JP2942167B2 - Resist material and pattern forming method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material used in manufacturing semiconductor devices and the like. For details, use UV light as the exposure energy source, especially deep UV light of 300 nm or less,
For example, the present invention relates to a resist material and a pattern forming method for forming a positive pattern using a KrF excimer laser beam or the like.

[0002]

2. Description of the Related Art In recent years, the energy source of an exposure apparatus used for microfabrication, especially for photolithography, has become shorter and shorter in wavelength due to high-density integration of semiconductor devices, and far ultraviolet light (300 nm or less), KrF Excimer laser light (24
8.4 nm) is under study. However, no highly practical resist material suitable for these wavelengths has been found yet.

[0003] For example, as a resist material using KrF excimer laser light or far ultraviolet light as a light source, a dissolution-inhibiting resist comprising a polymer having high transparency to light near 248.4 nm and a photosensitive compound having a diazodiketo group in a molecule. Materials have been developed (for example, see JP-A-1-809).
No. 44; Japanese Patent Application Laid-Open No. 1-154048;
JP-A-155338, JP-A-1-155339; JP-A-1-188852; Tani et al.
Proc. SPIE, 1086 , 22 (1989)
etc). However, these dissolution-inhibiting resist materials have low sensitivity in common and cannot be used for deep ultraviolet light or KrF excimer laser light, which requires a highly sensitive resist material.
In recent years, a chemically amplified resist material using an acid generated by exposure as a medium has been proposed as a method of reducing the amount of exposure energy (higher sensitivity) [H. Ito et al., Poly
m. Eng. Sci. , 23 , 1012 (1983)
Various reports have been made on this (eg, H. Ito et al., U.S. Pat. No. 4,491,628 (1985); Japanese Patent Publication No. 2-27660 ; JC.
Crivello et al., US Pat. No. 4,603,101 (1.
986); JP-A-62-115440;
R. Brunsvolt et al., Proc. SPIE, 10
86 , 357 (1989); X. Neenan
Proc. SPIE, 1086 , 2 (1989)
Year); G. FIG. Taracon et al., SPE Regi
onal Conference Technical
Papers, Ellenville, N .; Y. 19
1988, p. 11; JP-A-2-25850;
Jian et al., Polym. Mater. Sci. & En
g. , 66 , 41 (1992), etc.). However,
The polymers used in these existing chemically amplified resist materials are, for example, poly (p-tert-butoxycarbonyloxystyrene), poly (p-tert-butoxystyrene), poly (p-tert-butoxycarbonyloxy-α). -Methylstyrene), poly (p-tert-butoxy-α-methylstyrene), poly (tert-butyl p-isopropenylphenoxyacetate), poly (pt
phenol ethers such as tert-butoxycarbonyloxystyrene / sulfone), poly (p-tetrahydropyranyloxystyrene), poly {p- (1-methoxyethoxy) styrene}, and poly {p- (1-phenoxyethoxy) styrene} In the case of a system polymer, any of them has a defect that the film is easily peeled off during development due to poor adhesion to the substrate, and the heat resistance is poor and a good pattern cannot be obtained. Also, carboxylic acid polymers,
For example, in the case of poly (tert-butyl p-vinylbenzoate) or poly (tetrahydropyranyl p-vinylbenzoate), the light transmittance around 248.4 nm due to the benzoyl group is insufficient, and the In the case of poor imageability and poly (tert-butyl methacrylate), there are problems such as poor heat resistance and dry etching resistance of the polymer.

In addition, resist materials using a silicon-containing polymer have been disclosed (for example, Japanese Patent Publication No. 3-44290), but for example, poly (p-trimethylsilyloxystyrene) and poly (p-tert-butyl) When dimethylsilyloxystyrene) is used, there are problems such as low sensitivity, and it cannot be completely removed by ashing due to silicon content, and it is difficult to put it to practical use.

[0005] Recently, poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) has been proposed as a chemically amplified resist material which has improved the above disadvantages.
Resist material (JP-A-2-209977);
JP-A-3-206458), a resist material using poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene) (JP-A-2-19847; JP-A-2-61436);
JP-A-3-83063), resist material using poly (p-tert-butoxystyrene / p-hydroxystyrene) [JP-A-2-62544; JP-A-4-11258 (US Pat. No. 5,350,660) Specification)] etc. are reported. However, resist materials using these polymers are commonly used in Delay Ti
There is a problem of me (a problem that the dimensions change or the pattern shape is deteriorated due to the lapse of time from the application of the resist to the exposure or from the exposure to the heat treatment (PEB)).

[0006] In addition, a resist material using a polymer into which an acetal group or a ketal group is introduced as a protective group (for example, JP-A-2-19847; JP-A-2-61436; JP-A-4-19757) JP-A-5-217745; JP-A-5-249682). However, for example, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene), poly (p-1-methoxy-styrene)
1-methylethoxystyrene / p-hydroxystyrene),
These resist materials using poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / methyl methacrylate) or poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) have storage stability. There is a problem that it is defective, the size and shape of the defocus are greatly deteriorated, and the focus margin is small.
It is difficult to form a resist pattern stably. There are also problems such as scum (undissolved portion during development) and poor mask linearity. JP-A-3-282550 discloses poly (p-1-methoxy-1-
Although a resist material comprising methylethoxystyrene / p-hydroxystyrene) and a diphenyliodonium salt is disclosed, in this case, in addition to the above problems, there are further problems of poor substrate adhesion and delay time. Further, a resist material using the polymer according to the present invention, for example, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) has also been reported (Japanese Patent Application Laid-Open No. 6-94842). However, any of the resist materials described herein is a resist material for an electron beam, and when this material is exposed to ultraviolet rays, for example, KrF excimer laser light, the resolution of the bottom (foot) of the pattern is reduced. Is insufficient, or scum (residual melting during development) is generated, so that scum is transferred during etching.

[0007]

As described above, although the chemically amplified resist material has a higher sensitivity than the conventional resist material, the polymer has poor heat resistance and poor adhesion to a substrate. Insufficient light transmittance around 248.4 nm, Insufficient resolution, Pattern size fluctuates over time, pattern shape deteriorates, Storage stability is poor, Focus There are problems such as insufficient margin, poor mask linearity, or skirting or scum remaining in the pattern shape, and it is difficult to put it to practical use. Accordingly, there is a demand for a practical high-sensitivity resist material which has solved these problems.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been developed in view of the above circumstances.
High transmittance to excimer laser light, etc., high sensitivity to exposure by these light sources, electron beam and soft X-ray irradiation, extremely excellent heat resistance and adhesion to substrate, high resolution A rectangle with high performance, high-accuracy patterns without pattern dimension fluctuation over time, excellent storage stability, a wide focus margin, good mask linearity, and no footing or scum It is an object of the present invention to provide a practical resist material capable of obtaining the above pattern shape and a pattern forming method using the same.

[0009]

In order to achieve the above object, the present invention comprises the following constitutions. [(1) The following general formula [1]

[0010]

Embedded image

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or a carbon atom.
6 linear represents a branched or cyclic alkyl group or a linear or branched haloalkyl group having 1 to 6 carbon atoms (except in the case of R ² and R ³ are both hydrogen atoms ), R ² and R ³ may form a methylene chain having 2 to 5 carbon atoms, and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Represents a linear, branched or cyclic haloalkyl group, an acetyl group, or an aralkyl group represented by Formulas 1 to 6, wherein R ⁵ is a hydrogen atom, a halogen atom,
6 linear, branched or cyclic alkyl groups, 1 to 1 carbon atoms
6, linear, branched or cyclic alkoxy, tetrahydropyranyloxy, tetrahydrofuranyloxy, tert-butoxycarbonyloxy, tert
Represents a butoxycarbonylmethoxy group or an acetyloxy group, and k, r and m each independently represent a natural number (provided that 0.10 ≦ (k + m) / (k + r + m) ≦ 0.
90 and 0.01 ≦ m / (k + r + m) ≦ 0.25. And a polymer represented by the following general formula [2].
Compound represented by general formula [6]
Compound, photosensitive compound represented by general formula [9] and general formula
Selected from the group consisting of the photosensitive compounds represented by [12]
One or more photosensitive compounds and a solvent capable of dissolving them
For deep-ultraviolet light of 300 nm or less containing
material. [Wherein R ⁶ is a linear, branched or cyclic C 1-10 carbon atom
An alkyl group or a haloalkyl group having 1 to 10 carbon atoms
R ⁷ represents a linear, branched or cyclic C 1-10 carbon atom
An alkyl group, a haloalkyl group having 1 to 10 carbon atoms or
Z represents a sulfonyl group or a carbonyl group;
Represents ] [Wherein, R ¹³ represents a general formula [7] Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen
Represents an atom or a halogen atom, p is 0 or an integer of 1 to 3
Represents A group represented by｝, or a general formula [8] In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are
Each independently represents a hydrogen atom, a halogen atom,
Straight-chain or branched alkyl group, straight-chain having 1 to 5 carbon atoms
Or a branched alkoxy group, trifluoromethyl group, water
Represents an acid group, a trifluoromethoxy group or a nitro group. ｝
Represents a group represented by ] [ Wherein , R ¹³ is the same as described above, and R ²² is a hydrogen atom.
A hydroxyl group or a general formula [10] 中 In the formula, R ¹³ is the same as described above. Group represented by｝
And R ²³ represents a linear or branched alkyl having 1 to 5 carbon atoms.
A kill group or a general formula [11] In the formula, R ²⁴ and R ³⁰ are each independently a hydrogen atom,
A hydrogen atom, a linear or branched alkyl having 1 to 5 carbon atoms
Group, linear or branched alkoxy having 1 to 5 carbon atoms
Or a group represented by the above general formula [10]. Group represented by｝
Represent. ] [In the formula, R ²⁵ is a straight or branched chain having 1 to 4 carbon atoms.
Alkyl, phenyl, substituted phenyl, or aralkyl
R26 represents a hydrogen atom, a halogen atom, a carbon number
Represents a linear, branched or cyclic alkyl group of 1 to 6,
R ²⁷ is a linear or branched perfluoro having 1 to 8 carbon atoms.
Loalkyl group, linear, branched or cyclic having 1 to 8 carbon atoms
Alkyl group, 1-naltyl group, 2-naltyl group, 10
-Camphor group, phenyl group, tolyl group, 2,5-dic
Lorphenyl group, 1,3,4-trichlorophenyl group,
Or a trifluoromethylphenyl group. ]

(2) a step of applying the resist material described in the above (1) on a substrate; a step of exposing the substrate to light with a light of 300 nm or less through a mask after a heat treatment; And then developing using a developing solution. 』

In the general formula [1], an alkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁵ , and an alkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁴ Examples of the alkyl group of the haloalkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group (linear,
It may be branched or cyclic). Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁴ include a methyl group, an ethyl group,
Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group (which may be any of linear, branched or cyclic). Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ⁵ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group (any of linear, branched or cyclic) Is also possible). A halogen atom of a haloalkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁴ ;
And the halogen atom represented by R ⁵ include chlorine, bromine, fluorine and iodine. Examples of the aralkyl group represented by R ⁴ include a benzyl group, a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group.

As a preferred example of the polymer represented by the general formula [1] used in the resist composition of the present invention, in the general formula [1], R ¹ is a hydrogen atom, and R ² is a hydrogen atom or a carbon atom. A linear or branched alkyl group having 1 to 6 carbon atoms, R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ⁴ is a straight or branched alkyl group having 1 to 10 carbon atoms. A chain or branched alkyl group, wherein R ⁵ is a hydrogen atom, a linear or branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms; Or a cyclic alkoxy group, a tert-butoxycarbonyloxy group, a tert-butoxycarbonylmethoxy group, a tetrahydropinyloxy group, or an acetyloxy group, and more preferred examples are those in which R ¹ is a hydrogen atom; R ² is a hydrogen atom or a methyl group , R ³ is a methyl group or an ethyl group;
⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkyl group having 1 to 4 carbon atoms. Linear or branched alkoxy group, tert-butoxycarbonyloxy group, t
An ert-butoxycarbonylmethoxy group or an acetyloxy group is exemplified.

The polymer represented by the general formula [1] according to the present invention can be easily eliminated with a trace amount of an acid.

[0016]

Embedded image

(Wherein R ² , R ³ and R ⁴ are as defined above), ie, a monomer unit having an alkoxyalkoxy group, a haloalkoxyalkoxy group or an aralkyloxyalkoxy group, Equation [1
4]

[0018]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same as those described above), and the mask linearity is improved by suppressing the developing speed of the exposed portion, and the influence of the proximity effect. Is a monomer unit capable of suppressing the general formula [15]

[0020]

Embedded image

(Wherein R ¹ and R ⁵ are the same as described above). In particular, the functional group represented by the general formula [13] is an existing t
ert-butoxycarbonyloxy group, tert-butoxy group,
Compared with a functional group such as a tetrahydropyranyloxy group and a tert-butoxycarbonylmethyloxy group, the compound is very easily detached by the action of an acid, which is extremely advantageous in terms of improving resolution performance and maintaining pattern dimensions. Further, the monomer unit represented by the general formula [15] has an improved focus margin which is not possessed by the monomer unit represented by the general formula [14] having a functional group represented by the general formula [13], and has a higher mask linearity. This is extremely effective for improving defects. Further, it also contributes to improvement of the heat resistance of the polymer.

The monomer unit represented by the general formula [14] is specifically a p- or m-hydroxystyrene derivative, p-
Or due to monomers such as m-hydroxy-α-methylstyrene derivative, but specific examples of such monomers include, for example, p- or m-1-methoxy-1-methylethoxystyrene, p- or m-1-benzyloxy-1-methylethoxystyrene, p- or m-1-ethoxyethoxystyrene, p- or m-1-methoxyethoxystyrene, p- or m-1-
n-butoxyethoxystyrene, p- or m-1-isobutoxyethoxystyrene, p- or m-1- (1,1-dimethylethoxy) -1-methylethoxystyrene, p- or m-1- (1, 1-dimethylethoxy) ethoxystyrene, p- or m-1- (2-chloroethoxy) ethoxystyrene, p- or m-1- (2-ethylhexyloxy) ethoxystyrene, p- or m-1-ethoxy-1 -Methylethoxystyrene, p- or m-1-n-propoxyethoxystyrene, p- or m-1-methyl-1-n-propoxyethoxystyrene, p- or m-1-ethoxypropoxystyrene, p- or m -1-methoxybutoxystyrene, m- or p-1-methoxycyclohexyloxystyrene, m- or
p-Acetyloxy-1-methylethoxystyrene and p- or m-hydroxy-α-methylstyrene derivatives having the same protective group as the p- or m-hydroxystyrene derivative thereof.

The polymer according to the present invention has the general formula [1]
[4] other than the monomer unit represented by the general formula [15]
General formula [16] having a role of improving heat resistance and substrate adhesion of the monomer unit and the polymer represented by

[0024]

Embedded image

(Wherein, R ¹ is the same as described above). Specific examples of the monomer unit represented by the general formula [15] include styrene, p-chlorostyrene, o-, m- or p-methylstyrene, o-, m- or p-methoxystyrene,
pn-butylstyrene, p-ethoxystyrene, m- or p-te
rt-butoxystyrene, m- or p-tetrahydropyranyloxystyrene, m- or p-tetrahydrofuranyloxystyrene, m- or p-tert-butoxycarbonyloxystyrene, tert-butyl m- or p-vinylphenoxyacetate,
Monomer units such as m- or p-acetyloxystyrene and α-methylstyrene derivatives having the same substituents as these styrene derivatives are exemplified.

The monomer unit represented by the general formula [16] is derived from a monomer having a phenolic hydroxyl group. Specific examples of such a monomer include p-
Or m-vinylphenol, p- or m-hydroxy-α-methylstyrene, and the like.

In the polymer according to the present invention represented by the general formula [1], the monomer unit represented by the general formula [14] and the monomer unit represented by the general formula [15] are combined with the monomer unit represented by the general formula [16]. As the composition ratio of the monomer unit,
First, it is desirable that the total of the monomer unit represented by the general formula [14] and the monomer unit represented by the general formula [15] is 10 to 90 mol% based on the total amount of the polymer. More preferably, the content is 20 to 70 mol%, which makes the adhesion to the film and the mask linearity extremely good.

The composition ratio of the monomer unit represented by the general formula [15] to the total amount of the polymer is desirably from 1 to 25 mol%, but in particular, the mask linearity can be improved and the deterioration of the resolution performance can be suppressed. 20 mol% is more preferred.

In the polymer according to the present invention represented by the general formula [1], R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, R ³ is a methyl group or an ethyl group,
R ⁴ is a linear or branched alkyl group having 1 to 10 carbon atoms, and R ⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. The polymer represented by the linear or branched alkoxy group or acetyl group is a commercially available monomer as a raw material, is easily available, has a short number of synthesis steps, is advantageous in terms of cost, and is industrialized. It is more preferable because it is easy.

Specific examples of the polymer according to the present invention include:
For example, poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / styrene], poly [p-
(1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-chlorostyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-methylstyrene], Poly [p- (1-methoxy-1-
Methylethoxy) styrene / p-hydroxystyrene / p-
Methoxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-tert-
Butoxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-acetyloxystyrene], poly [p- (1-benzyloxy-1-
Methylethoxy) styrene / p-hydroxystyrene / styrene], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / p-chlorostyrene], poly [p- (1-benzyloxy) 1-methylethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / p-ethoxystyrene], poly [p -(1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / p-tert-butoxystyrene], poly (p-1-ethoxyethoxystyrene /
p-hydroxystyrene / styrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-chlorostyrene), poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene / p-methylstyrene), poly (p-1-
Ethoxyethoxystyrene / p-hydroxystyrene / m-
Methylstyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-ethoxystyrene), poly (p- 1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (p-1-ethoxyethoxystyrene) /
p-hydroxystyrene / p-acetyloxystyrene),
Poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / styrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-methoxyethoxystyrene / p -Hydroxystyrene / m-methylstyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-chlorostyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene) ), Poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-ethoxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (p- 1-methoxyethoxystyrene / p-hydroxystyrene / p-acetyloxystyrene), poly (p-
1-n-butoxyethoxystyrene / p-hydroxystyrene / pn-butylstyrene), poly (p-1-isobutoxyethoxystyrene / p-hydroxystyrene / o-methoxystyrene), poly {p-[(1,1 -Dimethylethoxy) -1-methylethoxy] styrene / p-hydroxystyrene / m-methoxystyrene｝, poly [p- (1,1-dimethylethoxy)-
1-methylethoxystyrene / p-hydroxystyrene / o-
Methylstyrene), poly [m-1- (2-chloroethoxy) ethoxystyrene / m-hydroxystyrene / styrene],
Poly [m-1- (2-ethylhexyloxy) ethoxystyrene / m-hydroxystyrene / m-methylstyrene], poly [p- (1-methoxy-1-methylethoxy) -α-methylstyrene / p-hydroxy- α-methylstyrene / styrene], poly [p- (1-ethoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly (p-1-n-propoxyethoxystyrene / p-hydroxy Styrene / p-methoxystyrene), poly [p- (1-methyl-1-n-propoxyethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly (m-1-ethoxypropoxystyrene / m-hydroxy Styrene / m-tert-butoxystyrene), poly (p-1-acetyloxy-1-methylethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (m-1-ethoxypropoxy) Styrene / m- hydroxystyrene / p- methylstyrene), poly [m-(1-methoxy-1-methylethoxy) styrene / m-
Hydroxystyrene / m-tert-butoxystyrene], poly (p-1-methoxycyclohexyloxystyrene / p-hydroxystyrene / styrene), poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-tetrahydrofura Nyloxystyrene], poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-tetrahydropyranyloxystyrene], poly [p- (1-methoxyethoxy) styrene / p-hydroxystyrene / p- Tetrahydropyranyloxystyrene], poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-
tert-butoxycarbonyloxystyrene], poly [p-
(1-methoxyethoxy) styrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-
Hydroxystyrene / p-tert-butoxycarbonyloxystyrene], poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-vinylphenoxyacetic acid t
ert-butyl], poly [p- (1-methoxyethoxy) styrene / p-hydroxystyrene / p-vinylphenoxyacetic acid t
ert-butyl], poly [m- (1-ethoxyethoxy) styrene / m-hydroxystyrene / m-tert-butoxycarbonyloxystyrene], poly [m- (1-ethoxyethoxy)
Styrene / m-hydroxystyrene / m-tert-butoxystyrene], poly [m- (1-methoxyethoxy) styrene /
m-hydroxystyrene / m-tert-butoxystyrene],
Examples thereof include poly [p- (1-methoxybutoxy) styrene / p-hydroxystyrene / styrene], but are not limited thereto.

The polymer according to the present invention is, for example, a)
To f) can be easily obtained by the following six methods. a) Method-1 The following general formula [17]

[0032]

Embedded image

(Wherein R ¹ is as defined above) and an optional amount of the following general formula [18]

[0034]

Embedded image

(Wherein, R ¹ is the same as described above, and R ²⁸ is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or 1 to 3 carbon atoms. And a monomer represented by the following formula: for example, a radical polymerization initiator [eg, 2,2′-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile),
2,2'-azobis (methyl 2-methylpropionate), 2,2 '
-Azo-based polymerization initiators such as azobis (ethyl 2-methylpropionate) and 2,2'-azobis (methyl 2-methylbutyrate) and peroxide-based polymerization initiators such as benzoyl peroxide and lauroyl peroxide. In the presence of toluene, 1,4-dioxane, 1,
2-dimethoxyethane, tetrahydrofuran, iso-propanol, 2-methoxypropanol, 1,3-dioxolan,
The polymerization reaction is carried out in an organic solvent such as ethyl acetate or methyl ethyl ketone in a stream of nitrogen or argon at 50 to 110 ° C for 1 to 10 hours. As a polymerization catalyst, a low molecular weight polymer is easily obtained due to its high solubility, and non-nitrile 2,2′-azobis (methyl 2-methylpropionate), 2,2, which is advantageous in terms of safety and toxicity. 2′-azobis (ethyl 2-methylpropionate) and 2,2′-azobis (methyl 2-methylbutyrate) are more preferred. In addition, anionic polymerization in which the reaction is carried out at an extremely low temperature in the presence of a catalyst such as butyllithium may be performed. After the reaction, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [19]

[0036]

Embedded image

Wherein R ¹ , R ²⁸ and m are the same as above, and q represents a natural number (provided that 0.75 ≦ q ≦ 0.99). Is isolated. The copolymer is then placed in an organic solvent such as tetrahydrofuran, acetone, methanol, ethanol, iso-propanol, n-propanol, n-butanol, sec-butanol, tert-butanol, 1,4-dioxane, 1,3-dioxolan, etc. Preferred acids are, for example, Lewis acids such as sulfuric acid, phosphoric acid, hydrochloric acid and hydrobromic acid, and organic acids such as p-toluenesulfonic acid, malonic acid and oxalic acid. ] And 1 to 20 at 30 to 110 ° C
The reaction is allowed to proceed for a period of time to completely eliminate the tert-butyl group as a functional group. After the reaction, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [20]

[0038]

Embedded image

(Wherein R ¹ , R ²⁸ , q and m are the same as described above). Further, the copolymer and an optional amount of the following general formula [2]
1]

[0040]

Embedded image

(Wherein R ³ and R ⁴ are the same as those described above) with tetrahydrofuran, acetone, methyl ethyl ketone, 1,4-dioxane, 1,3-dioxolan, Methylene, 1,2-dimethoxyethane, ethyl ether,
A suitable catalyst in an organic solvent such as ethyl acetate [eg, sulfuric acid, hydrochloric acid, phosphorus oxychloride, p-toluenesulfonic acid, chlorosulfonic acid / pyridine salt, sulfuric acid / pyridine salt, p-toluenesulfonic acid / pyridine salt, etc.] 10 ~ 100 ℃ in the presence of
For 1 to 30 hours to chemically introduce the functional group represented by the general formula [13] at an arbitrary ratio, and then perform post-treatment according to a conventional method for obtaining a polymer to obtain the desired polymer simply. Let go.

B) Method-2 After polymerizing the monomer represented by the above general formula [17] by the same operation method as in the method-1, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [17] 22]

[0043]

Embedded image

(Wherein x = q + m, and R ¹ is the same as described above). Next, this homopolymer is dissolved in an organic solvent such as tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolan, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Suitable acids [for example, Lewis acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and hydrobromic acid, and organic acids such as p-toluenesulfonic acid, malonic acid, and oxalic acid are preferable. ] And 1 to 10 at 30 to 100 ° C
The reaction is allowed to proceed for a period of time to remove the tert-butyl group as a functional group at an arbitrary ratio. After the reaction, post-treatment is performed according to a conventional method for obtaining a polymer, and the following general formula [23]

[0045]

Embedded image

(In the formula, R ¹ , m and q are the same as described above.)
Is isolated.
Further, after introducing a functional group represented by the above general formula [13] into this copolymer by the same operation method as in method 1, post-treatment is carried out in accordance with a conventional method for obtaining a polymer, and a desired polymer is isolated. I do.

C) Method-3 The following general formula [24]

[0048]

Embedded image

(Wherein R ¹ is as defined above) and an arbitrary amount of the monomer represented by the above general formula [18] are subjected to a polymerization reaction according to the same operation method as in method 1. After that, post-treatment is performed according to a conventional method for obtaining a polymer, and the following general formula [25]

[0050]

Embedded image

(Wherein R ¹ , R ²⁸ , m and q are the same as described above). This copolymer was then treated with tetrahydrofuran, 1,4-dioxane, 1,3-
Dioxolan, ethyl acetate, methanol, ethanol,
n-propanol, iso-propanol, n-butanol, se
In a solvent such as c-butanol, tert-butanol, water or the like, preferably in a nitrogen stream, a suitable base [for example, sodium hydroxide, potassium hydroxide, aqueous ammonia, hydroxylamine, tetramethylammonium hydroxide aqueous solution and the like is preferable. Or an appropriate acid [eg, sulfuric acid, hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, etc.]. ] At 10 to 120 ° C for 30 minutes to 20 hours to completely remove the acetyl group of the functional group. After the reaction, post-treatment is performed according to a conventional method for obtaining a polymer, and the following general formula [26]

[0052]

Embedded image

(Wherein R ¹ , R ²⁸ , m and q are the same as described above). Further, a functional group represented by the general formula [13] is introduced into the copolymer by the same operation method as in method 1,
Post-treatment is carried out in accordance with a conventional method for obtaining a polymer, and a target polymer is isolated.

D) Method-4 After polymerizing the monomer represented by the general formula [24] by the same operation method as in the method 1, post-treatment is carried out in accordance with a conventional method for obtaining a polymer, and the following general formula [24] 27]

[0055]

Embedded image

(Wherein R ¹ and x are the same as described above). Next, the homopolymer was treated with tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, methanol, ethanol, n-propal, iso-propanol, n-butanol, sec-butanol, tert-butanol, water and the like. An appropriate base [eg, sodium hydroxide, potassium hydroxide, aqueous ammonia, hydroxylamine, aqueous solution of tetramethylammonium hydroxide, or the like] is preferable in a solvent, preferably in a nitrogen stream. ] Or a suitable acid [eg, sulfuric acid, hydrochloric acid, phosphoric acid,
Hydrobromic acid, p-toluenesulfonic acid and the like are preferred. ] At 10 to 100 ° C for 30 minutes to 10 hours to remove an acetyl group as a functional group at an arbitrary ratio. After the reaction, post-treatment is performed according to a conventional method for obtaining a polymer, and the following general formula [28]

[0057]

Embedded image

(In the formula, R ¹ , q and m are the same as described above.)
Is isolated.
Further, after introducing a functional group represented by the above general formula [13] into this copolymer by the same operation method as in method 1, post-treatment is carried out in accordance with a conventional method for obtaining a polymer, and a desired polymer is isolated. I do.

E) Method-5 The monomer represented by the above general formula [17] and an arbitrary amount of the monomer represented by the above general formula [24] were prepared by the following method-1
The polymerization reaction is carried out in the same manner as described above, and after the reaction, the polymerization is carried out according to a conventional method for obtaining a polymer, and the following general formula [29]

[0060]

Embedded image

(In the formula, R ¹ , q and m are the same as described above.)
Or a copolymer represented by the following general formula [30]

[0062]

Embedded image

(In the formula, R ¹ , q and m are the same as described above.)
Is isolated. The copolymer is then added to a solvent such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, water and the like. Preferably, a suitable base [eg, sodium hydroxide, potassium hydroxide, aqueous ammonia, hydroxyamine, aqueous solution of tetramethylammonium hydroxide, or the like] is preferably used in a nitrogen stream. In the presence, the reaction is carried out at 10 to 120 ° C. for 30 minutes to 20 hours to completely remove the acetyl group as a functional group. After the reaction, the reaction is carried out according to a conventional method for obtaining a polymer, and the hydroxystyrene copolymer represented by the general formula [23] is isolated. Hereinafter, the target polymer is isolated by operating this copolymer in the same manner as in Method-2.

F) Method-6 The homopolymer represented by the general formula [22] obtained by the above method-2 or the general formula [27] obtained by the method-4 was respectively treated with tetrahydrofuran, 1,4-dioxane, In a solvent such as 1,3-dioxolan, ethyl acetate, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and water, a suitable acid [eg, sulfuric acid, hydrochloric acid, phosphorus Preferred are acids, hydrobromic acid, p-toluenesulfonic acid, malonic acid, oxalic acid and the like. ] In the presence
The reaction is carried out at 10 to 70 ° C. for 30 minutes to 10 hours, and tert-
The butyl or acetyl group is completely eliminated. After the reaction, the reaction is carried out according to a conventional method for obtaining a polymer, and the following general formula [31]

[0065]

Embedded image

(Wherein R ¹ and x are the same as described above). The homopolymer was then treated with tetrahydrofuran, 1,4-dioxane, ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, 1,3-dioxolane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert. -Suitable bases in organic solvents such as butanol and methylene chloride (eg potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine, N-methyl 2-pyrrolidone, piperidine, tetramethylammonium hydroxide aqueous solution, etc.) Or an appropriate acid [eg, sulfuric acid, hydrochloric acid, phosphoric acid, phosphorus oxychloride, p-toluenesulfonic acid, chlorosulfonic acid.
Pyridine salt, p-toluenesulfonic acid / pyridine salt, sulfuric acid / pyridine salt, etc.] in the presence of an arbitrary amount of a protecting group for a hydroxyl group, for example, di-tert-butyl dicarbonate, 2,3-dihydrofuran, 2,3 -Reaction with dihydropyran, tert-butyl monochloroacetate, acetyl chloride, acetic anhydride, isobutene, dimethyl sulfate, methyl iodide, etc. at 10 to 100 ° C for 30 minutes to 30 hours.After the reaction, follow the conventional method for obtaining a polymer. After the post-processing, the following general formula [32]

[0067]

Embedded image

[0068] (expressed in the formula, R ²⁹ is tert- butoxycarbonyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tert- butoxycarbonyl methoxy group, an acetyl group, tert- butoxy group, a methoxy group, R ¹ Is the same as described above.) Further, after introducing a functional group represented by the above general formula [13] into this copolymer by the same operation method as in method 1, post-treatment is carried out in accordance with a conventional method for obtaining a polymer, and a desired polymer is isolated. I do.

The average molecular weight of the polymer according to the present invention is not particularly limited as long as it can be used as a resist material. A more preferable range is the weight determined by GPC measurement using polystyrene as a standard. The average molecular weight is usually about 1,000 to 10,000, more preferably about 3,000 to 50,000.

The photosensitive compound capable of generating an acid upon exposure (hereinafter, abbreviated as "acid generator") used in the present invention is a photosensitive compound capable of generating an acid upon exposure to light, which adversely affects the formation of a resist pattern. In particular, it has good light transmittance around 248.4 nm and can maintain high transparency of the resist material.
An acid generator capable of increasing the light transmittance at about 48.4 nm and maintaining high transparency of the resist material is exemplified. Particularly preferred acid generators in the present invention include, for example, compounds represented by the following general formula [2], general formula [6], general formula [9] or general formula [12].

[0071]

Embedded image

[Wherein, R ⁶ and R ⁷ each independently represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and Z represents a sulfonyl group. Represents a group or a carbonyl group. ]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

Embedded image

[Wherein R ¹³ is a group represented by the general formula [7]:

[0081]

Embedded image

Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a halogen atom, and p is 0 or 1-3.
Represents an integer. A group represented by｝, or a general formula [8]

[0083]

Embedded image

Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹
Are each independently a hydrogen atom, a halogen atom, a carbon number of 1 to 5
A linear or branched alkyl group, a linear or branched alkoxy group having 1 to 5 carbon atoms, a trifluoromethyl group,
Represents a hydroxyl group, a trifluoromethoxy group or a nitro group. Represents a group represented by｝. ]

[0085]

Embedded image

[Wherein, R ¹³ is the same as described above, and R ²² is a hydrogen atom, a hydroxyl group or a compound of the general formula [10]

[0087]

Embedded image

In the formula, R ¹³ is the same as described above. And R ²³ represents a linear or branched alkyl group having 1 to 5 carbon atoms or a general formula [11].

[0089]

Embedded image

In the formula, R ²⁴ and R ³⁰ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkyl group having 1 to 5 carbon atoms, It represents a branched alkoxy group or the general formula [10]. Represents a group represented by｝. ]

[0091]

Embedded image

Wherein R ²⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a substituted phenyl group or an aralkyl group, and R ²⁶ represents a hydrogen atom, a halogen atom, A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R ²⁷ represents a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms, and a linear chain having 1 to 8 carbon atoms. -Like, branched or cyclic alkyl group, 1 naphthyl group, 2 naphthyl group,
Represents a 10-camphor group, a phenyl group, a tolyl group, a 2,5-dichlorophenyl group, a 1,3,4-trichlorophenyl group, or a trifluoromethylphenyl group. ]

In the general formula [2], examples of the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ⁶ and R ⁷ include a methyl group, an ethyl group and a propyl group. A butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group (which may be any of linear, branched or cyclic).

[0094]

[0095]

[0096]

In the general formula [7], R ¹⁴ , R ¹⁵ and R ¹⁶
Examples of the halogen atom represented by are chlorine, bromine, fluorine and iodine.

In the general formula [8], R ¹⁷ , R ¹⁸ , R ¹⁹ ,
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ²⁰ and R ²¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group (either linear or branched. ). Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group (either linear or branched). Examples of the halogen atom include chlorine, bromine, fluorine and iodine.

In the general formula [9], the alkyl group having 1 to 5 carbon atoms represented by R ²³ includes a methyl group, an ethyl group,
Examples thereof include a propyl group, a butyl group, and a pentyl group (either linear or branched).

In the general formula [11], examples of the alkyl group having 1 to 5 carbon atoms represented by R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group (linear or linear). It can be any of branched). Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group (either linear or branched). Examples of the halogen atom include chlorine, bromine, fluorine, and iodine.

In formula [12], examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁵ include a methyl group, an ethyl group, a propyl group and a butyl group (linear or branched). Any of the above). 1 to 6 carbon atoms represented by R ²⁶
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group (which may be linear, branched, or cyclic). Examples of the substituted phenyl group represented by R ²⁵ include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, and a chlorophenyl group (the substitution position may be any of the o-, m-, or p-position). . The aralkyl group represented by R ²⁵ includes a benzyl group and a phenethyl group. Examples of the halogen atom represented by R ²⁶ include chlorine, bromine, fluorine,
Iodine. Examples of the perfluoroalkyl group having 1 to 8 carbon atoms represented by R ²⁷ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group,
Examples include a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group (either linear or branched). Further, a carbon number of 1 to 8 represented by R ²⁷
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Examples thereof include an octyl group, a nonyl group, and a decyl group (which may be linear, branched, or cyclic ).

Specific examples of the preferred acid generator used in the present invention include, for example, 1-cyclohexylsulfonyl-1- (1,1-
Dimethylethylsulfonyl) diazomethane, bis (1,1-
Dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane,
1-diazo-1-cyclohexylsulfonyl-3,3-dimethylbutan-2-one, 1-diazo-1-methylsulfonyl-4-phenylbutan-2-one, 1-diazo-1- (1,1-dimethyl Ethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane and the like.

[0103]

[0104]

Further, as the compound represented by the general formula [6], for example, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (2,2,2-trifluoro) Ethanesulfonyloxy) benzene, 1,2,3-tris (2-chloroethanesulfonyloxy) benzene,
2,3-tris (p-trifluoromethylbenzenesulfonyloxy) benzene, 1,2,3-tris (p-nitrobenzenesulfonyloxy) benzene, 1,2,3-tris (2,3,4,5,6 -
Pentafluorobenzenesulfonyloxy) benzene,
1,2,3-tris (p-fluorobenzenesulfonyloxy)
Benzene, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,4-tris (p-trifluoromethyloxybenzenesulfonyloxy) benzene, 1,2,4-tris (2,
2,2-trifluoroethanesulfonyloxy) benzene,
1,3,5-tris (methanesulfonyloxy) benzene, 1,
3,5-tris (trifluoromethanesulfonyloxy) benzene, 1,3,5-tris (2,2,2-trifluoroethanesulfonyloxy) benzene, 1,3,5-tris (p-nitrobenzenesulfonyloxy) benzene , 1,3,5-tris (2,3,
4,5,6-pentafluorobenzenesulfonyloxy) benzene, 1,3,5-tris (p-fluorobenzenesulfonyloxy) benzene, 1,3,5-tris (2-chloroethanesulfonyloxy) benzene and the like Can be

Examples of the compound represented by the general formula [9] include, for example, 2,3,4-tris (methanesulfonyloxy)
Benzophenone, 2,3,4-tris (trifluoromethanesulfonyloxy) benzophenone, 2,3,4-tris (2-chloroethanesulfonyloxy) benzophenone, 2,3,4-
Tris (p-trifluoromethylbenzenesulfonyloxy) benzophenone, 2,3,4-tris (p-nitrobenzenesulfonyloxy) benzophenone, 2,3,4-tris (p-
Trifluoromethoxybenzenesulfonyloxy) benzophenone, 2,3,4-tris (p-fluorobenzenesulfonyloxy) acetophenone, 2,3,4-tris (2,3,4,5,
6-pentafluorobenzenesulfonyloxy) acetophenone, 2,3,4-tris (2-nitrobenzenesulfonyloxy) acetophenone, 2,3,4-tris (2,5-dichlorobenzenesulfonyloxy) acetophenone, 2,3, 4-tris (2,3,4-trichlorobenzenesulfonyloxy) acetophenone, 2,2 ', 4,4'-tetra (methanesulfonyloxy) benzophenone, 2,2', 4,4'-tetra (2,2 , 2-trifluoroethanesulfonyloxy) benzophenone, 2,
2 ', 4,4'-tetra (2-chloroethanesulfonyloxy) benzophenone, 2,2', 4,4'-tetra (2,5-dichlorobenzenesulfonyloxy) benzophenone, 2,2 ', 4, 4'-tetra (2,4,6-trimethylbenzenesulfonyloxy) benzophenone, 2,2 ', 4,4'-tetra (m-trifluoromethylbenzenesulfonyloxy) benzophenone and the like.

As the compound represented by the general formula [12], for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, diphenyl-p-tolylsulfonium perfluorooctanesulfonate,
Tris (p-tolyl) sulfonium perfluorooctanesulfonate, tris (p-chlorobenzene) sulfonium ・ trifluoromethanesulfonate, tris (p-tolyl) sulfonium ・ trifluoromethanesulfonate, dimethylphenylsulfonium ・ trifluoromethanesulfonate, dimethyltolylsulfonium ・Trifluoromethanesulfonate, dimethyltolylsulfonium / perfluorooctanesulfonate, triphenylsulfonium / p-toluenesulfonate, triphenylsulfonium / methanesulfonate, triphenylsulfonium / n-butanesulfonate, triphenylsulfonium / n-octanesulfonate, triphenylsulfonium・ 1-Naphthalenesulfonate, triphenylsulfonium ・ 2-Naphthalene Rufonate, triphenylsulfonium / 10-camphorsulfonate, triphenylsulfonium / 2,5-dichlorobenzenesulfonate,
Diphenyltolylsulfonium ・ 1,3,4-trichlorobenzenesulfonate, dimethyltolylsulfonium ・ p-toluenesulfonate, diphenyltolylsulfonium ・
Of course, 2,5-dichlorobenzenesulfonate and the like can be mentioned, but it goes without saying that it is not limited to these.

Preferred embodiments of the resist material of the present invention include a polymer represented by the general formula [1], an acid generator represented by the general formula [2], an acid generator represented by the general formula [6], 1 selected from the group consisting of an acid generator represented by the formula [9] and an acid generator represented by the general formula [12]
Combinations with more than one acid generator are included. As a preferable example when two or more acid generators are used in combination, the light transmittance around 248.4 nm is good, the high transparency of the resist material can be maintained, the PEB temperature dependency is small,
And one or more acid generators represented by the general formula [2], which generate a weak acid upon exposure, and an acid represented by the general formula [6], which has a high acid generation efficiency or a strong acid for a given exposure dose 1 selected from the group consisting of a generator, an acid generator represented by the general formula [9], and an acid generator represented by the general formula [12]
It is particularly preferable to use a combination of two or more kinds of acid generators in view of improving the shape of the bottom of the pattern and removing scum.

More preferably, a group consisting of at least one acid generator represented by the general formula [2], an acid generator represented by the general formula [9] and an acid generator represented by the general formula [12] A combination with one or more selected acid generators. Incidentally, one
One or more acid generators represented by the general formula [2] and constant exposure
The acid generation efficiency is high with respect to the amount or generates a strong acid.
The acid generator represented by the general formula [3] and the following general formula [5]
At least one member selected from the group consisting of acid generators represented by
It is also possible to use in combination with an acid generator. [Wherein, R ⁸ represents a hydrogen atom, a halogen atom, a carbon number of 1 to 5
A linear or branched alkyl group, a linear chain having 1 to 5 carbon atoms
Or branched alkoxy group or straight chain having 1 to 5 carbon atoms
A branched or branched haloalkyl group, wherein R ⁹ has 1 carbon atom
10 to 10 linear, branched or cyclic alkyl groups or carbons
A haloalkyl group of the formulas 1 to 10, or a general formula [4] 中 In the formula, R ¹⁰ is a hydrogen atom, a halogen atom, and has 1 to 1 carbon atoms.
5 straight-chain or branched alkyl groups having 1 to 5 carbon atoms
A chain or branched alkoxy group, or a straight chain having 1 to 5 carbon atoms
Represents a chain or branched haloalkyl group, wherein n is 0 or 1
Represents an integer of 1 to 3. Represents a group represented by｝. ] [Wherein, R ¹¹ is a hydrogen atom, a halogen atom, a carbon number of 1 to
5 linear or branched alkyl groups, aralkyl groups or
Represents a trifluoromethyl group, and R ¹² has 1 to 10 carbon atoms.
Linear, branched or cyclic alkyl group, aralkyl
A group, a linear or branched alkoxy group having 1 to 5 carbon atoms ,
Represents a phenyl group or a tolyl group. ] In the above general formula [3]
As the compound shown, for example, bis (p-toluenes)
Ruphonyl) diazomethane, methylsulfonyl-p-toluene
Ensulfonyldiazomethane, 1-diazo-1- (p-
Toluenesulfonyl) -3,3-dimethyl-2-butano
, Bis (p-chlorobenzenesulfonyl) diazometa
, Cyclohexylsulfonyl-p-toluenesulfoni
Rudiazomethane and the like. In addition, the above general formula
Examples of the compound represented by [5] include 1-p-toluene
Ensulfonyl-1-cyclohexylcarbonyldiazo
Methane, 1-diazo-1- (p-toluenesulfonyl)
-3,3-dimethylbutan-2-one, 1-diazo-1
-Benzenesulfonyl-3,3-dimethylbutane-2-
ON, 1-diazo-1- (p-toluenesulfonyl)-
3-methylbutan-2-one and the like.

When the acid generator represented by the general formula [12], which is extremely effective in terms of skirting and scum, is used alone, the pattern shape may be affected by the delay time. This problem can be overcome by using an overcoat film together. When the acid generator represented by the general formula [12] is used, dimensional fluctuation may occur. For example, the ratio of the monomer unit represented by the general formula [15] in the polymer represented by the general formula [1] may be used. Can be improved by increasing.

When two or more acid generators are used in combination, the composition ratio of the acid generator is such that the residual scum and the tail at the bottom of the pattern can be improved, and a stable pattern can be obtained without the problem of delay time. An acid generator represented by the general formula [6], an acid generator represented by the general formula [9] or a general formula represented by the general formula [9] with respect to 100 parts by weight of the acid generator represented by the general formula [2], which can maintain the shape and dimensions. The acid generator represented by [12] is used in an amount of 1 to 70 parts by weight, preferably 10 to 50 parts by weight.

As the acid generator other than the acid generator according to the present invention, various triphenylsulfonium salts and diphenyliodonium salts (the anions of these onium salts include PF ₆ ⁻ and AsF ₆ ^−). , BF ₄ ^-. etc.) and tris (trichloromethyl) if it -s- triazine / triethanolamine, and the like are known used alone it such as an acid generator for a chemically amplified resist material, Because the acid (Lewis acid) generated by exposure is a strong acid and is highly volatile, it is extremely susceptible to volatilization from the surface of the resist film after exposure and to the influence of an atmosphere such as an amine. As the time from exposure to development elapses, film formation by pattern formation (T-shape)
Occurs, the pattern formation size fluctuates greatly,
Or, there is a problem that a pattern cannot be formed at all, and further, there is a problem in storage stability such as a change in sensitivity during storage, and no pattern can be formed, which is not preferable.

As the solvent used in the present invention, any solvent can be used as long as it can dissolve the polymer and the acid generator and, if necessary, additives such as an ultraviolet absorber and a surfactant. Is usually good,
Those having no absorption around -400 nm are more preferably used. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, and 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidone, cyclohexanone, methyl ethyl ketone, 2-heptanone, 1,4-dioxane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, and the like, of course. It is not limited to these.

The resist material of the present invention generally comprises the above three components (the polymer according to the present invention, an acid generator and a solvent) as main components, and if necessary, these may be added with an ultraviolet absorber [eg 9- Diazofluorene and its derivatives, 1-diazo-2-tetralone, 2-diazo-1-tetralone, 9-diazo
Examples thereof include -10-phenanthrone, 9- (2-methoxyethoxy) methylanthracene, (2-ethoxyethoxy) methylanthracene, 9-anthracenemethyl acetate, and 9-anthracenemethyl propionate. ] Can of course be added. Furthermore, dyes and sensitivity modifiers usually used in this field [eg, polyvinyl pyridine,
Poly (vinylpyridine / methyl methacrylate), pyridine, piperidine, tetramethylammonium hydroxide, triethylamine, N-methyl-2-pyrrolidone and the like can be mentioned. And a plasticizer [for example, diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like]. ] Or a surfactant [for example, a nonionic surfactant, a fluorine-containing nonionic surfactant, and the like. It is also optional to appropriately add one or more of these from among them.

To form a pattern using the resist material according to the present invention, for example, the following may be performed. The resist material according to the present invention is applied on a semiconductor substrate such as a silicon wafer so as to have a thickness of about 0.5 to 2.0 μm (0.1 to 0.5 μm when used as an upper layer of three layers).
Prebaked in an oven at 70-130 ° C. for 10-30 minutes or on a hot plate at 70-130 ° C. for 1-2 minutes. Next, a mask for forming a target pattern is held over the resist film, for example, 300
After irradiating far ultraviolet light of nm or less so that the exposure amount becomes about 1 to 100 mJ / cm ² , the temperature is 70 to 150 ° C.
Bake for 2 minutes. Further, using a developing solution such as a 0.1 to 5% aqueous solution of tetramethylammonium hydroxide (TMAH), for about 0.5 to 3 minutes, dip method, puddle
If developed by a conventional method such as a spray method or a spray method,
A target pattern is formed on the substrate.

The mixing ratio of the polymer and the acid generator according to the present invention in the resist material is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer. Can be Further, the amount of the solvent in the resist material of the present invention is an amount that does not hinder the application of a positive resist material obtained as a result of dissolving the polymer and the acid generator according to the present invention onto a substrate. If not specifically limited, usually, 1 to 100 weight of the polymer
00-2000 weight, preferably 150-1000 weight.

The developing solution used in the above-described various pattern forming methods has an appropriate concentration so as to increase the difference in solubility between exposed and unexposed portions in accordance with the solubility of the resist material. May be selected, and is usually selected from the range of 0.01 to 20%. Examples of the alkaline aqueous solution used include organic amines such as TMAH, choline, and triethanolamine, for example, NaOH, KO
An aqueous solution containing an inorganic alkali such as H is exemplified.

The polymer according to the present invention has the functional group represented by the general formula [14] having the functional group represented by the general formula [13] as described above.
Due to comprising a monomer unit represented by
Compared to conventional polymers used for similar purposes, in the presence of an acid, it has a property of easily desorbing a functional group and easily becoming alkali-soluble, thus enabling high resolution performance, and It is possible to maintain a stable pattern size with respect to the elapse of time from exposure to heat treatment (baking). Also,
The polymer according to the present invention has heat resistance, has a dry etching system, and has excellent adhesion to a substrate, because it contains a hydroxystyrene unit represented by the general formula [16]. ing. Further, since the polymer according to the present invention contains the monomer unit represented by the general formula [15], the development speed of the exposed portion is suppressed to some extent, the focus margin is improved, and the mask linearity is improved. . At the same time, an effect of smoothing the pattern side wall also occurs. It also contributes to the improvement of the heat resistance of the polymer
But there is.

Among the monomer units represented by the general formula [15], those which are capable of removing a functional group in the presence of an acid and changing to a hydroxystyrene unit which is soluble in an alkali developing solution (for example, acetyloxy Group, methoxy group, tert-
Butoxy group, tetrahydrofuranyl group, tetrahydropyranyl group, tert-butoxycarbonyloxy group, t
tert-butoxycarbonylmethoxy group and the like. ) Is included, but in the present invention, the general formula [1]
3] formula that having a functional group represented by [14] is much faster towards the monomeric units represented by, the hydroxystyrene unit of functional groups by elimination under the action of readily acids.

Incidentally, Japanese Patent Application Laid-Open No. Hei 6-94842 (EPC Publication No. 0588544) reports an example of a polymer composed of three types of monomer units. However, this patent application relates to an electron beam resist. The purpose of the present invention is different from that of the present invention relating to a resist material for forming a positive pattern using ultraviolet light, particularly 300 nm or less deep ultraviolet light as an energy source. Therefore, even if a pattern is formed by ultraviolet rays, for example, KrF excimer laser light using the resist composition described in the above-mentioned patent application, the bottom (foot) of the pattern can be obtained.
Is insufficient or the scum is transferred during etching due to the occurrence of scum (residual melting during development), which is unusable.

The present invention provides a resist pattern using far ultraviolet light, KrF excimer laser light or the like by combining a polymer comprising three kinds of monomer units according to the present invention and a specific acid generator according to the present invention. It has solved various problems that have been a problem in the formation, and has made it possible to provide a resist material suitable for far ultraviolet light and KrF excimer laser light having various performances as described above. It has great features. Further, the resist material of the present invention has the effect of eliminating tails and scum at the bottom of the resist pattern when two or more acid generators according to the present invention are used in combination. This phenomenon is considered to be because an acid generator that generates a stronger acid or an acid generator that has a larger acid diffusion can uniformly remove the functional groups of the polymer to the bottom of the resist. From this viewpoint, the acid generator represented by the general formula [2], the acid generator represented by the general formula [3], and the acid generator represented by the general formula [9] as the acid generator in the resist composition of the present invention. The combination of the agent or the acid generator represented by the general formula [12] gives particularly good results.

The resist material of the present invention is made of far ultraviolet light, KrF
Although it is most suitable for pattern formation using ultraviolet light such as excimer laser light, it has been confirmed that an acid is generated even by i-ray exposure, electron beam or soft X-ray irradiation, and a chemical amplification action is caused. Therefore,
The resist material of the present invention is a resist material capable of forming a pattern by low-exposure deep ultraviolet light, KrF excimer laser light, i-ray light, electron beam, or soft X-ray irradiation utilizing chemical amplification.

[0123]

[Operation] The operation of the present invention will be described in a concrete example.
First, an acid is generated in a portion exposed to KrF excimer laser light, far ultraviolet light, or the like according to, for example, a photoreaction represented by the following Formula 1, Formula 3, Formula 4, or Formula 5.

[0124]

(Equation 1)

[0125]

[0126]

(Equation 3)

[0127]

(Equation 4)

[0128]

(Equation 5)

When a heat treatment is performed after the exposure step, the following formula 6 is obtained.
According to the reaction of the formula (1), a specific functional group of the polymer according to the present invention (in Formula 6, as an example of a 1-ethoxyethoxy group) undergoes a chemical change with an acid to become a hydroxyl group, becomes alkali-soluble, and becomes Eluted.

[0130]

(Equation 6)

On the other hand, since no acid is generated in the unexposed area, no chemical change occurs even when heat treatment is performed, and instead, the hydrophilic group site of the polymer used for the purpose of enhancing the adhesion to the substrate is replaced with an acid generator. An effect of protecting the developer from infiltration is exhibited. Thus, when a pattern is formed using the resist material of the present invention, a large difference in solubility in an alkali developing solution occurs between an exposed portion and an unexposed portion, and the polymer in the unexposed portion is formed on the substrate. On the other hand, since it has strong adhesion, it does not cause film peeling during development, and as a result, a positive pattern having good contrast is formed. Further, since the acid generated by the exposure acts as a catalyst as shown in the above formula 6, the exposure only needs to generate the necessary acid, and the amount of exposure energy can be reduced.

Hereinafter, the present invention will be described in more detail with reference to Examples, Production Examples, Reference Examples, and Comparative Examples. However, the present invention is not limited by these. Some of the acid generators used in Examples and Comparative Examples are described in, for example, JP-A-4-210960 (U.S. Pat. No. 5,216,135); and JP-A-4-211258 (US Pat. No. 5,350,660). Specification; EPC published patent No. 0,440,374);
No. 2 (EPC Publication No. 0,520,642); Y. Endo et al., Ch.
em. Pharm. Bull., 29 (12), 3753 (1981); M. Des
Bois et al., Bull. Chim. Soc. France, 1974 , 1956 or CDBeard et al., J. Org. Chem., 38 , 3673 (1973
Hashimoto et al., The Chemical Journal of Japan, 87 (10), 1069 (1966)
Year) and the like.

[0133]

【Example】

Production Example 1 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene) (1) 100 g (0.567 mol) of p-tert-butoxystyrene and p
2,4′-Azobis (methyl 2-methylpropionate) was added to 3.54 g (0.03 mol) of -methylstyrene, and a polymerization reaction was carried out in 1,4-dioxane under a nitrogen stream at 80 ° C. for 6 hours. After cooling, the reaction solution was poured into 5000 ml of an aqueous methanol solution to cause crystallization. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 92.3 g of poly (p-tert-butoxystyrene / p-methylstyrene) as white powder crystals. The composition ratio of p-tert-butoxystyrene unit and p-methylstyrene unit in the obtained polymer was about 95: 5 from ¹ HNMR measurement. Also, as a result of GPC measurement using polystyrene as a standard,
The weight average molecular weight was about 20000.

(2) 70 g of the poly (p-tert-butoxystyrene / p-methylstyrene) obtained in the above (1) was dissolved in 1,4-dioxane, 100 ml of concentrated hydrochloric acid was added, and the mixture was heated at 70 to 80 ° C. for 4 hours. The mixture was stirred and reacted. After cooling, the reaction solution was poured into 5000 ml of water for crystallization. The precipitated crystals are collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-
47.6 g of hydroxystyrene / p-methylstyrene) were obtained as white powdery crystals. The composition ratio of p-hydroxystyrene unit and p-methylstyrene unit in the obtained polymer is ¹ HNM
It was about 95: 5 from R measurement.

(3) 15.0 g of the poly (p-hydroxystyrene / p-methylstyrene) obtained in the above (2) and 3.5 g of ethyl vinyl ether were dissolved in 150 ml of 1,4-dioxane. Pyridinium toluenesulfonate was added, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction, 5000 ml of water
The crystals were poured into the solution, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 11.5 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene) as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit, and p-methylstyrene unit in the obtained polymer was about 35: 60: 5 from ¹ HNMR measurement. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

Production Example 2 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / styrene) (1) Using 81.1 g (0.46 mol) of p-tert-butoxystyrene and 4.6 g (0.04 mol) of styrene Polymerization reaction and post-treatment were carried out in the same manner as (1) of Production Example 1 to obtain 77.1 g of poly (p-tert-butoxystyrene / p-styrene) as white powdery crystals. The composition ratio of p-tert-butoxystyrene unit and styrene unit in the obtained polymer was about 92: 8 from ¹ HNMR measurement.
Met. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

(2) Using 70 g of the poly (p-tert-butoxystyrene / styrene) obtained in (1) above, (2) of Production Example 1
44.0 g of poly (p-hydroxystyrene / styrene) was obtained as white powdery crystals by the reaction and post-treatment in the same manner as in the above.
The composition ratio of p-hydroxystyrene unit and styrene unit in the obtained polymer was about 92: 8 from ¹ HNMR.

(3) 15.0 g of the poly (p-hydroxystyrene / styrene) obtained in the above (2) and vinyl ethyl ether 3.
Using 2 g, the reaction and post-treatment were conducted in the same manner as in Production Example 1 (3) to obtain 14.1 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / styrene) as white powdery crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and styrene unit in the obtained polymer was about 32: 60: 8 from ¹ HNMR measurement. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

Production Example 3 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) (1) 17.6 g of p-tert-butoxystyrene was added with a catalytic amount of 2,2′-
Addition of azobis (methyl 2-methylpropionate) is
The polymerization reaction was carried out in o-propanol at 80 ° C. for 6 hours under a nitrogen stream. After cooling, the reaction mixture was poured into 1000 ml of an aqueous methanol solution to cause crystallization. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain poly (p-tert-butoxystyrene).
6.7 g were obtained as white powder crystals. Weight average molecular weight about 2000
0 (GPC method: polystyrene standard).

(2) 15.0 g of the poly (p-tert-butoxystyrene) obtained in the above (1) was suspended in iso-propanol, 15 ml of concentrated hydrochloric acid was added, and the mixture was stirred and reacted at 70 to 80 ° C. for 4 hours. After cooling, the reaction solution was poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.6 g of poly (p-hydroxystyrene / p-tert-butoxystyrene) as white powder crystals. Was. The composition ratio of p-hydroxystyrene unit and p-tert-butoxystyrene unit in the obtained polymer was about 9: 1 from ¹ HNMR measurement.

(3) 15.7 g of poly (p-hydroxystyrene / p-tert-butoxystyrene) obtained in (2) and 3.2 g of ethyl vinyl ether were dissolved in 140 ml of 1,4-dioxane, and a catalytic amount of Pyridinium p-toluenesulfonate was added and reacted with stirring at room temperature for 24 hours. After the reaction, water
It was poured into 3000 ml, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) 16.0
g were obtained as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit and p-tert-butoxystyrene unit in the obtained polymer was ¹ HNM.
It was about 3: 6: 1 from the R measurement. Weight average molecular weight about 2000
0 (GPC method: polystyrene standard).

Production Example 4 Poly (p-1-methoxy-1-methylethoxystyrene / p-hydroxystyrene / p-tert-
Synthesis of butoxystyrene) The poly (p-hydroxystyrene / p-) obtained in Production Example 3 (2)
15.7 g of tert-butoxystyrene) and 3.2 g of 2-methoxy-1-propene were dissolved in 120 ml of tetrahydrofuran, a catalytic amount of phosphorus oxychloride was added thereto, and the mixture was stirred and reacted at room temperature for 16 hours. After the reaction, the reaction product was poured into 5000 ml of water and allowed to crystallize.
1-methylethoxystyrene / p-hydroxystyrene / p
-tert-butoxystyrene) 14.7 g was obtained as white powdery crystals. P-1-methoxy-1-methylethoxystyrene unit and p-hydroxystyrene unit of the obtained polymer and p-te
The composition ratio of rt-butoxystyrene unit was about 3: 6: 1 from ¹ HNMR measurement. Weight average molecular weight about 20000 (GPC
Method: polystyrene standard).

Production Example 5 Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene)
(1) 77.6 g (0.44 mol) of p-tert-butoxystyrene and p-tert-butoxystyrene
Production Example 1 using 8.1 g (0.06 mol) of methoxystyrene
The polymerization reaction and the post-treatment are carried out in the same manner as in (1) to obtain poly (p-tert-butoxystyrene / p-methoxystyrene) 7
7.1 g were obtained as white powder crystals. Pt of the obtained polymer
The composition ratio of ert-butoxystyrene unit to p-methoxystyrene unit was about 88:12 from ¹ HNMR measurement. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

(2) Using 68.5 g of the poly (p-tert-butoxystyrene / p-methoxystyrene) obtained in the above (1), the reaction and post-treatment were carried out in the same manner as in (2) of Production Example 1 to obtain the poly (p-tert-butoxystyrene / p-methoxystyrene). (P-
43.9 g of hydroxystyrene / p-methoxystyrene) were obtained as white powdery crystals. The composition ratio of p-hydroxystyrene unit and p-methoxystyrene unit in the obtained polymer is
It was about 88:12 from ¹ HNMR.

(3) Using 15.2 g of the poly (p-hydroxystyrene / p-methoxystyrene) obtained in the above (2) and 2.9 g of vinyl ethyl ether, the reaction and the reaction were carried out in the same manner as in (3) of Production Example 1. After treatment, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene) 1
4.4 g were obtained as white powder crystals. P-1 of the obtained polymer
The composition ratio of -ethoxystyrene unit, p-hydroxystyrene unit and p-methoxystyrene unit was about 30:58:12 from ¹ HNMR measurement. Weight average molecular weight about 20000 (GP
Method C: polystyrene standard).

Production Example 6 Poly (p-1-benzyloxy-1-)
Methylethoxystyrene / p-hydroxystyrene / p-te
Synthesis of (rt-butoxystyrene) (1) 15.0 g of the poly (p-tert-butoxystyrene) obtained in (1) of Production Example 3 was dissolved in 1,4-dioxane, and 20 ml of concentrated hydrochloric acid was added, followed by 70-80 ° C. For 4 hours with stirring. After cooling, the reaction solution was poured into 1000 ml of water and allowed to crystallize. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-hydroxystyrene / p-tert.
-Butoxystyrene) 9.4 g was obtained as white powdery crystals.
P-hydroxystyrene unit and p-tert of the obtained polymer
The composition ratio of -butoxystyrene unit was about 9 based on ¹ HNMR measurement.
5: 5.

(2) In the same manner as in Production Example 4, using 15.4 g of the poly (p-hydroxystyrene / p-tert-butoxystyrene) obtained in the above (1) and 5.9 g of 1-benzyloxy-1-propene. After the reaction and post-treatment, poly (p-1-benzyloxy-1-methylethoxystyrene / p-hydroxystyrene /
13.4 g of (p-tert-butoxystyrene) were obtained as white powdery crystals. The composition ratio of p-1-benzyloxystyrene unit, p-hydroxystyrene unit and p-tert-butoxystyrene unit in the obtained polymer was about 3: 6: 1 from ¹ HNMR measurement.
Met. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

Production Example 7 Synthesis of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-chlorostyrene) (1) 83.7 g (0.475 mol) of p-tert-butoxystyrene
Using 3.5 g (0.025 mol) of p-chlorostyrene, a polymerization reaction and post-treatment were carried out in the same manner as in (1) of Production Example 1 to obtain poly (p-chlorostyrene).
75.9 g of tert-butoxystyrene / p-chlorostyrene) were obtained as white powdery crystals. The composition ratio of p-tert-butoxystyrene unit and p-chlorostyrene unit in the obtained polymer was about 95: 5 by ¹ HNMR measurement. Weight average molecular weight approx.
22000 (GPC method: polystyrene standard).

(2) Using 61.0 g of the poly (p-tert-butoxystyrene / p-chlorostyrene) obtained in the above (1), the reaction and post-treatment were carried out in the same manner as in (2) of Production Example 1, and (P-
36.0 g of hydroxystyrene / p-chlorostyrene) were obtained as white powdery crystals. The composition ratio of p-hydroxystyrene unit and p-chlorostyrene unit in the obtained polymer is ¹ HNM
It was about 95: 5 from R measurement.

(3) Using 15.1 g of the poly (p-hydroxystyrene / p-chlorostyrene) obtained in the above (2) and 2.9 g of vinyl methyl ether, the reaction and the reaction were carried out in the same manner as in (3) of Production Example 1. After treatment, poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-chlorostyrene) 14.1
g were obtained as white powder crystals. The composition ratio of p-1-methoxyethoxystyrene unit, p-hydroxystyrene unit and p-chlorostyrene unit in the obtained polymer was about 35: 60: 5 from ¹ HNMR measurement. Weight average molecular weight about 22000 (G
PC method: polystyrene standard).

Production Example 8 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-acetyloxystyrene) (1) Using 32.4 g of p-acetyloxystyrene, the procedure of (1) of Production Example 3 was repeated. Polymerization reaction and post-treatment in the same manner
30.0 g of acetyloxy) styrene was obtained as white powdery crystals. Weight average molecular weight: about 15000 (GPC method: polystyrene standard).

(2) 13.8 g of the poly (p-acetyloxy) styrene obtained in the above (1) was dissolved in 1,4-dioxane, 5 ml of concentrated hydrochloric acid was added, and the mixture was stirred and reacted at 70 to 80 ° C. for 2 hours. Was.
After cooling, the reaction solution was poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.5 g of poly (p-hydroxystyrene / p-acetyloxystyrene) as white powder crystals. Was. The composition ratio of p-hydroxystyrene units and p-acetyloxystyrene units in the obtained polymer is ¹ H
It was about 9: 1 from NMR measurement.

(3) Using 9.5 g of the poly (p-hydroxystyrene / p-acetyloxystyrene) obtained in the above (2) and 2.2 g of ethyl vinyl ether, the reaction and the reaction were carried out in the same manner as in (3) of Production Example 3. The resulting crystals are collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-acetyloxystyrene).
9.9 g were obtained as white powder crystals. P-1 of the obtained polymer
The composition ratio of -ethoxyethoxystyrene unit to p-hydroxystyrene unit and p-acetyloxystyrene unit is
It was about 35:55:10 from ¹ HNMR measurement. Weight average molecular weight: about 17,500 (GPC method: polystyrene standard).

Production Example 9 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxystyrene) (1) Poly (p-acetyloxy) obtained in Production Example 8 (1) (Styrene) 16.2 g dissolved in 1,4-dioxane, concentrated hydrochloric acid 25m
and stirred for 4 hours under reflux. After cooling the reaction solution,
Inject into 1000 ml of water, crystallize, filter the precipitated crystals, wash with water,
After drying under reduced pressure, 11.4 g of poly (p-hydroxystyrene) was obtained as white powdery crystals.

(2) 10.8 g of the poly (p-hydroxystyrene) obtained in the above (1) was dissolved in 72 ml of 1,4-dioxane to give 2,3-dioxane.
1.5 g of dihydropyran and 0.05 g of p-toluenesulfonic acid / pyridine salt were added, and the mixture was stirred and reacted at 25 to 30 ° C. for 15 hours. The reaction solution was poured into 1000 ml of water and crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 10.0 g of poly (p-hydroxystyrene / p-tetrahydropyranyloxystyrene) as white powder crystals. The composition ratio of p-hydroxystyrene unit and p-tetrahydropyranyloxystyrene unit in the obtained polymer was about 92: 8 from ¹ HNMR measurement.

(3) Poly (p-hydroxystyrene / p-tetrahydropyranyloxystyrene) 9.5 obtained in (2) above
g of ethyl vinyl ether and 2.1 g of ethyl vinyl ether
The reaction and post-treatment were carried out in the same manner as in (3), and the resulting precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxy). 9.9 g of white powdery crystals were obtained. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and p-tetrahydropyranyloxystyrene unit in the obtained polymer was about 32: 60: 8 from ¹ HNMR measurement. Weight average molecular weight about 17000 (GP
Method C: polystyrene standard).

Production Example 10 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene) (1) Poly (p-tert) obtained in Production Example 3 (1) -Butoxystyrene) was suspended in iso-propanol, and concentrated hydrochloric acid was added to the suspension.
Then, the mixture was stirred and refluxed for 4 hours. After cooling the reaction solution,
Pour into 3000 ml of water, crystallize, filter the precipitated crystals, wash with water,
After drying under reduced pressure, 22.1 g of poly (p-hydroxystyrene) was obtained as white powdery crystals.

(2) 16.2 g of the poly (p-hydroxystyrene) obtained in the above (1) was dissolved in 60 ml of ethyl acetate, and 3.3 g of di-tert-butyl dicarbonate and 2.5 g of anhydrous potassium carbonate were added. The reaction was stirred at room temperature for 4 hours. After the reaction, ethyl acetate was distilled off under reduced pressure, the residue was dissolved in 80 ml of acetone, poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to obtain poly (p-hydroxystyrene / p- 12.1 g of tert-butoxycarbonyloxystyrene) were obtained as white powdery crystals. P-hydroxystyrene unit and pt of the obtained polymer
The composition ratio of the tert-butoxycarbonyloxystyrene unit was about 91: 9 from ¹ HNMR measurement.

(3) Poly (p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene) obtained in (2) above
Production Example 1 using 11.4 g and 2.5 g of ethyl vinyl ether
The reaction and post-treatment were carried out in the same manner as in (3) to obtain poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-te
rt-butoxycarbonyloxystyrene) 6.8 g was obtained as white powdery crystals. P-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit of the obtained polymer and p-
The composition ratio of the tert-butoxycarbonyloxystyrene unit was about 30: 61: 9 from ¹ HNMR measurement. Weight average molecular weight: about 21500 (GPC method: polystyrene standard).

Production Example 11 Synthesis of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate) (1) Poly (p-hydroxy) obtained in Production Example 10 (1) 16.2 g of styrene), 3.0 g of tert-butyl monochloroacetate and 2.8 g of anhydrous potassium carbonate are suspended in 200 ml of acetone.
The mixture was stirred and refluxed for 2 hours. After cooling, the insolubles were separated by filtration, and the filtrate was poured into 3000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to obtain poly (p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate). 15.8 g was obtained as white powdery crystals. The composition ratio of p-hydroxystyrene unit and tert-butyl p-vinylphenoxyacetate unit in the obtained polymer was about 9: 1 from ¹ HNMR measurement.

(2) Poly (p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate) obtained in (1) above 13.2
g of methyl vinyl ether and 2.0 g of methyl vinyl ether.
The reaction and post-treatment were carried out in the same manner as in (3) to obtain 10.6 g of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate) as white powder crystals. The composition ratio of p-1-methoxyethoxystyrene unit, p-hydroxystyrene unit and tert-butyl p-vinylphenoxyacetate unit of the obtained polymer is ¹ HNMR.
It was about 35:55:10 from the measurement. Weight average molecular weight about 210
00 (GPC method: polystyrene standard).

Production Example 12 Synthesis of 1,2,3-tris (trifluoromethanesulfonyloxy) benzene 1,2,3-benzenetriol 1.01 g (8.0
(1 mmol) was suspended in 60 ml of methylene chloride, 4.14 g (32.3 mmol) of γ-collidine was added, and 8.13 g of trifluoromethanesulfonic anhydride (28.
8 mmol) at -3 to 0 ° C. Then, after stirring and reacting at the same temperature for 6 hours, 50 ml of water and 50
ml, stirred and allowed to stand. Separate the organic layer,
50 ml of 5% aqueous sodium hydroxide solution, then 50 m of water
and washed with anhydrous magnesium sulfate. The drying agent was filtered off, the solvent was distilled off, and the residue was subjected to column chromatography separation (filler: Wakogel C-200; eluent: n-hexane / ethyl acetate = 1: 20 (V / V)), ,
1.82 g of 3-tris (trifluoromethanesulfonyloxy) benzene was obtained as white crystals. mp. 47.
5-48.5 ° C. ¹ H NMR δ ppm (CDCl ₃ ): 7.59 (3
H, aromatic hydrogen). IR (KBr tablet) νcm ^-1 : 3116,1137.

Production Example 13 Synthesis of 2,3,4-tris (trifluoromethanesulfonyloxy) acetophenone 1.68 g (10 mmol) of 2,3,4-trihydroxyacetophenone and 9.88 of trifluoromethanesulfonic anhydride
g (35 mmol) was reacted and worked up in the same manner as in Production Example 12, and the resulting crude yellow oil (5.3 g) was separated by column chromatography [filler: Wakogel C-20].
0; eluent: n-hexane / methylene chloride = 2/1]
2.77 g of 4-tris (trifluoromethanesulfonyloxy) acetophenone was obtained as white crystals. mp. 74.8
~ 76.4 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.68 (3H, s, C H 3), 7.67 (1
H, d, J = 8.8Hz), 7.89 (1H, d, J = 8.8Hz). IR (KBr tablet) νcm ^-1 : 3403,3108,2937,1715,1607,1364
_{(SO 2), 1123 (SO} 2).

Production Example 14 Synthesis of 2,2 ', 4,4'-tetra (trifluoromethanesulfonyloxy) benzophenone 2,2', 4,4'-tetrahydroxybenzophenone 2.46 g (1
0 mmol) and trifluoromethanesulfonic anhydride 1
The reaction and post-treatment were carried out in the same manner as in Production Example 12 using 3.3 g (47 mmol), and the resulting crude yellow oil (7.7 g) was obtained.
g) by column chromatography [filler: Wakogel C-200; eluent: n-hexane / methylene chloride = 7/3 (V /
V)] to give 2.1 g of 2,2 ', 4,4'-tetra (trifluoromethanesulfonyloxy) benzophenone as pale yellow crystals. mp. 94.0-96.0 ° C. _{^{1 HNMR δppm (CDCl 3):}} 7.35 (2H, d, J = 2.20Hz, aromatic hydrogen), 7.51 (2H, dd, J = 2.20Hz and J = 8.43 Hz, aromatic hydrogen), 7.88 (2H, d , J = 8.43Hz, aromatic ring hydrogen). IR (KBr tablet) νcm ⁻¹ : 3091,1683,1609,1138 (SO ₂ ).

Production Example 15 Synthesis of 1,2,3-tris (2,2,2-trifluoroethanesulfonyloxy) benzene 1.30 g (18 mmol) of 1,2,3-benzenetriol was added to methylene chloride (80 ml). Suspend and triethylamine 6.5
After injection of 3 g (64.5 mmol), 11.65 g (64 mmol) of 2,2,2-trifluoroethanesulfonyl chloride
Was added dropwise at -5 to 0 ° C. The mixture was stirred and reacted at the same temperature for 2 hours and left at room temperature overnight. The reaction solution was poured into 120 ml of cold water, extracted with methylene chloride (80 ml), and the organic layer was washed once with a saturated aqueous solution of sodium hydrogen carbonate (80 ml) and then with water (80 ml).
ml) and dried over anhydrous magnesium sulfate. The drying agent was filtered off, the solvent was distilled off, and the residual oily substance (8.3
g) by column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / ethyl acetate = 8/1 (V / V)]. The crystals were recrystallized from an n-hexane / methylene chloride mixture [2/1 (V / V)].
1.2 g of 1,2,3-tris (2,2,2-trifluoroethanesulfonyloxy) benzene was obtained as white flaky crystals. mp.
73.5-75.0 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 5.23 to 5.50 (6H, m, CH ₂ ×
3), 7.65-7.76 (3H, m, aromatic ring hydrogen). IR (KBr tablet) νcm ^-1 : 3022, 2968, 1334 (SO ₂ ), 1156 (S
O ₂ ).

Production Example 16 Synthesis of 2,3,4-tris (2,5-dichlorobenzenesulfonyloxy) acetophenone 1.18 g (7 mmol) of 2,3,4-trihydroxyacetophenone and 2.02 g (20 mmol) of triethylamine Was dissolved in methylene chloride (20 ml), cooled to 0 ° C, and a solution of 4.90 g (20 mmol) of 2,5-dichlorobenzenesulfonyl chloride in 10 ml of methylene chloride was added dropwise at 0 to 2 ° C. Then, the mixture was stirred and reacted at the same temperature for 1 hour, poured into ice water (100 ml), and extracted with methylene chloride (100 ml × 2).
The organic layer was washed with water (100 ml × 2) and dried over anhydrous magnesium sulfate. The drying agent was filtered off, the filtrate was concentrated, and 7.3 g of the residue was recrystallized from methanol to give 2,3,4-tris (2,5
-Dichlorobenzenesulfonyloxy) acetophenone
3.0 g were obtained as white crystals. mp. 165.0-166.5 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 3.43 (3H, s, CH ₃ CO), 7.46
(1H, d, J = 9 Hz, aromatic ring hydrogen), 7.64 (1H, d, J = 8 Hz, aromatic ring hydrogen), 7.79 to 7.98 (9H, m, aromatic ring hydrogen). IR (KBr tablet) νcm ^-1 : 1730 (C = O), 1190 (SO ₂ ).

Production Example 17 Synthesis of diphenyl-p-tolylsulfonium perfluorooctanesulfonate 2.02 g (10 mmol) of diphenyl sulfoxide was dissolved in toluene (30 ml), and 4.2 g (20 mmol) of trifluoroacetic anhydride was obtained at 10 ° C. or lower. ), And 5.0 g (10 mmol) of perfluorooctanesulfonic acid was injected into the mixture. The mixture was further stirred and reacted at 10 ° C. or lower for 1 hour and at room temperature for 2 hours.
After washing twice with 30 ml and then three times with 30 ml of n-hexane, 7.4 g of diphenyl-p-tolylsulfonium perfluorooctanesulfonate was obtained as a yellow viscous oil. _{^{1 HNMR δppm (CDCl 3):}} 2.44 (3H, s, C H 3), 7.46 (2H,
d, J = 8 Hz, aromatic ring hydrogen, 7.60 (2H, d, J = 8 Hz, aromatic ring hydrogen), 7.65 to 7.73 (10 H, m, aromatic ring hydrogen).

Production Example 18 Triphenylsulfonium
Synthesis of p-toluenesulfonate (1) 12 g of metallic magnesium was suspended in 500 ml of ethyl ether, and 83.5 g (0.54 mol) of benzene bromide was added dropwise with stirring under reflux, and the mixture was refluxed with stirring for 1 hour. Next, 500 ml of benzene was injected into the Grignard reagent, and the mixture was concentrated to 500 ml. A solution of 30 g (0.15 mol) of diphenylsulfoxide in 200 ml of benzene was poured into the residue, and the mixture was refluxed with stirring for 40 hours. After the mixture was cooled to 0 ° C, 50 ml of 40% borofluoric acid was added dropwise at 0 to 5 ° C, and the mixture was stirred and reacted at the same temperature for 5 hours. After standing at room temperature overnight, the separated aqueous layer was extracted with methylene chloride (100 ml ×
3) Then, the organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. Then, the crude crystals of the residue were recrystallized from a mixed solution of chloroform / ethyl ether to obtain 28 g of triphenylsulfonium borofluoride as white crystals. mp.
291-292 ° C.

(2) 1.0 g (3 mmol) of triphenylsulfonium borofluoride obtained in the above (1) was added to ethanol 180
Dissolve it in ml and add sodium p-toluenesulfonate
A solution of 0.58 g (3 mmol) in water (20 ml) was poured under vigorous stirring at room temperature and stirred at room temperature for 2 hours. After standing at room temperature overnight, the precipitate was separated by filtration, the filtrate was concentrated under reduced pressure, and the residue was recrystallized from a mixed solution of methanol / ethyl ether to obtain 1.15 g of triphenylsulfonium / p-toluenesulfonate as white needles. mp. 100-102 ° C.

Production Example 19 Triphenylsulfonium
Synthesis of 10-camphorsulfonate 1.0 g (3 mmol) of triphenylsulfonium borofluoride obtained in Production Example 18 (1) was dissolved in acetone (50 ml), and 0.80 g of potassium 10-camphorsulfonate was added thereto.
A solution of (3 mmol) in water (10 ml) was poured under vigorous stirring at room temperature and stirred for 1 hour at room temperature. After leaving overnight at room temperature,
The precipitate was separated by filtration, the filtrate was concentrated under reduced pressure, and the residue was recrystallized from methanol / ethyl ether to obtain 1.20 g of triphenylsulfonium / 10-camphorsulfonate as white needles. mp. 66 ° C (decomposition).

Reference Example 1 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) (1) A catalytic amount of 2,2 ′ was added to 17.6 g of p-tert-butoxystyrene.
-Azobisisobutyronitrile was added, and a polymerization reaction was carried out in toluene at 80 ° C for 6 hours in a nitrogen stream. After cooling, the reaction solution was poured into 1000 ml of methanol and allowed to crystallize. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain poly (p-te
(rt-butoxystyrene) 16.8 g was obtained as white powdery crystals. Weight average molecular weight: about 10,000 (GPC method: polystyrene standard).

(2) 15.0 g of the poly (p-tert-butoxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane, and concentrated hydrochloric acid was added.
10 ml was added and the mixture was stirred and refluxed for 4 hours. After cooling, the reaction solution was poured into 1000 ml of water to cause crystallization, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.7 g of poly (p-hydroxystyrene).
Was obtained as white powdery crystals.

(3) 4.0 g of the poly (p-hydroxystyrene) obtained in the above (2) and 1.2 g of ethyl vinyl ether were mixed with 1,4-
The mixture was dissolved in 35 ml of a mixture of dioxane and pyridine, a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction, the reaction mixture was poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 5.0 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene).
Was obtained as white powdery crystals. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 4: 6 from ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

Reference Example 2 Synthesis of poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene) Poly (p-hydroxystyrene) obtained in (2) of Reference Example 1
9.0 g is dissolved in 100 ml of 1,2-dimethoxyethane, and then
12.6 g of 2,3-dihydropyran and 0.5 ml of sulfuric acid were added and 30 to 4
Stirred at 0 ° C. for 15 hours. After the reaction, the reaction solution was concentrated under reduced pressure,
Neutralize the residue with sodium carbonate, pour into 1000 ml of water,
After crystallization, the precipitated crystals are collected by filtration, washed with water, and dried under reduced pressure to give poly (p-
11.0 g of tetrahydropyranyloxystyrene / p-hydroxystyrene) was obtained as white powdery crystals. P-tetrahydropyranyloxystyrene unit of the obtained polymer and
The composition ratio of the p-hydroxystyrene unit was about 3: 7 from ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC
Method: polystyrene standard).

Reference Example 3 Synthesis of poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) (1) p-tert-butoxycarbonyl obtained according to the method described in US Pat. No. 4,491,628 (1985) Using oxystyrene (22 g, 0.1 mol), 2,2'-azobis (2,4-
The polymerization reaction was carried out at 90 ° C. for 4 hours under a nitrogen stream in toluene in the presence of a catalyst (dimethylvaleronitrile). After cooling, the reaction solution was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.2 g of poly (p-tert-butoxycarbonyloxystyrene) as white powder crystals. Weight average molecular weight: about 12000 (GPC method: polystyrene standard).

(2) 7.0 g of the poly (p-tert-butoxycarbonyloxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane, 5 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 2 hours. After cooling, the reaction solution was poured into 1000 ml of water and allowed to crystallize,
The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 4.8 g of poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) as white powder crystals. P-tert-butoxycarbonyloxystyrene unit of the obtained polymer and p-
The composition ratio of the hydroxystyrene unit was about 4: 6 from ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC method:
Polystyrene standard).

Reference Example 4 Synthesis of poly (p-tert-butoxystyrene / p-hydroxystyrene) 15.0 g of the poly (p-tert-butoxystyrene) obtained in (1) of Reference Example 1 was added to 1,4-dioxane. The mixture was dissolved, 10 ml of concentrated hydrochloric acid was added, and the mixture was stirred and reacted at 80 to 85 ° C for 3 hours. After cooling, the reaction solution was poured into water and crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.8 g of poly (p-tert-butoxystyrene / p-hydroxystyrene) as white powder crystals. The composition ratio of p-tert-butoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 35:65 from ¹ HNMR measurement. Weight average molecular weight: about 9000 (GPC method: polystyrene standard).

Reference Example 5 Synthesis of 9-diazo-10-phenanthrone 2.08 g (20 mmol) of 9,10-phenanthrenequinone and
1.80 g (19 mmol) of p-toluenesulfonyl hydrazide was suspended in 20 ml of ethanol, and the mixture was stirred and refluxed for 10 minutes. After cooling, the precipitated crystals were collected by filtration, and the obtained crude crystals were recrystallized from cyclohexane / petroleum ether to give 9-diazo-10-
1.1 g of phenanthrone was obtained as yellow needles. mp.1
07-109 ° C. IR (KBr tablet) νcm ^-1 : 2106 (CN ₂ ), 1615 (C = O).

Reference Example 6 Synthesis of 1-diazo-2-tetralone 20.0 g (0.29 mol) of sodium ethoxide was dissolved in 600 ml of ethanol, and 42.4 g (0.2%) of 2-tetralone was added thereto.
9 mol) in ethanol (100 ml) was added dropwise at 0 ° C, and then at -15 ° C or lower, 59.2 g of p-toluenesulfonyl azide was added.
(0.3 mol) was added dropwise, and the mixture was stirred and reacted at -10 to 0 ° C for 3 hours. The reaction solution was poured into 1000 ml of water, extracted with methylene chloride (500 ml × 2), and the organic layer was washed with water (500 ml × 3).
It was dried over anhydrous magnesium sulfate. The drying agent was separated by filtration, and 72 g of a residual oil obtained by distilling off the solvent was subjected to column separation [filler: Wakogel C-200; eluent: n-hexane → methylene chloride / n-hexane (1/1)]. Then, recrystallization from n-hexane gave 6.0 g of 1-diazo-2-tetralone as yellow crystals. mp. 42.5-44.2 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 2.66 (2H, t, J = 7 Hz), 3.02
(2H, t, J = 7Hz), 6.98 (1H, d, J = 8Hz), 7.10 (1H,
t, J = 8Hz), 7.21 to 7.29 (2H, m). IR (Neat) νcm ^-1 : 2080 (CN ₂ ).

Reference Example 7 Synthesis of 2-diazo-1-tetralone (1) 4.4 g (30 mmol) of α-tetralone was added to ethanol
It was dissolved in 30 ml, cooled to 10 ° C., added with 4.5 g (36 mmol) of 90% potassium tert-butoxide, and then stirred at the same temperature for 30 minutes. Next, 3.5 g (30 mmol) of isoamyl nitrite was added dropwise at 10 ° C., and the mixture was stirred and reacted at the same temperature for 5 hours. The reaction solution was poured into water, neutralized with concentrated hydrochloric acid, extracted with methylene chloride, and the organic layer was separated and concentrated to obtain a dark brown oily substance 6.7.
g was crystallized from n-hexane, and the precipitated crystals were collected by filtration and dried to obtain 2.3 g of 2-oxyimino-1-tetralone as dark brown crystals. ¹ HNMR δ ppm (CDCl ₃ ): 3.07 (2H, t, J = 6 Hz), 3.18 (2
H, t, J = 6Hz), 7.30 (1H, d, J = 8Hz), 7.38 (1H, t, J = 8H)
z), 7.54 (1H, t, J = 8Hz), 8.12 (1H, d, J = 8Hz).

(2) 1.2 g (7 mmol) of 2-oximino-1-tetralone obtained in the above (1) and sodium hydroxide
0.4 g (10 mmol) is suspended in 10 ml of water.
After injecting 4 ml of 25% ammonia water, add 10 ml of hypochlorous acid to 10 ml.
The mixture was added dropwise at a temperature of 10 ° C. or less, and the mixture was stirred and reacted at 10 ° C. for 1 hour. After the reaction, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.90 g of crude crystals.
Next, the crude crystals were dissolved in methylene chloride, and after activated carbon treatment,
After concentration, the residue was crystallized from n-hexane, collected by filtration and dried to give 0.55 g of 2-diazo-1-tetralone as yellow crystals. mp. 50.0-52.0 ° C. _{^{1 HNMR δppm (CDCl 3):}} 3.01 (4H, m), 7.21 (1H, d, J = 7
Hz), 7.36 (1H, t, J = 7Hz), 7.42 (1H, t, J = 7Hz), 8.01
(1H, d, J = 8Hz). IR (KBr tablet) νcm ^-1 : 2073 (CN ₂ ), 1629 (C = O).

Reference Example 8 Synthesis of 9-diazofluorene (1) 3.7 g (20 mmol) of p-toluenesulfonylhydrazide was suspended in ethanol (60 ml), and 9-fluorenone was added.
3.6 g (20 mmol) was added, and the mixture was stirred and refluxed for 6 hours.
After cooling, the precipitated crystals were collected by filtration and dried to obtain 5.4 g of 9-fluorenone p-toluenesulfonylhydrazide as slightly yellow needles. mp. 173-174 ° C. IR (KBr tablet) νcm ^-1 : 3212, 3065, 1909, 1597, 1453,
1407, 1337, 1315.

(2) 1.7 g (5 mmol) of 9-fluorenone p-toluenesulfonylhydrazide and 0.3 g (5 mmol) of sodium ethoxide obtained in the above (1) were added to pyridine.
The suspension was suspended in 20 ml and stirred and reacted at 60 to 65 ° C. for 6 hours.
The reaction solution was poured into 100 ml of ice water and extracted with methylene chloride. The organic layer was separated and concentrated, and the brown oil obtained was separated by column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: ethyl acetate / n-hexane = 1 / 10] to give 0.6 g of 9-diazofluorene as orange-yellow needles. mp. 98.5-99.5C. _{^{1 HNMR δppm (CDCl 3):}} 7.32 (2H, t, J = 8Hz), 7.39 (2
H, t, J = 8Hz), 7.51 (2H, d, J = 8Hz), 7.94 (2H, d, J = 8H)
z). IR (KBr tablet) νcm ^-1 : 2087 (CN ₂ ).

Reference Example 9 Synthesis of 9- (2-methoxyethoxy) methylanthracene 1000 ml of 2-methoxyethanol was dissolved in 1500 ml of benzene, 3 ml of concentrated sulfuric acid was injected, and the mixture was heated to 80 ° C.
Then, 9-anthracene methanol 45 g (0.22 mol) of 2
-Methoxyethanol (450ml) solution was injected under reflux,
The mixture was stirred and refluxed for 1.5 hours. After standing at room temperature overnight, the extract was washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and the solvent was distilled off. 63 g of a crude oily residue was separated by column chromatography [filler: Wakogel C-gel]. 200; eluent: n-hexane / ethyl acetate = 50
/ 1 → 25/1 → 8/1 (V / V)] to give 47.6 g of 9- (2-methoxyethoxy) methylanthracene as an orange-yellow oil. ¹ H NMR δ ppm (CDCl ₃ ): 3.37 (3H, s, CH ₃ O—), 3.53 to
_{3.57 (2H, t, CH 3} OC H 2 O -), 3.73~3.77 (2H, t, CH 3 O-
_{CH 2 C H 2 O -)} , 5.55 (2H, s, ArC H 2 O-), 7.43~7.56
(4H, m, aromatic ring 2-H, 3-H, 6-H, 7-H), 7.99 (2H, d, J = 9H
z, aromatic ring 4-H, 5-H), 8.42 (2H, d, J = 9 Hz, aromatic ring 1-H, 8
-H), 8.44 (1H, s, aromatic ring 10-H). IR (Neat) νcm ^-1 : 1130.

Reference Example 10 Synthesis of poly (tert-butyl p-vinylphenoxyacetate / p-hydroxystyrene) 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Reference Example 1 and tert-monochloroacetic acid were used. 3.0 g of butyl and 2.8 g of anhydrous potassium carbonate are suspended in 35 ml of acetone,
The mixture was stirred and refluxed for 2 hours. After cooling, the insolubles were separated by filtration, and the filtrate was poured into 1000 ml of water and crystallized. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to obtain poly (p-vinylphenoxyacetic acid tert.
-Butyl / p-hydroxystyrene) in an amount of 5.2 g as white powdery crystals. P-phenoxyacetic acid ter of the obtained polymer
The composition ratio of t-butyl unit and p-hydroxystyrene unit is
It was about 1: 1 from ¹ HNMR measurement. Weight average molecular weight about 11
000 (GPC method: polystyrene standard).

Reference Example 11 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) (1) 28.2 g (0.16 mol) of p-tert-butoxystyrene and 3.1 g (0.04 mol) of fumaronitrile as a catalyst A polymerization reaction was carried out in a toluene solvent at 90 ° C. for 2 hours in a nitrogen stream in the presence of 2,2′-azobis (methyl 2-methylpropionate).
After the reaction, the reaction solution was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, washed and dried to obtain 21.3 g of poly (p-tert-butoxystyrene / fumaronitrile) as white powder crystals.

(2) Using 20.0 g of the poly (p-tert-butoxystyrene / fumaronitrile) obtained in the above (1), the reaction and post-treatment were carried out in the same manner as in (2) of Reference Example 1 to obtain poly (p-tert-butoxystyrene / fumaronitrile). -
10.6 g of hydroxystyrene / fumaronitrile) was obtained as white powdery crystals. Weight average molecular weight about 10,000 (GPC
Method: polystyrene standard).

(3) Using 9.0 g of the poly (p-hydroxystyrene / fumaronitrile) obtained in the above (2) and 3.0 g of ethyl vinyl ether, the reaction and post-treatment were carried out in the same manner as (3) of Reference Example 1. 8.8 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) was obtained as white powdery crystals. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 4: 6 from ¹ HNMR measurement. Weight average molecular weight: about 11000 (GPC method: polystyrene standard).

Reference Example 12 Synthesis of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene) Using 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Reference Example 1 and 4.0 g of methyl vinyl ether, The reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 1 to obtain 5.3 g of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene) as white powdery crystals. The composition ratio of p-1-methoxyethoxystyrene units and p-hydroxystyrene units in the obtained polymer was about 92: 8 from ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

Reference Example 13 N-trifluoromethanesulfonyloxy-bicyclo [2,2,1] -hept-5-ene-2,3
Synthesis of -dicarboximide A solution of 6.5 g (23 mmol) of trifluoromethanesulfonic anhydride in methylene chloride (20 ml) was cooled to 0 ° C, and N-hydroxy-bicyclo [2,2,1] -hept-5 was added thereto. A solution of 3.6 g (20 mmol) of -ene-2,3-dicarboximide and 1.6 g of pyridine in methylene chloride (10 ml) was added dropwise at 0 to 5 ° C. After stirring at the same temperature for 15 minutes, the reaction solution was washed with water (20 ml × 3), dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was recrystallized from ethanol to give N-trifluoromethanesulfonyloxy-bicyclo [ 6.1 g of [2,2,1] -hept-5-ene-2,3-dicarboximide were obtained as white needles. mp. 89-90 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.52 (1H, d, J = 9Hz), 1.79 (1
H, d, J = 9Hz), 3.36 (2H, s), 3.48 (2H, s), 6.16 (2H,
s). IR (KBr tablet) νcm ^-1 : 1757 (C = 0), 1159 (SO ₂ ).

Reference Example 14 Synthesis of dimethylphenylsulfonium trifluoromethanesulfonate 2.48 g (20 mmol) of thioanisole was dissolved in methylene chloride (20 ml), and 3.28 g (20 ml) of methyl trifluoromethanesulfonate was added at 10 ° C or lower. (Mmol) was added dropwise, and the mixture was stirred and refluxed for 2 hours. After cooling, the reaction solution was poured into n-hexane (75 ml), and the precipitated crystals were collected by filtration, washed with n-hexane, and dried to obtain 5.35 g of crude crystals. Then, the crude crystals were recrystallized from iso-propanol to obtain 4.8 g of dimethylphenylsulfonium trifluoromethanesulfonate as white flaky crystals. mp.
106.0-107.2 ° C. ¹ HNMR δ ppm (C
_{DCl 3): 3.00 (6H,} s, C H 3 × 2), 7.
32 (2H, t, J = 7 Hz), 7.42 (1H, t,
J = 7 Hz), 7.68 (2H, d, J = 7 Hz). IR (KBr tablet) vcm ^-1 : 3023,2947,1
451, 1426, 1254, 1228, 1154. Reference Example 15 Poly (p-tert-butoxystyrene /
p-hydroxystyrene / tert-butoxycarboni
Polyoxystyrene) obtained in (2) of Production Example 3
(P-hydroxystyrene / p-tert-butoxys
(Tylene) 17.0 g dissolved in ethyl acetate 60 ml,
8.3 g of di-tert-butyl dicarbonate and anhydrous potassium carbonate
6.3 g was added, and the mixture was stirred and reacted for 4 hours. After the reaction,
Ethyl acetate was distilled off under reduced pressure, and the residue was dissolved in 80 ml of acetone.
The solution is poured into 1000 ml of water and allowed to crystallize.
After filtration, washing with water and drying under reduced pressure, poly (p-tert-butoki)
Styrene / p-hydroxystyrene / p-tert-
17.3 g of butoxycarbonyloxystyrene) in white
Obtained as powder crystals. P-tert- of the obtained polymer
Butoxystyrene unit and p-hydroxystyrene unit
And p-tert-butoxycarbonyloxystyrene
The composition ratio of the unit is about 10: 65: 2 from ¹ HNMR measurement.
It was 5. Weight average molecular weight of about 21500 (GPC method:
Polystyrene standard).

Example 1 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) [Polymer of Production Example 3] 5.0 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Propylene glycol monomethyl ether acetate 19.7 g

The above resist material was spin-coated on each of three substrates (silicon wafers) and prebaked on a hot plate at 90 ° C. for 90 seconds to obtain a resist material film having a thickness of 1.0 μm. Then use a contact exposure machine (selectively pass only light around 250 nm using a band-pass filter) for 30 minutes.
After exposing the entire surface of the wafer for seconds, 60 seconds and 90 seconds,
Post-baking was performed on a hot plate at 100 ° C. for 90 seconds. Next, as a result of ¹ HNMR measurement of the polymer of each exposed resist material, all were p-hydroxystyrene units and p-tert-
The copolymer was a copolymer having a butoxystyrene unit composition ratio of about 9: 1, and no p-1-ethoxyethoxystyrene unit was detected at all. Therefore, it was confirmed that only the 1-ethoxyethyl group was selectively eliminated by undergoing a chemical amplification action in the presence of an acid generated by exposure, and the p-tert-butyl group was not chemically amplified at all.

Example 2 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / styrene) [Polymer of Production Example 2] 5.0 g Bis (1,1-dimethylethylsulfonyl) diazomethane 0.3 g Propylene glycol monomethyl ether acetate 14.7 g

A pattern forming method using the above resist material will be described with reference to FIG. The resist material 2 was spin-coated on a semiconductor substrate 1 and the like, and prebaked on a hot plate at 90 ° C. for 90 seconds to obtain a resist material film having a thickness of 1.0 μm (FIG. 1A). Next, 248.4 nm KrF excimer laser (NA 0.50) light 3 was selectively exposed through a mask 4 (FIG. 1b). Then, after post-baking on a hot plate at 100 ° C. for 90 seconds, development is performed for 60 seconds with an alkaline developing solution (2.38% tetramethylammonium hydroxide aqueous solution) to dissolve and remove only the exposed portions of the resist material, thereby forming the positive pattern 2a. (FIG. 1c). The obtained positive pattern has a rectangular 0.22 μm line and space resolution, and the exposure amount at this time is about 18
mJ / cm ² .

The change in pattern size with time from exposure to heat treatment (post-bake) was measured using this resist material. Even after 8 hours, a 0.22 μm line and space could be resolved without any problem. Was.

When the present resist material is used, FIG.
As shown in the figure, the mask linearity was good up to 0.25 μm. Further, when exposure was performed with defocus, the shape was not deteriorated to ± 0.8 μm with respect to the 0.30 μm line and space, and a sufficient focus margin was obtained. The pattern side wall was also smooth, and no scum was observed.

Further, after preparing this resist material and storing it at 23 ° C. for one month, a pattern was formed in the same manner as described above. As a result, a 0.22 μm line and space positive pattern was resolved at the same exposure dose, and the storage stability was improved. The properties were good.

Examples 3 to 16 Photoresist materials having the compositions shown in Tables 1 to 4 below were prepared.

[0200]

[Table 1]

[0201]

[Table 2]

[0202]

[Table 3]

[0203]

[Table 4]

Using each of the resist materials prepared above, a pattern was formed in the same manner as in Example 2. Table 5 shows the results.

[0205]

[Table 5]

As is clear from Table 5, in any of Examples 3 to 16, a positive pattern was formed in the same manner as in Example 2, and exposure and heat treatment (post-baking) were performed in the same manner as in Example 2. Even after 8 hours, 0.22 to 0.24 μm line and space could be resolved without any problem. 0.30μ
A focus margin of ± 0.8 μm or more with respect to m lines and spaces was obtained. Also, the mask linearity was good up to 0.25 μm. Further, any of the resist materials of Examples 3 to 16 had no problem in storage stability.

Example 17 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) 5.0 g bis (cyclohexylsulfonyl) diazomethane 0.3 g 1,2,3-tris (trifluoromethanesulfonyloxy) benzene [Production Example 12] Acid generator] 0.03 g propylene glycol monomethyl ether acetate 19.67 g

Using the above resist material, a pattern was formed in the same manner as in Example 2. The obtained pattern had a rectangular shape of 0.22 μm line and space resolution, and the exposure amount at this time was about 14 mJ / cm ² .

[0209] The change in pattern dimension with respect to the elapse of time from exposure to heat treatment (post-bake) was measured using this resist material.
And space was resolved without any problems.

When the present resist material was used, the mask linearity was good up to 0.25 μm. Further, when exposure was performed with defocus, a sufficient focus margin was obtained without shape deterioration up to ± 0.8 μm with respect to 0.30 μm line and space.

The pattern of the present resist material has smooth side walls. Further, since sufficient acid was supplied to the bottom of the resist, no tail or scum at the bottom of the pattern was observed at all, as shown in FIG. Further, after preparing this resist material and storing it at 23 ° C. for one month, a pattern was formed in the same manner as above. As a result, a positive pattern of 0.22 μm line and space was resolved at the same exposure dose, and the storage stability was good. Met.

Examples 18 to 29 Photoresist materials having the compositions shown in Tables 6 to 9 below were prepared, respectively.

[0213]

[Table 6]

[0214]

[Table 7]

[0215]

[Table 8]

[0216]

[Table 9]

Using each of the resist materials prepared above, a pattern was formed in the same manner as in Example 2. Table 10 shows the results.

[0218]

[Table 10]

As is clear from Table 10, Examples 18 to 2
9 in any of the embodiments 9 to 0.22 to 0.2 even after 8 hours from the exposure to the heat treatment (post-bake).
The 24 μm line and space was resolved without any problem. When the resist material was used, the mask linearity was good up to 0.25 μm. In addition, when exposure is performed with defocus, the side wall of the pattern made of the present resist material is smooth. Further, since sufficient acid was supplied to the bottom of the resist, no tail or scum was observed at the bottom of the pattern. ± 0.30μm line and space
A focus margin of 0.8 μm or more was obtained. Further, any of the resist materials of Examples 18 to 29 had no problem in storage stability.

Example 30 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) 5.0 g triphenylsulfonium / trifluoromethanesulfonate 0.3 g propylene glycol monomethyl ether acetate 14.7 g

The above resist material is spin-coated on a semiconductor substrate and prebaked on a hot plate at 90 ° C. for 90 seconds.
After forming a resist material film having a thickness of 1.0 μm, an overcoat material having the following composition was spin-coated on the resist material film so as to have a thickness of 0.1 to 0.15 μm. Polyacrylic acid 2.0 g Perfluorooctanesulfonic acid 2.5 g Nonionic fluorine-containing surfactant 0.2 g Water 95.3 g

Next, a pattern was formed in the same manner as in Example 2. The obtained pattern had a rectangular shape of 0.22 μm line and space resolution, and the exposure amount at this time was about 15 mJ / cm ² . The pattern dimension was measured with respect to the time elapsed from the exposure to the heat treatment. Even after 8 hours, the 0.22 μm line and space was resolved. By using this resist material together with the water-soluble overcoat material, the mask linearity is 0.25
It was good up to μm, and no tail or scum at the bottom of the pattern was observed at all. Further, there was no problem in storage stability.

Comparative Examples 1 to 14 For comparison, photoresist materials having the compositions shown in Tables 11 to 14 were respectively prepared, and patterns were formed in the same manner as in Example 2. The results are shown in Tables 15 and 16. After 30 minutes from the exposure in Comparative Example 1, heat treatment (post bake) was performed.
Pattern result when developed (Film tension phenomenon: T-shape)
FIG. 4 shows heat treatment and development 30 minutes after exposure in Comparative Examples 2 and 3, and Comparative Examples 4 to 8 and Comparative Examples 10 to 14.
FIG. 5 shows pattern results (pattern formation is impossible) when heat treatment and development were performed 15 minutes after exposure and when heat treatment and development were performed 8 hours after exposure in Comparative Example 9.

[0224]

[Table 11]

[0225]

[Table 12]

[0226]

[Table 13]

[0227]

[Table 14]

[0228]

[Table 15]

[0229]

[Table 16]

As is clear from Tables 15 and 16, and FIGS. 4 and 5, in each of these comparative examples, the resolution performance is inferior to that of the resist material using the polymer of the present invention. In addition, as is apparent from Comparative Examples 1 to 6, when it takes 15 to 30 minutes or more from the exposure to the heat treatment (post-bake), the film sticking phenomenon (T-shap
e) occurs or pattern formation becomes impossible. or,
When the resist material of Comparative Example 9 was subjected to heat treatment after 8 hours from exposure, pattern formation was impossible. Further, when the polymer according to the present invention was combined with the existing tris (trichloromethyl) -s-triazine / hydrogen donor as an acid generator to form a resist material, as is clear from the results of Comparative Example 13, the resist material was not exposed to light. If it takes 15 to 30 minutes before the heat treatment, pattern formation becomes impossible.

In Comparative Examples 10 to 12, at 23 ° C.
After standing for a week, a pattern was formed in the same manner as in Example 2. Both the exposed and unexposed portions were dissolved in the developing solution, and no pattern was obtained at all, resulting in poor storage stability.

Comparative Example 15 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) 5.0 g 2-methyl-2- (p-toluenesulfonyl) propiophenone 0.3 g Propylene glycol monomethyl ether acetate 14.7 g

A pattern was formed in the same manner as in Example 2 using the above resist material. As a result, 16 mJ / cm ²
A 0.22 μm line-and-space positive pattern was formed at the exposure amount of, but as shown in FIG. 6, the bottom of the pattern was a tail and the shape was poor. Further, as shown in FIG. 7, the mask linearity was poor.
Further, the focus margin for 0.30 μm line and space was insufficient at ± 0.6 μm.

Comparative Example 16 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) [Polymer of Reference Example 11] 5.0 g 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane 0.3 g Propylene glycol monomethyl ether acetate 14.7 g

Using the above resist material, a pattern was formed in the same manner as in Example 2. As a result, 18 mJ / cm ²
A 0.24 μm line-and-space positive pattern was formed at the exposure amount, but the focus margin and mask linearity for the 0.30 μm line-and-space were poor as in Comparative Example 15.

Comparative Example 17 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) [Polymer of Reference Example 1] 6.0 g Bis (cyclohexylsulfonyl) diazomethane 0.4 g Diethylene glycol dimethyl ether 13.6 g

Using the above resist material, a pattern was formed in the same manner as in Example 2. As a result, 15 mJ / cm ²
A 0.30 μm line-and-space positive pattern was formed at the exposure amount, but scum was observed at the bottom of the pattern as shown in FIG. Also, 0.30 as in Comparative Example 15.
The focus margin and mask linearity for the μm line and space were also poor.

Comparative Example 18 A photoresist material having the following composition was prepared. Poly (p-1-main butoxy ethoxy styrene / p- hydroxystyrene) [Polymer of Reference Example 12] 6.0 g of triphenylsulfonium trifluoromethanesulfonate 0.3g Propylene glycol monomethyl ether acetate 13.7g

Using the above resist material, a pattern was formed in the same manner as in Example 2. As a result, film peeling occurs during development due to poor substrate adhesion, and a sufficient pattern cannot be formed, or even if a pattern can be formed, the upper portion of the resist film as shown in FIG. Was rounded, and the bottom of the pattern was also tail-shaped, resulting in poor shape.

Comparative Example 19 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene) 5.0 g N-trifluoromethanesulfonyloxy-bicyclo [2,2,1] -hept-5-ene-2, 3-dicarboximide [Acid generator of Reference Example 13] 0.3 g Propylene glycol monomethyl ether acetate 14.7 g

Using the above resist material, a pattern was formed in the same manner as in Example 2. As a result, 9 mJ / cm ²
With a light exposure of 0.30 μm, a line-and-space positive pattern was formed. However, after storing at 23 ° C. for 3 days, the pattern was formed in the same manner. When the exposure amount was 4 mJ / cm ² , a 0.40 μm line and space positive pattern was formed, but 0.30 μm could not be resolved. . Further, a change in sensitivity was observed.

Comparative Example 20 A photoresist material having the following composition was prepared. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) [Polymer of Reference Example 1] 6.0 g Triphenylsulfonium trifluoromethanesulfonate 0.3 g Propylene glycol monomethyl ether acetate 13.7 g

Using the above resist material, a pattern was formed in the same manner as in Example 2. As a result, 6 mJ / c
Although positive pattern of 0.30μm lines and spaces are formed at an exposure amount of m ² after one hour after exposure heating, the case of performing the development, as compared with the case of performing heat development immediately after exposure A pattern having a size of 10% or more was formed. Comparative Example 21 A photoresist material having the following composition was used.
Prepared. Poly (p-tert-butoxystyrene / p- hydroxystyrene / p-te rt- butoxycarbonyloxystyrene) [Reference Example 12 polymer] 6.0 g of triphenylsulfonium trifluoromethanesulfonate 0.3g Propylene glycol monomethyl ether acetate 13 0.7 g using the above resist material in the same manner as in Example 2.
Was formed. As a result, 12 mJ / cm ² exposure
0.35μm line and space positive type
A turn was formed, but after 15 minutes from exposure, heating
When an image is formed, a film stretching phenomenon occurs and a pattern is formed.
Became impossible.

[0244]

As is apparent from the above description, a resist material using the polymer according to the present invention is applied to a light source having a wavelength of 300 nm or less, such as deep ultraviolet light (Deep UV), such as KrF excimer laser light (248.4 nm). Practical quarter-micron that has extremely high resolution performance and can maintain a stable pattern size over time from exposure to heat treatment (post-bake) when used as a resist material for exposure. A fine pattern having a good shape on the order can be easily obtained with a large depth of focus margin. Also, the mask linearity is good. Therefore, the present invention has great value for forming ultrafine patterns in the semiconductor industry and the like.

The resist material using the polymer according to the present invention is particularly effective for pattern formation using far ultraviolet light or KrF excimer laser light, but uses i-ray light, electron beam, soft X-ray, etc. It can be used satisfactorily even in the formation of a patterned pattern.

[0246]

[Brief description of the drawings]

FIG. 1 is a process sectional view of a positive pattern forming method using a resist material of the present invention.

FIG. 2 is a good mask linearity (mask fidelity) curve of the resist material obtained in Example 2.

FIG. 3 is a good pattern in which no tail or scum is observed at the bottom of the pattern obtained in Example 17.

FIG. 4 is a cross-sectional view of a film sticking phenomenon (T-shape) observed when a positive pattern is formed using the resist material of Comparative Example 1.

FIG. 5 is a cross-sectional view of a non-patternable pattern observed when an attempt was made to form a positive pattern using the resist materials of Comparative Examples 2 to 8.

FIG. 6 is a pattern with a defective shape in which a tail is observed at the bottom of the pattern obtained in Comparative Example 15.

FIG. 7 is a bad mask linearity (mask fidelity) curve of the resist material obtained in Comparative Example 15.

FIG. 8 is a defective pattern in which scum was observed at the bottom of the pattern obtained in Comparative Example 17.

FIG. 9 is a pattern with a defective shape observed when a pattern is formed in Comparative Example 18.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Resist material film concerning this invention, 3 ...
KrF excimer laser light, 4 ... mask, 2a ... resist pattern.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akiko Katsuyama 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Masataka Endo 1006 Odaka Kadoma Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. 56) References JP-A-5-281745 (JP, A) JP-A-6-194842 (JP, A) JP-A-5-249682 (JP, A) JP-A-4-211258 (JP, A) ) Surveyed field (Int.Cl. ⁶ , DB name) G03F ^7/ 00-7/18

Claims (14)

(57) [Claims] 1. The general formula [1] [Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms or a C 1 -C 1 alkyl group. -6 represents a linear or branched haloalkyl group (provided that R ² and R ³ are not both hydrogen atoms), and a methylene chain having 2 to 5 carbon atoms in R ² and R ³ . Wherein R ⁴ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic haloalkyl group having 1 to 6 carbon atoms, acetyl R ⁵ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aralkyl group; Cyclic alkoxy group, tetrahydropyranyloxy group, tetrahydrofuranyloxy group, te
represents an rt-butoxycarbonyloxy group, a tert-butoxycarbonylmethoxy group, or an acetyloxy group, and k, r and m each independently represent a natural number (however,
0.10 ≦ (k + m) / (k + r + m) ≦ 0.90 and 0.01 ≦ m / (k + r + m) ≦ 0.25. ]
And a photosensitive compound represented by the following general formula [2], a photosensitive compound represented by the general formula [6], a photosensitive compound represented by the general formula [9], and a general formula [12]
And a solvent capable of dissolving at least one photosensitive compound selected from the group consisting of the photosensitive compounds represented by the formula: [Wherein, R ⁶ represents a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and R ⁷ represents a straight-chain having 1 to 10 carbon atoms; It represents a branched or cyclic alkyl group, a haloalkyl group having 1 to 10 carbon atoms or a phenethyl group, and Z represents a sulfonyl group or a carbonyl group. ] [Wherein, R ¹³ represents a general formula [7] In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a halogen atom, and p represents 0 or an integer of 1 to 3. A group represented by｝, or a general formula [8] In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, 5 represents a linear or branched alkoxy group, trifluoromethyl group, hydroxyl group, trifluoromethoxy group or nitro group. ｝
Represents a group represented by ] [Wherein, R ¹³ is the same as described above, and R ²² is a hydrogen atom, a hydroxyl group, or a general formula [10] R ¹³ SO ₂ O- [10]}. In the formula, R ¹³ is the same as described above. And R ²³ represents a linear or branched alkyl group having 1 to 5 carbon atoms or a general formula [11]. In the formula, R ²⁴ and R ³⁰ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkyl group having 1 to 5 carbon atoms. Or the general formula [10]. Represents a group represented by｝. ] [Wherein, R ²⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a substituted phenyl group, or an aralkyl group, and R ²⁶ represents a hydrogen atom, a halogen atom, 6 represents a linear, branched or cyclic alkyl group,
R ²⁷ is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, 1-naphthyl group, 2-naphthyl group , 10
-Camphor group, phenyl group, tolyl group, 2,5-dichlorophenyl group, 1,3,4-trichlorophenyl group,
Or a trifluoromethylphenyl group. ] 2. The method according to claim 1, wherein the photosensitive compound which generates an acid upon exposure is at least one photosensitive compound represented by the general formula [2], or at least one photosensitive compound represented by the general formula [2]; 6], a combination with at least one selected from the group consisting of a photosensitive compound represented by the general formula [9] and a photosensitive compound represented by the general formula [12]. The resist material according to 1. 3. A photosensitive compound which generates an acid upon exposure to light, represented by one or more photosensitive compounds represented by the general formula [2], a photosensitive compound represented by the general formula [9] and a photosensitive compound represented by the general formula [12]. 3. The resist material according to claim 2, which is a combination with at least one selected from the group consisting of photosensitive compounds. 4. The resist material according to claim 1, further comprising an ultraviolet absorber. 5. R ^{1 of the} polymer represented by the general formula [1]
Is a hydrogen atom, R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ³ is a carbon atom having 1 carbon atom.
A linear or branched alkyl group having 1 to 6 carbon atoms, and R ⁴ is a linear or branched alkyl group having 1 to 10 carbon atoms;
R ⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a tetrahydropyranyloxy group, tert-butoxycarbonyl An oxy group, a tert-butoxycarbonylmethoxy group, or an acetyloxy group.
5. The resist material according to any one of 4. 6. R ^{1 of the} polymer represented by the general formula [1]
Is a hydrogen atom, R ² is a hydrogen atom or a methyl group, R ³ is a methyl group or an ethyl group, R ⁴ is a linear or branched alkyl group having 1 to ⁴ carbon atoms, R ⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or an acetyloxy group. The resist material as described. 7. The polymer (k) represented by the general formula [1]
The resist material according to any one of claims 1 to 6, wherein the range of (+ m) / (k + r + m) is 0.2 to 0.7, and the weight average molecular weight is 3,000 to 50,000. 8. A photosensitive compound which generates an acid upon exposure to light.
The following general formula [2] [Wherein R ⁶ is a linear, branched or cyclic C 1-10 carbon atom
An alkyl group or a haloalkyl group having 1 to 10 carbon atoms
R ⁷ represents a linear, branched or cyclic C 1-10 carbon atom
An alkyl group, a haloalkyl group having 1 to 10 carbon atoms or
Z represents a sulfonyl group or a carbonyl group;
Represents The compound of any one of claims 1 to 7, which is a compound represented by the formula
A resist material according to any of the above. 9. In the general formula [2], R ⁶ Has 3 or more carbon atoms
10 branched or cyclic alkyl groups; ⁷ Is carbon
A linear, branched or cyclic alkyl group of the formulas 1 to 10
9. The resist according to claim 8, wherein Z is a sulfonyl group.
Material. 10. In the general formula [2], R ⁶ And R ⁷ But
Each independently a branched or cyclic alkyl having 3 to 10 carbon atoms
The resist material according to claim 9, which is a hydroxyl group. 11. The compound represented by the general formula [2] is
(1,1-dimethyl Ethyl sulfonyl) diazomethane
The resist material according to claim 9, wherein 12. The compound represented by the general formula [2] is
(Cyclohexylsulfonyl) diazomethane,
The resist material according to claim 9. Claim 13 When the compound represented by the general formula [2] is 1
-Cyclohexylsulfonyl-1- (1,1-dimethyl
(Ethylsulfonyl) diazomethane.
Resist material listed. 14. After the step of applying the resist material according to claim 1 on a substrate and after the heat treatment, the resist material is applied through a mask.
A pattern forming method comprising: a step of exposing to deep ultraviolet rays of not more than 00 nm; and a step of performing a heat treatment, if necessary, and then developing with a developer.