JP2003330194A - Positive photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition free from problems relating to tailing in a pattern profile or line edge roughness so as to solve problems in the techniques to improve the performance of microphotofabrication using far UV rays, in particular, ArF excimer laser light. <P>SOLUTION: The positive photosensitive composition contains (A) a compound which generates an acid by radiation of active rays or radiation and (B) a resin which has a cyanide group in the side chain and is decomposed by the effect of an acid to increase the solubility in an alkali developer liquid. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. .

[0002]

BACKGROUND OF THE INVENTION A positive photoresist is applied to a substrate such as a semiconductor wafer, glass, ceramics or metal by spin coating method or roller coating method.
It is applied to a thickness of ˜2 μm. Then, heat and dry,
A positive pattern is formed by baking a circuit pattern or the like through an exposure mask by ultraviolet irradiation or the like, optionally baking after exposure and then developing. Further, etching is performed using this positive image as a mask, whereby patterned processing can be performed on the substrate. IC is a typical application field
And other semiconductor manufacturing processes, liquid crystal, circuit board manufacturing such as thermal heads, and other photofabrication processes.

Conventionally, in order to improve the resolution and obtain an image having a good pattern shape, it has been advantageous to use a resist having a high contrast (γ value), and technical development of a resist composition suitable for such a purpose has been carried out. I've been told. There are numerous publications disclosing such techniques. In particular, regarding the resin, which is the main part of the positive photoresist, many patent applications have been made regarding the monomer composition, molecular weight distribution, synthetic method, etc., and some results have been achieved. Also, with regard to the photosensitive material which is another main component, compounds having many structures which are effective for increasing the contrast have been disclosed. By designing a positive photoresist using these techniques, it has become possible to develop an ultrahigh resolution resist capable of resolving a pattern having a size comparable to the wavelength of light.

However, integrated circuits are becoming more and more integrated, and it is necessary to process an ultrafine pattern having a line width of 0.2 μm or less in the manufacture of semiconductor substrates such as VLSI. Is becoming.

Japanese Unexamined Patent Publication No. 2001-200016 describes a composition containing a copolymer of an alkyl vinyl ether monomer and maleic anhydride for the purpose of improving the adhesion to the lower film and the dry etching resistance. Japanese Patent Laid-Open No. 11-38628 describes a composition containing a copolymer of vinyl ether and maleic acid ester for the purpose of improving sensitivity, pattern profile and substrate adhesion.

Japanese Patent Laid-Open Nos. 2000-258915 and 2
No. 000-275843 has examined a resin containing a repeating unit having a cyano group from the viewpoint of improving the adhesion to a substrate. In JP-A-2001-188347, a repeating unit derived from a (meth) acrylic acid derivative having an alicyclic skeleton having an oxygen- or nitrogen-containing polar group and a repeating unit derived from another (meth) acrylic acid derivative having an alicyclic skeleton Attempts have been made to provide a resist composition which is excellent in storage stability and transparency, as well as in basic physical properties such as dry etching property, sensitivity, resolution and pattern shape, by using a resin having units.

However, these conventional resist materials do not have sufficient performance in terms of pattern skirting, line edge roughness and the like.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problems in the technology for improving the performance of microphotofabrication using far-ultraviolet light, especially ArF excimer laser light. Another object of the present invention is to provide a positive photosensitive composition that does not have any problems in terms of skirting and line edge roughness.

[0009]

The above object can be achieved by a positive type photosensitive composition having the following constitution.

(1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation, and (B) a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II) And a resin (acid-decomposable resin) containing a repeating unit represented by the general formula (N) and decomposed by the action of an acid to increase the solubility in an alkali developing solution. -Type photosensitive composition.

[0011]

[Chemical 5]

[0012]

[Chemical 6]

In the general formula (I), R_1aIs a hydrogen atom
Represents a hydrocarbon group, R_2aRepresents a hydrocarbon group. Incidentally, R
_1aAnd R_2aAnd may combine with each other to form a ring. General
In formula (II), Z is -O- or -N (R_3a) −
Represents Where R _3aIs a hydrogen atom, hydroxyl group, alkyl
Group, haloalkyl group or -OSO₂-R_4aRepresents Also
R_4aIs an alkyl group, haloalkyl group, cycloalkyl
Represents a group or camphor residue. In the general formula (N), R is water
Represents an elementary atom or a methyl group. A₁Is a single bond or a divalent
Represents a group. A₂Is a single bond, alkylene group, ether
Consists of groups, ester groups, or combinations thereof
Represents a group. Z₂Represents an aliphatic cyclic hydrocarbon group. l is 0
Or represents 1. A₃Is a single bond, alkylene group, ether
Group, ester group or a combination thereof
Represent R'represents a cyan group. m represents an integer of 1 to 3
You However, when l = 0, A₂And A₃At least one of
Is an alkylene group, an ether group, an ester group or the
It is a combination.

Furthermore, the following configurations can be mentioned as preferred embodiments.

(2) The acid-decomposable resin has the general formula (pI)
To (pV) containing a repeating unit having a group capable of decomposing by the action of an acid,
The positive photosensitive composition as described in 1.

[0016]

[Chemical 7]

In the formula, R ₁₁ is a methyl group, an ethyl group or n-
It represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ , and either R ₁₅ or R ₁₆ represent an alicyclic hydrocarbon group. R ₁₇
To R ₂₁ are each independently a hydrogen atom, a C 1 to C 4,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is an aliphatic group. Represents a cyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring.

(3) The compound (A) which generates an acid upon irradiation with actinic rays or radiation is a compound represented by the general formula (A2I) or the general formula (A2II). The positive photosensitive composition as described in 1) or (2).

[0019]

[Chemical 8]

In the general formula (A2I): R_1c~ R_5cAre each
Independently of a hydrogen atom, an alkyl group, an alkoxy group, or
Represents a logen atom. R_6cAnd R_7cAre each independently hydrogen
Represents an atom, an alkyl group, or an aryl group. Rx and Ry
Are each independently an alkyl group, a 2-oxoalkyl group,
Alkoxycarbonylmethyl group, allyl group, or vinyl
Represents a group. R_1c~ R_7cAny two or more, and Rx
And Ry may be bonded to each other to form a ring structure,
This ring structure is composed of oxygen atom, sulfur atom, ester bond, and
It may contain a mid bond. X^-Is sulfonic acid,
Represents an anion of rubic acid or sulfonylimide. one
In general formula (A2II): R^1d~ R^3dAre each independently
It represents a kill group or a 2-oxoalkyl group. R ^1d~ R
^3dAre two of them bonded together to form a ring structure
Good. X^-Represents an anion.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION [1] (A) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (Photoacid Generator) The photoacid generator used in the present invention is a photoinitiator for photocationic polymerization. , A photoinitiator for radical photopolymerization, a photobleaching agent for dyes, a photochromic agent, or known light used for a microresist or the like (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g rays, A compound capable of generating an acid by an h-ray, an i-ray, a KrF excimer laser light), an ArF excimer laser light, an electron beam, an X-ray, a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and other onium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include a photoacid generator having a nitrobenzyl-type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, a disulfone compound, a diazoketosulfone, a diazodisulfone compound, and the like.
Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), US Pat. No. 3,779, 778, and European Patent No. 126, 712 which generate an acid by light are also used. be able to.

Among the compounds which decompose when exposed to actinic rays or radiation to generate an acid, the photoacid generator preferably used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) an oxazole derivative or a general formula (PAG
An S-triazine derivative represented by 2).

[0025]

[Chemical 9]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —C (Y) ₃
Indicates. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0027]

[Chemical 10]

(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0029]

[Chemical 11]

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ^205's each independently represent a substituted or unsubstituted alkyl group or aryl group.

Z ⁻ represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonate anion such as perfluoroalkane sulfonate anion such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, sulfonate group Examples thereof include dyes contained therein, but are not limited thereto.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

In the above, Ph represents a phenyl group.
The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, US Pat. No. 2,807,6 is known.
48 and 4,247,473, JP-A-53-10.
It can be synthesized by the method described in No. 1,331.

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0046]

[Chemical formula 22]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0055]

[Chemical 28]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0057]

[Chemical 29]

[0058]

[Chemical 30]

In the present invention, as the photoacid generator, a compound having a phenacylsulfonium salt structure and a compound having an aromatic ring-free sulfonium salt structure which generate an acid upon irradiation with actinic rays or radiation are particularly preferable. Preferably used.

Examples of the compound having a phenacylsulfonium salt structure which generates an acid upon irradiation with actinic rays or radiation include compounds represented by the general formula (A2I).

[0061]

[Chemical 31]

In the above general formula (A2I), R _{1c to} R _1
5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry are each independently an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group,
Or represents a vinyl group. Any two or more _members out of R _{1c to} R _7c , and Rx and Ry may be bonded to each other to form a ring structure, and the ring structure contains an oxygen atom, a sulfur atom, an ester bond or an amide bond. You can leave. Examples of the X ⁻ anion include sulfonic acid, carboxylic acid, and sulfonylimide anions.

The alkyl group as R _{1c to} R _5c is a straight chain,
It may be branched or cyclic, and has, for example, 1 to 1 carbon atoms.
10 alkyl groups, preferably linear and branched alkyl groups having 1 to 5 carbon atoms (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group). And a cyclic alkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group). The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic. For example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group), a cyclic alkoxy group having 3 to 8 carbon atoms (for example, a cyclopentyloxy group,
And a cyclohexyloxy group). Preferably, any of R _{1c to} R _{5c is} a linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkoxy group,
More preferably, the sum of carbon numbers of R _1c to R _5c is 2 to 15. Thereby, the solvent solubility is further improved, and the generation of particles during storage is suppressed.

Examples of the alkyl group as R _6c and R _7c include the same as the alkyl group as R _{1c to} R _5c . Examples of the aryl group may include an aryl group having 6 to 14 carbon atoms (for example, a phenyl group). Alkyl groups as Rx and Ry are R _1c
The same examples of the alkyl group as R 5 to R _5c can be mentioned. 2-oxoalkyl group include a group having> C = O at the 2-position of the alkyl group as R _1c to R _5c. As the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as R _{1c to} R _5c can be mentioned. Examples of the group formed by combining Rx and Ry include a butylene group and a pentylene group.

The compound of formula (A2I) has a three-dimensional structure fixed by forming a ring, and the optical resolution is improved. R _1c
In the case where any two of R _{1c to} R _7c combine to form a ring structure, any one of R _{1c to} R _5c and R _6c and R _5c
It is preferable that any one of _7c is bonded to form a single bond or a linking group to form a ring, and particularly, it is preferable that R _5c and R _6c or R _7c are bonded to form a single bond or a linking group to form a ring. . As the linking group, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, -O-, -S-, -CO-, -CONR-.
(R is a hydrogen atom, an alkyl group, an acyl group), and a group formed by combining two or more of these, and further, an alkylene group which may have a substituent,
An alkylene group containing an oxygen atom and an alkylene group containing a sulfur atom are preferable. As the substituent, an alkyl group (preferably having 1 to 5 carbon atoms), an aryl group (preferably having 6 carbon atoms)
-10, for example, a phenyl group, an acyl group (for example, having 2 to 11 carbon atoms), and the like. Further, a methylene group, an ethylene group, a propylene group, -CH ₂ -O-,-
Preferred linking group to form a 5- to 7-membered ring as CH ₂ -S-, ethylene _{group, -CH 2 -O -, - CH} 2 -S- linking group to form a 6-membered ring, such as Particularly preferred. 6
By forming a member ring, the carbonyl plane and the C-S + sigma bond become closer to vertical, and the orbital interaction improves the optical resolution. Further, at any position of R _{1c to} R _7c and Rx and Ry, it is bonded via a single bond or a linking group,
It may be a compound having two or more structures of formula (A2I).

X ⁻ is preferably a sulfonate anion, more preferably an alkane sulfonate anion whose 1-position is substituted with a fluorine atom, or benzene sulfonic acid substituted with an electron-withdrawing group. The alkane moiety of the alkane sulfonate anion may be substituted with a substituent such as an alkoxy group (for example, having 1 to 8 carbon atoms) or a perfluoroalkoxy group (for example, having 1 to 8 carbon atoms). Examples of the electron-withdrawing group include chlorine atom, bromine atom, nitro group, cyano group, alkoxycarbonyl group, acyloxy group and acyl group. X ⁻ is more preferably a perfluoroalkanesulfonate anion having 1 to 8 carbon atoms, particularly preferably a perfluorooctanesulfonate anion, and most preferably a perfluorobutanesulfonate anion or a trifluoromethanesulfonate anion. . By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, the diffusibility of the generated acid is controlled, and the resolution is improved. Specific examples of the compound having a phenacylsulfonium salt structure that can be used in the present invention are shown below, but the present invention is not limited thereto.

[0067]

[Chemical 32]

[0068]

[Chemical 33]

[0069]

[Chemical 34]

[0070]

[Chemical 35]

[0071]

[Chemical 36]

[0072]

[Chemical 37]

[0073]

[Chemical 38]

[0074]

[Chemical Formula 39]

[0075]

[Chemical 40]

[0076]

[Chemical 41]

Examples of the compound having an aromatic ring-free sulfonium salt structure which generates an acid upon irradiation with actinic rays or radiation include an alkylsulfonium salt compound represented by the general formula (A2II).

[0078]

[Chemical 42]

In the formula, R ^{1d to} R ^3d each independently represent an alkyl group or a 2-oxoalkyl group (an alkyl group having> C═O at the 2-position). Two of R ^{1d to} R ^3d may combine with each other to form a ring structure. X ⁻ represents an anion. The alkyl group as R ^{1d to} R ^3d is a straight chain,
It may be branched or cyclic, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group),
Cyclic alkyl group having 3 to 10 carbon atoms (cyclopentyl group,
A cyclohexyl group and a norbornyl group). The 2-oxoalkyl group as R ^{1d to} R ^3d may be linear, branched or cyclic, and is preferably
The group having> C = O at the 2-position of the above alkyl group can be mentioned. R ^{1d to} R ^3d may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. Two of R ^{1d to} R ^3d may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two ^{members out} of R ^{1d to} R ^3d include an alkylene group (eg, butylene group, pentylene group). From the viewpoint of photoreactivity, a carbon-carbon double bond or a carbon-oxygen 2 bond is present in any one of R ^{1d to} R ^3d in the alkyl chain.
A group having a heavy bond may be present. The anion of X ⁻ is a sulfonic acid anion, preferably an alkanesulfonic acid anion in which the 1-position is substituted with a fluorine atom, and a benzenesulfonic acid substituted with an electron-withdrawing group, and more preferably 1 to 1 carbon atoms. No. 8 perfluoroalkane sulfonate anion, and most preferably perfluorobutane sulfonate anion and perfluorooctane sulfonate anion. By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, the diffusibility of the generated acid is controlled, and the resolution is improved. Incidentally, as the electron-withdrawing group, a chlorine atom, a bromine atom, a nitro group, a cyano group,
Examples thereof include an alkoxycarbonyl group, an acyloxy group and an acyl group. At least one of R ^{1d to} R ^3d of the compound represented by the general formula (A2II) may be bonded to at least one of R ^{1d to} R ^3d of the other compound represented by the general formula (A2II). The preferred specific examples of the compound having an alkylsulfonium salt structure which can be used in the present invention are shown below, but the present invention is not limited thereto.

[0080]

[Chemical 43]

[0081]

[Chemical 44]

[0082]

[Chemical formula 45]

In the present invention, the photo-acid generator may be used alone or in combination of two or more, and the total amount added is usually 0.1% based on the solid content of the positive photosensitive composition.
It is 1 to 20% by weight, preferably 0.3 to 15% by weight, and more preferably 0.5 to 10% by weight.

<Synthesis Example of Photoacid Generator> Hereinafter, a synthesis example of a typical photoacid generator will be described. Other photo-acid generators can be synthesized by a method similar to these.

(Synthesis of pentafluorobenzenesulfonic acid tetramethylammonium salt) 25 g of pentafluoropentenesulfonyl chloride was added to 100 ml of methanol under ice cooling.
Was dissolved in, and 100 g of 25% tetramethylammonium hydroxide aqueous solution was slowly added thereto. 3 at room temperature
A solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was obtained with stirring for a time. This solution was used for salt exchange with a sulfonium salt and an iodonium salt.

(Phenacyl tetrahydrothiophenium perfluorobutane sulfonate: Specific example (A2I-1)
Synthesis of tetrahydrothiophene (53.2 g) was dissolved in 400 ml of acetonitrile, and 100 g of phenacyl bromide dissolved in 300 ml of acetonitrile was slowly added to this solution. A powder was deposited when stirred at room temperature for 3 hours. The reaction solution was poured into 1500 ml of ethyl acetate,
The powder was collected by filtration and dried to obtain 137 g of phenacyltetrahydrothiophenium bromide. 60 g of potassium perfluorobutanesulfonate was dissolved in a mixed solvent of 200 ml of water and 200 ml of methanol, and 49.5 g of phenacyltetrahydrothiophenium bromide was added to 30 ml of water.
What was dissolved in 0 ml was added. The aqueous solution was extracted twice with 200 ml of chloroform, and the organic phase was washed with water and concentrated to obtain a crude product. To this, 300 ml of distilled water was added, heated at 100 ° C. for 30 minutes and then cooled to precipitate a solid. The solid was collected by filtration and reslurried with diisopropyl ether to obtain 77 g of phenacyltetrahydrothiophenium perfluorobutane sulfonate.

(Phenacyltetrahydrothiophenium perfluorooctane sulfonate: Specific example (A2I-
Synthesis of 3)) Phenacyltetrahydrothiophenium bromide was synthesized in the same manner as above by salt exchange with perfluorooctane sulfonic acid.

(Phenacyltetrahydrothiophenium trifluoromethanesulfonate: Specific example (A2I-2)
Synthesis of phenacyltetrahydrothiophenium bromide was synthesized in the same manner as above by salt exchange with trifluoromethanesulfonic acid.

(Synthesis of Specific Example (A2II-11)) Tetrahydrothiophene (11.8 g) was added to acetonitrile (100).
20 g of 1-bromo-3,3-dimethyl-2-butanone was slowly added to this solution. 2 at room temperature
After stirring for a day, powder was deposited. Ethyl acetate 1 in the reaction solution
After adding 00 ml, the powder was collected by filtration, washed with ethyl acetate and dried to obtain 24 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium bromide.
10 grams of potassium perfluorobutane sulfonate in 500 water
ml, dissolved in a mixed solvent of 100 ml of methanol, and added thereto, 7.75 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium bromide, 50 m of methanol.
What was dissolved in 1 was added. This aqueous solution was extracted twice with 100 ml of chloroform, and the organic phase was washed with water and concentrated to obtain an oily substance. Ethyl acetate was added to this to re-concentrate to obtain a solid substance. The solid substance was collected by filtration and reslurried with diisopropyl ether to obtain 9 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium perfluorobutanesulfonate. It was

2-oxocyclohexylmethyl (2-norbornyl) sulfonium trifluoromethanesulfonate (A2II-1) is described in JP-A-8-27102,
It can be synthesized using the method of Synthesis Example 1.

[2] Acid Decomposable Resin (Component (B)) (B) The resin used in the present invention is represented by the repeating unit (A1) represented by the general formula (I) and the general formula (II). A repeating unit (A2) and a repeating unit (A3) represented by the general formula (N), which are decomposed by the action of an acid to increase the solubility in an alkali developing solution (hereinafter referred to as “acid decomposability”). Abbreviated as "resin").

[0092]

[Chemical formula 46]

In the general formula (I), R _1a represents a hydrogen atom or a hydrocarbon group, and R _2a represents a hydrocarbon group. Incidentally, R
_1a and R _2a may combine with each other to form a ring.

R_1aThe hydrocarbon group as is preferably charcoal.
A prime number of 1 to 10, particularly preferably 1 to 5, for example,
A rukyl group (preferably a methyl group) can be mentioned.
It R _1aIs preferably a hydrogen atom or a methyl group.

The hydrocarbon group as R _2a preferably has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include an alkyl group and a cycloalkyl group.
The hydrocarbon group as R _1a and R _2a includes those having a substituent. The carbon number of the substituent is preferably 1 to 30. Examples of the substituent include a hydroxyl group, a halogen atom, an alkoxy group, an acyl group, an acylcarbonyl group and an acyloxy group. The ring structure in these substituents may contain a hetero atom, a hydroxyl group,
It may have a substituent such as an alkyl group (preferably having 1 to 5 carbon atoms) and an alkoxy group (preferably having 1 to 5 carbon atoms).

When R _1a and R _2a are bonded to each other to form a ring, examples thereof include a 4- to 8-membered ring such as a tetrahydrofuran ring and a tetrahydropyran ring.
This ring structure may also have a substituent as in the above.

Specific examples of the repeating unit (A1) represented by formula (I) are shown below, but the invention is not limited thereto.

[0098]

[Chemical 47]

The acid-decomposable resin of the present invention further has the formula (II)
The repeating unit (A2) represented by

[0100]

[Chemical 48]

In the general formula (II), Z is --O-- or
Is -N (R_3a) -Represents. Where R _3aIs hydrogen atom, water
Acid group, alkyl group, haloalkyl group or -OSO₂-R
_4aRepresents Also R_4aIs an alkyl group, a haloalkyl group,
Represents a cycloalkyl group or camphor residue.

The alkyl group for R _3a and R _4a is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the haloalkyl group for R _3a and R _4a include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R _4a include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.

The alkyl group as R _3a and R _4a , the haloalkyl group, the cycloalkyl group as R _4a or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkoxy group (preferably having a carbon number of 1 to 1).
4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group), an aryl group (preferably having a carbon number of 6 to 14, for example, a phenyl group), and the like.

Specific examples of the repeating unit (A2) represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0105]

[Chemical 49]

[0106]

[Chemical 50]

Next, the repeating unit (A3) represented by formula (N) will be described. In the general formula (N),
R represents a hydrogen atom or a methyl group. A ₁ represents a single bond or a divalent linking group. A ₂ represents a single bond, an alkylene group, an ether group, an ester group, or a group composed of a combination thereof. Z ₂ represents an aliphatic cyclic hydrocarbon group.

L represents 0 or 1. A ₃ represents a single bond, an alkylene group, an ether group, an ester group, or a combination thereof. R'represents a cyan group. m represents an integer of 1 to 3. m is preferably 1 or 2. In the formula (II), m monovalent groups —A ₃ R ′ are Z ₂ (l
When it is = 0, it means that it is replaced with A ₂ ). However, when 1 = 0, at least one of A ₂ and A ₃ is an alkylene group, an ether group, an ester group, or a combination thereof. A ₁ is preferably a single bond. A ₂ and A
Each of ₃ preferably has 5 or less carbon atoms.

The linking group for A ₁ is a single group selected from the group consisting of an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group and a urea group. Alternatively, it represents a combination of two or more groups. Above A ₁ , A ₂
Examples of the alkylene group as A ₃ and A ₃ include groups represented by the following formulas. — [C (R _b ) (R _c )] _r − In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10, preferably 1 to 3 carbon atoms.

The aliphatic cyclic hydrocarbon group as Z ₂ may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is 6
The number of carbon atoms is preferably -30, particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0111]

[Chemical 51]

[0112]

[Chemical 52]

[0113]

[Chemical 53]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are adamantyl group, decalin residue, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and tricyclodecanyl group.

The alicyclic hydrocarbon group as Z ₂ may have a substituent, and the substituent preferably has 5 carbon atoms.
Below, an alkyl group, a substituted alkyl group, a halogen atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group and the like can be mentioned. As an alkyl group,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Examples of the substituent of the substituted alkyl group include a halogen atom and an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The resin may contain a plurality of repeating units represented by the general formula (N). Specific examples of the repeating unit (A3) represented by formula (N) are shown below, but the invention is not limited thereto.

[0117]

[Chemical 54]

[0118]

[Chemical 55]

[0119]

[Chemical 56]

[0120]

[Chemical 57]

The acid-decomposable resin of the present invention is treated by an acid.
The group that decomposes to become alkali-soluble is represented by the general formula
Of the repeating unit represented by (I), (II) or (N)
May be present in any of the other repeating units
It may be contained. As a group that decomposes by the action of acid
Is -COOA⁰ , -OB⁰ List the groups represented by
be able to. Further, as a group containing these, -R⁰ −
COOA⁰ , Or -A_r -OB⁰ The group represented by
To be Where A⁰ Is -C (R⁰¹) (R⁰²)
(R⁰³), -Si (R⁰¹) (R⁰²) (R ⁰³), -C (R
⁰⁴) (R⁰⁵) -OR⁰⁶Represents a group or a lactone group.
B⁰ Is -A⁰ Or -CO-OA⁰ Indicates a group. R⁰¹,
R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same or different
May be present, hydrogen atom, alkyl group, cycloalkyl
Group, alkenyl group, aralkyl group or aryl group
Show, R⁰⁶Is an alkyl group, a cyclic alkyl group or an ant
Group. However, R⁰¹~ R⁰³At least two of
A group other than a hydrogen atom, and R ⁰¹~ R⁰³, And R⁰⁴~
R⁰⁶Two groups in the above may combine to form a ring. R
⁰Is a single bond or divalent or less, which may have a substituent.
The above aliphatic or aromatic hydrocarbon group is shown, and -Ar-
Is a divalent or lower valent which may have a monocyclic or polycyclic substituent.
The above aromatic groups are shown.

Here, the alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Preferred are those having 3 to 30 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four is preferable. Examples of the cyclic alkyl group include those having 3 to 30 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a tricyclodecanyl group and a dialkyl group. Examples thereof include a cyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group and a steroid residue. The aralkyl group has 7 to 7 carbon atoms.
There are 20 groups, which may have a substituent.
Examples thereof include a benzyl group, a phenethyl group and a cumyl group.

As the substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group. Group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group, and other alkoxycarbonyl groups, benzyl group, phenethyl group, cumyl group, and other aralkyl groups, Acryl groups such as aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanayl groups, valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups. Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group. Examples of the lactone group include those having the following structures.

[0124]

[Chemical 58]

In the above formula, R ^a , R ^b and R ^c are each independently
It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is
Represents an integer from 2 to 4.

When an ArF excimer laser is used as a light source for exposure, it is preferable to use a group represented by —C (═O) —X ₁ —R ₀ as a group that decomposes by the action of an acid. Here, R ₀ is a t-butyl group, t
-Tertiary alkyl group such as amyl group, isobornyl group, 1-
1-alkoxyethyl groups such as ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1-
Examples thereof include an alkoxymethyl group such as an ethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl group, a 3-oxocyclohexyl group, the above lactone group and the like. X ₁ represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

It is particularly preferable to contain a repeating unit having an acid-decomposable group represented by any of formulas (pI) to (pV). By containing this repeating unit, image forming property and dry etching resistance are improved.

[0128]

[Chemical 59]

In the formula, R ₁₁ is a methyl group, an ethyl group or n-
It represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ , and either R ₁₅ or R ₁₆ represent an alicyclic hydrocarbon group. R ₁₇
To R ₂₁ are each independently a hydrogen atom, a C 1 to C 4,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is an aliphatic group. Represents a cyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring.

In the above general formulas (pI) to (pV), the linking group of A is an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group. Base,
Or alone or 2 selected from the group consisting of urea groups
Represents a combination of one or more groups. Examples of the alkylene group in A include groups represented by the following formula. — [C (R _b ) (R _c )] _r − In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10.

In the general formulas (pI) to (pV), R ₁₂
The alkyl group for R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
Examples thereof include an ec-butyl group and a t-butyl group. Also,
The further substituent of the above alkyl group has 1 to 4 carbon atoms.
Examples thereof include alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0133]

[Chemical 60]

[0134]

[Chemical formula 61]

[0135]

[Chemical formula 62]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are adamantyl group, decalin residue, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and tricyclodecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represent Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Specific examples of the monomer corresponding to the repeating unit having a group represented by any of the above general formulas (pI) to (pV) are shown below.

[0139]

[Chemical formula 63]

[0140]

[Chemical 64]

[0141]

[Chemical 65]

[0142]

[Chemical formula 66]

[0143]

[Chemical formula 67]

[0144]

[Chemical 68]

Further, in order to improve the contact hole resolution and the defocus latitude, it is preferable to contain a repeating unit having a lactone residue, and in order to reduce development defects, a repeating unit having an alicyclic lactone residue is included. It is preferable to contain a unit. The alicyclic lactone is a structure in which a cyclic hydrocarbon group and a lactone ring are condensed, or one of cycloalkane rings of a polycyclic cyclic hydrocarbon group (a cyclic hydrocarbon ring in which two or more cycloalkane rings are combined) It means a structure substituted with a lactone ring. Examples of the lactone residue include butyrolactone (a1), and examples of the alicyclic lactone include (a2) norbornane lactone, (a3) cyclohexane lactone, and (a4) adamantane lactone.

Repeating unit having a lactone residue (a
Examples of 1) include a repeating unit represented by the following general formula (BL).

[0147]

[Chemical 69]

In formula (BL), R ₁ represents a hydrogen atom or a methyl group. W represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or an ester group alone or in combination of two or more groups. Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represent an integer of 0 to 3, and m + n is 2
The above is 6 or less.

In the general formula (BL), the alkyl group having 1 to 4 carbon atoms of Ra to Re is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples thereof include t-butyl group. Examples of the alkylene group of W include groups represented by the following formula. — [C (Rf) (Rg)] r— In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and they may be the same or different. . The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r is an integer of 1-10.

Examples of the further substituent in the above alkyl group include a carboxyl group, an acyloxy group, a cyano group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an acetylamide group, an alkoxycarbonyl group, An acyl group can be mentioned. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include an alkoxy group and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (BL) are shown below, but the invention is not limited thereto.

[0152]

[Chemical 70]

[0153]

[Chemical 71]

[0154]

[Chemical 72]

In the acid-decomposable resin of the present invention, the norbornane lactone monomer (a2) and the cyclohexane lactone monomer (a3) are each represented by the above general formula (V
Repeating units having groups represented by -1) to (V-2) and (V-3) to (V-4) are preferable.

As the repeating unit having norbornane lactone (a2), the following general formula (V-1) or (V-
The repeating unit which has group shown by 2) can be mentioned.

[0157]

[Chemical formula 73]

In the general formulas (V-1) to (V-2),
R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Two of R _{1b to} R _5b may combine with each other to form a ring.

Examples of the cyclohexane lactone (a3) include a repeating unit having a group represented by the following general formula (V-3) or (V-4).

[0160]

[Chemical 74]

In the general formulas (V-3) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Two of R _{1b to} R _5b may combine with each other to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
12 straight chain or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
It is a decyl group.

The cycloalkyl group for R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having a carbon number of 2 to 6, such as a vinyl group, a propenyl group, a butenyl group and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring and a cyclooctane ring. In addition, general formula (V-1)-
R _{1b to} R _5b in (V-4) may be linked to any of the carbon atoms constituting the cyclic skeleton.

Preferred examples of the substituent that the alkyl group, cycloalkyl group and alkenyl group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a nitro group and the like.

The repeating unit having a group represented by any one of the general formulas (V-1) to (V-4) is represented by the following general formula (AI).
The repeating unit represented by

[0166]

[Chemical 75]

In formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _b0 may have include those represented by the general formula (V-1) to
Examples of the preferable substituent that the alkyl group as R _1b in (V-4) may have include those exemplified above. Examples of the halogen atom of R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0168]

[Chemical 76]

In the above formula, R _ab and R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

Specific examples of the repeating unit represented by formula (AI) are shown below, but the contents of the present invention are not limited to these.

[0171]

[Chemical 77]

[0172]

[Chemical 78]

[0173]

[Chemical 79]

[0174]

[Chemical 80]

[0175]

[Chemical 81]

[0176]

[Chemical formula 82]

[0177]

[Chemical 83]

As the adamantane lactone (a4),
A repeating unit represented by the following general formula (AL) is preferable.

[0179]

[Chemical 84]

In the general formula (AL), A is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group or an ester group, which may be used alone or in combination of two or more groups. Represent R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In the general formula (AL), examples of the alkylene group represented by A include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are each a hydrogen atom, an alkyl group,
It represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r is an integer of 1-10.

In the general formula (AL), the cycloalkylene group represented by A includes those having 3 to 10 carbon atoms, and examples thereof include a cyclopentylene group, a cyclohexylene group and a cyclooctylene group.

The bridged alicyclic ring containing Z may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, formyl group, benzoyl group), an acyloxy group ( Examples thereof include a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having a carbon number of 1 to 4), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH ₃ etc.). still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having a carbon number of 1 to 4) or the like. In general formula (AL), the oxygen atom of the ester group bonded to A may be bonded at any position of the carbon atoms constituting the bridged alicyclic ring structure containing Z. The specific examples of the repeating units represented by formula (AL) are shown below, but the invention is not limited thereto.

[0184]

[Chemical 85]

[0185]

[Chemical 86]

Further, the acid-decomposable resin of the present invention preferably contains a repeating unit represented by the following general formula (III) in order to improve the edge roughness.

[0187]

[Chemical 87]

In formula (III), R ₃₀ represents a hydrogen atom or a methyl group. R _{31 to} R ₃₃ each independently represent a hydrogen atom, a hydroxyl group or an alkyl group, provided that at least one represents a hydroxyl group.

Further, in forming a hole pattern by underexposure, a wide exposure margin can be obtained, so that the general formula (I
In the repeating unit represented by II), it is more preferable that two of R _{31 to} R ₃₃ are hydroxyl groups.

Specific examples will be given below, but the present invention is not limited thereto.

[0191]

[Chemical 88]

Further, in order to improve heat resistance and etching resistance, it is preferable to contain a repeating unit represented by the general formula (IV).

[0193]

[Chemical 89]

In formula (IV), R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, —COOH,
A hydrocarbon group which may have a substituent, -COOR ₅ ,
-C (= O) -X-A -R 6, or a group decomposable by the action of an acid addition, may form a ring of at least two members to one of R ₁ to R _4. Here, R ₅ represents a hydrocarbon group which may have a substituent or a lactone residue. R ₆
Represents a hydrogen atom, —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group which may have a substituent, a hydrocarbon group which may have a substituent, or a lactone residue. X represents an oxygen atom, a sulfur atom, -NHSO ₂ -, or an -NHSO ₂ NH-. A is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, a sulfonamide group, or a N-sulfonylamide group, or a single group or two or more groups selected from the group consisting of Represents a combination. n represents 0 or 1.

[0195] As a structure of the group decomposable by the action of an acid is represented by _{-C (= O) -X 1 -R} p. Where R _p
Is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group or the like. -Alkoxyethyl group,
Alkoxymethyl group such as 1-methoxymethyl group, 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-methyl-2 Examples thereof include an adamantyl group, a mevalonic lactone residue, and a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group. X ₁
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

Examples of the halogen atom in R _{1 to} R ₄ include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. The hydrocarbon group for R _{1 to} R ₄ , R ₅ and R ₆ is preferably a linear, branched or cyclic alkyl group or a bridged hydrocarbon group. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. Examples of the cyclic alkyl group and the bridged hydrocarbon group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, and a tricyclodecanyl group. , A dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group and the like.

The ring formed by combining at least two members out of R _{1 to} R ₄ includes, for example, a lactone ring, a cyclopentene, cyclohexene, cycloheptane, cyclooctane and other rings having 5 to 12 carbon atoms. R ₆ above
As the alkoxy group in, preferable are those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. The above hydrocarbon group and alkoxy group may further have a substituent,
As the substituent, for example, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group) , Propoxy group, butoxy group, etc.), acyl group (eg formyl group,
Examples thereof include an acetyl group) and an acyloxy group (eg acetoxy group).

Examples of the alkylene group in A above include groups represented by the following formula. — [C (R _b ) (R _c )] _r − In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10.

Examples of the lactone residue as R ₅ and R ₆ include those represented by the following —Y. -Y group;

[0200]

[Chemical 90]

In the above-Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group. a and b are 1
Or represents 2. Examples of the alkyl group for R _{21 to} R ₃₀ include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. R ₂₁ ~ R
The alkyl group as ₃₀ may have a substituent. As the substituent, for example, a hydroxyl group, a carboxyl group,
Cyano group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, iodine atom), alkoxy group (preferably having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (Preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, acetoxy group), aryl group (preferably having 6 to 14 carbon atoms, such as phenyl group). Etc. can be mentioned.

Specific examples of the repeating unit represented by formula (IV) are shown below, but the invention is not limited thereto.

[0203]

[Chemical Formula 91]

[0204]

[Chemical Formula 92]

[0205]

[Chemical formula 93]

[0206]

[Chemical 94]

[0207]

[Chemical 95]

[0208]

[Chemical 96]

[0209]

[Chemical 97]

[0210]

[Chemical 98]

[0211]

[Chemical 99]

[0212]

[Chemical 100]

[0213]

[Chemical 101]

[0214]

[Chemical 102]

[0215]

[Chemical 103]

[0216]

[Chemical 104]

[0217]

[Chemical 105]

[0218]

[Chemical formula 106]

[0219]

[Chemical formula 107]

[0220]

[Chemical 108]

[0221]

[Chemical 109]

[0222]

[Chemical 110]

[0223]

[Chemical 111]

[0224]

[Chemical 112]

[0225]

[Chemical 113]

The acid-decomposable resin as the component (B) has, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustments such as (3) alkali developability, (4) film slippage (hydrophilicity / hydrophobicity, selection of alkali-soluble groups), (5) adhesion of the unexposed area to the substrate, and (6) dry etching resistance are possible. . Examples of such monomers include acrylic acid esters, methacrylic acid esters, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

The content of the repeating unit represented by the general formula (I) in the acid-decomposable resin is 2 to 5 in all repeating structural units.
0 mol% is preferable, more preferably 4 to 45 mol%,
More preferably, it is 6 to 40 mol%. General formula (II)
The content of the repeating unit represented by is preferably 15 to 70 mol% in all the repeating structural units, more preferably 20
˜65 mol%, more preferably 25 to 60 mol%. The content of the repeating unit represented by the general formula (N) is
It is preferably 2 to 30 mol% in all the repeating structural units, more preferably 4 to 25 mol%, and further preferably 5 to 20 mol%. The total amount of repeating units having an acid-decomposable group is preferably 20 to 60 mol%, more preferably 24 to 55 mol%, and further preferably 28 to 50 mol% in all repeating structural units. The content of the repeating unit having a group represented by any one of the general formulas (pI) to (pVI) is preferably 20 to 55 mol% in all repeating structural units, more preferably 24 to 50 mol%, and further preferably 28 to It is 45 mol%. The content of the repeating unit represented by the general formula (III) is preferably 3 to 40 mol%, more preferably 5 to 35 mol%, and further preferably 8 to 40 mol% in all repeating structural units. The content of the repeating unit represented by the general formula (IV) is preferably 3 to 40 mol%, more preferably 5 to 35 mol%, and further preferably 8 to 40 mol% in all repeating structural units. The content of the repeating unit having a lactone residue or an alicyclic lactone is preferably 5 to 50 mol% in all repeating structural units, more preferably 10 to 40 mol%, and further preferably 12 to 30 mol%.
Is. When the composition of the present invention is for ArF exposure, it is preferable that the resin does not have an aromatic group from the viewpoint of transparency to ArF light.

The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer species is charged in a batch or in the middle of the reaction into a reaction vessel, and if necessary, a reaction solvent, for example, tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether or methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further homogenized by dissolving in a solvent dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate described later, nitrogen, argon, etc. If necessary, heating is performed in an inert gas atmosphere, and polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.).
If desired, an initiator is added or added in portions, and after completion of the reaction, the reaction mixture is put into a solvent to recover the desired polymer by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is at least 30% by weight, preferably at least 40% by weight. Reaction temperature is 10 ° C to 150
C., preferably 30 to 120.degree. C., more preferably 50 to 100.degree.

The weight average molecular weight of the acid-decomposable resin according to the present invention is preferably 1,000 to 200,000, and preferably 3,0 as a polystyrene conversion value by the GPC method.
00-50,000, more preferably 5,000-3
It is 10,000. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable, and when it exceeds 200,000, developability is deteriorated and film forming property is deteriorated due to extremely high viscosity. It produces less favorable results.

In the positive photoresist composition for deep UV exposure of the present invention, the amount of the acid-decomposable resin according to the present invention to be incorporated in the entire composition is 40 to 9 in the total solid content of the resist.
It is preferably 9.99% by weight, more preferably 50-9.
It is 9.97% by weight.

It is preferable that the solid content of the photoacid generator (A) or the resin (B) is dissolved in the solvent in a solid content concentration of 3 to 25% by weight, more preferably 5 to 22% by weight.
More preferably, it is 7 to 20% by weight.

<< (C) Acid-decomposable dissolution inhibiting compound >> The positive photosensitive composition of the present invention has a group (C) which is decomposed by the action of an acid to increase the solubility in an alkali developing solution. ,
Dissolution-inhibiting low molecular weight compounds with a molecular weight of 3000 or less (hereinafter,
It is preferable to contain “(C) acid-decomposable dissolution inhibiting compound”). Proceeding of SPIE, 2724, 355 (1996), in particular, because it does not reduce the transmittance below 220 nm.
Alicyclic or aliphatic compounds containing an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in (3) above, are preferable as the (C) acid-decomposable dissolution inhibiting compound. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above for the acid-decomposable resin. The amount of the (C) acid-decomposable dissolution inhibiting compound added is preferably 3 to 50% by weight, and more preferably 5 to 40% by weight, based on the solid content of the entire positive photosensitive composition. . Specific examples of the acid-decomposable dissolution inhibiting compound (C) are shown below, but the invention is not limited thereto.

[0234]

[Chemical 114]

<< (D) Nitrogen-Containing Basic Compound >> The positive photosensitive composition of the present invention contains (D) a nitrogen-containing basic compound in order to reduce the change in performance over time from exposure to heating. It is preferable. Preferred structures include structures represented by the following formulas (A) to (E).

[0236]

[Chemical 115]

R ²⁵⁰ , R ^251, and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
~ 6 aminoalkyl group, hydroxyalkyl group having 1 to 6 carbon atoms or substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are bonded to each other to form a ring. Good.

[0238]

[Chemical formula 116]

(In the formulae, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine and the like, and mono, di, trialkylamines, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono or diethanolamine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

As a particularly preferred compound, guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-Aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4.
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
Examples thereof include 2,6-diisopropylaniline and N-cyclohexyl-N′-morpholinoethylthiourea, but are not limited thereto.

These (D) nitrogen-containing basic compounds may be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound (D) used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the photosensitive resin composition. If it is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained.
On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

<< (E) Fluorine-based and / or Silicon-based Surfactant >> The positive photosensitive resin composition of the present invention comprises a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based interface). It is preferable to contain any one of an activator and a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds. When the positive photosensitive composition of the present invention contains the above-mentioned surfactant, 25
When an exposure light source of 0 nm or less, particularly 220 nm or less is used, it is possible to provide a resist pattern with good sensitivity and resolution and less adhesiveness and development defects. Examples of these surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745 and JP-A-62-17095.
0, JP-A-63-34540, JP-A-7-230165, JP-A-8-6
2834, JP-A-9-54432, JP-A-9-5988, U.S. Pat.
405720, 5360692, 5528891, 5296330,
5436098, 5576143, 5294511, 5824451.
The surfactants described in No. 1 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include Ftop EF301 and EF30.
3, (New Akita Kasei Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F18
9, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382,
SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.),
Examples thereof include fluorine-based surfactants such as Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) and silicon-based surfactants. In addition, polysiloxane polymer KP-341
(Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

The amount of the surfactant used is preferably 0.000 with respect to the total amount of the positive type photosensitive composition (excluding the solvent).
It is 1 to 2% by weight, more preferably 0.001 to 1% by weight.

<< (F) Alkali-Soluble Resin >> The positive photoresist composition of the present invention contains (F) a resin which is insoluble in water and soluble in an alkali developing solution, which does not contain an acid-decomposable group. It is possible to improve the sensitivity. In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as such resins, but they have large absorption for light of 250 nm or less. It is preferable to use it by partially hydrogenating it, or to use it in an amount of 30% by weight or less based on the total amount of the resin. A resin containing a carboxyl group as an alkali-soluble group can also be used. The resin containing a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance. Specifically, a copolymer of methacrylic acid ester having an alicyclic hydrocarbon structure which does not exhibit acid decomposability and (meth) acrylic acid, or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a carboxyl group at the terminal. And the like.

<< Other Substances >> In the positive photosensitive composition of the present invention, a dye, a plasticizer, a surfactant other than the above component (E), a photosensitizer, and a developing solution may be added, if necessary. A compound or the like that promotes solubility can be contained. The compound capable of accelerating dissolution in a developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as above. The preferred addition amount of these dissolution accelerating compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, with respect to the resin that is decomposed by the action of the acid (B) and the solubility in the alkali developing solution is increased.
It is 30% by weight. If the addition amount exceeds 50% by weight, the development residue is deteriorated and a new defect that the pattern is deformed during development is not preferable.

Such phenol compounds having a molecular weight of 1000 or less can be prepared by those skilled in the art with reference to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent No. 219294. It can be easily synthesized. Specific examples of the alicyclic or aliphatic compound having a carboxyl group include cholic acid, deoxycholic acid, carboxylic acid derivative having a steroid structure such as lithocholic acid, adamantanecarboxylic acid derivative, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the above-mentioned (E) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate. These surfactants may be added alone or in some combinations.

<< Method of Use >> The photosensitive composition of the present invention comprises the above components dissolved in a predetermined solvent in a mixed state. It is used by coating it on a predetermined support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone,
Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or as a mixture. Among these, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl ethoxypropionate are used alone or in admixture of two kinds at a weight ratio of 1/9 to 9/1. Is preferred.

The positive type photosensitive composition dissolved in a solvent is coated on a predetermined substrate as follows. That is, the above-mentioned photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by a suitable coating method such as a spinner or a coater.
After coating, it is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is far ultraviolet rays having a wavelength of preferably 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193n
m), F ₂ excimer laser (157 nm), X-ray, electron beam and the like.

As the developer in the developing step, there are used inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. It is possible to use an alkaline aqueous solution of a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0251]

EXAMPLES The present invention will be specifically described below based on examples, but the scope of the present invention is not limited to the examples.

Synthesis of Resin (1) Acetoxyethyl vinyl ether, maleic anhydride, norbornenecarboxylic acid t-amyl ester, and 2-hydroxycyanonorbornyl acrylate in a molar ratio of 10/5.
A reaction vessel was charged at 0/30/10 and dissolved in tetrahydrofuran (dehydrated) to prepare a solution having a solid content of 50% by weight. This was heated to reflux under a nitrogen stream. Under reflux condition 2
After stirring for an hour, the reaction temperature was lowered to 60 ° C., and 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 14 hours, the reaction mixture was diluted 2-fold with tetrahydrofuran, and then poured into a mixed solvent of hexane / t-butyl methyl ether = 1/1 by volume of the reaction mixture to precipitate a white powder. . The precipitated powder was filtered out and dissolved in tetrahydrofuran,
0 times volume hexane / t-butyl methyl ether = 1 /
1 reprecipitated in a mixed solvent, and the precipitated white powder was collected by filtration, dried,
The target resin (1) was obtained. When the molecular weight analysis of the obtained resin (1) by GPC was tried, it was 8200 (weight average) in terms of polystyrene. Further, from the NMR spectrum, the composition of the resin (1) was acetoxyethyl vinyl ether / maleic anhydride / norbornenecarboxylic acid t-amyl ester / 2-hydroxycyanonorbornyl acrylate = 9/52/28/11 (molar ratio). It was In the same manner as in Synthesis Example (1), the following resin (2)
(10) was synthesized. (Repeating units are in order from the left of the structural formula.)

[0253]

[Table 1]

The structures of the above resins (1) to (10) are shown below.

[0255]

[Chemical 117]

[0256]

[Chemical 118]

[0257]

[Chemical formula 119]

<Resist Preparation> Examples 1 to 12 and Comparative Examples 1 to 3 (Preparation and Evaluation of Positive Resist Composition) As shown in Table 2, the resin (2 g) synthesized in the above Synthesis Example and light were used. Acid generator (amount shown in Table 2), organic basic compound (4 m
g), if necessary, a surfactant (5 mg) was added, dissolved in the solvent shown in Table 2 so that the solid content was 12% by weight, and then filtered through a 0.1 μm microfilter to give Example 1.
To 12 and Comparative Examples 1 to 3 were prepared. In addition, the ratio when the basic compound and the solvent are used in plural in Table 2 is a weight ratio.

[0259]

[Table 2]

(Explanation of Table 2) Resin R1 is described in JP-A-2001.
A resin having the following repeating unit prepared according to Synthesis Example 6 (Sample No. 2) of No. 200016.

[0261]

[Chemical 120]

Resin R2 is described in JP-A-2000-258915.
Resin A having the following repeating unit synthesized according to Resin Synthesis Example 1

[0263]

[Chemical 121]

The symbols for the surfactants are shown below. W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine type) W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine and silicone type) W3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W4: Polyoxyethylene nonylphenyl ether W5: Troisol S-366 (Troy Chemical Co., Ltd.)
Made)

The symbols for the basic compounds are shown below. E1: 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) E2: N, N-bis (2-hydroxyethyl) aniline E3: trioctylamine E4: triphenylimidazole E5: antipyrine E6: 2,6-diisopropylaniline E7: triisobutylamine E8: triisodecylamine

The symbols for the solvents are shown below. A1: Propylene glycol methyl ether acetate A2: 2-heptanone A3: γ-butyrolactone A4: Butyl acetate A5: Propylene carbonate A6: Propylene glycol monomethyl ether

(Evaluation Test) [Pattern Profile (Tailing)] A SiON substrate was used as a substrate having an inorganic antireflection film, a resist was applied, and the resist was baked at 130 ° C. for 90 seconds to apply a film thickness of 0.30 μm. did. The wafer thus obtained is subjected to ArF excimer laser stepper (ArF exposure machine 9300, manufactured by ISI).
A resolving power mask was mounted on and exposed while changing the exposure amount. After heating at 115 ° C. for 90 seconds in a clean room, development with a tetramethylammonium hydroxide developer (2.38% by weight) for 60 seconds, rinsing with distilled water, and drying to obtain 0.13 μm (line / space = 1 /
The pattern of 1.2) was formed. The pattern was observed by a scanning electron microscope (SEM), and the presence or absence of footing was observed. In each case, those not observed were marked with ◯, and those observed were marked with x. [Line edge roughness] A SiON substrate is used as a substrate having an inorganic antireflection film, and a resist is applied.
The coating was baked at 90 ° C. for 90 seconds to form a film having a thickness of 0.30 μm.
The wafer thus obtained was exposed while changing the exposure amount by loading a resolution mask on an ArF excimer laser stepper (ArF exposure machine 9300 manufactured by ISI). After heating in a clean room at 115 ° C for 90 seconds,
It was developed for 60 seconds with a tetramethylammonium hydroxide developer (2.38% by weight), rinsed with distilled water and dried to obtain a pattern. 125n in the mask
m line pattern (line / space = 1 / 1.2)
In the range of 5 μm in the longitudinal edge of the 125 nm line pattern obtained by the minimum exposure amount for reproducing
The distance from the reference line where the edge should exist was measured by S9220 manufactured by Hitachi, Ltd. at 50 points, the standard deviation was calculated, and 3σ was calculated. The smaller the value, the better the performance.

[0268]

[Table 3]

From the results shown in Table 3, it is understood that the composition of the present invention is excellent in both the characteristics of the pattern profile and the line edge roughness.

[0270]

INDUSTRIAL APPLICABILITY The present invention can provide a positive photosensitive composition free from the problems of footing and line edge roughness. Therefore, the positive photosensitive composition of the present invention is suitably used for microphotofabrication using far-ultraviolet light, especially ArF excimer laser light.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 222/40 C08F 222/40 G03F 7/004 503 G03F 7/004 503A H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA02 AA03 AA09 AA14 AB16 AB17 AC04 AC08 AD03 BE07 CB06 CB10 CB41 4J011 QA03 QA08 SA83 SA87 UA01 VA01 WA01 4J100 AE02 BC AE04P AE04PQAQBAQRQAQBAQRQAQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQ BC09P BC12R BC53P CA05 CA06 CA23 CA31 FA03 JA37

Claims (3)

[Claims] 1. A compound (A) which generates an acid upon irradiation with actinic rays or radiation, and (B) a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), And a resin containing a repeating unit represented by the general formula (N), which is decomposed by the action of an acid and has increased solubility in an alkali developing solution. [Chemical 1] [Chemical 2] In the general formula (I), R _1a represents a hydrogen atom or a hydrocarbon group, and R _2a represents a hydrocarbon group. Incidentally, R _1a and R _2a may be bonded to each other to form a ring. In the general formula (II), Z represents -O- or -N ( _R3a )-. Here, R _3a represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group or —OSO ₂ —R _4a . R _4a represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the general formula (N), R represents a hydrogen atom or a methyl group. A ₁ represents a single bond or a divalent linking group.
A ₂ represents a single bond, an alkylene group, an ether group, an ester group, or a group composed of a combination thereof. Z
₂ represents an aliphatic cyclic hydrocarbon group. l represents 0 or 1. A ₃ represents a single bond, an alkylene group, an ether group, an ester group, or a combination thereof. R '
Represents a cyan group. m represents an integer of 1 to 3. However, l
When = 0, at least one of A ₂ and A ₃ is an alkylene group, an ether group, an ester group or a combination thereof. 2. The resin as the component (B) has a general formula (pI) to (pI).
The positive photosensitive composition according to claim 1, which contains a repeating unit having a group represented by V) which is decomposed by the action of an acid. [Chemical 3] In the formula, R ₁₁ is a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group or se
represents a c-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R ₁₂ ~ R
Each ₁₆ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, R
_At least one of _{12 to} R ₁₄ , and either R ₁₅ or R ₁₆ represent an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that R ₁₇
At least one of R ₂₁ to R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ has 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently have 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may combine with each other to form a ring. 3. Irradiation with actinic rays or radiation of component (A)
The compound that generates more acid is represented by general formula (A2I) or general
A compound represented by formula (A2II):
The positive photosensitive composition according to claim 1 or 2. [Chemical 4] In general formula (A2I): R_1c~ R_5cAre each independently hydrogen
Atom, alkyl group, alkoxy group, or halogen atom
Represent R_6cAnd R_7cAre each independently a hydrogen atom,
Represents an aryl group or an aryl group. Rx and Ry are independent of each other
To an alkyl group, a 2-oxoalkyl group, an alkoxy group
It represents a rubonylmethyl group, an allyl group, or a vinyl group. R
_1c~ R_7cAny two or more of them, and Rx and Ry are
Each of them may be bonded to form a ring structure.
Contains oxygen atom, sulfur atom, ester bond, amide bond
You can leave. X^-Is sulfonic acid, carboxylic acid, or
Represents the anion of sulfonylimide. General formula (A2I
I) Middle: R^1d~ R^3dAre each independently an alkyl group or 2
Represents an -oxoalkyl group. R ^1d~ R^3dIs 2 of them
Two may combine with each other to form a ring structure. X^-Is
Represents an anion.