JP2000010285A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the occurrence of a cracking by incorporating a specified compd. besides an acid decomposable resin and a photo-acid generating agent. SOLUTION: This positive type photoresist compsn. contains a resin which is decomposed by the action of an acid to increase its alkali solubility, a compd. which generates the acid when irradiated with active rays of light or radiation and a compd. represented by the formula. In the formula, R1 is a di- to hexavalent combining group, R2-R4 may be mutually the same or different and are each a hydrocarbon group which may have a substituent, an amino group or the like, R6-R9 may be mutually the same or different and are each H, or the like, A is a divalent org. combining group or the like, (a) is an integer of 2-6, (1) is an integer of 0-6, (m) is an integer of 0-4 and (n) is an integer of 0-6. The compd. of the formula has at least one acid decomposable group in a part other than R1.

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 for use in an ultra-microlithography process such as the production of an VLSI or a high-capacity microchip and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a high-definition pattern using a far 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 VLSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to satisfy the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
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. For example,
When using 248 nm light of a KrF excimer laser, a hydroxystyrene-based polymer having a low light absorption is particularly used.
There has been proposed a resist composition using a polymer having an acetal group or a ketal group introduced as a protective group. JP-A-2-141636, JP-A-2-19847, JP-A-4
For example, Japanese Patent Application Laid-Open No. 5-281745 and Japanese Patent Application Laid-Open No. 5-281745 are examples. In addition, similar compositions using a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid-decomposable group are disclosed in JP-A-2-209977 and JP-A-3-209.
206458 and JP-A-2-19847. These are 24 KrF excimer lasers.
Although suitable when using 8 nm light, sensitivity is low when using an ArF excimer laser as the light source, because the absorbance is still essentially too high. In addition, there are other disadvantages associated therewith, such as deterioration of resolution, deterioration of focus tolerance, deterioration of pattern profile, and the like, and many points still need improvement.

[0005] Accordingly, a photoresist composition for an ArF light source is a photoresist composition in which a (meth) acrylic resin having a lower absorption than a partially hydroxylated styrene resin is combined with a compound capable of generating an acid by light. Resist compositions have been proposed. For example, JP-A-7-1
No. 99467 and No. 7-252324. Among them, JP-A-6-289615 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

Further, Japanese Patent Application Laid-Open No. Hei 7-234511 discloses an acid-decomposable resin having both an acrylic ester and a fumaric ester as a repeating unit. It is a fact that no good performance has been obtained.

Further, a resin into which an alicyclic hydrocarbon moiety has been introduced for the purpose of imparting dry etching resistance has been proposed. However, the introduction of an alicyclic hydrocarbon moiety has a disadvantage that the system becomes extremely hydrophobic. In addition, phenomena such as difficulty in developing with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution, and peeling of the resist from the substrate during the development are observed. 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. Although some results have been obtained, concerns about 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.

Japanese Patent Application Laid-Open No. 8-82925 discloses a photoresist composition containing a compound having a terpenoid skeleton, specifically, a photoacid generator having a terpenoid skeleton and a resin having a terpenoid skeleton. .
However, the technology substantially disclosed in this publication has insufficient sensitivity. Further, there is still room for improvement in resist pattern profiles and prevention of cracking.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of the above-mentioned technology for improving the performance inherent in microphotofabrication using far ultraviolet light, especially ArF excimer laser light, and to provide a short wavelength light source. An object of the present invention is to provide a positive photoresist composition having excellent sensitivity, excellent pattern profile, and capable of preventing cracking.

[0010]

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 have found that an acid-decomposable resin and a photoacid generator are further compounded with a compound having a specific structure. It has been found that the object of the present invention is achieved by using, and the present invention has been achieved. That is, the above object is achieved by the following constitutions.

(1) It contains a resin which decomposes under the action of an acid to increase solubility in alkali, a compound which generates an acid upon irradiation with actinic rays or radiation, and a compound represented by the following general formula (I). Positive photoresist composition for deep ultraviolet exposure.

[0012]

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In the general formula (I), R₁ Is a divalent to hexavalent ream
Represents a linking group. R_Two~ R_FourCan be the same or different,
A hydrocarbon group which may have a substituent, an alkoxy group,
Halogen atom, hydroxyl group, amino group, -COOR₀, -C
OOR _Five, -NH-C (= O) -R_FiveOr -NH-S
O_Two-R_FiveRepresents R_FiveMay have a substituent
Represents a hydrocarbon group. R₀Is -COOR₀In the action of acid
It represents a group constituting a more decomposable group (acid-decomposable group). R
₆~ R₉May be the same or different and represent a hydrogen atom,
A hydrocarbon group which may have a group, a halogen atom,
NO group, -COOR₀, -COOR_FiveOr -CO-X-
AR_TenRepresents X is an oxygen atom, a sulfur atom, -NH
-, -NHSO_Two-Or-NHSO_TwoRepresents NH-.
A represents a single bond or a divalent organic linking group. R
_TenIs an optionally substituted hydrocarbon group, lactone
Group, hydroxyl group, alkoxy group, carboxyl group, or shea
Represents a no group. a represents an integer of 2 to 6. l is 0-6
M represents an integer of 0 to 4 and n represents 0 to 6
Represents an integer. The compound represented by the general formula (I) includes R
₁And at least one other acid-decomposable group.

(2) The positive photoresist composition for deep ultraviolet exposure according to (1), wherein the resin has an alicyclic structure. (3) The positive photoresist composition for deep ultraviolet exposure according to the above (1) or (2), wherein far ultraviolet rays having a wavelength of 170 nm to 220 nm are used as the exposure light.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (Compound represented by Formula (I)) -C (= O) -O-
R ₀ constituting the acid-decomposable group represented by R ₀ is t
Tertiary alkyl groups such as -butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-alkoxyethyl group such as 1-isobutoxyethyl group and 1-cyclohexyloxyethyl group And lactone groups such as an alkoxymethyl group such as 1-methoxymethyl group and 1-ethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl group, a 3-oxocyclohexyl group, and a mevalonic lactone. Can be.

The hydrocarbon group for R _{2 to} R ₄ , R ₅ , R _{6 to} R ₉ and R ₁₀ is preferably an alkyl group or a cycloalkyl group. Examples of the alkyl group include those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a sec-butyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a tricyclodecanyl group, and a tetracyclododecanyl 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 fluorine atom, a chlorine atom, and a bromine atom. Further substituents on the hydrocarbon group include a hydroxyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a cyano group and the like.

As the divalent to hexavalent linking group for R ₁ , divalent to
Examples thereof include a trivalent nitrogen atom, a divalent to tetravalent carbon atom, and a divalent to hexavalent hydrocarbon group which may contain a hetero atom. Examples of the divalent to hexavalent hydrocarbon group which may contain a hetero atom include a divalent to hexavalent aliphatic hydrocarbon group and a divalent to hexavalent alicyclic group. ,
Examples include a sulfur atom and a nitrogen atom. Examples of the divalent to hexavalent aliphatic hydrocarbon group include divalent to hexavalent aliphatic hydrocarbon groups containing 2 to 4 carbon atoms. Examples of the divalent to hexavalent alicyclic group include those having 5 to 30 carbon atoms as a skeleton, and specific examples thereof include cyclopentane, cyclohexane, and a skeleton of an alicyclic structure described below. Divalent ~
Hexavalent ones are mentioned.

As the divalent linking group for A, an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group A single or a combination of two or more groups selected from the group consisting of As the alkylene group which may have a substituent,
The groups shown below can be exemplified. -[C (R _a ) (R _b )] _r-wherein R _a and R _{b are a} hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a halogen atom, a hydroxyl group, or an alkoxy group; they may be the same or different; and the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group. Represents a substituent selected from the group consisting of a group, an 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Individuals can be mentioned. r represents an integer of 1 to 10. The compound represented by the general formula (I) has at least one acid-decomposable group other than the moiety of R ₁ . The acid-decomposable group can be preferably contained in any of R _{6 to} R ₉ .

Among the above, R ₁ has 1 to 1 carbon atoms.
Six divalent to hexavalent alkyl residues, a nitrogen atom which may be alkyl-substituted, a cyclopentyl residue, a cyclohexyl residue, a norbornane residue, a tricyclodecane residue, a furan residue and a pyran residue are preferred. _{2 to} R ₄ each represent a methyl group, an ethyl group, a propyl group, an isopropyl group,
A hydroxyl group, a chlorine atom, a bromine atom, an amino group or an acid-decomposable group is preferred. As R _{6 to} R ₉ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyano group, an acid-decomposable group, a chlorine atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a hydroxyethoxycarbonyl group are preferable.

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

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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In the synthesis of the compound represented by the above general formula (I), a corresponding diterpenoid compound is reacted with an alcohol, followed by a Diels-Alder reaction with a vinyl compound, followed by a hydrogenation reaction. To obtain the desired compound. When introducing a substituent, Simonsen et al. Written by Terpe
ns Ed. 2 "can be referred to. In the present invention, the amount of the compound represented by the general formula (I) in the composition is usually 1 to 60 with respect to the total weight (solid content) in the composition.
%, Preferably 3 to 50% by weight.

Hereinafter, a resin (also referred to as an acid-decomposable resin) which is decomposed by the action of an acid and has increased solubility in an alkali developer will be described. First, as the acid-decomposable resin,
Those having a group that can be decomposed by the action of an acid (also referred to as an acid-decomposable group) and having an alicyclic structure are preferable. The alicyclic structure may be in the side chain, main chain, or both of the resin. The alicyclic structure includes those having a polycyclic structure and a bridged structure. Further, the acid-decomposable group may be contained in the alicyclic structure, or may be contained in another repeating unit. As the skeleton of the alicyclic structure, cyclopentane,
Examples include cyclohexane or the following structures.

[0028]

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[0029]

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Among the above, cyclopentane, cyclohexane, (5), (6), (7), (9), (10),
(13), (14), (15), (23), (28),
(36), (37), (42) and (47) are preferred.

Hereinafter, preferred examples of the acid-decomposable resin will be described. Acid-decomposable resin (a) At least one of monovalent polycyclic alicyclic groups represented by the following general formula (aI), (aII) or (aIII) is decomposed by the action of an acid to form an alkali. A resin having a group that increases solubility in a developer.

[0032]

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In the formulas (aI) to (aIII), R _{11 to} R ₁₅ may be the same or different, and may have a substituent, such as an alkyl group, a cycloalkyl group, an alkenyl group, an acyloxy group, alkynyl group, a halogen atom, a cyano group or, -R ₁₆ -O-R _{17 group, -R 18 -CO-O-R} 19 _{group, -R 20 -CO-NR 21 R} 22 groups, -R ₂₃ -O- CO-R ₂₄ groups, -R ₂₅ -CO-X ₁ -A ₁ -R ₂₆ , -R ₂₅ -CO-X ₁ -A ₂ -R ₂₇ , -R ₂₅ -CO-NHSO ₂ -X ₂ -A- Represents R ₂₇ or —COOZ.

R ₁₇ and R ₁₉ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, -Z or -O
-R ₁₇ or -CO-OR ₁₉ represents a group constituting a group (acid-decomposable group) which is decomposed by the action of an acid to increase solubility in an alkaline developer. Z is a group shown below.

[0035]

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R _{29 to} R ₃₆ may be the same or different;
Represents a hydrogen atom or an alkyl group which may have a substituent. a and b each represent 1 or 2. R _{21 to} R ₂₂ , R ₂₄
May be the same or different and represent a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group or an alkenyl group, and R ₂₁ and R ₂₂ may combine to form a ring . R ₁₆ , R ₁₈ , R ₂₀ and R ₂₃ may be the same or different and represent a single bond or an alkylene group, alkenylene group or cycloalkylene group which may have a substituent.

R ₂₅ represents a single bond, an alkylene group or a cycloalkylene group which may have a substituent. X ₁
Represents an oxygen atom, a sulfur atom, or -NH-. X ₂
Represents a single bond or -NH-. A is selected from the group consisting of a single bond, an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Represents a single or a combination of two or more groups.

A ₁ represents an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group,
It represents a single or a combination of two or more groups selected from the group consisting of ester groups. A ₂ is an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group alone or Represents a combination of two or more groups, provided that at least one is selected from a sulfonamide group, a urethane group, or a urea group.

R ₂₆ is -COOH, -COOR ₁₉ , -O
R ₁₇ , —COOZ, —CN, a hydroxyl group, or —CO—NH
It represents a -SO ₂ -R _40. R ₂₇ represents —COOH, —COO
R _19, -OR _17, -CN, a hydroxyl group, -CO-NH-
R ₄₀ , —CO—NH—SO ₂ —R ₄₀ , —Z, an alkyl group, a cycloalkyl group or an alkoxy group which may have a substituent; R ₄₀ represents an alkyl group or a cycloalkyl group which may have a substituent. l, m, n, p and q may be the same or different and represent 0 or an integer of 1 to 5.

[0040] Here, l, m, n, when p or q is 2 or more, each plurality of R ₁₁ to R ₁₅ may also be different from be the same, the two R ₁₁ to R ₁₅ Are substituted on the same carbon atom, two of which may represent a carbonyl group (＝ O) or a thiocarbonyl group (＝ S), and two of R ₁₁ to
When R ₁₅ substitutes on adjacent carbon atoms, these two may be bonded to each other to represent a double bond between the carbon atoms. When two or more of R _{11 to} R ₁₅ are each substituted, the two R _{11 to} R ₁₅ may be bonded to each other to form a ring. Formula (aI), (aII) or (aIII)
The position of the bond of the monovalent polycyclic alicyclic group represented by
Any position in the hydrocarbon polycyclic structure may be used.

[0041] Hereinafter, the acid-decomposable resin (a) will be described in detail.
You. Polycyclic alicyclic compounds of the above general formulas (aI) to (aIII)
Groups and acid-decomposable groups are bonded anywhere in the base resin
Can be done. That is, the general formulas (aI) to (a)
III) The polycyclic alicyclic group and the acid-decomposable group in the base resin
May be linked to different repeating units of
May be linked to a return unit, or both
It also includes the case where it coexists in fat. Tree according to the present invention
Groups represented by general formulas (aI) to (aIII) in fats and oils
The repeating structural unit having the general formula (aI)
Any compounds having a group represented by the general formula (aIII)
Any of these can be used, but preferably
Repeating structural units represented by formulas (aIV) to (aVI)
And more preferably represented by the following general formula (aIV)
Is a repeating structural unit.

[0042]

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In the formulas (aIV) to (aVI), R₆₅, R₆₆, R
₆₈~ R₇₀May be the same or different, a hydrogen atom, a halogen
Atom, cyano group, alkyl group or haloalkyl group
You. R₆₇Is a cyano group, -CO-OR₇₇Or -CO-N
R₇₈R₇₉Represents A may be the same or different, and is a single bond
Or an alkylene group which may have a substituent,
Alkenylene or cycloalkylene, ether
Group, thioether group, carbonyl group, ester group,
Group, sulfonamide group, urethane group, or urea group
A single or two or more groups selected from the group consisting of
Combination, -SO_Two -, -O-CO-R₈₀-, -CO-O
-R₈₁-Or -CO-NR ₈₂-R₈₃Represents-.

R ₇₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent, or a group constituting an acid-decomposable group by —CO—OR ₇₇ . R ₇₈ , R ₇₉ and R ₈₂ 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. R ₇₈ and R ₇₉ may combine to form a ring. R _{80 to} R ₈₁ and R ₈₃ may be the same or different and represent a single bond or a divalent alkylene group, alkenylene group or cycloalkylene group;
Further, these groups may form a divalent group together with an ether group, an ester group, an amide group, a urethane group or a ureide group. Y represents the above general formulas (aI) to (aII)
It represents a polycyclic alicyclic group represented by I).

The acid-decomposable resin (a) comprises at least one of the repeating structural units represented by the above general formula (aIV), (aV) or (aVI), and the following general formula (aVII):
It is preferable that the resin has at least one of the repeating structural units represented by (aVIII) or (aIX) and is decomposed by the action of an acid to increase the solubility in an alkaline developer.

[0046]

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In the formulas (aVII) to (aIX), R ₇₁ , R ₇₂ , R
₇₄ to R ₇₆ may be the same or different, represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ₇₃ has the same meaning as R ₆₇ described above. A has the same meaning as that described in the above general formulas (aIV) to (aVI). B is
It is a group that is decomposed by the action of an acid to increase solubility in an alkaline developer.

Further, the acid-decomposable resin (a) may further contain at least one of the repeating structural units having a carboxyl group and represented by the following general formula (aX), (aXI) or (aXII). preferable.

[0049]

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In the general formulas (aX) to (aXII), R ₈₄ ,
R ₈₅ and R _{87 to} R ₈₉ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ₈₆ represents a cyano group, a carboxyl group, —C
Represents O-OR ₉₀ or -CO-NR ₉₁ R ₉₂ ; A has the same meaning as that described in the general formulas (aIV) to (aVI).
R ₉₀ represents an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent. R ₉₁ and R ₉₂ may be the same or different and each represents a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group or an alkenyl group, and R ₉₁ and R ₉₂ combine to form a ring You may.

R _{11 to} R ₁₅ , R ₁₇ and R in the above formula
_{19, R 21, R 22,} R 24, R 29 ~R 36, R 40, R 45,
R ₆₅ , R ₆₆ , R _{68 to} R ₇₀ , R ₇₁ , R ₇₂ , R _{74 to} R ₇₉ , R
_As the alkyl group of ₈₂ , R ₈₄ , R ₈₅ , and R _{87 to} R ₉₂ , a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, which may optionally have a substituent, Examples thereof include those having 1 to 8 carbon atoms such as a hexyl group, a 2-ethylhexyl group and an octyl group. R _{11 to} R ₁₅ ,
_{R 17, R 19, R 21} , R 22, R 24, R 29 ~R 36, R 40, R
_{45, R 65, R 66,} R 68 ~R 70, R 71, R 72, R 74 ~
The cycloalkyl group for R ₇₉ , R ₈₂ , R ₈₄ , R ₈₅ , and R _{87 to} R ₉₂ is preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, which may have a substituent. -Methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group.

The alkenyl group preferably has 2 to 6 carbon atoms such as vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl and cyclohexenyl which may have a substituent. One. Examples of the alkoxy group represented by R _{11 to} R ₁₅ and R ₂₇ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group which may have a substituent. Examples of the acyloxy group for R _{11 to} R ₁₅ include those having 1 to 4 carbon atoms, such as an acetoxy group and a butyryloxy group, which may have a substituent. The alkynyl group represented by R _{11 to} R ₁₅ preferably has 2 to 4 carbon atoms such as an acetyl group and a propargyl group.

Here, l, m, n, p or q is 2 or more.
In the case, each of a plurality of R₁₁~ R_FifteenAre the same or different
Well, each R₁₁~ R_FifteenR of two of₁₁~ R_Fifteen
Are substituted on the same carbon atom, the two
Represents a nyl group (＝ O) or a thiocarbonyl group (＝ S)
Is also good. Furthermore, a plurality of R₁₁~ R_FifteenR of two of₁₁
~ R_FifteenIs substituted on an adjacent carbon atom.
Represents a double bond between those carbon atoms
May be. Where the double bond between the formed carbon atoms
Preferably does not form a conjugated double bond between carbon and carbon.
Good. Also, R₁₁~ R_FifteenReplaces two or more of each
In the case, two of them R₁₁~ R _FifteenAre bonded to each other to form a ring
It may be formed. Such a ring is preferably
Chloropropyl group, cyclopentyl group, cyclohexyl
Group, cycloheptyl group, tetrahydrofuranyl group, tet
May contain heteroatoms such as lahydropyranyl groups
A 3- to 8-membered ring is exemplified. These rings further have a substituent.
You may have. Formula (aI), (aII) or (a
III) Position of the bond of the monovalent polycyclic alicyclic group represented by
The position can be at any position in the hydrocarbon polycyclic structure.
Preferably at positions 3, 7 and 12 of the steroid skeleton
is there.

R ₆₅ , R ₆₆ , R _{68 to} R ₇₀ , R ₇₁ , R ₇₂ , R
_As the haloalkyl group of _{74 to} R ₇₆ , R ₈₄ , R ₈₅ , R _{87 to} R ₈₉ , preferably a fluorine atom, a chlorine atom or a bromine atom-substituted alkyl group having 1 to 4 carbon atoms, for example, a fluoromethyl group, Examples thereof include a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, and a bromoethyl group. In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The alkylene group of R ₁₆ , R ₁₈ , R ₂₀ , R ₂₃ and A is preferably a methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group which may have a substituent. Examples thereof include groups having 1 to 8 carbon atoms. The alkenylene group preferably has 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group which may have a substituent. Examples of the cycloalkylene group preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

Examples of the alkylene group which may have a substituent for R ₂₅ , A, A ₁ and A ₂ include the following groups. -[C (R _a ) (R _b )] _r-wherein R _a and R _{b are a} hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a halogen atom, a hydroxyl group, or an alkoxy group; they may be the same or different; and the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group. Represents a substituent selected from the group consisting of a group, an 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Individuals can be mentioned. r represents an integer of 1 to 10. Examples of the cycloalkylene group represented by R ₂₅ include those having 5 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group, which may have a substituent.

A ₂ contains at least one group selected from the group consisting of a sulfonamide group, a urethane group and a ureido group. A divalent group may be formed with a divalent group selected from the group consisting of an amide group, a urethane group, and a urea group alone or in combination of two or more groups. Formulas (aI) to (a) In III), l, m, n, p or q represents 0 or an integer of 1 to 5, preferably 0 or an integer of 1 to 2.

The alkylene group, alkenylene group and cycloalkylene group represented by R _{80 to} R ₈₁ and R ₈₃ are the same as those described above, and furthermore, these groups are combined with an ether group, an ester group or an amide group. , A urethane group and a ureido group together form a divalent group. Further, as the ring formed by combining R ₂₁ and R ₂₂ or R ₇₈ and R ₇₉ with a nitrogen atom, a ring forming a 5- to 8-membered ring is preferable, and specifically, pyrrolidine, piperidine, piperazine and the like are preferable. No.

R ₁₇ , R ₁₉ , R ₇₇ and B constitute an acid-decomposable group. Here, in the resin according to the present invention, the acid-decomposable group is represented by a group represented by the general formulas (aI) to (aIII) (for example, as -OR ₁₇ or -CO-OR ₁₉ ). And the compounds represented by the general formulas (aI) to (aIII)
In a repeating structural unit having a group represented by (for example,-
CO-OR ₇₇ ), may be further included in other repeating structural units, or may be included in a plurality of these positions. Examples of the acid-decomposable group include a group which is hydrolyzed by the action of an acid to form an acid, and a group which forms an acid by elimination of a carbon cation by the action of an acid. Preferably, the following general formula (XII
These are groups represented by (I) and (XIV). Thereby, the stability over time becomes excellent.

[0060]

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Here, R _{97 to} R ₉₉ may be the same or different and represent a hydrogen atom or an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. However, among R _{97 to} R _{99 in} the formula (XIII),
At least one is a group other than a hydrogen atom. R ₁₀₀ represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Further, R _{97 to} R of the formula (XIII)
_{Even if} two of ₉₉ or two of R _{97 to} R ₉₈ and R ₁₀₀ of the formula (XIV) combine to form a ring structure composed of 3 to 8 carbon atoms and hetero atoms. good. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, and the like. Z _{1 and} Z ₂ may be the same or different and represent an oxygen atom or a sulfur atom.

Here, as the alkyl group and the cycloalkyl group, the same groups as those described above for R _{11 to} R ₁₅ are preferable. The alkenyl group preferably has 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent. Can be Also,
As the acid-decomposable group, preferred is -C (= O)
—OR (where R represents a trialkylsilyl group such as a trimethylsilyl group, a t-butyldimethylsilyl group, a diisopropylmethylsilyl group, a mevalonic lactone group, or a 3-oxocyclohexyl group) may also be mentioned. it can.

Further substituents in each of the above-mentioned substituents are preferably a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₁₁ An alkyl group of ~ R ₁₅ ,
Methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, formyl group, acetyl group, acyl group such as benzoyl group, Examples include an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group.

In the resin according to the present invention, a repeating structural unit having an alicyclic group represented by the above general formulas (aI) to (aIII) (preferably a repeating structure represented by the general formulas (aIV) to (aVI)) The content of (unit) is adjusted by the balance with dry etching resistance, alkali developability, and the like, but is preferably 20 mol% or more, more preferably 30 to 80 mol%, based on all repeating units.
More preferably, it is in the range of 40 to 65 mol%.

In the resin according to the present invention, the content of the repeating structural unit having an acid-decomposable group (preferably the repeating structural unit represented by any one of formulas (aVII) to (aIX)) is as follows. It is adjusted according to the performance such as the substrate adhesion, but is preferably 5 to 8 for all the repeating units.
It is used in the range of 0 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%. Here, the content of the acid-decomposable group-containing repeating structural unit is determined by the total content of the resin including the acid-decomposable group contained in the repeating structural unit having a group represented by the general formulas (aI) to (aIII). Of the acid-decomposable group-containing repeating structural unit.

The synthesis of the monomer corresponding to the repeating unit of the acid-decomposable resin is generally carried out in the molecule by the general formulas (aI) to (a).
It can be obtained by an esterification reaction of an alcohol having a partial structure of III) with a carboxylic acid having a polymerizable functional group in the molecule or a derivative thereof, or a reaction with an imide. Further, the polymer containing the repeating unit of the present invention can be obtained by polymerizing the corresponding monomer using a general radical initiator such as an azo type, or by cationic polymerization or anionic polymerization according to a conventional method. If desired, the obtained polymer may be converted into a functional group. Hereinafter, specific examples (a1) to (a131) of the repeating structural units represented by formulas (aIV) to (aVI) are shown, but the present invention is not limited thereto.

[0067]

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[0075]

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[0080]

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[0081]

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[0082]

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[0084]

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[0085]

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[0086]

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[0087]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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Hereinafter, specific examples (b1) to (b42) and specific examples (b-43) of the repeating structural units represented by formulas (aVII) to (aXI) as the repeating unit having an acid-decomposable group will be given.
To (b-122), but the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0115]

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[0126]

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In the acid-decomposable resin (a), a carboxyl group may be contained in a repeating structural unit having a group represented by the above general formulas (aI) to (aIII), or a repeating structure having an acid-decomposable group. It may be contained in a unit or may be contained in another repeating structural unit different from them. Further, it may be contained in a plurality of positions among the substitution positions of these carboxyl groups. As the repeating structural unit having a carboxyl group, the repeating structural units represented by the above general formulas (aX) to (aXII) are preferable.

The content of the repeating structural unit having a carboxyl group (preferably the repeating structural units represented by formulas (aX) to (aXII)) in the resin according to the present invention is determined by alkali developability and substrate adhesion. Although it is adjusted by the performance such as sensitivity, it is preferably in the range of 0 to 60 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%, based on all repeating units.
Here, the content of the carboxyl group-containing repeating structural unit is determined by the above-mentioned general formula (aI) containing a carboxyl group.
(AIII) is the amount of all the carboxyl group-containing repeating structural units in the resin, including the repeating structural unit having a group represented by (aIII) and the carboxyl group-containing acid-decomposable group-containing repeating structural unit. The general formulas (aX) to
Specific example of repeating structural unit represented by (aXII) (c1)
To (c18), but the present invention is not limited thereto.

[0129]

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[0130]

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The repeating unit containing the general formulas (aI) to (aIII) is particularly preferably the general formula (aIV).
Further, as the acid-decomposable resin (a), general formula (aIV) alone,
Alternatively, a combination of general formula (aIV) and general formula (aVII), a combination of general formula (aIV) and general formula (aX), a general formula (aIV) and general formula (aVII), and a general formula (aX) Are preferred. Further, other polymerizable monomers described below may be combined.

A repeating structural unit having a group represented by any one of formulas (aI) to (aIII) (preferably a compound represented by formula (aIV)
To (aVI) repeating structural unit) and a repeating structural unit having an acid-decomposable group (preferably, formulas (aVII) to (aIX)).
A repeating structural unit having a carboxyl group, if necessary (preferably a compound of the general formula (a)
X) to (aXII)) or an acid-decomposable resin (a) containing another polymerizable monomer,
It is synthesized by radical, cationic or anionic polymerization of an unsaturated monomer corresponding to each structure. More specifically, each monomer is blended based on the preferred composition described above, a polymerization catalyst is added at a monomer concentration of about 10 to 40% by weight in an appropriate solvent, and the mixture is heated and polymerized as needed.

Acid-decomposable resin (b) A resin containing a repeating unit represented by the following general formula (bI) or (bII) and a group decomposed by the action of an acid.

[0134]

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In the formula, R_b1, R_b2Are each independently a hydrogen source
, Cyano group, hydroxyl group, -COOH, -COOR_b5, −
CO-NH-R_b6, -CO-NH-SO_Two -R_b6, Replace
An alkyl group, an alkoxy group or
Represents a cyclic hydrocarbon group or the following -Y group. R_b5Replace
Alkyl group, cyclic hydrocarbon group or
Represents the following -Y group. -Y group:

[0136]

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R _b6 represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. R _{29 to} R ₃₆ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2. R _b3 and R _b4 are
Each independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -N
Represents HSO ₂ NH—. A represents a single bond or a divalent linking group. Z is an atomic group for forming an alicyclic structure which may have a substituent together with two carbon atoms (C-C) (preferably a bridged aliphatic which may have a substituent) Atom group for forming a cyclic structure).

The general formula (bII) is represented by the following general formula (bII)
-A) or a general formula (bII-B).

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In the formulas (bII-A) and (bII-B), R _b10
To R _b13 each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _b5 (where R _b5 may have a substituent, an alkyl group, a cyclic hydrocarbon group, or the above -Y Represents a group), a group decomposed by the action of an acid, -C
(＝ O) —X—A—R _b14 , or an _optionally substituted alkyl group or cyclic hydrocarbon group. Also,
At least two members out of _{Rb10 to Rb13} may combine to form a ring. n represents 0 or 1. X is an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂
Represents NH-. R _b14 represents —COOH, —COOR _b5 ,
-CN, a hydroxyl group, an optionally substituted alkoxy _{group, -CO-NH-R b6,} -CO-NH-SO 2 -R b6
(R _b5 and R _b6 have the same _{meanings as} described above) or the above-described —Y group. A represents a single bond or a divalent linking group.

[0141] Hereinafter, the acid-decomposable resin (b) will be described.
You. In the above general formula (bI), R_b1, R_b2Are each
Independently, a hydrogen atom, a cyano group, a hydroxyl group, -COOH,-
COOR_b5, -CO-NH-R_b6, -CO-NH-SO
_Two -R_b6, An optionally substituted alkyl group, alcohol
Represents a xy group, a cyclic hydrocarbon group, or the above-described -Y group.
You. R_b6Represents an optionally substituted alkyl group or
Represents a cyclic hydrocarbon group. R_b5Has a substituent
May be an alkyl group, a cyclic hydrocarbon group or the above-described -Y group.
Represent. R of the above -Y group₂₉~ R₃₆Are each independently a hydrogen source
And represents an alkyl group which may have a substituent or a substituent.
a and b represent 1 or 2. X represents an oxygen atom, a sulfur atom,
-NH-, -NHSO_Two -Or-NHSO_Two NH-
You. A represents a divalent linking group.

The above R _b1 , R _b2 , R _b5 , R _b6 , R _{29 to} R ₃₆
Is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, further preferably a methyl group , Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s
an ec-butyl group and a t-butyl group. The above R _b1 ,
Examples of the cyclic hydrocarbon group for R _b2 , R _b5 , and R _b6 include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, 2-methyl-2-adamantyl, norbornyl, boronyl, isobornyl, and tricyclodecayl. Examples include a nyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. Examples of the alkoxy group in R _b1 and R _b2 include:
Examples thereof include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents of the above-mentioned alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

The divalent linking group represented by A in the general formula (bI) includes an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group,
A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups may be used. An alkylene group for the above A,
Examples of the substituted alkylene group include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. 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. r represents an integer of 1 to 10.

Specific examples of the repeating unit represented by the above general formula (bI) include the following [bI-1] to [bI-65].
However, the present invention is not limited to these specific examples.

[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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In the above general formula (bII), R _b3 and R _b4
Is independently a hydrogen atom, a cyano group, a halogen atom,
Or an alkyl group which may have a substituent. Z
Represents an atomic group for forming an alicyclic structure which may have a substituent together with two carbon atoms (C-C).

Examples of the halogen atom in R _b3 and R _b4 include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. As the alkyl group for R _b3 and R _b4 , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 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.

Further substituents in the alkyl groups of R _b3 and R _b4 include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and 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. And formyl group as acyl group,
An acetyl group and the like can be mentioned, and an acyloxy group can be an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferable. The skeleton of the alicyclic hydrocarbon to be formed includes the structures shown above.

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R _b10 to R _b in the general formula (bII-A) or (bII-B).
_b13 can be mentioned. Among the repeating units having a bridged alicyclic hydrocarbon, among the repeating units having the general formula (bII-
The repeating unit represented by A) or (bII-B) is more preferred. The above general formula (bII-A) or (bII-
In B), R _{b10 to} R _b13 each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR
_b5 (R _b5 represents an alkyl group, a cyclic hydrocarbon group or an —Y group similar to the above, which may have a substituent), a group decomposed by the action of an acid, —C (＝ O) —X _{-AR b14} ,
Or an alkyl group or a cyclic hydrocarbon group which may have a substituent. n represents 0 or 1. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHS
Representing the O ₂ NH-. R _b14 represents —COOH, —COOR
_b5, -CN, hydroxyl, optionally substituted alkoxy _{group, -CO-NH-R b6,} -CO-NH-SO 2 -
R _b6 (R _b5 and R _b6 have the same meanings as described above) or the same -Y group as in the above general formula (bI). A represents a single bond or a divalent linking group.

In the acid-decomposable resin (b), an acid-decomposable group
Is -C (= O) -XA-R _b1, -C (= O)-
XAR_b2Or Z in the general formula (bII)
May be included as a substituent. The structure of the acid-decomposable group
-C (= O) -X₁ -R₀ It is represented by Where R
₀ Are tertiary alkyl groups such as t-butyl group and t-amyl group.
Kill group, isobornyl group, 1-ethoxyethyl group, 1-
Butoxyethyl group, 1-isobutoxyethyl group, 1-si
1-alkoxyethyl such as chlorohexyloxyethyl group
Group, 1-methoxymethyl group, 1-ethoxymethyl group, etc.
Alkoxymethyl group, tetrahydropyranyl group, tetra
Hydrofuranyl group, trialkylsilyl group, 3-oxo
Examples include a cyclohexyl group. X₁ Is on
Synonymous with X.

Examples of the halogen atom in R _{b10 to} R _b13 include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R _{b10 to} R _b13 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group and t-butyl group.

The cyclic hydrocarbon group for R _{b10 to} R _b13 is, for example, a cyclic alkyl group or a bridged hydrocarbon group, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl. Groups, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like. Examples of the ring formed by bonding at least two of R _{b10 to} R _b13 include a ring having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R _b14 include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group of A include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, and a carbonyl group, similarly to the divalent linking group of A in formula (bI). , An ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified. Examples of the alkylene group and substituted alkylene group in A include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. 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. r represents an integer of 1 to 10.

In the acid-decomposable resin (b), the group decomposed by the action of an acid is a repeating unit represented by the general formula (bI), a repeating unit represented by the general formula (bII) or a copolymer component described below. May be contained in at least one of the repeating units of the formula (1).

The various substituents of R _{b10 to} R _{b13 in} the general formula (bII-A) or (bII-B) are
In the formula (bII), it also serves as a substituent of the atomic group for forming the alicyclic structure or the atomic group Z for forming the bridged alicyclic structure.

Specific examples of the repeating unit represented by formula (bII-A) or (bII-B) include the following [bII-1] to [bII-167]. It is not limited to these specific examples.

[0167]

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[0168]

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[0180]

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[0181]

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[0182]

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[0183]

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The acid-decomposable resin (b) comprises a repeating unit represented by the general formula (bI) and a compound represented by the general formula (bII) (general formula (b
II-A), including one or more of the respective repeating units represented by general formula (bII-B)), dry etching resistance, standard developer suitability, substrate adhesion, resist profile, Further, for the purpose of adjusting the resolution, heat resistance, sensitivity, and the like, which are general requirements of a resist, a copolymer containing repeating units of various monomers can be used. Preferred copolymer components include repeating units represented by the following general formulas [bIII] to [bIV].

[0185]

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Here, Z is an oxygen atom, -NH-, -N
(-R_b20)-, -N (-OSO_Two R _b20)-
R_b20Is also the same as the above (substituted) alkyl group, (substituted) ring
Hydrocarbon groups have meaning. The above general formula [bIII]
Specific examples of the repeating unit represented by the formulas
[BIII-1] to [bIII-8], [bIV-
1] to [bIV-8], and specific examples thereof.
However, the present invention is not limited to this.

[0187]

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[0188]

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In the acid-decomposable resin (b) according to the present invention, the repeating unit represented by the general formula (bI) and the general formula (bII) (the general formulas (bII-A) and (bII-B)) The content of the repeating unit represented by the formula (1) includes the desired resist dry etching resistance, sensitivity, pattern cracking prevention, substrate adhesion, resist profile, and the resolving power and heat resistance which are necessary requirements of general resists. , Etc., can be set as appropriate. Generally, the content of the repeating unit represented by the general formula (bI) or the repeating unit represented by the general formula (bII) in the acid-decomposable resin (b) according to the present invention, The amount is suitably at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, in the monomer repeating unit.

Further, in the acid-decomposable resin (b) according to the present invention, the content of the repeating unit based on the monomer of the preferable copolymer component in the resin is appropriately set according to the desired distaste performance. In general, the total number of moles of the repeating unit represented by the general formula (bI) and the repeating unit represented by the general formula (bII) is 99%.
It is preferably at most 90 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%.

In the acid-decomposable resin (b) according to the present invention, the group decomposed by the action of an acid is represented by the general formula (b)
It may be contained in any of the repeating unit represented by I), the repeating unit represented by the general formula (bII), and the repeating unit based on the monomer of the copolymerization component. The content of the repeating unit containing a decomposable group is suitably from 8 to 60 mol%, preferably from 10 to 55 mol%, more preferably from 12 to 50 mol%, based on all monomer repeating units of the resin. .

The acid-decomposable resin (b) according to the present invention generally comprises a monomer corresponding to the repeating unit represented by the general formula (bII), maleic anhydride, and a copolymerizable component. With the monomer of the polymerization component, copolymerized in the presence of a polymerization catalyst, the repeating unit of maleic anhydride of the obtained copolymer, esterification with alcohols under basic or acidic conditions, or It can be synthesized by hydrolyzing and then converting the carboxylic acid moiety generated thereafter to a desired substituent.

Acid-decomposable resin (c) A resin containing a repeating unit represented by the following general formula (cI) and decomposed by the action of an acid to increase the solubility in alkali.

[0194]

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In the formula, R _{c1 to} R _c8 may be the same or different, and represent a hydrogen atom, an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, An atom, a cyano group, a group that decomposes under the action of an acid, or-
Represents C (= O) -X-A-R _c9 . m / n; 1 / 9~9 / 1 m + n; 10~100 X; oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} ,
A divalent linking group selected from —NHSO ₂ NH—, R _c9 ; —COOH, —COOR _c10 (where R _c10 has the same _meaning as R _c11 and the definition of the following lactone structure), —CN, a hydroxyl group, and a substituent. An optionally substituted alkoxy group, -CO-
NH-R _c11, represents a -CO-NH-SO ₂ -R _c11 or -Y group shown above. R _c11 : an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, A: a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester A single group selected from the group consisting of a group, an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups.

The acid-decomposable resin (c) will be described below. In the general formula (cI), the group decomposed by the action of an acid in R _{c1 to} R _c8 (also referred to as an acid-decomposable group) includes a group represented by —C (＝ O) —X ₁ —R _0. No. Here, R ₀ is a tertiary alkyl group such as a t-butyl group, a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-cyclohexyloxy group. Examples include 1-alkoxyethyl groups such as ethyl groups, alkoxymethyl groups such as 1-methoxymethyl groups and 1-ethoxymethyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, trialkylsilyl groups, and 3-oxocyclohexyl groups. Can be. Here, X ₁ has the same meaning as X described above.

The alkyl group for R _{c1 to} R _c8 and R _c11 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Alkyl group, more preferably methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group for R _{c1 to} R _c8 include, for example, a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and a 2-methyl-2-adamantyl group. , Norbornyl, boronyl, isobornyl, tricyclodecanyl, dicyclopentenyl, nobornane epoxy, menthyl, isomenthyl, neomenthyl, tetracyclododecanyl and the like.

_Examples of the alkoxy group for R _c9 include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

As the cyclic alkyl group for R _c11 ,
Cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, Examples include an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group.

Further substituents in the above alkyl group, cyclic alkyl group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the alkylene group and substituted alkylene group in A include the groups shown below. -[C (R _a ) (R _b )] _r-wherein R _a and R _{b are a} hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a halogen atom, a hydroxyl group, or an alkoxy group; they may be the same or different; and the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group. Represents a substituent selected from the group consisting of a group, an 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Individuals can be mentioned. r represents an integer of 1 to 10. In the general formula (cI), examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

In the general formula (cI), the acid content
A decomposable group and -C (= O) -XA-R _c9Is the same repeating unit
May be included in both positions or included in separate repeating units
It may be.

The acid-decomposable resin (c) is obtained by polymerizing a monomer having a norbornene skeleton and, if necessary, conducting a polymer reaction. The polymerization reaction can be obtained by radical polymerization using a general radical initiator such as an azo initiator, but is more preferably synthesized by ring-opening polymerization using a coordination polymerization catalyst such as a transition metal complex. You. The resin obtained by the ring-opening polymerization is preferably reduced and used from the viewpoint of stability and optical absorption. Acid-decomposable resin (c)
May include, besides containing one or more monomer repeating units of the general formula (cI), dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, which is a general requirement of resist, It can be used as a copolymer with various monomer repeating units for the purpose of adjusting heat resistance, sensitivity and the like. Preferred examples of the copolymer component include a repeating unit represented by the following general formula (cV) or (cVI).

[0205]

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Here, Z has the same meaning as that described in the formula (bIII) or (bIV).
Preferred combinations of repeating units of the acid-decomposable resin (c) include the following. However, it is not limited to this.

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[0213]

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The group decomposed by the action of an acid in the acid-decomposable resin (c) is contained in the general formula (cI) or a copolymer component.

In the acid-decomposable resin (c), the molar ratio of each repeating unit is determined according to the dry etching resistance of the resist, suitability for a standard developer, substrate adhesion, resist profile, and the like.
Further, it is appropriately set in order to adjust resolution, heat resistance, sensitivity, and the like, which are general necessary requirements for a resist.

However, in the acid-decomposable resin (c), the compound represented by the general formula (c)
The content of the repeating unit represented by I) is at least 10 mol%, preferably at least 20 mol%, more preferably at least 30 mol%, based on all monomer repeating units. Also,
In the acid-decomposable resin (c), the content of the repeating unit containing an acid-decomposable group is from 10 to 90 mol%, preferably from 15 to 85 mol%, more preferably from 20 to 90 mol%, based on all monomer repeating units. ~ 80 mol%. The content of the carboxyl group imparting adhesion is 0.05 to 2.0 meq / g in the resin, preferably 0.1 to 1.8 meq / g,
More preferably, it is 0.3 to 1.5 meq / g.

The general formula (c) constituting the resin (c) which is decomposed by the action of an acid and has increased solubility in alkalis
Specific examples of each repeating unit represented by I) are shown below, but the content of the present invention is by no means limited to these.

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The content of the repeating unit based on the further monomer in the resin is preferably 99 mol% or less based on the total number of moles of the repeating structural unit represented by the general formula (cI). It is preferably at most 90 mol%, more preferably at most 80 mol%. If it exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, so that it is not preferable.

In addition to the above-mentioned acid-decomposable resins, the following resins can also be used in the present invention.・ Journal of Photopolymer Science and Technology V
ol. 10, No. 4 (1997), p545-p550, p. 545, and 5 copolymers, p.・ Journal of Photopolymer Science and Technology V
ol. 10, No. 4 (1997), p.562 to p.570, FIG.
4. A partially protected resin of the carboxylic acid polymer according to 1 ..・ Journal of Photopolymer Science and Technology V
ol. 10, No. 3 (1997), pp. 514 to 520, FIG.
The quaternary copolymer according to 1.・ SPIE, Vol. 3049, (1997), 116 in p113-p123
Resin 3a as described in scheme 1 on page.

Such an acid-decomposable resin can be further copolymerized as a repeating unit with the following monomers as long as the effects of the present invention can be effectively obtained, but are not limited thereto. Not something. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent,
(2) film-forming properties (glass transition point), (3) alkali developability, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portions to substrate, (6) Fine adjustment of dry etching resistance becomes possible. As such a comonomer, for example, acrylates,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, 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 esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg, 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, (where the alkyl group has 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, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes 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), 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;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the above-mentioned various repeating units may be used. Further, the content of the repeating unit based on the monomer of the further copolymerization component in the resin can also be appropriately set according to the desired performance of the resist, but generally, the total of the essential repeating units is calculated. It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total mole number.

The molecular weight of the acid-decomposable resin as described above is preferably 1,0 by weight average (Mw: polystyrene standard).
00 to 1,000,000, more preferably 1,500
~ 500,000, more preferably 2,000 ~ 20
000, more preferably 2,500 to 100,00
It is in the range of 0, and as the value is larger, the heat resistance and the like are improved, while the developability and the like are reduced. The balance is adjusted to a preferable range. In the present invention, the acid-decomposable resin (a) and the acid-decomposable resin (b) are preferable among the acid-decomposable resins as described above. By using these acid-decomposable resins, the occurrence of cracking can be more effectively prevented.

In the positive photoresist composition of the present invention, the addition amount of the acid-decomposable resin in the whole composition is preferably 40 to 99% by weight, more preferably 50 to 97% by weight based on the total resist solids. is there.

Next, the compound (photoacid generator) which generates an acid upon irradiation with actinic rays or radiation in the positive photoresist composition of the present invention will be described. The photoacid generator needs to satisfy two properties. That is,
(1) transparency to exposure light (provided that there is no light bleaching property); and (2) sufficient photodegradability to ensure resist sensitivity. However, at present, there is no clear guideline for molecular design that satisfies such contradictory requirements. For example, the following examples can be given. That is, JP-A-7-25846 and JP-A-7-2823
7, JP-A-7-92675, JP-A-8-2
Aliphatic alkulfonium salts having a 2-oxocyclohexyl group described in JP-A-7102, and N-
Hydroxysuccinimide sulfonates and the like can be mentioned. Furthermore, J. Photopolym. Sci. Techn
ol., Vol 7, No. 3, p 423 (1994) and the like, and sulfonium salts represented by the following general formula (VI), disulfones represented by the following general formula (VII), and the following general formula The compound represented by (VIII) can be mentioned.

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Here, R _{12 to} R ₁₅ each represent an alkyl group or a cyclic alkyl group. These may be the same or different from each other. Further, N-hydroxymaleimide sulphonates represented by the following general formula (IX) are also suitable.

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Here, R ₁₆ and R ₁₇ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group. R ₁₆ and R ₁₇ may be bonded via an alkylene group to form a ring. R ₁₈ represents an alkyl group, a perfluoroalkyl group, a cycloalkyl group or a substituted camphor. Such N-hydroxymaleimide sulphonates are particularly preferred in terms of photosensitivity.

As the alkyl group having 1 to 6 carbon atoms for R ₁₆ and R ₁₇ in the general formula (IX), a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group,
An n-hexyl group can be mentioned. Among them, preferred are a methyl group, an ethyl group and a propyl group, and a methyl group and an ethyl group are more preferred. Examples of the cycloalkyl group having 6 or less carbon atoms include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group. R ₁₆ ,
Examples of the case where R ₁₇ forms a ring with each other by an alkylene chain include a case where a cyclohexyl group, a norbornyl group, and a tricyclodecanyl group are formed.

As the alkyl group for R _18, a linear C 1-20 alkyl group such as a methyl group, an ethyl group, or a propyl group may be used.
Alkyl groups, isopropyl groups, isobutyl groups, t
Examples thereof include a branched alkyl group having 1 to 20 carbon atoms such as an tert-butyl group and a neopentyl group. It is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferably 4 to 15 carbon atoms.
Linear or branched alkyl groups. Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group and other straight-chain carbon atoms having 1 to 20 carbon atoms.
And a branched perfluoroalkyl group having 1 to 20 carbon atoms such as a perfluoroalkyl group, a heptafluoroisopropyl group, and a nonafluoro tert-butyl group. Preferably, it is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. As the cyclic alkyl group, a monocyclic cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, a decalyl group,
Examples thereof include a plurality of cyclic alkyl groups such as a norbornyl group and a tricyclodecanyl group.

The amount of such a photoacid generator added to the composition is 0.1% of the total solid content of the positive photoresist composition.
To 20% by weight, more preferably 0.5 to 15% by weight.
%, More preferably 1 to 10% by weight.

In the positive photoresist composition of the present invention, the following photoacid generator may be used in addition to the above photoacid generator.

The amount of the photoacid generator which can be used in combination as described below is 2% by weight or less, more preferably 1% by weight, of the solid content of the whole positive photoresist composition.
The following is good. For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, JP-A-3-140,14
Ammonium salts described in No. 0 etc., DCNecker etal, Macr
omolecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Co.
nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307.
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. Described iodonium salts, JVCrivello etal, Polymer J. 17, 73 (198
5), JVCrivello et al. J. Org. Chem., 43, 3055 (1978)
, WRWatt et al., J. Polymer Sci., Polymer Chem. Ed., 2
2,1789 (1984), JVCrivello etal, Polymer Bull., 14,
279 (1985), JVCrivello etal, Macromorecules, 14 (5),
1141 (1981), JVCrivello et al, J. PolymerSci., Polym
er Chem. Ed., 17, 2877 (1979), EP 370,693,
No. 161,811, No. 410,201, No. 339,049, No. 233,56
No. 7, 297,443, 297,442, U.S. Pat.
No. 377, No. 3,902,114, No. 4,760,013, No. 4,734,44
No. 4, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,
Nos. 604,580 and 3,604,581, and the sulfonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), JVCrivello etal, J. PolymerSci., Polymer Che
m.Ed., 17,1047 (1979), etc.
S.Wen etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 Toky
o, Oct (1988) and the like onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60 -239736
No., JP-A-61-169835, JP-A-61-169837, JP-A-61-169837
No. 62-58241, JP-A-62-212401, JP-A-63-70243,
Organic halogen compounds described in JP-A-63-298339, etc.
Meier et al., J. Rad. Curing, 13 (4), 26 (1986), TPGill
etal, Inorg.Chem., 19, 3007 (1980), D. Astruc, Acc.
Res., 19 (12), 377 (1896), and organic metal / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polym
er Sci., 25, 753 (1987), E. Reichmanis et al., J. Pholimer
Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al., J.
Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahe
dron Lett., (24) 2205 (1973), DHR Barton et al., J. Chem.
Soc., 3571 (1965), PMCollins et al., J. Chem.SoC., Per
kin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Le
tt., (17), 1445 (1975), JWWalker etal J. Am. Chem. So
c., 110, 7170 (1988), SCBusman et al, J. Imaging Techn
ol., 11 (4), 191 (1985), HMHoulihan et al, Macormolecu
les, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Che
m.Commun., 532 (1972), S.Hayase etal, Macromolecules, 1
8,1799 (1985), E. Reichmanisetal, J. Electrochem. Soc.,
Solid State Sci.Technol., 130 (6), FMHoulihan eta
1, Macromolcules, 21, 2001 (1988), European Patent 0290,750
Nos. 046,083, 156,535, 271,851, 0,
U.S. Pat.Nos. 3,901,710 and 4,181,531
, A photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-60-198538, JP-A-53-133022, etc.
TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Bern
er etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Po
lymer Preprints, Japan, 37 (3), European Patent No. 0199,672,
No. 84515, No. 044,115, No. 618,564, No. 0101,122
No. 4,371,605, U.S. Pat.
64-18143, JP-A-2-245756, compounds that generate sulfonic acid upon photolysis represented by iminosulfonate and the like described in JP-A-3-140109, and JP-A-61-166544. The disulfone compounds described above can be exemplified.

Further, a group capable of generating an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamada et al., Makromol.C
hem., 152, 153, 163 (1972), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17,3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-266.
No. 53, JP-A-55-164824, JP-A-62-69263, JP-A-Showa
63-146038, JP-A-63-163452, JP-A-62-153853
And the compounds described in JP-A-63-146029 and the like can be used.

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

Among the above compounds which can be used together and which generate an acid by being decomposed by irradiation with actinic rays or radiation, those particularly effectively used are exemplified below.

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

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied 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, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates, etc .; 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these 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. These surfactants may be added alone or in some combination.

The positive photoresist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.4 to 1.5 μm. Spinning the photosensitive composition onto a substrate (eg, silicon / silicon dioxide coating) such as used in the manufacture of precision integrated circuit devices;
After coating by an appropriate coating method such as a coater or the like, exposure is performed through a predetermined mask, baking and development are performed, whereby a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, and the like can be given.

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0267]

EXAMPLES Next, 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: (1) Synthesis of resin A 5.3 g of monomer a shown below, 9.6 g of cyanoethyl ester of monomer a, 3.2 g of t-butyl acrylate, 0.6 g of V-65 manufactured by Wako Pure Chemical Industries, Ltd. And a solution of 0.3 g of butyl mercaptan dissolved in 80 g of THF at 50 ° C. under a nitrogen stream.
Was dropped into a reaction vessel containing 10 g of THF heated over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours. Furthermore,
After adding 0.2 g of V-65, the mixture was again stirred for 4 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 3 L of water. The precipitated powder was collected by filtration, and 16 g of Resin A was recovered. Resin A obtained
Was 8,300 as measured by GPC using standard polystyrene standards.

[0268]

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(2) Synthesis of resin B 8- (t-butoxycarbonyl) tetracyclododeca-
An equimolar mixture of 3-ene and maleic anhydride was dissolved in THF to make a solution having a solid content of 60%. This was charged in a three-necked flask and heated to 60 ° C. under a nitrogen stream. After the temperature was stabilized, 5 radical initiators V-65 manufactured by Wako Pure Chemical Industries, Ltd. were added.
mol%, and heated as it was for 6 hours. After completion of the heating, the reaction solution was crystallized in a mixed solvent of toluene / hexane, and the precipitated powder was collected by filtration. The obtained powder was reacted with 2-cyanoethanol under basic conditions, and crystallized in distilled water after completion of the reaction. The precipitated white powder was washed again with water to obtain the target resin B. From the NMR spectrum of the obtained resin B, t
-It was confirmed that the butyl group remained and the desired product was formed. The resin B obtained was subjected to a molecular weight analysis by GPC, and as a result, the weight average molecular weight in terms of polystyrene was 10,600.

(3) Synthesis of Resin C 5-norbornene-2,3-dicarboxylic anhydride and
A reaction product of this and cyclopentadiene (50/50 by mole ratio)
A solution of 50) dissolved in dry chlorobenzene was added to a dry chlorobenzene solution containing 0.15 mol% of tungsten hexachloride and 0.3 mol% of triethylamine, followed by stirring. Stir at 30 ° C. for 18 hours, reprecipitate in methanol,
The white acid anhydride resin was removed. Next, this was reacted with glycine to open the acid anhydride site, and then reacted with t-butyl alcohol in the presence of dicyclohexylcarbodiimide to obtain the desired resin C. The composition ratio of each repeating unit (shown below) in the resin C was 18/32/18/32 from NMR measurement. GPC measurement of the obtained resin C showed that the weight average molecular weight in terms of standard polyhydroxystyrene was 13,200.

[0271]

Embedded image

(4) Synthesis of Resin D A resin having the following structure was synthesized according to Synthesis Example 2 of European Patent Publication No. 0789278. GPC measurement of the obtained resin D showed that the weight average molecular weight in terms of standard polyhydroxystyrene was 33,000. Resin D

[0273]

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(5) Synthesis of Resin (E) The copolymer (resin (E)) was prepared in exactly the same manner as the method of (Synthesis Example I-2) described on page (25) in JP-A-8-82925. E)) was obtained. Synthesis Example 2; (1) Synthesis of dissolution inhibitor [I-1] 100 g of abietic acid was converted to the corresponding acid chloride by reacting with thionyl chloride, and then this was cooled to 1/4 equivalent of pentaerythritol sufficiently cooled. Slowly add dropwise to the pyridine solution. After the addition was completed, the reaction mixture was heated to room temperature and stirred for 2 hours. After completion of the reaction, the reaction solution was crystallized in distilled water, and the precipitated solid was taken out by decantation and further washed with a 5% aqueous NaOH solution. The remaining solid was put into an autoclave, and then mixed with 100 g of t-butyl acrylate.
The mixture was heated and stirred at 00 ° C. for 10 hours. After completion of the reaction, excess t-butyl acrylate was distilled off from the reaction mixture under reduced pressure.
The remaining solid was hydrogenated by a conventional method. Finally, the product was purified by silica gel column chromatography to obtain 36 g of the target compound [I-1].

(2) Synthesis of dissolution inhibitor [I-5] The compound [I-5] was prepared in the same manner as in Synthesis Example (1) except that tricyclodecanedimethylol was used instead of pentaerythritol in Synthesis Example (1). -5] was synthesized. (3) Synthesis of dissolution inhibitor [I-12] Compound [I-12] was synthesized in the same manner as in Synthesis Example (1) except that triethanolamine was used instead of pentaerythritol in Synthesis Example (1). did.

[Examples / Comparative Examples] 10 g of each resin synthesized in the above synthesis example, 0.2 g of 4-hydroxynaphthyldimethylsulfonium triflate as a photoacid generator, and each general compound shown in Table 1 After dissolving 3 g of the compound represented by the formula (I) in 2-heptanone (mixing with 2-hydroxypropionic acid as needed) at a solid content of 14% by weight, the mixture was filtered through a 0.1 μm microfilter, and the positive type was filtered. A photoresist composition solution was prepared.

(Evaluation Test) The obtained positive type photoresist composition solution was applied on a silicon wafer by using a spin coater, dried at 135 ° C. for 90 seconds, and dried at about 0.5 μm.
Was prepared and exposed to an ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 135 ° 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.

[Sensitivity]: Defined as the minimum exposure (mJ / cm ² ) for reproducing a 0.35 μm mask pattern. [Profile]: Obtained pattern was observed with a scanning electron microscope, and a rectangular profile was obtained.
A sample having a non-rectangular profile was evaluated as x. [Cracking number]: Each resist film was applied to a thickness of 0.5 μm on a 4-inch Bare Si substrate,
Dried for seconds. Then stepper NSR-1505EX
1mm x 3mm rectangular large pattern using 2
mJ / cm ² ~100mJ / cm ² to 2mJ / cm ²
Expose 50 shots in increments and heat after exposure to 9 at 130 ° C.
Performed for 0 seconds. Then, develop with 2.38% TMAH,
Five shots of the pattern were observed with an optical microscope, counting from the pattern to which the coating film was first melted at the exposure part, and the number of cracks was counted. Table 1 shows the evaluation results.
Shown in

[0279]

[Table 1]

As is evident from Table 1, the comparative examples have problems in all respects. On the other hand, all of the positive photoresist compositions of the present invention are at a satisfactory level. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0281]

The present invention is particularly suitable for light in the wavelength range of 170 nm to 220 nm, and has excellent sensitivity.
Further, it is possible to provide a positive photoresist composition which can reduce the number of cracks and can obtain a good resist pattern profile.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasumasa Kawabe 4000F, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd.

Claims (3)

[Claims] Claims 1. An acid which decomposes under the action of an acid to alkali
For resin with increased solubility, actinic rays or radiation
A compound capable of generating more acid and represented by the following general formula (I)
For deep ultraviolet exposure, characterized by containing
Di-type photoresist composition. Embedded imageIn the general formula (I), R₁ Represents a divalent to hexavalent linking group.
R_Two~ R_FourMay be the same or different and have a substituent
Hydrocarbon group, alkoxy group, halogen atom
, Hydroxyl group, amino group, -COOR₀, -COOR _Five,
-NH-C (= O) -R_FiveOr -NH-SO_Two-R_Five
Represents R_FiveIs a hydrocarbon group which may have a substituent
Represents R₀Is -COOR₀Decomposed by the action of acid
(Acid-decomposable group). R₆~ R
₉May be the same or different and have a hydrogen atom or a substituent.
A hydrocarbon group, a halogen atom, a cyano group,
-COOR₀, -COOR_FiveOr -CO-X-A-R
_TenRepresents X represents an oxygen atom, a sulfur atom, -NH-, -N
HSO_Two-Or-NHSO_TwoRepresents NH-. A is simply
Represents a bond or a divalent organic linking group. R_TenIs a substituent
May have a hydrocarbon group, a lactone group, a hydroxyl group,
Represents an alkoxy group, a carboxyl group, or a cyano group.
a represents an integer of 2 to 6. l represents an integer of 0 to 6
And m represents an integer of 0 to 4, and n represents an integer of 0 to 6.
You. The compound represented by the general formula (I) includes R₁Parts other than
At least one acid-decomposable group per minute. 2. The positive photoresist composition for deep UV exposure according to claim 1, wherein the resin has an alicyclic structure. 3. Exposure light of 170 nm to 220 nm
The positive photoresist composition for exposure to far ultraviolet light according to claim 1 or 2, wherein far ultraviolet light having a wavelength of: