JP3444821B2 - Positive photoresist composition - Google Patents

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 production of an ultra-LSI or a high-capacity microchip and other photofabrication processes. More specifically, it relates to a positive photoresist composition capable of forming a highly detailed pattern by using light having a deep ultraviolet region including excimer laser light, particularly light having a wavelength of 250 nm or less.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having line widths of half micron or less. Has become. In order to meet the need, the wavelength of the exposure apparatus used for photolithography has become shorter and shorter, and now, excimer laser light (XeCl, KrF, ArF, etc.) with a short wavelength in far ultraviolet rays is being used.
Is being considered. A chemically amplified resist is used as a pattern for lithography in this wavelength region. Generally, chemically amplified resists are commonly called 2-component type, 2.5-component type,
It can be roughly divided into three types of three-component systems. 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 by 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 2-component system. The three-component system contains a photo-acid generator, an alkali-soluble resin and the above-mentioned low molecular weight compound.

The above chemically amplified resist is suitable as a photoresist for irradiation with ultraviolet rays or deep ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. For example,
A hydroxystyrene-based polymer which has a small light absorption particularly when using a 248 nm light of a KrF excimer laser.
A resist composition using a polymer having an acetal group or a ketal group introduced as a protective group has been proposed . JP
Rights 2-19847 Patent, JP-A-4-219757, JP-A-5-281745 JP-like are examples. In addition, similar compositions containing a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid decomposable group are disclosed in JP-A-2-209977, JP-A-3-206458, JP-A-2-19847 and the like. Proposed. These are suitable when using the 248 nm light of the KrF excimer laser, but when using the ArF excimer laser as the light source, they are inherently still too light-absorbent and therefore have low sensitivity. And other drawbacks associated with it,
For example, there are problems such as deterioration of resolution, deterioration of focus tolerance, and deterioration of pattern profile, and there are many points to be improved. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced for the purpose of imparting dry etching resistance has been proposed. As such a resin, a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid or a monomer having a hydroxyl group or a cyano group in the molecule is copolymerized with a monomer having an alicyclic hydrocarbon group. Resin.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate-based monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. ing. In addition, JP-A-9
-73173, JP-A-9-90637, JP-A-10
JP-A-161313 discloses an acid-sensitive compound containing an alkali-soluble group protected by a structure containing an alicyclic group and a structural unit capable of eliminating the alkali-soluble group with an acid to make it alkali-soluble. The resist material that was used is described. Further, a resin in which a hydrophilic 5-membered or 6-membered lactone group is introduced into a resin having these alicyclic groups for the purpose of improving affinity to an alkali developing solution and adhesion to a substrate is disclosed in JP-A 9-90637, JP-A-10-207069, and JP-A-10-274852.
And JP-A-10-239846. Even with the techniques described above, in the photoresist composition (especially, photoresist for exposure to deep ultraviolet rays), there still exist improvements due to the resin containing an acid-decomposable group, and further improvement in sensitivity, resolution and molecular weight. There are still many insufficient points such as improvement in adhesion to the substrate due to the simultaneous inclusion of an aliphatic cyclic hydrocarbon group therein, and improvement is desired. Furthermore,
In recent years, with the demand for miniaturization of semiconductor chips, the design pattern of the fine semiconductor has reached a fine region of 0.13 to 0.35 μm. However, these compositions have a problem that the resolution of the pattern is hindered by factors such as the edge roughness of the line pattern. Here, the edge roughness, the top and bottom edges of the line pattern of the resist, due to the characteristics of the resist,
It means that the edges appear uneven when the pattern is viewed from directly above because it irregularly fluctuates in the direction perpendicular to the line direction.

[0005]

SUMMARY OF THE INVENTION As described above, in the known techniques of conventional photoresist compositions, the sensitivity, resolution,
Adhesion with the substrate does not meet the recent performance requirements, and since the edges of the pattern show roughness and a stable pattern cannot be obtained, further improvement has been desired. Therefore, an object of the present invention is to provide a chemically amplified positive photoresist composition having high sensitivity, high resolution, good adhesion to a substrate, and improved edge roughness of a pattern. .

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to the constituent material of a resist composition in a positive type chemical amplification system, and as a result, by using an acid-decomposable resin having a specific structure , The present invention has been accomplished by knowing that the object is achieved. That is, the above object is achieved by the following configurations. (1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) the following general formula (I-1) to
A repeating unit having a group represented by at least one of (I-4), represented by the following general formulas (pI) to (pVI).
At least one group containing an alicyclic hydrocarbon structure
Repeats with alkali-soluble groups protected by seed groups
A unit and a repeating unit represented by the following general formula (a):
A positive photoresist composition, which comprises a resin that is decomposed by the action of an acid and has increased solubility in alkali.

[0007]

[Chemical 5]

In the general formulas (I-1) to (I-4); R ₁ to
R _{5 s} may be the same or different and each represents a hydrogen atom or an alkyl group, cycloalkyl group or alkenyl group which may have a substituent. Two of R _{1 to} R ₅ may combine with each other to form a ring.

[0009]

[Chemical 6]

In the general formulas (pI) to (pVI); R ₁₁ is
It 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 is 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 having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that R _{12 to} R ₁₄
At least one of them, or either R ₁₅ or R ₁₆ represents 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 , R ₂₃ and R ₂₅ are each independently hydrogen atom.
Child, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, and R ₂₄ has 1 to 4 carbon atoms.
, A linear or branched alkyl group or alicyclic hydrocarbon
However, at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group.

[0011]

[Chemical 7]

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, which} may be the same or different, each represents a hydrogen atom or a hydroxyl group. At least one of R _{32 to} R ₃₄ represents a hydroxyl group. (2) The group containing an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI) is a group represented by the following general formula (II), (1) The positive photoresist composition described in 1.

[0013]

[Chemical 8]

In the general formula (II), R ₂₈ has a substituent.
Represents an optionally substituted alkyl group. R _{29 to} R ₃₁ are the same
May be different, a hydroxy group, a halogen atom,
A carboxy group or an optionally substituted
Alkyl group, cycloalkyl group, alkenyl group, alkoxy group
Represents a Si group, an alkoxycarbonyl group or an acyl group.
p, q, and r each independently represent an integer of 0 or 1 to 3.
You (3) The positive photoresist composition as described in (1) or (2) above, which further contains (C) an acid diffusion inhibitor. (4) the compound of (A) is a, which is a sulfonate compound of sulfonium or iodonium
The positive photoresist composition according to any one of (1) to (3) . (5) The positive photoresist composition as described in any of (1) to (3) above, wherein the compound (A) is a sulfonate compound of N-hydroxyimide or a disulfonyldiazomethane compound. (6) As the exposure light, deep ultraviolet rays having a wavelength of 150 nm to 220 nm are used, (1) to (5) above
The positive photoresist composition as described in any one of 1.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. <(A) Compound that Generates Acid by Irradiation with Actinic Rays or Radiation (Photoacid Generator)> The (A) photoacid generator used in the present invention is a compound that generates an acid by irradiation with actinic rays or radiation. is there. The photo-acid generator used in the present invention is used in photo-initiator for photo-cationic polymerization, photo-initiator for photo-radical polymerization, photo-decoloring agent for dyes, photo-discoloring agent, micro resist, etc. Known light (400-200
nm ultraviolet ray, far ultraviolet ray, particularly preferably g ray, h
Ray, i-ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a molecular beam or an ion beam, and a compound that generates an acid, 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 compounds. Halides, photo-acid generators having an o-nitrobenzyl type protecting group, compounds that generate sulfonic acid by photolysis represented by iminosulfonates, disulfone compounds, diazoketosulfones, diazodisulfone compounds, etc. You can 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, V. N. R. Pillai, Syn
these, (1), 1 (1980), A.S. Abad
et al, Tetrahedron Lett. , (4
7) 4555 (1971), D.I. H. R. Barton
et al. Chem. Soc. , (C), 329
(1970), U.S. Pat. No. 3,779,778, European Patent 126,712, and the like, compounds capable of generating an acid by light can also be used.

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

[0018]

[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
Indicate. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0020]

[Chemical 10]

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

[0022]

[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 is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group. Z ⁻ represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Perfluoroalkane sulfonate anion such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ , toluene sulfonate anion, substituted benzene sulfonate anion such as dodecylbenzene sulfonate anion, pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion Examples thereof include, but are not limited to, condensed polynuclear aromatic sulfonate anions such as anthraquinone sulfonate anion and sulfonate group-containing dyes. Also R ²⁰³ , R
Two of ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

[0029]

[Chemical 17]

[0030]

[Chemical 18]

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described in, for example, J. W. Kn
apczyketal, J. Am. Chem. So
c. , 91, 145 (1969), A.S. L. Mayco
Ketal, J .; Org. Chem. , 35,253
2, (1970), E.I. Goethasetal, Bu
ll. Soc. Chem. Belg. , 73, 546
(1964), H .; M. Leicester, J .; Am
e. Chem. Soc. , 51, 3587 (192
9), J. V. Crivello et al. Po
lym. Chem. Ed. , 18, 2677 (198
0), U.S. Pat. Nos. 2,807,648 and 4,2.
47,473, JP-A-53-101,331 and the like.

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

[0033]

[Chemical 19]

In the formula, Ar³, Ar^FourReplace each independently
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. If A is replaced
Or unsubstituted alkylene group, alkenylene group, aryle
Group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

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

[0039]

[Chemical formula 23]

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.

[0041]

[Chemical formula 24]

In the present invention, as the photoacid generator, a sulfonate compound of sulfonium or iodonium (particularly preferably a compound represented by (PAG3) or (PAG4)), a sulfonate compound of N-hydroxyimide (particularly preferable). Is a compound represented by (PAG6)) or a disulfonyldiazomethane compound (particularly preferably (PAG6)
It is preferably a compound represented by AG7). As a result, the sensitivity and resolution are excellent, and the edge roughness of a fine pattern is excellent. The amount of these photo-acid generators added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1% by weight, based on the solid content in the composition. It is used in the range of 1 to 5% by weight. Addition amount of photo-acid generator is 0.0
If it is less than 01% by weight, the sensitivity is low, and if it is more than 40% by weight, the light absorption of the resist becomes too high, the profile is deteriorated and the process (particularly baking) margin is narrowed, which is not preferable.

<Resin which is decomposed by the action of (B) acid to increase its solubility in alkali> Resin which is decomposed by the action of (B) acid used in the composition of the present invention and whose solubility in alkali is increased (hereinafter , Also simply referred to as “resin of (B)” includes a repeating unit having a group represented by the above general formulas (I-1) and (I-4). General formula (I-1)-
In (I-4), the alkyl group for R _{1 to} R ₅ includes a linear or branched alkyl group, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , And 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 and decyl group. As the cycloalkyl group in R _{1 to} R ₅ , those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group are preferable. R
The alkenyl group for _{1 to} R ₅ has 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group and hexenyl group.
Individual ones are preferred. Examples of the ring formed by combining two members out of R _{1 to} R ₅ 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 the general formulas (I-1) and (I-2), R _{1 to} R ₅ may be linked to any of the 7 carbon atoms forming the cyclic skeleton.

Further, as a further substituent of the above-mentioned alkyl group, cycloalkyl group and alkenyl group, there are 1 to 1 carbon atoms.
Examples thereof 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. Preferred examples of the repeating unit having a group represented by formulas (I-1) to (I-4) include a repeating unit represented by the following formula (AI).

[0045]

[Chemical 25]

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 combining these. B represents a group represented by any one of formulas (I-1) to (I-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0047]

[Chemical formula 26]

In the above formula, Ra, Rb and r1 are as defined below. m represents an integer of 1 to 3.
Specific examples of the repeating unit represented by formula (AI) are shown below, but the content of the present invention is not limited thereto.

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

[Chemical 30]

[0053]

[Chemical 31]

[0054]

[Chemical 32]

[0055]

[Chemical 33]

In the present invention, the resin (B) is further protected with at least one group selected from the groups having an alicyclic hydrocarbon structure represented by the above general formulas (pI) to (pVI). By including the repeating unit having an alkali-soluble group, the effect of the present invention becomes more remarkable. General formula (p
In I) to (pVI), the alkyl group for R _{12 to} 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-
Examples thereof include a butyl group. Further, as the further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group,
Examples thereof include a carboxy group, an alkoxycarbonyl group and 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. In particular,
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 7 to 25.
Individuals are preferred. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among the groups containing an alicyclic hydrocarbon structure.

[0057]

[Chemical 34]

[0058]

[Chemical 35]

[0059]

[Chemical 36]

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 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.

As the substituents of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a cycloalkyl group,
Examples thereof 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,
Lower alkyl groups such as propyl group, isopropyl group and butyl group are preferable, more preferably methyl group, ethyl group,
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. As the alkoxy group (including the alkoxy group of the alkoxycarbonyl group), a methoxy group,
C1-C1 such as ethoxy, propoxy, butoxy
There can be four. 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 thereof 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 acetyl group, ethylcarbonyl group and propylcarbonyl group. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom.

Among the structures represented by the general formulas (pI) to (pVI), the general formula (pI) is preferable, and the group represented by the general formula (II) is more preferable. The alkyl group of R ₂₈ in formula (II), the halogen atom in R _{29 to} R ₃₁ , the alkyl group, the cycloalkyl group, the alkenyl group, the alkoxy group, the alkoxycarbonyl group, and the acyl group are the alicyclic hydrocarbon groups. Examples of the substituents are listed.

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

[0064]

[Chemical 37]

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

[0066]

[Chemical 38]

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 R may be the same or different. Examples of the halogen atom and alkyl group of R may be the same as those of R in the general formula (a) described later. A ′ has the same meaning as above. Ra is
It represents any group of the above formulas (pI) to (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) will be shown.

[0068]

[Chemical Formula 39]

[0069]

[Chemical 40]

[0070]

[Chemical 41]

[0071]

[Chemical 42]

[0072]

[Chemical 43]

[0073]

[Chemical 44]

The resin (B) in the present invention has the general formula
It contains the repeating unit represented by (a) . This improves developability and adhesion to the substrate. 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 formulas (I-1) to (I-4). Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. At least one of R _{32 to} R _{34 in} the general formula (a) is a hydroxyl group, preferably a dihydroxy body or a monohydroxy body, and more preferably a monohydroxy body. Further, the (B) resin in the present invention is a copolymer represented by the following general formulas (III-a) to (III) as other copolymerization components.
It is preferable to include the repeating unit represented by -d).
This improves the resolution of the contact hole pattern.

[0075]

[Chemical formula 45]

In the above formula, R₁Is synonymous with R above.
R_Five~ R₁₂Each independently have a hydrogen atom or a substituent
It represents an optional alkyl group. R is a hydrogen atom or
Is an alkyl group which may have a substituent, a cyclic alkyl group
It represents a kill group, an aryl group or an aralkyl group. m is 1
Represents an integer of -10. X has a single bond or a substituent
Optionally, alkylene group, cyclic alkylene group, ari
Group, ether group, thioether group, cal group
Bonyl group, ester group, amide group, sulfonamide
Group selected from the group consisting of a group, a urethane group, and a urea group.
Germany or a combination of at least two of these groups
And 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, an
It represents a xylene group or a divalent group in which these are combined.
R₁₃Is a single bond, an alkylene group, an arylene group, or
It represents a divalent group in which these are combined. R₁₅Is Alkyre
Group, arylene group, or divalent combination thereof.
Represents a group. R₁₄Is an optionally substituted alkyl
Group, cyclic alkyl group, aryl group or aralkyl group
You R ₁₆Is a hydrogen atom or has a substituent
Good alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official shown below
Represents any of the functional groups.

[0077]

[Chemical formula 46]

Examples of the alkyl group of R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , And 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, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group. , A dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, a steroid residue and the like.

Examples of the aryl group of R, R ₁₄ and R ₁₆ include those having 6 to 20 carbon atoms, which may have a substituent. Specific examples thereof include a phenyl group, a tolyl group and a naphthyl group. Examples of the aralkyl group of R, R ₁₄ , and R ₁₆ include those having 7 to 20 carbon atoms, and examples thereof include 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 vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 3-oxocyclohexenyl group, 3-oxo. Examples thereof include a cyclopentenyl group and a 3-oxoindenyl group. Of 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 which may have a substituent, or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, urethane Group, a single group selected from the group consisting of urea groups, or a combination of at least two or more of these groups,
A divalent group which is not decomposed by the action of an acid can be mentioned. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group combining these. 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, a phenylene group, a tolylene group,
Examples thereof include 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 formula. -[C (Ra) (Rb)] r1-In the formula, Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and 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. 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. r1 represents an integer of 1 to 10. Specific examples of the linking group X are shown below, but the contents of the present invention are not limited thereto.

[0081]

[Chemical 47]

Further substituents on the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include a carboxyl group, an acyloxy group, a cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples thereof include an alkoxy group, an acetylamide group, an alkoxycarbonyl group and an acyl group. 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 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 structure of the side chain in the general formula (III-b) are shown below, but the contents of the present invention are not limited thereto. .

[Chemical 48]

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) are shown below.
The contents of the present invention are not limited to these.

[0085]

[Chemical 49]

[0086]

[Chemical 50]

[0087]

[Chemical 51]

Specific examples of the repeating structural unit represented by formula (III-d) are shown below, but the contents of the present invention are not limited thereto.

[0089]

[Chemical 52]

[0090]

[Chemical 53]

[0091]

[Chemical 54]

In the general formula (III-b), R _{5 to} R _5
12 is 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 preferably 1 to 6. In formula (III-c), R ₁₃ is preferably an alkylene group such as a single bond, a methylene group, an ethylene group, a propylene group or a butylene group, and R ₁₄ is a methyl group, an ethyl group or the like having 1 carbon atom.
-10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups and naphthylmethyl groups are preferred. 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 formula (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. R ₁₆ is an optionally substituted 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 and an octyl group, a cyclohexyl group, Adamantyl group, norbornyl group, boronyl group, isobornyl group,
Menthyl group, morpholino group, 4-oxocyclohexyl group and optionally substituted phenyl group, toluyl group, mesityl group, naphthyl group and camphor residue are preferable. As these further substituents, a halogen atom such as a fluorine atom and an alkoxy group having 1 to 4 carbon atoms are preferable. In the present invention, general formula (III-a) to general formula (III
-D), general formula (III-b) and general formula (II
The repeating unit represented by Id) is preferred.

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

Examples of such repeating units 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) Membrane slippage (hydrophobicity, selection of alkali-soluble groups), (5) Adhesion of unexposed area to substrate,
(6) It is possible to finely adjust the dry etching resistance.
Examples of such copolymerizable monomers include addition polymerizable unsaturated bonds selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. The compound etc. which have one can be mentioned.

Specifically, for example, acrylic acid esters such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0) is preferred) Acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid-
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 such as alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (eg methyl methacrylate,
Ethylmethacrylate, propylmethacrylate, isopropylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate,
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 such as acrylamide, N-alkylacrylamide , (Alkyl group has 1 to 1 carbon atoms
0, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group and the like. ), N,
N-dialkyl acrylamide (alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group,
There are butyl group, isobutyl group, ethylhexyl group, cyclohexyl group and the like. ), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide etc .;

Methacrylamides, such as methacrylamide, N-alkylmethacrylamides (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl). Groups, etc.), N, N-dialkylmethacrylamides (such as ethyl groups, propyl groups, and butyl groups as alkyl groups), N-hydroxyethyl-N-methylmethacrylamide, etc .; allyl compounds such as allyl esters ( For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc .; vinyl ethers such as alkyl vinyl ethers (eg, Hex 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-ethylbutyl 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 barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .; dialkyl itaconates (eg dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid etc.); dialkyl esters of fumaric acid (eg dibutyl Fumarate etc.) or monoalkyl esters; other acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleironitrile. In addition, addition polymerizable unsaturated compounds copolymerizable with the above various repeating units may be used. In the resin (B), the content molar ratio of each repeating unit structure is generally required for the acid value, the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the density dependence of the resist profile, and the resist. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc.

In the resin (B), the compounds represented by the general formulas (I-1) to (I
-4) content of the repeating unit having a group represented by
It is 30 to 70 mol% in all repeating units, preferably 35 to 65 mol%, and more preferably 40 to 60 mol%. The content of the repeating unit having a group represented by any one of formulas (pI) to (pVI) is as follows.
It is usually 20 to 75 mol%, preferably 25 to 70 mol%, more preferably 30 to 65 mol%. (B)
In the resin, the content of the repeating unit represented by the general formula (a) is usually 0 mol% to 70 mol% in all the monomer repeating units.
It is preferably 10 to 40 mol%, more preferably 15 to 30 mol%. In addition, the content of the repeating units represented by the general formulas (III-a) to (III-d) in the resin (B) is usually 0.
1 mol% to 30 mol%, preferably 0.5 to 25
Mol%, more preferably 1 to 20 mol%.

The content of the repeating unit based on the monomer of the additional copolymerization component in the resin can be appropriately set according to the desired performance of the resist. Repeating units containing a group represented by any one of (I-1) to (I-4) and general formulas (pI) to (pI).
It is preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, based on the total number of mols of the repeating units having a group represented by VI). The weight average molecular weight Mw of the resin (B) is a polystyrene standard by gel permeation chromatography, preferably 1,000 to 1,000,000.
0, more preferably 1,500 to 500,000, further preferably 2,000 to 200,000, and particularly preferably 2,500 to 100,000. The larger the weight average molecular weight, the higher the heat resistance. While improving, the developability and the like decrease, and the balance is adjusted to a preferable range. The resin (B) used in the present invention can be synthesized by a conventional method, for example, a radical polymerization method. Hereinafter, specific examples of the resin (B) of the present invention will be listed, but the contents of the present invention are not limited thereto.

[0101]

[0102]

[0103]

[0104]

[0105]

[Chemical 59]

[0106]

[Chemical 60]

[0107]

[Chemical formula 61]

[0108]

[Chemical formula 62]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

In the above formula, m, n, p, and n1, n
2 and n3 each represent the molar ratio of the number of repetitions. (I-
The repeating unit having a group represented by any one of 1) to (I-4) is represented by n, and when two or more kinds are combined, n is represented.
They are distinguished by 1, n2, etc. The repeating unit having a group containing an alicyclic hydrocarbon structure represented by (pI) to (pVI) is represented by m. Formulas (III-a) to (III-
The repeating unit represented by d) is represented by p. When the repeating units represented by formulas (III-a) to (III-d) are included, m / n / p is (25 to 70) / (25
~ 65) / (3-40). General formula (III-a)
-(III-d) does not contain the repeating unit, m / n is (30-70) / (70-30). It may be a block copolymer or a random copolymer.
It may be a regular polymer or an irregular polymer. In the positive photoresist composition for deep UV exposure of the present invention, the addition amount of the resin (B) in the whole composition is preferably 40 to 99.99% by weight, more preferably 50 to 9% by weight based on the total resist solid content. It is 99.97% by weight.

In the positive resist composition of the present invention, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developing solution, and the like can be contained. The positive photoresist composition of the present invention includes
It may contain a fluorine-based and / or silicon-based surfactant. The positive photoresist composition of the present invention may contain one or more of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. it can. Examples of these surfactants include JP-A-62-36663, JP-A-61-226746, and JP-A-61-226745.
No. 62-170950, 63-345.
40, JP-A-7-230165, and JP-A-8-628.
34, JP-A-9-54432, and JP-A-9-5988.
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,
EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC
430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, R08.
(Manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, S
C101, 102, 103, 104, 105, 106
(Asahi Glass Co., Ltd.) fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The content of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.01% by weight 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 combinations. As the surfactant that can be used in addition to the above, specifically,
Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkylallyl Sorbitan fatty acid esters such as ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, po 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 to be added is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention.

The acid diffusion inhibitor (C) that can be used in the present invention is preferably added from the viewpoint of suppressing fluctuations in sensitivity and resolution with time after heating after exposure and development, and preferably organic bases. It is a sex compound. Examples of the organic basic compound include nitrogen-containing basic compounds having the following structures.

[0121]

[Chemical 71]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 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.

[0123]

[Chemical 72]

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.) A more preferable compound is a nitrogen-containing basic compound having two or more nitrogen atoms of different chemical environments in one molecule,
Particularly preferred is a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or a compound 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 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 aminomorpholine, substituted or unsubstituted amino An alkyl morpholine etc. are mentioned. Preferred substituents are amino groups, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups, alkoxy groups, acyl groups, acyloxy groups, aryl groups, aryloxy groups, nitro groups,
A hydroxyl group and a cyano group. Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,
1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2
-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
-Hydroxyethyl morpholine, N-benzyl morpholine, cyclohexyl morpholino ethyl thiourea (CH
METU) and other tertiary morpholine derivatives, JP-A-11-5
Examples thereof include hindered amines described in Japanese Patent No. 2575 (for example, those described in the above [0005]), but are not limited thereto. A particularly preferred example is
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, tertiary morpholines such as CHMETU, bis (1,
Examples thereof include hindered amines such as 2,2,6,6-pentamethyl-4-piperidyl) sebacate. Among them, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0]
Undeca-7-ene, 1,4-diazabicyclo [2,2
2,2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,
2,6,6-Pentamethyl-4-piperidyl) sebacate is preferred.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The nitrogen-containing basic compound is used in an amount of usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total 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.

The positive resist composition of the present invention is dissolved in a solvent which dissolves each of the above components and coated on a 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, lactic acid Ethyl, 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 in combination.

Among the above, the preferable solvent is 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone, and tetrahydrofuran. 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 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 composed of a light absorber and a polymer material can be used.
The former requires equipment such as a vacuum vapor deposition apparatus, a CVD apparatus, and a sputtering apparatus for forming a film. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin and a light absorber, and a maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a diamine-type light absorber, a resin binder containing the resin binder described in JP-A-6-118631 and a methylol melamine-based thermal crosslinking agent, and a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656 in the same molecule An acrylic resin-type antireflection film having, comprising a methylolmelamine described in JP-A-8-87115 and a benzophenone-based light absorber,
Examples thereof include a polyvinyl alcohol resin described in JP-A-8-179509 to which a low molecular weight light absorber is added. Further, as the organic antireflection film, DUV30 series or DUV-40 series manufactured by Brewer Science Co., or AC-2 or AC-3 manufactured by Shipley Co. may be used.

The resist solution is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (eg, a substrate optionally provided with the antireflection film), a spinner, and a coater. A good resist pattern can be obtained by applying a suitable coating method such as the above, exposing through a predetermined mask, baking and developing. 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, diethylamine and di-n.
-Secondary amines such as butylamine, triethylamine,
Tertiary amines such as methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pyrelidine. An alkaline aqueous solution can be used. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0129]

EXAMPLES The present invention will now be described in more detail 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, 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
5-exo of 2-endo-carboxylic acid-γ-lactone
-Methacrylate was charged at a molar ratio of 50/50, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5, and 100 m of a solution having a solid content concentration of 20%
1 was adjusted. 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-carboxylic acid-
5-exo-methacrylate of γ-lactone is 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
A product synthesized by acetoxy-lactonizing 2-endo-carboxylic acid, alkaline hydrolysis of acetoxy group to hydroxy group, and esterification with methacrylic acid chloride was used. J. Chem. Soc. ，
227 (1959), Tetrahedron, 21,
According to the method described in 1501 (1965). To this solution, 3 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. in a nitrogen atmosphere for 3 hours. After the completion of dropping, the reaction solution was heated for 3 hours, and V-65 was added again at 1 mol%.
Stir for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and crystallized in 3 L of distilled water to collect a precipitated white powder.
The polymer composition determined from C ¹³ NMR was 51/49. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 7,200.

[0130] Synthesis Examples 2-3, in the same manner as in Synthesis Example 1 of Resin of the present invention, the composition ratio shown in Table 1, the molecular weight of the tree
Fats (20) and (28) were comprised.

[0131]

[Table 1]

Synthesis of Comparative Example (Resin A4) According to the synthesis method described on page 8 of JP-A-10-274852, the compound described as A4 in the publication was synthesized as follows. 2-methyl-2-adamantyl methacrylate and α-methacryloyloxy-γ-butyrolactone were mixed in a molar ratio of 50:50 (40.0 g: 29.0 g).
Then, 2 parts by weight of all the monomers were added to prepare methyl isobutyl ketone to prepare a solution. There, azobisisobutyronitrile was used as an initiator in an amount of 2 mol% based on the total amount of monomers.
Add and heat at 80 ° C. for about 8 hours. Then, the operation of pouring the reaction solution into a large amount of heptane to cause precipitation was carried out twice to purify. As a result, a copolymer represented by the following formula was obtained. The composition molar ratio of each unit was 50:50, and the weight average molecular weight was about 8,000.

Examples 1 and 2, Comparative Example [Preparation and Evaluation of Photosensitive Composition] 1.4 g of the resin synthesized in the above Synthesis Example and 0.0 of the photo-acid generator.
3 g and 0.002 g of 1,5-diazabicyclo [4.3.0] -5-nonene were mixed and dissolved in propylene glycol monomethyl ether acetate at a solid content of 14 wt%, and then filtered through a 0.1 μm microfilter. Then
The positive resists of Examples 1 and 2 and Comparative Example were prepared.
Table 2 shows the resin of the present invention and the photo-acid generator used.

[0134]

[Table 2]

(Evaluation Test) The positive photoresist solution thus obtained was applied onto a silicon wafer using a spin coater and dried at 130 ° C. for 90 seconds to form a positive photoresist film of about 0.4 μm. ArF excimer laser (wavelength 193 nm, NA = 0.6, Ar manufactured by ISI)
Exposed with an F stepper). After the exposure, heat treatment was performed at 120 ° C. for 90 seconds, development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution, and rinsed with distilled water to obtain a resist pattern profile. For these, the sensitivity, resolution and edge roughness were evaluated as follows. The results of these evaluations are shown in Table 2.

[Sensitivity] The sensitivity was evaluated by the minimum exposure dose for reproducing a 0.15 μm line-and-space pattern. [Resolving power] The resolving power was evaluated by the limiting resolving power that can be reproduced at the minimum exposure amount for reproducing a 0.15 μm line-and-space pattern. [Edge Roughness] The edge roughness is measured with the edge roughness of an isolated pattern using a length-measuring scanning electron microscope (SEM), and the line pattern edge is detected at a plurality of positions in the measurement monitor, and the detected position The variance (3σ) of the above is used as an index of the edge roughness, and the smaller this value is, the more preferable. As is clear from the results of Table 2, the positive resist composition of the present invention is at a satisfactory level for all of them. That is, it is suitable for lithography using deep ultraviolet rays such as ArF excimer laser exposure.

[0137]

INDUSTRIAL APPLICABILITY The present invention can provide a positive resist composition which is suitable for far-ultraviolet light, particularly ArF excimer laser light, is excellent in sensitivity, resolution and edge roughness, and is excellent in the obtained resist pattern profile.

Continuation of the front page (56) Reference JP 2000-26446 (JP, A) JP 2000-159758 (JP, A) JP 2001-48931 (JP, A) JP 2001-48933 (JP, A) Open 2000-338673 (JP, A) JP 2000-338674 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (6)

(57) [Claims] 1. A compound which generates an acid upon irradiation with actinic rays or radiation, and (B) the following general formula (I-
1) to (I-4), a repeating unit having a group represented by at least one of the following general formulas (pI) to (pVI)
Of the groups containing alicyclic hydrocarbon structure represented by
Both having an alkali-soluble group protected by one group
Repeat unit and repeating unit represented by the following general formula (a)
A positive photoresist composition, which comprises a resin that is decomposed by the action of an acid and has an increased solubility in an alkali. [Chemical 1] In formulas (I-1) to (I-4); R _{1 to} R ₅ may be the same or different, and may be a hydrogen atom or a substituent, alkyl group, cycloalkyl group or alkenyl. Represents a group. Two of R _{1 to} R ₅ may combine with each other to form a ring. [Chemical 2] In 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 sec-.
Represents a butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R ₁₂ ~ R
₁₆ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that
At least one of R _{12 to} R ₁₄ , or R ₁₅ and R ₁₆
Any of the above represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ are
Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ is an alicyclic hydrocarbon; Represents a group. Further, either R ₁₉ or R ₂₁ has 1 to 4 carbon atoms.
Represents a linear or branched alkyl group or alicyclic hydrocarbon group. R ₂₂ , R ₂₃ and R ₂₅ are each independently water.
Represents a primary atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, and R ₂₄ represents 1 to 4 carbon atoms.
, Linear or branched alkyl groups or alicyclic hydrocarbons
Represents an elementary group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. [Chemical 3] In 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, which} may be the same or different, each represents a hydrogen atom or a hydroxyl group. At least one of R _{32 to} R ₃₄
One represents a hydroxyl group. 2. A group containing an alicyclic hydrocarbon structure represented by any one of the general formulas (pI) to (pVI) is represented by the following general formula (I
The positive photoresist composition according to claim 1, which is a group represented by I). [Chemical 4] In 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 may have a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl. Represents a group or an acyl group. p, q, r are
Each independently represents an integer of 0 or 1 to 3. Wherein further (C) positive photoresist composition according to claim 1 or 2, characterized by containing an acid diffusion controller. 4. A compound of (A) The positive photoresist composition according to any one of claims 1-3, characterized in that a sulfonium or iodonium sulfonate compound. 5. The compound of (A) is, N- sulfonate compounds of hydroxy imide or positive photoresist composition according to any one of claims 1-3, characterized in that a disulfonyldiazomethane compound. 6. The exposure light has a wavelength of 150 nm to 220.
claim 1, which comprises using a deep UV nm to 5
The positive photoresist composition as described in any one of 1.