JP2616250B2 - Bridged cyclic hydrocarbon alcohols and intermediate compounds for photosensitive materials - Google Patents

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 which require sub-micron-order microfabrication represented by VLSI, the demand for higher density and higher integration of devices is increasing, and fine pattern formation is required. The demands on photolithography technology for lithography are becoming more stringent.

[0003] As one of means for miniaturizing a pattern, it is known to shorten the wavelength of exposure light used for 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. 2
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 studied. Furthermore, a D having an integration degree of 1 Gbit or more (processing dimension 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 the target yield of the mass production process, that is, the time required for the exposure step, and the economical efficiency when a new light source is adopted in the production site, batch exposure is possible and the accumulation of the prior art is possible. Is more promising than electron beam exposure or X-ray exposure. For this reason, in order to manufacture an LSI having a degree of integration of 1 Gbit or more, even shorter wavelength light, ie, 220 nm
Development of photolithography technology using the following short wavelength light sources is urgently needed.

[0005] The photosensitive resin composition for this purpose needs to satisfy the improvement of laser cost performance because of the short life of gas, which is a material for laser oscillation, and the high cost of the laser device itself. . For this reason, resist materials used for fine processing are required to have high sensitivity in addition to high resolution corresponding to fine 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.
No. 0 describes a resist comprising 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 photoreaction efficiency (reaction per photon) is significantly higher than that of a conventional resist having 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. At present, most of the resists to be developed are of the chemical amplification type, and the adoption of a chemical amplification mechanism is indispensable for the development of a highly sensitive material corresponding to a shorter wavelength of the exposure light source.

[0006]

In the case of lithography using an excimer laser having a short wavelength of 220 nm or less as an 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 which does not contain an aromatic ring and has etching resistance has been 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 present inventors have already developed a novel photoacid generator which satisfies these requirements (Japanese Patent Application No. 5-17 / 1990).
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, Vol. 5 (No. 3), pp. 439-446 (1992), and JP-A-5-2652.
No. 12] or a copolymer of poly (norbornyl methacrylate) and poly (tert-butyl methacrylate) [M. Endor, the proceedings of
I EDM (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 since the dry etching resistance of the comonomer unit is extremely low, the dry etching resistance effect of the adamantane skeleton is significantly reduced, and the practical use as a dry etching resistant resin is poor. In addition, these copolymers having an alicyclic alkyl group generally have high hydrophobicity 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 novolak resin, which has been frequently used in conventional resists, it does not contain a polar part, and therefore has poor adhesion to a silicon substrate. Further, it has a disadvantage that it has low sensitivity due to low solubility in an aqueous alkaline developing solution, and that residue (scum) tends to be easily generated 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 (In the above formula, R ₁ is a tert-butoxycarbonyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R ₂ is tricyclo [5.2.1. 0
^2,6 ] decanedimethylene group, tricyclo [5.2.1.
0 ^2,6 ] decanediyl group , norbornanedimethylene group,
Represents an adamantanediyl 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 a tricyclo [5.2.1.0 ^2,6 ] decanedimethylene group, tricyclo [5.2.1. 0 ^2,6 ] decanediyl group , norbornane dimethylene group, adamantanediyl group, R ₅ is a hydrogen atom or a methyl group, and x is 0
-1 (more preferably 0.4-0.8), n is 10
Represents an integer of 500 (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 tricyclo [5.2.
1.0 ^2,6 ] decane dimethylene group, tricyclo [5.
2.1.0 ^2,6 ] decanediyl group , norbornane dimethylene group and adamantanediyl group. 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) (wherein R ₂ is the same as described above) is reacted with a solvent or a solvent (dry) in the presence of a small amount of an acid catalyst (eg, sulfuric acid). By reacting 3,4-dihydro-2H-pyran in a solution such as tetrahydrofuran at room temperature to 80 ° C. for 15 to 24 hours, the compound of the general formula (1) in which R ₁ is a 2-tetrahydropyranyl group can be synthesized. 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.

A compound in which R ₁ is a tert-butoxycarbonyl group among the useful intermediates represented by the general formula (1) 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
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 (b) having the monomer (a) and an R ₂ group different from the R ₂ group in the monomer (a) (represented as R ₄ in the general formula (3)) And by copolymerizing
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.

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 represented by the general formula (3) (x is 0.0) in a tetrabutylammonium hydroxide solution is the dissolution rate of the polymer represented by the general formula (3) (x is 0.35). It was about 1,000 times.

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

[0040]

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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 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)
Of the above carboxylic acid chloride and the compound represented by the general formula (1) in the presence of
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, and 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. A 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. Further, 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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(Where R ₇ and R ₈ are linear, branched, or cyclic alkyl groups, and R ₉ is linear, branched,
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]

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(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 ,
Or a haloalkyl group represented by perfluoroalkyl such as trifluoromethyl. ).

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 photoacid generator represented by
This is because photoacid generators [for example, triphenylsulfonium trifluoromethanesulfonate (hereinafter abbreviated as TPS) described in the above document by Krivero et al.], Which is frequently used for KrF excimer laser lithography, are extremely strong in the deep ultraviolet region of 220 nm or less. Due to its light-absorbing properties, its usage is limited for use as a photoacid 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, among the photoacid generators represented by the general formula (8), for example, about 50% was obtained in a coating film containing 5 parts by weight of N-hydroxysuccinimide trifluoromethanesulfonate. 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, trifluoromethylsulfonate Examples include, but are not limited to, phenylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate. In the photosensitive resin composition, the photoacid generator may be used alone or in combination of two or more. The content of the photoacid generator is usually from 0.2 to 25 parts by weight, preferably from 1 to 15 parts by weight, based on 100 parts by weight of the total solids including itself. If the content is less than 0.5 parts by weight, the sensitivity of the present invention is remarkably reduced, and it is difficult to form a pattern.
On the other hand, if the amount exceeds 25 parts by weight, it becomes difficult to form a uniform coating film, and there is a problem that a residue (scum) is easily generated after development. 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 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,
However, it is not limited to these.

[0051]

The present invention provides a novel compound which is an intermediate 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:
Remarkable change in the solubility of the resist is induced by the decomposition of the hydroxyl-protecting group using the proton acid generated by short-wavelength light exposure of 180 nm to 220 nm or less as a catalyst, and as a result, a fine pattern can be formed.

[0052]

Next, 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]

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(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
ompany, 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 numerical value in parentheses is C ₁₇ H ₂₈ O ₃ (MW 280.4
08). ).

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]

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(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.)

A 100 ml container with a calcium chloride drying tube
Tricyclodeca
4,8-dimethanol (Aldrich Chem)
ical Company, Inc. (U.S.A.),
Product number B4, 590-9) 19.6 g (0.1 mo
1) dry tetrahydrofuran solution (100 ml)
I was crowded.

There, potassium tert-butoxide 1
Add 1.2g (0.1mol) and use Teflon bar
Stirred. Further, di-tert-butyl dicarbonate 21.
8g (0.1mol) dry tetrahydrofuran solution
(100 ml) and stirred vigorously at room temperature for 10 hours.
Was.

Thereafter, 100 ml of ice water was added, and the mixture was stirred.
The solution obtained by adding 500 ml of roloform is washed with water, and
The organic layer was dehydrated with anhydrous magnesium sulfate and then filtered. The filtrate
The solvent was distilled off under reduced pressure. Silica gel column residue
Purification by chromatography gave 15 g of the desired product.

[0069]Elemental analysis value (% by weight): C, 68.7 (6
8.9); H, 9.8 (9.5) (however, numerical values in parentheses)
Is C ₁₇ H ₂₈ O _Four Table showing calculated values of (MW296.407)
You. ) IR (cm ^-1 ): 3370 (ν _OH ), 1760 (ν
_{C = O} ).

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

[0071]

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(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 the dropwise addition, the mixture was stirred at room temperature for 3 hours and filtered. The filtrate was sufficiently washed 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 was purified by silica gel chromatography (elution solvent: ethyl acetate / n-hexane), and the target portion was collected and dried under reduced pressure at 2 mmHg and room temperature for 24 hours to obtain the desired (2-tetrahydropyranyl) oxymethyltricyclohexane. 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]

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(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 (35% yield). 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]

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(Where X and Y each represent a tert-butoxycarbonyl group or a methacryloyl group;
Are not 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 numerical value in parentheses is C ₂₁ H ₃₂ O ₅ (MW 364.48)
4) represents the calculated value.

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 numerical value in parentheses is C ₁₅ H ₂₂ O ₄ (MW 266.3)
50) represents the calculated value. ).

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]

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(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 equipped with a three-way stopcock and a cooling tube, dry tetrahydrofuran 25 was placed 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. Further, 0.16 g of azobisisobutyronitrile as an initiator is used.
(1 mmol) and 60 ° C under an argon gas atmosphere.
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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(Provided that 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]

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(Where Z is tricyclodecane-4,8-
A diyl group, m represents a positive integer. In a 100 ml eggplant type flask equipped with a three-way stopcock and a cooling tube, dry tetrahydrofuran 30
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 reprecipitation purification was repeated once more in 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 27000.

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]

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(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]

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[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) in 5 ml of dehydrated methylene chloride was slowly added dropwise (the temperature of the reaction solution was 25
C). After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours and filtered. The filtrate was sufficiently washed 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 a 5% aqueous sodium carbonate solution, the organic layer was dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure using a rotary evaporator.
The residue was subjected to silica gel chromatography (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).

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,
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.

( Reference Example 12) The resist prepared in Reference Example 11 was used, and sufficiently purged with nitrogen.
The formed wafer was allowed to stand in the contact-type exposure experimental machine. A mask in which a pattern was drawn with 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 afterwards, 90 ° C, 60
Baked on a hot plate for 2 seconds, developed by an immersion method for 60 seconds with an alkali developing solution (aqueous solution containing 2.3 parts by weight of tetramethylammonium hydroxide) at a liquid temperature of 23 ° C., and subsequently purified water for 60 seconds Rinse treatment was performed respectively. 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, the exposure energy was 15 mJ /
At the time of cm ² , a resolution of 0.25 μm line and space was obtained. At this time, the resolved pattern was observed with a scanning electron microscope (SEM, manufactured by Hitachi, Ltd., SE-4100). However, phenomena such as residual development and pattern peeling were not 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 polymer or the photosensitive resin composition containing the dissolution inhibitor as a component has high transparency in the far ultraviolet region of 180 nm to 220 nm or less, and shows high sensitivity to exposure light of far ultraviolet rays, and high resolution. , Deep ultraviolet of 220 nm or less, especially Ar
Suitable for photoresist using 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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03F 7/027 G03F 7/027

Claims (6)

(57) [Claims] 1. A bridged cyclic hydrocarbon alcohol represented by the following general formula: R ₁ —O—R ₂ —OH (where R ₁ is a tert-butoxycarbonyl group, 2
-Tetrahydropyranyl group or 2-tetrahydrofuranyl group, R ₂ is tricyclo [5.2.1.0 ^2,6 ] decanedimethylene group, tricyclo [5.2.1.0 ^2,6 ]
Represents a decanediyl group, a norbornanedimethylene group, or an adamantanediyl group. ) 2. A tricyclo [5.2.1.0 ^{2, 6]} decane methylene group, characterized in that it is a tricyclo [5.2.1.0 ^{2, 6]} decane-4,8-dimethylene group The bridged cyclic hydrocarbon alcohol according to claim 1, wherein 3. The method according to claim 1, wherein the norbornane dimethylene group is any one of a norbornane-2,6-dimethylene group, a norbornane-2,3-dimethylene group and a norbornane-2,5-dimethylene group. The bridged cyclic hydrocarbon alcohol according to the above. 4. An intermediate compound for a photosensitive material for producing a polymer for a photosensitive resin compound, a monomer of a photosensitive resin compound, or a dissolution inhibitor represented by the following general formula. R ₁ —O—R ₂ —OH (where R ₁ is a tert-butoxycarbonyl group, 2
-Tetrahydropyranyl group or 2-tetrahydrofuranyl group, R ₂ is tricyclo [5.2.1.0 ^2,6 ] decanedimethylene group, tricyclo [5.2.1.0 ^2,6 ]
Represents a decanediyl group , a norbornanedimethylene group, or an adamantanediyl group. ) 5. A tricyclo [5.2.1.0 ^{2, 6]} decane methylene group, characterized in that it is a tricyclo [5.2.1.0 ^{2, 6]} decane-4,8-dimethylene group The intermediate compound for a photosensitive material according to claim 4, wherein 6. The method according to claim 4, wherein the norbornane dimethylene group is any one of a norbornane-2,6-dimethylene group, a norbornane-2,3-dimethylene group and a norbornane-2,5-dimethylene group. The intermediate compound for a photosensitive material according to the above.