JP2001056556A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the occurrence of development defects and edge roughness in development by incorporating a resin containing repeating units each having a specified group and increasing its alkali solubility under the action of an acid and a solvent containing a specified proportion of a specified solvent on the bases of the entire solvent. SOLUTION: The positive type photoresist composition contains a compound which generates an acid when irradiated with active light or radiation, a resin containing repeating units each having a group of the formula and increasing its alkali solubility under the action of the acid and a solvent containing 60-90 wt.% solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, etc. In the formula, R1 is H or 1-4C alkyl which may have a substituent, R2-R7 are each H, alkyl which may have a substituent, cycloalkyl which may have a substituent or alkenyl which may have a substituent and (m) and (n) are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity micro chip, and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a high-definition pattern by using light having a wavelength of not more than 250 nm, particularly a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as ultra LSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet this need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays is used.
The use of is being considered. A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol with a developing solution have been studied, and although tentative results have been obtained, the swelling of the resist film and the process become complicated. This does not necessarily mean that the problem has been solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in its main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. JP-A-11-109632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

A resin containing an acid-decomposable group used for a photoresist for exposure to far ultraviolet rays generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. For this reason, the resin becomes hydrophobic, and there is a problem caused by the hydrophobicity. Various means for improving the above have been studied, but the above techniques still have many unsatisfactory points (especially in terms of developability), and improvements are desired.

That is, the above-mentioned far ultraviolet ray, short wavelength light source,
For example, even in a technique using an ArF excimer laser (193 nm) as an exposure light source, there is still room for improvement in developability. Specifically, there have been problems of occurrence of development defects and occurrence of edge roughness. Here, the edge roughness refers to the top and bottom edges of a resist line pattern that fluctuate irregularly in a direction perpendicular to the line direction due to the characteristics of the resist. Means that the edge looks uneven. In addition, there is room for improvement in the problem of dependency on density.
Since various patterns are included as a tendency of recent devices, resists are required to have various performances. One of them is dependency on density. That is, the device has a portion where lines are dense, a pattern having a wider space than the lines, and an isolated line. Therefore, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and at present, the solution by a resist is not clear. In particular, in the above-mentioned resist system containing an alicyclic group, the performance difference between the isolated pattern and the dense pattern is remarkable, and improvement is desired.

On the other hand, conventionally, a coating solvent for a naphthoquinonediazide / novolak resin-based positive photoresist includes glycol ether and glycol ether esters such as 2-methoxyethanol and 2-ethoxyethanol, and acetates thereof. Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like have been very commonly used. However, with these solvents,
There are problems in toxicity, coating performance, solution storage stability, resist performance, etc., and improvement has been desired.

The coating performance, storage stability of the solution, and resist performance are attributes of components such as a binder polymer and a photoacid generator, and at the same time, are properties that are greatly affected by the solvent. Are known. However, the resist solvent must simultaneously satisfy all the requirements of coating performance, solution storage stability, safety, resist performance, and development defects.However, a polymer having an alicyclic hydrocarbon skeleton must be used. The fact is that the chemically amplified resist used has not been known so far.

[0010]

As described above, according to the known techniques of the conventional photoresist composition, sensitivity, resolution,
Since the adhesion to the substrate does not meet the recent required performance, development defects and roughness of the pattern edge are observed, and a stable pattern cannot be obtained. Therefore, further improvement has been desired. Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light, and specifically, sensitivity, resolution, An object of the present invention is to provide a positive photoresist composition which is excellent in dry etching resistance and adhesion to a substrate, and which solves problems of development defects and edge roughness during development. It is a further object of the present invention to provide a positive photoresist composition for deep ultraviolet exposure, which has excellent dependency on density.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, and as a result, by using a specific acid-decomposable resin and a specific additive, the present invention has been developed. Knowing that the object of the invention is achieved, the present invention has been achieved. That is, the above object is achieved by the following constitutions.

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) a repeating unit having a group represented by the following general formula (I); A resin having increased solubility, and (C) a solvent containing the following solvent (a) in an amount of 60 to 90% by weight based on the total solvent. (A) propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, A positive ultraviolet ray exposure positive electrode comprising at least one first solvent selected from methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. -Type photoresist composition.

[0013]

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In the general formula (I), R ₁ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. R _{2 to} R ₇ may be the same or different and represent a hydrogen atom, an optionally substituted alkyl group, cycloalkyl group or alkenyl group. However, at least one of R ₆ and R ₇ is a group other than a hydrogen atom. R ₆ and R ₇ may combine to form a ring. m and n each independently represent 0 or 1. However, m and n do not represent 0 at the same time.

(2) An alkali protected by the resin (B) further protected by at least one of groups having an alicyclic hydrocarbon structure represented by the following general formulas (pI) to (pVI): The positive photoresist composition for deep ultraviolet exposure according to the above (2), which contains a repeating unit having a soluble group.

[0016]

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In the general formulas (pI) to (pVI), R ₁₁ is
Represents a methyl group, an ethyl group, an n-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. Represents R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that R _{12 to} R ₁₄
And at least one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, 1 to 4 carbon atoms, a straight-chain or branched alkyl group or an alicyclic hydrocarbon group, provided that, R ₁₇
At least one of to R ₂₁ represents an alicyclic hydrocarbon group. Further, any one of R ₁₉ and R ₂₁ has 1 to 4 carbon atoms,
Represents a linear or branched alkyl group or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{22 to} R ₂₅ is an aliphatic group; Represents a cyclic hydrocarbon group.

(3) The general formulas (pI) to (pVI)
Wherein the group having an alicyclic hydrocarbon structure represented by is a group represented by the following general formula (II):
4. The positive photoresist composition for deep ultraviolet exposure according to item 1.

[0019]

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In the general formula (II), R ₂₈ represents an alkyl group which may have a substituent. R _{29 to} R ₃₁ may be the same or different, and may be a hydroxy group, a halogen atom, a carboxy group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkoxy group, alkoxycarbonyl Represents a group or an acyl group. p,
q and r each independently represent an integer of 0 or 1 to 3.

(4) The far ultraviolet rays according to any one of (1) to (3), wherein the resin (B) contains a repeating unit represented by the following general formula (a). Positive photoresist composition for exposure.

[0022]

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In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄ represents a hydroxyl group. (5) The positive photoresist composition for deep ultraviolet exposure according to any one of the above (1) to (4), further comprising (D) an acid diffusion inhibitor. (6) The positive photoresist composition for deep ultraviolet exposure according to any one of the above (1) to (5), wherein the compound (A) is a sulfonium or iodonium sulfonate compound. (7) The positive photo for deep ultraviolet exposure according to any one of (1) to (5), wherein the compound (A) is a sulfonate compound of N-hydroxyimide or a disulfonyldiazomethane compound. Resist composition. (8) The above-mentioned (1) to (7), wherein far-ultraviolet light having a wavelength of 150 nm to 220 nm is used as the exposure light.
A positive photoresist composition for deep ultraviolet exposure according to any one of the above.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. <(A) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator)> The (A) photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation. is there. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (400 to 200
nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h
Ray, i-ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a compound generating an acid by 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, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate that generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are used particularly effectively are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0028]

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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, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0030]

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

[0032]

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The formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group.

[0034] Z- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ^3-, etc. perfluoroalkane sulfonate anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, substituted benzenesulfonic acid anion such as pentafluorobenzenesulfonic acid anion, naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Examples thereof include, but are not limited to, condensed polynuclear aromatic sulfonic acid anions such as anions, and sulfonic acid group-containing dyes.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, J. Am
e.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Pol
18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) Disulfone derivatives represented by the following general formula (PAG5) or imidosulfonate derivatives represented by the following general formula (PAG6).

[0046]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0048]

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[0049]

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[0050]

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

[0052]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0054]

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In the present invention, sulfonium or iodonium sulfonate compounds (particularly preferably compounds represented by (PAG3) or (PAG4)) and N-hydroxyimide sulfonate compounds (particularly preferred) are used as the photoacid generator. Is a compound represented by (PAG6) or a disulfonyldiazomethane compound (particularly preferably (P
AG7). Thereby, the sensitivity and the resolving power are excellent, and the edge roughness of a fine pattern is also excellent.

The amount of the photoacid generator to be added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solid content in the composition. Is used in the range of 0.1 to 5% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile deteriorates,
The process (especially baking) margin is unfavorably reduced.

<(B) Resin whose solubility in alkali is increased by the action of acid> The resin (B) used in the composition of the present invention, whose solubility in alkali is increased by the action of acid (hereinafter simply referred to as "( B)))
It includes a repeating unit having a group represented by the general formula (I).

In the general formula (I), the optionally substituted alkyl group having 1 to 4 carbon atoms in R ₁ may be a linear or branched alkyl group having 1 to 4 carbon atoms. Represents Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-
Butyl group and the like. Examples of the alkyl group for R _{2 to} R ₇ include a linear or branched alkyl group, and may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. 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,
An octyl group, a nonyl group, and a decyl group. The cycloalkyl group represented by R _{2 to} R ₇ 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, a cyclooctyl group and the like. The alkenyl group for R _{2 to} R ₇ is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, and a hexenyl group. Examples of the ring formed by combining R ₆ and R ₇ 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.

Further, as the further substituent of the above-mentioned alkyl group, cycloalkyl group and alkenyl group, those having 1 to carbon atoms are preferable.
Examples include four 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. In the present invention, at least one of R ₆ and R ₇ is a group other than a hydrogen atom. Preferably, at least one of R ₆ and R ₇ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, particularly preferably. It is an alkyl group having 1 to 6 carbon atoms. In the present invention, R _{2 to} R ₄ are preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and particularly preferably. It is an alkyl group having 1 to 6 carbon atoms. m and n each independently represent 0 or 1. However,
m and n do not represent 0 at the same time. Preferred examples of the repeating unit having a group represented by the general formula (I) include a repeating unit represented by the following general formula (AI).

[0060]

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In the general formula (AI), R has the same meaning as R in the general formula (a) described later. A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. B represents a group represented by the general formula (I). In A ′, examples of the combined divalent group include those represented by the following formula.

[0062]

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In the above formula, Ra, Rb, and r1 have the same meanings as described below. m represents an integer of 1 to 3.
Hereinafter, specific examples of the repeating unit represented by the general formula (AI) will be shown, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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In the present invention, the resin (B) is further protected by at least one of groups having an alicyclic hydrocarbon structure represented by the following general formulas (pI) to (pVI). It is preferable to contain a repeating unit having an alkali-soluble group in that the effects of the present invention become more remarkable.
In the general formulas (pI) to (pVI), the alkyl group for R _{12 to} R ₂₅ may be substituted or unsubstituted, and may be a linear or branched alkyl group having 1 to 4 carbon atoms. Represents Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Further, as a further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group, alkoxycarbonyl group,
Examples thereof include a nitro group.

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

[0074]

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[0075]

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[0076]

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

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a cycloalkyl group,
Examples include an alkenyl group, an acyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. As the alkyl group, a methyl group, an ethyl group,
A lower alkyl group such as a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, and more preferably
A propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. An alkoxy group (including an alkoxy group of an alkoxycarbonyl group) includes a methoxy group,
C1-C1 such as ethoxy, propoxy and butoxy groups
Four things can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the acyl group include an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
Among the structures represented by the general formulas (pI) to (pVI), the structure represented by the general formula (pI) is preferable, and the group represented by the general formula (II) is more preferable. In formula (II), the alkyl group of R ₂₈ , the halogen atom, the alkyl group, the cycloalkyl group, the alkenyl group, the alkoxy group, the alkoxycarbonyl group, and the acyl group of R _{29 to} R ₃₁ are the same as the above-mentioned alicyclic hydrocarbon group. Examples of the substituent described above are exemplified.

The general formulas (pI) to (pV)
Examples of the alkali-soluble group protected by the structure represented by I) include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group and the like, and preferred are a carboxylic acid group and a sulfonic acid group. The alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above resin is preferably the following general formula (pVI)
Groups represented by I) to (pXI).

[0080]

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Here, R _{11 to} R ₂₅ and Z are the same as defined above. As the repeating unit having the alkali-soluble group protected by the structure represented by any one of formulas (pI) to (pVI), the repeating unit represented by the following formula (pA) is preferable.

[0082]

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In the general formula (pA), R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. Examples of the halogen atom and the alkyl group for R include the same examples as those for R in the general formula (a) described below. A ′ has the same meaning as described above. Ra is
Represents a group represented by any of the above formulas (pI) to (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown.

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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(B) The resin may further contain another repeating unit. The resin (B) in the invention preferably contains, as another copolymerization component, a repeating unit represented by the general formula (a). Thereby, the developability and the adhesion to the substrate are improved. Examples of the alkyl which may have a substituent of R in the general formula (a) include the same examples as R ₁ in the general formula (I). Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R _{32 to} R in the general formula (a)
_At least one of the ₃₄ is a hydroxyl group, preferably a dihydroxy form or a monohydroxy form, more preferably a monohydroxy form. Further, the resin (B) according to the present invention comprises, as another copolymerization component, the following general formula (III)
It preferably contains the repeating units represented by -a) to (III-d). Thereby, the removability of the exposed portion between the patterns during development is improved, and the resolution of the contact hole pattern is improved.

[0091]

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In the above formula, R₁Has the same meaning as R described above.
R_Five~ R₁₂Each independently has a hydrogen atom or a substituent
Represents an optionally substituted alkyl group. R represents a hydrogen atom or
Is an alkyl group which may have a substituent,
Represents a kill group, an aryl group or an aralkyl group. m is 1
Represents an integer of 10 to 10. X has a single bond or a substituent
An alkylene group, a cyclic alkylene group,
-Ene group, ether group, thioether group,
Bonyl group, ester group, amide group, sulfonamide
Group, a urethane group, or a urea group.
Germany or a combination of at least two of these groups
And represents a divalent group that is not decomposed by the action of an acid. Z
Is a single bond, an ether group, an ester group, an amide group,
Represents a kylene group or a divalent group obtained by combining them.
R₁₃Is a single bond, an alkylene group, an arylene group, or
It represents a divalent group obtained by combining these. R_FifteenIs an archille
Group, arylene group, or divalent
Represents a group. R₁₄Is an alkyl which may have a substituent
Group, cyclic alkyl group, aryl group or aralkyl group
You. R ₁₆Represents a hydrogen atom or a substituent
Good, alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official
Represents any functional group.

[0093]

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Examples of the alkyl group of R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ include a linear or branched alkyl group, which may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. 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,
An octyl group, a nonyl group, and a decyl group. R, R _14, R
_Examples of the cyclic alkyl group of ₁₆ include those having 3 to 30 carbon atoms, and specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a tricyclodecanyl group , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R, R ₁₄ and R ₁₆ has 6 to 20 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group represented by R, R ₁₄ and R ₁₆ include those having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group which may have a substituent. The alkenyl group for R ₁₆ has 2 carbon atoms.
To 6 alkenyl groups, specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 3-oxocyclohexenyl group, and a 3-oxo group. A cyclopentenyl group, a 3-oxoindenyl group and the like. Among these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X, an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group which may have a substituent. A group selected from the group consisting of urea groups, or a combination of at least two or more of these groups;
Examples include divalent groups that do not decompose under the action of an acid. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. Examples of the arylene group in X, R ₁₃ and R ₁₅ include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, phenylene group, tolylene group,
And a naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent. Examples of the alkylene group in X, Z, R ₁₃ and R ₁₅ include groups represented by the following formulas. -[C (Ra) (Rb)] r1 wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r1 represents an integer of 1 to 10. Specific examples of the linking group X are shown below, but the content of the present invention is not limited thereto.

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Further substituents in the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples include an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Here, 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 alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Hereinafter, specific examples of the structure of the terminal excluding X are shown below as specific examples of the structure of the side chain in the general formula (III-b), but the present invention is not limited thereto. .

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by formula (III-c) will be shown, but the content of the present invention is not limited thereto.

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Hereinafter, specific examples of the repeating structural unit represented by formula (III-d) will be shown, but the present invention is not limited thereto.

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In formula (III-b), R _{5 to} R ₁₂ are preferably a hydrogen atom or a methyl group. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is
1-6 are preferred. In the general formula (III-c), R ₁₃ is preferably a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, and R ₁₄ is a group having 1 carbon atom such as a methyl group or an ethyl group. Preferred are 10 to 10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups, and naphthylmethyl groups. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond. In the general formula (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. As R ₁₆ , an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, which may have a substituent;
Cyclohexyl group, adamantyl group, norbornyl group,
Boronyl, isobornyl, menthyl, morpholino, 4-oxocyclohexyl, and optionally substituted phenyl, toluyl, mesityl, naphthyl, and camphor residues are preferred. As these further substituents, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable.

In the present invention, general formulas (III-a) to (III-a)
Among (III-d), repeating units represented by formulas (III-b) and (III-d) are preferable.

In addition to the above, the resin (B) adjusts dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and the like, which are general requirements of a resist. It can be used as a copolymer with various monomer repeating units for the purpose.

Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3)
Alkali developability, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portion to substrate,
(6) Fine adjustment of dry etching resistance becomes possible.
Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from vinyl esters. And the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic acid esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cycloethyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group such as an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; other acrylic acid, methacrylic acid, croton Acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile,
Examples thereof include methacrylonitrile and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used.

In the resin (B), the molar ratio of each repeating unit structure is determined by the acid value, the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the dependency of the resist profile on the density of the resist, and the general properties of the resist. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, and the like, which are required in a global manner.

In the resin (B), the content of the repeating unit having a group represented by the general formula (I) is 30 to 70 mol%, preferably 35 to 65 mol%, of all the repeating units. Preferably it is 40 to 60 mol%. The content of the repeating unit having a group represented by any one of formulas (pI) to (pVI) is usually 20 to 75 in all the repeating units.
Mol%, preferably 25 to 70 mol%, more preferably 30 to 65 mol%. (B) In resin, general formula
The content of the repeating unit represented by (a) is usually from 0 mol% to 70 mol%, preferably from 10 to 40 mol%, more preferably from 15 to 30 mol%, based on all monomer repeating units.
It is. Further, in the resin (B), the general formulas (III-a) to (III-a)
The content of the repeating unit represented by (III-d) is usually 0.1 mol% to 30 mol% of all monomer repeating units,
Preferably 0.5 to 25 mol%, more preferably 1 to 2
0 mol%.

The content of the repeating unit based on the monomer of the additional copolymer component in the resin can be appropriately set according to the desired resist properties. It is preferably at most 99 mol%, more preferably at most 99 mol%, based on the total number of moles of the repeating unit containing the group represented by (I) and the repeating unit having the group represented by formulas (pI) to (pVI). Is at most 90 mol%, more preferably at most 80 mol%.

The weight average molecular weight Mw of the resin (B) is preferably from 1,000 to 1,000, as determined by gel permeation chromatography, using polystyrene standards.
000, more preferably 1,500 to 500,000,
It is more preferably in the range of 2,000 to 200,000, and particularly preferably in the range of 2,500 to 100,000. As the weight average molecular weight increases, heat resistance and the like improve, while developability and the like decrease. It is adjusted to a preferable range by the balance of.

The resin (B) used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method. Hereinafter, specific examples of the resin (B) of the present invention will be described, but the content of the present invention is not limited thereto.

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In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of the resin (B) added to the whole composition is preferably 40 to 99.99% by weight, more preferably of the total solid content of the resist. Is 50 to 99.97% by weight.

The positive resist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility in a developer can be contained.

The positive photoresist composition of the present invention may contain a fluorine-based and / or silicon-based surfactant. In the positive photoresist composition of the present invention,
Any one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or two or more thereof can be contained. As these surfactants, for example, JP-A-62-36663,
No. 61-226746, JP-A-61-226745, JP-A-62-170950
No., JP-A-63-34540, JP-A-7-230165, JP-A-8-62
No. 834, JP-A-9-54432 and JP-A-9-5988 can be mentioned, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
Fluorinated surfactants such as 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants can be exemplified. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination. As the surfactant that can be used in addition to the above, specifically,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether Ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, it may be mentioned nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention.

The acid diffusion inhibitor (D) which can be used in the present invention is preferably added in that it suppresses fluctuations in sensitivity and resolution over time from exposure to heating and development, and is preferably an organic base. Compound. Examples of the organic basic compound include a nitrogen-containing basic compound having the following structure.

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R
²⁵² may combine with each other to form a ring.

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, 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 aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group. Preferred specific compounds include guanidine, 1,1-dimethylguanidine,
1,3,3, -tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) 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] nona-
5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N
-Hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CH
Tertiary morpholine derivatives such as METU);
Hindered amines described in Japanese Patent No. 2575 (for example, those described in the Japanese Patent Publication [0005]), etc., are not limited thereto. Particularly preferred specific examples are
1,5-diazabicyclo [4.3.0] -5-nonene, 1,8
-Diazabicyclo [5.4.0] -7-undecene, 1,4
-Diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMET
Tertiary morpholines such as U, bis (1,2,2,6,6-
Hindered amines such as (pentamethyl-4-piperidyl) sebagate and the like. Among them, 1,5
-Diazabicyclo [4,3,0] non-5-ene, 1,
8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane,
4-Dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. If the amount is less than 0.001% by weight, the effect of the addition of 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 portion tends to deteriorate.

The positive resist composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. In the present invention, the following solvent is mixed with the first solvent of (C) and used as a total solvent. As a solvent to be mixed, ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl amyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, toluene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl pyruvate, methyl pyruvate, pyruvate Propyl acid, N, N-
Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N, N ′, N′-tetramethylurea, N-methylpyrrolidone, tetrahydrofuran, ethylene carbonate, propylene carbonate, β-methoxyisobutyrate methyl, ethyl butyrate, butyric acid Propyl, diacetone alcohol and the like are preferable, and these solvents are added to (C), and used by mixing at least one kind.

Among the above, preferred solvents to be mixed with the first solvent of (C) are γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol Examples thereof include glycol monoethyl ether, methyl lactate, ethyl lactate, N-methylpyrrolidone, methyl amyl ketone, ethyl amyl ketone, butyl acetate, isobutyl acetate, methyl pyruvate, ethyl pyruvate, and tetrahydrofuran. (C) First
The amount of the solvent used is 60 to 90% by weight based on the total solvent,
Preferably 65-85% by weight, more preferably 70-8%.
5% by weight.

Such a positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. In the present invention,
If necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection coating having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, one comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and described in JP-A-8-179509. Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is coated on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the antireflection film as required), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developing solution include inorganic alkalis 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, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0158]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Synthesis Example 1 Synthesis of Resin Example (1) of the Present Invention 2-Methyl-2-adamantyl methacrylate, 4,4
-Dimethyl-2-γ-butyrolactone methacrylate was charged at a molar ratio of 50/50 and dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5 to prepare 100 ml of a solution having a solid concentration of 20%. 3 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. over 3 hours in a nitrogen atmosphere. After dropping,
The reaction solution was heated for 3 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered. The polymer composition determined from C ¹³ NMR was 52/48. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 8,200.

Synthesis Examples 2 to 16 Synthesis of Resins (2) to (16) of the Present Invention Resins 2 to 16 having composition ratios and weight average molecular weights shown in Table 1 below were synthesized in the same manner as in Synthesis Example 1 above.

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[Table 1]

Embodiments 1 to 16 [Adjustment and Evaluation of Photosensitive Composition] 1.4 g of the resin shown in Table 2 synthesized in the above Synthesis Example, 0.03 g of a photoacid generator,
1.5 mg of 4-dimethylaminopyridine and 0.05 g of Megafac F-176 (manufactured by Dainippon Ink and Chemicals, Inc.) were blended and dissolved in the solvent described in Table 2 at a solid content of 14 wt%. The mixture was filtered through a 1 μm microfilter to prepare positive resists of Examples 1 to 16. The solvents described in Table 2 are shown below.

As the solvent, S1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S3: methyl 3-methoxypropionate S4: ethyl 3-ethoxypropionate S5: ethyl lactate S6: methyl amyl ketone S7: Butyl acetate S8: γ-butyrolactone S9: propylene carbonate S10: ethyl pyruvate

In this example and comparative examples, triphenylsulfonium triflate was used as a photoacid generator. As a comparative example, a positive resist was similarly prepared using a resin (A4) synthesized by a method similar to that described on page 8 of JP-A-10-274852.

(Evaluation Test) The obtained positive photoresist solution was applied on a silicon wafer using a spin coater, dried at 130 ° C. for 90 seconds, and a positive photoresist film of about 0.4 μm was formed. ArF excimer laser (193 nm Ar, NA = 0.6, manufactured by ISI)
F stepper). A heat treatment after the exposure was performed at 120 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. With respect to these, development defects, edge roughness and density dependency were evaluated as follows.

[Number of development defects]: Bare S of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the i-substrate, and dried at 140 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
Nik through a test mask with a duty ratio = 1: 3)
After exposure with an on-stepper NSR-1505EX, post-exposure heating was performed at 120 ° C. for 90 seconds. Subsequently, after paddle development with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, 30% with pure water.
Washed with water for 2 seconds and spin-dried. The sample thus obtained was used as KLA-2112 manufactured by KLA-Tencor Corporation.
The number of development defects was measured by a machine, and the obtained primary data value was defined as the number of development defects.

[Edge Roughness] The edge roughness was measured at the edge roughness of an isolated pattern using a length-measuring scanning electron microscope (SEM), and a line pattern edge was detected at a plurality of positions in a measurement monitor. The variance (3σ) of the variation in the detection position is used as an index of the edge roughness, and the smaller the value, the more preferable.

[Density Dependence] In a line-and-space pattern (dense pattern) having a line width of 0.22 μm and an isolated line pattern (sparse pattern), each was 0.22 μm.
The overlapping range of the depth of focus allowing ± 10% was determined. The larger this range is, the better the density dependency is. Table 2 shows the evaluation results.

[0168]

[Table 2]

As is evident from the results in Table 2, the positive resist compositions of the present invention are all at satisfactory levels. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0170]

The positive photoresist composition for deep ultraviolet exposure according to the present invention is suitably applied particularly to light in the wavelength region of far ultraviolet in the range of 150 nm to 220, and has sensitivity, resolution and dry etching resistance. In addition, adhesion of the substrate and prevention of development defects and edge roughness can be realized, a good resist pattern profile can be obtained, and the density dependency is excellent.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Kunihiko Kodama, Inventor Kunichi Kodama, 4000 Kawajiri, Yoshida-machi, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. CB14 CB41 CC01 CC03 4J100 AJ02R AL08P AL08Q AL08R AM21R BA02P BA03P BA05R BA08R BA11Q BA11R BA12P BA12R BA15P BA15R BA34R BA37R BA38R BA55R BA58R BA59R BB01R BC02P BC04R BC08R BC09BBCBCBCBC BCBC BC BC

Claims (8)

[Claims] 1. A compound which (A) generates an acid upon irradiation with actinic rays or radiation, (B) contains a repeating unit having a group represented by the following general formula (I), and is soluble in alkali by the action of an acid. (C) a solvent containing 60 to 90% by weight based on the total solvent of the following solvent (a): (a) propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy A positive type for deep ultraviolet exposure, comprising at least one first solvent selected from methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Photoresist composition. Embedded image In the general formula (I), R ₁ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. R _{2 to} R ₇
May be the same or different, and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. However, at least one of R ₆ and R ₇ is a group other than a hydrogen atom. R ₆ and R ₇ may combine to form a ring. m and n each independently represent 0 or 1. However, m and n do not represent 0 at the same time. 2. The resin of (B) further comprises the following general formula (p)
The composition according to claim 1, further comprising a repeating unit having an alkali-soluble group protected by at least one of the groups having an alicyclic hydrocarbon structure represented by (I) to (pVI). The positive photoresist composition for deep ultraviolet exposure according to the above. Embedded image In the general formulas (pI) to (pVI), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group;
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 or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Also, R ₁₉ ,
Any of R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ ~R
₂₅ independently represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that
At least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. 3. The group containing an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI) is represented by the following general formula (II):
The positive photoresist composition for deep-ultraviolet light exposure according to claim 2, which is a group represented by the formula: Embedded image In the general formula (II), R ₂₈ represents an alkyl group which may have a substituent. R _{29 to} R ₃₁ may be the same or different, and may be a hydroxy group, a halogen atom, a carboxy group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkoxy group, alkoxycarbonyl Represents a group or an acyl group. p, q, and r each independently represent an integer of 0 or 1 to 3. 4. The resin of (B) is represented by the following general formula (a):
The positive photoresist composition for deep-UV exposure according to any one of claims 1 to 3, comprising a repeating unit represented by the formula: Embedded image In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄
One represents a hydroxyl group. 5. The positive photoresist composition for deep-UV exposure according to claim 1, further comprising (D) an acid diffusion inhibitor. 6. The positive photoresist composition for deep ultraviolet exposure according to claim 1, wherein the compound (A) is a sulfonium or iodonium sulfonate compound. 7. The positive photoresist according to claim 1, wherein the compound (A) is a sulfonate compound of N-hydroxyimide or a disulfonyldiazomethane compound. Composition. 8. An exposure light having a wavelength of 150 nm to 220 nm.
8. The method according to claim 1, wherein far ultraviolet light of nm is used.
A positive photoresist composition for deep ultraviolet exposure according to any one of the above.