TW200839448A - Positive photoresist composition for liquid immersion lithography and method of forming resist pattern - Google Patents

Abstract

A positive photoresist composition for liquid immersion lithography, which enables the formation of a resist film having a highly hydrophobic surface and good lithography characteristics, and a method of forming a resist pattern are provided. The positive photoresist composition for liquid immersion lithography has a resin component (A) which increases its alkali solubility by an action of an acid, an acid releasing component (B) by an exposure, and a resin component (C) which has a fluorine atom and does not have an acid dissociable group, and the resin component (A) comprises a resin (A1) which has a structural unit (a) derived from an acrylic acid and has no fluorine atoms, and the resin component (C) contains a non-cyclic group-containing main chain resin (C1) and a cyclic group-containing main chain resin (C2).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type photoresist composition for use in a liquid immersion exposure process and a method for forming a photoresist pattern.

The present invention claims priority on the basis of Japanese Patent Application No. 2006-331780, filed on Dec. [Prior Art] In the lithography technique, a photoresist film obtained by a photoresist material is generally formed on a substrate, and a light mask formed by a specific pattern is formed on the photoresist film by light, electron lines, or the like. The selective exposure of the radiation is carried out by applying a development treatment to form the photoresist film into a specific shape of the photoresist pattern. With the miniaturization of semiconductor devices, the short wavelength of the exposure light source and the high number of openings (high NA) of the projection lens have been developed, and NA = 0.84 with an ArF excimer laser as a light source having a wavelength of 193 nm has been developed. Exposure machine. Along with the short wavelength of the exposure light source, the photoresist material has sought to have a sensitivity to the exposure light source, and it is possible to reproduce the lithographic etching characteristics such as the resolution of the fine size pattern. A photoresist material which satisfies this requirement is generally a base resin which contains a change in alkali solubility via an action of an acid, and an enhanced chemical type photoresist which generates an acid generator based on exposure -5-200839448

At present, the base resin of the enhanced chemical type resist used in the ArF excimer laser lithography etching, for example, has excellent transparency in the vicinity of 193 nm, and generally uses a main chain having (meth)acrylic acid. A resin (acrylic resin) or the like of a structural unit derived from an ester. Here, "(meth)acrylic acid" means one or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position. The "acrylic acid ester" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position. "(Meth)acrylate" means either an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position or both. One of the methods for lifting the analytic upwards, for example, a lithography method in which an exposure (immersion exposure) is performed under a liquid (immersion medium) having a refractive index higher than air between a pair of lenses and a sample of an exposure machine. That is, it is generally called liquid immersion lithography (hereinafter, also referred to as immersion exposure) (for example, Non-Patent Document 1). When using immersion exposure, it is known that even if a light source of the same exposure wavelength is used, it can achieve the same high resolution as in the case of using a light source of a shorter wavelength or a case of using a high NA lens, and further, it does not Reduce the focus depth of field. Further, the immersion exposure can be carried out using an existing exposure apparatus. Therefore, the immersion exposure is presumably at a low cost, and the formation of a high-resolution, and excellent focus depth of field of the photoresist pattern 'in the manufacture of semiconductor components requiring a large amount of investment equipment' is expensive, or From the point of view of the lithography characteristics such as the resolution degree, there are considerable concerns about how much the semi-conductor can be provided. The immersion exposure is effective in the formation of the pattern shape, and it can also be combined with super-analytical techniques such as the phase shift method and the deformation illumination method which are currently studied. At present, the immersion exposure technique is mainly active in the study of the use of ArF quasi-molecular lasers as a light source. Also, at present, the infiltration medium is mainly for the study of water.

In recent years, various fluorine-containing compounds have been developed in various technical fields, starting from characteristics such as water repellency and transparency. For example, in the field of photoresist materials, in the base resin which is a positive type of enhanced chemical type photoresist, it has been studied in a fluorine-containing polymer compound, and a methoxymethyl group, a tert-butyl group, a tert-butyl group are introduced. An acid labile group such as an oxocarbonyl group. However, when the fluorine-based polymer compound is used as a base resin of a positive-type photoresist composition, many gaseous pollutants (Out-gas) are formed after exposure, or resistance to dry etching gas (etching resistance) is not Full of shortcomings. Recently, a fluorine-containing polymer φ compound having excellent etching resistance, that is, a fluorine-containing polymer compound containing an acid-labile group having a cyclic hydrocarbon group has been proposed (for example, Non-Patent Document 2). [Non-Patent Document 1] Proceedings of SPIE), Vol. 5754, pp. 119-128 (2 005) [Non-Patent Document 2] Proceedings of SPIE-The International Society for Optical Engineering (2002), 4690, 7 6- 83. SUMMARY OF THE INVENTION In the immersion exposure, in addition to the usual lithographic etching characteristics (sensitivity, solution 200839448, etch resistance, etc.), a photoresist material having characteristics compatible with the immersion exposure technique is sought. Specifically, in the case where the immersion medium is water, as described in Non-Patent Document 1, in the case of immersion exposure using a scanning type immersion type exposure machine, it is sought to move the immersion medium following the movement of the lens. Water followability. The lower the water followability, the lower the exposure speed, and there are doubts that affect productivity.

Moreover, when the immersion exposure is performed, since the photoresist film or the lens is in contact with the immersion medium, the substance contained in the photoresist is dissolved in the immersion medium, and it is presumed that the photoresist film is deteriorated and the performance is lowered, and the dissolved material is The refractive index of the immersion medium is locally changed, and the dissolved material contaminates the surface of the lens and the like, which has a very bad influence on the lithographic etching characteristics. That is, it is inferred that the sensitivity is deteriorated, and the resulting photoresist pattern forms a T-coronal shape. The photoresist pattern causes problems such as surface roughness or swelling. The water follow-up property is presumed to improve the hydrophobicity of the photoresist film, but on the other hand, when the photoresist film is only hydrophobized, the lithographic etching property may be adversely affected, for example, it may cause structuring or The sensitivity is lowered, and a large amount of scum tends to occur. Therefore, in the immersion exposure, development of materials having moderate hydrophobicity is an extremely important issue. However, there is almost no understanding of materials that have the characteristics of lithography and immersion exposure. The present invention is based on the above-mentioned circumstances, and proposes a positive-type photoresist for immersion exposure which can form a light-proof layer having a high hydrophobicity on the surface and having good lithography characteristics. The method of forming the object and the photoresist pattern. A first embodiment of the present invention which solves the above problems is 'a positive-type photoresist composition for immersion exposure' which is a resin component (A) which contains an alkali solubility via an action of an acid and is based on exposure Producing sour acid

a green component (B), and a resin component (C) containing a fluorine atom and having no acid dissociable group, wherein the resin component (A) contains a structural unit (a) derived from acrylic acid, and The resin (A 1 ) containing a fluorine atom, and the resin component (C) is a resin (C1) containing a non-back-chain cyclic type and a resin (C2) having a cyclic chain type. Further, a second embodiment of the present invention is a method for forming a photoresist pattern, which comprises forming a light on a support using a positive resist composition of the first embodiment of the present invention. a step of resisting the film, a step of immersing the photoresist film by immersion, and a step of developing the photoresist film to form a photoresist pattern. In the specification and the patent application, "alkyl" is a linear, branched, and cyclic monovalent saturated hydrocarbon group unless otherwise specified. The "lower alkyl group" is an alkyl group having 1 to 5 carbon atoms. The "halogenated lower alkyl group" is a halogenated alkyl group having 1 to 5 carbon atoms. The "extension base" is a divalent saturated hydrocarbon group containing a linear chain, a branched chain, and a ring, unless otherwise specified. "Structural unit" means the monomer unit (m ο η 〇 m e r ) constituting a polymer compound (polymer, copolymer). "Exposure" is a tribute to the full illumination of radiation.

200839448 The present invention provides a method for forming an immersion type positive image and a photoresist pattern which can form a photoresist film having excellent fine lithographic etching characteristics on a film surface. Hereinafter, the present invention will be described in detail. <<Positive Photoresist Composition for Wetting Exposure>> The positive-type photoresist composition for immersion exposure of the present invention is a resin component (A) (hereinafter referred to as A) which increases alkali solubility, and is based on exposure The acid generating agent component is also referred to as (B) component, and the resin component (C) (hereinafter also referred to as (C) component) containing a fluorine atom and having no base. In the positive resist composition, the component (A) is insoluble in solubility, and when acid is generated in the component (B) by exposure, the alkali solubility of the component (A) is increased. Therefore, in the photoresist pattern, when the photoresist is obtained by using the photoresist film obtained by using the positive-type photoresist composition, the exposed portion can be converted into alkali-soluble, and the alkali-insoluble property is not changed. The result of alkali development is obstructive. [Resin (A1)] The resin component (A) is a resin (A1). Resin (a structural unit derived from acrylic acid (a), and does not contain a fluoroester. As long as it belongs to the above-mentioned substance, the resin (A1) is not specifically used. One or two or more of them are proposed as water absorbing, and The composition of the photoresist is also defined by the acid (also referred to as (B) (the selective exposure portion in the formation of the acid dissociable photo-presence is still capable of forming light A1). Type -10-

200839448 Resin for base resin for positive resist. [Structural unit (a)] In the resin (A1), the structural unit derived from acrylic acid (a contains a fluorine atom. In the specification and the patent application, "the structural unit of acrylic acid" means the ethylenic double bond of acrylic acid. The meaning of the structural unit that is cracked. Further, "acrylic acid" is a concept of a derivative containing a narrow meaning of CH2-CHCOOH, and a part or all of its hydrogen atom is replaced by a radical or an atom. The derivative of acrylic acid, for example, an α-position in which the α-position of the acrylic acid in a narrow sense is bonded by an α (atom or a group other than a hydrogen atom), an ester in which a hydrogen atom of a carboxyl group of the acrylic acid is substituted by an organic group, or the like. The "organic group" means a group containing a carbon atom, and the acrylate group is not particularly limited, and for example, it may be an ester group bonded to an acrylate in a structural unit such as a structural unit (al) described later. An acid dissociable dissolution inhibiting group, a lactone-containing cyclic group, a polar aliphatic hydrocarbon group, a polycyclic aliphatic hydrocarbon group, or the like). Each structure list 〜(a4) is one of the structural units (a). The position of the acrylic acid (the carbon atom in the α-position) is not particularly limited to the position of the carbon atom bonded to the carbonyl group. a substituent substituted with an α-substituted succinic acid, such as a lower-grade ketone group (but not containing a fluorinated lower alkyl group in the structural unit (a)), etc., which is not derived from the olefinic acid (other carbon atoms) Acrylic acrylic acid ~ (a 4 chain-based lipid position (al lower, is a lower-grade institute-11 - 200839448 structural unit (a), the lower alkyl group of the substituent at the alpha position, its specific content, for example, Lower linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. A halogenated lower alkyl group having a substituent at the α-position, for example, a part or all of a hydrogen atom in the lower alkyl group is substituted with a halogen atom other than a fluorine atom, for example, a chlorine atom, a bromine atom, an iodine atom or the like. .

In the structural unit (a), it is bonded to the alpha position of acrylic acid, preferably a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (but not a fluorinated lower alkyl group), and a hydrogen atom or a lower alkyl group. More preferably, it is preferable to use a hydrogen atom or a methyl group from the viewpoint of easy industrial availability. The structural unit (a) has a more specific content such as a structural unit represented by the following general formula (a).

Wherein R is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (but does not contain a fluorinated lower alkyl group), and X is a hydrogen atom or a lower alkyl group having no fluorine atom; The halogenated lower alkyl group (but not including the fluorinated lower alkyl group) is, for example, the same as the lower mercapto group or the lower alkyl group (but not the fluorinated lower alkyl group) in the above-mentioned substituent at the α position. -12- 200839448 The organic group of hydrazine is, for example, the same as the above-mentioned "organic group in acrylate". In the resin (A1), the ratio of the structural unit (a) to the total structural unit constituting the resin (A1) is preferably from 50 to 100 mol%, more preferably from 70 to 100 mol%. . In particular, when the effect of the present invention is particularly excellent, the resin (A 1 ) is preferably formed of a structural unit (a) derived only from acrylic acid.

Here, "formed only by the structural unit (a)" means that the main chain of the resin (A1) is composed only of the structural unit (a), and does not contain other structural units. • Structural unit (a 1 ) In the present invention, the resin (A1) is preferably a structural unit (a 1 ) derived from an acrylate having no fluorine atom and containing an acid dissociable dissolution inhibiting group. In the specification and the scope of the patent application, "the structural unit derived from acrylate" means the structural unit constituted by the cleavage of the ethylenic double bond of the acrylate. The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) may have the alkali-insoluble alkali dissolution inhibiting property of the entire resin (A 1 ) before dissociation, and the entire resin (A 1 ) may be changed after dissociation. In the case of an alkali-soluble substance, it is proposed to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for enhancing chemical resist. The acid dissociable dissolution inhibiting group, in general, is a group capable of forming a cyclic-13-200839448 or a chain tertiary alkyl ester with a carboxyl group in (meth)acrylic acid or the like; widely known For example, an acetal type acid dissociable dissolution inhibiting group such as an alkoxyalkyl group. Further, "(meth) acrylate" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methyl acrylate bonded to a methyl group.

Wherein the "trialkyl ester", for example, a hydrogen atom of a carboxyl group is substituted by a chain or a cycloalkyl group to form an ester, and an oxygen atom at the terminal of the carbonyloxy group (-C(◦)-0-) is bonded. The structure of a tertiary carbon atom such as the aforementioned alkyl group or cycloalkyl group. In the tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom is cleaved by the action of an acid. Further, the aforementioned base or ring base may have a substituent. In the following, the group having an acid dissociation property composed of a carboxyl group and a tertiary alkyl ester is referred to simply as a "triester alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group is, for example, an aliphatic branched chain acid dissociable dissolution inhibiting group, an aliphatic dissociable melting inhibiting group containing an aliphatic cyclic group, and the like. In the specification and the description of the present application, "aliphatic" means the relative entanglement of aromatics, and is not intended to be an aromatic group or a compound. The "aliphatic branched chain" means a branched chain structure which does not have aromaticity. The structure of the "aliphatic branched chain acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and generally it is preferably saturated. -14- 200839448 An aliphatic branched chain acid dissociable dissolution inhibiting group, preferably a C 3 to 8 tertiary alkyl group, specifically, for example, tert-butyl, tert-pentyl, tert-heptyl, etc. . The "aliphatic cyclic group" means a monocyclic group or a polycyclic group which does not have an aromatic group. The number of carbon atoms of the above "aliphatic cyclic group" is preferably 4 to 20.

The aliphatic cyclic group in the structural unit (a 1 ) may have a substituent or may not have a substituent. The substituent is, for example, a lower alkyl group having 1 to 5 carbon atoms, a halogen atom other than a fluorine atom, a halogenated lower alkyl group having 1 to 5 carbon atoms substituted by a halogen atom other than a fluorine atom, or an oxygen atom (=Ο). The "aliphatic cyclic group" removes the basic ring structure of the substituent, and does not limit the group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. The "hydrocarbyl group" can be either saturated or unsaturated, and it is generally preferred to saturate. The "aliphatic ring group" is preferably a polycyclic group. Specific examples of the aliphatic cyclic group, for example, a monocyclic alkane which may be substituted by a lower alkyl group, a halogen atom other than a fluorine atom or a halogenated alkyl group (but not containing a fluorinated alkyl group), or may be unsubstituted, A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, it is removed by a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, norbornane, isopentane, tricyclodecane or tetracyclododecane. The base temple obtained from more than one chlorine atom. Further, the acid dissociable dissolution inhibiting group containing an aliphatic cyclic group is, for example, a group having a tertiary carbon atom on a ring skeleton of a cyclic alkyl group, and the like, specifically, for example, 2-methyl-adamantyl group, Or 2-ethyladamantyl and the like. Or -15-200839448 A structural unit represented by the following formula (a 1") has a fat such as an adamantyl group bonded to a group of an oxygen atom of a carbonyloxy group (·C ( Ο )-〇_) a cyclic group, and a group of a branched alkyl group having a tertiary carbon atom bonded thereto

[In the formula, R is the same as described above; R15 and R16 are alkyl groups (may be linear or branched, preferably 1 to 5 carbon atoms)]

The "acetal type acid dissociable dissolution inhibiting group" is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group. Therefore, when an acid is generated by exposure, the bond between the awake type acid dissociable dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable dissolution inhibiting group is bonded is cut off based on the action of the acid. The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (Ρ 1 ). -16- 200839448 [p. 3] (p 1) c_〇^ch2)_y R2# [wherein, 1^', 2' are each independently a hydrogen atom or a lower alkyl group, and n is an integer from 0 to 3. γ is a lower alkyl group or an aliphatic cyclic group]

In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 〇. The lower alkyl group of RP or R2' is, for example, the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferable. In the present invention, it is preferred that at least one of R1' and :^2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (p 1 ) is preferably a group represented by the following formula (p 1 -1 ).

[In the formula, R1', η, and Y are the same as described above. The lower alkyl group of hydrazine is, for example, the same as the lower alkyl group of the above R. The aliphatic cyclic group of hydrazine can be appropriately selected and used, for example, from a monocyclic or polycyclic aliphatic cyclic group which has been proposed many times in A.rF photoresist or the like, and is, for example, the above-mentioned "fat". The family ring base is the same content. -17- 200839448 Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (p2). 〔化5〕 〇17 —C—Ό—R19 R18 · _ · · (p2)

[wherein, R17 and R18 are each independently a linear or branched alkyl group or a hydrogen atom, and R19 is a linear, branched or cyclic alkyl group, or R17 and R19 are each independently a linear chain. a chain or branched chain extending alkyl group, and the terminal of R17 and the terminal of R19 may be bonded to form a ring. In R17 and R18, the alkyl group preferably has a carbon number of 1 to 15, which may be a linear chain or a branched chain. Either ethyl or methyl groups are preferred, and methyl groups are most preferred. In particular, either R17 or R18 is a hydrogen atom, and the other is preferably a methyl group. When R19 is a linear, branched or cyclic alkyl group, it is preferably a carbon number of 1 to 15, and it may be any of a linear chain, a branched chain or a ring. When R19 is a linear or branched chain, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably ethyl. When R19 is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 1 carbon atoms. Specifically, it may be substituted by a halogenated alkyl group other than a fluorine atom (but not a fluorinated alkyl group), or an unsubstituted monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracyclic ring. Alkane, etc.-18-

200839448 Remove more than one hydrogen atom base in a multi-ring chain. Specifically, a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, norbornane, tricyclodecane or tetracyclododecane is removed from the group of 1 atom. Among them, it is preferred to remove one or more hydrogen atoms with adamantane. Further, in the above formula, the terminal of each of R17 and R19 independently a linear alkyl group (preferably, an alkylene group having 1 to 5 carbon atoms) may be bonded to the terminal of R17. At this time, R17 and R19, and an oxygen atom bonded to R19, form a cyclic group with a carbon atom bonded to R17. The ring-type 7-member ring is preferred, and a 4- to 6-member ring is preferred. The cyclic group is, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group or the like. The structural unit (al) is preferably one or more selected from the structural units represented by the following formula (al-0-l structural unit and the following formula (al-〇_2). [Chemical 6] In other words, for example, a chain or a fraction obtained by using a hydrogen atom or more, and R19 and the oxygen source are selected from the group shown by 4 to a specific example,

(wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl fluoride-containing lower alkyl group; and X1 is an acid dissociation group having a carbon number of 4 to 20) (but not an insoluble dissolution -19-200839448 [ 7]

(wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group (but no fluorinated lower alkyl group); X2 is an acid dissociable dissolution inhibiting group; Y2 is an alkylene group or an aliphatic cyclic group) In the formula (al-0-1), the lower alkyl group or the halogenated lower alkyl group of R is the same as the lower alkyl group which may be bonded to the α-position of the acrylate as the halogenated lower alkyl group. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and φ can be, for example, the above-mentioned tertiary alkyl ester type acid dissociable dissolution inhibiting group or acetal type acid dissociating dissolution inhibiting group, and has three stages. The alkyl ester type acid dissociable dissolution inhibiting group is preferred. In the formula (al-0-2), the R system is the same as the above. X2 is the same as X1 in the formula (al-0-l). Y2 is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group. In the case of the aliphatic cyclic group, the same as the above-mentioned "aliphatic cyclic group" can be used, for example, in addition to the group in which two or more hydrogen atoms are removed. -20- 200839448 In the structural unit (al), more specifically, for example, a structural unit represented by the following general formulae (a 1 -1 ) to (a 1 - 4 ).

[In the above formula, X ' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; Y is a lower-grade or lower aliphatic group having a carbon number of 1 to 5; η is an integer of 0 to 3; m It is 0 or 1; R is the same as the above; Ri', r2' are each independently a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. Among the above R1' and R2', at least one of them is a hydrogen atom. More preferably, it is a hydrogen atom at the same time. n is preferably 〇 or 1. The content of X ' is the same as that of the tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X1. -21 - 200839448

The aliphatic cyclic group of γ is, for example, the same as that exemplified in the description of the above "aliphatic cyclic group". The following are specific examples of structural units represented by the above formulas (al-l) to (al-4), -22-200839448 [Chemical 9

• CH?·Cl ch3 ch3,2JH^~ &quot;fCH2_p Seven H2—?+ 0 0 o f2Hs 〇==A〇 ?H2(CH2)2CH3

(al-1-3) (at-1-4) ch3

CH3 (a1-1~6) (CH2)3CH3

(at-1-8)

(al-1-9) (a1-1-7)

Cal-1-10)

(aH-16) -23 - 200839448

(a1-1-17) (al-1-18)

Ten CH2 is like a ten H2 〇=% ch3 〇=\ ch3 0=\(

(a1-1-2t) CH3

-CH2~CHj, 〇, )- c2h5

(al-t-22) (a1-l-23) (at-t-24) ten h2-4 -^ch2~ch}-ten h2〒 〇J ch3 €H3 〇4 CHaPHa 〇={. 6 (al +27)

CH2—CH-O

CH3 ch3 (at-1-25)

CH3 (at-1-26)

ch3fCH2jt CH 〇=\ ch3/CH3 a pHa (a1-1-28) ch3

(a1-t-29) -^CH2—c-^- —^CH2—〒叶乂. 142—〒+ 0=1 CH3 0===\ 〇=\ C2H5b b (at-t-30) (a1-1-31) (a1+32) -24- 200839448

卞 η2-(^ 十 Ch2-A 十 0=\ QH3 〇=\ c

Os

(al-t-34) (a1-Bu 35)-|ch2 - —(ch2-ch} 0=\ C2H5 0==^ n (al-1-36)

Ov -(ch2-ch^ °=\ QHa〇,

(a1-t-39) (a1-1-40) (al+38)

^H3 •CH2—(f+ -^ch2—(fj- -^ch2—〇, CH3 η3(Τ c2h5 o ch3 C2H5 (al-1-42) (a 卜卜43) (at-t-44) (at -t-45)

-25- 200839448 [Chem. 1 2]

-26- 200839448 〔化1 4〕 ch5 ^ch2-c·)- ο (at-2-22)

;O (a1-2-24)

-^ch2--ch)- ch3 -(cHa-仔o=\ 0,

0_ (a1-2-23)

(a1-2-34&gt; (a1-2-35) [Chem. 1 5]

-27- 200839448 〔化1 6〕 ?h3 ch3

^CH2-C^ -^CH2-C-jP -^CH2-CH^0 P Q P •ch2-ch-

o

o

o

0: P

o

(al-3-10) (al-3-1t) (al-3-12) -28- 200839448 [化1 7] ch3 ch3 -^ch2-c-^ 十ch2^^ -^ch2-ch| - ^-ch2-ch}· &quot;〇c) 0 0

o

H3c o

H3cfe C2h5fe

O

(a1-3-13) (a1-3-14) (a1-3*Ί5) (at~3&quot;*16)

O h3c o

o

o

C2H5 o

o C2n5^l I H3°

(a1-3-17) (a1-3-18) (a1-3-19) (al-3-20) CH3 ?h3-^CH2-C^ 十CH2-? 十弋(7)2 〇〇叶〇〇p P p

H3c

Q

O

C2H5

〇 Q

O

O c2h5-t \ h3c

o 〇

(a1-3-21) (a1-3-22) (al-3-23) (a1-3-24) -29- 200839448 turn 18 ch3 &quot;fCH2qH Bu 十十十 CH2^f

Ο Ο Ο

Ο ο

ο } ο ο

ο ο ;ο (al-4-t) (at-4-2) (a 卜 4-3) (al-4-4) (al-4-5> ch3 ten CH2j 吟 ten ten ch2—?h) — ch3. Gas. ~. People ten H0+ Bu

Q d /〇

o o

o o ) to

o (al-4-6)

o X) Ό (al+7) (al^8) (at-4-9) (a1-4-t0) t times + and ten T4H~H bearing -" float P P 0 gas 〇 °&gt;

(a1_4-11) (a1-4-12)

(at-4-13) (at-4-14) (al-4 -15) -30- 200839448 (19)

O

0 &gt;=0 Q Q

O家 O &gt;:〇〇v q 0

(a1-4-16) (a1-4-17) (al-4-18) (a1-4-19) Ca1 4-20)

O ^=0 o o

o

o 0, o&quot;

o °; 0 o 〇&gt;

今b i0 ώ (at 4 21) (at-4-22) (a1-4-23) (at-4-24) (a1-4-25)-(CH2^CH^ -(CH2-C^ &quot ;fCH2^CHf -^CH2-C^ ^CH^H}&quot; JD 〇0 〇〇/&gt;

O )=〇 )=〇 Production 〇 o 〇v 〇 q

o o ) o b °b °ύ (a1 -4-26) (al-4-27) (a1-4-28) (at -4-29) (at-4-30)

0 -31 -

200839448 Structural unit (a 1 ), which can be used alone or in combination. The structural unit (al ), which is represented by the formula (al-l), is a formula (al-1-Ol) containing structural units of the formula (a1-1·1) to (al-1-4) The structural unit shown, or the unit of the following formula (al-1-02) containing the structural unit of the formula (al-1-(al-1-41) is preferred. Among them, the formula (al-l) -01) The structure shown is more preferable, specifically, at least one selected from the formula (al-1-1) to (al-l-4 structural unit is the most preferable. For the following, pass 35) to the unit shown in the figure)

• · · (a1 - 1 - 01) (wherein R has the same content as above, and R1 1 is a lower alkyl group

-32- 200839448 (wherein R has the same content as described above, R12 is a lower alkyl group, and h is an integer of 1 to 3). In the formula (al-1-O1), R is the same as described above. The lower alkyl group of R11 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. In the formula (al-1-02), R is the same as described above. The lower alkyl group of R 1 2 is the same as the lower alkyl group represented by R

Further, methyl or ethyl is preferred, and ethyl is preferred. h is preferably 1 or 2, and 2 is the best. In the resin (A1), the ratio of the structural unit (al) is preferably from 10 to 80 mol%, more preferably from 20 to 70 mol%, based on the total of the structural units constituting the resin (A1). 25 to 50 mol% is the best. When it is more than the lower limit 値, the pattern can be easily formed when it is a photoresist composition, and when it is below the upper limit 値, it can be balanced with other structural units. • Structural unit (a2) The resin (A1), in addition to the structural unit (al), is preferably a structural unit (a2) derived from an acrylate having no fluorine atom and a cyclic group containing a lactone. Here, the lactone-containing cyclic group is a cyclic group containing one ring (lactone ring) of the -O-C(O)- structure. The lactone ring is counted as a ring unit, and the monocyclic group is only a lactone ring. If the ruthenium has other ring structures, it is called a polycyclic group regardless of its structure. The lactone ring group of the structural unit (a2) can effectively improve the adhesion of the photoresist film to the substrate in the case where the component of the polymer compound (A1 - 33 - 200839448) is used to form the photoresist film, and It is effective from the viewpoint of improving the affinity with the developer. Structural unit (a2), without any restrictions, can use any unit

Specifically, a monocyclic group containing a lactone, for example, a group obtained by removing one hydrogen atom from 7-butyrolactone or the like. Further, the polycyclic group having a lactone is, for example, a group obtained by removing one hydrogen atom from a bicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. In the example of the structural unit (a2), more specifically, for example, the structural unit shown by the following general formulas (a2-l) to (a2-5). 〔化22〕

Wherein R has the same content as described above, and R is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, an integer of m. 〇 or 1, and a is a carbon number of 1 to 5. Alkyl group or oxygen atom] In the formulae (a2-l) to (a2-5), R is the same as R in the above structural unit (al). The lower alkyl group of R' is the same as the lower alkyl group of R in the above structural unit (al). -34- 200839448 A alkylene group having a carbon number of 1 to 5, specifically, for example, a methyl group, an ethyl group, an η-propyl group, an extended isopropyl group or the like. Among the general formulae (a2-l) to (a2-5), R' is preferably a hydrogen atom from the viewpoint of industrial availability. The following are exemplifications of specific structural units of the above general formulae (a2-l) to (a2-5). 〔化23〕

Ch3 CH2-c)· 0===4^ 7 CH3 〇h (a2-t«1) (a24^2) ch3 (a2-1-3) ch3

(a2-14} 0=1 0=\f Ph3 9 CH3 (a2-1-5) Twist 24哬 200839448 [Chem. 24]

-36- 200839448 [Chem. 2 5]

-37 - 200839448 [Chem. 26]

-38 - 200839448 [化27]

CH3

Further, it is preferred to use at least one or more selected from the general formulae (a2-l) to (a2_3). Specifically, at least one of the chemical formulas (a2-ll), (a2-l-2), (a2-2-l), (a2-2-2), (a2-3-1), The selected ones of a2-3-2), (a2-3-9) and (a2-3-10) are the best. The structural unit (a2) may be used alone or in combination of two or more. The ratio of the structural unit (a2) in the resin (A1) is preferably from 5 to 70 mol% to 10 to 60% by mole based on the total of the structural units constituting the resin (A1). Preferably, it is preferably from 2 〇 to 5 〇 mol %. When the lower limit of the square 値 is above, the effect can be sufficiently achieved when the structural unit (a2) is contained. ‘After the upper limit 値, the balance with other structural units can be obtained. • Structural unit (a3) Resin (A1) ’ In addition to structural unit (al), or structural unit (al) and structural unit (a2), it may contain (a3) no fluorinogen.

And a structural unit derived from an acrylate having an aliphatic hydrocarbon group having a polar group. When the resin (A1) contains the structural unit (a3), the hydrophilicity of the component (a) can be increased, and the affinity with the developer can be improved, and the alkali solubility of the exposed portion can be improved, and the resolution can be expected to be improved. The polar group, for example, a hydroxyl group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of a hydrogen atom in the alkyl group is substituted with a fluorine atom, and the like, particularly preferably a hydroxyl group. The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group), or a polycyclic aliphatic hydrocarbon group (polycyclic group) or the like. The polycyclic group is, for example, a resin which can be used for a composition for a photoresist for an ArF excimer laser, and is appropriately selected from the contents of most proposals. The polycyclic group has a carbon number of 7 to 30. Further, a structural unit derived from an aliphatic polycyclic group acrylate having a hydroxyl group, a cyano group, a carboxyl group, or a hydroxyalkyl group in which a part of a hydrogen atom in the alkyl group is substituted by a fluorine atom is more preferable. The polycyclic group is, for example, a group obtained by removing one or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, iso-aracone or tri-40-200839448 cyclodecane or tetracyclododecane. In the above polycyclic group, it is more suitable for industrial use to remove two or more hydrogen atoms from adamantane, to remove two or more hydrogen atoms from norbornane, and to remove two or more hydrogen atoms from tetracyclododecane. use.

In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group having a polar group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit derived from hydroxyethyl acrylate is preferred. When the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a3-1) and a structural unit represented by (a3-2) are preferable. [28]

In the formula (a3 -1 ), it is preferable that j is 1 or 2, and 1 is more preferable. In the case where ί is 2, it is more preferable that the hydroxy group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is particularly preferable that the hydroxyl group is bonded to the 3 position of the adamantyl group. In the formula (a3-2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the norbornyl group. The structural unit () may be used alone or in combination of two or more -41 - 200839448. In the resin (A1), the ratio of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the entire structural unit constituting the polymer compound (A1). 5 to 25 mol% is the best • Structural unit (a 4 )

The resin (A 1 ) may contain other structural units (a4) other than the above structural units (al) to (a3) within the range in which the effects of the present invention are not impaired. The structural unit (a4) is not particularly limited as long as it does not contain a fluorine atom and is not classified into the other structural units of the structural units (al) to (a3), and an ArF excimer laser or KrF excimer can be used. A plurality of conventionally known structural units used for the resin component of a photoresist composition such as a laser (preferably for ArF excimer laser). The structural unit (a4) is preferably, for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group. The polycyclic group is, for example, the same as those exemplified in the above structural unit (a 1 ). It is possible to use a plurality of conventionally known structural units used for the resin component of the photoresist composition such as ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is industrially preferable, it is preferably obtained. The polycyclic group may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms. -42- 200839448 Structural unit (a4), specifically, for example, a structural unit represented by the following general formulae (a4 - 1) to (a4-5). 〔化 29〕 '

(In the formula, R is the same as described above.) The structural unit (a4) may be used singly or in combination of two or more.

When the structural unit (a 4 ) is contained in the resin (A 1 ), the ratio of the structural unit (a 4 ) is preferably from 1 to 30 mol% based on the total of the structural units constituting the resin (A1) component. It is more preferably contained in an amount of 10 to 20 mol%. In the present invention, the resin (A1) is preferably a copolymer having at least structural units (al), (a2) and (a3). The above copolymer, for example, a ternary copolymer obtained from the above structural units (al), (a2) and (a3), a 4-member copolymer obtained by structural units (al), (a2), (a3) and (a4) Wait. In the present invention, the resin (A1) is particularly preferably a copolymer containing three structural units which are combined by the following formula (A-1 1 ). -43 - 200839448 [化3 0]

Wherein R41, R43 and R44 are each independently a hydrogen atom, a lower alkyl group, or a lower alkyl group (halogenated lower alkyl group) obtained by substituting a hydrogen atom other than a fluorine atom, and R42 is a lower alkyl group; In A1-11), the lower alkyl group of R41, R43 and R44 is the same as the lower alkyl group of the above R, and R41, R43 and R44 are preferably a hydrogen atom or a lower alkyl group, and further a hydrogen atom or a methyl group. It is better. The lower alkyl group of R42 is the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferred. The resin (A1) can be obtained, for example, by polymerization of a monomer derived from each structural unit, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization. Further, the mass average molecular weight (Mw) of the entire component (A) (the polystyrene equivalent amount of the gel permeation chromatography method) is not particularly limited, and is generally preferably 2,000 to 50,000, and 3,000 to 30,000 to 30,000. Better, 5,000 to 20,000 is the best. When the upper limit of the range is 値 or less, sufficient solubility is obtained for the photoresist solvent when used as a photoresist, and when it is at least the lower limit of the range, a good dry urethane resistance or photoresist pattern can be obtained. - 200839448 Face shape. Further, the degree of dispersion (Mw/Mn) of the polymer compound (A1) is preferably in the range of from 1 Torr to 5.0, more preferably from 1.0 to 3.0, most preferably from 1.2 to 2.5. In the positive resist composition for immersion exposure of the present invention, the content of the component (A) may be adjusted in accordance with the thickness of the photoresist film to be formed.

In the component (A), the resin (A1) may be used singly or in combination of two or more. The content of the resin (A1) in the component (A) is preferably in the range of 50 to 1% by mass, more preferably 75 to 100% by mass, and most preferably 80 to 1% by mass. When the content of the resin (A1) is 50% by mass or more, the lithographic etching characteristics can be improved. In order to make the effect of the present invention superior, the content of the resin (A1) in the component (A) is preferably 100% by mass. &lt;(B) Component&gt; The component (B) is not particularly limited, and various materials which have been proposed so far as an acid generator for enhancing chemical resist can be used. As the acid generator, for example, an iron salt-based acid generator such as an iron iodide salt or a phosphonium salt, an oxime sulfonate-based acid generator, a dialkyl or bisarylsulfonyldiazomethane, or a poly( Disulfonyl) diazomethane acid generator such as diazomethane, nitrobenzyl sulfonate acid generator, iminosulfonate acid generator, second mill acid generator, etc. Compounds are known. The key salt acid generator is, for example, an acid generator represented by the following formula (b-〇). -45- 200839448 [Chemical 3 1] R52 (b - 〇) R53-/(CH2)u- R51S03·

Wherein R 5 1 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated group, and R is a hydrogen atom, a meridine, a halogen atom, a linear chain, a branched or cyclic alkyl group, a linear or branched halogenated ortho- or a linear or branched alkoxy group; R53 is an aryl group which may have a substituent; U" is an integer of 1 to 3] In the formula (bo), R5i is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. The aforementioned linear or branched alkyl group is The carbon number is preferably from 1 to 10, more preferably from 1 to 8 carbon atoms, and most preferably from 1 to 4 carbon atoms. The above cyclic alkyl group is preferably a carbon number of 4 to 12, and carbon. The number of 5 to 10 is better, and the number of carbon 6 to 10 is the best.

The fluorinated alkyl group is preferably a carbon number of 1 to 1 Torr, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The fluorination ratio of the fluorinated alkyl group (the ratio of the number of all hydrogen atoms in the alkyl group to the number of fluorine atoms) is preferably from 10 to 100%, more preferably from 50 to 100%, In particular, when all hydrogen atoms are substituted by fluorine atoms, it is most preferable that the strength of the acid is the strongest, and R51 is preferably a linear alkyl group or a linear fluorinated alkyl group. R52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogenated alkyl group, or a linear or branched -46-200839448 alkoxy group. In R52, the halogen atom is a fluorine atom, a bromine atom, a chlorine atom or an iodine atom, and a fluorine atom is preferred. In R52, the alkyl group is linear or branched, and the carbon number thereof is preferably from 1 to 5, particularly preferably from 1 to 4 carbon atoms, more preferably from 1 to 3.

In R52, the halogenated alkyl group is a straight or branched chain, and a part or all of a hydrogen atom in the alkyl group is substituted with a halogen atom. The alkyl group referred to therein is, for example, the same as the "alkyl group" in the above R51. The halogen atom to be replaced is, for example, the same as those described for the above "halogen atom". The halogenated alkyl group is preferably substituted with a halogen atom in an amount of 50 to 100% of the total number of hydrogen atoms, and more preferably all of them are substituted. In R52, the alkoxy group may be linear or branched, and its carbon number is preferably from 1 to 5, particularly from 1 to 4, more preferably from 1 to 3. R52 is preferably one in which all are hydrogen atoms. R53 is an aryl group having 6 to 2 carbon atoms which may have a substituent, and a basic ring (parent ring) structure in which a substituent is removed, such as a naphthyl group, a phenyl group, a fluorenyl group or the like. From the viewpoints of the effects of the present invention, exposure absorption of an ArF excimer laser or the like, etc., a phenyl group is more preferable. The substituent is, for example, a hydroxyl group, a lower alkyl group (linear or branched, preferably having a carbon number of 1 to 5, particularly preferably a methyl group). The aryl group of R53 is more preferably one having no substituent. u" is an integer of 1 to 3, more preferably 2 or 3, particularly preferably 3. The preferred examples of the acid generator represented by the formula (b-Ο) are as follows. 47- 200839448 〔化32〕

Other key acid generators other than the acid generator represented by the formula (b-0), for example, a compound represented by the following formula (b-Ι) or (b-2). 〔化33〕

&gt;21. Early ♦ R4&quot;SO;...(bH) R4&quot;SO;...(b-2) R6·· [wherein R1'' to R3'', R5" to R6", each independently being an aryl group Or an alkyl group; R4" is a linear, branched or cyclic alkyl group or a fluorinated alkyl group; at least one of R1" to R3'' is an aryl group, and at least one of R5" to R6'' R1'' to R3" in the formula (b-Ι) are each independently an aryl group or an alkyl group; at least i of Ri" to R3'' are aryl groups, and at least R" to r3" It is preferred that two or more aryl groups are preferred 'and R1'' to R3' are all aryl groups. The aryl group of R1 to R3 is not particularly limited, and is, for example, an aryl group having a carbon number of 6 to -48 - 200839448 20 and a part or all of a hydrogen atom of the aryl group may be an alkyl group, a decyloxy group, A halogen atom or the like may be substituted or unsubstituted. In view of the fact that the aryl group can be synthesized inexpensively, it is preferred to use an aryl group having 6 to 1 carbon atoms. Specifically, for example, a phenyl group, a naphthyl group or the like. The alkyl group which may be substituted for the hydrogen atom of the above aryl group is preferably a group having a carbon number of 1 to 5, and is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group which may be substituted for the hydrogen atom of the above aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group or an ethoxy group. The halogen atom which may be substituted for the hydrogen atom of the above aryl group is preferably a fluorine atom. The alkyl group of R1'' to R3" is not particularly limited, and may be, for example, a linear, branched or cyclic alkyl group having a carbon number of 1 to 1 Å, etc., in terms of improving resolution and the like. It is preferably a carbon number of 1 to 5. Specifically, for example, methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, η-pentyl, cyclopentylpentyl, hexyl And a cyclohexyl group, a fluorenyl group, a fluorenyl group, etc., in view of having excellent resolution and being inexpensively synthesized, for example, a methyl group or the like can be used, wherein R1" to R3" are respectively a phenyl group or a naphthyl group. For the best. R4" is a linear, branched or cyclic alkyl group or a fluorinated alkyl group. The above linear or branched alkyl group is preferably a carbon number of 1 to 1 Å, and a carbon number of 1 to 8 More preferably, it is most preferably a carbon number of 1 to 4. When the cyclic alkyl group is a cyclic group, it is preferably a carbon number of 4 to 15, and a carbon number of 4 to 10 is more preferable. The carbon number of 6 to 10 is the most preferred. The fluorinated alkyl group is preferably a carbon number of 1 to 1 ,, and a carbon number of 1 to 8 -49-

200839448 is better, with 1 to 4 carbon atoms being the best. Further, the conversion ratio (ratio of the fluorine atom in the alkyl group) is preferably from 1 Torr to 50 to 100%, and particularly preferably, the hydrogen atom is more strongly strengthened by the fluorine atom. R4'', in a linear or cyclic alkyl group, or a fluorinated alkane in the formula (b-2), R5'' to R6" are each independently R5'' to R6'', at least one is aromatic The base is further preferably R5'' to]. The aryl group of R5'' to R6", for example, the alkyl group of R5" to R6" with R1'' to R3'', for example, with R1'' In the case of R3'', all of R5'' to R6'' are phenyl groups, and R4" in the most general formula (b-2) is, for example, the same as the above formula (the same formula. Specific examples of the phosphonium salt represented by -1) and (b-2), such as diphenyl iodine trifluoromethane sulfonate or bis(4-tert-butylphenyl) iodine trifluoromethane Butane sulfonate, triphenylmethane trifluoromethanesulfonate, acid ester or its nonafluorobutane sulfonate, tris(4-methylphenyl alkane sulfonate, its heptafluoropropane sulfonate or Nonafluorobutane (4-hydroxynaphthyl)phosphonium trifluoromethanesulfonate, its seven or its nonafluorobutanesulfonate, monophenyldimethylhydrazine, its heptafluoropropanesulfonate or its nine Fluorine sulfonate, fluorinated alkyl fluoride 10%, better generation Preferably, the aryl or alkyl group; E16" is an aryl group which is the same as the same base. The R4" in the b-Ι) is an acid generator of nonafluorobutane sulfonate. Acid sulfonate or nonafluorofluoroheptafluoropropane sulfonate, trifluoromethanesulfonate, fluoropropane sulfonate, fluoromethanesulfonate, diphenyl monomethyl-50-

200839448 Trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluoroester, (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonate fluoropropane sulfonate or its nonafluoro Butane sulfonate, (4-methoxyphenophenyl mirror trifluoromethanesulfonate, its heptafluoropropane sulfonate or its alkane sulfonate, tris(4-tert-butyl)phenyl hydrazine Fluoromethanesulfonate heptafluoropropane sulfonate or nonafluorobutane sulfonate, [1-(4-)naphthyl]diphenylphosphonium trifluoromethanesulfonate, heptafluoropropane or its nonafluorobutanesulfonic acid An ester, a tris(1-naphthyl)phenylphosphonium trifluorate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, etc. The anion portion of the key salt may be a methanesulfonate or a η-propane. a key salt substituted with a sulfonic acid butane sulfonate or an η-octane sulfonate. Further, in the above formula (b-Ι) or (b-2), a moiety which can be used is represented by the following formula (b) -3) or (b-4) an anion-substituted key salt-based acid generator (the cation moiety is a compound of (b-Ι) or (b-2), butane, or a hepta group) Nonafluorobutyrate, methoxysulfonate methane And, cut off the feet ester, obtained from the same anion n-)

[wherein, X" is an alkylene group having at least one carbon atom substituted by a fluorine atom; Y", Z" are each independently an alkyl group having at least one hydrogen atom which is substituted by fluorine to have a carbon number of 1 to 10] X" is a linear or alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of 2 to 6, preferably a carbon number of 3 2 to 6 atoms, which is branched to 5, -51 - 200839448 The best is carbon number 3. Y", Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of from 1 to 10, preferably from 1 to 7, preferably It has a carbon number of 1 to 3. When the carbon number of the alkyl group of X" or the carbon number of the alkyl group of Y" or Z" is in the above range, it is preferably as small as possible because of the excellent solubility to the resist solvent.

Further, in the alkyl group of X" alkyl or Y'Z", the more the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, and the higher energy light or electron line with respect to 200 nm or less. In this case, it is preferable to improve transparency. The ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably the perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms. Base or perfluoroalkyl. In the present specification, the oxime sulfonate-based acid generator refers to a compound having at least one group represented by the following formula (1), and has a property of generating an acid by irradiation with radiation. The above-mentioned oxime sulfonate-based acid generator is often used in a reinforced chemical-type resist composition, and can be used arbitrarily. [Chemical Formula 3 5] -C=N-0-S02-R31 R32 β · (B- ” (In the formula (Β-1), R31 and R32 are each independently an organic group). The organic groups of R31 and R32 are contained. The group of a carbon atom may also contain an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom - 52 - 200839448, a halogen atom (a fluorine atom, a chlorine atom, etc.), etc.). The organic group is preferably a linear, branched or cyclic alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and for example, a fluorine atom or a carbon number may be used. A linear, branched or cyclic alkyl group to 6 wherein "having a substituent" means that a part or all of a hydrogen atom in an alkyl group or an aryl group is substituted with a substituent.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. It is especially good. The alkyl group is particularly preferably a partially or fully halogenated alkyl group (hereinafter also referred to as a halogenated alkyl group). Further, the partially halogenated alkyl group means an alkyl group obtained by substituting a part of a hydrogen atom with a halogen atom, and a completely halogenated alkyl group means an alkyl group obtained by substituting all hydrogen atoms with a halogen atom. A halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. That is, in the halogenated alkyl group, a fluorinated alkyl group is preferred. The aryl group is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 6 to 10. The aryl group is particularly preferably a partially or fully halogenated aryl group. Further, the partially halogenated aryl group means an aryl group obtained by substituting a part of a hydrogen atom with a halogen atom, and the fully halogenated aryl group means an aryl group obtained by substituting all hydrogen atoms with a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms which does not have a substituent. The organic group of R32 is preferably a linear, branched or cyclic alkyl 'aryl group or a cyano group. The alkyl group and the aryl group of R32 are, for example, the same as those of the aryl group and the aryl group exemplified in the above r31. • 53 - 200839448 R32, particularly a cyano group, an unsubstituted alkyl group having 1 to 8 carbon atoms, or a fluorinated alkyl group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (B-2) or (B-3). [Chem. 3 6] R34—〒=N—0—SOs—R35 R33 · · — (b-2)

[In the formula (B-2), R3 3 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group, R34 is an aryl group, and R35 is an alkyl group having no substituent or a halogenated alkyl group]. 〔化 3 7〕

• · (B-3) P”

[In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group, and r37 is a 2- or trivalent aromatic hydrocarbon group 'R38 is an alkyl group or an alkyl halide having no substituent. The base, P" is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R3 3 has a carbon number of from 1 to 10, and a carbon number of 1 to 8 is more preferable, and the carbon number is preferably 1 to 6. R33 is preferably a halogenated alkyl group and more preferably a fluorinated alkyl group. The fluorinated compound base in R33 is a gas atom in the Chlorination is preferred, more preferably 70% or more, and more preferably 90% or more of fluoride is fluorinated. -54- 200839448 R34 aryl group, such as phenyl, biphenyl, fluorenyl An aromatic ring of aromatic smoke such as a naphthyl group, an anthracyl group or a phenanthrene group, which removes a hydrogen atom group, and a part of a carbon atom constituting the ring of the aforementioned group is oxygen atom, sulfur A hetero atom such as an atom or a nitrogen atom is substituted for the obtained heteroaryl group, etc. Among them, a mercapto group is preferred.

The aryl group of R34 may have an alkyl group having a carbon number of from 10 to 10, a halogenated alkyl group, a hospitaloxy group or the like. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8 and more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group having no substituent of r35, preferably having a carbon number of 1 to 1 Torr, more preferably 1 to 8 carbon atoms, and most preferably having a carbon number of 1 to 6 as a halogenated alkyl group. Preferably, the fluorinated alkyl group is more preferred, and the partially or fully fluorinated alkyl group is preferred. The fluorinated alkyl group in R35 preferably has a hydrogen atom in the alkyl group of 50% or more, more preferably 70% or more, and is fluorinated at 90% or more to increase the acid produced. For better. The most preferred is a perfluorinated alkyl group in which the hydrogen atom is 100% replaced by fluorine. In the above formula (B-3), the alkyl group or the halogenated alkyl group having no substituent of &amp; 36 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent of the above R33. The 2 or 3 valent aromatic hydrocarbon group of R37, for example, a group obtained by further removing 1 or 2 hydrogen atoms from the aryl group of the above R34. The alkyl group or the halogenated alkyl group having no substituent of R38 is, for example, the same as the alkyl group or halogenated alkyl group having no substituent as described in the above -55 - 200839448 R35. P" is preferably 2.

Specific examples of the sulfonate-based acid generator, such as a-(p-toluenesulfonyloxyimido)-cyanide, α-(ρ-chlorophenylsulfonyloxyimino) -benzyl cyanide, α-(4-nitrophenylsulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)- Benzyl cyanide, α-(phenylsulfonyloxyimido)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, --(phenylsulfonyloxyimino)-2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2 -Chlorophenylsulfonyloxyimido)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-phthal-2-ylacetonitrile, α-(4-dodecane Benzosulfonyloxyimido)-benzyl cyanide, α-[(indole-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonate)醯 oxyimino)-4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonyloxyimino)-4-nonyl cyanide, α-(methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α-(A Sulfonoxyimino)-1 -cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)- 1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)·cyclohexylacetonitrile, --(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentyl Acetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimine Base)-1-ring-56- 200839448

Pentenyl acetonitrile, α-(isopropylsulfonyloxyimino)-1·cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, --(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, (isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(η-butylsulfonate Oxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimido)-phenylacetonitrile, α-(methylsulfonyloxyimino)-fluorene-methoxybenzene Acetonitrile, (trifluoromethylsulfonyloxyimido)-phenylacetonitrile, (trifluoromethylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, α-(ethylsulfonate Imino)-ρ-methoxyphenylacetonitrile, α-(propylsulfonyloxyimido)-indole-methylphenylacetonitrile, α-(methylsulfonyloxyimino)bromobenzene Acetonitrile and the like. In particular, the oxime sulfonate-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 9-2085-54 (paragraphs [〇〇12] to [0 0 1 4] to [Chem. 19]), W02004 The sulfonate-based acid generator disclosed in /074242A2 (Exampl e 1 to 40 of 65 to 8 5 pages) is also suitable for use. Further, preferred examples are, for example, the compounds exemplified below.

-57- 200839448化38] CH3

咖一 0—so2—cf3

(CF2)s-H CH30

Ch3o

=*N—Ο—S02-CFj ! C3F7 C-N—O—S02—CF3 〇ΡΛ—H ο a so2—cf3

N—0—S〇2~CF5 &lt;^~Ν—0—S02—C4F9 C3FT

\ /~\ /^9^N~°—S02—CF^ C3F7

N_0—S〇2—C4F9 (CF2)s-H

C=N—〇—S02—CF3 (CF2)e—H °Άγ—

C^N—0—S02—CF3 C3F7 C2H5

C*s=N—〇—S〇2—CF3 4f7 丨一 S〇2—CF3

N—〇—S02—CF3 O^s~〇· oxnr

C—N—OS〇2—C4F9 (CF2)6—H 0—so2—cf3 i〇Pih-»

C—N—〇一〇2—C6F13 CF2)e-H

C^N—O—S02~C4F9 {CF2)4-H-58 200839448 Further, among the above exemplified compounds, the following four compounds are preferred (Chem. 39)

Among the diazomethane acid generators, specific examples of dialkyl or bisaryl dialkyl diazo methanes such as bis(isopropylsulfonyl)diazomethane and bis(p-toluenesulfonyl)diazo Methane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazo Methane, etc. Further, JP-A-11-035551, JP-A-035552

The diazomethane acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 11-035573 is also suitably used. Further, poly(disulfonyl)diazomethane, for example, 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane disclosed in JP-A-11-322707, 1, 4 - bis(phenylsulfonyldiazomethanesulfonyl)butane, U6-bis(phenylsulfonyldiazomethanesulfonyl)hexane, iota,10-bis(phenylsulfonyldiazo Methanesulfonyl) decane, 1,2-bis(cyclohexylsulfonyldiazomethanesulfonyl)ethane, 1,3 -bis(cyclohexylsulfonyldiazomethane)propane, 1,6-bis(cyclohexylsulfonyldiazomethanesulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethanesulfonyl)decane, and the like. In the component (B), the acid generator may be used singly or in combination of two or more. In the present invention, in the above, the component (B) is preferably a sulfonium salt using a fluorinated alkylsulfonic acid ion as an anion.

In the positive-type resist composition for immersion exposure of the present invention, the content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A). In the above range, the formation of the pattern can be sufficiently performed. Further, a homogeneous solution can be obtained, which is preferable from the viewpoint of good preservation stability. &lt;(C) Component&gt; In the positive-type resist composition for immersion exposure of the present invention, the component (C) is a non-backbone cyclic type resin containing a fluorine atom and containing no acid dissociable group (C 1 And a resin (C2) having a main chain cyclic type containing a fluorine atom and not containing an acid dissociable group. When the component (C) is contained, the photoresist film obtained from the positive-type photoresist composition of the present invention has a high hydrophobicity on the surface, and can suppress the dissolution of substances such as water into the wetting medium as will be described later. Here, in the specification and the patent application, the "acid dissociable group" means a group which is dissociated by the action of an acid generated by the component (B) by exposure. For example, the lactone-containing cyclic group in the structural unit (a2), the polar group-containing aliphatic hydrocarbon group in the structural unit (a3), and the polycyclic aliphatic hydrocarbon group in the structural unit (a4); Does not contain an "acid dissociable group". -60- 200839448 The acid dissociable group is not particularly limited as long as it can be dissociated by the action of the acid produced by the component (B). For example, the presently proposed basis for enhancing the chemical resist can be used. The base of the acid dissociable dissolution inhibiting group of the resin can be used. Specific examples of the acid dissociable dissolution inhibiting group are, for example, the same as those exemplified as the acid dissociable dissolution inhibiting group of the structural unit (ai) in the structural unit (al).

In the above, the "dissolution inhibition" in the acid-dissociating dissolution-inhibiting group means that the group has a function of inhibiting the solubility of the component (A) (solubility inhibition property) with respect to a base such as an alkali developer. In the present invention, the "acid-dissociable group" may be a group having a solubility-inhibiting property or a group having no solubility-inhibiting property. [Resin (C1)] The resin (C1) is not particularly limited as long as it contains a fluorine atom and does not contain an acid-dissociable group-based resin. In the specification and the patent application, the "non-main chain cyclic resin" means any one of the carbon atoms constituting the main chain, and is not a resin constituting the carbon atom of the ring structure. When the resin (C 1 ) having such a structure is contained, a photoresist film having high water repellency on the surface of the film can be obtained. In the present invention, the resin (c 1 ) is preferably an alkali-soluble group. When it has an alkali-soluble group, it can have an effect of improving alkali solubility and improving various kinds of lithographic etching characteristics, such as an analytical property and a photoresist pattern shape. In particular, when it has a fluorinated hydroxyalkyl group as described later and has an alkali-soluble group of a fluorine atom, it has an effect of improving the hydrophobicity of the photoresist film and suppressing elution of the substance during immersion exposure. Therefore, when used as an immersion exposure, the usefulness can be further improved. The alkali-soluble group is a group which can improve the alkali solubility of the resin, and is preferably a group having a smaller pKa (Ka is an acid dissociation constant) which is the same as the phenolic hydroxyl group, and is not particularly limited. Further, it is preferable to use a base having a pKa of 6 to 12.

The alkali-soluble group, more specifically, a hydroxyl group (phenolic hydroxyl group, an alcoholic hydroxyl group), a carboxyl group or the like having a terminal having -OH, or the like. Specific examples of the alkali-soluble group having -OH at the end, for example, an alcoholic hydroxyl group; a hydrogen atom bonded to a carbon atom (a carbon atom at the alpha position) bonded to a hydroxyl group in a hydroxyalkyl group is replaced by an electron attracting group. a group (electron attracting group substituted hydroxyalkyl group); a carboxyl group or the like. Among them, the alkali-soluble group is preferably an electron-attracting group instead of a hydroxyalkyl group. The electron-attracting group is substituted with a hydroxyalkyl group, and the alkyl group is preferably a linear or branched chain. The carbon number of the electron-attracting group-substituted hydroxyalkyl group is not particularly limited, and is generally preferably 1 to 20, more preferably 4 to 16, and most preferably 4 to 12. The number of hydroxyl groups is not particularly limited, and generally one is preferred. The electron attracting group is, for example, a halogen atom or a halogenated alkyl group. A halogen atom such as a fluorine atom, a chlorine atom or the like is preferably a fluorine atom. In the halogenated alkyl group, the halogen is, for example, the same as the above-mentioned halogen atom, and the base group is a methyl group, an ethyl group, a propyl group or the like having a carbon number of 1 to 5, and a lower level j: the final group is preferably -62-200839448, more preferably A. Base or ethyl, most preferably methyl. The number of electron attracting groups is generally 1 or 2, preferably 2. The above electron-attracting group-substituted hydroxyalkyl group, more specifically and preferably, for example, having a -CR71R72OH group, R71 and R72, each independently being an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkyl halide group, wherein at least One is an electron attracting group selected from a halogen atom or a halogenated alkyl group.

In the resin (C 1 ), the electron-attracting group-substituted hydroxyalkyl group is preferably a fluorinated hydroxyalkyl group. Thus, the effects of the present invention can be improved. Also, it is effective to reduce the defect or LER (Line Edge Roughness). The defect refers to, for example, all disadvantages detected by the KLA Tankel Corporation's surface defect observation device (trade name "KLA") when viewed from directly above the developed photoresist pattern. Such disadvantages are, for example, scum, bubble, waste, or bridge between photoresist patterns, stains, precipitates, and the like after development. Wherein, "fluorinated hydroxyalkyl" refers to a hydroxyalkyl group in which one of the hydrogen atoms of the alkyl group is substituted by a group, and a residual hydrogen atom in the hydroxyalkyl group (the group is not substituted by a hydroxy group) Some or all of the hydrogen atoms are replaced by fluorine. In the above-mentioned fluorinated hydroxyalkyl group, the hydrogen atom of the hydroxyl group is more likely to be freed by fluorination. Among the fluorinated hydroxyalkyl groups, the alkyl group is preferably a straight chain or a branched chain. The carbon number of the alkyl group is not particularly limited, and is preferably 丨~2 〇, more preferably 4 to 16', and most preferably 4 to 12. The number of hydroxyl groups is not particularly limited, and one is preferably one. Wherein the fluorinated hydroxyalkyl group is bonded to the fluorinated alkyl group and/or fluorine by a carbon atom to which a hydroxyl group is bonded (here, -63-200839448 means a carbon atom at the alpha position of the hydroxyalkyl group). In particular, the fluorinated alkyl group bonded to the α-position is preferably a perfluoroalkyl group in which the hydrogen of the alkyl group is replaced by fluorine. In the present invention, in particular, the resin (C 1 ) is preferably a base having the following formula.

Atomic all (III

Wherein X is an integer of 〇~5, and y and ζ are each independently 1 to an integer. In the formula, X is preferably an integer of 0 to 3, and 0 or 1 is particularly preferably y and ζ, preferably. It is an integer of 1 to 3, and 1 is the best. The resin (C 1 ) is preferably a structural unit derived from acrylic acid (preferably, a derivative of acrylic acid, for example, α, a substituent substituent of an α-position of an acrylic acid (atom or a group other than a hydrogen atom) is substituted for α, The propyl ester obtained by substituting the hydrogen atom of the carboxyl group of the acrylic acid with an organic group. The "organic group" means a group containing a carbon atom, and the group in the acrylate is not particularly limited, and for example, a structural unit (aO) or a later-described structure Among the structural units listed in the pre-structural unit (al)~(a4), etc., C5

a") Carbonic acid enoic acid organic olefinic acid-64- 200839448 The group bonded by the ester branch of the ester (having a fluorinated hydroxyalkyl group, an acid dissociable dissolution inhibiting group, a lactone-containing group) a cyclic group, a polar group-containing aliphatic hydrocarbon group, a polycyclic aliphatic hydrocarbon group, etc.), etc. The α position of the acrylic acid (the carbon atom at the α position), unless otherwise specified, means a carbon atom bonded to a carbonyl group. The substituent of the α-substituted acrylic acid, for example, a lower alkyl group having 1 to 5 carbon atoms, a halogenated lower alkyl group or the like.

a lower alkyl group having a substituent at the alpha position, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, new A linear or branched alkyl group such as a pentyl group. The halogenated lower alkyl group having a substituent at the α-position is, for example, a group in which a part or all of a hydrogen atom in the lower alkyl group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an atom. Bonded to the α-position of propionic acid, preferably a hydrogen atom, a lower-grade or a halogenated lower alkyl group, and a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group is preferred. Obtaining the temple view 'is best with ammonia or methyl. The structural unit (a") is, for example, a structural unit represented by the following general formula (a"). -65· 200839448 〔化 4 1〕

Wherein R2() is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and X is a hydrogen atom or a monovalent organic group]

The lower alkyl group or the halogenated lower alkyl group of R20 is the same as the lower-grade or halogenated lower-grade base of the above-mentioned α-position substituent. The organic group of X is the same as the "organic group of the acrylate" described in the above structural unit (a"). The ratio of the 'structural unit (a') in the resin (C 1 ) to the total structural unit constituting the above-mentioned resin (C 1 ) is preferably a ratio of 50 to 100% by mol to contain 70 to 1%. It is more preferable that the Mo. % is 0. Particularly, in view of the effect of the present invention, the resin (C 1 ) is preferably formed of a structural unit (a") derived only from acrylic acid. Here, "formed only by the structural unit (a") means that the main chain of the resin (C i ) consists only of the structural unit (a"), and does not contain other structural units. In the present invention, the resin ( C 1 ) Preferably, the structural unit (aO ) derived from the acrylate having a fluorinated hydroxyalkyl group in the branched portion is preferred. In the specification and the patent application, the "branched portion" means that the main chain is not formed. Part of the meaning. The structural unit (aO), for example, X of the above formula (a") is a structural unit having a group of a fluoro-66 - 200839448 hydroxyalkyl group, and contains the following formula (in the present invention, particularly a structural unit (a0) The structural unit represented by a〇-2) is preferred.

[wherein, R 2 ^ is a hydrogen atom, a lower-order courtyard group, and a lower enthalpy R23 is independently a hydrogen atom or a monovalent aliphatic hydrazine; at least one of them is an aliphatic cyclic group; f is 〇~: self-independent is 1~ An integer of 5) The structural unit (unit (aO-2)) represented by the formula (aO-2) means a (CH2)fC(CbF2b+1)(CcF2c+1)-OH having a methyl group, and 1 The structural unit of the group substituted by a group. R2G in the formula (aO-2) is, for example, the same as the upper fin, and is preferably a hydrogen atom or a lower fluorenyl group. b and c are each an integer of from 1 to 5, and a halogenated alkyl group; R22, g group, an integer of R22 and R23 5; and b, c each, which is also referred to as a structural hydrogen atom, by one or two The R20 group in the aliphatic ring &amp; formula (a") is again a hydrogen atom or preferably a total of -1 to 3 - 3,394,394,48, and preferably 1 is preferred. f is preferably 1 to 5 The integer is more preferably an integer of 1 to 3, and more preferably 1. R22 and R23 are each independently a hydrogen atom or a monovalent aliphatic cyclic group, and at least one of R22 and R23 is an aliphatic cyclic group. In the present invention, in particular, one of R22 and R23 is a hydrogen atom, and the other is preferably an aliphatic cyclic group.

The aliphatic cyclic group in R22 or R23 may be either monocyclic or polycyclic. The "monocyclic aliphatic cyclic group" means a monocyclic group having no aromaticity, and the "polycyclic aliphatic ring group" means a polycyclic group having no aromaticity. The aliphatic cyclic group is a hydrocarbon group (alicyclic group) formed by carbon and hydrogen, and a part of a carbon atom constituting the ring of the alicyclic group is a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Substituted heterocyclic groups and the like. The aliphatic cyclic group is preferably an alicyclic group. The aliphatic ring group may be either saturated or unsaturated, and it is preferable to have a high transparency, an excellent resolution, or a depth of field (DOF) for an ArF excimer laser or the like. . The aliphatic cyclic group in R22 or R23 preferably has a carbon number of 5 to 15 and more preferably 6 to 12 2 . Among them, a group obtained by removing one or more hydrogen atoms of cyclohexane, cyclopentane, norbornane, tricyclodecane or tetracyclododecane is preferred, and in particular, one or more hydrogens are removed by cyclohexane. In the present invention, the structural unit (aO-2) is particularly a structural unit represented by the following general formula (a0--68-200839448 and easy to synthesize 2-1), and the effect is considered. And it is better to obtain high etching resistance and the like.

[wherein, R2G, f, b, and c are the same as described above. In the present invention, the structure is at least (a0), as described above, etc., and the branched portion has a fluorinated hydroxyalkyl group, and a single aliphatic group. The structural unit of the ring type is preferably, particularly the structural unit represented by the above). The structural unit (a0) can be used alone or in combination. In the resin (C1), the total structural unit of the structural unit (a0) to the resin (c 1 ) is preferably 3 〇 ^ , 50 to 1 〇〇 mol %, and 7 〇 〜 〇〇 〇〇 100% of the mole is especially good. When it is 30 mol% or more, a 〇 ) can improve the effect. For example, when the ratio of the resin (c 1 ) is a small amount, a higher infiltration volume can be obtained. The structural unit (a〇-2 ring or a polycyclic formula) (a0_2-l is a combination of two or more types) For example, it is best to form a composition of '100% Momo% to contain structural units (to make the photoresist composition medium resistant, and to improve the high lithography engraving characteristics of -69-200839448. The structural unit·resin (C1) may contain other structural units than the above structural unit (ao) insofar as it does not impair the effects of the present invention.

Other structural units, as long as they are not classified in the above structural unit (a〇), do not have an acid dissociable group, and any one of the carbon atoms constituting the main chain is not a carbon atom constituting a ring structure, and may be related to a structural unit (a0) When the structural unit derived from the copolymerized monomer is copolymerized, it is not particularly limited, and it can be used for ArF excimer laser or Kr F excimer laser (preferably for ArF excimer laser). Many structural units known in the past for use in resistive resins. Specific examples of the other structural unit include, for example, among the structural units (a2) to (a4) listed in the resin (A1), and none of the carbon atoms constituting the main chain constitute a ring structure. A carbon atom. In the resin (C 1 ), the combination and ratio of the structural unit (a0) to other structural units can be appropriately adjusted in accordance with the required characteristics. As described above, in particular, in view of improving the effects of the present invention, the resin (C 1 ) is preferably formed only by the structural unit (a0). The resin (C 1 ) may be a monomer derived from each structural unit, for example, using azobisisobutyronitrile (AIBN) or dimethyl-2,2'-azobis(2-methylpropionate). The radical polymerization initiator can be obtained by polymerization by a known radical polymerization or the like. The mass average molecular weight of the resin (C1) (Mw; the polystyrene-converted mass average molecular weight of the analytical cross-linked color layer-70-200839448 analytical method) is not particularly limited, and is generally preferably from 2000 to 40,000 to 2,000 to 30,000. For better, take 00 0~25000 as the best. In this range, a good dissolution rate can be obtained for the alkali developing solution, and it is preferable from the viewpoint of high resolution and the like. When the molecular weight is within this range, the lower one has a tendency to obtain good characteristics. Further, the degree of dispersion (Mw / Μη) is about 1.0 to 5 · ,, preferably 1 · 0 〜 3 · 0 〇

In the component (c), the resin (C 1 ) may be used singly or in combination of two or more kinds. The content of the resin (C 1 ) in the component (2) is preferably 0.1% by mass or more, preferably 0.1 to 90% by mass, more preferably 5 to 90% by mass. Preferably, it is preferably 10 to 85% by mass, and particularly preferably 15 to 80% by mass. When the content of the resin (C1) is 0.1% by mass or more, the resistance of the resist film to the wetting medium can be improved. Further, when it is 90% by mass or less, the lithographic etching characteristics can be improved.

[Resin (C2)] The resin (C2) is a main chain cyclic type resin containing a fluorine atom and having no acid dissociable group. Here, the "acid dissociable group" is the same as described above. For example, -Q-NH-S02-R5 or the like in the structural unit (a'l) to be described later is not included in the "acid dissociable group". In the present specification and the scope of the patent application, the term "main-chain-ring resin" means a structural unit constituting the resin, and has a single-ring or multi-ring ring structure - 71 - 200839448, and at least the ring of the aforementioned ring structure One, preferably two or more carbon atoms have a structural unit constituting a main chain (hereinafter, also referred to as a main chain cyclic type structural unit). When the resin (C2) having such a structure is contained, a photoresist film having a high hydrophobicity on the surface of the film can be obtained in the same manner as in the case of containing the resin (C1). Also, the etching resistance can be improved. The improvement in etching resistance is supposed to be obtained by having a main chain cyclic structural unit and increasing the carbon density.

The main chain cyclic structural unit is, for example, a structural unit derived from a polycycloolefin (polycyclic olefin), a structural unit containing an anhydrous substance of a dicarboxylic acid as exemplified in the structural unit (a ' 3 ) described later, and the like. Among them, the viewpoint of excellent etching resistance when used as a photoresist is preferable to use a structural unit derived from a polycycloolefin in the main chain. The structural unit derived from the polycycloolefin is preferably a structural unit having a basic skeleton represented by the following formula (a').

[In the formula, a is 0 or 1] In the formula (a,), a is 0 or 1, and in view of the fact that it is easy to obtain industrially, it is preferable to use 〇. "Structural unit having a basic skeleton represented by the general formula (a,)" -72- 200839448 refers to a structural unit represented by the general formula (a') (ie, bicyclo [2·2·1) -2-g The structural unit derived from an alkene (norbornene) and the structural unit derived from tetracyclo [4·4.0·12'5·ι·7, ι〇]-3-dodecene) may also be described later. The structural unit (a'l) to (&amp;'3) may have a substituent on the ring skeleton. That is, the "structural unit having the basic skeleton represented by the general formula (a,)" also includes the ring skeleton (bicyclo[2.2.1]-2-heptane or tetracyclo[4.4.0.12, 5.1. 7,1()]-3-dodecene)

A structural unit in which a part or all of a hydrogen atom to which a carbon atom is bonded is replaced by an atom other than a hydrogen atom or a substituent. The resin (C2) may have a structural unit other than the main chain cyclic structural unit', for example, may have the structural unit (a) (the structural unit derived from acrylic acid) listed in the above resin (A 1 ), and the like. In the case of the resin (C2), the main chain cyclic structure unit is preferably contained in a total structural unit of the resin (C 2 ) in an amount of 50 to 100% by mol, and contains 80. ~1 0 0% of the mole is better. In particular, it is preferable that the effect of the present invention is excellent, and the resin (C2) is preferably formed only of a main chain cyclic type structural unit. Here, "formed only by the main chain cyclic structural unit" means that the main chain of the resin (C2) is composed only of the main chain cyclic structural unit, and does not contain other structural units. The structural unit (a'l) resin (C2) is preferably a structural unit (a' 1 ) represented by the following formula (I) for improving the effects of the present invention. -73- 200839448 [化45]

(I)

[In the formula (I), R1 to R4 each independently represent a hydrogen atom, a straight alkyl group, a linear or branched fluorinated alkyl group, or a group represented by T) (la), and at least R1 to R4 1 is the former; a is 0 or 1] [Chem. 46] Η ? -Q-N - S - R511 〇 · · · · (1 chain or branched chain formula (la base (I a )

[In the formula (la), Q is a linear or branched chain having a carbon number of 1 to 5; and R5 is a fluorinated alkyl group]. The structural unit (a, l) represented by the formula (I) is a formula (a') In the structural unit of the basic skeleton which is represented, at least the group represented by the formula (1a) is present at a predetermined position (Ia). In the present invention, when the unit of the structure is present, the hydrophobicity can be improved. Moreover, the lithography etching characteristics can also be improved. The reason for the determination is still undetermined, but when the base (la) is present, the above-mentioned effect of the surface of the ring-shaped film on the ring can be improved as described above. -74-200839448 Photoresist film The effect of the hydrophobicity is also improved, and the alkali solubility of the resin (C 2 ) can be improved. Therefore, it is presumed that various lithographic etching characteristics such as an analytical property and a photoresist pattern shape can be improved. In the formula (I), a is the same as a in the above formula (a,)

The alkyl group of R1 to R4 may be a linear chain or a branched chain, and preferably an alkyl group having 1 to 10 carbon atoms is preferred. The alkyl group having 1 to 8 carbon atoms is more preferably a carbon number of 1. The base of ~5 is the best. The mercapto group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group or the like. The fluorinated alkyl group of R1 to R4 is a group in which one or all of hydrogen atoms in a linear or branched alkyl group is substituted by a fluorine atom. The alkyl group in the fluorinated alkyl group is, for example, the same as the alkyl group of the above R1 to R4. The fluorination rate of the fluorinated alkyl group (in the fluorinated alkyl group, the total number of hydrogen atoms and fluorine atoms, the ratio of the number of fluorine atoms (%)) is preferably 10 to 100%, and 30 to 100%. For better, 50 to 100% is the best. When the fluorination rate is 10% or more, it has an excellent effect of improving the hydrophobicity of the surface of the photoresist film. In the formula (la), the alkyl group of Q may be linear or branched, and is preferably an alkyl group having a carbon number of 1 to 1 Å, and an alkyl group having a carbon number of 1 to 8. More preferably, the alkylene group having a carbon number of 1 to 5 is most preferred. The alkylene group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butylene group, an extended butyl group, a pentyl group, an isoamyl group, a neopentyl group or the like. Among them, in view of the ease of synthesis and the like, it is preferred to use a linear alkyl group, particularly in the case of a methyl group. The fluorinated alkyl group of R5 is a hydrogen in a linear, branched or cyclic alkyl group. -75- 200839448 A group in which one or both of the atoms are replaced by a fluorine atom. The linear or branched alkyl group is, for example, the same as the fluorinated alkyl group of the above R1 to R4. The cyclic alkyl group is preferably a carbon number of 4 to 12, more preferably a carbon number of 5 to 10, and most preferably a carbon number of 6 to 10.

The fluorination rate of the fluorinated alkyl group (in the fluorinated alkyl group, the total number of hydrogen atoms and fluorine atoms, the ratio of the number of fluorine atoms (%)) is preferably 10 to 100%, and is 3 0 to 1 0 0 % is more preferable, and 50 to 100% is optimal, and 10% by weight, that is, all of the hydrogen atoms are replaced by fluorine atoms. When the fluorination rate is 1% or more, the hydrophobicity of the surface of the photoresist film is excellent. Therefore, even if the proportion of the resin (C2) in the component (C) is small, a sufficient hydrophobic effect can be obtained. The fluorinated alkyl group of R5 is preferably a linear or branched fluorinated alkyl group, more preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and particularly the hydrogen atom of the alkyl group is completely replaced by a fluorine atom. Perfluoroalkyl groups are preferred. Specific examples of the perfluoroalkyl group, such as a trifluoromethyl group and a pentafluoroethyl group, are preferably a trifluoromethyl group. In the present invention, at least one of R1 to R4 is a group (la) represented by the above formula (la), and the remaining 0 to 3 are a hydrogen atom, a linear or branched alkyl group, and a straight One or more selected from the group consisting of a chain or a branched fluorinated alkyl group. In the present invention, one of R1 to R4 is preferably a group (la), and particularly one of R1 to R4 is a group (la), and the other three are hydrogen atoms as a good structural unit (a' 1 ). In particular, it is preferably a structural unit represented by the following formula (lb). -76- 200839448 [化47]

In the formula (lb), 'a has the same content as described above. p is an integer of ι 〜1(), and is preferably an integer of 1 to 8, and 1 is optimal. q is an integer of 1 to 5, and is preferably an integer of 1 to 4, and 1 is most preferable. The structural unit (a'1) may be used singly or in combination of two or more.

In the resin (C2), the total of the structural unit (a'1) relative to the total structural unit constituting the resin (C2) is preferably 50 to 100 mol%, and is 80 to 100 mol%. Better. In particular, in view of the fact that the effect of the present invention is excellent, the resin (C 2 ) is preferably formed only by the structural unit (a'l). Here, "formed only by the structural unit (a' 1 )" means that the main chain of the resin (C2) is composed only of the structural unit (aM) and does not contain other structural units. The monomer derived from the structural unit (a, 1) can be prepared, for example, by the method disclosed in U.S. Patent No. 6,402,030. 200839448 • Other structural unit (a'3) The resin (C2) may further contain a structural unit (a'3) other than the above structural unit (a'l) within the effect of the present invention.

The structural unit (a' 3 ) may be copolymerized with a monomer derived from the structural unit (a' 1 ) as long as it is a structural unit which does not have an acid dissociable group and is not classified in the above structural unit (a ' 1 ). There is no particular limitation on the structural unit derived from the monomer. The structural unit (a' 3 ) can be used arbitrarily for the purpose of blending a structural unit derived from a compound having a known ethylenic double bond. The structural unit (a' 3 ), more specifically, for example, a structural unit derived from acrylic acid such as a structural unit (a2 ) to a structural unit (a4 ) exemplified in the above-mentioned resin (A 1 ), and a structure containing a dicarboxylic anhydride The structural unit derived from a unit, a polycycloolefin having no substituent, a structural unit derived from a polycycloolefin having a polycyclic alicyclic group, and the like. The structural unit containing an acid anhydride of a dicarboxylic acid means a structural unit having a structure of -^(〇)-〇-C(())-. The above unit is, for example, a structural unit containing a monocyclic or polycyclic cyclic acid anhydride, and more specifically, a structural unit derived from a monocyclic maleic anhydride represented by the following formula (a, 31) a structural unit derived from a polycyclic maleic anhydride represented by the following formula (a, 32), and a structural unit derived from the isoconic acid represented by the following formula (a, 33)

-78- 200839448 〔化48〕

[49]

A structural unit derived from a polycyclic olefin having no substituent, such as bicyclo[2 · 2 · 1]-2 -heptene (norbornene), tetracyclic [4.4.0 · 1 2, 5 · 1 · 7 , 1 0 〕-3-dodecene and the like.

Further, a structural unit derived from a polycyclic olefin having a polycyclic alicyclic group as a substituent, for example, on a ring of a structural unit derived from a polycycloolefin having no such substituent, as a substituent, for example, A structural unit of a polycyclic group such as a tricyclic fluorenyl group, an adamantyl group or a tetracyclododecyl group. In the resin (C2), the combination and ratio of structural units such as structural units (a'l) and (a'3) can be appropriately adjusted in accordance with the required characteristics. However, as described above, in particular, in view of making the effect of the present invention more excellent, the resin (C2) is preferably formed only by the structural unit (a' 1 ). The resin (C2), for example, a monomer derived from a specific structural unit, -79-200839448, can be polymerized by a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization or the like. be made of.

The mass average molecular weight of the resin (C2) (Mw; the polystyrene-converted mass average molecular weight obtained by gel permeation chromatography (GPC). The same applies hereinafter) is not particularly limited, and is generally preferably 2,000 or less. It is better to be less than 1 0000. When Mw is 20,000 or less, the effects of the present invention can be enhanced, and in particular, the lithographic characteristics of lithography such as resolution can be improved. Further, it has excellent solubility in an organic solvent or the like, and can suppress occurrence of foreign matter or development defects. Here, the foreign matter refers to a solid matter such as a microparticle produced in the solution when the composition is used as a solution. Further, the development defect refers to, for example, all defects which are detected when the surface defect observation device (trade name "KLA") of KLA Tankel Co., Ltd. is observed directly above the developed photoresist pattern. Such disadvantages include, for example, scumming, bubbles, waste, or bridge between photoresist patterns (bridge structure between photoresist patterns), stains, precipitates, and the like. The lower limit of Mw is not particularly limited, and is generally preferably 2,000 or more, more preferably 4,000 or more. When the Mw is 4,000 or more, the etching resistance can be improved, and the resist pattern is less likely to be swollen during development, and the collapse is less likely to occur. The degree of dispersion (Mw/Mn (number average molecular weight)) is preferably from about 1. 〇 to about 5.0, and more preferably from 1 · 〇 to 3.0. In the component (C), the resin (C2) may be used singly or in combination of two or more. The content of the resin (C2) in the component (C) is preferably 0.1% by mass or more, more preferably 0.1% by mass to 95% by mass, even more preferably 10% by mass to 80% by weight of the product. ~90% by mass is the best, and 20 to 85% by mass is particularly good. When the content of the resin (C2) is 0.1% by mass or more, the resistance to the wetting medium of the photoresist film can be improved. Also, it is 50 mass. The following can improve the lithography characteristics.

(C) The content of the component (A) is preferably 0.1% by mass or more, preferably 0.1 to 50% by mass, more preferably 0.5 to 25% by mass, and preferably 1.0 to 20% by mass. For the best, the best is 1.5~1〇% by mass. When the content of the component (C) component is 0.1% by mass or more, the resistance of the photoresist film to the wetting medium can be improved. Further, when it is 50% by mass or less, the fine shadow etching property can be improved because a good balance can be obtained with the component (A). In the present invention, the resins (C1) and (C2) used as the component (C) have a resin which is generally used as a base resin of a positive photoresist composition (having acid dissociation property) because it does not have an acid dissociable group. When the resin which dissolves the inhibiting group is compared, it has an advantage that it is easier to synthesize and can be obtained at low cost.

&lt;Arbitrary component&gt; The positive photoresist composition for immersion exposure of the present invention is used to enhance the shape of the photoresist pattern and the post-contact stability (post exposure stability of the latent image formed by the pattern-wise exposure) When the resist layer is added, an optional nitrogen-containing organic compound (D) (hereinafter also referred to as (D) component) may be further added. There is a proposal for a plurality of compounds in the component (D), and any of the known components may be used, and an aliphatic amine, particularly a secondary aliphatic compound, or a tertiary aliphatic amine, preferably a secondary amine, is preferably an aliphatic amine or a tertiary aliphatic amine. . Wherein the aliphatic amine is an amine having one or more aliphatic groups, and the carbon number of the aliphatic group is preferably from 1 to 12

An aliphatic amine such as an amine (alkylamine or alkanolamine) obtained by substituting at least one hydrogen atom of ammonia NH3 with an alkyl group having 1 or more and 1 or less carbon atoms or a hydroxyalkyl group. Specific examples thereof include monoalkylamines such as η-hexylamine, n-heptylamine, n-octylamine, η-decylamine, η-decylamine; diethylamine, di-n-propylamine, a dialkylamine such as di-η-heptylamine, di-η-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-η-butyl Amine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, three a trialkylamine such as η-dodecylamine; an alkanol such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine or tri-n-octanolamine amine. Among them, alkanolamine and trialkylamine are preferred, and alkanolamine is preferred. Among the alkanolammoniums, triethanolamine or triisopropanolamine is preferred. The cyclic amine is, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). An aliphatic monocyclic amine, specifically, for example, pyridine, piperazine or the like. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, for example, 1,5-diazabicyclo[4.3.0]-5-decene, 1,8-diaza Ring [5·4.0]-7-undecene, heptamethyltetrazole, 1,4-diazabicyclo[2.2.2]octane, and the like. They may be used alone or in combination of two or more. -82-

200839448 (D) The component (A) component is 100 parts by mass, and is generally in the range of 〇.〇1 to 5.0 parts by mass. The positive-type photoresist composition for immersion exposure of the present invention is used for preventing deterioration (Deterioration in sensitivity) or for improving the resist pattern, post exposure stability 〇latent image formed by the pattern-wise expo For example, at least one selected from the group consisting of an oxoacid of an organic residual phosphorus of any component and a derivative thereof (hereinafter also referred to as an (E) component ). An organic carboxylic acid such as acetic acid, malonic acid, citric acid, malic acid, benzoic acid, salicylic acid or the like, particularly salicylic acid. Phosphorus oxyacids and derivatives thereof, such as phosphoric acid, phosphine Phosphonic acid, Phosphinic acid, etc., are preferably phosphonic acids. The oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the above-mentioned oxo acid, and the like, and the hydrocarbon group is, for example, an aryl group having 1 to 5 carbon atoms and 6 to 15 carbon atoms. Phosphoric acid derivatives such as di-η-butyl phosphate, diphenyl phosphate, and the like. A phosphonic acid (P h 〇 s p h ο n i c a c i d ) derivative such as phosphonic acid di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate 'phosphonic acid dibenzyl ester, and the like. A phosphinic acid (P h 〇 s p h i n i c a c i d ) derivative such as a phosphinate such as a phenyl group. Using the sensitivity type f the f the acid and compound, succinic acid (wherein the hydrocarbon, alkyl i acid oxime, phosphine i, etc. phosphine: phosphonic acid-83-200839448 (E) component can be used alone, or 2 The above-mentioned combination may be used. (E) The component is generally used in an amount of from 1 to 5.0 parts by mass based on 100 parts by mass of the component (A).

The positive-type photoresist composition for immersion exposure of the present invention can be further blended with an additive which is suitable for mixing, for example, an additive resin which can improve the performance of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, Plasticizers, stabilizers, colorants, halo inhibitors, dyes, and the like. The positive resist composition for immersion exposure of the present invention can be produced by dissolving a material in an organic solvent (hereinafter also referred to as (S) component). (s) The component (s) can be used as long as it can dissolve the components to be used, and a suitable solution can be used. For example, one or two or more kinds of the above-mentioned conventionally used solvents can be used. For example, lactones such as 'r-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone 'methyl-η·pentanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, Polyols such as diethylene glycol, propylene glycol, dipropylene glycol and derivatives thereof; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate a compound having an ester bond; a monoalkyl ether or a monophenyl ether such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether; a derivative of a polyol having an ether-bonded compound or the like; a cyclic ether such as dioxane; a methyl lactate, an ethyl lactate (EL), a methyl acetate, an ethyl acetate, a butyl acetate, a pyruvic acid Ester of methyl ester, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; anisole, ethyl anisole, cresol methyl ether, -84 - 200839448 diphenyl Ether, dibenzyl ether, phenylethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, cumene, trimethyl Aromatic organic solvents such as benzene and the like. These organic solvents may be used singly or in combination of two or more. Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and 7-butyrolactone were used.

good. Further, a mixed solvent obtained by mixing PGMEA with a polar solvent is preferred, and the addition ratio (mass ratio) may be appropriately determined depending on the compatibility of PGMEA with a polar solvent, etc., preferably 1:9 to 9:1. More preferably 2: 8 to 8: 2 range. More specifically, when the polar solvent is ethyl lactate (EL), the mass of PGMEA : EL is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2. When the polar solvent is PGME, the mass of PGMEA: PGME is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2, most preferably from 3:7 to 7:3. Further, among the components (S), for example, a mixed solvent of at least one selected from PGMEA and EL and r-butyrolactone is preferably used. At this time, in the mixing ratio, the mass of the former and the latter is preferably 7 0 ·· 3 0 to 9 5 : 5 In addition, the (S) component, the other contains at least one mixed solvent of PGMEA and PGME, and r - The mixed solvent obtained by butyrolactone is preferred. The amount of (S) ingredients used is not particularly limited and can generally be combined with Tu-85-

200839448 The concentration of the substrate or the like, the thickness of the coating film, and the like can be appropriately selected and set in the range of 2 to 20% by mass in the resist composition of 5 to 15% by mass. For the dissolution of the (S) component of the material, for example, the above-mentioned conventional methods may be carried out only by mixing and stirring, and may be dispersed by using a high-speed stirrer, a homomixer, a 3-roller honing machine, or the like. mixing. Further, after mixing, it is also possible to use a sieve, a membrane or the like for filtration. The positive-type photoresist composition for immersion exposure of the present invention can form a photoresist film having a high hydrophobicity on the surface of the film as described above. Further, since the liquid has an etching property, it is extremely suitable for a process of using immersion exposure to form light. The reason why this effect can be obtained is not determined, but it is presumed that (C1) and (C2) have a fluorine-containing atom and do not have an acid dissociation structure, and the resin (A1) has an acrylic structure which does not contain a fluorine atom. φ The resin having a higher hydrophobicity (C 1 ) and (C2 ) distributed in the vicinity of the surface of the photoresist film by using the positive-type photoresist composition for immersion exposure, and having a higher hydrophilicity ( A 1 ) is distributed on the inside of the effect. Therefore, since the resin (C 1 ) and (C2 ) are in the vicinity of the outer surface of the photoresist film, for example, when the resin is used alone, the hydrophobicity of the surface of the obtained photoresist film can be improved by the resin (A 1 ). It is distributed on the inner side of the photoresist film, so it is presumed that the lithography etching property is good. When the immersion exposure step is performed, the front and the general components can be dispersed into the filter as needed. As described above, the lithographic pattern is a resin-based one. Therefore, the outer photoresist film can be distributed in A1) while maintaining the photoresist -86-200839448. The components in the film are dissolved in the infiltrating solvent (substance). Since dissolution and the like are suppressed, it has excellent resistance to the wetting medium, and is extremely suitable for use as an immersion exposure.

That is, the photoresist film formed by using the positive-type photoresist composition for immersion exposure of the present invention can be made to have a contact angle with respect to water, for example, when compared with the case where the component (C) is not added. For example, a static contact angle (the angle formed by the surface of the water droplet on the photoresist film in the horizontal state and the surface of the photoresist film) and a dynamic contact angle (the tilt of the photoresist film starts) The contact angle at the time of rolling, which includes the contact angle (advancing contact angle) of the front end of the falling direction of the water droplet, and the contact angle (receding contact angle) with the rear end of the rolling direction. The sliding angle (the tilt angle of the photoresist film when the water droplet starts to roll) changes when the sliding film is tilted. Specifically, the larger the static contact angle and the dynamic contact angle, the smaller the roll angle becomes. Wherein, the advancing angle is as shown in FIG. 1, and when the plane 2 on which the droplet 1 is placed is gradually inclined, when the droplet 1 starts to move on the plane 2 (falling), the lower end of the droplet 1 is la The surface of the droplet, formed at an angle 0 i to plane 2. Moreover, at this time (when the droplet 1 starts to move (fall) on the plane 2), the surface of the droplet in the upper end lb of the droplet 1 and the angle 02 formed by the plane 2 are receding angles, and the plane 2 The tilt angle 0 3 is the roll angle. In the immersion exposure, as described above, the solvent is wetted by the photoresist film in contact with water or the like during immersion exposure. Therefore, the elution of the substance is affected by the characteristics of the surface of the photoresist film - 87 - 200839448 (e.g., hydrophilicity, hydrophobicity, etc.). In the present invention, since the specific surface (C) is used, the hydrophobicity of the surface of the film can be improved, so that the effect of suppressing the elution of the substance can be enhanced. It is presumed that the surface of the film tends to bounce off the wetting medium by increasing the hydrophobicity of the surface of the film, and the contact area or contact time of the film surface with the wetting medium is lowered, so that the influence of the wetting medium can be reduced. For example, after the immersion exposure, when the wetting medium is removed, the wetting medium can be quickly removed from the surface of the photoresist film.

The static contact angle, the dynamic contact angle, and the roll angle can be measured, for example, in the following manner. First, the photoresist composition solution is spin-coated on a ruthenium substrate, and then heated under a specific condition, for example, at a temperature of 100 to 110 ° C for 60 seconds to form a photoresist film. Next, for the above-mentioned photoresist film, DROP MASTER-700 (manufactured by Kyowa Interface Science Co., Ltd.), AUTO SLIDING ANGLE: SA-30DM (manufactured by Kyowa Interface Science Co., Ltd.), and AUTO DISPENSER: AD-31 (manufactured by φ Kyowa Interface Science Co., Ltd.) were used. The measurement is performed by a commercially available measuring device. In the resistive film for immersion exposure of the present invention, in the photoresist film obtained by using the positive resist composition, the measurement of the receding angle is preferably 60 degrees (°) or more, and is preferably 60 to 150. For better, take 60~130. For the best 'to 65~1〇〇. It is especially good. The receding angle is 60. In the above case, the hydrophobicity of the surface of the photoresist film can be increased, and the effect of suppressing the elution of the substance can be enhanced. When the receding angle is 150 or less, the lithography etching property and the like can be further improved. For the same reason, the positive-type photoresist composition for immersion exposure of the present invention is preferably measured at a temperature of 80° or more in the photoresist film obtained by using the photoresist composition. It is preferably 80 to 110° to 80 to 100. For the best. For the same reason, the measurement of the static contact angle of the resistive film for immersion exposure of the present invention in the photoresist film obtained by using the photoresist composition is preferably 70° or more, and 70 to 100. ° is better, to 75~95. For the best.

Further, in the positive-type resist composition for immersion exposure of the present invention, the measurement of the roll-off angle in the photoresist film obtained by using the photoresist composition is preferably 25 or less, and more preferably 10 to 25°. Good, with 12~25° as the best, with 15~23° as the best. When the roll angle is 25 or less, the effect of suppressing the elution of the substance during immersion exposure can be improved. Further, when the roll angle is 10 ° or more, good lithographic etching characteristics and the like can be exhibited. The static contact angle, the dynamic contact angle and the roll angle can be adjusted to adjust the composition of the photoresist composition for immersion exposure, for example, adjusting the mixing ratio of (A) component to (C) component, or (A) component The structure unit (a3) and other components are adjusted in such a manner. For example, when the content of the component (C) to the component (A) is 0.1% by mass or more, the static contact angle and the dynamic contact angle can be greatly increased and the roll angle can be lowered as compared with the case where the component (C) is not added. As described above, in the present invention, it is possible to suppress the substance from being dissolved in the wetting solvent. Therefore, the deterioration of the photoresist film or the change in the refractive index in the solvent can be suppressed. Therefore, by suppressing variations in the refractive index of the wetting solvent, etc., it is possible to reduce the curvature of the formed photoresist pattern, or the unevenness of the line edge (the side of the pattern side -89-200839448), and the lithography of the shape and the like Engraved features. Further, since the contamination of the lens in the exposure device can be reduced, it is possible to contribute to the simplification of the process or the exposure apparatus even if it is not necessary to protect the lens. Further, the positive-type resist composition for immersion exposure of the present invention can form a high-resolution photoresist pattern, for example, a photoresist pattern having a size of 1 20 nm or less can be formed.

Further, when the positive-type resist composition for immersion type exposure of the present invention is used, foreign matter or development defects can be suppressed, and a pattern having a good shape can be formed. <<Formation Method of Photoresist Pattern>> Next, a method of forming the photoresist pattern of the present invention will be described. The method for forming a photoresist pattern of the present aspect is a step of forming a photoresist film on a support by using the positive-type photoresist composition for immersion exposure of the present invention, and exposing the photoresist film to a step of exposing the photoresist film The step of developing the photoresist film to form a photoresist pattern. The support is not particularly limited, and a conventionally known substance such as a substrate for an electronic component or an article in which a specific wiring pattern is formed may be used. More specifically, it is a substrate made of a metal such as a sand wafer, copper, chromium, iron, or aluminum, or a glass substrate. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used. Further, the support may be, for example, an article obtained by providing an inorganic or/or organic film on the above substrate. An inorganic film such as an inorganic antireflection film (inorganic BARC). Organic film, such as organic anti-reflective film (organic BARC). -90-

200839448 A method of forming a photoresist pattern of the present invention can be performed, for example, in accordance with the method. Bp, first, the above-mentioned photoresist composition of the present invention is spin-coated on a substrate such as a germanium wafer, and further at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds. The clock is pre-fired with applied bake (PAB) to form a photoresist film. The exposure source specific to the photoresist is selectively exposed with or without the desired reticle. That is, the exposure is performed by the reticle pattern, or the direct illuminating is performed without using the electron beam. After selective exposure, the exposure bake (PEB) is heated at a temperature of 80 to 150 ° for 120 seconds, preferably 60 to 90 seconds. Next, it is subjected to a water-soluble treatment using a base such as 0. 1 to 10% by mass of tetramethylammonium hydroxide (TMAH), and it is preferred to wash with water using pure water. After washing, for example, or by spraying on the surface of the substrate in the rotation, the positive-type photoresist composition for immersion exposure developed on the substrate on the substrate is washed and dried to obtain a photoresist pattern. An anti-reflection film of the machine can be disposed between the substrate and the coating layer of the photoresist composition. The wavelength used for exposure is not particularly limited to KrF excimer laser, ArF excimer laser, F2 excimer (extreme ultraviolet), VUV (vacuum ultraviolet), EB (wire, soft X-ray, etc.). The photoresist ArF excimer laser of the present invention is particularly effective. Under the conditions of the applicator and the like, the baking is performed (Post film, the type of use is selected by the reticle pattern, and the method is carried out, and the P 〇st liquid solution is used. The liquid is liquid to dissolve and dissolve. Then the machine is used or not available, shot, EUV 1 line), X composition pair -91 - 200839448 &lt;immersion exposure&gt; The positive photoresist composition of the present invention As described above, it is suitable for immersion exposure. The step of immersing the photoresist film by immersion may be performed, for example, in the following manner. First, the photoresist film obtained in the above manner and the lowermost exposure device are used.

The lens between the positions is filled with a solvent (soaking medium) having a refractive index higher than that of air, and in this state, exposure (immersion exposure) is performed with or without the desired mask pattern. The immersion medium is preferably a solvent which has a refractive index larger than that of air and which is smaller than the refractive index of the photoresist film formed by using the positive-type photoresist composition of the present invention. Further, the refractive index of the solvent is not particularly limited as long as it is within the above range. A solvent having a refractive index greater than that of air and smaller than the refractive index of the photoresist film, for example, water, a fluorine-based inert liquid, an oxime-based solvent, or the like. Specific examples of the fluorine-based inert liquid are, for example, liquids such as C3HC12F5, c4f9och3, C4F9, C2H5, and C5H3F7, and the like, and those having a boiling point of 70 to 180 ° C are preferred, and those having a boiling point of 80 to 160 ° C are more preferred. . In the fluorine-based inert liquid, when the boiling point is in the above range, the medium used for the wetting type can be removed simply after the end of the exposure, and it is preferably a fluorine-based inert liquid, particularly a hydrogen atom in an alkyl group. The perfluoroalkyl compound obtained by completely replacing the fluorine atom is preferred. The perfluoroalkyl compound is, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound, etc., in the form of -92-200839448. Further, more specifically, the above perfluoroalkyl ether compound, for example, perfluoro(2-butyl-tetrahydrofuran) (boiling point 102 ° C), the above perfluoroalkylamine compound, such as perfluorotributylamine (boiling point) 174 ° C) and so on.

The positive-type resist composition of the present invention is particularly susceptible to the adverse effects of water, and has a refractive index higher than that of air from the viewpoints of excellent sensitivity and shape of the resist pattern. The solvent with a large refractive index is optimal for water. Moreover, water is also preferable in terms of cost, safety, environmental and extensive use. Next, after the end of the immersion exposure step, post exposure bake (PEB) is performed. Next, it is subjected to development treatment using an alkali developer, and it is preferred to wash with water using pure water. For water washing, for example, water droplets may be sprayed or sprayed on the surface of the substrate to be rotated, and the developer on the substrate and the positive-type photoresist composition for immersion exposure dissolved in the developer may be washed away. Subsequent drying is carried out to obtain a photoresist pattern obtained by patterning the reticle pattern. [Embodiment] The present invention will be described in more detail by way of specific examples, but the invention is not limited thereto. [Example 1 and Comparative Examples 1 to 2] The components shown in Table 1 were mixed and dissolved to prepare a positive-type photoresist composition -93-200839448 [Table 1]

Each of the abbreviations in Table 1 has the following meanings. Further, the number 値 in [ ] in Table 1 is the added amount (parts by mass). (A)-1: A polymer represented by the following chemical formula (A)-1. In the chemical formula (A) -1, the number described in the lower right of () is the ratio of each structural unit (% by mole). (B) -1 : (4-Methylphenyl)diphenylphosphonium hexafluoro-η-butanesulfonate.

(Divisional scores (C scores (C scores (D scores (E scores (points divided into s points (Example 1 (A)-l 『 _ (B)-lm (C)-lm (C )-3 『5] (D&gt;1 Γ1.2] (E)-l Γ1.321 (〇H [0.11 (S&gt;1 [2200] (S)-2 [l〇l Comparative Example 1 (A)- l _ (B)-lm - - (D)-l Γ1.21 (E)-l Π.321 (〇)-l [〇.n (S)-l [2200] (S)-2 \m Compare Example 2 (A)-l [100] (B)-l [8] - (C)-3 『5] (D)-l [1.2] (E)-l [1.321 (〇)-i [0.1] (S)-l [2200] (S)-2 『10] (C) -1, (C) -3 : The polymers represented by the following chemical formulas (c)-1 and (C)-3, respectively. In the chemical formula (C)-l, (C)-3, the number shown in the lower right of ( ) is the ratio of the structural unit (% by mole) ° (D ) -1 : tri-n-pentylamine. (Ε ) -1 : Salicylic acid. (〇) -1 : Surfactant XR-104 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (S) -1: PGMEA/PGME 2/4 (mass ratio) mixed solution

-94- 200839448 (s ) -2 : r -butyrolactone. [化50]

[Mw = 7000, Mw/Mn = 1.7]

[Mw = 19000, Mw / Mn = 1.4] [Chemical 52]

CF3 _ · · · (c - 3 &gt; [Mw = 5000, Mw / Mn = 1.4] The above (A)-l is a monomer derived from each structural unit, and is copolymerized by a dropping polymerization method known from -95-200839448 The above (C)-1 is obtained by polymerizing a monomer derived from a structural unit by a known dropwise polymerization method. The following evaluation is carried out using the obtained positive-type photoresist composition solution base. Evaluation&gt;

The hydrophobicity of the photoresist film was evaluated by measuring the static contact angle, the roll angle, the receding angle, and the like (hereinafter referred to as contact angle, etc.) of the surface of the resist film before and after the exposure in the following order. The photoresist compositions of Example 1 and Comparative Examples 1 and 2 were coated on a 8-inch wafer using a spin coater, and subjected to 1 l ° C for 60 seconds on a hot plate. It was baked (pab) and dried to form a photoresist film having a film thickness of 150 nm. On the surface of the photoresist film (photoresist film before exposure), 50/zL of water was dropped, and the contact angle and the like were measured using DROP MASTER-700 manufactured by Kyowa Interface Science Co., Ltd. Further, a photoresist film was formed in the same manner as above, and then an open-face exposure was performed using an ArF excimer laser (193 nm) using an ArF exposure apparatus NSR-S302 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, σ = 0.75). (Exposure without a mask) (exposure amount: 20 mJ/cm2), and the contact angle of the surface of the photoresist film (photoresist film after exposure) was measured in the same manner as above. The measurement results of the contact angle of the photoresist film before and after the exposure are as shown in Table 2. -96- 200839448 [Table 2] Static contact angle after exposure (°) Rolling angle (°) Back angle (°) Static contact angle (°) Rolling angle (°) Back angle (°) Example 1 87.2 18 75.8 88.3 19 74.0 Comparative Example 1 66.8 25 53.8 66.5 28 50.1 Comparative Example 2 68.1 23 56.5 69.1 24 56.0

As shown in the results, the photoresist film obtained by using the photoresist composition of Example 1 was compared with the photoresist film obtained by using the photoresist compositions of Comparative Examples 1 to 2, and it was confirmed that it was exposed before exposure. After exposure, both the static contact angle and the receding angle are displayed, and the roll-off angle is small. When (C)_1 and (C)-3 are added, a film with higher hydrophobicity can be obtained. &lt;Measurement of the eluted material&gt; A photoresist film was formed in the same manner as in the above hydrophobicity evaluation except that an 8-inch wafer treated with hexamethyldioxane (HMDS) was used. Next, using VRC310S (trade name, manufactured by SES Co., Ltd.), one drop (50 // 1 ) of pure water is moved at a linear velocity from the center of the wafer at room temperature, etc. The total contact area of the photoresist film contacted by the droplet was 221.56 cm 2 ). Thereafter, the droplet was taken, and analyzed using an analytical device Agilent-HPl 100 LC-MSD (trade name, manufactured by Agilent Technologies), and the cationic portion (PAG +) and -97- of the component (B) before exposure were measured. 200839448 The amount of dissolution of the anion (PAG-), and (D) components (χ1〇-12111〇1 /cm) 'and ask for the total amount of g (χΐ〇12mol/cm2). These results are shown in Table 3. Further, a photoresist film was formed in the same manner as above, using an ArF exposure apparatus NSR-S3 02A (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 〇. 60, (7 = 0.75 ) ' with an ArF excimer laser (193 nm) Open frame exposure (not exposed by reticle) (exposure amount 20mJ/cm2).

Next, the exposed photoresist film was subjected to the same analysis as described above, and the cation portion (pa G + ) h anion portion (PAG —) of the (B) component after exposure and the dissolution amount of the (D) component were determined. (xl0- 12^!/ cm2 ) and find the total amount (χΙΟ - 12m〇i/ cm2 ). These results are shown in Table 3. [Table 3] Dissolution amount (xl (T12mol/cm2) Total after exposure before exposure (B 戚 points (D minus points (B 戚 points (D 分 cents PAG + PAG-PAG + PAG - Example 1 6.54 6.92 0.08 0.01 19.13 0.00 32.68 Comparative Example 1 24.16 31.26 13.89 0.64 52.63 6.21 128.79 Comparative Example 2 28.76 3L60 8.76 0.13 50.59 2.46 122.31 From the results of Table 3, it was found that in the case of using the photoresist composition of Example 1, the infiltrating medium (water was dissolved before and after the exposure treatment) In the case where the (B) component and the (D) component are eluted in a small amount, it is confirmed that it has a high inhibitory substance eluting effect in the immersion exposure.

200839448 &lt;Evaluation of lithographic etching characteristics&gt; "Analytical property and sensitivity" The photoresist compositions of Examples 1 and Comparative Examples 1 and 2 were sequentially formed into a photoresist pattern. The organic anti-reflective film composition "ARC-29A" (product name: Liwa Technology Co., Ltd.) was applied to a 8-inch twin crystal using a spin coater, and then fired at 205 ° C for 60 seconds on a hot plate. It was baked and dried to form an organic antireflection film having a film thickness of 77 nm. The photoresist compositions of Example 1 and Comparative ~2 were respectively applied to the anti-reflection using a spin coater, and subjected to pre-baking (PAB) drying at 120 ° C for 60 seconds on a hot plate to form a film thickness. 150nm photoresist film. For this photoresist film, an ArF exposure device NSR-S302 (manufactured by Ris; NA (number of openings) = 0.60, 2/3 wheel illumination) was used to carry out excimer laser (193 nm) via a mask pattern. After selective irradiation, PEB treatment was carried out for 60 seconds at 1 l ° ° C, and development treatment was carried out at 23 ° C with a 2.3.8% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), followed by 3 After 0 seconds, the water was washed with pure water, and after drying, a pattern having a line width of 120 nm and a pitch of 240 nm and a pattern of a resist pattern (hereinafter also referred to as an L/S pattern) were formed. Further, the optimum exposure amount (Εορ) of the S pattern having a line width of 120 nm and a pitch of 240 nm (unit: mJ/cm2 (energy per area), that is, sensitivity, is obtained. The result is that any photoresist is used. The examples of the objects have the same sensitivity. According to the above, the general shape of the circle: Example 1 film, dry light ArF. With the next 30 seconds warp space: L / unit composition -99- 200839448 "LWR (line width) Uneven)

In the L/S pattern formed by the above Εορ, a length measuring SEM (scanning electron microscope, force idle voltage 800V, trade name: S-9220, manufactured by Hitachi, Ltd.) was used, and the line width was determined by the line. Five locations were measured in the longitudinal direction, and three times 标准 (3 σ ) of the standard deviation (σ) was calculated from the result as a measure of LWR. The smaller the 3 σ is, the smaller the unevenness of the line width is, and the L/S pattern with a more uniform width can be obtained. As a result, it was found that the example of any of the photoresist compositions was the same after 3 σ. [Evaluation of MEF (Mask Error Factor)] In the above Εορ, the L/S pattern with a line width of 120 nm and a pitch of 260 nm is used as the target mask pattern, with a line width of 130 nm and a pitch of 2 The L/S pattern of the 60 nm L/S pattern is used as the target mask pattern to form the L/S pattern, and the MEF値 is obtained according to the following calculation formula.

MEF= I CD130-CD120 I / I MD130-MD120 I In the above formula, CD13Q and CD12G are the actual line widths of the L/S pattern formed by using the mask pattern of the line width of 130 nm and 120 nm as the target, respectively. ). MDi3G and MD^o respectively represent the reticle pattern as the line width (nm) of the standard I bar, MDuosISO, MDi2 〇=120. In addition, the MEF is a reticle pattern with different line widths or calibers at a fixed pitch, and -100-200839448 judges how to faithfully reproduce (mask reproducibility) at the same exposure level. The closer the number of MEFs is to one, the higher the reproducibility of the mask. As a result, it is known that the case of using any of the photoresist compositions is the same after 3 σ. From the above results, it was found that the photoresist composition of Example 1 exhibited good performance at the same level as the photoresist compositions of Comparative Examples 1 to 2 in various lithographic etching characteristics.

[Examples 2 to 7, Comparative Example 3] The components shown in Table 4 were mixed and dissolved to prepare a positive-type photoresist composition [Table 4] (Α戚分(C Cheng Cheng (D Cheng Cheng ( s 实施 实施 Example 1 (Α&gt;2 (Β)-1 (C)-2 (C)-3 (D&gt;2 (S)-1 [100] ί51 rn m [0.251 [22001 Example 3 (Α) -2 (Β)-1 (C)-2 (C&gt;3 (D)-2 (S)-l [100] [51 『31 m [0.25] [2200] Example 4 (Α)-2 (Β )-1 (C&gt;2 (C)-3 (Ο)-! LJ (S)-l [100] [51 * m 『31 [0.251 [22001 Example 5 (Α)-2 (Β&gt;1 (C )-2 (C)-3 (D&gt;2 (S&gt;1 Γ1001 [51 『3] _ Γ 31 [0.251 [2200] Example 6 (Α)-2 (Β)-1 (C), 2 (C) -3 (〇)-2 (S&gt;1 [1001 Γ51 m [51 [0.251 [22001 Example 7 (Α)-2 (Β)-1 (C)-2 (C)-3 (D)-2 - 2=-d_ (S&gt;1 "1001 [51 [31 『51 [0.251 [2200] Comparative Example 3 (Α&gt;2 (Β)-1 (C&gt;3 (〇&gt;2 (S&gt;1 Π〇〇1 [5] m [0.251 [22001 The abbreviations in Table 4 have the following meanings. Again, [] -101 - in Table 4.

The number in 200839448 is the amount added (parts by mass). (A) -2 : In the poly (A) -2 represented by the following chemical formula (A) - 2, the number shown in the lower right of () is the ratio (mol%). (C) -2 : In the polymerization formula (C)-2 represented by the following chemical formula (C)-2, the numbers shown on the lower right side of () are the respective ratios (mol%). (D) -2 ··Triethanolamine. Further, (C) -3, (B) -1 and (S) -1 are the same as those in the table, and in (C)-3, Mw = 5000, Mw / Mn compound. Each structural item is made. Chemical structural unit 1 shows: 1 · 4 〇 [chemical 5 3]

[Mw = 10000, Mw / Mn = 2_0] [Chem. 54]

-102- 200839448 [Mw^12000, Mw/Mn 22.8] The following evaluation was carried out using the obtained positive-type photoresist composition for immersion exposure. &lt;hydrophobicity evaluation&gt;

The hydrophobicity of the photoresist film was evaluated by measuring the static contact angle, the roll angle, the receding angle, the advancing angle, and the like (hereinafter referred to as the contact angle, etc.) of the surface of the photoresist film before and after the exposure in the following order. The organic anti-reflection film composition "ARC-29A" (trade name, manufactured by Privah Technology Co., Ltd.) was applied onto a 8-inch wafer using a spin coater, and then subjected to 205 ° C on a hot plate. After baking for 60 seconds, it was dried to form an organic anti-reflection film having a film thickness of 77 nm. The photoresist compositions of Examples 2 to 7 and Comparative Example 3 were each coated on the antireflection film using a spin coater, and subjected to pre-baking (PAB) at 100 ° C for 60 seconds on a hot plate. After drying, a photoresist film having a film thickness of 150 nm was formed. On the surface of the photoresist film (photoresist film before exposure), 50//L of water was dropped, and the contact angle and the like were measured using DROP MASTER-700 manufactured by Kyowa Interface Science Co., Ltd. Further, a photoresist film was formed in the same manner as above, and then an ArF exposure apparatus NSR-S3 02 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, σ = 〇·75) was used, and an ArF excimer laser (193 mm) was used. Open-frame exposure (exposure without masking) (exposure amount 20 mJ/cm2), and contact angle of the surface of the photoresist film (photoresist film after exposure) were also measured in the same manner as above. -103- 200839448 The measurement results of the contact angle of the photoresist film before and after exposure are shown in Tables 5 and 6. 〔table 5〕

Exposure ·, r· static contact angle (°) roll angle (°) back angle (°) advancing angle (°) Example 2 81.2 22 68.5 92.0 Example 3 90.7 19 79.0 98.9 Example 4 79.3 23 67.4 91.8 Implementation Example 5 92.0 18 79.4 98.4 Example 6 79.4 23 68.6 92.0 Example 7 91.5 18 77.7 99.0 Comparative Example 3 67.4 26 52.5 78.3 [Table 6] Exposure: Post-static contact angle (°) Roll-off angle (°) Back angle (° Advance angle (°) Example 2 82.4 26 65.7 92.1 Example 3 93.7 20 77.9 98.6 Example 4 81.1 26 65.1 91.6 Example 5 93.2 20 78.7 98.5 Example 6 80.3 25 65.4 91.5 Example 7 92.5 18 80.1 98.5 Comparative Example 3 66.5 30 50.0 79.0 As shown by the results, the photoresist film obtained by using the photoresist compositions of Examples 2 to 7 was confirmed as compared with the photoresist film obtained by using the photoresist composition of Comparative Example 1. It shows the static contact angle, receding angle and advancing angle of -104-200839448 before and after exposure, while the roll angle is smaller 'adding (C) -2 and (C) -3 , a film with higher hydrophobicity can be obtained. Further, when the analytical properties of the positive-type resist composition for immersion exposure of Examples 2 to 7 were evaluated by the same method as the above-described evaluation of the lithographic etching characteristics, it was confirmed that an L/S pattern having a line width of 120 nm and a pitch of 240 nm was formed. type.

According to the content of the present invention, the photoresist composition of the present invention can form a photoresist film having high hydrophobicity, can inhibit the elution of substances during the impregnation exposure, and has good lithographic etching characteristics, so it is very suitable for being infiltrated. The exposure is used for the photoresist composition. Therefore, the present invention is extremely useful in the industry. [Simple description of the drawing] Fig. 1 is a view showing the advancing angle (0 i ), the receding angle (0 2 ), and the roll-off angle (0 3 ). [Main component symbol description]

2: plane 1 a : lower end of droplet 1 1 b : upper end of droplet 1 0 : angle of surface of droplet with plane 2 Θ 2 : receding angle Θ 3 : rolling angle -105-

Claims (1)

200839448 X. Patent Application No. 1 · A positive-type photoresist composition for immersion exposure, which increases the alkali solubility of the resin component (A) by the action of an acid, and generates an acid generator component (B) And a resin component (C) containing a fluorine-based acid dissociable group, wherein the former component (A) contains a structural unit derived from acrylic acid (2 a resin containing a fluorine atom (A1), and the foregoing resin component ( C) a main chain cyclic type resin (C1), and a main chain ring type resin. The immersion exposure composition according to claim 1, wherein the resin (C1) is fluorinated. The composition for immersion exposure according to the first aspect of the invention, wherein the resin (C 1 ) is a unit (a ' ') having an acrylic acid. 4. The immersion type according to item 3 of the patent application The composition for exposure, wherein the resin (C 1 ) is a structural unit (aO) derived from acrylic acid having a hydroxyalkyl group having a branch portion of φ. 5 · The composition for immersion exposure according to item 4 of the patent application Object, wherein the aforementioned structural unit (a〇) is There a〇 lower structure unit-2) represented by the for containing a promoter based on exposure of said resin not having I), not containing a non-(C2). Positive photoresist alkyl. Positive-type photoresist-derived junction, positive-type photoresist, fluorinated, positive-type photoresist, general formula (-106- 200839448 Wherein R2() is a hydrogen atom, a lower alkyl group or a lower halogenated alkyl group; and R22 and R23 are each independently a hydrogen atom or a monovalent aliphatic ring group, and at least one of R22 and R23 is an aliphatic ring type. Base; f is an integer of 〇~5; b and c are each independently an integer of 1 to 5] 6. The positive-type resist composition for immersion exposure according to the first aspect of the invention, wherein the resin (C2) has a structural unit (a'l) represented by the following formula (I), [In the formula (I), R1 to R4 are each independently a hydrogen atom, a linear or branched chain-107-200839448-like, a linear or branched fluorinated courtyard group, or the following formula (la) The base (la) represented, at least one of R1 2 3 to R4 is the aforementioned group (Ia); a is 〇 or 1] [Chemical 3] 0 Λ Η II ^ _Q-N-S-R5 (I 0 · [In the formula (la), Q is a linear or branched alkyl group having a carbon number of 1 to 5; and r5 is a fluorinated group]. 7. The positive-type resist composition for immersion exposure according to the first aspect of the invention, wherein the content of the resin component (C) is from 0.1 to 50% by mass based on the resin component (A). 8. The positive-type resist composition for immersion exposure according to the first aspect of the invention, wherein the resin (A1) has a structural unit derived from an acrylate having no fluorine atom and having an acid dissociable dissolution inhibiting group. (al 9) The positive-type photoresist composition for immersion exposure according to the eighth aspect of the invention, wherein the resin (A1) has an acrylate having no fluorine atom and containing a lactone-containing cyclic group. Derived structural unit (a2) -108-i 1 0. The positive-type photoresist 2 composition for immersion exposure according to claim 9 of the invention, wherein the aforementioned resin (A1) has no fluorine atom and 3 The structural unit derived from the acrylate containing a polar group-containing aliphatic hydrocarbon group 4 (a3) 〇 200839448 11. The immersion-type exposure composition according to claim 1, wherein the cerium contains the nitrogen-containing organic compound (D). 12. A method for forming a photoresist pattern, characterized by the step of forming a photoresist film on a positive-type photoresist assembly for immersion exposure of claim 1 and immersing the photoresist film With the aforementioned Barrier film is developed to form a resist pattern comprising the step of using the positive resist composition in the step branched to an exposure of -109·