3) (x is 0.0 to 0.8) has good adhesion to a silicon substrate. The dissolution rate of the polymer (x is 0.0) represented by the general formula (3) in a tetrabutylammonium hydroxide solution is the dissolution rate of the polymer (x is 0.35) represented by the general formula (3). Was about a thousand times.

The compound represented by the general formula (4) is synthesized, for example, as follows. That is, the general formula (6)

[0040]

[Chemical 4]

(In the above formula, R ₁ and R ₂ are the same as above, R ₆ is a monovalent to tetravalent saturated hydrocarbon residue, and k is 1 to 4
Where the valence value and the k value are equal. The carboxylic acid represented by the formula (1) is reacted with oxalic acid chloride or thionyl chloride in a molar amount of 1 to 5 times the amount of the carboxylic acid unit to convert to the corresponding carboxylic acid chloride. Thereafter, for example, in a solvent of dehydrated methylene chloride or tetrahydrofuran, an excess of base (for example, 2 times or more (more preferably, 5 times or more) per carboxylic acid chloride residue)
Triethylamine) in the presence of the above-mentioned carboxylic acid chloride and the compound represented by the general formula (1) at 1 to 50 ° C. under ice cooling.
By reacting for up to 20 hours, a compound represented by the general formula (4) is obtained.

Examples of the carboxylic acid compound represented by the general formula (6) include acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, myristic acid, palmitic acid, stearic acid, malonic acid, succinic acid, glutaric acid. Adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
2,3,5-hexanetricarboxylic acid, 3,4-dicarboxymethylpimelic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,
2-cyclohexanedicarboxylic acid, 1,4-dicarboxymethylcyclohexane, 1,3,5-cyclohexanetricarboxylic acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4-cyclohexanetetra Carboxylic acid, camphoric acid, 1,3-adamantanedicarboxylic acid and the like are used.

A photosensitive resin composition comprising a resin represented by the general formula (3), a photosensitive agent and a solvent can be produced. The compound represented by the general formula (4) may be further added to these compositions. It is preferable that the photoacid generator used is a photoacid generator that generates an acid by light having a wavelength of 300 nm or less, preferably 220 nm or less, and a polymer represented by the general formula (3). Any photoacid generator may be used as long as the mixture of the photoacid generator is sufficiently dissolved in an organic solvent and the solution can form a uniform coating film by a film forming method such as spin coating. Also, they may be used alone or in combination of two or more, or may be used in combination with an appropriate sensitizer. Examples of usable photoacid generators include, for example, Journal of the Organic Chemistry (Jo
urnalof the Organic Chemi
story) 43, No. 15, pp. 3055-3058 (1978). V. JV Crivello et al., A triphenylsulfonium salt derivative, and other onium salts represented by the derivative (for example, compounds such as sulfonium salt, iodonium salt, phosphonium salt, diazonium salt, and ammonium salt); 6-dinitrobenzyl esters [T.
X. TX Neenan et al., SPIE Proceedings, 1086, 2-10 (1989).
Year) (Proceedings of SPIE, vo
l 1086, pp2-10 (1989)], 1, 2,
3-tri (methanesulfonyloxy) benzene [Takumi Ueno et al., Proceeding of PME (Pro
seeding of PME) '89, Kodansha, 41
3-424 (1990)], JP-A-5-13441
No. 6 discloses a sulfosuccinimide disclosed in Japanese Patent Application No.
General formula (7) disclosed in Japanese Patent Application No. 174528 and Japanese Patent Application No. 5-174532.

[0044]

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(Wherein R ₇ and R ₈ are linear, branched, or cyclic alkyl groups, R ₉ is linear, branched, or
Or a cyclic alkyl group, a 2-oxo cyclic alkyl group,
Or a 2-oxo linear or branched alkyl group, Y
￣ is BF ₄ ￣, AsF ₆ ￣, SbF ₆ ￣, PF ₆ ￣, C
It is a counter ion such as F ₃ COO￣, ClO ₄ ￣ or CF ₃ SO ₃ ￣. ) Or general formula (8)

[0046]

[Chemical 6]

(Where R ₁₀ and R ₁₁ are each independently hydrogen, a linear, branched or cyclic alkyl group, and R ₁₂ is a hydrogen, a linear, branched or cyclic alkyl group ,
Alternatively, it is a haloalkyl group represented by perfluoroalkyl such as trifluoromethyl. ) Is a photoacid generator.

When the exposure light having a wavelength of 220 nm or less is used, in order to enhance the light transmittance of the photosensitive resin composition, the photoacid generators described above, particularly, the general formula (7) or the general formula (8)
It is more preferable to use a photo-acid generator represented by
This is because the photoacid generator widely used for KrF excimer laser lithography [eg, triphenylsulfonium trifluoromethanesulfonate (hereinafter abbreviated as TPS) described in the above-mentioned reference of Krivero et al.] Is extremely strong in the far ultraviolet region of 220 nm or less. Since it has a light-absorbing property, its use amount is limited for use as the photo-acid generator in the present invention. Here, for example, comparing the transmittance at 193.4 nm, which is the center wavelength of ArF excimer laser light,
The transmittance of a coating film (1 μm thick) of the general formula (3) containing 1.5 parts by weight of TPS with respect to the total film weight is about 40%. The transmittance was about 6%. On the other hand, among the sulfonium salt derivatives represented by the following general formula (7), the transmittance of a PMMA coating film containing, for example, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate is 5 parts by weight. 71%, and another 30
Even the coating film containing parts by weight showed a high transmittance of 55%. Further, of the photo-acid generators represented by the general formula (8), for example, the coating film containing 5 parts by weight of N-hydroxysuccinimide trifluoromethanesulfonate was about 50%. As described above, each of the photoacid generators represented by the general formulas (7) and (8) has remarkably little light absorption in the far ultraviolet region of 185.5 to 220 nm, and is ArF excimer in terms of transparency to exposure light. Obviously, it is more suitable as a component of a resist for laser lithography. Specifically, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, tricyclomethane Examples include, but are not limited to, phenylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, and the like. In the photosensitive resin composition, the photoacid generator may be used alone or in combination of two or more. The content of the photo-acid generator is usually 0.2 to 25 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the total solid content including itself. If this content is less than 0.5 parts by weight, the sensitivity of the present invention is significantly reduced, and it is difficult to form a pattern.
On the other hand, if it exceeds 25 parts by weight, it becomes difficult to form a uniform coating film, and a residue (scum) is likely to occur after development, which causes problems. As a preferable solvent to be used, any solvent can be used as long as a component comprising a polymer compound and an alkylsulfonium salt is sufficiently dissolved, and the solution is an organic solvent capable of forming a uniform coating film by a method such as a spin coating method. May be. Moreover, you may use individually or in mixture of 2 or more types. Specifically, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate,
Ethyl lactate, 2-methoxybutyl acetate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, 3-
Methyl methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Examples thereof include monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like, but are not limited thereto.

The "basic" constituents of the photosensitive resin composition are the above-mentioned photoacid generator, polymer compound and solvent, and may be represented by the general formula (4) if necessary. Other components such as dissolution inhibitors (dissolution inhibitors) or other dissolution inhibitors (dissolution inhibitors), surfactants, dyes, stabilizers, coatability improvers, and dyes may be added.

When a fine pattern is formed using the photosensitive composition described above, a developer suitable for the solubility of the polymer compound to be used is an appropriate organic solvent, a mixed solvent thereof, or a suitable solvent. An alkaline organic solvent solution, an alkaline aqueous solution or a mixture thereof having a suitable concentration may be selected. As the organic solvent used, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclopentanone, cyclohexanone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, Examples thereof include alcohols such as tert-butyl alcohol, cyclopentanol, and cyclohexanol, and organic solvents such as tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, isoamyl acetate, benzene, toluene, xylene, and phenol. Examples of the aqueous alkali solution used include, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia; and organic acids such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine, and triethylamine. Amines, and tetramethylammonium hydroxide, tetraethylammonium hydroxide,
An aqueous solution containing an organic ammonium salt such as trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, or an organic solvent, and a mixture thereof,
It is not limited to these.

[0051]

The present invention provides a novel compound which is an intermediate raw material for producing a novel vinyl group-containing monomer and a polymer thereof. By utilizing the polymer produced via the intermediate of the present invention, high transparency of light of 180 nm to 220 nm, high dry etching resistance, and having a functional group capable of exhibiting a solubility difference before and after exposure, A new resist resin material and a dissolution inhibitor with improved substrate adhesion are provided, and a photosensitive composition comprising these and a photosensitive agent (photoacid generator) provides:
Degradation of the hydroxyl group protecting group using a protonic acid as a catalyst generated by exposure to light having a short wavelength of 180 nm to 220 nm or less induces a marked change in the solubility of the resist, and as a result, a fine pattern can be formed.

[0052]

EXAMPLES The present invention will be described in more detail with reference to examples and reference examples, but the present invention is not limited to these examples.

Example 1 Synthesis of (2-tetrahydropyranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol

[0054]

[Chemical 7]

(However, X and Y each represent a 2-tetrahydropyranyl group or a hydrogen atom, and X and Y are not the same at the same time.) For 200 ml with thermometer, nitrogen gas inlet tube and reflux tube 3. In a one-necked flask, add 3,4-dihydro-2H-pyran.
0 g (0.11 mol) and tricyclodecane-4,8-
Dimethanol (Aldrich Chemical C
company, Inc. (USA), product number B4, 590-9), and after stirring 19.6 g (0.1 mol), the mixture was stirred. To this was added 5 drops of 50% sulfuric acid. Thereafter, the reaction was carried out at 50 ° C. for 24 hours. After cooling to room temperature,
After adding 3 g of solid sodium carbonate and 10 g of anhydrous sodium sulfate and stirring for 2 hours, the mixture was filtered to collect a filtrate. The filtrate was treated with 0.2 g of calcium hydride. The residue obtained by removing excess dihydropyran under reduced pressure using a rotary evaporator is purified by a silica gel column to obtain 18.2 g (yield 65%) of (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol. Was. oil.

Elemental analysis value (% by weight): C, 72.5 (7
2.8); H, 9.9 (10.1) (however, the values in parentheses are C ₁₇ H ₂₈ O ₃ (MW 280.4
08) represents the calculated value. ).

IR (cm ^-1 ): 3350 (ν _OH ), 103
0 (ν _COC ).

Example 2 Synthesis of (2-tetrahydrofuranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol

[0059]

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(However, X and Y each represent a 2-tetrahydrofuranyl group or a hydrogen atom, and X and Y are not the same at the same time.) As in Example 1, except that 3,4-dihydro- Synthesis was performed using 6.3 g (0.09 mol) of 2,3-dihydrofuran instead of 10.0 g (0.11 mol) of 2H-pyran. Yield 9.5 g (40%). oil.

Elemental analysis value (% by weight): C, 72.2 (7
2.1); H, 9.9 (9.8) (However, the numerical value in parentheses is C ₁₆ H ₂₆ O ₃ (MW 266.3)
81) represents the calculated value. ).

IR (cm ^-1 ): 3370 (ν _OH ), 103
0 (ν _COC ).

Example 3 Synthesis of tert-butoxycarbonyloxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol

[0064]

[Chemical 9]

(However, X and Y represent a tert-butoxycarbonyl group or a hydrogen atom, and X and Y are not the same at the same time.) In a 100 ml eggplant-shaped flask equipped with a calcium chloride drying tube, under an argon gas atmosphere. , Tricyclodecane-4,8-
Dimethanol (Aldrich Chemical C
company, Inc. (U.S.A.), product number B4,590-9, 19.6 g (0.1 mol) and 100 ml of dry tetrahydrofuran were charged. 11.2 g (0.1 mol) of potassium tert-butoxide was added thereto.
Was added, and the mixture was thoroughly stirred with a Teflon bar. Further, a dry tetrahydrofuran solution (100 ml) of 21.8 g (0.1 mol) of di-tert-butyl dicarbonate was added, and the mixture was vigorously stirred at room temperature for 10 hours. Thereafter, 100 ml of ice water was added and stirred, and then 500 ml of chloroform was added to wash the resulting solution with water. The organic layer was dehydrated with anhydrous magnesium sulfate and then filtered. The solvent was distilled off from the filtrate under reduced pressure. By purifying the residue by silica gel column chromatography, the target product 1
5 g was obtained.

Elemental analysis value (% by weight): C, 68.7 (6
8.9); H, 9.8 (9.5) (however, the values in parentheses are C ₁₇ H ₂₈ O ₄ (MW 296.4)
The calculated value of 07) is shown. ) IR (cm ^-1 ): 3370 (ν _OH ), 1760
(Ν _{C = 0} ), (Example 4) Synthesis of (2-tetrahydropyranyl) oxymethylnorbornyl alcohol

[0067]

[Chemical 10]

(However, X and Y represent a 2-tetrahydropyranyl group or a hydrogen atom, and X and Y are not the same at the same time.) As in Example 1, but tricyclodecane-4 , 8-
Instead of 19.6 g (100 mmol) of dimethanol, norbornane-2,3-diol (reference (Hence (K.
Heyns) et al., Chemiche Berichte, 105, 10.
19 (1972); Lambert (JB Lambe).
rt) et al., Journal of the American Chemical Society, 100, 2501). ) 12.8 g (100 mmol) was used for the synthesis. Yield 4.0 g (19% yield). oil.

Elemental analysis value (% by weight): C, 68.0 (6
7.9); H, 9.8 (9.5) (however, the values in parentheses are C ₁₂ H ₂₀ O ₃ (MW 212.2)
89) represents the calculated value. ) IR (cm ^-1 ): 3350 (ν _OH ), 1030
(Ν _COC ).

Reference Example 1 Synthesis of (2-tetrahydropyranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol methacrylate

[0071]

[Chemical 11]

(However, X and Y represent a 2-tetrahydropyranyl group or a methacryloyl group, and X and Y are not the same at the same time.) (2-tetrahydropyranyl) obtained in Example 1 11.2 g of oxymethyltricyclodecanemethanol (0.
04 mol), 0.01 g of phenothiazine, 20 ml of dehydrated triethylamine, 20 ml of dehydrated methylene chloride and 20 ml of dehydrated ether were charged into a 100 ml flask equipped with a silica gel drying tube and stirred. While this solution was cooled with ice, a solution of 4.18 g (0.04 mol) of methacryloyl chloride dissolved in 5 ml of dehydrated methylene chloride was slowly added dropwise (the temperature of the reaction solution was kept at 25 ° C. or lower). After completion of dropping, the mixture was stirred at room temperature for 3 hours and then filtered. The filter cake was washed thoroughly with ether. The filtrate was collected, and the solvent was distilled off under reduced pressure using a rotary evaporator. After dissolving the residue in ether, 5%
After washing with an aqueous sodium carbonate solution and dehydrating the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure using a rotary evaporator. The residue is purified by silica gel chromatography (eluting solvent: ethyl acetate / n-hexane), and then the target portion is collected and dried under reduced pressure at 2 mmHg and room temperature for 24 hours to obtain the desired (2-tetrahydropyranyl) oxymethyltricyclo. 6.2 g (yield 45%) of decane methanol methacrylate was obtained. oil.

Elemental analysis value (% by weight) C: 72.2 (72.4) H: 9.6 (9.3) However, the numerical value in parentheses is C ₂₁ H ₃₂ O ₄ (MW 348.48)
3) represents the calculated value.

IR (cm ^-1 ): 1720 (ν _{C = 0} ), 16
40 (ν _{C = C} ), 1030 (ν _COC ), ν _OH characteristic absorption band disappearance ¹ H-NMR (CDCl ₃ , internal standard substance: tetramethylsilane) δ (ppm): 0.9 to 2.4 (m) , 23
H) 3.2-3.6 (s, 4H), 3.8 (s, 2
H), 4.6 (m, 1H), 5.5 (s, 1H), 6.
1 (m, 1H) (Reference Example 2) Synthesis of (2-tetrahydrofuranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol methacrylate

[0075]

[Chemical 12]

(However, X and Y represent a 2-tetrahydrofuranyl group or a methacryloyl group, and X and Y are not the same at the same time.) As in Reference Example 1, except that (2-tetrahydropyranyl) ) Oxymethyltricyclodecanemethanol 11.2
Synthesis was performed using 10.6 g (0.04 mol) of (2-tetrahydrofuranyl) oxymethyltricyclodecanemethanol synthesized according to Example 2 instead of g (0.04 mol). Yield 4.7 g (yield 35%). oil.

Elemental analysis value (% by weight): C, 71.5 (7
1.8); H, 9.2 (9.0) (however, the numerical value in parentheses represents the calculated value of C ₂₀ H ₃₀ O ₄ (MW 334.456)).

IR (cm ^-1 ): 1720 (ν _{C = 0} ), 16
40 (ν _{C = C} ), 1030 (ν _COC ), disappearance of ν _OH characteristic absorption band (Reference Example 3) Synthesis of tert-butoxycarbonyloxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol methacrylate

[0079]

[Chemical 13]

(Where X and Y each represent a tert-butoxycarbonyl group or a methacryloyl group;
Cannot be the same at the same time. As in Reference Example 1, except that (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol 11.2 was used.
The synthesis was performed using 11.8 g (0.04 mol) of tert-butoxycarbonyloxymethyltricyclodecanemethanol synthesized according to Example 3 instead of g (0.04 mol). Yield 5.1 g (35% yield).

IR (cm ⁻¹ ): 1760 (ν _{C = 0} ), 17
20 (ν _{C = 0} ), 1640 (ν _{C = C} ), disappearance of the ν _OH characteristic absorption band Elemental analysis value (% by weight): C, 68.9 (69.2);
H, 8.9 (8.8) However, the value in parentheses is C ₂₁ H ₃₂ O ₅ (MW364.48)
It represents the calculated value of 4).

Reference Example 4 Synthesis of (2-tetrahydropyranyl) oxymethylnorbornyl alcohol acrylate

[0083]

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(However, X and Y each represent a 2-tetrahydropyranyl group or an acryloyl group, and X and Y are not the same at the same time.) As in Reference Example 1, except that (2-tetrahydropyranyl) F) Oxymethyltricyclodecanemethanol 11.2
g (0.04 mol) was replaced with 8.4 g (0.04 mol) of (2-tetrahydropyranyl) oxynorbornyl alcohol synthesized according to Example 4, and further to 4.18 g (0.04 mol) of methacryloyl chloride. Synthesis was performed using 3.62 g (0.04 mol) of acryloyl chloride instead. Yield 3.4 g (30% yield). oil.

Elemental analysis value (% by weight): C, 68.4 (6
8.0); H, 8.3 (8.0) (however, the values in parentheses are C ₁₅ H ₂₂ O ₄ (MW266.3).
It represents the calculated value of 50). ).

IR (cm ^-1 ): 1720 (ν _{C = 0} ), 16
40 (ν _{C = C} ), 1030 (ν _COC ), disappearance of the ν _OH characteristic absorption band (Reference Example 5) (2-tetrahydropyranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decane methanol Synthesis of methacrylate polymers

[0087]

[Chemical 15]

(Provided that Z ₁ is tricyclodecane-4,8
-Diyl group, Z ₂ represents a 2-tetrahydropyranyl group, and m represents a positive integer. ) In a 100 ml eggplant-shaped flask with a three-way stopcock and a cooling tube, dry tetrahydrofuran 25 was added under an argon gas atmosphere.
5.0 g (14.3 mmol) of (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol methacrylate synthesized in Reference Example 1 was dissolved in the ml. Furthermore, 0.16 g of azobisisobutyronitrile which is an initiator
(1 mmol), and under an argon gas atmosphere, 60 ° C
For 30 minutes. After cooling the reaction system to room temperature, the reaction solution was poured into 0.3 liter of hexane. Collect the precipitate,
The reprecipitation purification was repeated once more in the same solvent system. The precipitate of the precipitated polymer was collected by filtration, and dried under reduced pressure at 2 mmHg and 40 ° C. for 24 hours to obtain 2.1 g of an intended polymer powder (yield: 42%). The weight average molecular weight in terms of polystyrene was 22000 (analyzer: Shimadzu Corporation LC-9A / SPD-6A; analytical column: Showa Denko GPCKF-80M, elution solvent: tetrahydrofuran).

Elemental analysis value (% by weight) C: 72.2 (72.4) H: 9.5 (9.3) However, the numerical value in parentheses is (C ₂₁ H ₃₂ O ₄ ) _m (unit: MW3)
48.483).

IR (cm ^-1 ): 1720 (ν _{C = 0} ), ν
_{Absence of C = C} characteristic absorption band (Reference Example 6) Synthesis of polymer of (2-tetrahydrofuranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol methacrylate

[0091]

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(However, Z ₁ is tricyclodecane-4,8
-Diyl group, Z ₂ is a tetrahydrofuran-2-yl group,
m represents a positive integer. (2)) (2-Tetrahydrofuranyl) oxymethyl synthesized according to Reference Example 2 in the same manner as Reference Example 5 except that (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol methacrylate was replaced with 5.0 g (14.3 mmol). Synthesis was performed using 4.78 g (14.3 mmol) of tricyclodecanemethanol methacrylate.
Yield 1.7 g (35% yield). The weight average molecular weight in terms of polystyrene was 19000. Elemental analysis value (% by weight): C, 71.7 (71.8);
H, 9.1 (9.0) (However, the numerical value in parentheses is (C ₂₀ H ₃₀ O ₄ ) _m (unit MW)
334.456). ) IR (cm ^-1 ): 1720 (ν _{C = 0} ), disappearance of the ν _{C = C} characteristic absorption band (Reference Example 7) tert-butoxycarbonyloxymethyltricyclo [5.2.1.0 ^2,6 ] decane Synthesis of Methanol Methacrylate Polymer

[0093]

[Chemical 17]

(Where Z is tricyclodecane-4,8-
The diyl group and m represent a positive integer. ) In a 100 ml eggplant-shaped flask with a three-way stopcock and a cooling tube, dry tetrahydrofuran 30 was added under an argon gas atmosphere.
2.5 g (6.9 mmol) of tert-butoxycarbonyloxymethyltricyclodecanemethanol methacrylate synthesized in Reference Example 3 was dissolved in ml. Further, 0.033 g of azobisisobutyronitrile as an initiator is used.
(0.2 mmol) and added under an argon gas atmosphere.
Heat at 0 ° C. for 3 hours. After cooling the reaction system to room temperature, the reaction solution was poured into 0.3 liter of ether. The precipitate was collected and the reprecipitation purification was repeated once more using the same solvent system. The precipitated polymer precipitate was collected by filtration and dried under reduced pressure at 2 mmHg and 40 ° C. for 24 hours to obtain 1.3 g of an intended polymer powder (yield: 52%). The weight average molecular weight in terms of polystyrene was 58,000. Elemental analysis value (% by weight) C: 69.0 (69.2) H: 8.7 (8.8) However, the numerical value in parentheses is (C ₂₁ H ₃₂ O ₅ ) _m (unit MW3)
64.482).

IR (cm ^-1 ): 1760 (ν _{C = 0} ), 17
20 (ν _{C = 0} ), ν _{C = C} characteristic absorption band disappears (Reference Example 8) Synthesis of polymer of (2-tetrahydropyranyl) oxymethylnorbornyl alcohol acrylate

[0096]

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(Provided that Z ₁ is a norbornanediyl group, Z 1
₂ represents a 2-tetrahydropyranyl group, and m represents a positive integer. (2) (2-tetrahydropyranyl) oxy synthesized according to Reference Example 4 in the same manner as in Reference Example 5, except that (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol methacrylate was replaced with 5.0 g (14.3 mmol). Methyl norbornyl alcohol acrylate 3.81
g (14.3 mmol) was used for synthesis. Yield 1.
9 g (yield 50%). The weight average molecular weight in terms of polystyrene was 27,000.

Elemental analysis value (% by weight): C, 68.3 (6
8.0); H, 8.2 (8.0) (however, the numerical value in parentheses is (C ₁₅ H ₂₂ O ₄ ) _m (MW 26
6.350). ) IR (cm ^-1 ): 1720 (ν _{C = 0} ), 1030 (ν
_COC ), ν _{C = C} characteristic absorption band disappears (Reference Example 9) (2-tetrahydropyranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethanol methacrylate and tricyclo [5.2.1] 0.0 ^2,6 ] decane dimethanol monomethacrylate copolymer

[0099]

[Chemical 19]

(Provided that Z ₁ is tricyclodecane-4,8
-Diyl group, Z ₂ is a 2-tetrahydropyranyl group, m is a positive integer, and x represents 0 to 1. ) (2-tetrahydropyranyl) was synthesized in the same manner as in Reference Example 4, except that (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol methacrylate was replaced with 5.0 g (14.3 mmol). Oxymethyltricyclodecanemethanol methacrylate 2.0 g (5.7 mmol) and hydroxymethyltricyclodecanemethanol monomethacrylate 2.3 g
(8.6 mmol) to obtain 1.8 g of the desired copolymer powder. The weight average molecular weight in terms of polystyrene was 23,000. The copolymer composition is x = 0.5
It was 8.

IR (cm ^-1 ): 3370 (ν _OH ), 172
0 (ν _{C = 0} ), 1030 (ν _COC ), disappearance of the ν _{C = C} characteristic absorption band, (Reference Example 10) 1,3,5-cyclohexanetricarboxylic acid tri {(2
Synthesis of -tetrahydropyranyl) oxymethyltricyclo [5.2.1.0 ^2,6 ] decanemethyl} ester

[0102]

Embedded image

[0103] (wherein, X is 2-tetrahydropyranyl group, Y is tricyclo [5.2.1.0 ^{2, 6]} decane -
A 4,8-diyl group and Z represent a 1,3,5-cyclohexanetriyl group. ) 11.2 g of (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol obtained in Example 1 (0.
04 mol), 0.01 g of phenothiazine, 60 ml of dehydrated triethylamine, 20 ml of dehydrated methylene chloride and 20 ml of dehydrated ether were charged into a 100 ml flask equipped with a silica gel drying tube and stirred. While cooling this solution on ice, 1,3,5-cyclohexanetricarboxylic acid chloride3.
A solution of 2 g (0.012 mol) dissolved in 5 ml of dehydrated methylene chloride was slowly added dropwise (the temperature of the reaction solution was 25
C). After completion of dropping, the mixture was stirred at room temperature for 3 hours and then filtered. The filter cake was washed thoroughly with ether. The filtrate was collected, and the solvent was distilled off under reduced pressure using a rotary evaporator. The residue was dissolved in ether, washed with 5% aqueous sodium carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure using a rotary evaporator.
The residue was chromatographed on silica gel (elution solvent: ethyl acetate / n
-Hexane), and the target part was collected and dried under reduced pressure at 2 mmHg and room temperature for 24 hours to obtain the target substance.
4 g (70% yield) were obtained.

Elemental analysis value (% by weight) C: 72.1 (71.8) H: 9.2 (9.0) However, the numerical value in parentheses is C ₆₀ H ₉₀ O ₁₂ (MW 1003.3).
68) represents the calculated value.

IR (cm ^-1 ): 1720 (ν _{C = 0} ),
1030 (ν _COC ) (Reference Example 11) A resist material having the following composition was prepared. The following experiments were performed under a yellow lamp. (A) Resin (Reference Example 9) 0.950 g (b) Cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate (photoacid generator: compound of general formula (4)) 0.050 g (c) propylene glycol Monomethyl ether acetate (solvent) 4.000 g The above mixture was filtered using a 0.2 μm Teflon filter to prepare a resist. The above resist material is spin-coated on a 3-inch silicon substrate, and the temperature is kept at 80 ° C.
Baking was performed on a hot plate for 0 seconds to form a thin film having a thickness of 0.7 μm. The wavelength dependence of the transmittance of the obtained film was measured using an ultraviolet-visible spectrophotometer. As a result, the transmittance of this thin film at 193.4 nm was 71%, indicating that the film was sufficiently transparent as a single-layer resist. It was confirmed.

Example 12 Using the resist prepared in Reference Example 11, a film-formed wafer was allowed to stand in a contact type exposure experiment machine sufficiently purged with nitrogen. A mask having a pattern of chrome on a quartz plate was brought into close contact with the resist film, and ArF excimer laser light was irradiated through the mask.
Immediately thereafter, it was baked on a hot plate at 90 ° C. for 60 seconds, and then developed by an immersion method for 60 seconds with an alkali developing solution having a liquid temperature of 23 ° C. (an aqueous solution containing 2.3 parts by weight of tetramethylammonium hydroxide). And rinsed with pure water for 60 seconds. As a result, only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive pattern was obtained. In this experiment, when the exposure energy is 15 mJ / cm ² , 0.25 μm
Line and space resolution was obtained. At this time, a scanning electron microscope (SEM, Hitachi, SE-410
The pattern resolved in 0) was observed, but no phenomenon such as residual development and pattern peeling was observed.

[0107]

As is apparent from the above description, a novel vinyl group-containing monomer is produced using the useful intermediate compound (new substance) of the present invention, and a new polymer is obtained by polymerizing the monomer. Coupling and dissolution inhibitors can be provided. The photosensitive resin composition containing the above-mentioned polymer or dissolution inhibitor has high transparency in the far ultraviolet region of 180 nm to 220 nm or less, and exhibits high sensitivity and resolution for far ultraviolet exposure light. Deep UV of 220nm or less, especially Ar
It is suitable for a photoresist that uses F excimer laser as exposure light. Further, by using the photosensitive resin composition of the present invention, it becomes possible to form a fine pattern necessary for manufacturing a semiconductor element.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/004 502 7/027 H01L 21/027

Claims (1)

[Claims] 1. A bridged cyclic hydrocarbon alcohol represented by the following general formula: R ₁ —O—R ₂ —OH (wherein R ₁ is a tert-butoxycarbonyl group, 2
-Tetrahydropyranyl group or 2-tetrahydrofuranyl group, R ₂ represents a saturated hydrocarbon divalent group having a bridged cyclic saturated hydrocarbon group and having 7 to 12 carbon atoms. )