JP2001328964A - New polycyclic unsaturated hydrocarbon derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polycyclic unsaturated hydrocarbon derivative useful as a monomer for producing radiation-sensitive resists which have good dry etching resistance and excellent transparency for radiations having wavelengths of <=160 nm. SOLUTION: This polycyclic unsaturated hydrocarbon derivative represented by the general formula [X is an acid-dissociating dissolution-inhibiting group; Y is an electron-attracting group; (m) is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the following radiation wavelength 160 nm, for example, with respect to F ₂ laser beam, useful novel polycyclic as monomers for the preparation of radiation-sensitive resist having excellent transparency not The present invention relates to a saturated hydrocarbon derivative and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the degree of integration of semiconductor devices has been further increased, and LSIs having a design rule of 0.20 μm have already been mass-produced.
SI production plans are also being advanced at a rapid pace. further,
In such a semiconductor lithography technique, a chemically amplified positive or negative resist is used as a resist, or a combination thereof with an organic or inorganic antireflection film is used. Innovative exposure masks such as masks, annular illumination, scanning method, and high NA (N
A: By the exposure device such as the numerical aperture of the lens)
The design rule is about to be put to practical use up to around 0.13 μm.

On the other hand, as a next-generation or next-generation lithography process of 0.15 μm or less, F ₂ laser light (157 nm) and Ar ₂ laser light (126 nm) are used.
m) or extreme ultraviolet (EU)
V; 13 nm), a lithography process using radiation of 160 nm or less as a light source is effective.

In designing a resist suitable for lithography using such short wavelength light, the conventional Kr
As with the F resist and ArF resist, it is necessary to increase the transparency of the base resin, which is a major factor that determines the resolution and dry etching resistance of the resist pattern, and to provide a structure with excellent dry etching resistance. It is.

For this reason, as a base resin for a resist,
Resins having a polycyclic hydrocarbon group in the side chain have been studied, and a fluoropolymer using a fluorinated methacrylic acid ester monomer having a trifluoro group introduced into the α-carbon atom of an acrylic acid ester has been studied so far (Japanese Patent Application Laid-Open No. JP-A-61-190511, JP-A-64-43512, JP-A-3-261
952, JP-A-4-42229, JP-A-4-42
-52648), α-trifluoromethyl-1-
A homopolymer or a copolymer of adamantyl acrylate has been proposed (JP-A-9-43848). However, these are all resins having an acrylate ester unit in the main chain and having a polycyclic hydrocarbon group in the side chain. In a resin having such a structure, transparency and resistance to short wavelengths of 160 nm or less are obtained. The dry etching property is insufficient.

[0006]

Under such circumstances, the present invention provides a monomer for producing a radiation-sensitive resist having excellent transparency to radiation having a wavelength of 160 nm or less and excellent dry etching resistance. The present invention has been made for the purpose of providing a novel polycyclic unsaturated hydrocarbon derivative useful as a compound.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, Diels-Alder of acrylic acid having an electron-withdrawing group at the α-position and cyclopentadiene or dicyclopentadiene. After reacting to obtain a polycyclic unsaturated carboxylic acid, polymerizing a polycyclic unsaturated hydrocarbon derivative in which a hydrogen atom of a hydroxyl group of the unsaturated carboxylic acid is substituted with an acid dissociable, dissolution inhibiting group, a wavelength of 160 nm
The inventors have found that a radiation-sensitive resist having excellent transparency to the following radiation and good dry etching resistance can be obtained, and the present invention has been completed based on this finding.

That is, the present invention provides a compound represented by the general formula

Embedded image (Wherein X is an acid dissociable, dissolution inhibiting group, Y is an electron withdrawing group,
m is 0 or 1) is intended to provide a polycyclic unsaturated hydrocarbon derivative represented by the formula: According to the present invention, the polycyclic unsaturated hydrocarbon derivative may be a cyclopentadiene or dicyclopentadiene having a general formula

Embedded image (Y in the formula has the same meaning as described above) represented by the following formula:

Embedded image (Where Y and m in the formula have the same meanings as described above), and then obtain an unsaturated carboxylic acid or a reactive derivative thereof and a compound serving as an acid dissociable, dissolution inhibiting group. Can be produced by subjecting the compound to an esterification reaction.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polycyclic unsaturated hydrocarbon derivative represented by the above general formula (I) of the present invention is a novel compound which has not been described in any literature, and if it is polymerized, its wavelength is 160 nm.
The following radiation-sensitive resist having excellent transparency to radiation and good dry etching resistance can be obtained. In addition,
It has been theoretically confirmed in a calculation by a molecular orbital method that the transparency of a polymer using a polycyclic unsaturated hydrocarbon derivative as a monomer is improved.

The acid dissociable, dissolution inhibiting group represented by X in the above general formula (I) is a compound which suppresses alkali solubility of a polymer by substituting a hydrogen atom of a hydroxyl group of a carboxylic acid (protecting a carboxyl group). And any one capable of increasing the alkali solubility of the polymer by dissociating by the action of an acid generated from an acid generator by irradiation with radiation, and conventionally used in KrF positive resists and ArF positive resists. Any of various groups can be selected and used.

Examples of the acid dissociable, dissolution inhibiting group represented by X include a cyclic ether group such as an unsubstituted or fluorine-substituted tertiary alkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a 1-ethoxyethyl group, Examples thereof include a chain ether group such as a 1-methoxypropyl group, and among them, an unsubstituted or fluorine-substituted tertiary alkyl group and a cyclic ether group are preferable, and an unsubstituted or fluorine-substituted group is particularly preferable. Tertiary alkyl groups are preferred.

Examples of the unsubstituted tertiary alkyl group include a branched alkyl group such as a tert-butyl group and a tert-amyl group, a 2-alkyladamantyl group such as a 2-methyladamantyl group and a 2-ethyladamantyl group, 1
And 1-alkylcyclohexyl groups such as -methylcyclohexyl group and 1-ethylcyclohexyl group.

The fluorine-substituted tertiary alkyl group includes those in which the hydrogen atom of the unsubstituted tertiary alkyl group is substituted with a fluorine atom, specifically 1,1-difluoromethyl-ethyl. And the like. Those having a fluorine-substituted tertiary alkyl group as an acid dissociable, dissolution inhibiting group are preferable because the transparency of a polymer obtained from this compound is further improved.

These acid dissociable, dissolution inhibiting groups include t
ert-butyl group, 1,1-difluoromethyl-ethyl group and 1-ethylcyclohexyl group are preferable, but they can provide a resist excellent in acid dissociation property, high sensitivity, and good dry etching resistance, In addition, a 1-ethylcyclohexyl group is particularly preferable in that a polycyclic unsaturated hydrocarbon derivative can be easily and inexpensively produced.

On the other hand, examples of the electron-withdrawing group represented by Y in the general formula (I) include a halogen atom or a halogen-substituted hydrocarbon group, specifically, a fluorine atom, a chlorine atom, a fluorinated alkyl group and the like. Although a strong electron-withdrawing group can be considered to contribute to transparency, a fluorine atom and a perfluoro-lower alkyl group are preferable. As the perfluoro lower alkyl group, a trifluoromethyl group is particularly preferable.

When m is 0, the ring structure of the polycyclic unsaturated hydrocarbon derivative represented by the general formula (I) is bicyclo [2.2.1] -2-heptene (norbornene).
When m is 1, tetracyclo [4.4.0.
1 ^2.5. The 1 ^7.10] -3-dodecene ring. Among these, those having a norbornene ring in which m is 0, that is, those having the general formula

Embedded image (X and Y in the formula have the same meanings as described above) are practical and preferable because raw materials can be obtained at low cost and can be easily produced.

Among the compounds represented by the general formula (IV),

Embedded image (Wherein R ¹ is an unsubstituted or fluorine-substituted tertiary alkyl group).

The polycyclic unsaturated hydrocarbon derivative of the present invention represented by the general formula (I) includes, for example, compounds having the following structures.

Embedded image

Embedded image

The method for producing the polycyclic unsaturated hydrocarbon derivative of the present invention represented by the general formula (I) is not particularly limited, but according to the method of the present invention shown below, the desired polycyclic unsaturated compound can be efficiently produced. Formula unsaturated hydrocarbon derivatives can be produced.

In the method of the present invention, first, the reaction formula

Embedded image (Y and m in the formula have the same meanings as described above), and a cyclopentadiene or dicyclopentadiene represented by the formula (VI) is subjected to a Diels-Alder reaction with an acrylic acid derivative represented by the general formula (II). Thus, a polycyclic unsaturated carboxylic acid represented by the general formula (III) is produced. Examples of the acrylic acid derivative represented by the general formula (II) include α-fluoroacrylic acid and α-trifluoromethylacrylic acid.

Next, the thus obtained polycyclic unsaturated carboxylic acid represented by the above general formula (III) or a reactive derivative thereof and a compound giving an acid dissociable, dissolution inhibiting group are subjected to an esterification reaction. As a result, the polycyclic unsaturated hydrocarbon derivative of the present invention represented by the general formula (I) is produced. Examples of the compound providing the acid dissociable, dissolution inhibiting group include tert-butyl alcohol, 1-ethyl-1-hydroxycyclohexane, and 2-methyl-2.
Alcohols such as adamantanol; unsaturated compounds such as 2,3-dihydropyran and ethyl vinyl ether.

When the compound providing an acid dissociable, dissolution inhibiting group is an alcohol, the polycyclic unsaturated carboxylic acid represented by the general formula (III) or a reactive functional derivative thereof is reacted with the alcohol. , Esterify. Such reactive functional derivatives include, for example, acid halides.
On the other hand, when the compound that provides an acid dissociable, dissolution inhibiting group is an unsaturated compound, esterification is performed by adding a polycyclic unsaturated carboxylic acid represented by the general formula (III) to the unsaturated compound.

Examples of the polymer containing the polycyclic unsaturated hydrocarbon derivative of the present invention as a monomer include, for example,

Embedded image (N in the formula represents the degree of polymerization, and X and Y have the same meaning as described above).

The polymer obtained from the polycyclic unsaturated hydrocarbon derivative of the present invention has excellent transparency to radiation having a wavelength of 160 nm or less and excellent dry etching resistance, and thus is suitably used as a base resin of a radiation-sensitive resist. . As the radiation having a wavelength of 160 nm or less, for example, F ₂ laser light (157 nm), Ar ₂ laser light (126 n
m), extreme ultraviolet (EUV; 13 nm) and the like.

[0025]

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

Reference Example 1 (2-trifluoromethyl-2-
Production of carboxy-5-norbornene)

Embedded image 14 g (0.1 mol) of α-trifluoromethylacrylic acid is dissolved in 100 ml of diethyl ether, and 6.6 g (0.1 mol) of cyclopentadiene obtained by heating and distilling dicyclopentadiene is stirred at room temperature. While dropping over 15 minutes. The solution was then allowed to react for 12 hours at 0 ° C. in an ice bath. After completion of the reaction, the product was recrystallized from diethyl ether to give 2-trifluoromethyl-2-carboxy-5 represented by the above structural formula.
-16.5 g (80% yield) of norbornene was obtained. This compound was identified by proton NMR and infrared absorption spectrum, and the following results were obtained. Proton NMR ( ¹ H-NMR solvent CDCl ₃ ) δ = 9.6 (br, 1H), 6.35 (m, 1H),
6.2 (m, 1H), 3.4 (d, 1H), 3.0
(M, 1H), 2.05 (d, 2H), 1.78 (d,
1H), 1.5 (d, 1H) Infrared absorption spectrum data 3000 cm ^-1 (attributed to -OH), 1715 cm ^-1 (-
(Attribution to CO-) From the above results, the compound was confirmed to be the above compound.

Reference Example 2 (2-trifluoromethyl-2-
Production of chlorocarbonyl-5-norbornene)

Embedded image A mixture of 2.06 g (0.01 mol) of the compound obtained in Reference Example 1 and 7.0 g (0.059 mol) of thionyl chloride was added to 5
After heating under reflux for an hour, excess thionyl chloride was distilled off. A part thereof was subjected to an infrared absorption spectrum, a peak shift of 1795 cm ⁻¹ (ν _{C = 0} ) of a carbonyl group was confirmed, and the residue was used as an acid chloride as it was.

Example 1 (2-trifluoromethyl-2-
Production of tert-butyloxycarbonyl-5-norbornene

Embedded image 3.7 g (0.05 mol) of tert-butyl alcohol
And 1.2 g (0.01 mol) of triethylamine were dissolved in 10 ml of diethyl ether, stirred at room temperature, and a solution of 1.26 g (0.005 mol) of the compound obtained in Reference Example 2 in 5 ml of diethyl ether was added dropwise. After further stirring for 24 hours, the reaction solution was washed with saturated saline and dried using sodium sulfate. After distilling off diethyl ether, distillation under reduced pressure was performed to give 2-trifluoromethyl-2-ter.
t-butyloxycarbonyl-5-norbornene 0.5
g (38% yield). This compound was identified by proton NMR and infrared absorption spectrum, and the following results were obtained. Proton NMR ( ¹ H-NMR solvent CDCl ₃ ) δ = 6.4 (m, 1H), 6.25 (m, 1H), 3.
5 (s, 1H), 3.05 (s, 1H), 2.15
(M, 2H), 1.82 (d, 1H), 1.55 (d,
1H), 1.30 (s, 9H) Infrared absorption spectrum data 1775 cm ^-1 (ν _{C = 0} ) From the above results, the compound was confirmed to be the above compound.

Example 2 (2-trifluoromethyl-2-
Production of tetrahydropyranyloxycarbonyl-5-norbornene

Embedded image 10.3 g (0.05 mol) of the compound obtained in Reference Example 1
And 6.3 g (0.075 mol) of 2,3-dihydropyran
Was dissolved in 100 ml of diethyl ether, and 0.005 mol of p-toluenesulfonic acid was added thereto.
The reaction was performed for 5 hours. The reaction solution was washed with saturated saline, dried over sodium sulfate, and distilled under reduced pressure after distilling off diethyl ether to obtain 10 g of 2-trifluoromethyl-2-tetrahydropyranyloxycarbonyl 5-norbornene (yield: 70%). Obtained. This compound was identified by proton NMR.
And the infrared absorption spectrum, the following results were obtained. Proton NMR ( ¹ H-NMR solvent CDCl ₃ ) δ = 6.35 (m, 1H), 6.15 (m, 1H),
6.05 (m, 1H), 4.9 (m, 1H), 3.7-
3.9 (m, 2H), 3.35-3.6 (m, 2H),
3.05 (s, 1H), 2.05 (m, 2H), 1.4
5-1.9 (m, 6H) Infrared absorption spectrum data 1746 cm ^-1 (ν _{C = 0} ) From the above results, the compound was confirmed to be the above compound.

Example 3 (2-trifluoromethyl-2-
(Production of (1-ethyl-1-cyclohexyl) oxycarbonyl-5-norbornene)

Embedded image 6.4 g of 1-ethyl-1-hydroxycyclohexane
(0.05 mol) and triethylamine 1.2 g (0.0
1 mol) was dissolved in 20 ml of diethyl ether and stirred at room temperature, and 1.26 g of the compound obtained in Reference Example 2 was added thereto.
(0.005 mol) of a diethyl ether (5 ml) solution was added dropwise, and the mixture was further stirred for 24 hours. The reaction solution was washed with saturated saline, dried over sodium sulfate, distilled off diethyl ether, and distilled under reduced pressure to give 2-trifluoromethyl-2-
0.5 g of (1-ethyl-1-cyclohexyl) oxycarbonyl-5-norbornene was obtained (yield 32%). This compound was identified by proton NMR and infrared absorption spectrum, and the following results were obtained. Proton NMR ( ¹ H-NMR solvent CDCl ₃ ) δ = 6.4 (m, 1H), 6.25 (m, 1H), 3.
52 (s, 1H), 3.05 (s, 1H), 2.15
(M, 2H), 1.82 (d, 1H), 1.2-1.8
(M, 13H), 0.9 (t, 3H) Infrared absorption spectrum data 1775 cm ^-1 (ν _{C = 0} ) From the above results, the compound was confirmed to be the above compound.

[0031]

Industrial Applicability The polycyclic unsaturated hydrocarbon derivative of the present invention is a novel compound, which exhibits excellent transparency to radiation having a wavelength of 160 nm or less and has good dry etching resistance. It is useful as a monomer for producing a resist.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 309/12 C07D 309/12 4J100 G03F 7/039 601 G03F 7/039 601 // C08F 32/00 C08F 32 / 00 C08G 61/08 C08G 61/08 F term (reference) 2H025 AA00 AA09 AB16 AC08 AD01 AD03 BG00 BJ10 4C037 DA06 KA09 4C062 AA21 4H006 AA01 AA02 AB46 AB91 AC21 AC28 AC48 BM30 BM71 BT22 CA34 CB38 CA46 CE12 4J100 AK32Q AR11P BA02P BA15P BA20P BB07P BB17P BB18P BC04P BC09P BC53P CA01 CA04 JA38

Claims (9)

[Claims] 1. A compound of the general formula (Wherein X is an acid dissociable, dissolution inhibiting group, Y is an electron withdrawing group,
m is 0 or 1). 2. A compound of the general formula The polycyclic unsaturated hydrocarbon derivative according to claim 1, wherein X is an acid dissociable, dissolution inhibiting group, and Y is an electron withdrawing group. 3. The polycyclic unsaturated hydrocarbon derivative according to claim 1, wherein X in the general formula is an unsubstituted or fluorine-substituted tertiary alkyl group. 4. The polycyclic ring according to claim 3, wherein the unsubstituted or fluorine-substituted tertiary alkyl group is a tert-butyl group, a 1-alkylcyclohexyl group, a 2-alkyladamantyl group or a fluorine substituent thereof. Formula unsaturated hydrocarbon derivatives. 5. The polycyclic unsaturated hydrocarbon derivative according to claim 1, wherein X in the general formula is a cyclic ether group. 6. The polycyclic unsaturated hydrocarbon derivative according to claim 5, wherein the cyclic ether group is a tetrahydropyranyl group or a tetrahydrofuranyl group. 7. The polycyclic unsaturated hydrocarbon derivative according to claim 1, wherein Y in the general formula is a fluorine atom or a perfluoro lower alkyl group. 8. The polycyclic unsaturated hydrocarbon derivative according to claim 7, wherein the perfluoro lower alkyl group is a trifluoromethyl group. 9. A cyclopentadiene or dicyclopentadiene having the general formula: (Y in the formula is an electron-withdrawing group) is condensed by a Diels-Alder reaction to obtain a compound represented by the general formula: (Wherein m is 0 or 1 and Y has the same meaning as described above), to obtain a polycyclic unsaturated carboxylic acid represented by the formula:
Wherein the unsaturated carboxylic acid or a reactive derivative thereof is esterified with a compound serving as an acid dissociable, dissolution inhibiting group; (Wherein X is an acid dissociable, dissolution inhibiting group, and Y and m have the same meanings as described above).