JP2006251551A - Positive resist composition and pattern forming method using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition having excellent sensitivity, resolution, further excellent pattern formation, density dependency and dissolution contrast concerning the pattern formation due to irradiation of an electron beam, a KrF excimer laser beam or EUV light, and also to provide a pattern forming method using the resist composition. <P>SOLUTION: The positive resist composition contains: (A) a resin for increasing dissolubility to an alkaline developer by acid action having a specific repeated unit; and (B) a compound generating sulfonic acid, bis(alkyl sufonyl)amide or tris(alkyl sulfonyl) methine due to irradiation of an active optical beam or radiation. In gel permeation chromatography analysis, the resin of (A) has ≤5% in an area% of an oligomer component of a molecular weight of <1,000, and has ≤10% in an area% of a high molecular weight component of a molecular weight of ≥15,000. The pattern forming method uses the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive resist composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photo-publishing processes. More specifically, the present invention relates to a positive photoresist capable of forming a high-definition pattern using KrF excimer laser light, electron beam, EUV light, etc., and a semiconductor device using KrF excimer laser light, electron beam, EUV light The present invention relates to a positive resist composition that can be suitably used for microfabrication and a pattern formation method using the same.

  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. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is being developed.

  Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern forming technology, and a positive 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 positive resists for electron beams and EUV, if high sensitivity is to be pursued, not only the resolution will be lowered. The development of resists that satisfy these characteristics at the same time is strongly desired. Here, the density dependency means a pattern dimension difference between a portion where the resist pattern density is high and a portion where the resist pattern density is low. If this difference is large, the process margin becomes narrow during actual pattern formation. One of the important issues in resist technology development is how to reduce the size. High sensitivity, high resolution, good pattern shape, and good density dependence are in a trade-off relationship, and how to satisfy them simultaneously is very important.

Furthermore, in lithography using KrF excimer laser light, it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good density dependency at the same time. is there.
As a resist suitable for the lithography process using KrF excimer laser light, electron beam, or EUV light, a chemically amplified resist utilizing an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity. In the resist, as a main component, a phenolic polymer (hereinafter abbreviated as a phenolic acid-decomposable resin) having a property that is insoluble or hardly soluble in an antari developer and becomes soluble in an antari developer by the action of an acid, and A chemically amplified resist composition comprising an acid generator is effectively used.

With respect to these positive resists, several resist compositions using a phenolic acid-decomposable resin obtained by copolymerizing an acid-decomposable acrylate monomer having an alicyclic group as an acid-decomposable group have been known. For example, positive resist compositions disclosed in Patent Documents 1 to 5 can be exemplified. Further, Patent Document 6 discloses an example using a compound that generates sulfonic acid by irradiation with actinic rays or radiation and a compound that generates carboxylic acid.
However, in any combination of these, the current situation is that high sensitivity, high resolution, good pattern shape, and good density dependence are not satisfied at the same time in the ultrafine region.

US Pat. No. 5,561,194 JP 2001-166474 A JP 2001-166478 A JP 2003-107708 A JP 2001-194792 A JP 2001-107707 A

  The object of the present invention is to solve the problem of performance improvement technology in microfabrication of semiconductor elements using actinic rays or radiation, in particular KrF excimer laser light, electron beam or EUV light, and has high sensitivity and high resolution. It is an object to provide a positive resist composition that simultaneously satisfies the properties, good pattern shape, and good density dependence, and also has good dissolution contrast, and a pattern forming method using the same.

  The present invention is achieved by the following configurations.

(1) (A) Action of an acid having a repeating unit represented by the following general formula (A1) and / or a repeating unit represented by the general formula (A2) and a repeating unit represented by the general formula (A3) A resin whose solubility in an alkaline developer increases, and
(B) A positive resist composition containing a compound that generates sulfonic acid, bis (alkylsulfonyl) amide or tris (alkylsulfonyl) methine upon irradiation with actinic rays or radiation,
The resin (A) is characterized in that, in gel permeation chromatography analysis, the area percentage of oligomer components having a molecular weight of less than 1000 is 5% or less, and the area percentage of high molecular weight components having a molecular weight of 15000 or more is 10% or less. A positive resist composition.

In general formulas (A1) and (A2),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
Z represents a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkoxy group or an acyloxy group.
A ₁ represents an alkyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group that does not have acid decomposability.
m and n each independently represent 0-4.
In general formula (A3),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
L represents a single bond or a divalent linking group.
X represents a group that is decomposed by the action of an acid.

  (2) The positive resist composition as described in (1), wherein the resin as the component (A) has a weight average molecular weight of 3000 to 15000.

  (3) In (1) or (2), Z in the general formula (A1) and / or X in the general formula (A3) is a group having an alicyclic group or an aromatic group. The positive resist composition for electron beam, X-ray or EUV described.

  (4) (B) As a compound that generates sulfonic acid upon irradiation with actinic rays or radiation, a compound that generates arylsulfonic acid is included, and a compound that generates organic carboxylic acid upon irradiation with actinic rays or radiation is included. The positive resist composition as described in any one of (1) to (3) above.

  (5) (B) A compound that generates arylsulfonic acid and a compound that generates alkylsulfonic acid as a compound that generates sulfonic acid upon irradiation with actinic rays or radiation (1) to The positive resist composition according to any one of (3).

  (6) A pattern forming method comprising the steps of: exposing, heating and developing after applying the positive resist composition according to any one of (1) to (5) on a substrate.

  (7) The pattern forming method as described in (6), wherein the exposure is performed with an X-ray, an electron beam or EUV light.

  According to the present invention, a positive resist composition excellent in sensitivity and resolution as well as pattern shape, density dependence, and dissolution contrast in pattern formation by irradiation with an electron beam, KrF excimer laser light, EUV light, etc. A pattern forming method using the same can be provided.

Hereinafter, the compounds used in the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[1] Resin (A) whose solubility in an alkaline developer is increased by the action of an acid
The resin (resin (A)) whose solubility in an alkali developer is increased by the action of an acid used in the present invention is a repeating unit represented by the following general formula (A1) and / or the general formula (A2). And a repeating unit represented by the general formula (A3).

In general formulas (A1) and (A2),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
Z represents a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkoxy group or an acyloxy group.
A ₁ represents an alkyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group that does not have acid decomposability.
m and n each independently represent 0-4.
In general formula (A3),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
L represents a single bond or a divalent linking group.
X represents a group that is decomposed by the action of an acid.

In General Formula (A3), R ₁ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

In general formula (A3), a group decomposable by the action of an acid as X (hereinafter, also referred to as “acid-decomposable group”) is decomposed by the action of an acid generated by exposure to form a structure of general formula (A3). In which a carboxylic acid derived from an ester group is generated. The acid-decomposable group preferably contains an alicyclic group.
The alicyclic group of the acid-decomposable group containing an alicyclic group as X may be a bridged alicyclic group, and more specifically, the following general formula (pI) to general formula (pVI) described later. And an alicyclic hydrocarbon group as the group represented by

  The acid-decomposable group containing an alicyclic group as X is preferably a group represented by the following general formula (pI) to general formula (pVI).

In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z forms an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to do.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Any of R ₁₅ and R ₁₆ is preferably an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ One is preferably an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ One is preferably an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pVI), the alkyl group in R _{12 to} R ₂₅ may be substituted or unsubstituted, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Represents. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

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

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

  Examples of the substituent for these alicyclic hydrocarbon groups include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The alkyl group and the alkoxy group may have a further substituent. Examples of further substituents on the alkyl group and alkoxy group include a hydroxyl group, a halogen atom, and an alkoxy group.

  In particular, X is preferably a group represented by the general formula (3).

R ₄ , R ₅ and Y each independently represent an alkyl group or an alicyclic hydrocarbon group.

The group represented by the general formula (3) is preferably a group in which one of R _{12 to} R ₁₄ in the general formula (pII) is an alicyclic hydrocarbon group.

  Specific examples of the monomer corresponding to the repeating unit represented by the general formula (A3) are shown below.

In the general formulas (A1) and (A2), Z is preferably an alkyl group, an alkoxy group, a cyano group, a halogen atom, or a perfluoro group (C _m F _{2m + 1} group, m is an integer of 1 to 4 ). Z is more preferably a hydrogen atom, a methyl group, or a C _m F _{2m + 1} group (m is preferably 1).

The alkyl group as Z may have a substituent, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, Preferred examples include sec-butyl group, hexyl group and octyl group.
The alkoxy group as Z may have a substituent, for example, the above alkoxy group having 1 to 8 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group And a cyclohexyloxy group.

R ₁ is the same as in R ₁ in the general formula (A3).

  In general formula (A1), the OH group may be in any position on the benzene ring, but is preferably the meta position or the para position of the styrene skeleton, and particularly preferably the para position.

  Although the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.

In general formula (A2), A ₁ is preferably an alkyl group, alkylcarbonyl, or arylcarbonyl.
The alkyl group may have a substituent, for example, an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Can be mentioned.
Examples of the alkylcarbonyl group include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, t-butylcarbonyl group, cyclohexylcarbonyl group, adamantanecarbonyl group. And norbornanecarbonyl group.
Examples of the arylcarbonyl group include a benzenecarbonyl group, a toluenecarbonyl group, a mesitylenecarbonyl group, and a naphthalenecarbonyl group.

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

  The resin (A) preferably further has a repeating unit represented by the general formula (A4).

In general formula (A4),
R ₂ represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a perfluoro group having 1 to 4 carbon atoms.
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group.
n represents an integer of 0 to 4.
W represents a group that is not decomposed by the action of an acid.

  W represents a group that is not decomposed by the action of an acid (also referred to as an acid stabilizing group). Specifically, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acyl group, an alkylamide group, An arylamidomethyl group, an arylamide group, etc. are mentioned. The acid stabilizing group is preferably an acyl group or an alkylamide group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group.

  In the acid stable group of W, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. As the alkyl group, those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable, and as the alkenyl group, carbon number such as vinyl group, propenyl group, allyl group and butenyl group. Those having 2 to 4 carbon atoms are preferred, those having 2 to 4 carbon atoms such as vinyl, propenyl, allyl and butenyl groups are preferred as alkenyl groups, and phenyl, xylyl and toluyl groups are preferred as aryl groups. And those having 6 to 14 carbon atoms such as cumenyl group, naphthyl group and anthracenyl group are preferable. W may be at any position on the benzene ring, but is preferably a meta position or a para position of the styrene skeleton, particularly preferably a para position.

  Although the specific example of the repeating unit represented by general formula (A4) below is given, it is not limited to these.

The content of the repeating unit represented by the general formula (A1) and / or (A2) in the resin (A) is preferably 20 to 97 mol%, more preferably 30 to 95 mol% in all repeating units. Especially preferably, it is 50-95 mol%.
The content of the repeating unit represented by the general formula (A3) in the resin (A) is preferably 3 to 80 mol%, more preferably 5 to 70 mol%, particularly preferably 5 in all repeating units. ˜50 mol%.

  The resin (A) may have a repeating unit represented by the general formula (A4), and is preferable from the viewpoints of improving the film quality and suppressing the decrease in film thickness of the unexposed area. The content of the repeating unit represented by the general formula (A4) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 40 mol% in each of all the repeating units. 30 mol%.

The resin (A) is copolymerized with other polymerizable monomers suitable so that an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability for an alkali developer. In order to improve the film quality, other hydrophobic polymerizable monomers such as alkyl acrylate and alkyl methacrylate may be copolymerized.
Furthermore, the resin (A) may contain a monomer having another acid-decomposable group in addition to the acid-decomposable group contained in the general formula (A3). , —C (═O) —X ₁ —R ₀ can be exemplified.

In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

The resin (A) is characterized in that, in gel permeation chromatography analysis, the area percentage of oligomer components having a molecular weight of less than 1000 is 5% or less, and the area percentage of high molecular weight components having a molecular weight of 15000 or more is 10% or less. To do.
In gel permeation chromatography analysis, the following method is used alone or in combination for a resin having an area percentage of oligomer components with a molecular weight of less than 1000 of 5% or less and an area percentage of high molecular weight components with a molecular weight of 15000 or more of 10% or less. From the viewpoint of cost, the method (4) is preferred industrially.
(1) Size fractionation chromatography using Sephadex, etc. (2) Silica gel column chromatography (3) Living radical polymerization method (4) Multiple polymer fractionation using two types of solvents with different polarities

The weight average molecular weight (Mw) of the resin (A) is preferably in the range of 1,000 to 15,000, and more preferably in the range of 3,000 to 10,000. The dispersity (Mw / Mn) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.
Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

Moreover, you may use resin (A) in combination of 2 or more types, respectively.
The total amount of the resin (A) added is generally 10 to 96% by mass, preferably 15 to 96% by mass, and particularly preferably 20 to 95% by mass with respect to the total solid content of the positive resist composition. %.

  Although the specific example of resin (A) is given to the following, it does not limit these.

[2] Compound (B) which generates sulfonic acid, bis (alkylsulfonyl) amide or tris (alkylsulfonyl) methine upon irradiation with actinic rays or radiation
Compound ("Compound (B)" or "Sulphonic acid generation" which generates sulfonic acid, bis (alkylsulfonyl) amide or tris (alkylsulfonyl) methine upon irradiation with actinic rays or radiation contained in the positive resist composition of the present invention Is also a compound that generates sulfonic acid, bis (alkylsulfonyl) amide or tris (alkylsulfonyl) methine upon irradiation with actinic rays or radiation such as KrF excimer laser light, electron beam, EUV, etc., for example, Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium 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, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 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.

In the present invention, examples of sulfonic acid generators that are preferable from the viewpoint of improving image performance such as resolution and pattern shape include sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, and disulfones.
Among these, examples of particularly preferable ones are listed below.

Although content of a compound (B) is used at 5-20 mass% on the basis of solid content of a resist composition, Preferably it is 6-18 mass%, Most preferably, it is 7-16 mass%. It is 5% by mass or more from the viewpoint of sensitivity and line edge roughness, and 20% by mass or less from the viewpoint of resolution, pattern shape, and film quality. Moreover, 1 type may be used for a compound (B), and 2 or more types may be mixed and used for it. For example, as the compound (B), a compound that generates aryl sulfonic acid upon irradiation with actinic rays or radiation and a compound that generates alkyl sulfonic acid upon irradiation with actinic rays or radiation may be used in combination.
Compound (B) can be synthesized by a known method such as the synthesis method described in JP-A-2002-27806.

[3] Compound (C) that generates carboxylic acid upon irradiation with actinic rays or radiation
The positive resist composition of the present invention includes a compound (also referred to as a compound (C) or a carboxylic acid generator) that generates a carboxylic acid upon irradiation with actinic rays or radiation together with a sulfonic acid generator (compound (B)). May be used.
As the carboxylic acid generator, a compound represented by the following general formula (C) is preferable.

In the general formula (C), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. Z represents a sulfur atom or an iodine atom. When Z is a sulfur atom, p is 1, and when Z is an iodine atom, p is 0.

In the general formula (C), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these groups may have a substituent.
Examples of the substituent that the alkyl group, cycloalkyl group or alkenyl group may have include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), an aryl group (a phenyl group, a naphthyl group, etc.), a hydroxy group, An alkoxy group (methoxy group, ethoxy group, butoxy group, etc.) etc. can be mentioned.
Examples of the substituent that the aryl group may have include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), nitro group, cyano group, alkyl group (methyl group, ethyl group, t-butyl group, t -Amyl group, octyl group, etc.), hydroxy group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.) and the like.

R _{21 to} R ₂₃ are preferably each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms. And more preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 15 carbon atoms. Each of these groups may have a substituent.

R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have are the same as those described as examples of the substituent when R ₂₁ is an alkyl group. Examples of the substituent for the aryl group, the R ₂₁ may be the same as those mentioned as examples of the substituent when it is an aryl group.

R ₂₄ is preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 24 carbon atoms, and more Preferably, they are a C1-C18 alkyl group, a C3-C18 cycloalkyl group, and a C6-C18 aryl group, Most preferably, a C1-C12 alkyl group, C3-C3 A cycloalkyl group having 12 carbon atoms and an aryl group having 6 to 15 carbon atoms. Each of these groups may have a substituent.

Z represents a sulfur atom or an iodine atom. p is 1 when Z is a sulfur atom, and 0 when Z is an iodine atom.
Two or more of the cation moieties of formula (C) are bonded by a single bond or a linking group (for example, -S-, -O-, etc.) to form a cation structure having a plurality of cation moieties of formula (C). May be.

  The preferred specific examples of the compound (C) that generates a carboxylic acid upon irradiation with actinic rays or radiation are shown below, but of course not limited thereto.

The content of the compound (C) in the positive resist composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, based on the total solid content of the composition. Particularly preferably, the content is 0.05 to 3% by mass. In addition, these compounds that generate a carboxylic acid upon irradiation with actinic rays or radiation may be used alone or in combination of two or more.
The compound (C) / compound (B) (mass ratio) is usually 99.9 / 0.1 to 50/50, preferably 99/1 to 60/40, particularly preferably 98/2 to 70/30. .
Compound (C) can be synthesized by a known method such as a synthesis method described in JP-A-2002-27806.

[4] Organic Basic Compound In the present invention, it is preferable to use an organic basic compound from the viewpoint of improving performance such as resolution and improving storage stability. As the organic basic compound, a compound containing a nitrogen atom (nitrogen-containing basic compound) is more preferable.
A preferable organic basic compound in the present invention is a compound having a stronger basicity 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.

In the formula (A), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms. Here, R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
The alkyl group, cycloalkyl group and aryl group as R ²⁰⁰ , R ²⁰¹ and R ²⁰² may have a substituent. As the alkyl group and cycloalkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms and an aminocycloalkyl group, and a hydroxyalkyl group having 1 to 20 carbon atoms are preferable.
In the formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group.
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 guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and the like. Preferred substituents that these may have include amino groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups (substituent alkyl groups, particularly aminoalkyl groups), alkoxy groups, acyl groups, and acyloxy groups. , Aryl group, aryloxy group, nitro group, hydroxyl group, cyano group and the like.

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, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl)- Examples include 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. It is not limited to this.
These nitrogen-containing basic compounds are used alone or in combination of two or more.

  A tetraalkylammonium salt type nitrogen-containing basic compound can also be used. Of these, tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.) is particularly preferable. These nitrogen-containing basic compounds are used alone or in combination of two or more.

  The use ratio of the acid generator and the organic basic compound in the composition is preferably (total amount of acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. By setting the molar ratio to 2.5 or more, high sensitivity is obtained, and by setting the molar ratio to 300 or less, it is possible to suppress the resist pattern from becoming thicker over time until post-exposure heat treatment and improve resolution. . (Total amount of acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[5] Surfactants In the present invention, surfactants can be used, which are preferable from the viewpoints of film-forming properties, pattern adhesion, development defect reduction, and the like.

  Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan mono palmitate - door,

Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Shin-Akita Kasei) (Made by Co., Ltd.), MegaFuck F171, F173 (Dainippon Ink Chemical Co., Ltd.), Florad FC430, FC431 (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.) and the like, or silicon-based surfactants, organosiloxane polymer KP341 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 some combination.

The surfactant is any one of fluorine and / or silicon surfactants (fluorine surfactants and silicon surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540 No. 7, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720. , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). It may be a unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) Copolymer) of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive resist composition (excluding the solvent).

[6] Other components The positive resist composition of the present invention may further contain a dye, a photobase generator and the like, if necessary.

1. Dye A dye can be used in the present invention.
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.

2. 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.

3. Solvents The resist composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. The solid content concentration of all resist components is usually preferably 2 to 30% by mass, more preferably 3 to 25% by mass.
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.

  The positive resist composition of the present invention is applied onto a substrate to form a thin film. The thickness of this coating film is preferably 0.05 to 4.0 μm.

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

  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 JP-B-7-69611, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a coalescence and a diamine type light absorbing agent, a resin binder described in JP-A-6-186863 and a methylolmelamine thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. An acrylic resin-type antireflection film in the same molecule, a composition comprising methylol melamine and a benzophenone-based light absorber described in JP-A-8-87115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like.

  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 forming process on the resist film is carried out on the substrate (eg, silicon / silicon dioxide coated substrate, glass substrate, ITO substrate, quartz / chromium oxide coated substrate, etc.). A resist pattern is formed by applying a resist composition, forming a resist film, and then irradiating actinic rays or radiation such as KrF excimer laser light, electron beam, EUV light, etc., heating, developing, rinsing and drying. Can be formed.

Examples of the alkaline developer used in development include 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. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, An aqueous solution (usually 0.1 to 20% by mass) of an alkali such as a quaternary ammonium salt such as choline or a cyclic amine such as pyrrole or piperidine 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.
The pH of the alkali developer is usually 10-15.

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

Synthesis Example 1 (Synthesis of Resin Example (A-10))
p-Hydroxystyrene and 2-ethyl-2-adamantyl methacrylate were charged at a ratio (molar ratio) of 65/35 and dissolved in tetrahydrofuran to prepare 100 mL of a solution having a solid concentration of 20% by mass. To this solution was added 2 mol% of a polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd., and this was added dropwise to 10 mL of tetrahydrofuran heated to 60 ° C. over 4 hours in a nitrogen atmosphere. After completion of dropping, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 3 L of hexane, and the precipitated white powder was collected by filtration.
The composition ratio of the polymer determined from C ¹³ NMR was 64/36. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 9500, the content of oligomer components having a molecular weight of less than 1000 was 6%, and the content of high molecular weight components having a molecular weight of 15000 or more was 12%. Moreover, the ratio of the composition component whose molar content of the repeating unit (A2) measured by HPLC-NMR is 10% or less was 16% by weight. (This is referred to as “unpurified resin A-10 ′”)
This polymer was dissolved in 100 ml of acetone, and distilled water was added to precipitate the polymer. The precipitate was washed with distilled water and then dried under reduced pressure. After dissolving the polymer in 100 ml of ethyl acetate, hexane was added and the precipitated polymer was powdered by drying under reduced pressure. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement for this powder was 11,000, the content of oligomer components having a molecular weight of less than 1000 was 4%, and the content of high molecular weight components having a molecular weight of 15000 or more was 8%. Moreover, the molar content of the repeating unit (A2) measured by HPLC-NMR was 10% or less, and the proportion of the composition was 13% by weight.
Resins exemplified in the structure shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 above.

  The sulfonic acid generator and carboxylic acid generator used in the examples of the present invention were synthesized by a known synthesis method such as the synthesis method described in JP-A-2002-27806.

Example 1
(1) Preparation and coating of positive resist Resin A-2 0.93g
Sulfonic acid generator B-2 0.065g
Carboxylic acid generator C-2 0.005g
Is dissolved in 8.8 g of propylene glycol monomethyl ether acetate, 0.001 g of D-1 (see below) as an organic basic compound, and Megafac F176 (manufactured by Dainippon Ink & Chemicals, Inc.) as a surfactant. 0.001 g) (abbreviated as W-1) was added and dissolved, and the resulting 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 0.25 μm.

(2) Creation of positive resist pattern This resist film was irradiated with an electron beam using an electron beam drawing apparatus (Hitachi Ltd. 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 (S-4300, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 0.15 μm line (line: space = 1: 1).
(2-2) Resolving power The resolving power was defined as the limiting resolving power (the line and space were separated and resolved) at the irradiation dose showing the above sensitivity.
(2-3) Pattern shape The cross-sectional shape of the 0.15 μm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), rectangular, slightly tapered, tapered. A three-stage evaluation was performed.
(2-4) Density dependency Measure the line width of the dense pattern (line: space = 1: 1) and the line width of the isolated pattern in the 0.15 μm line pattern at the irradiation dose showing the above sensitivity, and calculate the difference. Dependent on sparse and dense.

As a result of Example 1, the sensitivity was 6.0 μC / cm ² , the resolving power was 0.09 μm, the pattern shape was rectangular, and the density dependency was 12 nm, which was very good.

Examples 2-13
Using the compounds shown in Table 2, resist preparation / coating and electron beam exposure evaluation were carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 1
Resist preparation / coating shown in Table 2 was carried out in the same manner as in Example 1 except that the unpurified resin (A-10 ′) described in Synthesis Example 1 was used as the acid-decomposable resin, and electron beam exposure evaluation Went. The evaluation results are also shown in Table 2.

Abbreviations in Table 2 are shown below.
[Organic basic compounds]
D-1: tri-n-hexylamine D-2: 2,4,6-triphenylimidazole D-3: tetra- (n-butyl) ammonium hydroxide

[Other components (surfactant)]
W-1: Fluorosurfactant, MegaFuck F-176 (Dainippon Ink Science Co., Ltd.)
W-2: Fluorine / silicone surfactant, MegaFac R08 (Dainippon Ink and Chemicals)
W-3: Silicone surfactant, siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

  From Table 2, it can be seen that the positive resist composition of the present invention is higher in sensitivity and resolution than the comparative example with respect to pattern formation by electron beam irradiation, and is excellent in pattern shape and density dependency. .

Example 14
In the same manner as in Example 1, the resists shown in Table 3 were prepared and coated to obtain a resist film. However, the film thickness was 0.40 μm.

(3) Formation of positive pattern The obtained resist film was subjected to pattern exposure using a KrF excimer laser stepper (FPA3000EX-5 manufactured by Canon Inc., wavelength 248 nm). The post-exposure processing was performed in the same manner as in Example 1. The pattern was evaluated as follows.
(3-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 0.18 μm line (line: space = 1: 1).
(3-2) Resolving power The resolving power was defined as the limiting resolving power (line and space were separated and resolving) at the irradiation dose showing the above sensitivity.
(3-3) Pattern shape The cross-sectional shape of the 0.18μm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), rectangular, slightly tapered, tapered. A three-stage evaluation was performed.
(3-4) Dense / Dense Dependence Measure the line width of the dense pattern (line: space = 1: 1) and the line width of the isolated pattern in the 0.18μm line pattern at the irradiation dose showing the above sensitivity, and calculate the difference between them. Dependent on sparse and dense.

The results of Example 14 were very good because the sensitivity was 32 mJ / cm ² , the resolving power was 0.15 μm, the pattern shape was rectangular, and the density dependence was 8 nm.

Examples 15-20
Using the compounds shown in Table 3, resist preparation / coating and KrF excimer laser exposure evaluation were performed in exactly the same manner as in Example 14. The evaluation results are shown in Table 3.

Comparative Example 2
Resist preparation / coating shown in Table 3 was carried out in the same manner as in Example 14 except that the resin (A-10 ′) used in Comparative Example 1 was used as the resin, and KrF excimer laser exposure evaluation was performed. The evaluation results are also shown in Table 3.

  From Table 3, it can be seen that the positive resist composition of the present invention is higher in sensitivity and resolution than the comparative example, and is excellent in pattern shape and density dependence, as compared with the comparative example, regarding pattern formation by KrF excimer laser exposure. .

Examples 21 to 23 and Comparative Example 3
A positive resist composition was prepared in the same manner as in Example 1 except that the compounds shown in Table 4 were used, to obtain a resist film. However, the resist film thickness was 0.13 μm. The resulting 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. Then, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure dose 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 4.

  From Table 4, 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.

Claims (7)

(A) Alkali development by the action of an acid having a repeating unit represented by the following general formula (A1) and / or a repeating unit represented by the general formula (A2) and a repeating unit represented by the general formula (A3) A resin whose solubility in the liquid increases, and
(B) A positive resist composition containing a compound that generates sulfonic acid, bis (alkylsulfonyl) amide or tris (alkylsulfonyl) methine upon irradiation with actinic rays or radiation,
The resin (A) is characterized in that, in gel permeation chromatography analysis, the area percentage of oligomer components having a molecular weight of less than 1000 is 5% or less, and the area percentage of high molecular weight components having a molecular weight of 15000 or more is 10% or less. A positive resist composition.

In general formulas (A1) and (A2),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
Z represents a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkoxy group or an acyloxy group.
A ₁ represents an alkyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group that does not have acid decomposability.
m and n each independently represent 0-4.
In general formula (A3),
R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, a cyano group, a chloro atom, a hydroxymethyl group, or an alkoxymethyl group.
L represents a single bond or a divalent linking group.
X represents a group that is decomposed by the action of an acid. 2. The positive resist composition according to claim 1, wherein the resin as the component (A) has a weight average molecular weight of 3000 to 15000. 3.   The electron beam according to claim 1 or 2, wherein Z in the general formula (A1) and / or X in the general formula (A3) is an alicyclic group or a group having an aromatic group, A positive resist composition for X-ray or EUV.   (B) A compound that generates an arylsulfonic acid as a compound that generates sulfonic acid upon irradiation with actinic rays or radiation, and a compound that generates an organic carboxylic acid upon irradiation with active rays or radiation. The positive resist composition according to claim 1.   (B) As a compound which generate | occur | produces a sulfonic acid by irradiation of actinic light or a radiation, the compound which generate | occur | produces an aryl sulfonic acid and the compound which generate | occur | produces an alkyl sulfonic acid are contained together. A positive resist composition as described above.   A pattern forming method comprising the steps of: exposing, heating, and developing after applying the positive resist composition according to claim 1 onto a substrate.   The pattern forming method according to claim 6, wherein exposure is performed with an X-ray, an electron beam, or EUV light.