JP2004310004A - Resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition having excellent sensitivity and resolution and giving a favorable pattern profile. <P>SOLUTION: The resist composition comprising: (A) a compound which generates an active seed by irradiation of actinic ray or radiation, (B) a compound which reacts with the active seed generated from the compound (A) and/or performs an electron transfer and generates an active seed different from the active seed generated from the compound (A), and (C) a compound which performs the electron transfer from the active seed generated from the compound (B) and generates an acid, wherein supposing that the half wave of the oxidation potential of the active seed generated from the compound (B) is Epa and the half wave of the reduction potential of the compound (C) is Epc, the relationship: Epc-Epa>0 is satisfied. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resist composition that is suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other fabrication processes. More particularly, the present invention relates to negative and positive resist compositions capable of forming highly refined patterns using electron beams, X-rays, or extreme ultraviolet rays (EUV).

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. In addition to the excimer laser light, lithography using electron beams and X-rays is currently being developed.

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technology, and a negative resist with high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, in the negative resist for electron beams, when trying to increase sensitivity, the resolution and pattern shape decrease. There is a strong demand for the development of resists that deteriorate and that satisfy these characteristics simultaneously. High sensitivity, high resolution, and good pattern shape are in a trade-off relationship, and it is very important how to satisfy this simultaneously.

  As a resist suitable for such an electron beam or X-ray lithography process, a chemically amplified resist using an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity. A chemically amplified composition comprising a soluble resin, a crosslinking agent, and an acid generator is effectively used.

Various studies have been made so far for improving the performance of chemically amplified negative resists, and the following studies have been made particularly from the viewpoint of acid generators. Patent Document 1 (Japanese Patent Publication No. 8-3635) discloses an organic halogen compound, Patent Document 2 (Japanese Patent Application Laid-Open No. 2-52348) discloses an aromatic compound substituted with Br, Cl, and Patent Document 3 (Japanese Patent Application Laid-Open No. No. 367864) and Patent Document 4 (JP-A-4-367865) include an aromatic compound having an alkyl group and an alkoxy group substituted with Br and Cl, and Patent Document 5 (JP-A-3-87746). Is a haloalkanesulfonate compound, Patent Document 6 (JP-A-6-199770) discloses iodonium, a sulfonium compound, Patent Document 7 (Patent No. 2968055) contains a trifluoromethanesulfonate compound having a phenolic hydroxy group, Patent Document 8 (JP 2001-142200 A) describes specific benzenes having a phenolic hydroxy group. Honeto compounds are disclosed, respectively.
However, in any combination of these compounds, high sensitivity, high resolution, and good pattern shape in the ultrafine region were not satisfactory at the same time.

On the other hand, with regard to positive resists for electron beams or X-rays, resist techniques for KrF excimer lasers have been mainly diverted so far. For example, Patent Document 9 (Japanese Patent Laid-Open No. 2000-181065) discloses a combination of a compound that generates an acid upon irradiation with an electron beam and an amine compound having a boiling point of 250 ° C. or lower. Further, Patent Document 10 (European Patent No. 0919867) discloses a combination. A combined use of a polymer having an acid-decomposable group, an acid generator and an electron beam sensitizer, and further a combined use of an amide compound are disclosed in Patent Document 11 (Japanese Patent Publication No. 7-508840). Further, Patent Document 12 (Japanese Patent Laid-Open No. 3-200968) uses maleimide compounds, Patent Document 13 (Japanese Patent Laid-Open No. 7-92680) uses sulfonamide compounds, and Patent Document 14 (Japanese Patent Laid-Open No. 11-44950). The sulfone imide compound containing the —SO ₂ —NH—SO ₂ — partial structure is disclosed in Japanese Patent Publication No. H. No. ₂ ), but in these attempts to improve, both have high sensitivity, high resolution, and a rectangular resist shape. It was not something that made them compatible.

Also, in lithography using an excimer laser beam with a short wavelength such as KrF or ArF as an exposure light source, an ultrafine pattern formation of 0.20 μm or less is targeted, but as with electron beam lithography, sensitivity and resolution are also the same. Therefore, there has been a strong demand for a resist composition that does not satisfy both of the properties and the pattern shape.
Japanese Patent Publication No. 8-3635 JP-A-2-52348 JP-A-4-367864 JP-A-4-367865 Japanese Patent Laid-Open No. 3-87746 JP-A-6-199770 Japanese Patent No. 2968055 JP 2001-142200 A JP 2000-181065 A European Patent No. 0919867 Japanese National Patent Publication No. 7-508840 Japanese Patent Laid-Open No. 3-200968 Japanese Patent Laid-Open No. 7-92680 JP 11-44950 A

  Accordingly, an object of the present invention is to solve the problem of performance improvement technology in microfabrication of a semiconductor element, and in particular, high sensitivity in microfabrication of a semiconductor element using electron beam, X-ray or extreme ultraviolet (EUV), An object of the present invention is to provide a resist composition that simultaneously satisfies the characteristics of high resolution and good pattern shape.

As a result of intensive studies, the present inventors have found that the above object can be solved by dramatically increasing the amount of acid generation by effectively activating a specific acid generator with a plurality of active species. The inventors have found the resist composition of the present invention.
That is, the present invention has the following configuration.

(1) (A) a compound that generates active species upon irradiation with actinic rays or radiation,
(B) a compound that reacts and / or electron-transfers with an active species generated from the compound of (A) and generates an active species different from the active species generated from the compound of (A), and (C) a compound of (B) A compound that generates an acid by electron transfer from an active species generated from
Containing
When the half wave of the oxidation potential of the active species generated from the compound (B) is Epa and the half wave of the reduction potential of the compound (C) is Epc, the relation of Epc−Epa> 0 is satisfied. ,
A resist composition characterized by the above.

(2) The resist composition as described in (1) above, wherein the compound of (A) contains a structure represented by the following general formula (a).

^{Ra-Rb-COO - (a} )

In the general formula (a), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO. ^- or -SO ₃ ^- represents a. Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —.

  (3) The compound of (A) is selected from at least one selected from compounds represented by the general formula (a) and combinations represented by the general formulas (I) to (IV). The resist composition according to (1) or (2).

In the general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a hydroxyl group. Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

  (4) The resist composition according to any one of (1) to (3), wherein the compound of (A) is a compound represented by the following general formula (V).

In the general formula (V), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO. ^- or -SO ₃ ^- represents a. Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. .
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ may be bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom.

  (5) The resist composition as described in any one of (1) to (3) above, wherein the compound of (A) is a compound represented by the following general formula (VI) or (VII): Stuff.

In the above general formula (VI) or (VII), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl having 1 to 20 carbon atoms. Represents a group, —COO 2 ^— or —SO ₃ ^— . Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. .
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ may be bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

(6) The resist composition as described in any one of (1) to (5) above, wherein Epc of the compound of (C) is more positive than −1.15V.
(7) The compound of (C) is a compound that has a partial structure represented by the following general formula (VIII) and a counter ion and generates an acid upon irradiation with actinic rays or radiation. (1) The resist composition according to any one of (6).

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more.

  (8) The compound of (B) is a phenol derivative containing 1 to 10 benzene ring atom groups in the molecule, and further having at least one hydroxymethyl group and alkoxymethyl group in the molecule. The resist composition according to any one of (1) to (7), wherein the resist composition is characterized in that

  (9) The resist composition according to any one of (1) to (8), wherein the compound of (B) contains a structure represented by the following general formula (b).

In the general formula (b),
Rf represents a substituted or unsubstituted aryl group, a substituted or unsubstituted straight chain, branched chain, or alicyclic hydrocarbon group, or a combination thereof, and may be interposed via a carbonyl group, an oxygen atom, or a sulfur atom. n represents an integer of 1 to 10.

(10) The resist composition as described in any one of (1) to (8) above, wherein the compound of (B) is a cyclic ether compound.
(11) The resist composition according to any one of (1) to (10), further comprising (E) a nitrogen-containing basic compound.
(12) The resist composition as described in any one of (1) to (11) above, wherein the actinic ray or radiation is selected from an electron beam, an X-ray or extreme ultraviolet (EUV).

(13) (A) at least one selected from compounds consisting of a combination represented by general formula (a) and general formulas (I) to (IV),
(B) a crosslinking agent that undergoes an addition reaction with the alkali-soluble resin of component (D1) by the action of an acid,
(C) a compound having a partial structure represented by the following general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D1) an alkali-soluble resin,
A negative resist composition comprising:

^{Ra-Rb-COO - (a} )
In general formula (a):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .
Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —.

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more.

(14) (A) at least one selected from compounds consisting of the general formula (a ′) and a combination represented by the general formulas (I) to (IV);
(B) a crosslinking agent that undergoes an addition reaction with the alkali-soluble resin of component (D1) by the action of an acid,
(C) a compound having a partial structure represented by the above general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D1) an alkali-soluble resin,
A negative resist composition comprising:

Ra-O ^- (a ')
In general formula (a ′):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .

(15) The component (A) is at least one selected from a compound consisting of a combination represented by the general formula (a) and the general formula (I) or (II). The negative resist composition as described in (13).

(16) The negative resist composition as described in any one of (13) to (15) above, further comprising (E) a nitrogen-containing organic basic compound.

(17) (A) at least one selected from a compound consisting of a combination represented by the general formula (a) and the general formulas (I) to (IV);
(C) a compound having a partial structure represented by the above general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D2) in an alkaline developer by the action of the acid. A resin whose solubility increases,
A positive resist composition comprising:

(18) (A) at least one selected from compounds consisting of a combination represented by the general formula (a ′) and the general formulas (I) to (IV);
(C) a compound that has a partial structure represented by the above general formula (VIII) and a counter ion and generates an acid upon irradiation with an actinic ray or radiation, and
(D2) a resin whose solubility in an alkaline developer is increased by the action of an acid;
A positive resist composition comprising:

(19) The component (A) is at least one selected from the compounds represented by the general formula (a) and a combination represented by the general formula (I) or (II). The positive resist composition as described in (17).
(20) The positive resist composition as described in any one of (17) to (19) above, further comprising (E) a nitrogen-containing organic basic compound.
(21) The resist composition as described in any of (13) to (20) above, wherein the actinic ray or radiation is selected from an electron beam, an X-ray and EUV light.

  According to the present invention, it is possible to provide a resist composition that is excellent in sensitivity and resolving power and also in pattern shape with respect to pattern formation by irradiation with actinic rays or radiation, particularly electron beam, X-ray, or EUV light.

SPIE., 3999, pp. 386 (2000) reports a mechanism of acid growth using exo-Norborneol as a secondary alcohol and diphenyliodonium triflate as an acid generator. However, in the above report, there is a description that acid does not grow in phenolic resins, actually PHS (polyhydroxystyrene) and novolak.
In the present invention, the compound (A) is referred to as an initiator, the compound (B) as a mediator, and the compound (C) as an acid generator. In the present invention, the efficiency of acid growth is dramatically increased by adding an initiator, and the above problem that acid growth is suppressed by a phenolic resin is overcome. In particular, it is important to select an appropriate (B) mediator and (A) to add an initiator. As a result, the present invention can be applied not only to the positive type but also to the negative type. In particular, since the negative type contains a large amount of phenolic resin, the present invention is very effective.

  The mechanism of the present invention is estimated as follows.

  In the above formula, the electron beam is used as the radiation. As (B), cyclic ether is used in the above, but if a phenolic crosslinking agent having a hydroxymethyl group and an alkoxymethyl group in the molecule is used, it is particularly effective as a negative type.

The role of the compound (B) of the present invention is estimated below. Hereinafter, the compounds (A) to (C) of the present invention may be simply referred to as (A) to (C).
(B) is considered to play a role of transporting active species such as radicals generated from (A) to (C) (acid generator). In the absence of (B), the active species generated from (A) have a short lifetime, and are considered to be deactivated before reaching (C). Thus, the present invention is presumed to utilize the property that the radical (B) is stabilized to some extent and has sufficient instability to transfer electrons to (C).

Hereinafter, the compounds used in the present invention will be described in detail.
1. Compound (A)
The compound (A) that generates an active species that reacts with (B) and / or transfers an electron upon irradiation with an actinic ray or radiation is preferably a compound that generates an active radical upon irradiation with an actinic ray or radiation.
As a preferred specific example, a compound containing a carboxylate, particularly a compound containing a structure represented by the following general formula (a) can be mentioned.
^{Ra-Rb-COO - (a} )

In the general formula (a), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO. ^- or -SO ₃ ^- represents a.
Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a pyrenyl group.
Examples of the substituent on the aryl group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched fluorine substituted alkyl group having 1 to 3 carbon atoms. , Hydroxyl group, thiol group, alkyloxy group having 1 to 5 carbon atoms, nitro group, cyano group, formyl group, —COO ⁻ , —SO ₃ ^{— and the} like Is mentioned.
Examples of the linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, and hexyl group. , Heptyl group, octyl group, nonyl group, lauryl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like.
Examples of the substituent on the linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyloxy group having 1 to 5 carbon atoms, a thiol group, Cyano group, nitro group, formyl group, —COO ⁻ , —SO ₃ ⁻ , vinyl group, amide group, phenyl group (fluorine atom, chlorine atom, bromine atom, iodine atom, linear or branched having 1 to 5 carbon atoms) Chain alkyl group, linear or branched fluorine-substituted alkyl group having 1 to 3 carbon atoms, hydroxyl group, thiol group, alkyloxy group having 1 to 5 carbon atoms, nitro group, cyano group, formyl group, —COO ⁻ , —SO ₃ ^-) substituted phenyl group, a naphthyl group, an anthranyl group, a cyclohexyl group, a norbornyl group, and the like.
Examples of the substituent on the cyclic alkyl group include fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, thiol group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, etc. Is mentioned.

In the general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a hydroxyl group. Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formulas (I) to (IV), the linear and branched alkyl groups represented by R _{1 to} R ₃₈ and R _{39 to} R ₄₂ may have a methyl group, an ethyl group, or propyl, which may have a substituent. And those having 1 to 20 carbon atoms such as a group, n-butyl group, sec-butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
Examples of the linear or branched alkoxy group represented by R _{1 to} R ₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group. Such a thing with 1-4 carbon atoms is mentioned.
Examples of the cyclic alkoxy group include a cyclopentyloxy group such as a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the halogen atom represented by R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group of R ₃₈ and R _{39 to} R ₄₂ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. .
These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

In particular, the linear, branched or cyclic alkyl group of R _{39 to} R ₄₂ may be passed through an oxygen atom, a sulfur atom, a nitrogen atom, —C (═O) —, or a complex thereof. A group, a cyclic alkyl group, a halogen atom or the like may be substituted. In particular, the aryl group of R _{39 to} R ₄₂ may be substituted with a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or the like.

And selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom formed by combining two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , and R _{28 to} R _37. Examples of the ring containing one or more kinds include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, and a pyrrole ring.

  In the present invention, the compound (A) is more preferably represented by the following general formula (V).

In the general formula (V), Ra is the same as Ra in the general formula (a). Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R ₁ to R ₁₅ are the same as R ₁ to R ₁₅ in the general formula (I).

  In the compound (A), the following general formulas (VI) and (VII) are also represented as more preferred compounds.

In the general formula (VI), Ra is the same as Ra in the general formula (a). Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R ₁ to R ₁₅ are the same as R ₁ to R ₁₅ in the general formula (I).

In the general formula (VII), Ra is the same as Ra in the general formula (a). Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R ₃₉ to R ₄₁ are the same as R ₃₉ to R ₄₁ in the general formula (IV).

  Specific examples of the component (A) compound that can be used in the present invention are shown below, but the present invention is not limited thereto.

  In the present invention, the amount of the component (A) is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, and still more preferably 0.03 to 5% by mass in the total solid content of the resist composition. %.

2. Compound (B)
The compound (B) of the present invention is a compound that reacts and / or electron-transfers with the active species generated from (A) and generates an active species different from the active species generated from (A). This reaction basically represents a redox reaction. Examples are given below.
When the active species generated from (A) is a radical, the radical extracts a hydrogen atom from the compound (B) and newly generates a radical in the compound (B). At this time, the compound (A) changes to a neutral compound. The above reaction is not limited to this, and a hydrogen atom may be replaced with another organic group.
Further, when the radical generated from (A) is reducible, it is possible to emit one electron and transfer the electron to the compound (B). This is an example of electron transfer. After one-electron reduction, the compound (B) is preferably decomposed to newly generate active species such as radicals. In this case, the reduction reaction of the compound (B) is performed, but the reverse reaction is also possible for the compound (B).

  The “compound that generates an active species different from the active species generated from (A)” is specifically a compound that generates an active species that reacts and / or transfers electrons with (C), and is a reducing radical. Is preferably used. Examples of reducing radicals include the following examples of partial structures.

  In the above examples, R represents an alkyl group, and when there are two R, they may be connected to form a ring. Ar represents an aryl group.

In the above examples, with respect to (R-0), (R-1), (R-3), (R-6), (R-7), and (R-9), Epa of the reducing radical is shown. It is as follows.
(R-0): -0.98V, (R-1): -1.20V, (R-3): -1.30V, (R-6): -1.10V, (R-7): -0.80V, (R-9): -1.05V.

  As specific examples of (B), secondary alcohol compounds, alicyclic secondary alcohol compounds, cyclic ether compounds, vinyl ether compounds, phenol derivatives having a hydroxymethyl group and an alkoxymethyl group in the molecule are preferably used.

In particular, in the negative resist composition of the present invention, a crosslinking agent (hereinafter also referred to as “crosslinking agent”) that undergoes an addition reaction with the alkali-soluble resin by the action of an acid together with the alkali-soluble resin is used as the component (B). . Here, a known crosslinking agent can be used effectively.
A compound or resin having two or more hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, or alkoxymethyl ether groups, or an epoxy compound is preferable.

  More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated or alkoxymethylated phenolic compounds or resins, and alkoxymethyletherified phenolic compounds or resins, etc. Is mentioned.

More preferably, the compound of (B) has a molecular weight of 1200 or less, 3 to 5 benzene rings in the molecule, and further having two or more hydroxymethyl groups or alkoxymethyl groups. Mention may be made of phenol derivatives in which methyl groups are concentrated on at least one of the benzene rings or are distributed and bonded. By using such a phenol derivative, the effect of the present invention can be made more remarkable.
As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, sec-butoxymethyl group, and t-butoxymethyl group are preferable. Further, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propyl group are also preferable.
Among these phenol derivatives, particularly preferable ones are listed below.

(In formula, L < ¹ > -L < ⁸ > may be the same or different and shows a hydroxymethyl group, a methoxymethyl group, or an ethoxymethyl group.)
A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in European Patent 632003 and the like.
A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage.
Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

  The compound (B) is used in an added amount of 3 to 65% by mass, preferably 5 to 50% by mass in the total solid content of the resist composition. When the addition amount of the crosslinking agent is less than 3% by mass, the residual film ratio is lowered, and when it exceeds 65% by mass, the resolving power is lowered, and the stability during storage of the resist solution is not preferable.

  In the present invention, the most preferred example of the compound (B) is a phenol derivative having any one of the following structures.

  In addition to the above phenol derivatives, compounds containing a structure represented by the following formula (b) can also be suitably used as (B).

In the general formula (b),
Rf represents a substituted or unsubstituted aryl group, a substituted or unsubstituted linear, branched or alicyclic hydrocarbon group or a combination thereof, and may be interposed via a carbonyl group, an oxygen atom, or a sulfur atom. .
n represents an integer of 1 to 10.

As an aryl group, a C6-C16 aryl group is preferable, for example, a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, a pyrenyl group etc. are mentioned.
Examples of the substituent on the aryl group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched fluorine-substituted alkyl group having 1 to 3 carbon atoms. , Hydroxyl group, thiol group, alkyloxy group having 1 to 5 carbon atoms, nitro group, cyano group and the like.
As the linear, branched, or alicyclic hydrocarbon group, a linear, branched, or alicyclic hydrocarbon group having 1 to 8 carbon atoms is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples include butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, lauryl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group. It is done.
Examples of the substituent on the linear or branched hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyloxy group having 1 to 5 carbon atoms, a thiol group, a cyano group, a nitro group, and a vinyl group. Vinyl ether group, amide group, phenyl group, naphthyl group, anthranyl group, cyclohexyl group, norbornyl group and the like.
Examples of the substituent on the alicyclic hydrocarbon group include fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, thiol group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl. Groups and the like.
Such a compound (B) is particularly preferably contained in a positive resist composition.

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

The compound (B) is also preferably a cyclic ether compound.
The cyclic ether compound preferably has a boiling point of 100 ° C. or higher at room temperature and atmospheric pressure, and more preferably 120 ° C. or higher.

  Hereinafter, although the specific example of a cyclic ether compound is given, this invention is not limited to this.

3. Compound (C)
The compound (C) of the present invention is a compound that generates an acid by electron transfer from the active species generated from (B). In the present invention, the active species Epa (1/2 wave of oxidation potential) generated from (B) and the Epc (1/2 wave of reduction potential) of (C) satisfy Epc−Epa> 0. The requirement is to satisfy the relationship. In particular, it is preferable that Epc of (C) is more positive than −1.15V.

When determining the oxidation potential, first, sweeping is started so as to increase the potential to the plus side (example: ± 0 V → + 2.0 V). Then, the oxidation wave is measured when oxidation occurs. Usually, the results of the oxidation and reduction potential measurement are plotted with the horizontal axis representing the potential and the vertical axis representing the amount of current flowing between the electrodes. That is, the oxidation wave means a waveform having a peak (vertex) that swings above the baseline indicating a state in which no current flows. This waveform is expressed as a half wave of the oxidation potential, and the peak (vertex) potential of the waveform is expressed as Epa.
Similarly, with regard to the reduction potential, when sweeping is started so as to increase the potential to the negative side (example: ± 0 V → −2.0 V), the reduction wave is measured when reduction occurs. A waveform having a peak (vertex) that swings below the baseline indicating that no current flows is expressed as a half wave of the reduction potential, and a potential at the peak (vertex) of the waveform is expressed as Epc. To do.

In order to cause electron transfer between a donor (hereinafter abbreviated as D) and an acceptor (hereinafter abbreviated as A), it is necessary to satisfy ΔGel <0 in the Rehm-Weller equation shown below.

ΔGel (kcal / mol-1) = 23.06 [E0 (D + / D) -E0 (A / A-)]-wp

ΔGel: Change in free energy of electron transfer reaction
E0 (D + / D): Oxidation potential when donor is oxidized by one electron
E0 (A / A-): Reduction potential when the acceptor is reduced by one electron
wp: work of attractive force due to electrostatic interaction between two ions
wp represents the work of attraction by electrostatic interaction between two ions, but the contribution to ΔGel is small. Therefore, ΔGel <0 may be approximated to [E0 (D + / D) −E0 (A / A −)] <0. Here, E0 (D + / D) represents an oxidation potential when the donor is oxidized by one electron, and corresponds to Epa. E0 (A / A-) represents the reduction potential when the acceptor is reduced by one electron, and corresponds to Epc. That is, Epa−Epc <0 (synonymous with Epc−Epa> 0) needs to be satisfied in order to cause electron transfer between the donor and the acceptor. Further details of the above equation are described in George J. Kavarmos, “Photoelectron Transfer”, chapter 1.6.
In the present invention, by satisfying the above formula, the active species generated from the compound (B), mainly the radical-containing compound, act as a donor and can transfer electrons to the acceptor (C) compound. It is characterized by acid growth to be used.

In the compound (C) used in the present invention, Epc (1/2 wave of reduction potential) is preferably on the positive side of −1.15 V (in E / V vs Ag / AgCl acetonitrile). Here, −1.15 V is a measure of the oxidation potential of the radical species generated from (B), which is highly reducible. Specific examples of the radical-containing compound having an oxidation potential more negative than −1.15 V include the above (R-2) to (R-7). These compounds are considered highly reducible. On the other hand, (R-0) is mentioned as a radical containing compound with an oxidation potential more positive than -1.15V. When the oxidation potential of the radical species generated from (B) is more positive than −1.15 V, it is easily predicted that it will be difficult to cause electron transfer to the acceptor because the corresponding radical species is stable. it can.
In the present invention, a sulfonium salt is preferably used as the compound that generates an acid by electron transfer from the active species generated from the compound (B) of the component (C).

Epc and Epa in the present invention are values measured by the following method.
Using a measuring instrument connected with an arbitrary function generator, potentiostat, and measuring vessel, 0.1M n-Bu ₄ N · ClO ₄ (for Hanai Polaro) is measured as a supporting electrolyte in the measuring vessel. It was dissolved in acetonitrile (manufactured by Kanto Chemical) as a solvent and used. The electrode used was a Pt electrode as the working electrode and Ag / AgCl (saturated KCl) as the reference electrode. As the salt bridge connecting the reference electrode and the measurement container, agar containing 1 M KNO ₃ supporting salt was filled and used. Under the above conditions, the sample was dissolved in a measurement container so as to be 1 × 10 ⁻⁴ M, and measured at a sweep rate of 50 mV / cm ² to 1 V / cm ² at 25 ° C. As a supplement, the experimental method and values for Epa of the compound (B) can be measured by Ber. Bunsenges. Phys. Chem., 75, 458 (1971). Chem. Phys., 44, 2297 (1966), Radiat. Phys. Chem., 15, 603 (1980) and the like.
When measured under the above conditions, the reference compound ferrocene (Fe (C ₅ H ₅ ) ₂ / [Fe (C ₅ H ₅ ) ₂ ] ⁺ ) showed Epa = + 0.52 V, Epc = + 0.30 V. .

  In the present invention, preferred examples of the compound (C) include acid generators having the structures of the following formulas (3), (4) and (5).

  The positive Epc means Epc−Epa> 0. For example, in the general formula (3), −0.65-(− 1.15)> 0, which satisfies the above condition.

  Specific examples of the compound (C) are shown below, but the present invention is not limited thereto.

  Moreover, the compound (acid generator) which has the partial structure represented with the following general formula (VIII), and a counter ion and generate | occur | produces an acid by irradiation of actinic light or a radiation can also be used suitably as a compound (C).

In general formula (VIII), X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different. R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may combine to form a ring. A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different. l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0. m represents an integer of 0 to 10. n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more.

The alkyl group of R ₁ and R ₂ is preferably an alkyl group having 1 to 8 carbon atoms, and may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, such as a methyl group, an ethyl group, a propyl group. Group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc. Can be mentioned.
The aryl group of R ₁ and R ₂ is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a pyrenyl group.
The hydrocarbon structure connecting A and B between X ⁺ is preferably a hydrocarbon structure having 4 to 16 carbon atoms and a conjugated bond consisting of a single bond and a double bond or triple bond. You may have an atom. Preferable specific examples of such a hydrocarbon structure include, for example, a benzene ring, a naphthalene ring, a thiophene ring, a furan ring, and a hydrocarbon structure having the following conjugated bond.

The alkyl group of R ₁ and R ₂ , the aryl group, and the hydrocarbon structure of A and B may not have a substituent or may have a substituent. Examples of the substituent that the alkyl structure of R ₁ and R ₂ , the aryl group, and the hydrocarbon structure of A and B may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a carbon number of 1 to 5 Linear, branched alkyl group, cyclic alkyl group having 3 to 8 carbon atoms, linear chain having 1 to 3 carbon atoms, branched fluorine-substituted alkyl group, hydroxyl group, thiol group, 1 to 5 carbon atoms Specific examples include alkyloxy groups, nitro groups, cyano groups, formyl groups, phenyl groups, naphthyl groups, phenylthio groups, phenoxy groups, and the like.

In the partial structure represented by the general formula (VIII), at least one of X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugation.
Examples of the structure in which linked X ⁺ are in the same conjugate include the following structures.

The compound having a partial structure represented by the general formula (VIII) and generating an acid upon irradiation with actinic rays or radiation has a counter ion together with the partial structure.
Examples of the counter ion include an aliphatic sulfonate anion, an aromatic sulfonate anion, an aliphatic carboxylic acid, and an aromatic carboxylate anion.

The aliphatic group in the aliphatic sulfonate anion and the aliphatic carboxylate anion is preferably an aliphatic group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aromatic group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The aliphatic sulfonate anion, aromatic sulfonate anion, aliphatic carboxylic acid, and aromatic carboxylate anion may not have a substituent or may have a substituent.
Examples of the substituent which the aliphatic sulfonate anion, aromatic sulfonate anion, aliphatic carboxylic acid and aromatic carboxylate anion may have include, for example, a halogen atom such as a fluorine atom, an alkyl group, an alkoxy group, an alkylthio Groups and the like.
The aliphatic sulfonate anion, aromatic sulfonate anion, aliphatic carboxylic acid and aromatic carboxylate anion preferably have a fluorine atom as a substituent.

In the partial structure represented by the general formula (VIII), R ₁ and R ₂ are preferably aryl groups, A and B are preferably aromatic rings, R ₁ and R ₂ are phenyl groups, and B is a benzene ring. More preferably, n = 2 and m = 0.

  Hereinafter, although the specific example of the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation which has the partial structure represented by general formula (VIII) is given, this invention is not limited to this.

  An acid generator (C) can be used individually by 1 type or in combination of 2 or more types.

  The content of the acid generator (C) in the resist composition is preferably from 0.1 to 20% by mass, more preferably from 0.2 to 15% by mass, and still more preferably from 0.1 to 20% by mass, based on the solid content of the composition. 3 to 15% by mass. By setting the content of the acid generator (C) to 0.3% by mass or more, a decrease in sensitivity and a decrease in resolution can be prevented. On the other hand, by setting the content to 15% by mass or less, development defects can be reduced.

(C) Acid generating compound that can be used in combination other than component In the present invention, in addition to component (C), a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid may be used in combination.
The amount of the photoacid generator that can be used in combination with the component (C) of the present invention is usually 100/0 to 20/80, preferably 100/0, in molar ratio (component (C) / other acid generator). -40/60, more preferably 100 / 0-50 / 50.
As such a photoacid generator that can be used in combination, it is used for photoinitiators of photocationic polymerization, photoinitiators of radical photopolymerization, photodecolorants of dyes, photochromic agents, or microresists. Known compounds that generate acids upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62- The compounds described in Japanese Patent No. 153853 and JP-A Nos. 63-146029 and the like can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Examples of particularly preferable compounds among the compounds that are decomposed by irradiation with actinic rays or radiation that may be used in combination are listed below.

  In the above, Epc of z1 and z10 are −1.51V and −1.40V, respectively.

4). Binder resin (D)
The resist composition of the present invention can take either a positive type or a negative type depending on the selection of the binder resin.
4-1. When used as a negative resist composition A binder resin (also referred to as alkali-soluble resin (D1)) when the resist composition of the present invention is used as a negative resist will be described.
The binder resin is obtained by partially protecting or modifying the phenol novolac resin, polyvinyl phenol resin, copolymer having a structural unit derived from vinyl phenol, and polyvinyl phenol resin, which have been disclosed so far in negative chemically amplified resists. A polymer having a phenol skeleton such as a resin can be widely used. Preferable examples include phenol resins containing a repeating structural unit represented by the following general formula (X).

In general formula (X), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
R ₂ represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group or acyl group.
R ₃ and R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a hydrogen atom, a halogen atom, a cyano group or a substituent. Represent. When R ₃ and R ₄ are hydrogen atoms, it means that R ₃ and R ₄ do not constitute a substituent on the benzene ring of formula (X).
A is a single bond or an optionally substituted alkylene group, alkenylene group, cycloalkylene group or arylene group, or —O—, —SO ₂ —, —O—CO—R ₅ —, —CO—O. —R ₆ — or —CO—N (R ₇ ) —R ₈ — is represented.

R ₅ , R ₆ , R ₈ may be a single bond or an optionally substituted alkylene group, alkenylene group, cycloalkylene group or arylene group, or at least one of these groups and an ether structure, an ester structure, It represents a divalent group formed by combining at least one selected from the group of amide structure, urethane structure and ureido structure.
R ₇ represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, aralkyl group or aryl group.
n represents an integer of 1 to 3. A plurality of R ₂ or R ₂ and R ₃ or R ₄ may combine to form a ring.

The alkyl group for R _{1 to} R ₄ and R ₇ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group. Preferred examples include a group, hexyl group, 2-ethylhexyl group, and octyl group.
The cycloalkyl group of R _{2 to} R ₄ and R ₇ may be monocyclic or polycyclic. As the monocyclic type, for example, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms can be preferably exemplified. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and the like.
Examples of the alkenyl group represented by R ₃ and R ₄ include alkenyl groups having 2 to 8 carbon atoms, and specific examples include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

Examples of the aryl group represented by R _{2 to} R ₄ and R ₇ include an aryl group having 6 to 15 carbon atoms, and specifically include a phenyl group, a tolyl group, a dimethylphenyl group, and 2,4,6-trimethyl. A phenyl group, a naphthyl group, an anthryl group, etc. can be mentioned preferably.
As an aralkyl group of R _{2 to} R ₄ and R ₇ , for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.

The acyl group of R ₂ is, for example, an acyl group having 1 to 8 carbon atoms, and specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a benzoyl group, and the like are preferable. it can.

The alkylene group for A, R ₅ , R ₆ , and R ₈ is preferably an optionally substituted group having 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. There are ~ 8.
As the alkenylene group of A, R ₅ , R ₆ , and R ₈ , those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group, and a butenylene group, which may preferably have a substituent, may be mentioned.

Examples of the cycloalkylene group of A, R ₅ , R ₆ , and R ₈ preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group, which may have a substituent. .
The arylene group for A, R ₅ , R ₆ , and R ₈ is preferably an arylene group having 6 to 12 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, alkenyl group, alkylene group, alkenylene group, cycloalkylene group, arylene group and the like may have a substituent.
Substituents substituted with these groups include those having active hydrogen such as amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyl) Oxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group and the like. In particular, those having active hydrogen such as amino group, hydroxyl group and carboxyl group are preferred.

In addition, as a ring formed by combining a plurality of R ₂ or R ₂ and R ₃ or R ₄ , a 4- to 7-membered ring containing an oxygen atom such as a benzofuran ring, a benzodioxonol ring, or a benzopyran ring is included. Can be mentioned.

  The binder resin of the present invention (D) may be a resin consisting only of the repeating structural unit represented by the formula (X), but for the purpose of further improving the performance of the negative resist of the present invention, other polymerizations are possible. A copolymerizable monomer may be copolymerized.

  Examples of copolymerizable monomers that can be used include those shown below. For example, an addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters other than the above. A compound having one.

Among these, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide and the like, and monomers that improve alkali solubility, such as maleimide, are preferable as the copolymer component.
As content of the other polymerizable monomer in resin in this invention, 50 mol% or less is preferable with respect to all the repeating units, More preferably, it is 30 mol% or less.

  Specific examples of the resin having a repeating structural unit represented by the formula (X) are shown below, but the present invention is not limited thereto.

  N in the above specific examples represents a positive integer. x, y, z represents the molar ratio of the resin composition, and in the case of a resin composed of two components, x = 10 to 95, y = 5 to 90, preferably x = 40 to 90, y = 10 to 60 Is done. In the resin composed of three components, x = 10 to 90, y = 5 to 85, z = 5 to 85, preferably x = 40 to 80, y = 10 to 50, z = 10 to 50 are used. .

The binder resin for negative resist compositions, preferably a resin having a repeating structural unit represented by the general formula (X), has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000. Used in the range of ~ 50,000. The molecular weight distribution is 1 to 10, preferably 1 to 3, more preferably 1 to 1.5. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the sidewall of the resist pattern, and the better the roughness.
Content of the repeating structural unit represented by general formula (X) is 5-100 mol% with respect to the whole resin, Preferably it is 10-90 mol%.

The alkali-soluble polymer containing the structural unit represented by the general formula (X) used in the present invention is Macromolecules (1995), 28 (11), 3787-3789, Polym. Bull. (Berlin) (1990), 24 ( 4), 385 to 389, and the method described in JP-A-8-286375. That is, the target alkali-soluble polymer can be obtained by radical polymerization or living anion polymerization.
These resins may be used alone or in combination.

Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
The alkali dissolution rate of the alkali-soluble polymer is preferably at least 20 kg / sec as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferred is 200 liters / second or more.
The alkali-soluble polymer of the present invention may be used alone, but other alkali-soluble polymers can be used in combination. As for the use ratio, other alkali-soluble polymers other than the present invention can be used in combination with a maximum of 100 parts by mass with respect to 100 parts by mass of the alkali-soluble polymer of the present invention. Examples of the alkali-soluble polymer that can be used together are shown below.

For example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof can be mentioned, but are not limited thereto.
The addition amount of the negative binder resin is 30 to 95% by mass, preferably 40 to 90% by mass, and more preferably 50 to 80% by mass with respect to the total solid content of the negative resist composition.

  The alkali-soluble polymer as a binder for a negative resist composition used in the present invention preferably has any one of repeating units represented by the following formula (b-2) or (b-3).

In general formula (b-2) and (b-3), R ₁ has the same meaning as R ₁ in the general formula (X).
A has the same meaning as A in formula (X).
R _{101 to} R ₁₀₆ each independently have a hydroxy group, a carboxy group, an amino group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, An alkenyl group, an aryl group, an aralkyl group, an N-alkylamino group or an N-dialkylamino group, preferably a hydroxy group, a linear or branched alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms An alkoxy group having 1 to 6 carbon atoms, a phenyl group, and more preferably a hydroxy group or a linear or branched alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n- Propyl group, n-butyl group, t-butyl group, etc.), C 1-3 alkoxy group (methoxy group, ethoxy group, etc.), phenyl group . a to f each independently represent an integer of 0 to 3, preferably an integer of 0 to 2.

Examples of the alkyl group in the alkyl group and alkoxy group, the alkylcarbonyloxy group, the alkylsulfonyloxy group, the N-alkylamino group, and the N-dialkylamino group include linear and branched alkyl groups such as methyl Preferred examples include a group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group. The cycloalkyl group may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and the like.
Preferred examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
Preferable examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, and an anthryl group.
Specific examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group and the like.

  Y represents any one selected from the following condensed polycyclic aromatic structures.

In the condensed polycyclic aromatic structure represented by Y, the position of the bonding hand bonded to the main chain, or the position of the bond that binds to the substituent, any bond on the condensed polycyclic aromatic structure It may be the position.

The alkyl group, cycloalkyl group, aryl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, aralkyl group, alkenyl group, N-alkylamino group, N-dialkylamino group and the like have a substituent. May be.
Substituents substituted with these groups include those having active hydrogen such as amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyl) Oxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group and the like.

  The content of the repeating unit represented by the general formula (b-2) and / or (b-3) in the resin in the present invention is preferably 3 to 50 mol% with respect to all the repeating units, It is more preferable to set it as 5-40 mol%.

  Examples of the alkali-soluble polymer having a condensed polycyclic aromatic structure used in the present invention are shown below, but the present invention is not limited thereto.

  As the binder for use in a negative resist composition, a copolymer having a repeating unit having a monocyclic aromatic structure and a repeating unit having a polycyclic aromatic structure is more preferable.

4-2. When used as a positive resist composition Next, a binder resin when the resist composition of the present invention is used as a positive resist will be described.
As the binder resin used in the positive resist composition of the present invention, a polymer that is insoluble or hardly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid can be used. That is, a resin (hereinafter referred to as “acid-decomposable resin”) having a group that can be decomposed by an acid (hereinafter also referred to as “acid-decomposable group”) in the main chain or side chain of the resin, or both the main chain and side chain Can also be used. Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.

A preferred group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid, and is decomposed by the action of an acid. By forming, the solubility of the acid-decomposable resin in an alkaline developer is increased.
The acid-decomposable group is preferably a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, Tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

  The acid-decomposable group is preferably a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, Tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

  Next, the base resin in the case where these acid-decomposable groups are bonded as side chains is an alkali-soluble resin having —OH or —COOH groups in the side chains. For example, the alkali-soluble resin mentioned later can be mentioned.

The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / sec as measured with 0.261 N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferred is 330 Å / sec or more (Å is angstrom).
From this point of view, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). , Part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, and hydrogenated novolac resin.

  The binder resin for positive resist composition used in the present invention is disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, etc. It can be obtained by reacting an alkali-soluble resin with a precursor of a group capable of decomposing with an acid, or by copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded thereto with various monomers.

  Specific examples of the binder resin for a positive resist composition used in the present invention are shown below, but are not limited thereto.

  The content of the group capable of decomposing with an acid is such that the number of groups (B) capable of decomposing with an acid in the resin and the number of alkali-soluble groups not protected by the group capable of decomposing with an acid (S) are B / ( B + S). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40. Within the above range, film shrinkage after PEB, poor adhesion to the substrate and scum can be prevented, and no standing wave remains on the pattern side wall, which is preferable.

The weight average molecular weight (Mw) of the binder resin for a positive resist composition is preferably in the range of 1,000 to 200,000 from the viewpoint of film reduction and sensitivity. More preferably, it is 2,000-200,000, More preferably, it is the range of 5,000-100,000, Most preferably, it is the range of 8,000-50,000.
Moreover, molecular weight distribution (Mw / Mn) becomes like this. Preferably it is 1.0-4.0, More preferably, it is 1.0-2.0, Most preferably, it is 1.0-1.6.
Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
Two or more binder polymers for positive resist compositions may be used in combination.

  In the positive resist composition of the present invention, the blending amount of the acid-decomposable resin in the entire composition is preferably 40 to 99.99% by mass, more preferably 50 to 99.97% by mass in the total resist solid content. is there.

5). Other components used in the composition of the present invention The resist composition of the present invention may further contain, if necessary, a nitrogen-containing basic compound, a dye, a solvent, a surfactant, a plasticizer, and a photodegradable base compound. , A photobase generator and the like can be contained.

5-1. Nitrogen-containing basic compounds (component E)
A preferable nitrogen-containing basic compound that can be used in the present invention is a compound that is more basic than phenol.
As a preferable chemical environment, structures of the following formulas (A) to (E) can be exemplified. Formulas (B) to (E) may be part of a ring structure.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may combine with each other to form a ring.
R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.
Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group.

  Preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, substituted or unsubstituted Substituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4 , 5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4- Aminoethylpyridine, 3-aminopyrrolidine, Perazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, Pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3 0.0] non-5-ene, tri-n-butylamine and the like, but are not limited thereto.
These nitrogen-containing basic compounds are used alone or in combination of two or more.

  The use ratio of the acid generator and the nitrogen-containing basic compound in the composition is (acid generator) / (nitrogen-containing basic compound) (molar ratio) = 2.5 to 300 in terms of sensitivity and resolution. To preferred. (Acid generator) / (nitrogen-containing basic compound) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

5-2. Dyes Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI522015) and the like.

5-3. Solvents The composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. Solvents used here include 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-dimethyl Formamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. Or mixed to use.

5-4. Surfactants A surfactant may be added to the solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (Manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink, Inc.), Florad FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101 , SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), silicon surfactants, organosiloxane polymer KP34 (Shin-Etsu Chemical Co., Ltd.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.).
The compounding amount of these surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the solid content in the composition of the present invention.
These surfactants may be added alone or in several combinations.

5-5. Plasticizer Plasticizers that can be used in the resist composition of the present invention include JP-A-4-221960, JP-A-8-262720, European Patent 735422, European Patent 416873, European Patent 439371, and US Pat. No. 5,846,690. Compounds described in each specification, specifically, di (2-ethylhexyl) adipate, n-hexyl benzoate, di-n-octyl phthalate, di-n-butyl phthalate, benzyl-n-butyl phthalate, And dihydroabiethyl phthalate.

5-6. Further, the composition of the present invention includes JP-A-7-28247, European Patent 616258, US Pat. No. 5,525,443, JP-A-9-127700, European Patent 762207. Ammonium salts described in U.S. Pat. No. 5,783,354, specifically, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, betaine, etc. can be added, and JP-A-5-232706 and 6- No. 11835, No. 6-242606, No. 6-266100, No. 7-333851, No. 7-333844, U.S. Pat. No. 5,663,035, and European Patent No. 677788. It is also possible to add a compound (photobase).

5-7. Photobase generator As photobase generators that can be added to the composition of the present invention, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, JP-A-6-194835, Examples thereof include compounds described in JP-A-8-146608, JP-A-10-83079 and European Patent No. 622682, specifically, 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4- Methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate and the like can be suitably used. These photobase generators are added for the purpose of improving the resist shape and the like.

  The resist composition of the present invention is applied onto a substrate to form a thin film. The thickness of this coating film is preferably 0.1 to 4.0 μm.

  In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary. Further, an antireflection film can be applied to the upper layer of the resist.

  As the antireflection film used as the lower layer of the resist, either an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or an organic film type made of a light absorber and a polymer material may be used. it can. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in Japanese Patent Publication No. 7-69611, an alkali-soluble resin, and a light absorber, and an anhydrous maleate described in US Pat. No. 5,294,680. A reaction product of an acid copolymer and a diamine type light absorbent, a resin binder described in JP-A-6-186863 and a methylolmelamine-based thermal crosslinking agent, a carboxylic acid group described in JP-A-6-118656 and an epoxy An acrylic resin type antireflection film having a group and a light-absorbing group in the same molecule, those comprising a methylol melamine and a benzophenone-based light absorber described in JP-A-8-87115, and a polyvinyl alcohol resin described in JP-A-8-179509 The thing etc. which added the low molecular light absorber are mentioned.

  In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

  In the manufacture of precision integrated circuit elements, the pattern formation process on the resist film is applied directly or in advance on a substrate (eg, silicon / silicon dioxide cover, glass substrate, metal substrate, etc.). A good resist pattern is obtained by applying the resist composition of the present invention on the antireflection film, then irradiating it with an excimer laser beam, an electron beam or an X-ray drawing apparatus, heating, developing, rinsing and drying. Can be formed. Here, as the exposure light source, an apparatus using an electron beam or X-ray as the exposure light source is preferably used.

As a developing solution of the resist composition of the present invention, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine are used. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Aqueous solutions of alkalis such as quaternary ammonium salts such as copper and choline, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

<Example of negative resist composition>
1. Composition example of composition material (1) Binder resin Synthesis example 1 (synthesis of resin example (27))
3.9 g (0.024 mol) of 4-acetoxystyrene and 0.8 g (0.006 mol) of 4-methoxystyrene were dissolved in 30 ml of 1-methoxy-2-propanol at 70 ° C. under a nitrogen stream and stirring. Polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65) 50 mg, 4-acetoxystyrene 9.1 g (0.056 mol), A solution of 1.9 g (0.014 mol) of 4-methoxystyrene in 70 ml of 1-methoxy-2-propanol was added dropwise over 2 hours. Two hours later, 50 mg of initiator was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C. and stirring was continued for 1 hour. The reaction solution was allowed to cool and then poured into 1 L of ion exchange water with vigorous stirring to precipitate a white resin. The obtained resin was dried, dissolved in 100 mL of methanol, 25% tetramethylammonium hydroxide was added, the acetoxy group in the resin was hydrolyzed, and then neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. After washing with ion-exchanged water and drying under reduced pressure, 11.6 g of the resin (27) of the present invention was obtained. When the molecular weight was measured by GPC, it was 9,200 in terms of weight average (Mw: polystyrene conversion) and 2.2 in terms of dispersity (Mw / Mn).
Thereafter, each binder resin was synthesized in the same manner.

(2) Compound (B)
Synthesis of cross-linking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene 20 g (Honshu Chemical Industry ( Trisp-PA) was added to a 10% aqueous potassium hydroxide solution and stirred and dissolved. Next, 60 ml of 37% formalin aqueous solution was gradually added at room temperature over 1 hour while stirring this solution. The mixture was further stirred at room temperature for 6 hours, and then poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, sufficiently washed with water, and then recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative [HM-1] having a hydroxymethyl group. The purity was 92% (liquid chromatography method).

Synthesis of [MM-1] 20 g of the phenol derivative [HM-1] having a hydroxymethyl group obtained in the above synthesis example was added to 1 liter of methanol and dissolved by heating under stirring. Next, 1 ml of concentrated sulfuric acid was added to this solution and heated under reflux for 12 hours. After completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added. After sufficiently concentrating the mixture, 300 ml of ethyl acetate was added. The solution was washed with water and then concentrated to dryness to obtain 22 g of a white derivative of a phenol derivative [MM-1] having a methoxymethyl group. The purity was 90% (liquid chromatography method).
Further, a phenol derivative was synthesized in the same manner.

(3) Acid generator (C)
Synthesis Example 1 (Synthesis of acid generator (A-2))
In 200 ml of methylene chloride, 17.6 g (80 mmol) of iodosylbenzene was added and stirred. To the resulting suspension, 14 ml (160 mmol) of trifluoromethanesulfonic acid was added dropwise and stirred for 3 hours. Further, 6.24 g (80 mmol) of benzene was added dropwise and stirred for 2 hours. The resulting precipitate was filtered, washed with ether and dried. As a result, 1,4-bis [phenyl [(trifluoromethanesulfonyl) oxy] iodo] benzene was obtained.
Suspended 1,4-bis [phenyl [(trifluoromethanesulfonyl) oxy] iodo] benzene 31.6 g (40 mmol), copper (II) acetate 360 mg (2 mmol), diphenyl sulfide 54.4 ml (330 mmol) at 200 ° C. Stir for 30 minutes. This was cooled to room temperature, washed with ether and dried to obtain an acid generator (A-2).
Other compounds were synthesized using the same method.

2. Example [Example 1]
(1) Preparation and coating of negative resist solution Binder resin: Resin (27) 0.70 g
Compound (A): a-37 0.0025 g
Compound (B): Crosslinker MM-1 0.25 g
Compound (C): Acid generator C-1 0.04 g
(E) component: OE-1 0.002 g
Surfactant 0.001 g
Other acid generators: z1 0.02 g
Was dissolved in 8.5 g of propylene glycol monomethyl ether acetate, and the resulting solution was microfiltered with a membrane filter having a 0.1 μm aperture to obtain a negative resist solution.
This negative resist solution was applied on a 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.3 μm.

(2) Creation of negative resist pattern This resist film was irradiated using an electron beam drawing apparatus (HL750 manufactured by Hitachi, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated for sensitivity, resolution, and pattern shape by the following methods.

(2-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-300 manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when resolving 0.15 μm (line: space = 1: 1) was defined as sensitivity.

(2-2) Resolution The resolution was the limiting resolution (line and space were separated and resolved) at the exposure amount showing the above sensitivity.

(2-3) Pattern profile The cross-sectional shape of the 0.15 μm line pattern at the exposure amount showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) A five-step evaluation was performed: slightly skirted, rectangular, slightly round top, and round top.

[Examples 2 to 13]
A negative resist solution was prepared and a negative pattern was formed in the same manner as in Example 1 except that each component shown in Table 1 and Table 2 was used. The evaluation results are shown in Table 2.

[Comparative Examples 1-8]
Preparation of negative resist solution, negative type in the same manner as in Example 1 except that each component shown in Table 2 was used without using the acid generator (C) or the compound (A) of the present invention. Pattern formation was performed. The evaluation results are shown in Table 2.

  Tables 1 and 2 show the (Epc (C) -Epa (B)) values of the negative resist compositions of Examples 1 to 13 and Comparative Examples 1 to 8.

In the table, the nitrogen-containing basic compound of component (E) represents the following (all are manufactured by Tokyo Chemical Industry Co., Ltd.).
OE-1: 1,5-diazabicyclo [4.3.0] non-5-ene OE-2: 2,4,5-triphenylimidazole OE-3: 4-dimethylaminopyridine OE-4: tri-n -Butylamine

The solvent in the table represents the following.
S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether

The surfactant in the table represents the following.
W-1: Megafuck F176 (Dainippon Ink Co., Ltd.)
W-2: Siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Example of positive resist composition>
Synthesis of Binder Resin (B-1) 10 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda Co., Ltd.) was dissolved in 50 ml of pyridine, and this was stirred at room temperature, and di-t-butyl dicarbonate 3. 63 g was added dropwise.
After stirring for 3 hours at room temperature, the solution was added dropwise to a solution of 1 L of ion exchange water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain Resin Example (B-1).
Other resins were synthesized by the same method.

[Examples 14 to 20 and Comparative Examples 9 to 16]
The same components (compounds (A) and (B) as in Examples 1 to 13 except that a binder resin for a positive resist composition was used instead of the binder resin for a negative resist composition used in Examples 1 to 13. ), Acid generator (C), nitrogen-containing basic compound (E), solvent, surfactant).
(1) Coating of resist composition Each component shown in Table 3 and Table 4 was dissolved in 8.5 g of the total amount of solvent to prepare a resist composition solution.
Each obtained sample solution was microfiltered with a 0.1 μm aperture membrane filter to obtain a resist solution.
This resist solution was applied onto a 6-inch silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron, and baked at 110 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.30 μm.

(2) Preparation of resist pattern and its evaluation This resist film was irradiated with an electron beam using an electron beam drawing apparatus (Hitachi HL750, acceleration voltage 50 KeV). After irradiation, it was baked at 110 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following method.

(2-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope. The sensitivity was defined as the minimum irradiation energy when resolving a 0.15 μm line (line: space = 1: 1).
(2-2) Resolution The resolution was defined as the limiting resolution (line and space separated and resolved) at the irradiation dose showing the above sensitivity.
(2-3) Pattern profile The cross-sectional shape of the 0.14 μm line pattern at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope, and the bottom, slightly bottom, rectangular, slightly round top, and round top are observed. A five-step evaluation was performed.
The evaluation results are shown in Table 3 and Table 4.
Tables 3 and 4 also show the (Epc (C) -Epa (B)) values of the positive resist compositions of Examples 14 to 20 and Comparative Examples 9 to 16.

Examples 21 and 22 and Comparative Examples 17 to 19
Using the resist compositions of Examples 14 and 18 and Comparative Examples 9, 12, and 14, resist films were obtained in the same manner as in Example 14. However, the resist film thickness was 0.25 μm. The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount by 0.5 mJ in the range of 0 to 5.0 mJ, and further baked at 110 ° C. for 90 seconds. Thereafter, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.
The results are shown in Table 5.

  From Table 5, it can be seen that the positive resist composition of the present invention is superior in sensitivity and high contrast as compared with the composition of the comparative example in the property evaluation by irradiation with EUV light.

[Examples 23 to 26]
Using the components shown in Table 6 below, preparation of a negative resist solution, formation of a negative pattern, and evaluation were carried out in the same manner as in Example 1. The evaluation results are shown in Table 6 below together with the (Epc (C) -Epa (B)) value of each composition.

  From Table 6, it is clear that the negative resist composition of the present invention has high sensitivity, high resolution, and excellent pattern profile.

[Examples 27 to 30]
The other components shown in Table 7 below were used, and the others were prepared in the same manner as in Example 1 to prepare a positive resist solution, form a positive pattern, and evaluated. The evaluation results are shown in Table 7 below together with the (Epc (C) -Epa (B)) value of each composition.

  From Table 7, it is clear that the positive resist composition of the present invention has high sensitivity and high resolution and an excellent pattern profile.

  As described above, it can be seen that the composition of the present invention has good performance regardless of whether it is used in a negative or positive form.

Examples 2-1 to 2-23 and comparative examples 2-1 to 2-7
Using each component shown in Tables 8 to 10, a negative resist solution was prepared and evaluated for sensitivity and resolution (resolution) according to Examples 1 to 13 and Comparative Examples 1 to 8. The evaluation results are shown in Tables 8-10.

  From the above table, it can be seen that the negative resist composition of the present invention is excellent in sensitivity and resolution and has good performance.

Examples 2-24 to 2-37 and Comparative Examples 2-8 to 2-15
Using each component shown in Tables 11 to 12, the positive resist solutions were prepared and evaluated for sensitivity and resolution (resolution) according to Examples 1 to 13 and Comparative Examples 1 to 8. The evaluation results are shown in Tables 11-12.

  From the above table, it can be seen that the positive resist composition of the present invention is excellent in sensitivity and resolving power and has good performance.

Claims (21)

(A) a compound that generates active species upon irradiation with actinic rays or radiation,
(B) a compound that reacts and / or electron-transfers with an active species generated from the compound of (A) and generates an active species different from the active species generated from the compound of (A), and (C) a compound of (B) A compound that generates an acid by electron transfer from an active species generated from
Containing
When the half wave of the oxidation potential of the active species generated from the compound (B) is Epa and the half wave of the reduction potential of the compound (C) is Epc, the relation of Epc−Epa> 0 is satisfied. A resist composition characterized by that. 2. The resist composition according to claim 1, wherein the compound (A) contains a structure represented by the following general formula (a).

^{Ra-Rb-COO - (a} )

In the general formula (a), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO. ^- or -SO ₃ ^- represents a. Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —. The compound of (A) is selected from at least one selected from compounds consisting of a combination represented by general formula (a) and general formulas (I) to (IV). 2. The resist composition according to 2.

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group. The resist composition according to any one of claims 1 to 3, wherein the compound (A) is a compound represented by the following general formula (V).

In the general formula (V), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO. ^- or -SO ₃ ^- represents a. Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. .
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ may be bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom. The resist composition according to any one of claims 1 to 3, wherein the compound (A) is a compound represented by the following general formula (VI) or (VII).

In the above general formula (VI) or (VII), Ra is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl having 1 to 20 carbon atoms. Represents a group, —COO 2 ^— or —SO ₃ ^— . Rc represents _{CH 2, CHRa, C (Ra} ) 2.
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. .
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ may be bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group. The resist composition according to any one of claims 1 to 5, wherein Epc of the compound (C) is more positive than -1.15V. The compound (C) is a compound that has a partial structure represented by the following general formula (VIII) and a counter ion and generates an acid upon irradiation with actinic rays or radiation. 7. The resist composition according to any one of 6 above.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more. The compound (B) is a phenol derivative containing 1 to 10 benzene ring atom groups in the molecule, and further having at least one hydroxymethyl group and alkoxymethyl group in the molecule. The resist composition according to any one of claims 1 to 7. The resist composition according to any one of claims 1 to 8, wherein the compound (B) contains a structure represented by the following general formula (b).

In the general formula (b),
Rf represents a substituted or unsubstituted aryl group, a substituted or unsubstituted straight chain, branched chain, or alicyclic hydrocarbon group, or a combination thereof, and may be interposed via a carbonyl group, an oxygen atom, or a sulfur atom. n represents an integer of 1 to 10. The resist composition according to claim 1, wherein the compound (B) is a cyclic ether compound. The resist composition according to any one of claims 1 to 10, further comprising (E) a nitrogen-containing basic compound. The resist composition according to any one of claims 1 to 11, wherein the actinic ray or radiation is selected from an electron beam, an X-ray and extreme ultraviolet rays (EUV). (A) at least one selected from compounds consisting of the general formula (a) and a combination represented by the general formulas (I) to (IV);
(B) a crosslinking agent that undergoes an addition reaction with the alkali-soluble resin of component (D1) by the action of an acid,
(C) a compound having a partial structure represented by the following general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D1) an alkali-soluble resin,
A negative resist composition comprising:
^{Ra-Rb-COO - (a} )
In general formula (a):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .
Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —.

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more. (A) at least one selected from compounds consisting of a combination represented by general formula (a ′) and general formulas (I) to (IV),
(B) a crosslinking agent that undergoes an addition reaction with the alkali-soluble resin of component (D1) by the action of an acid,
(C) a compound having a partial structure represented by the following general formula (VIII) and a counter ion, which generates an acid upon irradiation with an actinic ray or radiation, and
(D1) an alkali-soluble resin,
A negative resist composition comprising:
Ra-O ^- (a ')
In general formula (a ′):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more. The component (A) is at least one selected from compounds consisting of a combination represented by the general formula (a) and the general formula (I) or (II). The negative resist composition as described. Furthermore, (E) a nitrogen-containing organic basic compound is contained, The negative resist composition as described in any one of Claims 13-15 characterized by the above-mentioned. (A) at least one selected from compounds consisting of a combination represented by general formula (a) and general formulas (I) to (IV);
(C) a compound having a partial structure represented by the following general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D2) in an alkaline developer by the action of the acid. A resin whose solubility increases,
A positive resist composition comprising:
^{Ra-Rb-COO - (a} )
In general formula (a):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .
Rb represents a single bond, —C (═O) —, —NH—, or —S (═O) ₂ —.

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more. (A) at least one selected from compounds consisting of a combination represented by general formula (a ′) and general formulas (I) to (IV),
(C) a compound having a partial structure represented by the following general formula (VIII) and a counter ion, which generates an acid upon irradiation with actinic rays or radiation, and (D2) in an alkaline developer by the action of the acid. A resin whose solubility increases,
A positive resist composition comprising:
Ra-O ^- (a ')
In general formula (a ′):
Ra represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, —COO ⁻ or —SO ₃ ^— . .

In the above general formulas (I) to (IV), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group Represents a halogen atom or a —S—R ₃₈ group.
_R38 represents a linear, branched or cyclic alkyl group, or an aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other, and one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom A ring containing more than one species may be formed.
R _{39 to} R ₄₂ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.

In the general formula (VIII),
X represents a sulfur atom or an iodine atom. A plurality of X may be the same or different.
R ₁ and R ₂ each independently represents an alkyl group or an aryl group. When the R ₁ is a plurality, the plurality of R ₁ may be the same or different. When R ₂ is in plurality, a plurality of R ₂ may be the same or different. R ₁ and R ₂ , R ₁ and A, R ₁ and B, R ₂ and A, and R ₂ and B may be combined to form a ring.
A and B each independently represent a hydrocarbon structure connecting X ⁺ . However, at least one between X ⁺ linked via A or B represents a structure in which the linked X ⁺ is in the same conjugate. When there are a plurality of A, the plurality of A may be the same or different.
l represents 0 or 1; However, when X is a sulfur atom, l enclosing R ₁ bonded to X ⁺ represents 1, and when X is an iodine atom, l enclosing R ₁ bonded to X ⁺ represents 0.
m represents an integer of 0 to 10.
n represents an integer of 1 to 6. However, when m is 0, n represents an integer of 2 or more. The component (A) is at least one selected from a compound consisting of a combination represented by the general formula (a) and the general formula (I) or (II). The positive resist composition as described. The positive resist composition according to any one of claims 17 to 19, further comprising (E) a nitrogen-containing organic basic compound. The resist composition according to any one of claims 13 to 20, wherein the actinic ray or radiation is selected from an electron beam, an X-ray, and EUV light.