JP3409619B2 - Polymer composition and resist material comprising the same - Google Patents

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a resist material used in the production of semiconductor devices and the like and a polymer composition used therein. More specifically, the present invention relates to a resist material and a polymer composition used therefor when a positive pattern is formed by using ultraviolet rays, particularly far ultraviolet rays having a wavelength of 300 nm or less, for example, KrF excimer laser light as an exposure energy source.

[0002]

2. Description of the Related Art In recent years, with the high integration of semiconductor devices, the energy sources of exposure apparatuses used for microfabrication, especially photolithography, have become shorter and shorter in wavelength, and now far-ultraviolet light (300 nm or less) and KrF excimer are used. Laser light (24
8.4 nm) etc. are being studied. However, a highly practical resist material suitable for these wavelengths has not been found yet.

For example, as a resist material using KrF excimer laser light or far-ultraviolet light as a light source, a dissolution-inhibiting resist material comprising a polymer having a high transparency to light around 248.4 nm and a photosensitive compound having a diazodiketo group in the molecule. Have been developed (for example, Japanese Patent Laid-Open No. 1-80944;
JP-A 1-154048; JP-A 1-155338; JP-A
1-155339; JP 1-188852; Y. Tani et al., Pr.
oc.SPIE, 1086 , 22 (1989) etc.). However, these dissolution-inhibiting resist materials have low sensitivity in common, and cannot be used for far-ultraviolet light and KrF excimer laser light applications where high-sensitivity resist materials are required. Further, in recent years, as a method of reducing the exposure energy amount (higher sensitivity), a chemically amplified resist material using an acid generated by exposure as a medium has been proposed [H.Ito et al., Polym.Eng.Sci., 23 , 1012 (1983
)], And various reports have been made regarding this (for example, H. Ito et al., US Pat. No. 4,491,628 (1985); JP-A-2-
27660; JC Crivello et al., U.S. Pat. No. 4,603,101.
(1986); JP 62-115440 A; WRBrunsvolt et al., Pr.
oc.SPIE, 1086 , 357 (1989); TXNeenan et al., Proc.SPIE,
1086 , 2 (1989) RG Tarascon et al., SPE Regional C
onference TechnicalPapers, Ellenville, NY 1988
Y. Jian et al., Polym.
Mater.Sci. & Eng., 66 , 41 (1992) etc.). However, in these existing chemically amplified resist materials, the polymers used are, for example, poly (p-tert-butoxycarbonyloxystyrene), poly (p-tert-butoxystyrene), poly (p-tert-butoxycarbonyl). Oxy-α-
Methylstyrene), poly (p-tert-butoxy-α-methylstyrene), poly (p-isopropenylphenoxyacetic acid)
tert-butyl), poly (p-tert-butoxycarbonyloxystyrene / sulfone), poly (p-tetrahydropyranyloxystyrene), poly {p- (1-methoxyethoxy) styrene}, poly {p- (1- In the case of phenol ether-based polymers such as phenoxyethoxy) styrene}, the adhesion to the substrate is poor, so that the film is easily peeled off during development, and the heat resistance is poor, so that a good pattern cannot be obtained. It has drawbacks. Also, carboxylic acid-based polymers such as poly (tert-butyl p-vinylbenzoate)
In the case of poly (tetrahydropyranyl p-vinylbenzoate), etc., the resolution is poor due to insufficient light transmission around 248.4 nm due to the benzoyl group, and poly (methacrylic acid tert. -Butyl) has problems such as poor heat resistance and dry etching resistance of the polymer.

In addition, a resist material using a silicon-containing polymer is disclosed (for example, Japanese Examined Patent Publication No. 3-44290), but for example, poly (p-trimethylsilyloxystyrene) or poly (p-tert-butyl). When dimethylsilyloxystyrene) is used, it is difficult to put into practical use because it has low sensitivity and cannot be completely removed by ashing because it contains silicon.

Further, as a chemically amplified resist material which has recently improved the above-mentioned drawbacks, poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) has been used.
Resist material using (JP-A-2-209977;
3-206458), a resist material using poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene) (JP-A-2-19847; JP-A-2-61436;
JP-A-3-83063), a resist material using poly (p-tert-butoxystyrene / p-hydroxystyrene) [JP-A-2-62544; JP-A-4-21258 (US Pat. No. 5,350,660). )] Etc. have been reported. However, common resist materials using these polymers are insufficient in high resolution performance required in recent years, and
Delay time problem discussed in practical application (between resist coating and exposure, or exposure to heat treatment (P
EB) problems such as dimensional variation and pattern shape deterioration due to the passage of time, and substrate dependence problems (for semiconductor substrates SiO ₂ , Si ₃ N ₄ , Ti ₃ N ₄ , BPSG).
Alternatively, polysilicon or the like is used, but there is a problem that a pattern is formed or not due to the difference in the substrate).

In addition to these, a polymer having an acetal group or a ketal group introduced as a protective group (for example, poly (p-1-methoxyethoxystyrene / p-hydroxystyrene)) and an acid such as a triphenylsulfonium salt derivative or a diphenyliodonium salt. A resist material using a generator (for example, Japanese Patent Application Laid-Open No. 2-161436; Japanese Patent Application Laid-Open No. 4-219757;
1745; JP-A-3-282550) and the like are reported. However, these materials have a common problem of scum (unmelted residue during development) (the generated scum is transferred to the underlying substrate during etching), substrate dependency and Delay Time. There is. JP-A-5-24968
No. 2 discloses poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene), poly (p-1-methoxy-1-methylethoxystyrene / p-hydroxystyrene), poly (p-
1-ethoxyethoxystyrene / p-hydroxystyrene /
A resist material in which a polymer such as methyl methacrylate) or poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) and an acid generator such as a diazodisulfone compound are combined has been reported. These materials are excellent in many respects such as resolution and delay time, but there are still problems with substrate dependence and scum generation. Further, in JP-A-6-194842, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-
Materials in which a polymer such as butoxystyrene) and an acid generator such as a diazodisulfone compound are combined are disclosed. However, these resist materials are also excellent in resolution performance, mask linearity, heat resistance, delay time, etc., but have problems in substrate dependency and scum generation. In addition, in EP-A-679,951, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) and poly (p-tert-butoxycarbonyloxystyrene / p-
A resist material characterized by using a mixture of two polymers (hydroxystyrene) has been reported. However, this material also has problems in terms of resolution performance and Delay Time.

As described above, although the chemically amplified resist material has higher sensitivity than the conventional resist material,
Poor heat resistance of the polymer, poor adhesion to the substrate, insufficient light transmission around 248.4 nm, insufficient resolution performance, pattern dimensions fluctuating over time,
Problems such as deterioration of pattern shape, poor storage stability, lack of focus margin, defective mask linearity, or left hem and scum on pattern shape, and large substrate dependency Therefore, it has not been put to practical use. Therefore, there is a great demand for a practical high-sensitivity resist material that solves these problems.

[0008]

SUMMARY OF THE INVENTION In view of the above situation, the problem to be solved by the present invention is that ultraviolet rays, especially 300n
It has high transparency to far-ultraviolet light of m or less, KrF excimer laser light, etc.
It has high sensitivity to line irradiation, excellent heat resistance and adhesion to the substrate, high resolution performance, high precision pattern can be obtained without pattern dimension fluctuation with time, and storage stability And a wide range of focus margins, good mask linearity, substrate dependence, and a practical resist material that can obtain a rectangular pattern shape without skirting or scum, and a polymer composition used therefor It is to provide things.

[0009]

The present invention has been made for the purpose of solving the above problems, and has the following constitution.

[(1) (i) Chemistry by heating in the presence of acid
Functional group that can be easily alkali-soluble under changes
(Hereinafter, abbreviated as functional group A)The following general formula [4]

[0011]

[Chemical 14]

[In the formula, R represents a hydrogen atom or a lower alkyl group.
And R ² and R ³ are each independently a hydrogen atom or halogen.
Represents an alkyl group or an allyl group which may be substituted with
However, both may be bonded to form an alkylene ring.
(However, it is excluded when both R ² and R ³ are hydrogen atoms.),
R ⁴ is an alkyl group optionally substituted with halogen or
Represents an aralkyl group. A polymer comprising monomer units as a component represented by (hereinafter, polymer 1 and substantially
Write down. ) And (ii) a functional group capable of undergoing a chemical change by heating in the presence of an acid to become alkali-soluble, but a functional group less susceptible to a chemical change than the functional group A in the above (i) (hereinafter, The following general formula having a functional group B)
[7]

[0013]

[Chemical 15]

[Wherein R ⁶ is a hydrogen atom or lower alkyl
R ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkyl group
Coxy group, acyloxy group, saturated heterocyclic oxy group or R
_{^{8 O-CO- (CH 2)}} Z -O- ( where, R ⁸ is an alkyl group
And Z represents 0 or a natural number. Group)
You ] A polymer comprising a monomer unit represented by the following as a constituent ( hereinafter abbreviated as polymer 2),
A polymer composition comprising (i) the following general formula [2
3]

[0015]

[Chemical 16]

[Wherein R ⁹ And R ^Ten Each independently
Represents a kill group or a haloalkyl group, A is a sulfonyl group or
Represents a carbonyl group. ] By the irradiation shown by
A substance that generates an acid, and (ii) the following general formula [24]

[0017]

[Chemical 17]

[Wherein R ¹¹ Is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group or a haloalkyl group,
R ¹² Is an alkyl group, a haloalkyl group, or the following general formula
[25]

[0019]

[Chemical 18]

{Wherein R ¹³ Is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group, or a haloalkyl group.
And q represents an integer of 0 or 1 to 3. } Is represented. ],under
General formula [26]

[0021]

[Chemical 19]

[Wherein R ¹⁴ Is a hydrogen atom, a halogen atom,
Represents an alkyl group or a trifluoromethyl group, R ¹⁵ A
Alkyl group, aralkyl group, alkoxy group, phenyl group or
Represents a tolyl group. ], The following general formula [27]

[0023]

[Chemical 20]

[Wherein R ¹⁶ Is an alkyl group, a phenyl group,
Represents a substituted phenyl group or an aralkyl group, R ¹⁷ And R ¹⁸
Are each independently a hydrogen atom, an alkyl group, a phenyl group,
Represents a substituted phenyl group or an aralkyl group, and R ¹⁹ Is Fluo
Low alkyl group, trifluoromethylphenyl group, methyl
Represents a group or a tolyl group. ], The following general formula [28]

[0025]

[Chemical 21]

[In the formula, R ²⁹ Is an alkyl group, fluoroal
Kill group, phenyl group, substituted phenyl group or aralkyl group
Represents R ³⁰ And R ³¹ Are each independently a hydrogen atom, methyl
Group, methoxy group, nitro group, cyano group, hydroxyl group or the following
General formula [29]

[0027]

[Chemical formula 22]

(In the formula, R ³³ Is an alkyl group, fluoroal
Kill group, phenyl group, substituted phenyl group or aralkyl group
And B represents a sulfonyl group or a carbonyl group. )
Represents R ³² Represents a hydrogen atom, a methyl group or an ethyl group
You ] Or the following general formula [30]

[0029]

[Chemical formula 23]

[Wherein R ³⁴ Is an alkyl group, fluoroal
Kill group, phenyl group, substituted phenyl group or aralkyl group
Represents R ³⁵ Is a hydrogen atom, methyl group, fluoroalkyl
Group, methoxy group, nitro group, cyano group, hydroxyl group or above
This represents the general formula [29]. ] By the irradiation shown by
A resist composition comprising a substance that generates an acid.
Therefore, the weight average molecular weight of polymer 2 is the weight of polymer 1.
Chemically amplified polymer characterized by being smaller than the average molecular weight
Diresist material.

[0031] (2) as the component each of the polymers 1 and polymer 2, as described in further comprising at (1) a monomer unit capable of imparting heat resistance and substrate adhesion to the polymer Les
Gist material .

[0032] (3) a resist material according to further comprising at the third monomer unit as at least one of the constituents of the polymer 1 and polymer 2 (2).

[0033] (4) In addition, the comprising a phenolic compound having a weight average molecular weight between 300 and 15,000 (1) to the polymer composition according to any one of (3).

[0034] (5) above, further comprising an ultraviolet absorber
The resist material according to (1) or (2) .

(6) The resist material according to any one of (1) to (5) above is applied onto a semiconductor substrate, heated, irradiated with radiation through a mask, and then heated if necessary, and then developed. A method of forming a pattern, comprising: ]

In the present invention, the monomer unit having the functional group A in the polymer 1 is, for example, the following general formula [4]

[0037]

[Chemical formula 24]

[0038] In the formula, R represents a hydrogen atom or a lower alkyl group, R ² and R ³ represent independently a hydrogen atom, a halogen atom-substituted alkyl group optionally or allyl group, both bound And may form an alkylene ring (provided that both R ² and R ³ are hydrogen atoms).
R ⁴ represents an alkyl group which may be substituted with halogen or an aralkyl group. ] The monomer unit shown by these is mentioned.

As the monomer unit having the functional group B in the polymer 2, for example, the following general formula [7]

[0040]

[Chemical 25]

[0041] [wherein, R ⁶ represents a hydrogen atom or a lower alkyl group, R ⁷ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acyloxy group, a saturated heterocyclic oxy group, or R
_{^{8 O-CO- (CH 2)}} Z -O- ( where, R ⁸ represents an alkyl group, Z is. Represents 0 or a natural number) represents a group represented by. ] The monomer unit shown by these is mentioned.

In the present invention, the monomer unit capable of imparting heat resistance and substrate adhesion to the polymer is, for example, the following general formula [5]

[0043]

[Chemical formula 26]

[0044] In the formula, R is the same as above. ] The monomer unit shown by these is mentioned.

As the polymer 1 in the present invention, for example, the following general formula [1]

[0046]

[Chemical 27]

[ Wherein R, R ² , R ³ and R ⁴ are the same as defined above, R ¹ represents a hydrogen atom or a lower alkyl group, R ⁵ represents a cyano group, an optionally esterified carboxyl group or Represents a phenyl group which may have a substituent, m and n represent a natural number, and k represents 0 or a natural number (provided that m
> K. ). ] The polymer shown by these is mentioned.

As the polymer 2 in the present invention, for example, the following general formula [2]

[0049]

[Chemical 28]

[ Wherein R ⁶ and R ⁷ are the same as defined above, R ²¹ represents a hydrogen atom or a lower alkyl group, R ²² represents a cyano group,
It represents a carboxyl group which may be esterified or a phenyl group which may have a substituent, p and r represent natural numbers, and f represents 0 or a natural number (provided that p> f). ] The polymer shown by these is mentioned.

In the above general formulas [1], [4] and [5], the lower alkyl group represented by R, the lower alkyl group represented by R ¹ in the general formula [1], the general formula [2] And the lower alkyl group represented by R ⁶ in [7] and the lower alkyl group represented by R ²¹ in the general formula [2] each independently have 1 to 6 carbon atoms, for example, methyl. Examples thereof include a group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like, which may be linear or branched.

In the general formulas [1] and [4], the alkyl group represented by R ² , R ³ and R ^4, which may be substituted with halogen, includes straight-chain, branched, It may be cyclic, and preferably has 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group. Group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group Groups and the like.

[0053] As the halogen of R ^2, R ³ and an alkyl group which may be substituted by a halogen represented by R ⁴ is chlorine, bromine, fluorine, and iodine.

[0054] The aralkyl group represented by R ^4, for example a benzyl group, phenethyl group, phenylpropyl group,
Examples thereof include a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group.

As the optionally esterified carboxyl group represented by R ⁵ in the general formula [1], the carboxyl group and the hydrogen atom of the carboxyl group are replaced by, for example, an alkyl group having 1 to 6 carbon atoms. And a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and the like.

Examples of the substituent of the phenyl group which may have a substituent represented by R ⁵ include a halogen atom such as chlorine, bromine, fluorine and iodine, a linear, branched or cyclic alkyl group, It preferably has 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
Cyclopropyl group, n-butyl group, isobutyl group, tert-
Butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group Group or the like, a linear or branched alkoxy group, preferably having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert. -Butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-
A hexyloxy group, an isohexyloxy group, etc., and a linear, branched or cyclic acyl group having 2 to 7 carbon atoms such as acetyl group, propionyl group, n-butyryl group, isobutyryl group, n -Pentanoyl group, pivaloyl group, isovaleryl group, cyclohexanecarbonyl group, etc., and 5- or 6-membered saturated heterocyclic oxy group such as tetrahydrofuranyloxy group, tetrahydropyranyloxy group, R ²⁵
_{O-CO- (CH 2) j} O- ( where, j is 0 or 1.) Include groups represented by. Here, the lower alkyl group represented by R ²⁵ has a carbon number of 1 to 6, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. It may be branched or cyclic, and R ²⁵ O-CO- (C
Specific examples of the group represented by H ₂ ) _j O- include, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an isopropoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an isobutoxycarbonyloxy group, and a tert-pentyloxy group. Examples thereof include a carbonyloxy group, an ethoxycarbonylmethoxy group, a tert-butoxycarbonylmethoxy group, a 1-methylcyclopentyloxycarbonylmethoxy group, and a 1-methylcyclohexyloxycarbonylmethoxy group.

The lower alkyl group represented by R7 in the general formulas [2] and [7] preferably has 1 to 10 carbon atoms.
6 is a linear or branched alkyl group, and specific examples thereof include an isopropyl group, an isobutyl group,
tert-butyl group, sec-butyl group, isopentyl group, tert-
Preferable examples are a pentyl group, a 1-methylpentyl group, an isohexyl group and the like.

The lower alkoxy group represented by R ⁷ is preferably a linear or branched alkoxy group having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, iso Propoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-
Examples thereof include a hexyloxy group and an isohexyloxy group.

Examples of the acyloxy group represented by R ⁷ include
It is preferably a linear, branched or cyclic acyloxy group having 1 to 6 carbon atoms, for example, an acetyloxy group,
Examples thereof include a propionyloxy group, an n-butyryloxy group, an isobutyryloxy group, an n-pentanoyloxy group, a pivaloyloxy group, an isovaleryloxy group and a cyclohexanecarbonyloxy group.

The saturated heterocyclic oxy group represented by R ⁷ is preferably a 5- or 6-membered one, and examples thereof include a tetrahydrofuranyloxy group and a tetrahydropyranyloxy group.

R ⁸ represented by [0061] _{^{R 7 O-CO- (CH 2}} ) Z -
R ⁸ of the O-group is a straight chain having 1 to 10 carbon atoms,
Branched or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-
Butyl group, n-pentyl group, isopentyl group, 1-methylcyclohexyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group , it includes ^{decyl, R 8 O-CO- (CH} 2)
Specific examples of the _Z- O- group include, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an isopropoxycarbonyloxy group, an isobutoxycarbonyloxy group, a tert-butoxycarbonyloxy group, a tert-pentyloxycarbonyloxy group, 1 -Methylcyclohexyloxycarbonylmethyloxy group, tert-butoxycarbonylmethyloxy group, 1-methylcyclopentyloxycarbonylmethyloxy group and the like.

As the optionally esterified carboxyl group represented by R ²² in the general formula [2], the carboxyl group and the hydrogen atom of the carboxyl group are replaced by, for example, an alkyl group having 1 to 6 carbon atoms. And a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and the like.

[0063] The substituent of the phenyl group optionally having a substituent represented by R ^22, chlorine, bromine, fluorine, halogen atom such as iodine, straight-chain, branched or cyclic alkyl group, It preferably has 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
Cyclopropyl group, n-butyl group, isobutyl group, tert-
Butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, A decyl group or the like, a linear or branched alkoxy group, preferably having 1 to 6 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group, etc., straight-chain, branched or cyclic having 2 to 7 carbon atoms An acyl group such as acetyl group, propionyl group, n-butyryl group, isobutyryl group, n-pentanoyl group, pivaloyl group, isovaleryl group, cyclohexane Carbonyl group, etc., 5- to 6-membered saturated heterocyclic oxy group such as tetrahydrofuranyloxy group, tetrahydropyranyloxy group, 1-methoxy-1-methylethoxy group, benzyloxy-1-methylethoxy group, 1-ethoxy Ethoxy group, 1-methoxyethoxy group, 1-n-butoxyethoxy group, 1-isobutoxyethoxy group, 1- (1,1-dimethylethoxy) -1-methylethoxy group, 1- (1,1-dimethylethoxy group ) Ethoxy group, 1-ethoxy-1-methylethoxy group, 1-n-propoxyethoxy group, 1-methyl-1-n-propoxyethoxy group, 1-ethoxypropoxy group, 1-methoxybutoxy group, 1-methoxycyclohexyl group Oxy group, 1-acetyloxy-1-methyl eth
Xy group or 1-benzyloxyethoxy group, R ²⁵ O-CO
_{- (CH 2) j O- (} . However, j is 0 or 1) and a group represented by the like. Here, the lower alkyl group represented by R ²⁵ has a carbon number of 1 to 4, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group, and R ²⁵ O—CO— (CH ₂ ) Specific examples of the group represented by _j O- include, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an isopropoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an isobutoxycarbonyloxy group, a tert-pentyloxycarbonyloxy group. , Ethoxycarbonylmethoxy group, tert
Examples include -butoxycarbonylmethoxy group, 1-methylcyclopentyloxycarbonylmethoxy group and 1-methylcyclohexyloxycarbonylmethoxy group.

[0064] The resist composition of the present invention in accordance comprising the polymer composition of the present invention comprising a polymer 1 and polymer 2 the present invention can easily be eliminated by traces of acid, for example the following general formula [3]

[0065]

[Chemical 29]

[0066] (wherein, R ^2, R ³ and R ⁴ are the same. As defined above) functional group represented by, i.e., an alkoxyalkoxy group, a halo alkoxyalkyl group, aralkyloxy alkyl group, alkoxy 1-allyl alkoxy Group, a haloalkoxy 1-allylalkoxy group or an aralkyloxy 1-allylalkoxy group, that is, a general formula [4]

[0067]

[Chemical 30]

[0068] (wherein, R, R ^2, R ³ and R ⁴ are the same. As defined above) to improve the monomer unit represented by, substrate adhesion and heat resistance, for example, the following general formula [5]

[0069]

[Chemical 31]

[0070] (wherein, R is as. Defined above) or better and a monomer unit represented by, or to improve the light transmittance of the exposed portion, the sidewall geometry to suppress the development rate of the exposed area, mask linearity A monomer unit optionally used for the purpose of improving the reaction efficiency, that is, for example, the following general formula [6]

[0071]

[Chemical 32]

[0072] (wherein, R ¹ and R ⁵ are the same. Above) composed of a monomer unit represented by, for example, the following general formula [1]

[0073]

[Chemical 33]

[0074] ^{(wherein, R, R 1, R 2} , R 3, R 4, R 5,
m, n and k are the same as above. ) Polymer 1
When,

A monomer unit having a function of decreasing the dissolution rate in a developing solution, that is, for example, the following general formula [7]

[0076]

[Chemical 34]

A monomer unit represented by the following formula (wherein R ⁶ and R ⁷ are the same as above) and good adhesion to the substrate and heat resistance can be obtained, for example, by the following general formula [8]

[0078]

[Chemical 35]

[0079] and a monomer unit represented by (wherein, R ⁶ is as defined above.)

[0080] Monomer units used as necessary for the purpose of or adjust the rate of dissolution during development, i.e., for example, the following general formula [9]

[0081]

[Chemical 36]

[0082] (wherein, R ²¹ and R ²² are the same. Above) composed of a monomer unit represented by the following general formula [2]

[0083]

[Chemical 37]

The polymer is characterized in that it is used in combination with the polymer 2 represented by the formula (wherein R ⁶ , R ⁷ , R ²¹ , R ²² , p, r and f are the same as above).

[0085] The polymer 1, the resist material of the present invention comprising the polymer composition of the present invention comprising a phenolic compound polymer 2 and a weight average molecular weight between 300 and 15,000, for example above general formula [1] In addition to the polymer represented by the formula [2] and the polymer represented by the general formula [2], a weight average molecular weight of 30 having a role of adjusting the dissolution rate at the time of development.
It is characterized in that a combination of 0 to 15,000 phenolic compounds is used.

[0086] In addition, polymers 1 and a weight average molecular weight of 300
The resist material containing the polymer composition of the present invention containing 1 to 15,000 phenolic compounds is, for example, a polymer represented by the above general formula [1] and a weight average molecular weight having a role of adjusting the dissolution rate during development. It is characterized in that it is used in combination with 300 to 15,000 phenolic compounds.

When the above-mentioned polymer composition of the present invention is used as a polymer component for a resist material, the polymer represented by the general formula [1] has a functional group represented by the general formula [3] which is an existing tert-butoxycarbonyloxy group. Group, tert-butoxy group, tetrahydropyranyloxy group, tert-butoxycarbonylmethoxy group compared to functional groups and the like, due to the fact that it is extremely easy to leave due to the action of acid It is extremely advantageous in terms of dimension maintenance (Delay Time).

Further, the polymer represented by the general formula [2] and the phenolic compound having a weight average molecular weight of 300 to 15,000 have the effect of suppressing the dissolution rate in a developing solution at the time of development, and therefore the general formula The polymer represented by [1] is very effective in improving the focus margin which the polymer does not possess or hardly possesses, in improving the defect of mask linearity and in improving the shape of the pattern side wall. It also contributes to the improvement of the heat resistance of the polymer. By using the polymer represented by the general formula [1], the polymer represented by the general formula [2] and the phenolic compound having a weight average molecular weight of 300 to 15,000 in an arbitrary ratio, The effects of solving the problems by complementing the weaknesses of the same polymers, namely, resolution performance, substrate adhesion,
It is possible to maintain the pattern size at the Delay Time and improve the mask linearity and the focus margin. Particularly in the polymer represented by the general formula [2],
When the monomer unit represented by the general formula [9] is less than the monomer unit represented by the general formula [7] and the weight average molecular weight thereof is smaller than the weight average molecular weight of the polymer represented by the general formula [1], Or the weight average molecular weight is 30
When a phenolic compound of 0 to 15,000 is used in combination, the problem of substrate dependence can be improved and its effect is maximized.

[0089] The monomer unit represented by the general formula [4], for example, p- or m- hydroxystyrene derivatives, include p- or m- hydroxy -α- monomer units of a monomer such as methyl styrene derivatives, it like Specific examples of the monomer include, for example, p- or m-1-methoxy-1-methylethoxystyrene, p- or m-1-benzyloxy-1-methylethoxystyrene, p- or m-1-ethoxyethoxy. Styrene, 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
Mention may be made of p-1-acetyloxy-1-methylethoxystyrene and p- or m-hydroxy-α-methylstyrene derivatives having the same protecting groups as p- or m-hydroxystyrene derivatives.

[0090] The monomer unit represented by the general formula [7], and specific examples, m- or p- methoxy styrene,
m- or p-isopropoxystyrene, m- or p-tert-butoxystyrene, m- or p-cyclohexyloxystyrene, m- or p-1-methylcyclohexyloxystyrene,
m- or p-1-methylcyclopentyloxystyrene, m- or p-tetrahydropyranyloxystyrene, m- or p-tetrahydrofuranyloxystyrene, m- or p-acetyloxystyrene, m- or p-isobutyryl Oxystyrene, m- or p-pivaloyloxystyrene, m- or p-cyclohexanecarbonyloxystyrene, m- or p-methoxycarbonyloxystyrene, m- or p-ethoxycarbonyloxystyrene, m- or p-iso Propoxycarbonyloxystyrene, m- or p-isobutoxycarbonyloxystyrene, m- or p-sec-butoxycarbonyloxystyrene, m- or p-tert-butoxycarbonyloxystyrene, m- or p-isoamyloxycarbonyloxystyrene , M- or p-tert-amyloxycarbonyloxystyrene, m- or p-vinylphenoxyacetic acid 1- Chill cyclopentyl, include m- or p- vinylphenoxyacetate 1-methylcyclohexyl and the like, or which like monomer units of a monomer such as α- methyl styrene derivatives having a styrene derivative and similar substituents.

[0091] The monomer unit represented by the general formula [6], specifically, for example, styrene, alpha-methylstyrene styrene, p- chlorostyrene, o-, m- or p- methylstyrene,
o-, m- or p-methoxystyrene, pn-butylstyrene,
p-ethoxystyrene, m- or p-1-methylcyclohexyloxystyrene, m- or p-1-methylcyclopentyloxystyrene, m- or p-tert-butoxystyrene, m-or
p-tetrahydropyranyloxystyrene, m- or p-tetrahydrofuranyloxystyrene, m- or p-methoxycarbonyloxystyrene, m- or p-ethoxycarbonyloxystyrene, m- or p-isopropoxycarbonyloxystyrene, m -Or p-isobutoxycarbonyloxystyrene, m- or p-tert-butoxycarbonyloxystyrene, m- or p-isoamyloxycarbonyloxystyrene, m- or p-tert-amyloxycarbonyloxystyrene, m- or p -Vinylphenoxyacetate tert-butyl, m- or p-vinylphenoxyacetate 1-methylcyclopentyl, m- or p-vinylphenoxyacetate 1-methylcyclohexyl, etc. or α-methyl having the same substituents as these styrene derivatives Monomer units of monomers such as styrene derivatives and acrylonitrile, methacryl , Acrylic acid, methyl methacrylate, butyl tert- methacrylic acid, monomer units of a monomer of cyclohexyl methacrylate.

[0092] The monomer unit represented by the general formula [9], for example, p- or m- hydroxystyrene derivatives, include p- or m- hydroxy -α- monomer units of a monomer such as methyl styrene derivatives, it like Specific examples of the monomer of, for example, p- or m-1-methoxy-1-methylethoxystyrene, p- or m-benzyloxy-1-methylethoxystyrene, p- or m-1-ethoxyethoxystyrene,
p- or m-1-methoxyethotostyrene, p- or m-1-n-butoxyethoxystyrene, p- or m-1-isobutoxyethoxystyrene, p- or m-1- (1,1-dimethyl Ethoxy)-
1-methylethoxystyrene, p- or m-1- (1,1-dimethylethoxy) 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-1-acetyloxy-1-methylethoxystyrene and these p-
Alternatively, a p- or m-hydroxy-α-methylstyrene derivative having the same protecting group as the m-hydroxystyrene derivative may be mentioned.

Further, the monomer unit represented by the general formula [5], which is a constituent component of the polymer represented by the general formula [1], and the general unit which is a constituent component of the polymer represented by the general formula [2]. Each of the monomer units represented by the formula [8] is a monomer having a phenolic hydroxyl group,
Specific examples of such monomers include, for example, p- or m-vinylphenol, p- or m-hydroxy-α-methylstyrene and the like.

The polymer represented by the general formula [1] and the polymer represented by the general formula [2] may be composed of the same monomer unit in some cases, but the polymer represented by the general formula [1] is not exposed. The monomer unit represented by the general formula [4] is used more than the monomer unit represented by the general formula [6] in order to maximize the difference in the dissolution rate in the developing solution between the parts and ensure the resolution performance. On the other hand, the polymer represented by the general formula [2] is controlled by the general formula [9] in order to improve the side wall shape and the substrate dependence by controlling the developing rate.
Since the number of monomer units represented by is smaller than that of the general formula [7], the polymer is different.

In the polymer represented by the general formula [1],
The total of the monomer unit represented by the general formula [4] and the monomer unit represented by the general formula [6] is represented by the general formula [1].
The composition ratio in the polymer represented by is usually 10 to 9
It is 0 mol%, and in any case, it can be used as the resist material of the present invention, but from the viewpoint of making the heat resistance of the polymer, the adhesion to the substrate and the mask linearity extremely good, 20 to 50 mol% is more preferable. preferable.

The composition ratio of the monomer unit represented by the general formula [6] in the polymer represented by the general formula [1] is usually 0 to 25 mol%, but the deterioration of the resolution performance is particularly caused. From the viewpoint that the mask linearity can be improved while suppressing it, 0 to 15 mol% is more preferable. Further, it is particularly preferable that the monomer unit represented by the general formula [4] is contained in a larger amount than the monomer unit represented by the general formula [6] from the viewpoint of resolution performance and the like.

In the polymer represented by the general formula [2],
The composition ratio of the monomer unit represented by the general formula [7] in the polymer represented by the general formula [2] is usually 1
It is 0 to 50 mol%, and in any case, it can be used as the resist material of the present invention, but has the effect of suppressing the heat resistance of the polymer, the adhesion to the substrate, and the phenomenon of the film layering of the surface layer due to the delay time. Considering this, 15 to 40 mol% is more preferable.

The composition ratio of the monomer unit represented by the general formula [9] in the polymer represented by the general formula [2] is usually 0 to 20 mol%, but particularly the resolution performance is maintained. However, in terms of improving the side wall shape, 0 to 15
Mol% is more preferred. Further, it is particularly preferable that the monomer unit represented by the general formula [7] is contained in a larger amount than the monomer unit represented by the general formula [9] from the viewpoint of improving the side wall shape and improving the substrate dependency.

[0099] Specific examples of the polymer represented by the general formula [1], for example, poly [p- (1-methoxy-1-methylethoxy) styrene / p- hydroxystyrene], poly [p-
(1-Benzyloxy-1-methylethoxy) styrene / p-
Hydroxystyrene], poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene], poly [p- (1-
Methoxyethoxystyrene) / p-hydroxystyrene], poly [p-1-n-butoxyethoxystyrene / p-hydroxystyrene], poly [p- (1,1-dimethylethoxy)
-1-Methylethoxystyrene / p-hydroxystyrene], 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-1-methylcyclohexyloxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / P-hydroxystyrene / methyl methacrylate], poly [p- (1-methoxy-
1-methylethoxy) styrene / p-hydroxystyrene /
Tert-butyl methacrylate], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / acrylonitrile], 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-methyl) Ethoxy) 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-
Methyl styrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / methyl methacrylate), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / cyclohexyl methacrylate), poly (p-1- Ethoxyethoxystyrene / p-hydroxystyrene / tert-butyl methacrylate), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / acrylonitrile), 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 / acrylic acid), poly (p-1-ethoxyethylene) Xystyrene / p-hydroxystyrene / p-methoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-ethoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p- Hydroxystyrene / p-isopropoxycarbonyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-isobutyloxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) / P-isobutoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-isoamyloxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p -1-Methylcyclohexyloxystyrene), 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-methoxyethoxy) Styrene / 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 -1-Methylcyclohexyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / methyl methacrylate), poly (p-1-methoxyethoxystyrene / p-
Hydroxystyrene / tert-butyl methacrylate),
Poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / acrylonitrile), poly (p-1-n-butoxyethoxystyrene / p-hydroxystyrene / pn-butylstyrene), poly (p-1-isobutoxyethoxy) styrene/
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 (p-1-ethoxy Ethoxystyrene / p-hydroxystyrene / p-acetoxystyrene), poly (p-1-
Ethoxyethoxystyrene / p-hydroxystyrene / p-
Pivaloyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-cyclohexanecarbonyloxystyrene), 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-
Hydroxystyrene / p-methoxystyrene), poly [p-
(1-Methyl-1-n-propoxyethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly (m-1-ethoxypropoxystyrene / m-hydroxystyrene / m-
tert-butoxystyrene), poly (m-1-ethoxypropoxystyrene / m-hydroxystyrene / p-methylstyrene), poly [m- (1-methoxy-1-methylethoxy) styrene / m-hydroxystyrene / m- tert-butoxystyrene], poly [p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydrofuranyloxystyrene], poly [p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxy Styrene], poly [p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxystyrene], poly [p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene ], Poly [p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxy Styrene], poly [p-(1-methoxy-1-methylethoxy)
Styrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene], poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-vinylphenoxyacetate tert-butyl), poly (p-1-methoxyethoxy) Styrene / p-hydroxystyrene / p-vinylphenoxyacetic acid tert-butyl), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-vinylphenoxyacetic acid 1-methylcyclohexyl), poly [m-1-ethoxy Ethoxystyrene / m-hydroxystyrene / m-tert-butoxycarbonyloxystyrene], poly (m-1-ethoxyethoxystyrene / m-hydroxystyrene / m-tert-butoxystyrene), poly (m-1-methoxyethoxystyrene) / M-hydroxystyrene / m-tert-butoxystyrene), poly (p-1-ethoxyethoxystyrene / m-1-ethoxy) Ethoxystyrene / p-hydroxystyrene / m-hydroxystyrene / p-tert-butoxystyrene / m-tert-
Butoxystyrene), poly (p-1-methoxybutoxystyrene / p-hydroxystyrene / styrene), and the like, but of course the invention is not limited thereto.

[0100] Specific examples of the polymer represented by the general formula [2], for example, poly (p- hydroxystyrene / styrene), poly (p- methyl styrene / p- hydroxystyrene), poly (p- methoxystyrene / p -Hydroxystyrene), poly (p-ethylstyrene / p-hydroxystyrene), poly (p-ethoxystyrene / p-hydroxystyrene), poly (p-isopropoxystyrene / p-hydroxystyrene), poly (p-tert -Butylstyrene / p-hydroxystyrene), poly (p-tert-butoxystyrene / p-
Hydroxystyrene), poly (1-methylcyclohexyloxystyrene / p-hydroxystyrene), poly (m-te
rt-butoxystyrene / m-hydroxystyrene), poly (p-methoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-isopropoxycarbonyloxystyrene) / P-hydroxystyrene),
Poly (p-isobutoxycarbonyloxystyrene / p-hydroxystyrene), Poly (m-isobutoxycarbonyloxystyrene / m-hydroxystyrene), Poly (p-te
rt-Butoxycarbonyloxystyrene / p-hydroxystyrene), poly (m-tert-butoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-isoamyloxycarbonyloxystyrene / p-hydroxystyrene), poly (m- Isoamyloxycarbonyloxystyrene / m-hydroxystyrene), poly (p-tert-amyloxycarbonyloxystyrene / p-hydroxystyrene), poly (p-acetyloxystyrene / p-hydroxystyrene), poly (p-isobutyl) Royloxystyrene / p-hydroxystyrene), poly (p-pivaloyloxystyrene / p-hydroxystyrene), poly (p-cyclohexanecarbonyloxystyrene / p-hydroxystyrene), poly (p-sec-butoxycarbonyloxy) Styrene / p-hydroxystyrene), poly (p -Tetrahydrofuranyloxystyrene / p-hydroxystyrene), poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene), poly (m-tetrahydropyranyloxystyrene / m-hydroxystyrene), poly (p-vinylphenoxy) Tert-butyl acetate / p-hydroxystyrene),
Poly (p-vinylphenoxyacetic acid 1-methylcyclohexyl / p-hydroxystyrene), poly (styrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-methylstyrene / p-hydroxystyrene / p- 1-methoxyethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-tert-butylstyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene) , Poly (styrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-methylstyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (m-methylstyrene / p-hydroxy) Styrene / p-1-ethoxyethoxystyrene, poly (p-methoxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene Poly (p-
tert-butylstyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (styrene / p-hydroxystyrene) /
p-1-methoxy-1-methylethoxystyrene), poly (p-
Methylstyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-methoxy-1-methylethoxystyrene), poly (p-tert- Butylstyrene / p-
Hydroxystyrene / p-methoxy-1-methylethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (styrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-methylstyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-1-benzyloxy) Ethoxystyrene), poly (p-tert-butylstyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene /
p-1-benzyloxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-
1-ethoxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-tert-
Butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-tert
-Butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-te
rt-butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene) , Poly (p-acetyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene),
Poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly ( p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-vinylphenoxyacetic acid 1-methylcyclohexyl / p-hydroxystyrene / p-1-methoxyethoxystyrene ), Poly (p-vinylphenoxyacetic acid 1-
Methylcyclohexyl / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-vinylphenoxyacetic acid 1-methylcyclohexyl / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), etc. However, of course, it is not limited to these.

The polymer represented by the general formula [1] or the general formula [2] can be easily obtained by, for example, any of the following methods a) to d).

A ) Method-1 The following general formula [10]

[0103]

[Chemical 38]

[0104] (wherein, R is as. Defined above) and the monomer represented by any amount of the following general formula optionally [11]

[0105]

[Chemical Formula 39]

[0106] (wherein, R ¹ and R ⁵ are the same. As above) and a monomer represented by, a conventional method of polymer preparation, for example, radical polymerization initiators [such as 2,2' Azobisuisobuchi Ronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (methyl 2-methylpropionate), 2 Azo polymerization initiators such as 2,2'-azobis (ethyl 2-methylpropionate) and 2,2'-azobis (methyl 2-methylbutyrate), benzoyl peroxide, lauroyl peroxide, bis (4-tert-butyl) Cyclohexyl) peroxydicarbonate, ditert-butyl peroxide, tert-butylperoxy 2-ethylhexanoate, tert-butylperoxybenzoate, 1,1-bis (t
ert-butylperoxy) -3,3,5-trimethylcyclohexane and other peroxide-based polymerization initiators, etc.] in the presence of toluene, 1,4-dioxane, 1,2-dimethoxyethane, tetrahydrofuran, iso-propanol 50-120 in an organic solvent such as 2-methoxypropanol, 1,3-dioxolane, ethyl acetate or methyl ethyl ketone under a nitrogen or argon stream.
Polymerization reaction is carried out at a temperature of 1 to 10 hours. As the polymerization initiator, a low molecular weight polymer is easily obtained because of its high solubility in an organic solvent, and a non-nitrile type 2,2′-azobis (2-methyl) is advantageous in terms of safety and toxicity. More preferred are methyl propionate), 2,2′-azobis (ethyl 2-methylpropionate) and 2,2′-azobis (methyl 2-methylbutyrate). Further, in addition to this, for the purpose of obtaining a polymer having a small dispersity, n-butyllithium, under the catalyst of naphthalene potassium, etc., ethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, methyl ethyl ketone, 1,3-dioxolane,
Anionic living polymerization is preferred in which the reaction is carried out in a dehydrated organic solvent such as ethyl acetate or toluene in a stream of nitrogen or argon at an extremely low temperature of -50 ° C or lower for 1 to 20 hours. After the reaction, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [12] is used.

[0107]

[Chemical 40]

[ Wherein R, R ¹ , R ⁵ and k are the same as defined above, and e represents a natural number (provided that 0.75 ≦ e / (k +
e) ≦ 0.99. ). ] The polymer shown by is isolated. Then, this polymer is used 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-dioxolane, etc. Acids such as inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid and hydrobromic acid, and other Lewis acids, organic acids such as p-toluenesulfonic acid, malonic acid and oxalic acid are preferable. ] And 30 to 110 ° C. for 1 to 20 hours to completely eliminate the functional tert-butyl group. After the reaction, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [13] is used.

[0109]

[Chemical 41]

The hydroxystyrene polymer represented by the formula (wherein R, R ¹ , R ⁵ , e and k are the same as above) is isolated. Furthermore, this polymer and an arbitrary amount of the following general formula [1
4]

[0111]

[Chemical 42]

[0112] (wherein, R ³ and R ⁴ are the same. As above) and a vinyl ether compound represented by or isopropenyl ether compounds, tetrahydrofuran, acetone, methyl ethyl ketone, 1,4-dioxane, 1,3-dioxolane, chloride Methylene, 1,2-dimethoxyethane, ethyl ether,
In an organic solvent such as ethyl acetate or propylene glycol monomethyl ether acetate, a suitable catalyst [eg, sulfuric acid, hydrochloric acid, phosphorus oxychloride, p-toluenesulfonic acid, camphorsulfonic acid, chlorosulfonic acid / pyridine salt, sulfuric acid / pyridine salt, p-toluenesulfonic acid, pyridine salt, etc.], the reaction is performed at 10 to 100 ° C. for 1 to 30 hours to chemically introduce the functional group represented by the general formula [3] at an arbitrary ratio, and then to increase the concentration. Post-treatment is carried out according to a conventional method for obtaining a molecule to isolate the polymer represented by the above general formula [1] or general formula [2].

[0113] b) After polymerization by the same procedure as Method 1 a monomer represented by way -2 above general formula [10], perform post-processing in a conventional manner of a polymer acquisition method, the following general formula [ 15]

[0114]

[Chemical 43]

The homopolymer represented by the formula (wherein R is the same as above and d is a natural number) is isolated. Then, this homopolymer in an organic solvent such as tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, Suitable acids [for example, inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid and hydrobromic acid and other Lewis acids, organic acids such as p-toluenesulfonic acid, malonic acid and oxalic acid are preferred. ]
Reacts at 30-100 ° C for 1-10 hours
The t-butyl group is eliminated at any ratio. After the reaction, post-treatment is carried out according to a conventional method for obtaining a polymer, and the following general formula [1
6]

[0116]

[Chemical 44]

A hydroxystyrene copolymer represented by the formula : wherein R, R ¹ and k are the same as described above and c = m + n is isolated. This copolymer corresponds to a polymer of f = 0 in the general formula [2]. Furthermore, after introducing the functional group represented by the above general formula [3] into this copolymer by the same operation method as in method-1, post-treatment is carried out according to a conventional method for obtaining a polymer, and the above general formula [1] ( However, the polymer represented by k ≠ 0 or the general formula [2] (however, f ≠ 0) is isolated.

[0118] c) how -3 above general formula [10] or the following general formula [17]

[0119]

[Chemical formula 45]

[0120] (wherein, R is as. Above) after each the same procedure as Method 1 a monomer represented by the polymerized reaction, the post-processing according to a conventional method of polymer acquisition method, the General formula [15] or the following general formula [18]

[0121]

[Chemical formula 46]

The homopolymer represented by the formula (wherein R and d are the same as above) is isolated. Then, this homopolymer is prepared from tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, methanol, ethanol, n-propal, iso-propanol, n-butanol, sec-butanol, tert-butanol, water, etc. In a solvent, if necessary under a nitrogen stream, a suitable base [eg, sodium hydroxide, potassium hydroxide, ammonia water, hydroxylamine, various tetraalkylammonium hydroxide aqueous solutions, various trialkylamines, various triaralkylamines, etc. Is preferred. ], Or a suitable acid [eg, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid and other Lewis acids, p-
Toluenesulfonic acid, malonic acid, oxalic acid and the like are preferable. ], The reaction is carried out at 10 to 70 ° C. for 30 minutes to 10 hours to completely eliminate the functional tert-butyl group or acetyl group. After the reaction, the reaction is performed according to a conventional method for obtaining a polymer, and the following general formula [19] is used.

[0123]

[Chemical 47]

The hydroxystyrene polymer represented by the formula (wherein R and d are the same as above) is isolated. Further, after introducing the functional group represented by the above general formula [3] into this homopolymer by the same operation method as the method-1, post-treatment is carried out according to a conventional method for obtaining a polymer to obtain the above general formula [1]. The polymer represented by (however, k = 0) is isolated.

[0125] d) methods -4 above, tetrahydrofuran homopolymer represented by the obtained formula by the method -3 [19], 1,4-dioxane, ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, 1,3 In an organic solvent such as dioxolane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, methylene chloride, a suitable base [eg potassium hydroxide, sodium hydroxide, sodium carbonate , Potassium carbonate, triethylamine, N-methyl-2-pyrrolidone, piperidine, various tetraalkylammonium hydroxide aqueous solutions, various trialkylamines, various triaralkylamines and the like are preferable. ] In the presence of any amount of a protecting agent for hydroxyl group, for example, dialkyl dicarbonate such as ditert-butyl dicarbonate, alkyl chlorocarbonate such as methyl chlorocarbonate, 2,3-dihydrofuran, 2,3-dihydropyran, Reaction with tert-butyl monochloroacetate, 1-methylcyclohexyl monochloroacetate, isobutene, dimethylsulfate, methyl iodide, 1-methylcyclohexyl chloride, etc. at 10 to 100 ° C for 30 minutes to 30 hours. Post-treatment is performed according to a conventional method to obtain the polymer represented by the general formula [13].

[0126] After further introducing a functional group represented by the general formula [3] by the same procedure as Method 1 in the copolymer, by performing a post-treatment by a conventional method of polymer acquisition method,
The general formula [1] (where k ≠ 0) or the general formula [2]
A polymer represented by (provided that f ≠ 0) is obtained.

When the polymer composition of the present invention is used as a resist material, a preferable example of the polymer represented by the general formula [1] is that R and R ¹ are each independently a hydrogen atom or a lower alkyl group, and R ^{One of 2} and R ³ is a hydrogen atom or a lower alkyl group and the other is a lower alkyl group, R ⁴ is a lower alkyl group, and R ⁵ is a lower alkyl group, a lower alkoxy group, an acyloxy group as a substituent, Saturated heterocyclic oxy group or R ²⁵ O—CO— (CH ₂ ) _j
A phenyl group substituted with a group represented by O- (wherein R ²⁵ is a lower alkyl group, j is 0 or 1), and m
And n is a natural number, k is 0 or a natural number (where 0.1 ≦ (m
+ K) / (m + n + k) ≦ 0.9, 0 ≦ k / (m + n +
k) ≦ 0.25, and m> k. ).

As preferred examples of the polymer represented by the general formula [2], R ⁶ and R ²¹ are each independently a hydrogen atom, and R ⁷ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acyloxy group. group, a saturated heterocyclic oxy group, or _{^{R 8 O-CO- (CH 2}} ) Z -O- ( where, R ⁸ is a lower alkyl group, Z is 0 or 1.) a group represented by,
One of R ²² and R ²³ is a hydrogen atom or a lower alkyl group, R ²⁴ is a lower alkyl group, and p, r and f are natural numbers (provided that 0.1 ≦ p / (p + r + f) ≦ 0.5, 0).
≦ f / (p + r + f) ≦ 0.2 and f <p. ).

[0129] The average molecular weight of the polymer represented by the general formula [1] or general formula [2] include without particular limitation as long as it can be utilized as a resist material, a preferable range and the standard polystyrene G
The weight average molecular weight obtained by the PC measurement method is represented by the general formula [1].
The polymer represented by the formula is usually about 5,000 to 50,000, more preferably about 7,000 to 30,000.
The polymer represented by the formula (1) is usually about 1,000 to 25,000, more preferably about 2,000 to 15,000. Further, the weight average molecular weight of the polymer represented by the general formula [1] is larger than the weight average molecular weight of the polymer represented by the general formula [2], resolution performance, dimensional change at Delay Time, improvement of pattern side wall, substrate It is especially important in terms of improving dependence. There is no particular restriction on the specific difference in molecular weight, and this effect is recognized if the value of general formula [1] is slightly larger than that of general formula [2], but in general A polymer in which the weight average molecular weight of the polymer represented by [1] is larger than the weight average molecular weight of the polymer represented by the general formula [2] by about 10% or more is preferably used. Further, when the degree of dispersion of the polymer represented by the general formula [1] or the general formula [2] is in the range of 1.0 to 2.0, the elution rate to the developing solution at the exposed portion becomes uniform during development, and as a result,
It is preferable because the pattern side wall is improved.

[0130] a polymer represented by the general formula [1], a polymer represented by the general formula [2] weight ratio is usually 10: 9
To 10: 1, preferably about 3: 2 to 4: 1 which is effective in terms of heat resistance, mask linearity and proximity effect, Delay Time and resolution performance.

[0131] Phenolic compounds of the present invention the following general formula [20]

[0132]

[Chemical 48]

[0133] (wherein, R ²⁶ is a hydrogen atom,. A methyl group or an ethyl group) and phenol represented by any amount of the following general formula [21]

[0134]

[Chemical 49]

[ Wherein R ²⁷ represents a hydrogen atom, a lower alkyl group or an optionally substituted phenyl group], or an arbitrary amount of the following general formula [22]

[0136]

[Chemical 50]

[0137] (wherein, R ²⁸ is a hydrogen atom,. A methyl group or an ethyl group) and a dimethylol compound represented by
50 to 180 in the presence of an acid (for example, oxalic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, etc.), for example, in water, diethylene glycol, glycerin, etc. or a mixed solvent thereof, or without a solvent. The reaction may be carried out by stirring at 0.5 ° C. for 0.5 to 20 hours, and after the reaction, it is isolated by a treatment method such as concentration to dryness, injection into water, or fractionation.

In the general formula [21], the lower alkyl group represented by R ²⁷ is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, Examples thereof include n-propyl group and isopropyl group. Further, as the substituent of the optionally substituted phenyl group represented by R ²⁷ in the general formula [21], for example, halogen atoms such as chlorine, bromine, iodine and fluorine, methyl group, ethyl group, tert- An alkyl group such as a butyl group or a methoxy group,
Examples thereof include an alkoxy group such as an ethoxy group.

[0139] Specific examples of the phenolic compounds of the present invention, for example, a phenolic resin, include polycondensate of phenols and methylol compounds, specifically p- cresol / formaldehyde polycondensate, m- Cresol /
Formaldehyde polycondensate, p-cresol / m-cresol / formaldehyde polycondensate, phenol / formaldehyde polycondensate, p-cresol / acetaldehyde polycondensate, p-cresol / acetaldehyde polycondensate, m-
Cresol / acetaldehyde polycondensate, p-cresol / m-cresol / acetaldehyde polycondensate, phenol / acetaldehyde polycondensate, p-cresol / propionaldehyde polycondensate, m-cresol / propionaldehyde polycondensate, p-cresol / Propionaldehyde polycondensate, m-cresol / propionaldehyde polycondensate, phenol / propionaldehyde polycondensate, p-
Cresol / benzaldehyde polycondensate, m-cresol / benzaldehyde polycondensate, p-cresol / m-cresol / benzaldehyde polycondensate, phenol / benzaldehyde polycondensate, p-cresol / p-methylbenzaldehyde polycondensate, m- Cresol / p-methylbenzaldehyde polycondensate, p-cresol / m-cresol / p-methylbenzaldehyde polycondensate, phenol / p-methylbenzaldehyde polycondensate, p-cresol / 1,4-benzenedimethanol polycondensate , M-cresol / 1,4-benzenedimethanol polycondensate, p-cresol / m-cresol / 1,
4-benzenedimethanol polycondensate and the like can be mentioned.

As the phenolic compound of the present invention, in addition to the above resins, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 3,
4-dihydroxy-4- (2,4-dihydroxyphenyl) -7-
Also included are hydroxy-2,2,4-trimethyl-2H-1-benzopyran.

[0141] The molecular weight of the phenolic compounds of this invention include without particular limitation as long as it can be used as a resist material, the weight average molecular weight of 300 to that measured by GPC method using ordinary polystyrene as the standard 150
00 can be mentioned, but it is possible to improve the side wall shape and substrate dependence while maintaining the resolution performance and heat resistance.
It is preferably about -10000, more preferably about 300-8000.

[0142] and a phenolic compound of the present invention, the general formula
The total amount of the polymer represented by [1] and the polymer represented by the general formula [2] is usually 3: 7 to 1:99, and preferably the side wall shape is improved, the substrate dependence is improved, and the resolution performance is improved. In terms of points, it is about 2: 8 to 1:49.

When the polymer composition of the present invention is used as a resist material, in addition to the polymer composition of the present invention, radiation is used.
A substance that generates an acid upon irradiation with rays (hereinafter abbreviated as “acid generator”) is included as another constituent component. These components are generally used in a state of being dissolved in a solvent.

[0144] As the acid generator used in the present invention, release
Any substance can be used as long as it is a substance capable of generating an acid by irradiation with radiation and does not adversely affect the resist pattern formation, but particularly high light transmittance around 248.4 nm maintains high transparency of the resist material. Yes, or by exposure 248.
An acid generator that can enhance the light transmittance around 4 nm and maintain the high transparency of the resist material is preferable. Examples of particularly preferable acid generators in the present invention include, for example, the following general formula [23], general formula [24], general formula [26],
Examples thereof include the compounds represented by the general formula [27], the general formula [28] and the general formula [30].

[0145]

[Chemical 51]

[0146] represents wherein the R ⁹ and R ¹⁰ are each independently an alkyl group or a haloalkyl group, A represents a sulfonyl group or a carbonyl group. ]

[0147]

[Chemical 52]

[0148] In the formula, R ¹¹ is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group or a haloalkyl group,
R ¹² is an alkyl group, a haloalkyl group, or the following general formula [25]

[0149]

[Chemical 53]

[In the formula, R ¹³ is a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group, or a haloalkyl group, and q represents 0 or an integer of 1 to 3. } Is represented. ]

[0151]

[Chemical 54]

[0152] In the formulas, R ¹⁴ represents a hydrogen atom, a halogen atom,
It represents an alkyl group or a trifluoromethyl group, and R ¹⁵ represents an alkyl group, an aralkyl group, an alkoxy group, a phenyl group or a tolyl group. ]

[0153]

[Chemical 55]

[ Wherein R ¹⁶ is an alkyl group, a phenyl group,
A substituted phenyl group or an aralkyl group, R ¹⁷ and R ¹⁸
Each independently represent a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or an aralkyl group, and R ¹⁹ represents a fluoroalkyl group, a trifluoromethylphenyl group, a methyl group, or a tolyl group. ]

[0155]

[Chemical 56]

[ Wherein R ²⁹ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, and R ³⁰ and R ³¹ are each independently a hydrogen atom, a methyl group, a methoxy group or a nitro group. , A cyano group, a hydroxyl group or the following general formula [29]

[0157]

[Chemical 57]

[0158] (wherein, R ³³ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, B is a sulfonyl group or a carbonyl group.)
And R ³² represents a hydrogen atom, a methyl group or an ethyl group. ]

[0159]

[Chemical 58]

[ Wherein, R ³⁴ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, and R ³⁵ represents a hydrogen atom, a methyl group, a fluoroalkyl group, a methoxy group, a nitro group or a cyano group. Represents a hydroxyl group or the above general formula [29]. ]

In the general formula [23], the alkyl group represented by R ⁹ and R ¹⁰ and the haloalkyl group may be linear, branched or cyclic, preferably carbon. The number is 1 to 10, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-
Butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-
Examples thereof include a hexyl group, an isohexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Further, as the halogen of the haloalkyl group, chlorine,
Examples thereof include bromine, fluorine and iodine.

In the general formula [24], the alkyl group represented by R ¹¹ and the haloalkyl group may be linear or branched, and preferably have 1 to 5 carbon atoms. , For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
Examples thereof include an ert-butyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, and a 1-methylpentyl group, and the halogen atom represented by R ¹¹ or the halogen of the haloalkyl group is chlorine or bromine. , Fluorine, iodine and the like. The alkoxy group represented by R ¹¹ may be linear or branched, and preferably has 1 to 5 carbon atoms, for example, a methoxy group, an ethoxy group,
n-propoxy group, isopropoxy group, n-butoxy group,
Isobutoxy group, tert-butoxy group, sec-butoxy group,
Examples include n-pentyloxy group and isopentyloxy group. The alkyl group represented by R ¹² and the alkyl group of the haloalkyl group may be linear, branched or cyclic, and preferably have 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t
ert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group ,
Examples of the halogen of the haloalkyl group include chlorine, bromine, fluorine and iodine.

In the general formula [25], the alkyl group represented by R ¹³ and the haloalkyl group may be linear or branched, and preferably have 1 to 6 carbon atoms. , For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
ert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, n
-A hexyl group, an isohexyl group and the like can be mentioned. The alkoxy group having 1 to 6 carbon atoms represented by R ¹³ may be linear or branched, and preferably has 1 to 5 carbon atoms.
, For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n- Examples thereof include a hexyloxy group and an isohexyloxy group. Examples of the halogen atom represented by R ¹³ or the halogen of the haloalkyl group include chlorine, bromine, fluorine and iodine.

In the general formula [26], the alkyl group represented by R ¹⁴ may be linear or branched, and preferably has 1 to 5 carbon atoms, for example, a methyl group. , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, etc. Can be mentioned. Examples of the halogen atom represented by R ¹⁴ include chlorine, bromine, fluorine and iodine. The alkyl group represented by R ¹⁵ includes
It may be linear, branched or cyclic and preferably has 1 to 10 carbon atoms, for example, methyl group, ethyl group, n
-Propyl group, isopropyl group, cyclopropyl group, n-
Butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl Group, octyl group, nonyl group, decyl group and the like.

The aralkyl group represented by R ¹⁵ includes, for example, benzyl group, phenethyl group, phenylpropyl group,
Examples thereof include a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group. The C 1-6 alkoxy group represented by R ¹⁵ may be linear or branched and includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group. , Isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group and the like.

In the general formula [27], R ¹⁶ , R ¹⁷ and R
^The alkyl group represented by ¹⁸ may be linear, branched or cyclic, and preferably has 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group , Cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, Examples of the substituted phenyl group include an isohexyl group, a cyclohexyl group, a heptyl group, and an octyl group, and examples thereof include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, and a chlorophenyl group. Benzyl group, phenethyl group, phenylpropyl group,
Examples thereof include a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group. The alkyl group of the fluoroalkyl group represented by R ¹⁹ may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group. , Isopropyl group, n-
Butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, heptyl group, octyl group, etc. The total number of substituted fluorine atoms is preferably 1-17.

In formula [28], the alkyl group represented by R ²⁹ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms, for example Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, a chlorophenyl group, and the like, and an aralkyl group includes a benzyl group,
Examples thereof include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group. The alkyl group of the fluoroalkyl group may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group. , N-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group,
Examples thereof include isopentyl group, n-hexyl group, heptyl group and octyl group, and the total number of substituted fluorine atoms is preferably 1 to 17.

In the general formula [29], the alkyl group represented by R ³³ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms, for example Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, a chlorophenyl group, and the like, and an aralkyl group includes a benzyl group,
Examples thereof include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group. The alkyl group of the fluoroalkyl group may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group. , N-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group, etc., the total of substituted fluorine atoms Number is 1
Preferred are those of 17 to 17.

In the general formula [30], the alkyl group represented by R ³⁴ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms, for example Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, a chlorophenyl group, and the like, and an aralkyl group includes a benzyl group,
Examples thereof include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group and an ethylbenzyl group. The alkyl group of the fluoroalkyl group represented by R ³⁴ and R ³⁵ may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, methyl group, ethyl group. , N-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group and the like, The total number of substituted fluorine atoms is preferably 1-17.

[0170] Specific examples of preferred acid generator used At a present invention, as the acid generating agent represented by the general formula [23], for example, 1-cyclohexyl sulfonyl-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- Dimethylethylsulfonyl) -3,3-dimethyl-2-butanone,
1-Acetyl-1- (1-methylethylsulfonyl) diazomethane and the like can be mentioned.

[0171] As the acid generator represented by the general formula [24], such as bis (p- toluenesulfonyl) diazomethane, bis (2,4-dimethyl-benzenesulfonyl) diazomethane, methylsulfonyl -p- toluenesulfonyl diazomethane, bis ( p-tert-butylphenylsulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, cyclohexylsulfonyl-p-toluenesulfonyldiazomethane and the like can be mentioned.

[0172] As the acid generator represented by the general formula [26], for example, 1-p-toluenesulfonyl-1-cyclohexylcarbonyl diazomethane, 1-diazo-1- (p-toluenesulfonyl) -3,3-dimethylbutane -2-one, 1-diazo-
1-benzenesulfonyl-3,3-dimethylbutan-2-one,
1-diazo-1- (p-toluenesulfonyl) -3-methylbutan-2-one and the like can be mentioned.

[0173] As the acid generator represented by the general formula [27], for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, diphenyl -p- tolyl sulfonium perfluoro octane sulfonate, tris (p -Tolyl) sulfonium perfluorooctane sulfonate, tris (p-chlorobenzene) sulfonium trifluoromethanesulfonate, tris (p-tolyl) sulfonium trifluoromethanesulfonate,
Trimethylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethyl-p-tolylsulfonium
Examples thereof include trifluoromethanesulfonate, dimethyl-p-tolylsulfonium perfluorooctanesulfonate, and the like.

[0174] As the acid generator represented by the general formula [28], for example 2,6-di - trifluoromethanesulfonyloxy acetophenone, 2,6-di - trifluoromethanesulfonyloxy propiophenone, 2,3,4 Tris-trifluoromethanesulfonyloxyacetophenone, 2,6-di-
Methanesulfonyloxyacetophenone, 2,6-di-methanesulfonyloxypropiophenone, 2,3,4-tris-
Methanesulfonyloxyacetophenone, 2-trifluoromethanesulfonyloxyacetophenone, 2-methanesulfonyloxyacetophenone, 2-n-butanesulfonyloxyacetophenone, 2,6-di-n-butanesulfonyloxyacetophenone, 2,3,4-tris- n-butanesulfonyloxyacetophenone, 2,6-di-perfluoropropanecarboxyacetophenone, 2,3,4-tris-perfluoropropanecarboxyacetophenone, 2,6-di-p-toluenesulfonylacetophenone, 2,6-di -P-toluenesulfonylpropiophenone, 2,6-di-trifluoroacetyloxyacetophenone, 2-trifluoroacetyloxy-6-methoxyacetophenone, 6-hydroxy-2-
Perfluorobutanesulfonyloxyacetophenone,
Examples thereof include 2-trifluoroacetyloxy-6-nitroacetophenone, 2,3,4-tris-trifluoroacetyloxyacetophenone and 2,6-di-perfluoropropanoyloxyacetophenone.

[0175] As the acid generator represented by the general formula [30], for example 1,2,3-tris - methanesulfonyloxy benzene, 1,2,3-tris -p- toluenesulfonyloxy benzene, 1,2, 3-Tris-trifluoroacetyloxybenzene, 1,2,3-tris-perfluorobutanesulfonyloxybenzene, 1,2,3-tris-cyclohexylsulfonyloxybenzene, 1.2-di-methanesulfonyloxy-
3-nitrobenzene, 2,3-di-methanesulfonyloxyphenol, 1,2,4-tris-p-toluenesulfonyloxybenzene, 1,2,4-tris-methanesulfonyloxybenzene, 1,2,4-tris -Trifluoroacetyloxybenzene, 1,2,4-tris-cyclohexylsulfonyloxybenzene, 1,2-di-n-butanesulfonyloxy-3-nitrobenzene, 1,2,3-tris-perfluorooctanesulfonyloxybenzene , 1,2-di-perfluorobutanesulfonyloxyphenol and the like.

[0176] The resist composition of the present invention have the general formula [1] polymer and the general formula represented by [2] in shown are polymers each 1 or more, or polymers and the general formula represented by the general formula [1] [2] 1 or more of each of the polymers shown in 1 and 1 or more of the phenolic compound having a weight average molecular weight of 300 to 15,000 and good light transmittance around 248.4 nm, which can maintain the high transparency of the resist material, and the heat treatment after exposure. (PEB) An acid generator represented by the general formula [23] which has a low temperature dependency and generates a weak acid upon exposure to light, and a general formula which has a high acid generation efficiency or generates a strong acid at a constant exposure dose. Two
4], general formula [26], general formula [27], general formula [2
8] or an acid generator represented by the general formula [30] is used in combination.

[0177] That is, the resist material of the present invention has the effect of eliminating tail and scum skirt portion of the resist pattern. This phenomenon is considered to be due to the fact that an acid generator that generates a stronger acid or an acid generator that has a larger acid diffusion can uniformly desorb the functional group of the polymer to the bottom of the resist. From this viewpoint, as the acid generator in the resist composition of the present invention, the acid generator represented by the general formula [23], the general formula [24], the general formula [26], the general formula [27], and the general formula [ 28] or a combination with an acid generator represented by the general formula [30] gives particularly good results.

[0178] As the composition ratio of two or more acid generator, the general formula of the photoacid generator 100 parts by weight of the formula [23] [24], general formula [26], general formula [ Two
7], the general formula [28] or the general formula [30] is 1 to 70 parts by weight, preferably 10 to 50 parts by weight.

When the acid generator represented by the general formula [27], which is extremely effective in terms of skirting and scumming, is used alone, it causes the problem of pattern shape failure and dimensional variation due to the influence of Delay Time. However, by using an overcoat film together, this problem can be overcome, and therefore it can be used in the present invention.

Further , as an acid generator other than the particularly preferred acid generator in the present invention, various triphenylsulfonium salts and diphenyliodonium salts which have been conventionally used (as anions of these onium salts, PF
_{^{6 -, AsF 6 -, BF}} 4 - , and the like. ) And tris (trichloromethyl) -s-triazine / triethanolamine, tris (trichloromethyl) -s-triazine /
Acetamide and the like alone cannot be used because they are extremely susceptible to the effect of Delay Time, but can be used in combination with the acid generator represented by the general formula [23].

The solvent used in the resist composition of the present invention includes the polymer composition of the present invention, an acid generator and additives such as an ultraviolet absorber, an acid compound and a surfactant which are optionally used. Any one can be used as long as it can dissolve and, but usually, one having good film-forming property and having no absorption around 220 to 400 nm is 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, 3-methoxypropionic acid. Methyl, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone,
Methyl ethyl ketone, 2-heptanone, 1,4-dioxane,
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and ethylene glycol monoisopropyl ether, but the present invention is not limited thereto.

The mixing ratio of the polymer composition according to the present invention and the acid generator in the resist material is 100
The amount of the acid generator is 1 to 30 parts by weight, preferably 1 part by weight.
Up to 20 parts by weight. Further, as the amount of the solvent in the resist composition of the present invention, there is an obstacle in applying a positive resist composition obtained as a result of dissolving the polymer of the present invention and an acid generator and other additives onto a substrate. The amount is not particularly limited as long as it does not cause any trouble, but it is usually 1 to 20 parts by weight, preferably 1.5 to 10 parts by weight with respect to 1 part by weight of the polymer.

[0183] The resist composition of the present invention, three components usually the (polymer composition according to the present invention, an acid generator, and a solvent)
In addition to these, a UV absorber and an acidic compound are used as needed for the purpose of improving the side wall shape and improving scum and skirting at the interface with the substrate. Further, a surfactant may be used for the purpose of improving film-forming property, striation and wettability.

[0184] Examples of the ultraviolet absorber which is optionally used in the resist composition of the present invention include 9-diazofluorene and its derivatives, 1-diazo-2-tetralone, 2-diazo-1-tetralone, and 9-diazo-2-tetralone. -Diazo-10-phenanthrone, 2,
2 ', 4,4'-Tetrakis (o-naphthoquinonediazide-4-sulfonyloxy) benzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 1,2,3-tris (o-naphthoquinonediazide-4) -Sulfonyloxy) propane, 9- (2-methoxyethoxy) methylanthracene, 9- (2-ethoxyethoxy) methylanthracene, 9- (4-methoxybutoxy) methylanthracene, 9-anthracenemethyl acetate, dihydroxyflavanone, quercetin, Trihydroxyflavanone, tetrahydroxyflavanone, 4'6-
Examples thereof include dihydroxy-2-naphthobenzophenone, 4,4'-dihydroxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone, but the following general formula [31] has a strong absorption particularly near 248.4 nm.

[0185]

[Chemical 59]

[0186] In the shown is 9-diazo-10-phenanthrone,
Or the following general formula [32]

[0187]

[Chemical 60]

[0188] In the formula, R ²⁰ represents an alkyl group, x and y represents a natural number independently from each 1-4. ] The anthracene derivative shown by these is preferable.

In formula [32], the alkyl group represented by R ²⁰ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms, for example Methyl group , ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1 -Methylpentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.

Further , as the acidic compound which is optionally used in the resist material of the present invention, for example,
Phthalic acid, succinic acid, malonic acid, benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-
Organic acids such as acetylbenzoic acid, o-acetyloxybenzoic acid, o-nitrobenzoic acid, thiosalicylic acid, and thionicotinic acid, salicylaldehyde, salicylhydroxamic acid, succinimide, phthalimide, saccharin, and ascorbic acid. .

[0191] As the surfactant, such as polyethylene glycol distearate, polyethylene glycol dilaurate, polyethylene glycol, polypropylene glycol, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonyl In addition to nonionic surfactants such as ether and polyoxyethylene octylphenyl ether, various commercially available nonionic surfactants, fluorine-containing nonionic surfactants, fluorine-containing cationic surfactants, fluorine-containing anionic surfactants , Cationic surfactants, and anionic surfactants. In the present invention, among the above-mentioned surfactants, the film forming property of the resist film is good, for example, Florard (Sumitomo 3M Ltd. trade name), Surflon (Asahi Glass).
Fluorine-containing nonionic interfaces such as Unidyne (trade name), Unidyne (Daikin Industry Co., Ltd.), Megafac (Dainippon Ink Co., Ltd. trade name), F-top (Tochem Products Co., Ltd. trade name) Activators are particularly preferred.

[0192] Furthermore normal sensitivity adjustment agent used in the art, for example, polyvinylpyridine, poly (vinylpyridine / methyl methacrylate), pyridine, piperidine,
Tribenzylamine, N-methyl-2-pyrrolidone, monoalkylamines [Alkyl group has 1 to 12 carbon atoms
And a linear, branched or cyclic alkyl group which is, specifically, 2-methylcyclohexyl, 4-t-butylcyclohexylamine and the like are preferably mentioned. ], Dialkylamines [Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, and specifically, dicyclohexylamine, di-n-octylamine and the like are preferable. Can be mentioned. ], Trialkylamines [as an alkyl group, a carbon number of 1 to
Examples of the linear, branched or cyclic alkyl group of 12 are specifically tri-n-propylamine, tri-n-butylamine, trioctylamine, trihexylamine, dicyclohexylmethylamine and dicyclohexylethylamine. , Triethylamine, N-methyl-di-n
-Octylamine, dimethyl-n-dodecylamine, tris (2-ethylhexyl) amine and the like are preferable. ], Mono-, di-, or trialkanolamines [specifically, triisopropanolamine and the like are preferred. ], Tetraalkylammonium hydroxides [Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, and specific examples include tetramethylammonium hydroxide and tetraethylammonium hydroxy. And tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide are preferred. ] And the like, and plasticizers such as diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like may be appropriately used if necessary.

[0193] The resist composition of the invention are usable normal either on a semiconductor substrate to form a radiation sensitive absorbing film Any semiconductor substrate, a semiconductor substrate which has formed particularly sensitive radiation absorbing coating by The use of is more effective.

Examples of the semiconductor substrate include aluminum, polysilicon, aluminum-silicon, tungsten silicide and the like. When a radiation-sensitive absorbing film is formed on these semiconductor substrates, for example, Si ₃ N ₄ , Ti ₃ N ₄ , an inorganic antireflection film (S
It may be formed by chemical vapor deposition (CVD), sputtering or the like using a radiation-sensitive absorption coating material such as iON or amorphous carbon).

To form a pattern using a resist material using the novel polymer composition according to the present invention, for example, the following may be carried out.

The resist material containing the novel polymer composition according to the present invention is applied to a semiconductor substrate such as a silicon wafer or a semiconductor substrate having a radiation-sensitive absorption film formed thereon so as to have a thickness of about 0.5 to 2.0 μm. (When used as an upper layer of 3 layers, about 0.1 to 0.5 μm), and this is applied in an oven at 70 to 130 ° C. for 10 to 30 minutes, or on a hot plate at 70 to 150 ° C. for 1 to 2 minutes. Pre-bake. Then, a mask for forming a desired pattern is held over the resist film, and, for example, far-ultraviolet light of 300 nm or less is irradiated so that the exposure amount is about 1 to 100 mJ / cm ² , and then 70 to 70 on a hot plate. Bake at 150 ° C for 1-2 minutes. Further, using a developer such as a 0.1 to 5% tetramethylammonium hydroxide (TMAH) aqueous solution, a conventional method such as a dip method, a puddle method or a spray method for about 0.5 to 3 minutes. When developed, a desired pattern is formed on the substrate.

The developing solution used in the various pattern forming methods as described above is an alkali having an appropriate concentration capable of increasing the solubility difference between the exposed and unexposed areas depending on the solubility of the resist material. The aqueous solution 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, and aqueous solutions containing inorganic alkalis such as NaOH and KOH.

[0198] The resist composition of the present invention, a combination of a polymer polymer and weight average molecular weight represented by the general formula [1] is represented by the smaller general formula than that of the polymer of the formula [1] [2], Alternatively, the polymer represented by the general formula [1] is combined with the polymer represented by the general formula [2] and a phenolic compound having a weight average molecular weight of 300 to 15,000. The polymer shown is used for the same conventional purpose because it contains a monomer unit represented by the general formula [4] having a functional group represented by the general formula [3] as a constituent component as described above. Compared to other polymers, it has the property of more easily desorbing a functional group in the presence of an acid to become alkali-soluble, which enables high resolution performance, and from exposure to heat treatment (baking). Until It is possible to maintain a stable pattern dimension with respect to time. Further, due to the fact that it further contains the hydroxystyrene unit represented by the general formula [5] as a constituent component, it has heat resistance, has a dry etching system, and has excellent adhesion to the substrate. There is.
On the other hand, the polymer represented by the general formula [2] can be used by adjusting the constitutional ratio of the monomer unit represented by the general formula [7] and the monomer unit represented by the general formula [9] before use. To a certain extent to improve the focus margin and improve the mask linearity. At the same time, the effect of smoothing the pattern side wall is produced.

[0199] a polymer represented further by the general formula [1],
Phenolic compounds with a weight average molecular weight of 300 to 15,000
It is surprising that by combining the polymer represented by the general formula [2], the problem of substrate dependence can be solved in addition to the above-mentioned effects.

[0200] Incidentally, in the monomer unit is represented by the general formula [7], relative ease that the functional groups by elimination varies soluble hydroxystyrene unit in an alkaline developer in the presence of an acid ( For example, those in which R ⁷ is a tert-butyloxy group, a tetrahydrofuranyloxy group, a tetrahydropyranyloxy group, a tert-butoxycarbonyloxy group, a tert-butoxycarbonylmethyloxy group, a 1-methylcyclohexyloxycarbonylmethyloxy group, etc.) However, in the present invention, the monomer unit represented by the general formula [4] having the functional group represented by the general formula [3] is much faster, and is easily functionalized by the action of an acid. Since the group is eliminated to form a hydroxystyrene unit, does the monomer unit represented by the general formula [7] participate in the chemical amplification action at all?
Almost no involvement.

The present invention is a combination of a polymer represented by the general formula [1], a polymer represented by the general formula [2], and optionally a phenolic compound having a weight average molecular weight of 300 to 15,000, in combination. By using it and combining it with a specific acid generator according to the present invention, various problems that have been problems in the resist pattern formation using far ultraviolet light, KrF excimer laser light, etc. This is a significant effect in that it is possible to provide a resist material having various properties as described above and suitable for far ultraviolet light and KrF excimer laser light.

[0202] resist material of the present invention is far-ultraviolet light, KrF
Excimer laser light, i-line exposure, electron beam and soft X
It has been confirmed that acid is generated even by irradiation with rays and chemically amplified. Therefore, the resist material of the present invention is a resist material which can be patterned by a low exposure amount of far-ultraviolet light, KrF excimer laser light, i-ray light, electron beam or soft X-ray irradiation utilizing the chemical amplification effect.

[0203]

The operation of the present invention will be described with reference to specific examples. First, the portion exposed by KrF excimer laser light, far-ultraviolet light or the like is represented by, for example, the following formula 1, formula 2, formula 3, formula 4, or formula 5. Acid is generated according to the photoreaction.

[0204]

[Formula 1]

[0205]

[Formula 2]

[0206]

[Formula 3]

[0207]

[Formula 4]

[0208]

[Formula 5]

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

[0210]

[Formula 6]

[0211] On the other hand, since the unexposed portion is acid does not occur, chemical change does not occur even when heat treatment, rather a hydrophilic group moiety of the polymer used for the purpose of strengthening adhesion to the substrate is an acid generator alkali A function of protecting from the infiltration of the developer is developed. Thus, when patterning is performed using the resist material of the present invention, a large difference in solubility in the alkali developing solution occurs between the exposed portion and the 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 catalytically as shown in the formula 6, the exposure need only generate the necessary acid, and the exposure energy amount can be reduced.

The present invention will be described in more detail below with reference to Examples, Production Examples, Reference Examples and Comparative Examples, but the present invention is not limited by these. Regarding some of the polymers, acid generators, and ultraviolet absorbers used in Examples and Comparative Examples, for example, JP-A-4-210960 (US Pat. No. 5,216,135); JP-A-4-21258 ( US Patent No. 5,350,660; European Published Patent No. 0,440,374
JP-A-5-249682 (European Published Patent No. 0,520,
642); JP-A-4-51259; Y. Endo et al., Chem. Ph.
arm. Bull., 29 (12), 3753 (1981); M. Desbois
Bull. Chim. Soc. France, 1974 , 1956 or
It was synthesized by the method described in CDBeard et al., J. Org. Chem., 38 , page 3673 (1973).

[0213]

EXAMPLES Production Example 1 Synthesis of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene) (1) p-tert-butoxystyrene 100 g (0.567 mol) and p-methylstyrene 3.54 g (0.03 mol) was dissolved in 300 ml of 1,4-dioxane, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto, and the mixture was allowed to polymerize at 80 ° C for 6 hours under a nitrogen stream. It was After cooling the reaction solution, it was poured into 5000 ml of an aqueous methanol solution for crystallization. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to give poly (p-te-
92.3 g of rt-butoxystyrene / p-methylstyrene) was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene unit and p-methylstyrene unit of the obtained polymer was about 95: 5 by ¹ HNMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight is about
It was 20000.

[0214] (2) above (1) obtained in poly (p-tert-butoxystyrene / p- methylstyrene) and 70g was dissolved in 1,4-dioxane was added concentrated hydrochloric acid 100 ml 4 hours at 70 to 80 ° C. The reaction was carried out with stirring. After cooling, the reaction solution was poured into 5000 ml of water for crystallization. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene / p-methylstyrene) 47.6.
g was obtained as a white powder crystal. The composition ratio of p-hydroxystyrene unit and p-methylstyrene unit of the obtained polymer was about 95: 5 by 1HNMR measurement. Weight average molecular weight approx.
14500 (GPC method: polystyrene standard).

[0215] (3) above (2) obtained in poly (p- hydroxystyrene / p- methylstyrene) and 15.0g of ethyl vinyl ether 3.5g were dissolved in 1,4-dioxane 150 ml, this catalytic amount of p- toluenesulfonic Sulfonic acid pyridinium salt was added, and the mixture was reacted with stirring at room temperature for 24 hours. After the reaction,
It was poured into 5000 ml and crystallized. Precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene) 11.5g.
Was obtained as a white powder crystal. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and p-methylstyrene unit of the obtained polymer was about 35: 60: 5 by ¹ HNMR measurement. Weight average Weight average molecular weight About
18000, dispersity 1.86 (GPC method: polystyrene standard).

[0216] Using Preparative Example 2 Poly Synthesis of (p-1-ethoxyethoxystyrene / p- hydroxystyrene / styrene) (1) p-tert-butoxystyrene 81.1 g (0.46 mol) styrene 4.6 g (0.04 mol) Manufacturing example 1 (1)
Polymerization reaction and post-treatment are performed in the same manner as in
-Butoxystyrene / p-styrene) (77.1 g) was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene unit and styrene unit of the obtained polymer was about 92: 8 by ¹ HNMR measurement. Weight average molecular weight about 20000 (GPC
Method: polystyrene standard).

[0217] (2) above (1) obtained in poly (p-tert-butoxystyrene / styrene) of Production Example 1 using 70 g (2)
Reaction and post-treatment were carried out in the same manner as in (4) above to obtain 44.0 g of poly (p-hydroxystyrene / styrene) as white powder crystals. The composition ratio of p-hydroxystyrene unit and styrene unit of the obtained polymer was about 92: 8 by ¹ HNMR. Weight average molecular weight of about 15,000 (GPC method: polystyrene standard).

[0218] (3) poly obtained in the above (2) (p-hydroxystyrene / styrene) 15.0 g vinyl ethyl ether
Reaction and post-treatment were carried out in the same manner as in Production Example 1 (3) using 3.2 g of poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene / styrene) 14.1 g was obtained as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and styrene unit of the obtained polymer was about 32: 60: 8 by ¹ HNMR measurement. Weight average molecular weight about 18,000, dispersity 1.85 (GPC
Method: polystyrene standard).

[0219] was dissolved Production Example 3 Poly Synthesis of (p-1-ethoxyethoxystyrene / p- hydroxystyrene / p-tert-butoxystyrene) and (1) p-tert-butoxystyrene 17.6g in iso- propanol 50 ml, A catalytic amount of 2,2'-azobis (2-
Methyl methyl propionate) is added, and under a nitrogen stream,
Polymerization reaction was carried out at 80 ° C. for 6 hours. After cooling the reaction solution, it was poured into 1000 ml of an aqueous methanol solution for crystallization. The precipitated crystals were collected by filtration, washed with methanol and dried under reduced pressure to give poly (p-tert-
Butoxystyrene) (16.7 g) was obtained as white powder crystals.
Weight average molecular weight of about 20000 (GPC method: polystyrene standard).

[0220] (2) 4 hours of stirring the reaction at 70 to 80 ° C. was added and the resulting poly (p-tert-butoxystyrene) was suspended 15.0g in iso- propanol concentrated hydrochloric acid 15ml in the above (1). After cooling, the reaction solution was poured into 1000 ml of water for crystallization.
The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.4 g of poly (p-hydroxystyrene / p-tert-butoxystyrene) as white powder crystals. The composition ratio of p-hydroxystyrene unit and p-tert-butoxystyrene unit of the obtained polymer was about 94: 6 by ¹ HNMR measurement. Weight average molecular weight approx.
15000 (GPC method: polystyrene standard).

[0221] (3) above (2) obtained in poly (p- hydroxystyrene / p-tert-butoxystyrene) 15.7 g of ethyl vinyl ether 3.2g were dissolved in 1,4-dioxane 140 ml, this catalytic amount P-toluenesulfonic acid pyridinium salt was added, and the mixture was reacted with stirring at room temperature for 24 hours. After the reaction, the reaction solution was poured into 3000 ml of water for crystallization. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 15.5 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and p-tert-butoxystyrene unit of the obtained polymer was about 30: 64: 6 by ¹ HNMR measurement. Weight average molecular weight of about 18,000, dispersity 1.90 (GPC method: polystyrene standard).

[0222] Production Example 4 poly obtained in the synthesis of Production Example 3 of (2) (p-1- methoxy-1-methylethoxy styrene / p- hydroxystyrene / p-tert-butoxystyrene) (p-hydroxystyrene /
p-tert-butoxystyrene) 15.7 g and 2-methoxy-1-
3.2 g of propene was dissolved in 120 ml of tetrahydrofuran, a catalytic amount of phosphorus oxychloride was added, and the mixture was reacted with stirring at room temperature for 16 hours. After the reaction, pour into 5000 ml of water,
It was allowed to crystallize. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 14.3 g of poly (p-1-methoxy-1-methylethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) as white powder crystals. The composition ratio of p-1-methoxy-1-methylethoxystyrene unit, p-hydroxystyrene unit and p-tert-butoxystyrene unit of the obtained polymer was about 34: 60: 6 by ¹ HNMR measurement. Weight average molecular weight of about 17800, dispersity 1.90 (GPC method: polystyrene standard).

[0223] Production Example 5 Poly Synthesis of (p-1-ethoxyethoxystyrene / p- hydroxystyrene / p- tetrahydropyranyloxystyrene-) (1) p-acetyloxy styrene 32.4g with Production Example 3
Polymerization reaction and post-treatment were carried out in the same manner as in (1) above to obtain 30.0 g of poly (p-acetyloxy) styrene as white powder crystals. Weight average molecular weight of about 15,000 (GPC method: polystyrene standard).

[0224] (2) was dissolved the obtained poly (p- acetyloxy styrene) 16.2 g (1) in 1,4-dioxane was stirred for 4 hours under reflux of concentrated hydrochloric acid 25 ml. After cooling the reaction solution, it was poured into 1000 ml of water for crystallization. The precipitated crystals are collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene).
11.4 g was obtained as white powder crystals. Weight average molecular weight about 12
000 (GPC method: polystyrene standard).

[0225] (3) The obtained poly (p- hydroxystyrene) 10.8 g (2) was dissolved in 1,4-dioxane 72 ml, 2,3-
Dihydropyran (1.2 g) and p-toluenesulfonic acid / pyridine salt (0.05 g) were added, and the mixture was reacted with stirring at 25 to 30 ° C for 15 hours. The reaction solution was poured into 1000 ml of water for crystallization.
The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to give poly (p-hydroxystyrene / p-tetrahydropyranyloxystyrene).
10.0 g was obtained as white powder crystals. P- of the obtained polymer
The composition ratio of the hydroxystyrene unit and the p-tetrahydropyranyloxystyrene unit was about 95: 5 by ¹ HNMR measurement. Weight average molecular weight of about 13,000 (GPC method: polystyrene standard).

[0226] (4) the poly obtained in (3) (p-hydroxystyrene / p- tetrahydropyranyloxystyrene styrene) 9.
Using Production Example 3 using 5 g and 2.7 g of ethyl vinyl ether
The reaction and post-treatment are carried out in the same manner as in (3), and the resulting precipitated crystals are collected by filtration, washed with water and dried under reduced pressure to give poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxy). Styrene) (9.9 g) was obtained as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and p-tetrahydropyranyloxystyrene unit in the obtained polymer was about 35: 60: 5 by ¹ HNMR measurement. Weight average molecular weight of about 16,000,
Dispersity 1.78 (GPC method: polystyrene standard).

[0227] Poly obtained in the synthesis of preparation 6 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene / p-tert-butoxycarbonyloxystyrene) (1) of Production Example 3 (1) (p-tert -Butoxystyrene) 35.3g suspended in iso-propanol, concentrated hydrochloric acid
50 ml was added and the mixture was stirred and refluxed for 4 hours. After cooling the reaction solution, water
It was poured into 3000 ml and crystallized. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene) 22.1
g was obtained as a white powder crystal. Weight average molecular weight about 14500
(GPC method: polystyrene standard).

[0228] (2) poly (p- hydroxystyrene) 16.2 g obtained in the above (1) was dissolved in ethyl acetate 60 ml, di tert- butyl 3.0g and triethylamine 2.7g
Was added, and the mixture was reacted with stirring 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 and poured into 1000 ml of water for crystallization. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene /
12.0 g of p-tert-butoxycarbonyloxystyrene) was obtained as white powder crystals. The composition ratio of the obtained p-hydroxystyrene unit and p-tert-butoxycarbonyloxystyrene unit was about 94: 6 by ¹ HNMR measurement. Weight average molecular weight of about 16500 (GPC method: polystyrene standard).

[0229] (3) the poly obtained in (2) (p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene)
Reaction and post-treatment were carried out in the same manner as in Production Example 1 (3) using 11.4 g and 2.5 g of ethyl vinyl ether to give poly (p-
1-ethoxyethoxystyrene / p-hydroxystyrene /
p-tert-Butoxycarbonyloxystyrene) (6.7 g) was obtained as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit, p-hydroxystyrene unit and p-tert-butoxycarbonyloxystyrene unit of the obtained polymer was about 30: 64: 6 by ¹ HNMR measurement. Weight average molecular weight about 20000, dispersity 1.90 (GPC method: polystyrene standard).

[0230] obtained in the same manner as in Production Example 7 Poly Synthesis of (p-1-methoxy-ethoxy styrene / p- hydroxystyrene / p- vinylphenoxyacetate tert- butyl) (1) of Preparation Example 6 (1) poly (P-Hydroxystyrene) 16.2 g, tert-butyl monochloroacetate 2.7 g and anhydrous potassium carbonate 2.5 g were added to acetone 20
It was suspended in 0 ml and refluxed with stirring for 2 hours. After cooling, the insoluble matter was filtered off, and the filtrate was poured into 3000 ml of water for crystallization. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 15.8 g of poly (p-hydroxystyrene / p-vinylphenoxyacetate tert-butyl) as white powder crystals. P- hydroxystyrene unit of the obtained polymer and p- vinylphenoxyacetate component ratio of acetic acid tert- butyl unit ¹ from HNMR measurement about 93:
It was 7. Weight average molecular weight of about 16000 (GPC method:
Polystyrene standards).

[0231] (2) the poly (p- hydroxystyrene / p- vinylphenoxyacetate tert- butyl) obtained in (1) 13.
Using 2 g 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 was ¹ HNMR.
From about 33: 60: 7. Weight average molecular weight about 1950
0, dispersity 1.88 (GPC method: polystyrene standard).

[0232] Production Example 8 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene) Synthesis of preparation 6 (1) Poly obtained in the same manner as (p- hydroxystyrene) 8 g of ethyl vinyl ether 2.4g Was subjected to the reaction and post-treatment in the same manner as in Production Example 1 (3) to obtain 9.2 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) as a slightly brown powder crystal. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3 from ¹ H NMR measurement.
It was 8:62. Weight average molecular weight about 18500, dispersity 1.
88 (GPC method: polystyrene standard).

Production Example 9 Synthesis of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene) 8 g of poly (p-hydroxystyrene) obtained in the same manner as in Production Example 6 (1) and 2.2 g of methyl vinyl ether. Was subjected to the reaction and post-treatment in the same manner as in (3) of Production Example 1 to obtain 8.6 g of poly (p-1-methoxyethoxystyrene / p-hydroxystyrene) as light brown powder crystals. The composition ratio of p-1-methoxyethoxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 4: 6 by ¹ HNMR measurement. Weight average molecular weight about 18,000, dispersity
1.89 (GPC method: polystyrene standard).

[0234] Synthesis of preparation 10 Poly (p- tetrahydropyranyloxystyrene-/ p- hydroxystyrene) (1) a p-tert-butoxystyrene 17.6g was dissolved in toluene, to which a catalytic amount of 2,2'- Azobisisobutyronitrile was added, and a polymerization reaction was carried out at 80 ° C. for 6 hours under a nitrogen stream. After cooling the reaction solution, it was poured into 1000 ml of methanol for crystallization. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 16.8 g of poly (p-tert-butoxystyrene) as white powder crystals. Weight average molecular weight about 10,000 (GP
Method C: polystyrene standard).

[0235] (2) obtained above poly (p-tert-butoxystyrene) 15.0 g (1) was dissolved in 1,4-dioxane concentrated hydrochloric acid
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 for crystallization. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene) 9.7.
g was obtained as a white powder crystal. Weight average molecular weight about 7500
(GPC method: polystyrene standard).

[0236] (3) the poly (p- hydroxystyrene) 9.0 g obtained in (2) was dissolved in 1,2-dimethoxyethane 100 ml, which in 2,3-dihydropyran 12.6g and sulfuric 0.5m
1 was added and the mixture was reacted at 30-40 ° C for 15 hours with stirring. After the reaction, the reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium carbonate, and
It was poured into 1000 ml and crystallized. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 11.0 g of poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene) as white powder crystals. The composition ratio of p-tetrahydropyranyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight of about 10,000, dispersity of 1.60 (GPC method: polystyrene standard).

[0237] Production Example 11 Poly (p-tert-butoxycarbonyloxystyrene / p- hydroxystyrene) Synthesis of preparation 10 (2) poly obtained in the same manner as (p- hydroxystyrene) 18.0 g, dicarbonate Ditert-butyl 10.
Using 6 g and 18.0 g of triethylamine,
Reaction and post-treatment are carried out in the same manner as in (2), and poly (p-tert
18.2 g of (butoxycarbonyloxystyrene / p-hydroxystyrene) was obtained as white powder crystals. The composition ratio of p-tert-butoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight of about 10,000, dispersity of 1.65 (GPC method: polystyrene standard).

[0238] Production Example 12 Poly Synthesis of Production Example 10 (1) of (p-tert-butoxystyrene / p- hydroxystyrene) and obtained in the same manner as poly (p-tert
-Butoxystyrene) (15.0 g) was dissolved in 1,4-dioxane, 10 ml of concentrated hydrochloric acid was added, and the mixture was reacted with stirring at 80 to 85 ° C for 3 hours. After cooling the reaction solution, it was poured into water for crystallization.
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 of the obtained polymer was
It was about 3: 7 from ¹ H NMR measurement. Weight average molecular weight about 8
500, dispersity 1.65 (GPC method: polystyrene standard).

[0239] Production Example 13 Poly Synthesis of (p-tert-butoxycarbonyloxystyrene / p- hydroxystyrene) (1) with p-tert-butoxystyrene 17.6g Preparation 1
Polymerization was carried out in the same manner as in (1) of 0, and the reaction solution was treated to obtain 12.5 g of poly (p-tert-butoxystyrene) as white powder crystals. Weight average molecular weight of about 3500 (GPC method: polystyrene standard).

[0240] (2) above, the reaction was carried out in the same manner as (1) obtained in poly (p-tert-butoxystyrene) 12.0 g using of preparation 10 (2), poly (p- hydroxy Styrene) (8.2 g) was obtained as a white powder crystal. Weight average molecular weight of about 3000 (GPC method: polystyrene standard).

[0241] (3) above the reaction was carried out in the same manner as obtained in poly (p- hydroxystyrene) with 8.0g of preparation 6 (2) (2), poly (p-tert-butoxy Carbonyloxystyrene / p-hydroxystyrene) 7.
6 g was obtained as light brown powder crystals. Pt of the obtained polymer
The composition ratio of ert-butoxycarbonyloxystyrene unit and p-hydroxystyrene unit was about 3: 7 by ¹ HNMR measurement.
Met. Weight average molecular weight about 4000, dispersity 1.60
(GPC method: polystyrene standard).

[0242] Production Example 14 Poly (p- vinylphenoxyacetate tert- butyl / p- hydroxystyrene) Synthesis said poly obtained in Production Example 10 (2) (p- hydroxystyrene) 4.0 g and monochloroacetic acid tert- Butyl 2.5
g and anhydrous potassium carbonate (2.5 g) were suspended in acetone (35 ml), and the mixture was stirred and refluxed for 2 hours. After cooling, the insoluble material was filtered off, and the filtrate was poured into 1000 ml of water for crystallization. Precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-vinylphenoxyacetate tert-butyl acetate / p-hydroxystyrene) (5.2 g).
Was obtained as a white powder crystal. The composition ratio of the tert-butyl p-phenoxyacetate unit and the p-hydroxystyrene unit of the obtained polymer was about 35:65 by ¹ HNMR measurement. Weight average molecular weight of about 11,000, dispersity of 1.65 (GPC method: polystyrene standard).

[0243] Production Example 15 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene / fumaronitrile) Synthesis (1) p-tert-butoxystyrene 33.4 g (0.19 mol) and fumaronitrile 0.8 g (0.01 mole) of catalyst Quantity of 2,2 '
-In the presence of azobis (methyl 2-methylpropionate),
Polymerization reaction was carried out in a toluene solvent at 90 ° C. for 2 hours under a nitrogen stream. After the reaction, the reaction solution was poured into methanol for crystallization. The precipitated crystals were collected by filtration, washed and dried to obtain 23.5 g of poly (p-tert-butoxystyrene / fumaronitrile) as white powder crystals. Weight average molecular weight of about 24500 (GPC
Method: polystyrene standard).

[0244] (2) the reaction was carried out in the same manner as in Production Example 1 (2) using poly (p-tert-butoxystyrene / fumaronitrile) 20.0 g obtained in the above (1), poly (p -
Hydroxystyrene / fumaronitrile) (10.9 g) was obtained as white powder crystals. Weight average molecular weight 16500 (GPC
Method: polystyrene standard).

[0245] (3) the reaction was carried out in the same manner as above to obtain poly (p- hydroxystyrene / fumaronitrile) with 9.0g and ethyl vinyl ether 2.8g of Preparation 1 (2) (3), Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile) 8.3
g was obtained as a white powder crystal. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight about 20000, dispersity 1.85 (GPC method: polystyrene standard).

[0246] Synthesis of preparation 16 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene) (1) Poly (p-tert-butoxystyrene) [weight average molecular weight of about 20,000, polydispersity 1.2 (GPC method: Polystyrene Standard); manufactured by Nippon Soda Co., Ltd.]
Reaction and post-treatment were carried out in the same manner as in (1) to obtain 10.5 g of poly (p-hydroxystyrene) as white powder crystals. Weight average molecular weight of about 14,000 (GPC method: polystyrene standard).

[0247] (2) the monodisperse poly obtained in (1) (p-hydroxystyrene) 8 g of ethyl vinyl ether 2.4g
Was subjected to the reaction and post-treatment in the same manner as in (3) of Production Example 1 to obtain 9.0 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) as white powder crystals. The obtained polymer has p-1-ethoxyethoxystyrene unit and p-
The composition ratio of hydroxystyrene unit was about 3 from ¹ H NMR measurement.
It was 5:65. Weight average molecular weight about 17500, dispersity 1.
15 (GPC method: polystyrene standard).

[0248] Production Example 17 Poly (p- iso-butoxycarbonyloxystyrene / p- hydroxystyrene) Synthesis of poly (p- hydroxystyrene) [weight average molecular weight of about
10,000, dispersity 1.1 (GPC method: polystyrene standard); manufactured by Nippon Soda Co., Ltd.] 18.0 g, using 10.6 g of diisobutyl dicarbonate synthesized from isobutyl chlorocarbonate and potassium carbonate in the same manner as in (6) of Production Example 6. The reaction and post-treatment were carried out to obtain 16.5 g of poly (p-isobutoxycarbonyloxystyrene / p-hydroxystyrene) as light brown powder crystals. The composition ratio of p-isobutoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 28:72 by ¹ HNMR measurement. Weight average molecular weight about 13,000, dispersity 1.05 (GPC method:
Polystyrene standards).

[0249] Synthesis of preparation 18 Poly (p- ethoxycarbonyloxy styrene / p- hydroxystyrene) (1) a p-tert-butoxystyrene 17.6g was dissolved in toluene, to which a catalytic amount of 2,2'-azobis (2,4-Dimethylvaleronitrile) was added, and a polymerization reaction was carried out at 70 ° C. for 6 hours under a nitrogen stream. After the reaction, the same treatment as in (1) of Production Example 10 was conducted to give 16.5 g of poly (p-tert-butoxystyrene).
Was obtained as a white powder crystal. The weight average molecular weight of the obtained polymer was about 95 by the GPC method using polystyrene as a standard.
It was 00.

[0250] (2) above (1) obtained in the poly using (p-tert-butoxystyrene) 15.0 g was reacted and after-treatment in the same manner as in Production Example 10 (2), poly (p- hydroxystyrene ) 9.0 g was obtained as a white powder crystal. Weight average molecular weight approx.
7000 (GPC method: polystyrene standard).

[0251] (3) above, the reaction was carried out in the same manner as in Production Example 6 (2) using poly (p- hydroxystyrene) 9.0 g and diethyl pyrocarbonate 4.0g obtained in (2), poly 9.0 g of (p-ethoxycarbonyloxystyrene / p-hydroxystyrene) was obtained as white powder crystals. The composition ratio of p-ethoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight about 9,000, dispersity
1.60 (GPC method: polystyrene standard).

[0252] Production Example 19 Poly (p- isopropoxycarbonyloxy styrene / p- hydroxystyrene) in Production Example 18 (2) and similar-obtained poly (p- hydroxystyrene) 12.0 g and chlorocarbonate isopropyl
The reaction and post-treatment were carried out in the same manner as in Production Example 6 (2) using 4.5 g to obtain 11.7 g of poly (p-isopropoxycarbonyloxystyrene / p-hydroxystyrene) as white powder crystals. The composition ratio of p-isopropoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight of about 9,000, dispersity of 1.64 (GPC method: polystyrene standard).

[0253] Production Example 20 Poly (p-tert-butoxycarbonyloxystyrene / p- hydroxystyrene) Preparation Example 6 of the (1) described above-obtained poly (p- hydroxystyrene) 18.0 g and dicarbonate Di tert-butyl 10.6
The reaction and post-treatment were carried out in the same manner as in Production Example 6 (2) using g to give 18.2 g of poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) as white powder crystals. The composition ratio of p-tert-butoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 28:72 from ¹ HNMR measurement. Weight average molecular weight of about 19,000, dispersity of 1.85 (GPC method: polystyrene standard).

[0254] Production Example 21 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene) Synthesis of preparation 10 (2) poly obtained in the same manner as (p- hydroxystyrene) 16.0 g and vinyl ethyl ether Four.
Reaction and post-treatment were carried out in the same manner as in (3) of Production Example 1 using 5 g of poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene) (15.5 g) was obtained as white powder crystals. The composition ratio of p-1-ethoxyethoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 38:62 by ¹ HNMR measurement. Weight average molecular weight of about 9500, dispersity 1.65 (GPC method: polystyrene standard).

[0255] Production Example 22 Poly Synthesis of (p-1-ethoxyethoxystyrene / p- hydroxystyrene / p-tert-butoxystyrene) (1) p-acetyloxy styrene 48.6 g (0.3 mol) p
-tert-Butoxystyrene 17.6 g (0.1 mol) and a catalytic amount of 2,2'-azobis (2-methylisovaleronitrile) were used for the reaction and post-treatment in the same manner as in Production Example 3 (1), 59.7 g of poly (p-tert-butoxystyrene / p-acetyloxystyrene) was obtained as white powder crystals. The obtained polymer p-acetyloxystyrene unit and p-tert-
The composition ratio of butoxystyrene units was about 3: 1 by ¹ HNMR measurement. Weight average molecular weight about 10500, dispersity
1.32 (GPC method: polystyrene standard).

(2) 46.3 g of poly (p-acetyloxystyrene / p-tert-butoxystyrene) obtained in (1) above and
16% tetramethylammonium hydroxide aqueous solution 10
0 ml was used and the mixture was refluxed with stirring in 300 ml of isopropanol for 4 hours. The reaction solution was neutralized with acetic acid and then concentrated under reduced pressure, the residue was dissolved in 150 ml of acetone and poured into 5000 ml of water.
It was allowed to crystallize. The precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-hydroxystyrene / p-tert-butoxystyrene).
33.8 g was obtained as white powder crystals. Of the obtained polymer
The composition ratio of p-hydroxystyrene unit and p-tert-butoxystyrene unit was about 3: 1 by ¹ HNMR measurement. Weight average molecular weight of about 8540, dispersity 1.30 (GPC method: polystyrene standard).

[0257] (3) In the same manner as above to obtain poly (p- hydroxystyrene / p-tert-butoxystyrene) 26.8 g and with the ethyl vinyl ether 1.5g of Preparation 1 (2) (3) Reaction Then, post-treatment was carried out to obtain 25.0 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) as white powder crystals. The obtained polymer has p-1-ethoxyethoxystyrene unit and p-
The constituent ratio of the hydroxystyrene unit and the p-tert-butoxystyrene unit was about 10:65:25 by ¹ HNMR measurement. Weight average molecular weight about 9200, dispersity 1.30 (GPC
Method: polystyrene standard).

[0258] Production Example 23 p-cresol / m- cresol / formaldehyde polycondensate (weight average molecular weight of 800)
Synthesis of p-cresol 60.0 g (0.55 mol), m-cresol 6
To a mixture of 0.0 g (0.55 mol) and oxalic acid dihydrate 2.4 g, 37% formaldehyde aqueous solution (33.7 g, 0.42 mol) was added dropwise with stirring at 100 ° C, and then stirred at 100 ± 5 ° C for 4 hours with stirring. Let After the reaction, 2000 ml of water was injected to cause precipitation. After removing the supernatant liquid by decantation, the precipitate was dissolved in 120 ml of acetone, and 1200 ml of water was added to cause precipitation. Next, the supernatant was decanted and the precipitate was concentrated to dryness under reduced pressure to obtain 74.5 g of a residual p-cresol / m-cresol / formaldehyde polycondensate as a slightly yellow waxy crystal. Weight average molecular weight about 880, dispersity 2.07 (GPC
Method: polystyrene standard).

[0259] Production Example 24 p-cresol / m- cresol / formaldehyde polycondensate (weight average molecular weight 1500)
Synthesis of p-cresol 60.0 g (0.55 mol), m-cresol 6
0.0g (0.55mol) and 37% formaldehyde aqueous solution 4
Using 5.0 g (0.55 mol), the reaction and post-treatment were carried out in the same manner as in Production Example 23 to obtain 90.4 g of residual p-cresol / m-cresol / formaldehyde polycondensate as pale yellow wax crystals. Weight average molecular weight about 1580, dispersity 2.49 (G
PC method: polystyrene standard).

[0260] Production Example 25 p-cresol / m- cresol / formaldehyde polycondensate (weight average molecular weight 6000)
Synthesis of p-cresol 30.0 g (0.28 mol), m-cresol 3
0.0g (0.28mol) and 37% formaldehyde aqueous solution 4
The reaction and post-treatment were carried out in the same manner as in Production Example 23 using 0.5 g (0.50 mol) to obtain 38.4 g of a residual p-cresol / m-cresol / formaldehyde polycondensate as fine white waxy crystals. Weight average molecular weight of about 6600, dispersity of 6.82
(GPC method: polystyrene standard).

[0261] Synthesis (1) p-tert-butoxystyrene 17.6g of Preparation 26 Poly (p-1-ethoxyethoxystyrene / p- hydroxystyrene / p- isopropoxycarbonyloxy styrene) was dissolved in toluene, to which A catalytic amount of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and a polymerization reaction was carried out at 70 ° C. for 6 hours under a nitrogen stream. After the reaction, it was treated in the same manner as in Production Example 10 (1) to give 16.5 g of poly (p-tert-butoxystyrene).
Was obtained as a white powder crystal. The weight average molecular weight of the obtained polymer was about 95 by the GPC method using polystyrene as a standard.
It was 00.

[0262] (2) above, the reaction was carried out in the same manner as (1) obtained in poly (p-tert-butoxystyrene) by using 15.0g of preparation 10 (2), poly (p- hydroxy Styrene) 9.0 g was obtained as white powder crystals. Weight average molecular weight of about 7,000 (GPC method: polystyrene standard).

[0263] (3) above, the reaction was carried out in the same manner as in Production Example 6 (2) using poly (p- hydroxystyrene) 12.0 g and chloride isopropyl carbonate 3.0g was obtained in (2), poly (P-Isopropoxycarbonyloxystyrene / p-hydroxystyrene) (11.7 g) was obtained as white powder crystals. The composition ratio of p-isopropoxycarbonyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 2: 8 by ¹ HNMR measurement. Weight average molecular weight of about 8,000, dispersity 1.60 (GPC method: polystyrene standard).

[0264] (4) the poly obtained in (3) (p-isopropoxycarbonyloxy styrene / p- hydroxystyrene)
Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-isopropoxycarbonyloxystyrene) was reacted and post-treated in the same manner as in Production Example 1 (3) using 10.0 g and ethyl vinyl ether 0.8 g. ) 8.
9 g was obtained as white powder crystals. P-1 of the obtained polymer
The composition ratio of the ethoxyethoxystyrene unit to the p-hydroxystyrene unit and the p-isopropoxycarbonyloxystyrene unit was about 10:70:20 by ¹ H NMR measurement.
Weight average molecular weight of about 8300, dispersity 1.60 (GPC method: polystyrene standard).

[0265] Production Example 27 p- cresol / 1,4-dihydroxymethylbenzene synthetic p- cresol 38.4 g (0.36 mol) of polycondensates and xylene-.alpha.,
35.0 g (0.25 mol) of α'-diol was dissolved by heating, 0.15 g of methanesulfonic acid was added thereto at 90 to 100 ° C, and the mixture was reacted with stirring at the same temperature for 2 hours. After cooling, inject 100 ml of acetone, dissolve and inject in 2000 ml of water,
It was stirred. After standing, the supernatant was removed by decantation, the residue was dissolved in 100 ml of acetone, and 2000 ml of water was added.
Poured into and stirred. After standing, the supernatant was removed by decantation, the residue was dried under reduced pressure, and p-cresol / 1,4-dihydroxymethylbenzene polycondensate 65.0 g
Was obtained as a slightly yellow powdery crystal. Weight average molecular weight of about 6700,
Dispersion degree 3.50 (GPC method: polystyrene standard).

[0266] was prepared photoresist material consisting Example 1 the following compositions. Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) [weight average molecular weight 18000, dispersity 1.90: polymer of Production Example 3] 4.5 g poly (p-tert-butoxycarbonyloxystyrene / P-hydroxystyrene) [weight average molecular weight 10000, dispersity 1.65: polymer of Production Example 11] 1.5 g bis (1,1-dimethylethylsulfonyl) diazomethane 0.2 g bis (p-toluenesulfonyl) diazomethane 0.1 g propylene glycol monomethyl Ether acetate 22.7 g A pattern forming method using the above resist material will be described with reference to FIG. Chemical vapor deposition (CV
D) or the Ti ₃ N ₄ substrate 2 obtained by sputtering was spin-coated with the resist material 3 and prebaked at 90 ° C. for 90 seconds on a hot plate to obtain a resist material film with a thickness of 1.0 μm. (FIG. 1a). Then, 248.4 nm KrF excimer laser (NA 0.55) light 4 was selectively exposed through a mask 5 (FIG. 1b). Then, after post-baking on a hot plate at 100 ° C for 90 seconds, by developing with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, only the exposed portion of the resist material is dissolved and removed to form a positive pattern 3a. Obtained (Fig. 1c). The obtained positive pattern has a rectangular shape and a 0.24 μm line.
It had an and space resolution performance, and the exposure dose at this time was 28 mJ / cm ² .

In order to measure the heat resistance of the resist material of the present invention, the resist of the present invention was exposed, post-baked, and after development, the formed pattern was baked at 130 ° C. for 150 seconds on a hot plate. As a result, the shape is rectangular, 0.24
The line and space of μm was resolved, and the heat resistance of the resist film was confirmed.

[0268] resist material heat treatment from the exposure using (post-baking) up to the line and space of 0.24μm be passed but 4 hours was measured pattern size change over time of the present invention will be resolved without any problem It was

When the resist material of the present invention is used, FIG.
As shown in (4), the mask linearity was good up to 0.25 μm. Further, when exposed by defocus, there was no deterioration in shape up to ± 0.7 μm with respect to 0.30 μm line and space, and a sufficient focus margin was obtained. The pattern sidewall was also smooth, and no scum was observed.

Further , as a result of patterning the resist material of the present invention on a SiO ₂ substrate in the same manner as described above, 18 mJ
A 0.20 μm line and space was resolved in a rectangular shape with an exposure dose of / cm ² . When exposed with defocus,
± 0.7 μm for 0.25 μm line and space
There was no deterioration of the shape until now, and a sufficient focus margin was obtained.

[0271] Further the resist material of the present invention is prepared 23 ° C.
After storing for 1 month at 1, the pattern was formed in the same manner as above. As a result, a positive type pattern of 0.24 μm line and space was resolved with the same exposure amount, and the storage stability was good.

[0272] The photoresist material consisting of the composition of Example 2-30 Table 1-15 were respectively prepared.

[0273]

[Table 1] Table 1

[0274]

[Table 2] Table 2

[0275]

[Table 3] Table 3

[0276]

[Table 4] Table 4

[0277]

[Table 5] Table 5

[0278]

[Table 6] Table 6

[0279]

[Table 7] Table 7

[0280]

[Table 8] Table 8

[0281]

[Table 9] Table 9

[0282]

[Table 10] Table 10

[0283]

[Table 11] Table 11

[0284]

[Table 12] Table 12

[0285]

[Table 13] Table 13

[0286]

[Table 14] Table 14

[0287]

[Table 15] Table 15

[0288] each using the resist material prepared on people were to patterning in the same manner as in Example 1. Ti
The evaluation results on the ₃ N ₄ substrate are shown in Tables 16 and 17 , and Si
The evaluation results on the O ₂ substrate are shown in Tables 18 and 19 .

[0289]

[Table 16] Table 16

[0290]

[Table 17] Table 17

[0291]

[Table 18] Table 18

[0292]

[Table 19] Table 19

As is clear from Tables 16 to 19, Examples 2 to 2
In any of 30 Examples, a positive type pattern was formed in the same manner as in Example 1, and as in Example 1, 4 hours passed from exposure to heat treatment (post-baking) on the Ti ₃ N ₄ substrate. Even then, the 0.24 μm line and space was resolved without any problems. In addition, a focus margin of ± 0.7 μm or more was obtained for a 0.30 μm line and space.
The mask linearity was also good up to 0.25 μm.
In addition, all the resist materials of Examples 2 to 30 are SiO 2.
Other substrates such as ₂ also showed good performance and had no substrate dependence. Further, there was no problem in storage stability with any of the resist materials of Examples 2 to 30 .

When Example 10 and Examples 19 to 21 are compared, tert-butoxy, which is generally said to be easily eliminated by the action of an acid, in the polymer represented by the general formula [2]. It has been found that the use of a polymer having an ethoxycarbonyloxy group or an isopropoxycarbonyloxy group, which is less likely to be removed than a carbonyloxy group, is superior in the resolution performance on a SiO ₂ substrate. This is the general formula [2]
It has been proved that the polymer represented by is hardly involved in the chemical amplification reaction.

[0295] was prepared resist material consisting of Comparative Example 1 the following compositions. Poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) [weight average molecular weight 10000, dispersity 1.65: polymer of Production Example 11] 6.0 g biscyclohexylsulfonyldiazomethane 0.2 g bis (p-toluenesulfonyl) diazomethane 0.1 g Propylene glycol monomethyl ether acetate 22.7g

[0296] was carried out to pattern formation in the same manner as in Example 1 using a resist material having the above composition. as a result,
Even at the exposure dose of 80 mJ / cm ² , 0.30 μm could not be resolved.

[0297] For Comparative Example 2 to 21 compare, the photoresist material consisting of the composition shown in Table 20 to Table 26 were respectively prepared.

[0298]

[Table 20] Table 20

[0299]

[Table 21] Table 21

[Table 22] Table 22

[0300]

[Table 23] Table 23

[0301]

[Table 24] Table 24

[0302]

[Table 25] Table 25

[0303]

[Table 26] Table 26

[0304] each using the resist material prepared on people were to patterning in the same manner as in Example 1. The results are shown in Table 27 .

[0305]

[Table 27] Table 27

Further , the unresolvable pattern shapes of 0.30 μm in Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 10, and Comparative Example 17 are shown in FIG. 2, and Comparative Example 4, Comparative Example 11, and Comparative Example. 1
3, the comparative example 14, the comparative example 16 and the comparative example 21 pattern shape (0.30 μm shape insufficient) is shown in FIG. 3, the comparative example 6, the comparative example 7 and the comparative example 9 pattern shape (0.30 μm defective shape). 4 shows the pattern shapes of Comparative Example 5, Comparative Example 8, Comparative Example 12, Comparative Example 15, Comparative Example 18, Comparative Example 18, Comparative Example 19 and Comparative Example 20 (shape defects of 0.30 μm) in FIG. 5, respectively. Further, FIG. 6 shows the pattern shapes with poor heat resistance of Comparative Example 5, Comparative Example 8, Comparative Example 12, and Comparative Example 15.

As is clear from Table 27 and FIGS. 2 to 5, in these comparative examples, the resolution performance is inferior as compared with the resist material of the present invention. In addition, even if 0.30 μm is resolved,
As is clear from the above, the heat resistance is poor. In particular, Example 1
From 0 and Comparative Examples 18 to 21, the weight average molecular weight of the polymer represented by the general formula [2] is smaller than that of the polymer represented by the general formula [1], and further represented by the general formula [2]. Even if the weight average molecular weight of the polymer is smaller than that of the polymer represented by the general formula [1], it is clear that the use amount of the polymer represented by the general formula [2] is small to achieve the present invention. is there.

[0308] was prepared resist material consisting of Comparative Example 22 the following composition. Poly (p-1-methoxyethoxystyrene / p-hydroxystyrene) [weight average molecular weight 18000, dispersity 1.89: polymer of Production Example 9] 1.5 g poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p- (tert-butoxystyrene) [weight average molecular weight 9200, dispersity 1.30: polymer of Production Example 22] 4.5 g biscyclohexylsulfonyldiazomethane 0.3 g bis (p-toluenesulfonyl) diazomethane 0.1 g N, N-dimethylacetamide 0.3 g propylene glycol Monomethyl ether acetate 24.3g

[0309] was carried out to pattern formation in the same manner as in Example 1 using a resist material having the above composition. as a result,
A 0.24 μm line and space pattern was resolved with an exposure dose of 32 mJ / cm ² , but the pattern shape was poor as shown in FIG. In addition, when heat treatment was performed 4 hours after the exposure, the dimension changed to 0.35 μm.

From the results of Example 25 and Comparative Example 22, it is clear that one of the conditions for achieving the present invention is that the amount of the polymer represented by the general formula [2] used is smaller than that in the general formula [1]. Is.

[0311]

As is apparent from the above description, the resist material using the polymer composition of the present invention as a polymer component is used as a light source of 300 nm or less on a Ti ₃ N ₄ substrate, for example, deep ultraviolet light (Deep UV), For example, when used as a resist material for exposure of KrF excimer laser light (248.4 nm), etc., it has extremely high resolution performance as compared with conventional resist materials, shows a good pattern shape, a good mask linearity, and Stable pattern dimensions can be maintained over time from exposure to heat treatment (post bake),
A practical fine pattern with a good quarter-micron shape can be easily obtained with a large depth of focus margin.
Further, the resist material according to the present invention has been confirmed to have excellent performance even when used on other substrates, and there is no problem of substrate dependence which is a problem with conventional resist materials. Therefore,
The present invention has great value for the formation of ultrafine patterns in the semiconductor industry and the like. The resist material according to the present invention is particularly effective in pattern formation using far-ultraviolet light and KrF excimer laser light, but is also effective in pattern formation using i-ray light, electron beams, soft X-rays and the like. It can be used.

[0312]

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view of 0.30 μm L / S pattern formation failure observed in Comparative Examples 1 to 3, Comparative Example 10 and Comparative Example 17.

3 is a comparative example 4, a comparative example 11, a comparative example 13;
˜14, 0.30 μ observed in Comparative Example 16 and Comparative Example 21
It is sectional drawing of m L / S pattern defectiveness.

FIG. 4 is a cross-sectional view of 0.30 μm L / S pattern shape defects observed in Comparative Examples 6 to 7 and Comparative Example 9.

5 is a comparative example 5, a comparative example 8, a comparative example 12,
0.30 μm observed in Comparative Example 15, Comparative Examples 18 and 20
It is sectional drawing of L / S pattern shape defect.

FIG. 6 shows the pattern shape of poor heat resistance after development and baking at 130 ° C. for 150 seconds observed in Comparative Example 5, Comparative Example 8, Comparative Example 12, and Comparative Example 15.

[Explanation of symbols]

1 ... Aluminum substrate, 2 ... Ti ₃ N ₄ substrate, 3 ... Resist material film according to the present invention, 4 ... KrF excimer laser light, 5 ... Mask, 3a ... Resist pattern .

Continuation of front page (56) Reference JP-A-7-199468 (JP, A) JP-A-7-181680 (JP, A) JP-A-7-146558 (JP, A) JP-A-6-266111 (JP , A) JP 6-95389 (JP, A) JP 4-217251 (JP, A) JP 4-134345 (JP, A) JP 3-206458 (JP, A) JP 8-15864 (JP, A) JP-A-8-262721 (JP, A) JP-A-9-5987 (JP, A) JP-A-9-6001 (JP, A) JP-A-9-6002 (JP, A) A) JP 9-22117 (JP, A) JP 9-127698 (JP, A) JP 9-90639 (JP, A) JP 9-211866 (JP, A) JP 8 -160622 (JP, A) JP-A-8-337616 (JP, A) JP-A-9-160244 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00- 7/42

Claims (11)

(57) [Claims] 1. (i) In the presence of acid, heating causes chemical change
Functional groups that can be easily alkali-soluble by receiving (hereinafter,
Abbreviated as functional group A. ) HasThe following general formula [4] [Chemical 1] [In the formula, R represents a hydrogen atom or a lower alkyl group, ²
And R ³ Are independently replaced by hydrogen atom and halogen.
Represents an optionally substituted alkyl group or an allyl group, and the two are bonded to each other.
May combine with each other to form an alkylene ring (provided that R is ²
And R ³ Except when both are hydrogen atoms. ), R ^Four Is a halogen
Alkyl group or aralkyl group optionally substituted with
Represents ]Contains monomer units as constituents
Polymer (Less than,Polymer 1Is abbreviated.)
And (ii) in the presence of acid, undergoes a chemical change due to heating
Although it is a functional group that can be soluble in potassium, in (i) above
Functional group that is less susceptible to chemical changes than functional group A (hereinafter,
Abbreviated as functional group B. ) HasThe following general formula [7] [Chemical 2] [In the formula, R ⁶ Represents a hydrogen atom or a lower alkyl group, R ⁷
Is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
Ruoxy group, saturated heterocyclic oxy group or R ⁸ O-CO-
(CH ₂ ) _Z -O- (However, R ⁸ Represents an alkyl group, Z
Represents 0 or a natural number. ) Represents a group represented by. ]
Be donePolymer containing monomer units as constituents
ー (Less than,Polymer 2Is abbreviated.), AndComprises
Polymer compositionAnd (i) the following general formula [23] [Chemical 3] [In the formula, R ⁹ And R ^Ten Are each independently an alkyl group or
Is a sulfonyl group or carbonyl.
Represents a group. ] Generates an acid by irradiation
Substances, and (ii) the following general formula [24] [Chemical 4] [In the formula, R ¹¹ Is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group or a haloalkyl group, R ¹² Is Archi
Group, haloalkyl group, or the following general formula [25] [Chemical 5] {In the formula, R ¹³ Is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group or a haloalkyl group, q is 0 or
It represents an integer of 1 to 3. } Is represented. ], The following general formula [2
6] [Chemical 6] [In the formula, R ¹⁴ Is a hydrogen atom, a halogen atom, an alkyl group or
Represents a trifluoromethyl group, R ¹⁵ Is an alkyl group,
Aralkyl group, alkoxy group, phenyl group or tolyl group
Represent ], The following general formula [27] [Chemical 7] [In the formula, R ¹⁶ Is an alkyl group, phenyl group, substituted phenyl
Represents a group or an aralkyl group, and R ¹⁷ And R ¹⁸ Are each independent
Hydrogen atom, alkyl group, phenyl group, substituted phenyl
A group or an aralkyl group, R ¹⁹ Is fluoroalkyl
Group, trifluoromethylphenyl group, methyl group, or
Represents a ryl group. ], The following general formula [28] [Chemical 8] [In the formula, R ²⁹ Is an alkyl group, fluoroalkyl group,
Represents a nyl group, a substituted phenyl group or an aralkyl group, and R ³⁰
And R ³¹ Are each independently a hydrogen atom, methyl group, methoxy
Group, nitro group, cyano group, hydroxyl group or the following general formula [2
9] [Chemical 9] (In the formula, R ³³ Is an alkyl group, fluoroalkyl group,
Represents a nyl group, a substituted phenyl group or an aralkyl group, and B represents
Represents a sulfonyl group or a carbonyl group. ), R ³²
Represents a hydrogen atom, a methyl group or an ethyl group. ] Or the following
General formula [30] [Chemical 10] [In the formula, R ³⁴ Is an alkyl group, fluoroalkyl group,
Represents a nyl group, a substituted phenyl group or an aralkyl group, and R ³⁵
Is a hydrogen atom, methyl group, fluoroalkyl group, methoxy
Group, nitro group, cyano group, hydroxyl group or the above general formula [2
9]. ] Generates an acid by irradiation
And a resist composition comprising:
The weight average molecular weight of the mer 2 is the weight average molecular weight of the polymer 1.
Less than Chemically amplified positive resist characterized by
material. 2. The resist according to claim 1, wherein each of Polymer 1 and Polymer 2 further comprises, as a constituent, a monomer unit capable of imparting heat resistance and substrate adhesion to the polymer.
Material . 3. The resist material according to claim 2, wherein at least one of Polymer 1 and Polymer 2 further comprises a third monomer unit as a constituent component. 4. The resist material according to claim 1, further comprising a phenolic compound having a weight average molecular weight of 300 to 15,000. 5. A monomer unit capable of imparting heat resistance and substrate adhesion to a polymer is represented by the following general formula [5] : [In the formula, R represents a hydrogen atom or a lower alkyl group. Resist material according to any one of claims 2-4 is a monomer unit represented by. 6. A polymer 1 is represented by the following general formula [1] : [Wherein R, R ² , R ³ and R ⁴ are the same as defined above, R ¹ represents a hydrogen atom or a lower alkyl group, and R ⁵ represents a cyano group, an optionally esterified carboxyl group or a substituent. It represents a phenyl group which may be present, m and n represent natural numbers, and k represents 0 or a natural number (provided that m> k). Resist material according to any one of claims 2-4 is a polymer represented by. 7. A polymer 2 is represented by the following general formula [2] : [Wherein R ⁶ and R ⁷ are the same as defined above, R ²¹ represents a hydrogen atom or a lower alkyl group, and R ²² may have a cyano group, an optionally esterified carboxyl group or a substituent. Represents a good phenyl group, p and r represent natural numbers, and f
Represents 0 or a natural number (provided that p> f). ] The resist material according to claim 6 , which is a polymer represented by
Fee . 8. The method according to claim 1, further comprising an ultraviolet absorber .
7. The resist material according to any one of 7 . 9. The weight average molecular weight of the polymer represented by the general formula [1] is 5,000 to 50,000, the formula [2] according to claim 7 which is a 1,000～25,000 polymer represented by
8. The resist material according to any one of 8 . 10. In the general formula [1], 0.1 ≦ (m + k) /
(M + n + k) ≦ 0.9, 0 ≦ k / (m + n + k) ≦ 0.2
5, and m> k, and 0.1 ≦ p / in the general formula [2].
(P + r + f) ≦ 0.5, 0 ≦ f / (p + r + f) ≦ 0.2
0, Le according to any one of claims 7 to 9 which is and p> f
Gist material . 11. applying the resist material according to any one of claims 1 to 10 on a semiconductor substrate, heated, through a mask
A pattern forming method, which comprises irradiating with radiation , then heating if necessary, and then developing. [0001]