JP2003327688A - Monomer for resist material, polymer for resist material and acid dissociable group-containing resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a monomer for forming a resist highly transparent to radiation and satisfying a fundamental function, a polymer for a resist material and an acid dissociable group-containing resin used in a chemical amplification type resist. <P>SOLUTION: The acid dissociable group-containing resin is insoluble or hardly soluble in alkali and becomes easily soluble in alkali by the action of an acid and has a repeating unit represented by formula (8) (wherein R<SP>1</SP>and R<SP>3</SP>are each a divalent organic group containing a fluorine atom, R<SP>2</SP>is a lower hydrocarbon group and X is a side chain containing an acid dissociable group). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition, and particularly to far ultraviolet rays such as KrF excimer laser, ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm), synchrotron radiation and the like. The present invention relates to a monomer for forming a chemically amplified resist useful for fine processing using various kinds of radiation such as charged particle beams such as X-rays and electron beams, a polymer for a resist material, and an acid-labile group-containing resin.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit devices, in order to obtain a higher degree of integration, K
A lithographic technique using short-wave radiation represented by rF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm) is widely used. As a resist suitable for irradiation by such an excimer laser, an acid-dissociable group-containing resin that is alkali-insoluble or sparingly soluble and becomes alkali-soluble by the action of an acid, and a component that generates an acid by irradiation of radiation are used. A resist utilizing a chemical amplification effect (hereinafter referred to as “chemical amplification resist”) has already been proposed. Examples of the introduction of a fluorine atom in the acid-labile group-containing resin include a plurality of resins (M.Shirai, et.al., J.Photopolym.Sci.Tecnol., 1).
4,621 (2001), D.Schmaljohann, et.al., J.Photopolym.Sc
i.Tecnol., 13,451 (2000), CKOber, et.al., J.Photopol
ym.Sci.Tecnol., 14,613 (2001),) is known. In addition, a polyether polymer using a bisoxetane compound is known (T.Nishikubo, A. Kameyama, MI.
to, T.Nakajima, and H.Miyazaki, J.Polym.Sci.Part A: Po
lym. Chem., 37, 2781 (1999).

[0003]

However, excimer laser light, especially F ₂ excimer laser (wavelength 157) is used.
(nm) light is a light having a wavelength belonging to vacuum ultraviolet, and therefore most organic compounds absorb the light, so that there is a problem that the transparency of the resist is lowered. Further, since the wavelength is short, the energy of the light is strong, which causes a problem that photo-crosslinking or photolysis is caused in the resist. When photocrosslinking or photolysis occurs, the sensitivity, resolution, dry etching resistance, etc. of the resist are reduced. The present invention has been made in order to address such problems, high transparency to radiation, a monomer for forming a polymer for a resist material that satisfies the basic performance required for a resist,
An object is to provide a polymer for a resist material and an acid dissociable group-containing resin used in a chemically amplified resist.

[0004]

The monomer for resist material according to the present invention is characterized by being represented by the following formula (1).

[Chemical 5] (Here, R ¹ is a divalent organic group containing a fluorine atom,
R ² is a lower hydrocarbon group. The polymer for resist material according to the present invention is characterized by being a polyaddition reaction product of the monomer represented by the above formula (1) and the following formula (7).

[Chemical 6] (Here, R ³ is a divalent organic group containing a fluorine atom.) The acid-dissociable group-containing resin according to the present invention has a repeating unit represented by the following formula (8), and is insoluble in alkali or alkali. It is characterized in that it is poorly soluble and becomes easily soluble in alkali by the action of acid.

[Chemical 7] (Here, R ¹ and R ³ are divalent organic groups containing a fluorine atom, R ² is a lower hydrocarbon group, and X is a side chain containing an acid dissociable group.)

A resist material having a reactive hydroxyl group in its side chain is obtained by subjecting a fluorine-containing bisoxetane compound represented by the formula (1) and a fluorine-containing diol compound represented by the formula (7) to a polyaddition reaction. A polymer for use is obtained. By utilizing the polymer reaction of the side chain of the polymer for resist material, the molecular design of the acid dissociable group-containing resin can be facilitated. The present invention is based on such findings.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing bisoxetane compound represented by the above formula (1) will be described. In the formula (1), R ¹ is a divalent organic group containing a fluorine atom,
Preferred is a fluorine atom-containing group containing a phenyl ring and a cyclohexane ring. The fluorine atom-containing group is a divalent organic group represented by any one of the following formulas (2) to (6), and R ² is a lower hydrocarbon group.

[Chemical 8] n and m represent an integer of 0 to 4, and n + m is 1 to 8
Represents the integer. The preferred values of n and m are 2 and n + m is 4. In formulas (2) to (6), R ¹ of the fluorine-containing bisoxetane compound is preferably formula (3), formula (4) or formula (6). R ² is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. Among the fluorine-containing bisoxetane compounds, more preferable specific examples are represented by the following formula (9)
~ Represented by formula (11). R ² is a methyl group or an ethyl group. Among the methyl groups or ethyl groups, a methyl group having less steric hindrance is preferred because a high molecular weight polymer for resist material can be obtained in high yield.

[Chemical 9]

Fluorine-containing bisoxetane compounds include diol compounds such as bisphenol AF, 3-halogenated methyl-3-alkyloxetane and 3-alkyl-3-
It is obtained by reacting with an oxetane compound such as oxetanylmethyl tosylate. As the fluorine-containing diol compound, a compound obtained by protecting a phenolic hydroxyl group such as a fluorine-containing halogenated phenol with an acetyl group or the like and then subjecting it to dehalogenation condensation, or a commercially available compound can be purified and used. As the oxetane compound, a commercially available compound can be purified and used.

The fluorine-containing diol compound to be polyadded with the fluorine-containing bisoxetane compound is represented by the following formula (7)
It is represented by.

[Chemical 10] In the formula (7), R ³ is a divalent organic group containing a fluorine atom, and preferably a fluorine atom-containing group containing a phenyl ring or a cyclohexane ring. Examples of the fluorine atom-containing group include divalent organic groups represented by any one of the formulas (2) to (6) exemplified as R ¹ . Formula (2)-
As R ³ of the fluorine-containing diol compound in the formula (6), the formula (4) is preferable.

The polymer for resist material according to the present invention is obtained by subjecting the monomer represented by the above formula (1) and the monomer represented by the above formula (7) to polyaddition reaction in approximately equimolar amounts. Is obtained by The reaction is preferably carried out without a solvent in the presence of a catalyst. By the polyaddition reaction, a polymer for a resist material having a repeating unit represented by the following formula (12), each having an ether bond in the main chain and a hydroxyl group in the side chain, can be obtained.

[Chemical 11] In the formula (12), R ¹ and R ² are R ¹ and R ² represented in formula (1), R ³ is R ³ represented by formula (7).

The catalyst, the reaction temperature and the reaction time when the resist material polymer is polymerized without a solvent will be described. As the catalyst, tetraphenylphosphonium chloride (hereinafter abbreviated as TTPC), tetraphenylphosphonium bromide (hereinafter abbreviated as TTPB), tetraphenylphosphonium iodide (hereinafter abbreviated as TTPI), 18-crown. Complex of -6-ether and potassium chloride (hereinafter abbreviated as 18-C-6 / KCl), complex of 18-crown-6-ether and potassium bromide (hereinafter, 18-C-6 / KBr) , 18-crown-6-ether and potassium iodide complex (hereinafter abbreviated as 18-C-6 / KI),
1,8-diazabicyclo [5.4.0] undec-7-
Examples thereof include ene (hereinafter abbreviated as DBU), 4-dimethylaminopyridine (hereinafter abbreviated as DMAP), N-methylimidazole (hereinafter abbreviated as NMI), and the like. Among the above catalysts, in particular, the reaction of the phenolic hydroxyl group represented by the formula (7) with the oxetanyl group can be preferentially promoted over the reaction of the primary hydroxyl group and oxetanyl group formed by the reaction formation. It is preferable that the catalyst can be used. In order to selectively proceed this reaction, a basic catalyst that can promote deprotonation of the phenolic hydroxyl group is preferable. Suitable basic catalysts are DBU, D
Examples include MAP and NMI. Also, TTPC, TT
As a result of the experiment, it was found that an onium salt such as PB also preferentially advances the reaction between the phenolic hydroxyl group and the oxetanyl group. Therefore, as a catalyst for obtaining a polymer for resist material in high yield and high molecular weight, DBU, DMA is used.
A cocatalyst of a basic catalyst such as P and an onium salt is preferable. The reaction temperature is 150 to 250 ° C., preferably 1
It is 60 to 200 ° C. If the reaction temperature is lower than 150 ° C, the degree of polymerization does not increase, and if it exceeds 250 ° C, a gelation reaction may occur. The reaction time is 1 to 200 hours, preferably 20 to 150 hours. If the reaction time is less than 1 hour, the degree of polymerization and the yield do not increase, and even if the reaction time exceeds 200 hours, the degree of polymerization does not increase above a predetermined value.

By modifying the primary hydroxyl group contained in the repeating unit represented by the formula (12), an acid-labile group-containing resin having the repeating unit represented by the above formula (8) can be obtained. In formula (8), X is a side chain containing an acid dissociable group, and an example of suitable X is a tert-butyl ester residue. Further, X is 1 represented by the formula (8).
The acid-dissociable group-containing resin can be used as long as it contains at least 50 equivalent%, preferably 60 equivalent% of the total hydroxyl equivalents of the primary hydroxyl groups. The introduction of X into the resist material polymer is carried out by reacting tert-butyl-monobromoacetic acid with the resist material polymer having the repeating unit represented by the formula (12), or by subjecting an acrylate or the like to a Michael addition reaction. Etc. Specific examples of the acrylate used in the Michael addition reaction include te
rt-butyl-α-trifluoromethyl acrylate,
tert-Butyl acrylate may be mentioned. The acid-dissociable group-containing resin has a polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) determined by gel permeation chromatography (GPC) in consideration of solubility in a solvent, polymer reactivity of hydroxyl groups in side chains, and the like. As 1000-100
000, preferably 1,000 to 80,000, more preferably 2,000 to 70,000. In this case, when the Mn of the resin is less than 1,000, the heat resistance when used as a resist tends to decrease, while when it exceeds 100000, the developability when used as a resist tends to decrease. In addition, the ratio of polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) to Mn by gel permeation chromatography (GPC) of the resin (Mw / M).
n) is usually 1-8, preferably 1-3. The acid-dissociable group-containing resin is mixed with a radiation-sensitive acid generator that dissociates the acid-dissociable group by the action of an acid generated by exposure, and the total solid content concentration is usually 3 to 50% by weight. ,
The radiation-sensitive resin composition is obtained by dissolving in a solvent so that the amount is preferably 5 to 25% by weight. As the solvent of the radiation-sensitive resin composition, linear or branched ketones,
Cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionates, alkyl 3-alkoxypropions, γ-
Butyrolactone and the like are preferable. These can be used alone or as a mixture.

As the radiation-sensitive acid generator, visible light,
Any component that generates an acid upon exposure to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, and X-rays can be used, and consists of a mother nucleus and the generated acid. As the mother nucleus, onium salt compounds such as iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, pyridinium salts, sulfonimide compounds, sulfone compounds, sulfonate compounds, disulfonyldiazomethane compounds , Disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds and the like. Examples of the generated acid include alkyl or fluorinated alkyl sulfonic acid, alkyl or fluorinated alkyl carboxylic acid, alkyl or fluorinated alkyl sulfonylimidic acid. The above acid generators can be used alone or in admixture of two or more. The amount of the acid generator to be used is usually 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the acid dissociative group-containing resin, from the viewpoint of ensuring sensitivity and developability as a resist. 7 parts by weight. In this case, if the amount of the acid generator used is less than 0.1 parts by weight, the sensitivity and developability tend to decrease, while if it exceeds 10 parts by weight, the transparency to radiation decreases and the rectangular resist pattern is formed. Tends to be difficult to obtain.

The radiation-sensitive resin composition includes (1) an acid diffusion which has a function of controlling a diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film and suppressing an unfavorable chemical reaction in an unexposed area. Contains a control agent, (2) an acid-dissociable organic group which exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, etc.
Alicyclic additives, (3) surfactants that improve the coatability and developability, (4) sensitizers that improve the sensitivity, (5) antihalation agents, and adhesion aids Agent,
Additives such as a storage stabilizer and an antifoaming agent can be further added. The radiation-sensitive resin composition is particularly useful as a chemically amplified resist.

[0014]

EXAMPLES Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. All parts are by weight unless otherwise specified. Each measurement / evaluation in Examples, Comparative Examples and Reference Examples was performed by the following devices and methods. Infrared spectrophotometer (IR): JASCO Corporation FT /
IR-420 Nuclear Magnetic Resonance Measurement System ( ¹ H NMR): JEOL Ltd.
JNM-FX200, 500 type (200, 500MH
z) Nuclear magnetic resonance measuring device ( ¹³ C NMR): JEOL Ltd. JNM-α500 type (125 MHz) Nuclear magnetic resonance measuring device ( ¹⁹ F NMR): JEOL Ltd JNM-α500 type (470 MHz) Gel permeation chromatography Device (GP
C): Tosoh Corporation Gel Permeation Chromatography (GP
C) Model HLC-8220, (column: TSKgel, eluent: DMF, standard: polystyrene) Thermogravimetric reduction measuring device (TG / DTA): Seiko Instruments Co., Ltd.
s EXTAR 6000TG-DTA6200 (measurement condition: under nitrogen stream, temperature rising rate 10 ° C / min, open aluminum pan) Melting point measuring device: Yanako MP Co., Ltd.
-50OD Elemental Analyzer: PE2400 manufactured by Perkin Elmer
SeriesII CHNS / OAAnalyzer Vacuum Ultraviolet Spectrometer: JASCO VU
-201

Reference Example 1 As a raw material for introducing an oxetanyl group, 3-methyl-3-oxetanylmethyl tosylate (hereinafter referred to as MOM
It is abbreviated as T. ) Was prepared by the following method. 3-Methylenol-3-methyloloxetane 1 purified by distillation under reduced pressure
0.22 g (100 mmol) was placed in a 300 ml three-necked eggplant flask, the pressure was reduced, and nitrogen leak was performed 5 times, and then 15 ml of triethanolamine (1
10 mmol) and 50 ml of tetrahydrofuran (hereinafter abbreviated as THF) were added, and the mixture was stirred at room temperature. Thereafter, 19.06 g (100%) of tosyl chloride (TsCl) dissolved in 30 ml of THF was added.
Was added and the reaction was carried out at room temperature for 24 hours. After the reaction was completed, it was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained solid is THF: n-hexane =
Purification by recrystallization four times using a mixed solvent of 7:12 yielded 13.59 g (yield 53%) of a white solid having a melting point of 61.4-62.2 ° C. The structure was confirmed by IR and ¹ H NMR spectrum. The results are shown in Table 1.

[Table 1]

Example 1 Bisphenol AF di (3-) which is a monomer for a resist material
Ethyl-3-oxetanyl-methyl) ether (hereinafter,
It is abbreviated as BPAFE. ) Was obtained by the following method. Bisphenol AF (hereinafter abbreviated as BPAF) 1
6.81 g (50 mmol), potassium hydroxide 9.9
0 g (150 mmol), tetra-n-butylammonium bromide (hereinafter abbreviated as TBAB) 3.08
g (5 mol%) was placed in a 300 ml three-necked eggplant flask, the pressure was reduced, and nitrogen leak was performed 5 times.
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
100 ml was added, and the mixture was stirred at 90 ° C. for 1 hour. Then, 20.31 g (150 mmol) of 3-chloromethyl-3-ethyloxetane (hereinafter referred to as CMEO) purified by distillation under reduced pressure was added, and the reaction was continued for 3 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography (Al ₂ O ₃ ) [developing solvent; ethyl acetate: n-
Hexane = 1: 5] for isolation. The obtained solid was purified by recrystallizing twice using n-hexane to obtain a white solid having a melting point of 131.2 to 132.1 ° C.
4.74 g (yield 93%) was obtained. Structure confirmation is IR, ¹ H
NMR and ¹³ C NMR spectra, elemental analysis were performed. The results are shown in Table 2.

[0017]

[Table 2] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed near 980 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from an oxetanyl group was observed around 50 to 4.50 ppm. Further, since the values of elemental analysis were in agreement, BPAFEO was obtained.

Example 2 Bisphenol AF di (3-) which is a monomer for a resist material
Methyl-3-oxetanyl-methyl) ether (hereinafter,
It is abbreviated as BPAFMO. ) Was obtained by the following method. BP
AF 0.841 g (2.5 mmol), potassium hydroxide 0.495 g (7.5 mmol), TBAB 0.1
54 g (5 mol%) was placed in a 50 ml two-necked eggplant flask, and the pressure was reduced to perform nitrogen leak 5 times.
P10 ml was added and the mixture was stirred at 90 ° C. for 1 hour. Thereafter, 2.563 g (10 mmol) of MOMT was added, and the reaction was continued for 3 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was isolated using column chromatography (Al ₂ O ₃ ) [developing solvent; ethyl acetate: n-hexane = 1: 5]. The obtained solid was purified by recrystallizing twice using n-hexane, and had a melting point of 110.2 to 111.
1.019 g (yield 85%) of a white solid at 1 ° C. was obtained.
Structural confirmation is IR, ¹ H NMR, ¹³ C NMR and ¹⁹ F
It was performed by NMR spectrum and elemental analysis. The results are shown in Table 3.

[0019]

[Table 3] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed near 980 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from an oxetanyl group was observed around 50 to 4.50 ppm. Further, since the values of elemental analysis were in agreement, BPAFMO was obtained.

Example 3 1,3-bis (hexafluorohydroxyisopropyl) benzendi (3-ethyl-), a monomer for resist material
3-oxetanyl-methyl) ether (hereinafter, 1,3-
It is abbreviated as HFABEO. ) Was obtained by the following method. In the same manner as in Example 1, 1,3 purified by vacuum distillation
-Bis (hexafluorohydroxyisopropyl) benzene (hereinafter abbreviated as 1,3-HFAB) 6.15
2 g (15 mmol), potassium hydroxide 3.960 g
(60 mmol), TBAB 0.463 g (5 mol%), and NMP 100 ml were added, and the mixture was stirred at 90 ° C. for 5 minutes.
Stir for time. After that, CMEO 8.077g
(60 mmol) was added and the reaction was continued for 24 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography (Al
₂ O ₃ ) [Developing solvent; ethyl acetate: n-hexane = 1: 1
5]. The obtained solid was purified by recrystallizing twice using n-hexane to give a melting point of 5
8.103 g (yield 89%) of a white solid having a temperature of 8.6 to 59.5 ° C. was obtained. Structure confirmation is IR, ¹ H NMR, ¹³ CNM
It was conducted by R and ¹⁹ F NMR spectra and elemental analysis. The results are shown in Table 4.

[0021]

[Table 4] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed near 980 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from an oxetanyl group was observed around 50 to 4.50 ppm. Furthermore, since the values of elemental analysis were in agreement, 1,3-HFABEO was obtained.

Example 4 1,3-bis (hexafluorohydroxyisopropyl) benzendi (3-methyl-), which is a monomer for resist materials
3-oxetanyl-methyl) ether (hereinafter, 1,3-
It is abbreviated as HFABMO. ) Was obtained by the following method. By the same operation as in Example 2, 1,3-HFAB 2.05
1 g (5 mmol), potassium hydroxide 1.122 g
(20 mmol), TBAB 0.154 g (5 mol%), and NMP 20 ml were added, and the mixture was added at 90 ° C. for 12 hours.
Stir for time. After that, 5.126g of MOMT
(20 mmol) was added and the reaction was continued for 24 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography (Al
₂ O ₃ ) [Developing solvent; ethyl acetate: n-hexane = 1: 1
5]. The obtained solid was purified by recrystallizing twice using n-hexane to give a melting point of 5
8.103 g (yield 89%) of a white solid having a temperature of 8.6 to 59.5 ° C. was obtained. Structure confirmation is IR, ¹ H NMR, ¹³ C N
It was performed by MR and ¹⁹ F NMR spectrum and elemental analysis. The results are shown in Table 5.

[0023]

[Table 5] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed at 986 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from the oxetanyl group was observed at about 4.50 ppm. Furthermore, 1,3-HFABMO was obtained because the elemental analysis values were in agreement.

Example 5 1,4-bis (hexafluorohydroxyisopropyl) cyclohexanedi (3-ethyl-3-oxetanyl-methyl) ether (hereinafter referred to as "monomer for resist material")
It is abbreviated as 1,4-HFACEO. ) Was obtained by the following method. By the same operation as in Example 1, 1,4-HFAC
2.081 g (5 mmol), potassium hydroxide 1.1
22 g (20 mmol), TBAB 0.154 g (5
Mol%), and add 20 ml of NMP at 90 ° C for 2
It was stirred for 4 hours. After that, CMEO 2.692
g (20 mmol) was added and the reaction was continued for 48 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography (Al
₂ O ₃ ) [Developing solvent; ethyl acetate: n-hexane = 1: 1
5]. The obtained solid was purified by recrystallizing twice using n-hexane to give a melting point of 7
2.106g (69% of yield) of white solid of 5.8-76.7 degreeC was obtained. Structure confirmation is IR, ¹ H NMR, ¹³ C N
It was performed by MR and ¹⁹ F NMR spectrum and elemental analysis. The results are shown in Table 6.

[0025]

[Table 6] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed at 983 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from the oxetanyl group was observed at about 4.50 ppm. Furthermore, 1,4-HFACEO was obtained because the elemental analysis values were in agreement.

Example 6 1,4-bis (hexafluorohydroxyisopropyl) cyclohexanedi (3-methyl-3-oxetanyl-methyl) ether (hereinafter referred to as a monomer for a resist material)
It is abbreviated as 1,4-HFACMO. ) Was obtained by the following method. By the same operation as in Example 1, 1,4-HFAC
2.081 g (5 mmol), potassium hydroxide 1.1
22 g (20 mmol), TBAB 0.154 g (5
Mol%), and add 20 ml of NMP at 90 ° C for 2
It was stirred for 4 hours. After that, MOMT 5.126
g (20 mmol) was added and the reaction was continued for 48 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography (Al
₂ O ₃ ) [Developing solvent; ethyl acetate: n-hexane = 1: 1
5]. The obtained solid was purified by recrystallizing twice using n-hexane to give a melting point of 8
1.837 g (yield 63%) of a white solid having a temperature of 5.6 to 86.5 ° C. was obtained. Structure confirmation is IR, ¹ H NMR, ¹³ C N
It was performed by MR and ¹⁹ F NMR spectrum and elemental analysis. The results are shown in Table 7.

[0027]

[Table 7] From the IR spectrum, the absorption due to the hydroxyl group near 3500 cm ^-1 disappeared, and a new absorption due to the oxetanyl group was observed at 984 cm ^-1 . In addition, the signal due to the hydroxyl group disappeared from the ¹ H NMR spectrum, and
A methylene proton derived from the oxetanyl group was observed at about 4.50 ppm. Furthermore, 1,4-HFACMO was obtained because the elemental analysis values were in agreement.

Example 7 Fluorine-containing polyether, which is a polymer for resist material, was used as BP.
Obtained by polyaddition reaction of AFEO with BPAF. 9.4 mg (5 mol%) of TPPC as a catalyst was weighed in an ampoule tube in a nitrogen gas dry back (10% or less in relative humidity), and dried under reduced pressure at 60 ° C. for 5 hours. afterwards,
BPFEO 266.3 mg (0.5
Mmol), 168.1 mg (0.5 mmol) of BPAF and 3.8 mg (5 mol%) of DBU as a catalyst were added, and the mixture was frozen and degassed with nitrogen three times, and then sealed with a tube to give 190
The reaction was carried out at 120 ° C. for 120 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate and washed with distilled water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, and then used as a good solvent in THF and a poor solvent in ether / n-hexane [1:
5, V / V] mixed solvent was used for reprecipitation purification twice, and white solid polymer (P-5a) 366.4 m was obtained by drying under reduced pressure.
g (84% yield) was obtained. The structure of the obtained polymer was confirmed by IR, ¹ H NMR, ¹⁹ F NMR spectrum and elemental analysis. The results are shown in Table 8. GPC (D
Mn calculated by MF) was 8200, and Mw / Mn was 2.61.

[0029]

[Table 8] Attributed to oxetanyl group by IR spectrum 98
3cm absorption of ^-1 disappeared and new absorption has been confirmed that due to the hydroxyl group at 3396cm ^-1. Further, from the ¹ H NMR spectrum, the signal due to the oxetanyl group at around 4.35 to 4.36 ppm disappeared, and the signal due to the side chain hydroxyl group was confirmed at 4.75 ppm. In addition, ¹⁹ F
From the NMR spectrum, a signal attributable to the trifluoromethyl group was observed at -62.4 ppm, which confirmed that a fluorine atom was present in the structure. Since the elemental analysis values were in agreement, the target soluble fluorine-containing polyether (P-5a) having a primary hydroxyl group in the side chain was obtained.

Example 8 Fluorine-containing polyether, which is a polymer for resist material, was used as BP.
Obtained by a polyaddition reaction of AFMO and BPAF. By the same operation as in Example 7, TPPC / DBU as a catalyst was used.
Using 9.4 mg / 3.8 mg (5 mol% / 5 mol%), 252.2 mg (0.5 mmol) of BPAFMO and 168.1 mg (0.5 mmol) of BPAFMO were added, and the reaction was carried out at 190 ° C. for 72 hours. I did. After completion of the reaction, the reaction solution was diluted with ethyl acetate and washed with distilled water three times. After drying the ethyl acetate phase over anhydrous magnesium sulfate,
The polymer (P-6a) 3 was obtained as a white solid by reprecipitation purification twice using THF as a good solvent and an ether / n-hexane [1: 5, V / V] mixed solvent as a poor solvent, and drying under reduced pressure.
90.9 mg (yield 93%) was obtained. The structure of the obtained polymer was confirmed by IR, ¹ H NMR and ¹⁹ F NMR spectra. The results are shown in Table 9. GPC (DM
M) calculated by F) is 9100 and Mw / Mn is 4.
It was 67.

[0031]

[Table 9] Attributed to oxetanyl group by IR spectrum 98
0cm absorption of ^-1 disappeared, a new absorption was observed due to the hydroxyl group at 3412cm ^-1. Further, from the ¹ H NMR spectrum, a signal due to an oxetanyl group at around 4.32 to 4.51 ppm disappeared, and a signal due to a side chain hydroxyl group was confirmed at 4.81 ppm. In addition, ¹⁹ F
From the NMR spectrum, a signal due to a trifluoromethyl group was observed at -62.6 ppm, and it was confirmed that a fluorine atom was present in the structure. Therefore, the target soluble compound having a primary hydroxyl group in its side chain was obtained. Fluorine-containing polyether (P-6a) was obtained.

Example 9 Fluorine-containing polyether which is a polymer for resist material was
Obtained by polyaddition reaction of 3-HFABEO with BPAF. By the same operation as in Example 7, TPPC was used as a catalyst.
/ DBU 9.4 mg / 3.8 mg (5 mol% / 5 mol%) and 1,3-HFABEO 303.2 mg
(0.5 mmol), BPAF 168.1 mg (0.
5 mmol) was added and the reaction was carried out at 190 ° C. for 120 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate and washed with distilled water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, and then reprecipitated and purified twice using THF as a good solvent and ether / n-hexane [1: 5, V / V] mixed solvent as a poor solvent, and dried under reduced pressure to obtain a white solid. 184.7 mg (yield 40%) of the polymer (P-7a) was obtained. The structure of the obtained polymer was confirmed by IR, ¹ H NMR, ¹⁹ F
It was performed by NMR spectrum. The results are shown in Table 10. Mn calculated by GPC (DMF) is 1070.
0 and Mw / Mn were 1.80.

[0033]

[Table 10] Attributed to oxetanyl group by IR spectrum 98
7cm absorption of ^-1 disappeared and new absorption has been confirmed that due to the hydroxyl group at 3427cm ^-1. In addition, from the ¹ H NMR spectrum, a signal due to an oxetanyl group at around 4.34 to 4.41 ppm disappeared, and a signal due to a side chain hydroxyl group was confirmed at 4.78 ppm. In addition, ¹⁹ F
1,3-H at -68.9 ppm from NMR spectrum
A signal due to the trifluoromethyl group in the FABEO skeleton and a signal due to the trifluoromethyl group in the BPAF skeleton were observed at -62.6 ppm, and it was confirmed that a fluorine atom was present in the structure. From
A soluble fluorine-containing polyether (P-7a) having a target side chain with a primary hydroxyl group was obtained.

Example 10 Fluorine-containing polyether, a polymer for resist materials
Obtained by polyaddition reaction of 3-HFABMO and BPAF
It was By the same operation as in Example 7, TPPC was used as a catalyst.
/ DBU 9.4 mg / 3.8 mg (5 mol% / 5 mol
%), 1,3-HFABMO 282.2 mg
(0.5 mmol), BPAF 168.1 mg (0.
5 mmol) was added and the reaction was carried out at 190 ° C. for 72 hours.
It was After completion of the reaction, dilute the reaction solution with ethyl acetate and distill.
Washed 3 times with water. The ethyl acetate phase was mixed with anhydrous magnesium sulfate.
After drying with a solvent, use THF as a good solvent and ether as a poor solvent.
Using a mixed solvent of hexane / n-hexane [1: 5, V / V]
A white solid polymer that was purified twice by reprecipitation and dried under reduced pressure.
344.4 mg (yield 77%) of (P-8a) was obtained. Profit
Confirm the structure of the obtained polymer by IR, ¹1 H NMR,¹⁹F
It was performed by NMR spectrum. The results are shown in Table 11.
You Mn calculated by GPC (DMF) is 1050.
0 and Mw / Mn were 2.09.

[0035]

[Table 11] Attributed to oxetanyl group by IR spectrum 98
6cm absorption of ^-1 disappeared, a new absorption was observed due to the hydroxyl group at 3427cm ^-1. Further, from the ¹ H NMR spectrum, a signal due to the oxetanyl group at around 4.30 to 4.44 ppm disappeared, and a signal due to the side chain hydroxyl group was confirmed at 4.83 ppm. In addition, ¹⁹ F
1,3-H at -69.0 ppm from NMR spectrum
A signal due to the trifluoromethyl group in the FABMO skeleton and a signal due to the trifluoromethyl group in the BPAF skeleton were observed at -62.6 ppm, and it was confirmed that a fluorine atom was present in the structure. From
A soluble fluorine-containing polyether (P-8a) having a target side chain having a primary hydroxyl group was obtained.

Example 11 Fluorine-containing polyether which is a polymer for resist material was
Obtained by polyaddition reaction of 4-HFACEO with BPAF. By the same operation as in Example 7, TPPC was used as a catalyst.
/ DBU 9.4 mg / 3.8 mg (5 mol% / 5 mol%) was used and 1,4-HFACEO 306.2 mg
(0.5 mmol), BPAF 168.1 mg (0.
5 mmol) was added and the reaction was carried out at 190 ° C. for 120 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate and washed with distilled water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, and then reprecipitated and purified twice using THF as a good solvent and ether / n-hexane [1: 5, V / V] mixed solvent as a poor solvent, and dried under reduced pressure to obtain a white solid. 191.6 mg (yield 40%) of the polymer (P-9a) was obtained. The structure of the obtained polymer was confirmed by IR, ¹ H NMR, ¹⁹ F
It was performed by NMR spectrum. The results are shown in Table 12. Mn calculated by GPC (DMF) is 1080.
0 and Mw / Mn were 1.89.

[0037]

[Table 12] Attributed to oxetanyl group by IR spectrum 98
3cm absorption of ^-1 disappeared and new absorption has been confirmed that due to the hydroxyl group at 3409cm ^-1. Further, from the ¹ H NMR spectrum, the signal due to the oxetanyl group around 3.79 to 3.84 ppm disappeared, and the signal due to the side chain hydroxyl group was confirmed at 4.66 ppm. In addition, ¹⁹ F
1,4-H at -66.5 ppm from NMR spectrum
A signal due to the trifluoromethyl group in the FACEO skeleton and a signal due to the trifluoromethyl group in the BPAF skeleton were observed at -62.6 ppm, and it was confirmed that a fluorine atom was present in the structure. From
A soluble fluorine-containing polyether (P-9a) having a target side chain with a primary hydroxyl group was obtained.

Example 12 Fluorine-containing polyether which is a polymer for resist material was
Obtained by polyaddition reaction of 4-HFACMO with BPAF. By the same operation as in Example 7, TPPC was used as a catalyst.
/ DBU 9.4 mg / 3.8 mg (5 mol% / 5 mol%) and 1,4-HFACMO 292.2 mg
(0.5 mmol), BPAF 168.1 mg (0.
5 mmol) was added and the reaction was carried out at 190 ° C. for 72 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate and washed with distilled water three times. The ethyl acetate phase was dried over anhydrous magnesium sulfate, and then reprecipitated and purified twice using THF as a good solvent and ether / n-hexane [1: 5, V / V] mixed solvent as a poor solvent, and dried under reduced pressure to obtain a white solid. 381.4 mg (yield 83%) of the polymer (P-10a) was obtained.
The structure of the obtained polymer was confirmed by IR, ¹ H NMR, ¹⁹ F
It was performed by NMR spectrum. The results are shown in Table 13. Mn calculated by GPC (DMF) is 1070.
0 and Mw / Mn were 2.85.

[0039]

[Table 13] Attributed to oxetanyl group by IR spectrum 98
4cm absorption of ^-1 disappeared, a new absorption was observed due to the hydroxyl group at 3400 cm ^-1. Further, from the ¹ H NMR spectrum, the signal due to the oxetanyl group around 3.75 to 3.78 ppm disappeared, and the signal due to the side chain hydroxyl group was confirmed at 4.73 ppm. In addition, ¹⁹ F
1,4-H at -66.5 ppm from NMR spectrum
A signal due to the trifluoromethyl group in the FACMO skeleton and a signal due to the trifluoromethyl group in the BPAF skeleton were observed at -62.6 ppm, and it was confirmed that a fluorine atom was present in the structure. From
A soluble fluorine-containing polyether (P-10a) having a target side chain with a primary hydroxyl group was obtained.

Example 13 An acid-labile group-containing resin was obtained by polymer reaction of the above resist material polymer. The fluorine-containing polyether (P-1) obtained in Example 12 was placed in a 20 ml two-necked eggplant flask.
0a) 137.8 mg (0.3 mmol / OHeq) was weighed and dissolved in 3 ml of NMP. Then, cesium carbonate (Cs ₂ CO ₃ ) 488.7 as a base
mg (1.5 mmol), TBAB 4.6 mg (5 mol%) and BBAc 585.2 mg (3.0 mmol) were added, and the reaction was carried out at 100 ° C. for 48 hours. After completion of the reaction, the reaction mixture was poured into an aqueous citric acid solution to precipitate a polymer. The obtained polymer is TH as a good solvent.
F, purified by re-precipitation using n-hexane as a poor solvent, and dried under reduced pressure to obtain a pale yellow powder polymer (P-10b) 13
3.0 mg was obtained. The structure of the obtained polymer was confirmed by I
It was performed by R, ¹ H NMR and ¹⁹ F NMR spectra. The results are shown in Table 14 and FIG.

[0041]

[Table 14] From the IR spectrum, the absorption due to the hydroxyl group at 3504 cm ^-1 decreased, and a new absorption due to the carbonyl group was observed at 1751 cm ^-1 (Fig. 1). ^{From the 1} H NMR spectrum, a new signal due to the side chain hydroxyl group at 4.74 ppm decreased, and tert at around 1.40 ppm.
-A new signal due to the butyl group was confirmed. Furthermore, from the ¹⁹ F NMR spectrum, a signal attributable to the trifluoromethyl group in the 1,4-HFACMO skeleton was observed at -66.5 ppm, and a signal attributable to the trifluoromethyl group in the BPAF skeleton was observed at -62.6 ppm. From this, it became clear that the target fluorinated polyether having a tert-butyl ester residue in the side chain was obtained. In addition, from the analysis of the ¹ H NMR spectrum, the ratio of the tert-butyl ester residue (etherification rate (DE)) was 60 equivalent% with respect to the total hydroxyl equivalents of the primary hydroxyl groups (Fig. 1).

The thermal properties of the polymer for resist material or the resin containing an acid-dissociable group obtained in Examples 7 to 13 were measured by TG.
By measurement, the transmittance of excimer laser light was evaluated by vacuum ultraviolet spectrum measurement. Also, the solubility in various solvents was investigated. (1) Thermal Properties TG of the polymer for resist material P-10a and the acid dissociable group-containing resin P-10b were measured using a thermogravimetric reduction measuring device.
About 5 mg of the sample was placed in an open-type aluminum pan, and measurement was performed at a temperature rising rate of 10 ° C./min under a nitrogen stream. The result is shown in Figure 2.
Shown in. In the acid-dissociable group-containing resin P-10b, a thermogravimetric reduction due to the thermal decomposition of the tert-butyl ester residue was observed at around 210 ° C, and the thermal decomposition of the main chain started at around 400 ° C. (2) The concentration of the polymer for the light transmissive resist material should be 5% by weight.
Dissolved in heptanone. This solution was filtered through a 0.45 μm membrane filter, and then applied on a magnesium fluoride disk using a spin coater at various rotation speeds for 30 seconds. Then, bake at 140 ° C for 90 seconds,
The film thickness was adjusted to 100 mμ. The transmittance of this coating plate was measured in a wavelength range of 130 to 200 nm under vacuum conditions using a vacuum ultraviolet spectrophotometer VU-201 manufactured by JASCO Corporation. The results are shown in Fig. 3. Especially in the main chain skeleton 1,
In Examples 9 to 12 in which 3-HFAB or 1,4-HFAC was introduced, the transmittance at 157 nm was 48 to.
It showed an excellent value of 55%.

(3) Solubility test was conducted by adding 2 ml of various solvents to 2 mg of the soluble resist material polymer or the resin having an acid dissociable group. As a result, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, ethyl acetate, chloroform, THF, 1,4-dioxane, anisole, toluene, chlorobenzene, o-dichlorobenzene, acetonitrile, dimethylformamide, dimethylacetamide, NMP, dimethyl. The polymers for resist materials obtained in Examples 7 to 12 and the acid-dissociable group-containing resin obtained in Example 13 were dissolved at room temperature in sulfoxide.

[0044]

The acid-labile group-containing resin according to the present invention is obtained by modifying the side chain of the resist material polymer obtained by polyaddition reaction of the resist material monomer according to the present invention. _{2 It} has excellent transparency for excimer laser (wavelength 157 nm), and can be used very suitably for manufacturing integrated circuit devices, which are expected to be further miniaturized in the future.

[Brief description of drawings]

FIG. 1 is an IR chart of a resist material polymer and an acid-labile group-containing resin.

FIG. 2 is a TG of a resist material polymer and an acid-labile group-containing resin.

FIG. 3 is a vacuum ultraviolet spectrum of a polymer for resist material.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Atsushi Kameyama             1-10 Nishi-Kanagawa, Kanagawa-ku, Yokohama-shi, Kanagawa             No. 3 Clio Higashi Kanagawa Ichibankan No. 705 (72) Inventor Hiroto Kudo             4-11 Rokkakubashi, Kanagawa-ku, Yokohama-shi, Kanagawa             No. 28 Room 102, Lark Hills Building B F-term (reference) 2H025 AA01 AA02 AA03 AB16 AC04                       AC08 AD03 BE00 BE10 BG00                       CB21 CB41 FA17                 4C048 TT02                 4J005 AA12 BA00 BB01 BB02

Claims (4)

[Claims] 1. A monomer for a resist material represented by the following formula (1). [Chemical 1] (Here, R ¹ is a divalent organic group containing a fluorine atom,
R ² is a lower hydrocarbon group. ) 2. The R ¹ is represented by the following formulas (2) to (6):
^{2. The} monomer for resist material according to claim 1, wherein R ² is a hydrocarbon group having 1 to 3 carbon atoms. [Chemical 2] (Here, n and m represent an integer of 0 to 4, and n + m represents an integer of 1 to 8.) 3. The formula (1) according to claim 1 and the following formula (7):
A polymer for a resist material, which is a polyaddition reaction product with. [Chemical 3] (Here, R ³ is a divalent organic group containing a fluorine atom.) 4. An acid-dissociable group-containing resin which is alkali-insoluble or sparingly soluble in alkali and becomes readily soluble in alkali by the action of an acid, which resin has a repeating unit represented by the following formula (8). An acid-dissociable group-containing resin characterized by the above. [Chemical 4] (Here, R ¹ and R ³ are divalent organic groups containing a fluorine atom, R ² is a lower hydrocarbon group, and X is a side chain containing an acid dissociable group.)