KR20030023455A - Positive resist composition - Google Patents

Abstract

PURPOSE: Provided is a positive resist composition having excellent SEM(scanning electron microscopy) resistance and resolution, and further having improved defocus latitude. CONSTITUTION: The positive resist composition comprises (A) at least two of resins having at least one of monomer selected from (a1) butyrolactones, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones, which have a dissolution rate in an alkali developer increased by the action of an acid; and (B) a compound which generates an acid by irradiation with active light or radiation. The positive resist composition is characterized in that the mixture of the resins(A) comprises at least two kinds of the monomer units(a1)-(a4).

Description

Positive Resist Composition {POSITIVE RESIST COMPOSITION}

The present invention relates to a positive resist composition used in microlithography processes such as the production of ultra-LSI and high-capacity microchips or other photofabrication processes.

In recent years, integrated circuits have been further increased, and in the manufacture of semiconductor substrates such as ultra-LSIs, processing of ultrafine patterns having line widths of 1/2 micron or less has been required. In order to satisfy this need, the wavelength of use of the exposure apparatus used for photolithography is further shortened, and until now, the use of short wavelength excimer laser light (XeCl, KrF, ArF, etc.) has been examined. .

There is a chemical amplification resist used for the pattern formation of lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types, namely two-component, 2.5-component and three-component. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. This binder resin is a resin which decomposes by the action of an acid and retains in the molecule a group (also called an acid-decomposable group) which increases the solubility of the resin in an alkaline developer. The 2,5-component system contains a low molecular compound which further has an acid-decomposable group in this two-component system. The three-component system contains a photoacid generator, an alkali soluble resin and the low molecular weight compound.

Although the chemical amplification resist is suitable for photoresist for ultraviolet or far ultraviolet irradiation, it is necessary to further correspond to the required characteristics in use.

As the photoresist composition for the ArF light source, a resin in which an alicyclic hydrocarbon site is introduced for the purpose of imparting dry etching resistance has been proposed. However, since the system becomes extremely hydrophobic as a disadvantage of introduction of the alicyclic hydrocarbon site, it is widely used as a conventional resist developer. The development in the tetramethylammonium hydroxide (TMAH) aqueous solution which has been used becomes difficult, or the phenomenon which the resist peels from a board | substrate during development is discovered.

In response to the hydrophobicization of the resist, the reaction such as mixing an organic solvent such as isopropyl alcohol in the developer has been examined, and a predetermined result has been observed. However, problems such as swelling of the resist film and complicated processes are necessarily solved. I can not say. In the approach of improving the resist, there are many measures to supplement a small number of alicyclic hydrocarbon sites by introducing a hydrophilic group.

Japanese Patent Application Laid-Open No. 10-10739 discloses an energy sensitive resist material containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornane ring in a main chain, a maleic anhydride, and a monomer having a carboxyl group. Japanese Patent Laid-Open No. 10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in a main chain and a radiation-sensitive acid generator. Japanese Patent Application Laid-Open No. 11-109632 describes the use of a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group as a radiation photosensitive material.

As mentioned above, resin containing an acid-decomposable group used for the photoresist for far-ultraviolet exposure generally contains an aliphatic cyclic hydrocarbon group in a molecule | numerator simultaneously. For this reason, resin became hydrophobic and there existed a problem resulting from this. Although the above various means for improving this have been examined variously, there are still many points which are inadequate with the said technique, and improvement is desired.

On the other hand, in order to improve various resist performances, it has been proposed until now to use a resin having a lactone structure as the binder resin in the resist composition. For example, Japanese Patent Application Laid-Open Nos. 9-90637 and 10-319595 describe resist compositions containing a polymer having a butyrolactone structure in the side chain of monomer units. JP-A-10-207069 and JP-A-11-12326 disclose a positive resist composition containing an acrylic resin having a butyrolactone moiety. Patent Publication No. Hei 10-274852 describes a chemically amplified positive resist composition containing a resin having a butyrolactone moiety that may be substituted with alkyl.

Japanese Patent No. 3042618 describes a photoresist composition containing a polymer obtained by copolymerizing a (meth) acrylate derivative having a norbornanelactone structure with another polymerizable compound. Japanese Patent Laid-Open No. 2000-159758 discloses a resist material containing a high molecular compound having a norbornanelactone structure in a repeating unit.

Japanese Patent Application Laid-Open No. 2001-64273 describes a resist composition using a polymer having a cyclohexanelactone structure.

Japanese Patent Application Laid-Open No. 2001-122294 discloses a photosensitive composition containing a resin having an adamantane lactone structure.

According to the said patent, although the improvement in resolution or SEM tolerance was shown compared with the conventional resist composition, both are trade-off relationship so far, and improving both SEM tolerance and resolution in this field is It became important problem of, and further improvement was desired.

Accordingly, it is an object of the present invention to provide a positive resist composition which is excellent in SEM resistance and resolution and has improved defocus latitude.

The present inventors carefully examined the constituent materials of the positive chemically amplified resist composition, and found that an acid-decomposable resin having a plurality of specific lactone monomers as constituent units may be used by combining a plurality of acid-decomposable resins having a specific lactone monomer unit. By using it, it turned out that the objective of this invention is achieved, and the present invention was reached.

That is, the said object is achieved by the following structures.

(1) (A) (a1) butyrolactone, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones, and has one or more monomer units selected from Two or more kinds of resins having an increased dissolution rate in an alkaline developer due to the action of, and

(B) The positive resist composition containing the compound which generate | occur | produces an acid by irradiation of actinic light or radiation, WHEREIN: The mixture of said resin (A) contains 2 or more types of the monomer units of said (a1)-(a4). A positive resist composition, characterized in that.

(2) The positive resist composition as described in (1), wherein the butyrolactone monomer unit of (a1) is a repeating unit represented by the following general formula (II) in the resin of (A).

(In General Formula (II), R ₁ represents a hydrogen atom or a methyl group.

W represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group and an ester group.

Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.)

(3) In (1), the norbornanelactone monomer unit of (a2) in the resin of (A) is a repeating unit having a group represented by the following general formula (V-1) or (V-2). Positive resist composition made into.

(In General Formulas (V-1) to (V-2), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.)

(4) The cyclohexane lactone monomer unit of (a3) in (1) is a repeating unit having a group represented by the following general formula (V-3) or (V-4) in (A). Positive resist composition made into.

(In General Formulas (V-3) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.)

(5) The positive resist composition as described in (1), wherein the adamantane lactone monomer unit of (a4) is a repeating unit represented by the following general formula (I) in the resin of (A).

(In Formula (I), A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or an ester group selected from the group consisting of two or more groups. R is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.)

(6) The repeating unit according to any one of (1) to (5), wherein the resin of (A) has a partial structure containing an alicyclic hydrocarbon represented by the following general formulas (pI) to (pVI): A positive resist composition further comprising at least one selected.

(Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms) Indicates.

R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group; Indicates.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group.

R ₂₂ to R ₂₅ each independently represent a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.)

(7) (A) (a1) butyrolactones, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones having at least two monomers selected as structural units , A resin which increases the dissolution rate in an alkaline developer by the action of an acid, and

(B) A positive resist composition comprising a compound which generates an acid by irradiation with actinic light or radiation.

(8) The positive resist composition as described in the item (7), wherein in the resin (A), (a1) is a repeating unit represented by the following general formula (II).

(In General Formula (II), R ₁ represents a hydrogen atom or a methyl group.

W represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group and an ester group.

Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.)

(9) The positive resist composition as described in (7), wherein in the resin of (A), (a2) is a repeating unit having a group represented by the following general formula (V-1) or (V-2).

(In General Formulas (V-1) to (V-2), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.)

(10) The positive resist composition as described in (7), wherein in the resin of (A), (a3) is a repeating unit having a group represented by the following general formula (V-3) or (V-4).

(In General Formulas (V-3) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.)

(11) The positive resist composition as described in (1), wherein in the resin of (A), (a4) is a repeating unit represented by the following general formula (I).

(In Formula (I), A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or an ester group selected from the group consisting of two or more groups. R is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.)

(12) The repeating unit according to any one of (7) to (11), wherein the resin of (A) has a partial structure containing an alicyclic hydrocarbon represented by the following general formulas (pI) to (pVI): A positive resist composition further comprising at least one selected.

(Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms) Indicates.

R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group; Indicates.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group.

R ₂₂ to R ₂₅ each independently represent a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.)

Hereinafter, the component used for this invention is demonstrated in detail.

[1] A resin ("acid-decomposable resin") in which the dissolution rate in an alkaline developer increases due to the action of (A) acid.

As the acid-decomposable resin (A) of the present invention, at least one monomer unit selected from (a1) butyrolactones, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones Two or more kinds of resins having an increase in the dissolution rate with respect to the alkaline developer due to the action of acid.

In the acid-decomposable resin of the present invention, as the butyrolactone monomer unit of (a1), a repeating unit represented by the general formula (II) is preferable.

Moreover, as another acid-decomposable resin (A) of this invention, 2 selected from (a1) butyrolactone, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones The resin which has a monomer more than a species as a structural unit, and the dissolution rate to an alkaline developing solution increases by the action of an acid is used.

In the acid-decomposable resin of the present invention, the butyrolactone monomer of (a1) is preferably a repeating unit represented by the general formula (II).

Here, in general formula (II), R <_1> represents a hydrogen atom or a methyl group.

Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n respectively independently represent the integer of 0-3, and m + n is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms for Ra to Re include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

In general formula (II), group represented by a following formula can be mentioned as an alkylene group of W.

[C (Rf) (Rg)] r-

In the formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxy group and an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably is selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r is an integer of 1-10.

Examples of the other substituent in the alkyl group include a carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxy group, alkoxy group, substituted alkoxy group, acetylamide group, alkoxycarbonyl group and acyl group.

Here, as an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, are mentioned. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned. As a substituent of a substituted alkoxy group, an alkoxy group can be mentioned. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned. As acyloxy group, an acetoxy group etc. are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom.

Hereinafter, although the specific example of the monomer corresponded to the repeating unit represented by General formula (II) is shown, it is not limited to these.

In the specific example of said general formula (II), especially (II-17)-(II-36) are preferable at the point that an exposure margin is obtained more favorable.

In the acid-decomposable resins of the present invention, the norbornanelactone monomer units of (a2) and the cyclohexane lactone monomer units of (a3) are represented by the general formulas (V-1) to (V-2) and (V-), respectively. A repeating unit having a group represented by 3) to (V-4) is preferable.

In General Formulas (V-1) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group. Two of R _1b to R _5b may be bonded to each other to form a ring.

In general formula (V-1)-(V-4), a linear or branched alkyl group may be mentioned as an alkyl group in R <_1b> -R <_5b> , and you may have a substituent.

As a linear or branched alkyl group, a C1-C12 linear or branched alkyl group is preferable, More preferably, it is a C1-C10 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, and a propyl group , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

As a cycloalkyl group in R <_1b> -R <_5b> , C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, are preferable.

As an alkenyl group in R <_1b> -R <_5b> , C2-C6 things, such as a vinyl group, a propenyl group, butenyl group, and a hexenyl group, are preferable.

Examples of the ring formed by bonding of two of R _1b to R _5b include a 3-8 membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring.

Furthermore, R _1b to R _5b in General Formulas (V-1) to (V-4) may be linked to any one of the carbon atoms constituting the cyclic skeleton.

Preferable substituents which the alkyl group, cycloalkyl group and alkenyl group may have include 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 having 2 to 5 carbon atoms, A C2-C5 acyloxy group, a cyano group, a hydroxyl group, a carboxyl group, a C2-C5 alkoxycarbonyl group, a nitro group, etc. are mentioned.

As a repeating unit which has group represented by general formula (V-1)-(V-4), the repeating unit represented by the following general formula (AI), etc. can be mentioned.

In General Formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. As a preferable substituent which the alkyl group of R <_b0> may hold, what was illustrated above as a preferable substituent which the alkyl group as R < _1b in the said General Formula (V-1)-(V-4) may hold is mentioned.

_Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R _b0 is preferably a hydrogen atom.

A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or the bivalent group which combined these.

B ₂ represents a group represented by any one of General Formulas (V-1) to (V-4). In A ', the thing of the following formula is mentioned as a divalent group combined above, for example.

In the above formula, R _ab , R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxy group, or an alkoxy group, and both may be the same or different.

The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and a C1-C4 alkoxy group can be mentioned.

As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r1 represents the integer of 1-10, Preferably the integer of 1-4 is represented. m represents an integer of 1 to 3, preferably 1 or 2.

Although the specific example of the repeating unit represented by general formula (AI) is listed below, the content of this invention is not limited to these.

In the acid-decomposable resin of the present invention, the adamantane lactone monomer unit of (a4) is preferably a repeating unit represented by the general formula (I).

In general formula (I), the group represented by a following formula is mentioned as an alkylene group of A.

-[C (Rnf) (Rng)] r-

In the formula, Rnf and Rng represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxy group and an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably is selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r is an integer of 1-10.

In general formula (I), the C3-C10 thing is mentioned as a cycloalkylene group of A, A cyclopentylene group, a cyclohexylene group, a cyclooctylene group, etc. can be mentioned.

The bridged alicyclic ring containing Z may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (for example, formyl group, benzoyl group), and an acyloxy group (for example, is propyl carbonyloxy group, benzoyl group), an alkyl group (preferably having 1 to 4 carbon atoms), a carboxyl group, a hydroxy group, an alkylsulfonyl nilsul sulfamoyl group (-CONHSO ₂ CH _3, etc.) are exemplified. In addition, the alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms).

In general formula (I), the oxygen atom of the ester group couple | bonded with A may couple | bond with any position of the carbon atom which comprises the Z containing bridged alicyclic ring structure.

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

(A) The acid-decomposable resin of the present invention is at least one selected from the above (a1) butyrolactone, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones Any mixture of two or more kinds of resins having a monomer unit and in which the dissolution rate in an alkaline developer increases due to the action of an acid may be used, but a preferred combination is a mixture of a resin having (a1) and a resin having (a2). , a mixture of a resin having (a1) and a resin having (a4), a mixture of a resin having (a2) and a resin having (a3), a mixture of a resin having (a2) and a resin having (a4), and A mixture of a resin having (a3) and a resin having (a4), more preferably a mixture of a resin having (a1) and a resin having (a2), a resin having (a1) and a resin having (a4) , A mixture of a resin having (a2) and a resin having (a3), and a mixture of a resin having (a3) and a resin having (a4) All.

In addition, the mixing ratio of the lactone monomer is preferably 10/90 to 90/10 in any combination of lactones, more preferably 20/80 to 80/20, particularly preferably 30/70 to 70/30 to be.

(A) The acid-decomposable resin of the present invention is selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pVI) in addition to the lactone monomer unit. It is preferable that it is resin containing a species or more.

In addition, as (A) acid-decomposable resin of another this invention, it selects from said (a1) butyrolactone, (a2) norbornane lactone, (a3) cyclohexane lactone, and (a4) adamantane lactone. Any resin may be used as long as it is a resin having two or more monomers as a structural unit and the dissolution rate of the alkaline developer is increased by the action of an acid, but the alicyclic hydrocarbon represented by the above general formula (pI) to general formula (pVI). It is preferable that it is resin further containing 1 or more types chosen from the group of the repeating unit which has the partial structure containing.

In general formula (pI)-the general formula (pVI), as an alkyl group in R <_12> -R <_25> , the linear or branched alkyl group which has 1-4 carbon atoms which may be either substituted or unsubstituted is represented. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like.

Other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxy group, carboxyl group, alkoxycarbonyl group, Nitro group etc. can be mentioned.

The alicyclic hydrocarbon group or the alicyclic hydrocarbon group formed by Z and a carbon atom in R ₁₁ to R ₂₅ may be monocyclic or polycyclic. Specifically, the group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. can be mentioned. 6-30 carbon atoms are preferable, and 7-25 carbon atoms are especially preferable. These alicyclic hydrocarbon groups may have a substituent.

Below, the structural example of an alicyclic part is shown in an alicyclic hydrocarbon group.

In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, noadamantyl group, decalin residue group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, Cyclooctyl group, cyclodecanyl group, cyclododecanyl group, etc. are mentioned. More preferable are adamantyl group, decalin residue group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group and cyclododecanyl group.

As a substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably represents a substituent selected from the group consisting of methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned. As said alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be mentioned.

The structures represented by the general formulas (pI) to (pVI) in the resin can be used for the protection of alkali-soluble groups. Alkali soluble groups include various groups known in the art.

Specifically, a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group, etc. are mentioned, Preferably they are a carboxylic acid group and a sulfonic acid group.

As alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, Preferably, the group represented by the following general formula (pVII)-(pXI) is mentioned.

Wherein R ₁₁ to R ₂₅ and Z are the same as defined above, respectively.

In the said resin, as a repeating unit which has alkali-soluble group protected by the structure represented by general formula (pI)-(pVI), the repeating unit represented by the following general formula (pA) is preferable.

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different, respectively.

A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Indicates.

R _a represents any one of the formulas (pI) to (pVI).

Hereinafter, the specific example of the monomer corresponded to the repeating unit represented by general formula (pA) is shown.

The acid-decomposable resin of the present invention may further contain a repeating unit having a group represented by the following general formula (VII).

In general formula (VII), R <_2c> -R <_4c> represents a hydrogen atom or a hydroxyl group each independently. Provided that at least one of R _2c to R _4c represents a hydroxy group.

The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, more preferably a dihydroxy body.

As a repeating unit which has group represented by general formula (VII), the repeating unit represented by the following general formula (AII), etc. can be mentioned.

In General Formula (AII), R _1C represents a hydrogen atom or a methyl group.

R _2c to R _4c each independently represent a hydrogen atom or a hydroxyl group. Provided that at least one of R _2c to R _4c represents a hydroxy group.

Although the specific example of the repeating unit which has a structure represented by general formula (AII) is listed below, it is not limited to these.

The acid-decomposable resin (A) is, in addition to the repeating structural unit, various repeating structural units for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and general necessary characteristics of resolution, heat resistance, sensitivity, and the like. It may contain.

Such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for an acid-decomposable resin, especially

(1) solubility in coating solvents,

(2) film forming property (glass transition point),

(3) alkali developability,

(4) membrane loss (hydrophilic, alkali-soluble group selection),

(5) adhesion to the unexposed portion of the substrate,

(6) dry etching resistance,

Fine adjustment of the back and the like becomes possible.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like And the like.

Specifically, the following monomers can be enumerated.

Acrylates (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group):

Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate t-octyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, 2, 2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimetholpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydro Furfuryl acrylate and the like.

Methacrylates (preferably alkyl methacrylates having 1 to 10 carbon atoms in the alkyl group):

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholpropane mono Methacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides:

Acrylamides and N-alkylacrylamides (as alkyl groups having from 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group And the like), NN-dialkylacrylamides (alkyl groups include those having 1 to 10 carbon atoms, such as methyl, ethyl, butyl, isobutyl, ethylhexyl, and cyclohexyl groups), and N- Hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide and the like.

Methacrylamides:

Methacrylamide, N-alkyl methacrylamides (alkyl groups include those having 1 to 10 carbon atoms, such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl and cyclohexyl groups), N , N-dialkyl methacrylamides (alkyl groups include ethyl group, propyl group and butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like.

Allyl Compounds:

Allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetacetate, allyl lactate, and the like), allyloxyethanol and the like.

Vinyl ethers:

Alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl) Vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl Ethers, etc.).

Vinyl esters:

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chlor acetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetate acetate, vinyl lactate , Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkylitaconates:

Dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like.

Dialkyl esters or monoalkyl esters of fumaric acid:

Dibutyl fumarate and the like.

Others include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile and maleylonitrile.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponded to the said various repeating structural unit, it may be copolymerized.

In the acid-decomposable resin, the content molar ratio of each repeating unit is appropriately set in order to adjust the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, or the resolution, heat resistance, sensitivity, and the like, which are generally necessary capabilities of the resist.

In the acid-decomposable resin of the present invention, the content of the repeating unit having a butyrolactone monomer unit, preferably a group represented by the general formula (II), is preferably 5 to 60 mol% in the total repeating units, more preferably. Is 10-55 mol%, More preferably, it is 15-50 mol%.

In the acid-decomposable resin of the present invention, the content of the repeating unit having a norbornanelactone monomer unit, preferably a group represented by the general formula (V-1) or (V-2) is 5 to 60 moles in the total repeating units. % Is preferable, More preferably, it is 10-50 mol%, More preferably, it is 15-40 mol%.

In the acid-decomposable resin of the present invention, the content of the repeating unit having a cyclohexane lactone monomer unit, preferably a group represented by the general formula (V-3) or (V-4) is 5 to 60 mol in all the repeating units. % Is preferable, More preferably, it is 10-55 mol%, More preferably, it is 15-50 mol%.

In the acid-decomposable resin of the present invention, the content of the repeating unit having an adamantane lactone monomer unit, preferably a group represented by the general formula (I), is preferably 3 to 40 mol% of the total repeating units, more preferably. Is 5 to 35 mol%, more preferably 8 to 30 mol%.

Moreover, as for content of the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by general formula (pI)-(pVI), in acid-decomposable resin, 25-70 mol% is preferable in all the repeating units, More preferably, Is 30 to 65 mol%, more preferably 35 to 60 mol%.

Moreover, although content in resin of the repeating unit based on the monomer of the said other copolymerization component can also be set suitably according to the development of a desired resist, in general, the repeating unit which has the said lactone structure, and the said general formula (pI)-(pVI) It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total moles of the total moles of the total repeating units having an alicyclic hydrocarbon containing an alicyclic hydrocarbon.

In the acid-decomposable resin of the present invention, the content of the repeating unit having a norbornanelactone monomer unit, preferably a group represented by the general formula (V-1) or (V-2) is 3 to 50 mol in all repeating units. % Is preferable, More preferably, it is 5-45 mol%, More preferably, it is 10-40 mol%.

In addition, in the acid-decomposable resin of the present invention, the content of the repeating unit having a cyclohexane lactone monomer unit, preferably a group represented by general formulas (V-3) to (V-4), is in the total repeating units. 3-50 mol% is preferable, More preferably, it is 5-45 mol%, More preferably, it is 10-40 mol%.

In the other acid-decomposable resin of the present invention, the content of the repeating unit having an adamantane lactone monomer unit, preferably a group represented by the general formula (I) is preferably 2 to 30 mol%, more preferably in the total repeating units. Preferably it is 4-25 mol%, More preferably, it is 6-20 mol%.

In the other acid-decomposable resin of the present invention, the content of the structural units of (a1) to (a4) is preferably 5 to 75 mol%, more preferably 9 to 70 mol%, even more preferably in the total repeating units. It is 16-65 mol%.

Moreover, content of the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by general formula (pI)-(pVI) among the acid-decomposable resin in this invention is 25-70 mol% among all the repeating units. It is preferable, More preferably, it is 30-65 mol%, More preferably, it is 35-60 mol%.

Moreover, although content in resin of the repeating unit based on the monomer of the said other copolymerization component in another this invention can also be set suitably according to desired resist performance, generally, the repeating unit which has the said lactone structure, and the said 99 mol% or less is preferable with respect to the total mole number containing the repeating unit which has the partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pVI), More preferably, it is 90 mol% or less, More preferably It is less than 80 mol%.

In the other acid-decomposable resin used in the present invention, the combination selected from the structural units of (a1) to (a4) is preferably a combination of (a1) and (a2), (a1) and (a4) , Combinations of (a2) and (a3), combinations of (a2) and (a4), and combinations of (a3) and (a4), and combinations of (a1) and (a2), (a1) And a combination of (a4), (a2) and (a3), and (a3) and (a4) are more preferable.

Acid-decomposable resins used in the present invention can be synthesized according to conventional methods (eg, radical polymerization). For example, in a general synthesis method, monomer species are injected into the reaction vessel in a batch or during the reaction, and if necessary, a reaction solvent such as ether such as tetrahydrofuran, 1,4-dioxane or diisopropyl ether, methyl Ketones, such as ethyl ketone or methyl isobutyl ketone, ester solvents, such as ethyl acetate, or the composition of this invention, such as propylene glycol monomethyl ether acetate mentioned later, are made to melt | dissolve in the solvent which melt | dissolved, and made uniform, and then, nitrogen, argon, etc. Under the inert gas atmosphere, polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as required. If desired, an initiator is added or divided and added, and after completion of the reaction, it is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The reaction concentration is 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. Reaction temperature is 10-150 degreeC, Preferably it is 30-120 degreeC, More preferably, it is 50-100 degreeC.

The weight average molecular weight of resin which concerns on this invention is polystyrene conversion value by GPC method, Preferably it is 1,000-200,000. If the weight average molecular weight is less than 1,000, it is not preferable because of deterioration of heat resistance or dry etching resistance, and if it exceeds 200,000, developability is deteriorated or the viscosity is very high. .

In the positive resist composition of the present invention, the compounding amount of all the resins in the present invention is preferably 40 to 99.99% by weight, more preferably 50 to 99.97% by weight in the total resist solids.

[2] (B) A compound which generates an acid by irradiation of actinic light or radiation (photoacid generator)

The photoacid generator used in the present invention is a compound that generates an acid by irradiation with actinic light or radiation.

Photoacid generators used in the present invention include photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, micro resists, and the like. Particularly preferred are those compounds which generate an acid by g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and mixtures thereof. .

In addition, other photoacid generators used in the present invention include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, and arsonium salts, organic halogen compounds, and organic metals. Photo-degraded compounds that generate sulfonic acid, such as organic halides, photoacid generators having o-nitrobenzyl-type protecting groups, iminosulfonates, disulfone compounds, diazoketosulphone compounds, diazodisulfone compounds, and the like, are listed. Can be.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by these light in the main chain or side chain of a polymer can be used.

See also V. N. R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetra hedron Lett., (47), 4555 (1971), D. H. R. Barton et al, J. Chem. Soc., (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 and the like can also be used a compound that generates an acid by light.

Among the compounds which decompose by the above-mentioned actinic radiation or radiation to generate an acid, other photoacid generators which are particularly effectively used together will be described below.

(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the following general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds can be enumerated specifically, it is not limited to these.

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

Here, formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group.

Z ^- represents a pair anion such as _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, a pentafluoro- Condensed polynuclear aromatic sulfonic anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes and the like, such as robenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion, may be mentioned, but is not limited thereto.

In addition, two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ , Ar ² may be bonded to each other through a single bond or a substituent.

Although the compound shown below can be mentioned as a specific example, It is not limited to these.

In the above, Ph represents a phenyl group.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and can be synthesized, for example, by the methods described in US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Application Laid-open No. 53-101331.

(3) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is mentioned as a specific example, It is not limited to these.

(4) Diazodisulfone derivatives represented by the following general formula (PAG7).

Here, R represents the aryl group which may have a linear, branched or cyclic alkyl group, or a substituent.

Although the compound shown below is mentioned as a specific example, it is not limited to these.

The addition amount of these photo-acid generators is normally used in 0.01-30 weight% based on solid content in a composition, Preferably it is 0.3-20 weight%, More preferably, it is used in the range of 0.5-10 weight%.

If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity tends to be lowered. If the amount of the photoacid generator is more than 30% by weight, the light absorption of the resist is excessively high, leading to deterioration of the profile and narrow process (especially bake) margins. have.

[3] additives

The positive resist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic base compound, a compound for promoting solubility in a developer, and the like, as necessary.

The positive resist composition of the present invention preferably contains (C) fluorine-based and / or silicone-based surfactants.

The positive resist composition of the present invention preferably contains any one or two or more of fluorine-based surfactants, silicone-based surfactants, and surfactants containing both fluorine and silicon atoms.

When the positive resist composition of the present invention contains the acid-decomposable resin and the surfactant, it is effective when the line width of the pattern is even thinner, and the development defect is further improved.

As these surfactants, for example, Japanese Patent Application Laid-Open No. 62-36663, Patent Publication No. 61-226746, Patent Publication No. 61-226745, Patent Publication No. 62-170950, Patent Publication No. 63-34540, and Patent Publication Korean Patent No. Hei 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, and US Pat. The surfactants described in Nos. 5436098, 5576143, 5294511 and 5824451 can be enumerated, and the following commercially available surfactants can be used as they are.

As commercially available surfactants that can be used, for example, F-Top EF301, EF303, (manufactured by Shin-Aki Takasei Co., Ltd.), Florid FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack F171, F173, F176, F189 , R08 (manufactured by Dainippon Ink, Inc.), Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) And fluorine-based surfactants or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

The compounding quantity of surfactant is 0.001 weight%-2 weight% normally, based on solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%. These surfactants may be added alone, or may be added in any combination.

As surfactants which can be used other than the above, specifically, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxy Polyoxyethylene alkylallyl ethers such as ethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostea Latex, polyoxyethylene sorbitan triolei And nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like.

The compounding quantity of these surfactant is 2 weight part or less normally per 100 weight part of solid content in the composition of this invention, Preferably it is 1 weight part or less.

Preferred (D) organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Especially, a nitrogen containing basic compound is preferable.

Where R²⁵⁰, R²⁵¹And R²⁵²Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R²⁵¹And R²⁵²May combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms)

Further, preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms in different chemical environments in one molecule, and particularly preferably compounds or alkyls containing both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms. A compound having an amino group. Preferred embodiments include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted Piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted 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, hydroxy group, cyano group.

Preferred embodiments of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethyl Aminopyridine, 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) -pyrroli Dean, 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-pyra Lean, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] ound Car-7-ene, 1,4-diazabicyclo [2.2.2] octane, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmol Tertiary morpholine derivatives such as porin, N-benzyl morpholine, cyclohexyl morpholinoethylthiourea (CHMETU), and hindered amines described in Japanese Patent Application Laid-Open No. 11-52575 (for example, those described in the above publication). ), But are not limited to these.

In a particularly preferred embodiment, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabi 3, such as cyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU, etc. Hindered amines, such as a class morpholines and bis (1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, etc. can be mentioned.

Among these, 1, 5- diazabicyclo [4.3.0] nona-5-ene and 1, 8- diazabicyclo [5. 4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl 4-piperidyl) sebacate is preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more thereof. The usage-amount of a nitrogen-containing basic compound is 0.001-10 weight% normally with respect to solid content of the whole composition of the photosensitive resin composition, Preferably it is 0.01-5 weight%. If it is less than 0.001 weight%, the effect of this invention cannot be acquired. On the other hand, when it exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

The positive resist composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. As a solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-meth Oxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), toluene, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methylmethoxypropionate, ethyl Oxypropionate, methylpyruvate, ethylpyruvate, propylpyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone, tetrahydrofuran and the like are preferred, and these solvents alone or in combination Use it.

Among the above, preferred solvents include propylene glycol monomethyl ether acetate, 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, butyl acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, N-methylpyrrolidone, tetrahydrofuran and the like.

Such a positive resist composition of the present invention is applied onto a substrate to form a thin film. As for the film thickness of this coating film, 0.2-1.2 micrometers is preferable.

Inorganic substrates that can be used in the present invention generally include a Bare Si substrate, an SOG substrate, or a substrate having an inorganic antireflection film described below.

In addition, in the present invention, a commercially available inorganic or organic antireflection film can be used.

As the anti-reflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, etc., and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. for film formation. Examples of the organic antireflection film include a condensation product of a diphenylamine derivative described in Japanese Patent Publication No. Hei 7-69611 and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorber, but the maleic anhydride disclosed in US Pat. No. 5,294,680. A reaction product of a copolymer with a diamine-type light absorber, containing a resin binder as described in Japanese Patent Application Laid-Open No. 6-118631 and a methirolmelamine-based thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light absorption as described in Japanese Patent Application Laid-Open No. Hei 6-118656. An acrylic resin antireflection film having a group in the same molecule, consisting of a methirolmelamine and a benzophenone light absorber described in Japanese Patent Application Laid-open No. Hei 8-87115, and a low molecular weight in the polyvinyl alcohol resin described in Japanese Patent Application Laid-open No. Hei 8-179509 The thing which added the light absorber etc. are mentioned.

As the organic anti-reflection coating, DUV-30 series, DUV-40 series, ARC25, AC-2, AC-3, AR19, AR20 from Brewer Science, etc. may be used.

The resist solution is applied to a substrate (e.g., silicon / silicon dioxide coating) on a substrate (e.g., on the substrate on which the anti-reflection film is formed, if necessary) by a suitable coating method such as spinner, coater, etc., for use in the manufacture of precision integrated circuit devices. After that, a good resist pattern can be obtained by exposing through a predetermined mask, baking and developing. The exposure light is preferably light having a wavelength of 150 to 250 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), an X-ray, an electron beam, etc. are mentioned.

As a developing solution, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, primary amines, such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine; Alkaline aqueous solutions, such as alcohol amines, such as dimethylethanolamine and a triethanolamine, quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines, such as a pyrrole and piperidine, can be used.

Moreover, alcohol and surfactant can be added to the alkaline aqueous solution in an appropriate amount.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Synthesis Example (1): Synthesis of Lactone-Based Monomer Copolymer Resin (1-1)

The lactone monomer, 2-methyl-2-adamantyl methacrylate and hydroxyadamantane methacrylate of the present invention were injected at a ratio of 30/50/20, dissolved in methyl ethyl ketone, and the solid content concentration was 22%. 450 g of solution was prepared. 10 mol% of Waco Pure Chemicals V-601 was added to this solution, and it was dripped at 50 g of methyl ethyl ketone heated at 65 degreeC over 6 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized with 5 L of distilled water / isopropyl alcohol = 3/1 mixed solvent, the precipitated white powder was collected by filtration, and the obtained powder was recrystallized with 1 L of methanol to be the target resin. (1-1) was recovered.

The polymer composition ratio determined from NMR was 32/49/19. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 10200.

Resins (1-2) to (1-10) were synthesized in the same manner as in Synthesis Example (1). The composition ratios and molecular weights of the above resins (1-2) to (1-10) are shown below. (Repeat units 1, 2, 3, and 4 are sequentially from the left of the structural formula.)

Suzy Lactone Repeating Unit 1 (mol%) Repeat unit 2 (mol%) Repeat unit 3 (mol%) Repeat unit 4 (mol%) Weight average molecular weight 1-2 36 35 29 - 9600 1-3 36 48 16 - 11100 1-4 20 46 20 14 11300 1-5 22 48 20 10 11900 1-6 30 48 22 - 10800 1-7 20 50 26 4 13100 1-8 20 52 28 - 10300 1-9 30 40 20 10 10700 1-10 14 48 30 8 12600

In addition, the structures of the resins (1-1) to (1-10) are shown below.

Synthesis Example (2) Synthesis of Norbornane lactone monomer copolymer resin (2-1)

The norbornane lactone monomer, 2-methyl-2-adamantyl methacrylate, and dihydroxyadamantane methacrylate of the present invention are injected at a ratio of 35/50/15, and added to 1,4-dioxane. It dissolved and 450g of the solution of 22% of solid content concentration was prepared. 10 mol% of Waco Pure Chemicals V-601 was added to this solution, and it was dripped at 50 g of 1, 4- dioxanes heated at 65 degreeC over 6 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized with 5 L of a mixed solvent of distilled water / isopropyl alcohol = 3/1, and the precipitated white powder was collected by filtration, and the obtained powder was recrystallized with 1 L of methanol to obtain the target resin. (2-1) was recovered.

The polymer composition ratio determined from NMR was 36/48/16. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 11300.

Resins (2-2) to (2-10) were synthesized in the same manner as in Synthesis Example (2). The composition ratios and molecular weights of the above resins (2-2) to (2-10) are shown below. (Repeat units 1, 2, 3, and 4 are sequentially from the left of the structural formula.)

Suzy Norbornane lactone repeat unit 1 (mol%) Repeat unit 2 (mol%) Repeat unit 3 (mol%) Repeat unit 4 (mol%) Weight average molecular weight 2-2 24 50 14 12 12600 2-3 37 45 15 3 13200 2-4 35 51 14 - 13300 2-5 31 49 12 8 12700 2-6 35 51 14 - 13800 2-7 30 42 16 12 13400 2-8 42 50 8 - 12300 2-9 34 48 12 6 13700 2-10 20 52 22 6 12900

In addition, the structures of the resins (2-1) to (2-10) are shown below.

Synthesis Example (3) Synthesis of Cyclohexanelactone Monomer Copolymer Resin (3-1)

The cyclohexane lactone monomer, 2-adamantyl-2-propyl methacrylate, hydroxyadamantane methacrylate, and methacrylic acid of the present invention are injected at a ratio of 25/50/15/10, N, N It was dissolved in dimethylacetamide to prepare 450 g of a solution having a solid content concentration of 22%. 10 mol% of Waco Pure Chemicals V-601 was added to this solution, and it was dripped at 50 g of N, N- dimethylacetamide heated to 70 degreeC over 6 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, crystallized with 5 L of a mixed solvent of distilled water / isopropyl alcohol = 3/1, the precipitated white powder was collected by filtration, and the obtained powder was recrystallized with 1 L of methanol to obtain the target resin. (3-1) was recovered.

The polymer composition ratio determined from NMR was 25/49/16/10. In addition, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 13600.

Resins (3-2) to (3-10) were synthesized in the same manner as in Synthesis Example (3). The composition ratios and molecular weights of the above resins (3-2) to (3-10) are shown below. (Repeat units 1, 2, 3, and 4 are sequentially from the left of the structural formula.)

Suzy Lactone Repeating Unit 1 (mol%) Repeat unit 2 (mol%) Repeat unit 3 (mol%) Repeat unit 4 (mol%) Weight average molecular weight 3-2 32 52 16 - 14100 3-3 34 48 18 - 14400 3-4 22 40 10 28 15300 3-5 38 38 10 14 14700 3-6 20 48 20 12 13900 3-7 35 40 7 18 13400 3-8 28 42 20 10 14900 3-9 25 53 12 10 15700 3-10 24 38 18 20 15900

In addition, the structures of the resins (3-1) to (3-10) are shown below.

Synthesis Example (4) Synthesis of Adamantanelactone monomer copolymer resin (4-1)

The adamantanelactone monomer, 2-adamantyl-2-propyl methacrylate, and hydroxyadamantane methacrylate of the present invention were injected at a ratio of 15/50/35, and then injected into N, N-dimethylacetamide. It dissolved and 450g of the solution of 22% of solid content concentration was prepared. 5 mol% of Wako Pure Chemicals V-60 was added to this solution, and 3 mol% of mercaptopropionic acid 2-ethylhexyl esters were added, and this was heated to 70 degreeC over 6 hours under nitrogen atmosphere, N, N-dimethyl It was dripped at 50 g of acetamide. After completion of the dropwise addition, the reaction solution was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized with 5 L of a mixed solvent of distilled water / isopropyl alcohol = 3/1, and the precipitated white powder was collected by filtration, and the obtained powder was further recrystallized from 1 L of methanol and 1 L of distilled water. To recover the desired resin (4-1).

The polymolecular composition ratio calculated | required from NMR was 14/50/36. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 10900.

Resins (4-2) to (4-7) were synthesized in the same manner as in Synthesis Example (4). The composition ratios and molecular weights of the above resins (4-2) to (4-7) are shown below. (Repeat units 1, 2, 3, and 4 are sequentially from the left of the structural formula.)

Suzy Lactone Repeating Unit 1 (mol%) Repeat unit 2 (mol%) Repeat unit 3 (mol%) Repeat unit 4 (mol%) Weight average molecular weight 4-2 12 54 34 - 14100 4-3 14 44 36 6 14400 4-4 12 50 32 6 15300 4-5 10 55 25 10 14700 4-6 11 54 35 - 13900 4-7 13 45 30 12 13400

In addition, the structures of the resins (4-1) to (4-7) are shown below.

Examples 1 to 24 and Comparative Examples 1 to 4

(Preparation and Evaluation of Positive Resist Composition)

2 g each of the resin mixtures shown in Tables 1 to 4 or the following comparative resins 1 to 4 synthesized in the above Synthesis Examples,

Photoacid generator,

Organic basic compound (amine) (4mg) as needed

Surfactant (10mg), if necessary

, As shown in Table 5, dissolved in an 80/20 mixed solvent of PGMEA / ethyl lactate at a ratio of 14% by weight of solids, respectively, and then filtered through a 0.1 µm microfilter. Examples 1 to 24 and Comparative Examples The positive resist composition of 1-4 was prepared.

Comparative Resin 1 (Resin A4 described in Japanese Patent Application Laid-open No. Hei 10-274852)

Comparative resin 2 (resin (20) described in Japanese Patent Laid-Open No. 2000-109154)

Comparative resin 3 (resin (28) described in Japanese Patent Laid-Open No. 2000-109154)

Comparative Resin 4 (Copolymer 3 of Japanese Patent Application Laid-Open No. 2000-122294)

As surfactant,

W1: Megapack F176 (Dainippon Ink Co., Ltd.)

W2: Megapack R08 (manufactured by Dainippon Ink, Inc.) (Fluorine and Silicon)

W3: polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.)

W4: polyoxyethylene nonylphenyl ether

W5: Troisol S-366 (Trical)

Indicates.

As an amine,

1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN),

2 is bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,

3 is tri-n-octylamine,

4 is hydroxyantipyridine,

5 is antipyrine,

6 is 2,6-diisopropylaniline

Indicates.

Evaluation test

First, DUV-30J manufactured by Brewer Science Co., Ltd. was coated with a spin coater on a silicon wafer for 160 nm and dried, and then the positive resist composition solution obtained thereon was applied with a spin coater and dried at 130 ° C. for 90 seconds. A positive photoresist film of about 0.4 mu m was prepared and exposed to it by an ArF excimer laser (193 nm). The heat treatment after exposure was performed at 120 degreeC for 90 second, it developed in 2.38% of tetramethylammonium hydroxide aqueous solution, it rinsed with midstream water, and the resist pattern profile was obtained.

The resist pattern of the silicon wafer thus obtained was observed with a scanning microscope (SEM), and the resist was evaluated as follows.

[Defocus Latitude (DOF)]: The defocus latitude showed an acceptable width of the mask in the range of ± 10% in the exposure amount for reproducing a pattern of 0.15 mu m in the contact hole pattern.

[Contact Hole Pattern Resolution]: The diameter (μm) of the mask of the resolvable contact hole was shown at an exposure amount that reproduces 0.15 μm.

[SEM Resistance (Shrinkage)]: A 160 nm isolated line pattern was observed with SEM (scanning electron microscope) (accelerated voltage 800V, current value (4.4pA)) manufactured by KLA Tencol, and the line width and initial value after irradiation of the electron beam for 45 seconds. The percentage change in between was measured. The smaller this value is, the better.

Change rate (%) = (line width after irradiation-line width after irradiation) / line width initial value before irradiation x100

These evaluation results are shown in Table 6.

As apparent from the results in Table 6, it can be seen that the positive resist composition of the present invention is excellent in contact hole pattern resolution and SEM resistance, and the defocus latitude is also improved.

Synthesis Example (5) Synthesis of Resin (5-1)

Two lactone monomers (butyrolactone monomer and norbornane lactone monomer) and 2-methyl-2-adamantyl methacrylate of the present invention are injected at a ratio of 20/30/50, and dissolved in 1.4-dioxane. Then, 450 g of a solution having a solid content concentration of 22% was prepared. 10 mol% of Waco Pure Chemicals V-601 was added to this solution, and it was dripped at 50 g of 1, 4- dioxanes heated at 75 degreeC over 6 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized with 5 L of a mixed solvent of distilled water / isopropyl alcohol = 3/1, and the precipitated white powder was collected by filtration, and the obtained powder was recrystallized with 1 L of methanol to obtain the target resin. (5-1) was recovered.

The polymer composition ratio determined from NMR was 22/29/49. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 11400.

Resins (5-2) to (5-13) were synthesized in the same manner as in Synthesis Example (5-1).

The composition ratios and molecular weights of the above resins (5-2) to (5-13) are shown below. (Repeat units 1, 2, 3, and 4 are sequentially from the left of the structural formula.)

Suzy Lactone Repeating Unit 1 (mol%) Lactone Repeating Unit 2 (mol%) Repeat unit 3 (mol%) Repeat unit 4 (mol%) Weight average molecular weight 5-2 23 30 47 - 10800 5-3 24 20 36 20 9700 5-4 10 42 40 8 11300 5-5 30 9 51 10 11600 5-6 6 32 47 15 9200 5-7 16 8 42 34 9300 5-8 35 10 52 3 11300 5-9 29 8 50 13 11800 5-10 12 11 48 29 10300 5-11 30 11 49 10 12600 5-12 24 12 50 14 12300 5-13 27 13 48 12 11900

In addition, the structures of the resins (5-1) to (5-13) are shown below.

Examples 25-37 and Comparative Examples 5-8

(Preparation and Evaluation of Positive Resist Composition)

2 g of resin shown in Table 7 synthesized in Synthesis Example,

Photoacid generator,

Organic basic compound (amine) (4mg) as needed

Surfactant (10mg), if necessary

, As shown in Table 8, dissolved in a mixed solvent of PGMEA / ethyl lactate 70/30 at a solid content of 14% by weight, and then filtered through a 0.1 µm microfilter. Examples 25 to 37 and Comparative Example 5 The positive resist composition of -8 was prepared.

Comparative resins 1 to 4 used in Comparative Examples 5 to 8 are the same as Comparative resins 1 to 4 used in Comparative Examples 1 to 4, respectively, and surfactants W1 to W5 and amines 1 to 6 which are basic compounds are also examples. It is the same as the surfactants W1 to W5 and the amines 1 to 6 used for 1 to 24.

Evaluation test

First, AR19 produced by Brewer Science Co., Ltd. was coated on a silicon wafer by using a spin coater at 82 nm and dried, and then the positive resist composition solution obtained thereon was applied using a spin coater and dried at 130 ° C. for 90 seconds to obtain about 0.4 A micrometer positive photoresist film was produced and exposed to it by an ArF excimer laser (193 nm). The heat treatment after exposure was performed at 120 degreeC for 90 second, it developed in 2.38% of tetramethylammonium hydroxide aqueous solution, it rinsed with midstream water, and the resist pattern profile was obtained.

The resist pattern of the silicon wafer thus obtained was observed with a scanning microscope (SEM), and the resist was evaluated as follows.

[Defocus Latitude (DOF)]: The defocus latitude showed an acceptable width of the mask in the range of ± 10% in the exposure amount for reproducing a pattern of 0.15 mu m in the contact hole pattern.

[Contact Hole Pattern Resolution]: The diameter (μm) of the mask of the resolvable contact hole was shown at an exposure amount that reproduces 0.15 μm.

[SEM Resistance (Shrinkage)]: The isolation line pattern of 140 nm was observed with SEM (scanning electron microscope) (accelerated voltage 800V, current value (4.4pA)) manufactured by KLA Tencol, and the line width and initial value after irradiation of the electron beam for 45 seconds. The percentage change in between was measured. The smaller this value is, the better.

Change rate (%) = (line width after irradiation-line width after irradiation) / line width initial value before irradiation x100

Table 9 shows the results of these evaluations.

As is apparent from the results in Table 9, it can be seen that the positive resist composition of the present invention is excellent in contact hole pattern shape force and SEM resistance, and the defocus latitude is also improved.

The positive resist composition of the present invention is suitable for far ultraviolet light, especially ArF excimer laser light having a wavelength of 193 nm, excellent contact hole pattern resolution and SEM resistance, and improved defocus latitude.

Therefore, it is preferably used for lithography using far ultraviolet rays which is based on ArF excimer laser exposure.

Claims (12)

(A) (a1) butyrolactone, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones. Two or more kinds of resins having an increased dissolution rate in alkaline developing solution, and (B) The positive resist composition containing the compound which generate | occur | produces an acid by irradiation of actinic light or radiation, WHEREIN: The mixture of said resin (A) contains 2 or more types of the monomer units of said (a1)-(a4). A positive resist composition, characterized in that. The positive resist composition according to claim 1, wherein the butyrolactone monomer unit of (a1) is a repeating unit represented by the following general formula (II) in the resin of (A). (In General Formula (II), R ₁ represents a hydrogen atom or a methyl group. W represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group and an ester group. Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.) The positive electrode according to claim 1, wherein in the resin of (A), the norbornanelactone monomer unit of (a2) is a repeating unit having a group represented by the following general formula (V-1) or (V-2). Resist composition. (In General Formulas (V-1) to (V-2), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.) The positive electrode according to claim 1, wherein the cyclohexanelactone monomer unit of (a3) in the resin of (A) is a repeating unit having a group represented by the following general formula (V-3) or (V-4). Resist composition. (In General Formulas (V-3) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.) The positive resist composition according to claim 1, wherein the adamantane lactone monomer unit of (a4) is a repeating unit represented by the following general formula (I) in the resin of (A). (In Formula (I), A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or an ester group selected from the group consisting of two or more groups. R is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.) The resin of any one of Claims 1-5 is chosen from the repeating unit which has the partial structure containing alicyclic hydrocarbon represented by the following general formula (pI)-general formula (pVI). The positive resist composition further containing 1 or more types. (Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms) Indicates. R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group; Indicates. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group. R ₂₂ to R ₂₅ each independently represent a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.) (A) (a1) butyrolactones, (a2) norbornane lactones, (a3) cyclohexane lactones, and (a4) adamantane lactones, which have two or more monomers selected as structural units, A resin in which the dissolution rate for an alkaline developer increases due to the action, and (B) A positive resist composition containing a compound that generates an acid by irradiation with actinic light or radiation. The positive resist composition according to claim 7, wherein in the resin (A), (a1) is a repeating unit represented by the following general formula (II). (In General Formula (II), R ₁ represents a hydrogen atom or a methyl group. W represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group and an ester group. Ra, Rb, Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.) The positive resist composition according to claim 7, wherein in the resin of (A), (a2) is a repeating unit having a group represented by the following general formula (V-1) or (V-2). (In General Formulas (V-1) to (V-2), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.) The positive resist composition according to claim 7, wherein in the resin of (A), (a3) is a repeating unit having a group represented by the following general formula (V-3) or (V-4). (In General Formulas (V-3) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, or an alkenyl group. In R _1b to R _5b Two may combine to form a ring.) The positive resist composition according to claim 7, wherein in the resin of (A), (a4) is a repeating unit represented by the following general formula (I). (In Formula (I), A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or an ester group selected from the group consisting of two or more groups. R is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.) The resin of any one of Claims 7-11 is chosen from the repeating unit which has the partial structure containing alicyclic hydrocarbon represented by the following general formula (pI)-general formula (pVI). The positive resist composition further containing 1 or more types. (Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms) Indicates. R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group; Indicates. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group. R ₂₂ to R ₂₅ each independently represent a C 1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.)