TW200809410A - Resist material for immersion lithography - Google Patents

Abstract

Disclosed is a resist material for an immersion lithography. The resist material comprises a polymer (F) produced by the polymerization of a polymerizable compound (fm) having a fluorine-containing bridged ring structure and having a repeating unit (F). The resist material can be increased in its alkali solubility by the action of an acid. For example, the polymerizable compound (fm) is at least one compound (f) selected from the group consisting of compounds represented by the formulae (f1), (f2), (f3) and (f4) [wherein RF represents -H, -F, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms; and XF represents -F, -OH or -CH2OH.

Description

200809410 (1) Nine, the invention belongs to the technical field of the invention. The present invention relates to a photoresist material for immersion lithography, a photoresist for immersion lithography, a photoresist composition for immersion lithography, and a micro-impregnation composition. The formation of a photoresist by photoresist and the formation of a photoresist pattern. [Prior Art] In the manufacture of an integrated circuit such as a semiconductor, a photosensitive photoresist which is projected onto a substrate by using a pattern of a photomask obtained by irradiating light from an exposure light source onto a substrate is used to transfer the image pattern. Photolithography for photosensitive photoresist. Usually, the pattern image is projected onto a desired position of the photosensitive photoresist by a projection lens that relatively moves the photosensitive photoresist. The resolution of the image transferred to the photosensitive photoresist is increased as the light of the exposure light source is shorter, so the short-wavelength light of 22 Onm or less (ArF excimer laser light, F2 laser light, etc.) is used as the exposure light source. ) is under review. Therefore, the photoresist materials used in the lithography method using the short-wavelength light are also enthusiastically reviewed. For example, a photosensitive photoresist material used in a lithography method using F2 laser light as an exposure light source is described in Patent Document 1, and a polymer containing polyfluoroadamantyl (meth) acrylate (the following 3) A photoresist of a compound such as a copolymer).

200809410 (2) In recent years, an exposure step in which a wavelength of light becomes a reciprocal phenomenon of a refractive index of a liquid medium in a liquid medium, that is, a liquid medium between a lower portion of the projection lens and an upper portion of the photosensitive photoresist (Ultra-pure water, etc.) (hereinafter, also referred to as an immersion liquid) is filled with a projection lens to project a pattern image of the reticle onto the substrate. The immersion lithography method of the immersion exposure step of the photosensitive photoresist It is under review (refer to Patent Document 2). . The photosensitive photoresist material used in the immersion lithography method is described in Patent Document 3, and contains a photoresist composition for immersion lithography of a copolymer of the following three compounds and a fluorine-based surfactant. [Chemical 2]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-182796, Patent Document 2: International Publication No. 99/0495, No. WO Patent Publication No. JP-A No. 2005-234178. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION In the method, since the immersion liquid is filled between the projection lens and the photosensitive photoresist, the components in the photosensitive photoresist (photoacid generator, etc.) may be dissolved in the immersion liquid, or the photosensitive photoresist may be impregnated. The uneasy feeling of swelling of the liquid. Further, in the immersion lithography method, in order to move the photosensitive lens to -6 - 200809410 (3), the projection lens satisfies the immersion liquid well, and a dynamic photoresist material is desired. For example, the impregnation liquid is impregnated with water, and a photoresist material excellent in dynamic water repellency is expected. However, such a photoresist material excellent in dynamic water repellency, such as the fluorine-based surfactant described in Patent Document 3, a fluorochemical compound and a non-cyclic fluoroalkyl (meth) compound, and a patent The dynamics of the photoresist composition of Document 3 is rejected by the projection lens which is moved by the immersion of the photoresist composition of Patent Document 3 on the photosensitive resist to trace the immersion liquid, so that the dynamic water repellency is high, and the projection is shifted. It is easy to catch up with the photoresist material for immersion lithography. MEANS FOR SOLVING THE PROBLEMS The inventors of the present invention have excellent immersion lithography which is excellent in photoresist characteristics (relative transparency, uranium etching resistance, etc.) and excellent in liquid repellency, especially dynamic liquid repellency. Review. As a result, it was first found that such a property is excellent in a photoresist material. That is, the present invention has the following gist. [1] A photoresist material for immersion lithography, which is F), the polymer (F) comprising a repeating unit formed by polymerization of a fluorine-containing crosslinkable compound (fm) The solubility is increased. In the lithography method with excellent liquid repellency, 尙 is not known. The example is only that the polyacrylic acid has a low water repellency. In the lithography method, it is not easy to immerse the mirror. Impregnation lithography of a photoresist material for short-wavelength light (water, etc.) containing a polymer (polymerization of a ring structure of Fu), and acid-7-200809410 (4) [2] such as [1] The photoresist material for immersion lithography, wherein the polymerizable compound (fm) is selected from the group consisting of the following formula (f 1 ), the following formula (f2), the compound of the following formula (f3) and the following formula (f4); More than one compound (f).

The symbol in the formula indicates the following meaning, RF: hydrogen atom, fluorine atom, a carbyl group having a carbon number of 1 to 3 or a fluoroalkyl group having a carbon number of 1 to 3 XF: a fluorine atom, a hydroxyl group or a hydroxymethyl group, The fluorine atom in the compound (f) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. [3] a photoresist for immersion lithography which is characterized in that alkali solubility is increased by an action of an acid, and is characterized by containing a polymerization of a polymerizable compound (fm) having a fluorine-containing crosslinked ring structure. The repeating unit (Ru) is a repeating unit (Ru) formed by polymerization of a polymerizable compound (rm) having a group which has an alkali solubility by an action of an acid. [4] The photoresist for immersion lithography according to [3], wherein the polymerizable compound (fm) is a compound (f). [5] The photoresist for immersion lithography according to [3] or [4], wherein 200809410 (5) The polymerizable compound (rm) has the following formula (url), and the following formula (nr2) a polymerizable compound of the formula shown by ur3) or the following formula (ur4), [Chemical 4] c=o

I 〇 XR2.(L_XR2 !r2 -C(CF3)2(〇ZR3) —C(CF3)(〇ZR4) (ur2) (ur3) (ur4)

The symbol in the formula indicates the following meaning, XR1: a group having a carbon number of 1 to 6, qM: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula, XR2: at a carbon number of 1~ In the 20-valent monovalent hydrocarbon group, three XR2 groups may be the same or different, and ZR3 and ZR4 are each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and are a group having a carbon number of 1 to 20, , XR1, QR1, XR2, ZR3 or ZR4, a carbon atom-carbon interposable group - 〇-, a group of the formula -c(o)〇- or a formula -c(〇)- The carbon atom in xR1, QR1, xR2, ZR3 or ZR4 may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. [6] The photoresist for immersion lithography according to any one of [3] to [5] wherein the polymerizable compound (rm) is selected from the following formula (r1), the following formula (r2) and A compound of more than one group of compounds represented by the following formula (r3)-9- 200809410 (6) [Chemical 5]

Cf2=cf-qR3—ch=ch2 (r3) The notation in the formula indicates the following meaning,

Rr: a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms XR1: an alkyl group having 1 to 6 carbon atoms, QR1: together with a carbon atom in the formula to form a cyclic hydrocarbon group a divalent group having a carbon number of 4 to 20, XR2: in a monovalent hydrocarbon group having 1 to 20 carbon atoms, 3 XR2s may be the same or different, QR3: a formula -CF2C(CF3)(OZR4)(CH2)m - a group of the formula -CH2CH((CH2)nC(CF3)2(OZR3))(CH2)m- or a formula of -CH2CH(C(0)0ZR3)(CH2)m- a group, ZR3 and ZR4: each independently, in the alkyl group, alkoxyalkyl group, alkoxycarbonyl group or alkylcarbonyl group, a carbon number of 1 to 20, and further, XR1, QR1, XR2, ZR3 or a carbon atom _ interposable - 〇 - shown, the formula - c (o) o - or the base of the formula _c (0) _, qR1, xR2, ZR3 or ZR4 It can bind a fluorine atom, a hydroxyl group or a carboxyl group. [7] The photoresist for immersion lithography according to any one of [3] to [6], wherein the repeat unit (Fu) is 1 to 45 -10 - 200809410 with respect to the full repeat unit. (7) Moer% 'Refractive unit (Ru) contains 1% by mole of polymer. [8] A photoresist forming composition for immersion lithography, characterized by having a photoresist for immersion lithography, a photoacid generator, and an organic solvent, which are contained in any one of [7]. . [9] A method for forming a photoresist pattern of a photoresist pattern on a substrate, which is a method for forming a photoresist pattern caused by immersion lithography, which is characterized by 'in order, [8 The immersion lithography process is performed by applying a photoresist forming composition onto a substrate, forming a photoresist film on the substrate, immersing the lithography step, and developing the step. [1 〇] - a photoresist composition for immersion lithography which is characterized by an increase in alkali solubility due to the action of an acid, which is characterized by containing, polymer (F): containing a polymerizable structure having a fluorine-containing crosslinked ring structure A repeating unit (Fu) formed by polymerization of a compound (fm), and a polymer (R): a repeating unit formed by polymerization of a polymerizable compound (,) which increases alkali solubility by an action of an acid (Ru). [11] A photoresist composition for immersion lithography according to [1 〇], wherein the polymerizable compound (fm) is a compound (f). [12] The photoresist composition for immersion lithography according to [10] or [11], wherein the polymerizable compound (rm) has the formula (url), formula (ur2), formula (ur3) or formula (ur4) a polymerizable compound of the group shown. [13] The photoresist composition for immersion lithography according to any one of [10] to [12] wherein the polymerizable compound (rm) is a compound (r). [1] The photoresist composition for immersion lithography according to any one of [1 0] to [1 3], wherein the polymer (F) is made to be 0·1~ with respect to the polymer (R). -11 - 200809410 (8) 30% by mass. [1] A photoresist forming composition for immersion lithography, which is a photoresist composition for immersion lithography containing any one of [1〇]~[14], a photoacid generator , and organic solvents. [1 6] a method for forming a photoresist pattern of forming a photoresist pattern on a substrate, which is a method for forming a photoresist pattern caused by immersion lithography, which is characterized in that, in order, it will be as The immersion lithography method of [1 5] is applied to a substrate by a photoresist forming composition, a step of forming a photoresist film on the substrate, a immersion lithography step, and a development step. Advantageous Effects of Invention According to the present invention, it is possible to provide a photoresist material for immersion lithography which is excellent in photoresist characteristics and excellent in dynamic water repellency. By using the photoresist material for immersion dialysis of the present invention, it is possible to realize a stable and high-speed implementation of the immersion lithography method of the reticle with high resolution transfer. BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the compound represented by the formula (Π) shows the compound (f 1 ) • , the base group (url) represented by the formula (url), and the formula -CF2C(CF3)(0ZR3) (CH2)m- shows the base - CF2C(CF3)(OZR3)(CH2)m-. Other compounds are the same as other bases. In addition, the base symbol is the same as before without special records. The present invention provides a polymer-containing (F) containing a repeating unit formed of a polymerized material of the polymerizable compound (fm) having a fluorine-containing crosslinked ring structure (-12-200809410 (9)) Fu) A photoresist material for immersion lithography (hereinafter also referred to as a photoresist material of the present invention) in which alkali solubility is increased by the action of an acid. The photoresist material of the present invention is excellent in liquid repellency, particularly dynamic liquid repellency, and is particularly excellent in water repellency, particularly dynamic water repellency. The reason for this is not clear 'but we believe that the polymer (F) contained in the photoresist material of the present invention has a bulky structure from a fluorine-containing crosslinked ring structure, and has an acyclic fluorine-containing structure. In comparison with the fluoropolymer, it is easy to align at the outermost surface when the coating film is formed. Therefore, according to the present invention, it is difficult to immerse the impregnating liquid', and the photoresist material which can slide well with respect to the immersion liquid can be easily prepared. In the present invention, the polymerizable compound (fm) is preferably a compound having a monovalent polymerizable group and a monovalent fluorine-containing crosslinked cyclic hydrocarbon group. a monovalent polymerizable group, preferably a monovalent group of a carbon atom-carbon atom double bond having a polymerizability, and a vinyl group, a (meth) acryloyloxy group, a 2-fluoro-propyl propylene group The base ' or 2-chloroindolyl propyl ethoxy group is preferably '(methyl) propylene fluorenyloxy. However, the (meth) propylene fluorenyloxy group means an acryloyloxy group or a methacryl oxime group (the same applies hereinafter). The monovalent fluorine-containing crosslinked cyclic hydrocarbon group is preferably an aliphatic group, and particularly preferably a saturated β aliphatic group. Further, a carbon atom in the monovalent fluorine-containing crosslinked cyclic hydrocarbon group may be intercalated with -〇-, -c(0)0- or -C(O)-. Further, the carbon atom of the monovalent fluorine-containing crosslinked cyclic hydrocarbon group may be bonded to a group containing a hydroxyl group or a carboxyl group. In the monovalent fluorine-containing crosslinked cyclic hydrocarbon group, one of the valent groups of the hydrogen atom of the crosslinked cyclic saturated hydrocarbon compound is removed, and more than 50% of the residual hydrogen atom is substituted by the fluorine atom. The residual hydrogen atom is preferably 80% or more by being replaced by a fluorine-13-200809410 (10) atom, and all of them are particularly preferably replaced by a fluorine atom. The crosslinked cyclic saturated hydrocarbon compound is preferably one or more crosslinked cyclic saturated hydrocarbon compounds selected from the group consisting of the following compound (1) and the following compound (2). [Chemical 6]

Further, the fluorine atom in the compound (f) may be substituted by a perfluorocarbon group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. Further, in the compound (f) having an asymmetric carbon, the three-dimensional configuration of the asymmetric center may be inward or outward. A hydrogen atom or a methyl group is preferred. XF is preferably a fluorine atom. Specific examples of the polymerizable compound (fm) can be exemplified by the following compounds -14- 200809410 (11)

The compounds (f2), (f3) and (f4) are novel compounds. The manufacturing method will be described later. In the present invention, the weight average molecular weight of the polymer (F) is preferably from 1,000 to 100,000, and more preferably from 1,000 to 50,000. The present invention provides a polymerizable compound (fm) having a fluorine-containing crosslinked ring structure. The repeating unit (Fu) formed by the polymerization and the repeating unit (RU) having a base which has an alkali solubility increase due to the action of an acid, and the immersion lithography which increases the alkali solubility due to the action of an acid A photoresist polymer (hereinafter referred to as a photoresist polymer of the present invention). The photoresist polymer of the present invention is excellent in liquid repellency, especially dynamic liquid repellency, particularly in water repellency, especially in dynamic water repellency. The reason for this is not clear, and it is considered that the photoresist polymer of the present invention is formed of a polymer having a bulky structure derived from a fluorine-containing crosslinked ring structure, as compared with a fluorine-containing polymer having an acyclic fluorine-containing structure. When the coating film is formed, it is easy to align at the outermost surface. Therefore, in the immersion lithography method using the photosensitive photoresist prepared by the photoresist of the present invention, the projection lens which moves at high speed on the photosensitive photoresist can follow the immersion liquid well. Further, since the photoresist polymer of the present invention contains a repeating unit (Ru), it is a polymer which increases alkali solubility due to the action of an acid. The exposed portion of the photosensitive resist prepared by the photoresist of the present invention can be easily removed by an alkali solution. Therefore, with the photoresist polymer of the present invention, it is possible to realize a stable high-speed implementation of the immersion lithography method in which the pattern image of the reticle can be highly resolved. The repeating unit (RU) is preferably a repeating unit formed by polymerization of a polymerizable compound having the following group (url), (ur2), (ur3) or (ui:4), and is selected from the group consisting of The repeating unit formed by the polymerization of one or more compounds (r) in which the compound (r 1 ), (r2) and the compound (r3) are grouped is particularly preferable. The mark in the formula is the same as before without special explanation. -16- (13) (13)200809410 [Chemical 9] ^\ X^-C

J TR2 -C(CF3}2(OZR3) -C(CF3}(OZrV (ur1) (ur2) (ur3) (ur4>ch2=< ch2=c , c=o c=

II xRi.Jr-^v xR2-c—xR2 () |R2 cf2=cf-qR3-ch=ch2 (r1)Q (Γ2) (r3) XR1 contains an alkyl group having 1 to 6 carbon atoms or ether oxygen The alkyl group having 1 to 6 carbon atoms is preferred, and methyl or ethyl is particularly preferred. The divalent group formed by the carbon atom of QR 1 and the formula is preferably an aliphatic group, and particularly preferably a saturated aliphatic group. The divalent group may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. The divalent group is preferably a polycyclic hydrocarbon group. It is particularly preferred to crosslink a cyclic hydrocarbon group. It is preferred that all three of the XR2 systems are alkyl groups having 1 to 3 carbon atoms, or two alkyl groups having 1 to 3 carbon atoms and one monovalent cyclic hydrocarbon group having 4 to 20 carbon atoms. ZR3 and ZR4 are each independently, preferably an alkyl group having 1 to 12 carbon atoms or an alkoxymethyl group having 1 to 12 carbon atoms. RR is particularly preferred as a hydrogen atom or a methyl group. The m in QR3 is preferably 1. η in QR3 is preferably 0. Any of the bases shown by the following formula is preferred. -17- 200809410 (14) [Chem. 10]

The base (ur3) is preferably -C(CF3)2(〇C(ZR11)3) or -C(CF3)2(OCH2OZR11), with -c(cf3)2(oc(ch3)3),_C(CF3) ) 2(0CH20CH3), -C(CF3)2(OCH2OCH2CH3), -C(CF3)2(〇CH2OC(CH3)3), or any of the following groups (but 'ZR11 shows carbon number 1~12 An alkyl group or an alkoxymethyl group having 1 to 12 carbon atoms. The same applies hereinafter.). [Chem. 12] —C(CF3)20CH20—C(CF3)2〇CH20'

The base (ur4) is preferably -C(CF3)(〇C(Zr11)3)- or -C(CF3)(OCH2OZR11)-, -C(CF3)(OC(CH3)3), _C(CF3) (OCH2OCH3)-, -C(CF3)(0CH20CH2CH3)_, _(:(0?3)(0(:1120(:((:113)3)-) or any of the following groups. - 200809410 (15) [Chem. 13]

Compound (rl), (Π4), particularly good. It is preferred to describe the compound (r 1 1 ), (r 1 2 ), (r 1 3 'l5) or (rl6) to the compound (rll) [Chemical 14]

(Π3) (M4) (Π5) (r16) The compound (r2) is preferably a compound (r2l) or (r22). , c=o I ο I CH3—C-CH3

(Γ21) cH2=cr ch2 二卜οο CH3- 十~CH3 ch3 (r22) Compound (r3) is CF2 = CFCH2CH(C(CF3)2(OC(Zr11)3))CH2CH = CH2 , CF2 = CFCH2CH(C (CF3)2(OCH2OZr11))CH2CH=CH2, CF2 = CFCF2C(CF3)(OC(ZR11)3)CH2CH=CH2, or cf2 = cfcf2c(cf3)(och2ozr11)ch2ch2 CH2 is preferred. Specific examples of the compound (r 1 ) include the following compounds. -19- (16) 200809410 W 匕16] /Η /Η3 /F /CF3 yH CH3 ch2=c ch2=c ch2=c ch2=c ch2=c ch〇=c >=〇>=〇>=〇>=〇>=0>=0 0 0 0 oo 〇CH3·^^ ch3-^^| ch3-^^ ch3ch2-^^j ch3ch2-^^| ,ch3 /CF3 /H ch2= c ch2=c ooo o ch2=c^ >=〇o CH3CH2^^^| CH3CH2-^^^| CH3(CH2)3^^| CH3(CH^\y^ CHaCCH^ /CF3 ch2=c ch2= c >=〇>=〇ooo CH3{CH2)3^^^^ CH30(CH2)4七卜! ch3o(ch2)4 ch2=c )=°

CHa=C ,ch3 )=°

CH2 two c >=°

Ch2=c

Ch2=c /Cp3 )=° >=° CH30(CH2)4

0 CH30(CH2)4

.CHa

M /CH3 /F CH2=C CHa 二 C CH2=C CH2=C" ' CH2=C, CH2=C, )=〇^=0 )=〇^=0 ^=0 )=0 cn3^<ryj Ch3^〇4 ch3^cx/ ch3〇v ^ 〇. PH2CH3 v /〇2〇3 >0F3

H ^CH3 F CF3 .F ch2=c ch2 two c ch2=c ch2=c ch2=c ch2=c' y=〇)=〇y=〇y==〇)=〇^=〇o ch2ch3 o ch2ch3 o Ch2ch3 o ch2ch3 o ch2ch3 /H /CH3 f yCF3 ch2=c ch2=c CH2=C ch2 two c )=〇/=° )=〇)=〇q CH3 〇ch3 cT ch3 O cHa =0 Compound (r2) Specific examples include the following compounds [Chem. 17]

CH3-C-CH3 ch3-ch2=c 〆",丫=0 ch2=c: C-CH3 ch3 .ch3 c=o I 0 1 CH3—C—CH3 CH, specific examples of compound (r3), The following compounds are given. -20- 200809410 (17) CF2=CFCF2C(CF3)(OCH2OCH3)CH2CH=CH2 CF2»CFCF2C(CF3)(OCH2〇CH2CH3)CH2CH=CH2 CF2=CFCF2C(CF3)(OCH2OC(CH3}3) CH2CH»CH2 CF2=CFCH2CH(C(CF3>2OCH2OCH3)CH2CH*CH2 CF2=CFCH2CH(C(CF3}2OCH2OCH2CH3)CH2CH=CH2 CF2=CFCH2CH(C(CF3)2OCH2OC(CH3)3>CH2CH=CH2 cf2=cfcf> C々h2ch=ch2 cf3 och2o

IQ cf2=cfcf>c(h2ch=ch2 cf3 och2o

The photoresist polymer of the present invention preferably has a weight (Fu) of 1 to 45 mol% and a repeating unit (Ru) of 10 or more, based on the total recoating unit. The photoresist polymer of the present invention preferably has a weight (Fu) of 2.5 to 30 mol% relative to the total recoating unit. In this case, a liquid in which the photoresist of the present invention is dispersed or dissolved in an organic solvent can be produced. The photoresist polymer of the present invention is preferably further composed of 20 to 90 mol%, more preferably 30 to 90%, based on the total recoating unit. In this case, the exposed portion of the photoresist polymer can be removed from the alkali solution. The photoresist polymer of the present invention may contain a repeating unit other than the unit (Fu) unit (Ru) (hereinafter, also referred to as another single FRU). In this case, the photoresist polymer of the present invention is preferably contained in another unit (FRU) in an amount of 20 to 60 mol% relative to the unit of the coating, and is not particularly limited to have the following uql) or The polymerization unit (qm) of (uq2) is preferably formed by a polymerization unit (QU), and is selected from the group consisting of the following compound (ql) and (polymerization of one or more compounds (q) in a group) : Unit I ear %: Unit in tone: Composition: Unit 60 is not covered by i ( (Full weight q2): Unit-21 - 200809410 (18) Tejia. [Chem. 19] (uq1) ^R° ^Rq , CH2=<ch2=< Γ r. r° 〇b H~h (uq2) (q1) (q2) The symbol in the formula indicates the following meaning (the same applies hereinafter). QQ1: a valence group having a carbon number of 4 to 2 0 which forms a crosslinked cyclic hydrocarbon group together with a carbon atom in the formula. qQ2: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula. , carbon atoms in Qq1 or qQ2 - carbon atoms can be inserted between -〇-, -C(0)0- or -C(O)-', QQ1. The carbon atoms in qQ2 can bind fluorine atoms, hydroxyl groups or carboxyl groups. RQ: hydrogen atom, fluorine atom, The alkyl group having 1 to 3 or the fluoroalkyl group having 1 to 3 carbon atoms. The trivalent group formed by the carbon atom in the formula 1 is preferably an aliphatic group and a saturated aliphatic group. The divalent group formed by the carbon atom in the formula is preferably an aliphatic group, particularly preferably a saturated aliphatic group. The divalent group may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group.卩... or the carbon atom in QQ2 - the case where -0, -C(0)CK or -C(O)- can be inserted between carbon atoms is preferably inserted in -C(〇)〇-. In QQ1 or Qq2 A carbon atom having a fluorine atom, a hydroxyl group or a carboxyl group is preferably bonded with a hydroxyl group or a fluorene-22-200809410 (19) group. RQ is preferably a hydrogen atom or a methyl group. The group (uql) has the following group (uqll). , (uql2) , (uql3) , (uql4) or (uql5) is preferred. W 匕 20]

The base (uq2) is preferably a group (uq21), (uq22), (uq23), (uq2 4 ) , ( uq2 5 ) , ( uq2 6 ) , ( uq2 7 ) , ( uq2 8 ) or (uq29 ).

[化22]

pQ pQ 〇Q pQ pQ

CH2=CC CH2=〇r CH2=C= CH2=CC CH〇=CC , c=o , c=o , c=o , c=o , c=o L· HOi^c o

Oo (q14) (q11) (q12) (q13) (q15) q22 Compound (q2) is compound (q21 -23- 200809410 (20) q23 ) , ( q24 ) , ( q25 ) , ( q27 ) , ( q2 ) 8) or (q29) is preferred. [0], R0, rq ch2 = 〇Cc = 〇ch2 = c; c =: 〇o, rq, c = o I o , rq ch2 = c [ ch2 = c [ ^c = o , c = o I o

CH〇=C (q21) rq ch2=c o , c=o I o

c II Η2 c a rq

ο II c丨ο H one

(q29) Ό o (q26)

o o

(q27) (q28) Specific examples of the compound (q 1 ) include the following compounds: CH 2 = C == 〇 CH2 = 0H2 = CCI = 0 eve3. CH2=C:i=0

III I I

^ L· i^〇H i^〇HH〇i6^〇H ch2=c

Oo CH2=<=〇 Call C¥<i3〇

I I I I I ^Loh i^o i^o 0 0 o o Specific examples of the compound (q2) include the following compounds -24- 200809410 (21) [Chem. 25]

The weight average molecular weight of the photoresist polymer of the present invention is preferably 100,000 or more preferably from 1,000 to 50,000. In a preferred aspect of the photoresist polymer of the present invention, the unit may be a unit of repetition, such that the repeat unit (Fu) contains 1 to 45 mol%, and the weight (Ru) contains 30 to 60 mol% of the polymer. . In terms of the special aspect, it can be exemplified as a relative unit in a polymer containing a repeat unit (F u ) unit (Ru ) and other units (FRU ), and a repeat unit (Fu) containing 1 to 45 m. %, repeat RU) contains 30 to 60 mol%, and other units (FRU) contain 20, ear % of polymer. In this aspect, the repeating unit (Ru) is preferably a repeating unit in which the compound (r 1 ) is aggregated, and the unit of the compound (r 1 1 ) is particularly preferably formed by polymerization. The other unit (FRU) in this aspect is preferably a unit formed by polymerization of the compound (ql2 q22), (q23), (q25) or (q26). 1 000 〜 For the full coverage unit, repeat the weight of the whole weight unit (^ 60 Mohe formed by the weight of the heavy-25-200809410 (22) The weight average molecular weight of the polymer in this aspect is preferably 1000~30000. The photoresist polymer of the present invention is generally used for modulating a chemically amplified photosensitive resist in the application to the immersion lithography method. The photoresist polymer of the present invention is preferably a photoacid generator. The photoresist polymer of the present invention is generally used for coating on a substrate in the application to the immersion lithography method. The photoresist polymer of the present invention is preferably prepared into a liquid composition. A photoresist forming composition for immersion lithography comprising the photoresist polymer of the present invention, a photoacid generator and an organic solvent (hereinafter referred to as a photoresist forming composition (1)). A photoresist forming composition (1) The photo-resistive polymer photoacid generator of the present invention is preferably contained in an amount of 1 to 10% by mass. The photoresist-forming composition (1) contains 100% by mass based on the organic solvent of the photoresist polymer of the present invention. ~ 1 0000% by mass is preferred. Photoacid generator, The compound having a group capable of causing an acid to be generated by irradiation with active light is not particularly limited (however, active light means a broad sympathy containing radiation. The same applies hereinafter.) The compound may be non-polymerized. The compound may be a polymer compound. The photoacid generator may be used alone or in combination of two or more. The photoacid generator is selected from the group consisting of a key salt, a halogen-containing compound, and a diazoketone. It is preferred that one or more photoacid generators of a compound such as a ruthenium compound, a ruthenium compound, a diazo bismuth, a diazo ketone oxime, an imide sulfonate or a diflavonoid are preferred. -26- 200809410 (23) Specific examples of the photoacid generator include diphenyl iodine triflate, diphenyl iodine sulfonate, and diphenyl iodine hexafluoroantimonate. , diphenyl iodide dodecyl benzene sulfonate, bis(4-tributylphenyl) iodine triflate, bis(4-tributylphenyl) iodine 12 Benzene sulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenyl decanoate, triphenylsulfonium perfluorooctane salt, triphenyl sulfonium Chain acid salt, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenyl camphorquinone, 1-(naphthylethylidenemethyl)thiolanium triflate , cyclohexylmethyl (2-oxocyclohexyl) fluorene triflate, dicyclohexyl (2-oxocyclohexyl) fluorene trifluoromethanesulfonate, dimethyl (4-hydroxynaphthalene) Ethyl sulfonate, dimethyl (4-hydroxynaphthyl) fluorenyl dodecyl benzene sulfonate, dimethyl (4-hydroxynaphthyl) anthracene naphthalene sulfonate, triphenyl camphorsulfonic acid Salt, (4-hydroxyphenyl)benzylmethylindole tosylate '(4-methoxyphenyl)phenyl iodide iron trifluoromethanesulfonate, bis(tertiary butylphenyl) iodine Trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, methoxyphenyl-bis(trichloromethyl)-S-triazine, naphthyl-bis(trichloromethane) -s-triterpene, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 4-tribenzhydrylmethyl (Phenacyl) fluorene, thiophene醯Methyl maple, bis(phenylsulfonyl)methane, benzoin tosylate, 1,8-naphthalene dicarboxylic acid quinone imine trifluoromethyl Salt. The organic solvent is not particularly limited as long as it is a solvent having high compatibility with the photoresist of the present invention. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent. Specific examples of the fluorine-based organic solvent include CC12FCH3 '-27- 200809410 (24) CF3CF2CHC12, CC1F2CF2CHC1F and the like hydrochlorofluorocarbons; CF3CHFCHFCF2CF3, CF3(CF2)5H, CF3(CF2)3C2H5, CF3(CF2) Hydrogen fluorocarbons such as 5C2H5, CF3(CF2)7C2H5, etc.; hydrofluorobenzenes such as 1,3 trifluoromethyl)benzene; hydrofluoroketones; hydrofluoroalkyl groups: CF3CF2CF2CF2OCH3, (CF3)2CFCF(CF3)CF2OCH3 , hydrofluoroethers such as CF3CH2OCF2CHF2; CHF2CF2CH2OH, fluoroalcohols. Specific examples of the non-fluorine-based organic solvent include methyl alcohol alcohol, diacetone alcohol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-, 2-ethylbutanol, Alcohols such as pentanol, hexanol, heptanol; ketones such as acetone isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrole r-butyrolactone; Ethyl acetate, propyl methyl ether propionate, propylene glycol monoethyl ether acetate, carbitol ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Θ-甲Methyl oxyacid, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate, esters, etc.; toluene, An aromatic hydrocarbon such as xylene; propylene glycol ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, ethylene dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, single Ethylene glycol mono- or dialkyl ethers such as methyl ether; hydrazine, hydrazine-dimethyl, hydrazine, hydrazine-dimethylacetamide, and the like. The present invention provides a repeating unit (Fu) comprising a polymer (F) and a polymer (R polymer (F) comprising: a polymerizable (fm) having a fluorine-containing crosslinked ring structure, the polymer - bis (benzenes; hydrogen in spring, ethyl 1-propanol, methyl D-butanone, glycol monoester, ethyl isobutyrate ethyl lactate monomethylol monoisopropyl glycol formamide), the compound i ( R ) -28 - (25) (25) 200809410 A repeating unit (Ru) formed by polymerization of a polymerizable compound (rm) which increases alkali solubility by an action of an acid, causing a base due to an action of an acid A photoresist composition for immersion lithography having an increased solubility (hereinafter referred to as a photoresist composition of the present invention). The photoresist composition of the present invention is excellent in liquid repellency, particularly dynamic liquid repellency, particularly Water repellency, especially dynamic water repellency, is not clear. The polymer (F) contained in the photoresist composition of the present invention is considered to have a bulky structure from a fluorine-containing crosslinked ring structure. Compared with a fluoropolymer having an acyclic fluorine-containing structure, when the coating film is formed, thus The outermost surface is easy to align. Therefore, in the immersion lithography method using the photosensitive photoresist prepared by the photoresist composition of the present invention, the projection lens can be moved at high speed on the photosensitive photoresist, and the immersion liquid can be good. Further, since the photoresist composition of the present invention contains a polymer (R), it is a composition which increases alkali solubility due to the action of an acid. Photosensitive light modulated by the photoresist composition of the present invention The exposed portion of the resist can be easily removed by the alkali solution. Therefore, with the photoresist composition of the present invention, it is possible to realize a stable high-speed implementation of the pattern image of the mask by the high-resolution transfer immersion lithography method. The polymer (F) (hereinafter referred to as polymer (FS)) in the photoresist composition of the present invention may be a polymer formed by repeating only the unit (Fu), or may contain a repeat unit (Fu) and Repetitive units other than the unit (Fu) (hereinafter referred to as the other unit (F Su )). In summary, the polymer (FS), with respect to the full re-equipment unit, causes the repeat unit (fu) to contain 10% or more of 'more than 20% by mole or more is preferred In the case where the polymer (FS ) contains other units (FS u ), it is preferably -29-(26) (26) 200809410, and the unit (FSU) is contained in an amount of 90 mol% or less, relative to the total repeat unit. Contains 80% or less. Other units (FSU) are preferably repeated units (RU) or repeated units (Qu), with compound (r 1) ' ( r2) , ( q1 ) or (q2) The repeating unit formed by the polymerization is particularly preferable. The weight average molecular weight of the polymer (FS) is preferably from 1 〇〇〇 to 100,000, and from the viewpoint of compatibility with the polymer (R) and developability, it is 1,000. ~30000 Tejia. Preferred examples of the polymer (F S ) include the following polymers (FSH) and the following polymers (FSe). Polymer (F S η ): a polymer formed only by repeating units (Fu). Polymer (FSe): In a polymer containing a repeat unit (Fu) and other units (FSU), the repeat unit (Fu) contains 10 to 50 mol%, and other units (with respect to the full repeat unit) FSU) contains 50 to 90 mole % of polymer. Other units (FSU) in the polymer (FSC) are preferably in units of repeating (Ru) or repeating units (Qu). The repeating unit (Ru) is preferably a repeating unit formed by polymerization of the compound (Γ 1 1 ). The repeating unit (Qu) is particularly excellent in a repeating unit formed by polymerization of the compound (ql2), (q22), (q23), (q25) or (q26). The weight average molecular weight of the polymer in this aspect is preferably from 1,000 to 30,000. In the present invention, the polymer (R) is preferably a polymer containing 10 mol% or more of the repeat unit (Ru) with respect to the total repeat unit. -30- 200809410 (27) The repeating unit (RU) is preferably a repeating unit formed by the polymerization of the compound (r), and the repeating unit formed by the polymerization of the compound (r 1 ) is a good compound (r 1 1 The repeating unit formed by the polymerization is optimal. The polymer (R) preferably contains a repeating unit (Qu). The repeating unit (QU) is a repeating unit formed by polymerization of a repeating unit (QBlU) formed by polymerization of a polymerizable compound having the following group (uqBl) or a polymerizable compound having the following group (uqB2) ( Preferably, QB2U) is particularly preferably a repeating unit formed by polymerization of the following compound (qBl) or (qB2). [Chem. 26]

(uqB1) (uqB2) (qB1) (qB2) The symbol in the formula indicates the following meaning (the same applies hereinafter). qQBI: a carbon atom having a carbon number of 5 to 20 which forms a crosslinked cyclic hydrocarbon group together with a carbon atom in the formula, wherein the carbon atom in the group has a fluorine atom-bonding group or a mercapto group. Further, a carbon atom-carbon atom in Qqb1 may be inserted - C(0)0- or -c(o)- 〇qQB2: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula In the carbon atom in the group, a group of _C(0)0 or -C(〇)_ can be inserted. Further, the carbon atom in Qqb2 may be bonded, and the fluorine atom, the hydroxyl group or the carboxyl group 〇qQB 1 and the trivalent group formed by the carbon atom in the formula are preferably an aliphatic group -31 - 200809410 (28), which is a saturated aliphatic group. Kitjay. Further, in the case where -c (〇) 〇 - or -c (Ο)- can be inserted between the carbon atom and the carbon atom in QQB1, it is preferable to insert -C (Ο) 0 -. The divalent group formed by QQB2 and the carbon atom in the formula is preferably an aliphatic group, and is preferably a saturated aliphatic group. The divalent group may be a monocyclic hydrocarbon group' or a polycyclic hydrocarbon group. The base (uqBl) is preferably a group (uql2) or (uql3). The base (uqB2) is preferably a group (uq22), (uq23), (uq25) or (uq2 6 ). The compound (qB 1 ) is preferably a compound (q 1 2 ) or (q 1 3 ). The compound (qB2) is preferably a compound (q22), (q23), (q25) or (q26). The weight average molecular weight of the polymer (R) is preferably from 1,000 to 10,000. Preferably, the polymer (R) is in the form of a repeating unit (Ru), a repeating unit (QB1U), and a heavy aspect. In the polymer of the cover unit (QB2U), the repeat unit (RU) contains 20 to 50 mol%, and the repeat unit (QB1U) contains 30 to 50 mol% and the repeat unit (QB2U). ) contains 20 to 30 mole % of polymer. In this preferred embodiment, the repeating unit (QB1U) is preferably a repeating unit formed by polymerization of the compound (qi2) or (ql3). Further, the repeat unit (QB2U) is particularly excellent in a repeating unit formed by polymerization of the compound (q22), (q23), (q25) or (q26). The weight average molecular weight of the polymer in this aspect is preferably from 1,000 to 100,000 to 32, and 200809410 (29), and more preferably from 1,000 to 50,000. The photoresist composition of the present invention comprises a polymer (FS) and a polymer (R), and the polymer (FS) is preferably contained in an amount of 0.1 to 30% by mass, based on the polymer (R). 1 〇% by mass is excellent. In this case, the polymer (FS) and the polymer (R) are easily dissolved, and the film forming property of the photoresist composition of the present invention is excellent. The photoresist composition of the present invention is suitable for use in the immersion lithography method and is generally used for the modulation of chemically enhanced photosensitive photoresist. The photoresist composition of the present invention is preferably a photoacid generator. Further, the photoresist composition of the present invention can be generally applied to a substrate for use in the immersion lithography method. The photoresist composition of the present invention is preferably prepared into a liquid composition. The present invention provides a photoresist forming composition for immersion lithography comprising the photoresist composition of the present invention, a photoacid generator and an organic solvent (hereinafter referred to as a photoresist forming composition (2)). The photoresist forming composition (2) is preferably contained in an amount of 1 to 1% by mass based on the polymer (R) photoacid generator. The photoresist forming composition (2) is preferably contained in an amount of 100% by mass to 1% by mass based on the total amount of the organic solvent of the polymer (R). As the photoacid generator, a photoacid generator can be used together with the photoresist forming composition (1). As the organic solvent, an organic solvent can be used together with the photoresist forming composition (1). The photoresist forming composition of the present invention (however, it means the photoresist composition (1) or the photoresist composition (2)) is used for the immersion lithography method. -33- 200809410 (30) In the immersion lithography method, the photoresist forming composition of the present invention is applied onto a substrate (such as a wafer or the like) in sequence: a step of forming a photoresist film on the substrate, impregnating micro The immersion lithography method of the shadowing step, the developing step, the engraving step, and the photoresist film peeling step. In the immersion lithography step, the light of the exposure light source is irradiated onto the pattern image of the reticle obtained by the reticle, so that the immersion liquid is filled between the projection lens and the photoresist film, and the relative movement is transmitted through the photoresist film. The projection lens is projected onto a desired position of the photoresist film. Exposure source with g-line (wavelength 4 3 6 nm), i-line (wavelength 3 6 5 nm), KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm) or F2 excimer laser light (wavelength) 157 nm) is preferable, and ArF excimer laser light or F2 excimer laser light is preferable, and ArF excimer laser light is excellent. The immersion liquid may be an oily liquid medium (decahydronaphthalene or the like), may be an aqueous liquid medium (ultra-pure water, etc.), and a liquid medium containing water as a main component is preferable, and ultrapure water is particularly preferable. As the developing step, a step of removing the exposed portion of the photoresist film with an alkali solution can be exemplified. The alkali solution is not particularly limited, and may be an alkali aqueous solution containing one or more alkali compounds selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine. . The present invention provides a repeating unit (Rp) formed by polymerization of a repeating unit (Fp) formed by the following compound (fp), and a polymerization of the following compound (rlp) or (r2p), and The repeating unit (Fp) contains 1 to 40 mol% of the immersion exposure photo-resistance-34-(31) 200809410 compound (hereinafter referred to as a photoresist polymer (p)) . [化27]

CH2WfifP

CH2 二 c〆 〇>=〇 Xr2p - i-Xr4P xr3p (r2P) 4 旦, the symbol in the formula indicates the following meaning (the same applies hereinafter).

Rfp ' ΙΓρ : is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having a carbon number of 丨3. PP : 0 or 1 〇

Xfp : In the case where PP is 0, it is a fluorine atom or a hydroxyl group, and when pp is 1, it is a fluorine atom or a hydroxymethyl group. XUp: an alkyl group having a carbon number of 1 to 6 which may be inserted between a carbon atom and a carbon atom. QW: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula. The carbon atom-carbon atom in Qfp can be inserted between -〇_, -C(0)0_ or -C(O)-, and the carbon atom in Qfp is selected from a fluorine atom, a hydroxyl group, a sulfhydryl group, or a Among the groups of one or more groups in which the oxy 'institutional oxy-oxyl group, the oxycarbonyl group and the ortho-based group are grouped, there are those having a carbon number of 1 to 10 in combination.

Xr2P, Xr3p and xf4p are each independently a hydrocarbon group having a carbon number of 1 to 20. In the hydrocarbon group, a carbon atom-carbon atom may be interposed between -0-, -C(0)0- or -C(〇)-, and further, the carbon atom in the hydrocarbon group is selected from a fluorine atom, a hydroxyl group, a carboxyl group, Or a group in which one or more groups of alkoxy groups, alkoxy alkoxy groups, alkoxycarbonyl groups and alkylcarbonyl groups are bonded to a carbon number of 1 to 10 can be bonded. -35- (32) (32) 200809410 The photoresist (P) of the present invention contains a repeating unit (Fp) formed by the polymerization of the compound (fp), so that the water repellency is excellent and the dynamic water repellency is excellent. The reason is not clear. It is believed that the photoresist (P) has a bulky polyfluoroadamantyl group in the side chain of the repeat unit (Fp). Therefore, it is considered that the photoresist (P) containing a repeating unit (Fp) is excellent in water repellency, is difficult to be immersed in water, and is excellent in dynamic water repellency, and can slide well against water. The photoresist polymer (P) contains 1 to 40 mol% with respect to the total repeat unit repeat unit (Fp). More preferably, it is 2.5 to 30% by mole relative to the full repeat unit (Fp). In this case, the water repellency of the photoresist (P) is not only excellent, but the photoresist (P) is easy to disperse or dissolve in a general-purpose organic solvent, so that it is easy to prepare a photoresist composition for liquid immersion exposure. The compound (fP) is preferably the following compound (f〇P) or the following compound (flP). W 匕 28]

However, the symbol in the formula indicates the following meaning (the same applies hereinafter).

Rflp is a hydrogen atom. The fluorine atom is an alkyl group having 1 to 3 carbon atoms or a fluorine group having 1 to 3 carbon atoms. The hydrogen atom 'fluorine atom' is preferably a methyl group or a trifluoromethyl group, and the methyl group is particularly preferred. XfGP in the compound (f〇p) indicates a fluorine atom or a hydroxyl group. -36- 200809410 (33) In the compound (fip), xflp represents a fluorine atom or a hydroxymethyl group. The compound (πρ) is a novel compound. Compound (flP) The compound (π-3P) is reacted with water to obtain the following compound (f 1 _ followed by reacting the compound (fl-2P) with H_CH0 to obtain the following fl-1P), followed by making the compound (with CH2) = CRfli can be produced by reaction. [Chem. 29] The next 2P), compound (C(0)C1

However, when Xfl is a fluorine atom, Xbp indicates that the fluorocarbon 3 is a hydroxymethyl group, and the fluorocarbonyl group, xap is a fluorine atom at xflp, and a hydrogen atom is represented by a case where XflP is a hydroxymethyl group. Specific examples of the compound (fp) are the same as those described in the specific examples of the polymerizable compound. Further, in the photoresist polymer (P) of the present invention, it is considered that the carboxylate portion of the heavy (RP) is cleaved by the action of an acid to form a carboxylate acid to increase the alkali solubility. Therefore, the exposed portion of the resist composition for immersion exposure of the present invention after liquid immersion can be easily removed. Rrp in the compound (irlP) is preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Xflp is preferably a hospital having a carbon number of 1 to 6, preferably a methyl group, an ethyl group or a butyl group, and preferably a methyl group or an ethyl group. ‘, xflp case (fm cover unit base, so light step alkali solution methyl or propyl or -37- (34) (34) 200809410

The ring formed by Qi and a carbon atom in the formula may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group, and a polycyclic hydrocarbon group is preferred, and a crosslinked cyclic hydrocarbon group is particularly preferred. The cyclic groups are preferably an aliphatic group and a saturated aliphatic group. In the QP, a carbon atom-carbon atom is inserted between -〇-, -c(o)〇- or -C(c〇_, preferably -C(0)0- is inserted. The carbon atom in Qrp, In a group selected from the group consisting of a fluorine atom, a hydroxyl group, a carboxyl group, or an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group and a decyloxy group, a group having a carbon number of 1 to 10 is bonded. In the case of a combination of a hydroxyl group or -OCH2OXblpp (however, Xblpp represents an alkyl group having 1 to 9 carbon atoms), it is preferred to bind a hydroxyl group, -〇CH2OCH2CH3, -OCH2OCH3 or -OCH2OC(CH3)3. Compound (r2p) The XF2p~Xf4p are each independently, and the saturated hydrocarbon group having a carbon number of 1 to 20 is particularly preferable. In the preferred aspect of t2p to XMp, X〃p~χΜρ is an alkyl group having a carbon number of 1 to 3 (see The methyl group is preferably in the form of an alkyl group having a carbon number of 1 to 3 (preferably a methyl group), and the 乂^" and ΧΜρ are in the form of a 1-adamantyl group. The repeating unit formed by the polymerization of the compound (rlp) is preferred. Specific examples of the compounds (rlp) and (r2p) are the same as those described in the specific examples of the compound (rl) and the compound (r2). Block polymerization The substance (P) is preferably 20 to 90 mol%, more preferably 30 to 60 mol%, relative to the total recoating unit. In this case, the photoresist polymer (P) Not only is water repellency excellent, but also the exposed portion can be easily removed by alkali solubility after immersion exposure.

Rqp R«IP Rqp Rqp ch2=c ch2=c ch2=c CH2 II C ^===o 〉2 o >:_·〇 V7- o 〇〇 o 〇

200809410 (35) Photoresist polymer (P) may contain repeating units other than repeating unit (Fp) and heavy RP) (hereinafter, also referred to as other units (other units (Fp) are not particularly limited to compounds ( The repetitive unit formed by the polymerization of the repeating unit (QlP) formed by the polymerization of qllp ql2P), or q21p) or (q22p) (good. [30] δι (qll, however, the symbol in the formula indicates The meaning of the following (the same below.

Rqp : each independently, showing a hydrogen atom, a fluorine atom, a carbon-alkyl group or a fluorine-containing alkyl group having 1 to 3 carbon atoms.

Qqpii, Qqpi2: is a group having a ring carbon number of 4 to 20 in combination with a carbon atom in the formula, and a - 〇- or -c(0)_ insertion group between carbon atoms and carbon atoms (however, QqP" a valence group, (valent group). Further, the carbon atom in the group is selected from a group consisting of a fluorine atom, a group, or an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group and an alkylcarbonyl group. There are carbon number 1 to 10 base combination.

Qqpn, QqP22: together with the carbon atom in the formula to form a group having a cyclic number of 4 to 20 (however, Qqp2i is a trivalent group, Qqp22 is a medium, and a carbon atom in the group is selected from a hydroxyl group, a carboxyl group, or an alkoxy group) One of the groups of the alkoxy group, the alkoxycarbonyl group and the alkylcarbonyl group has a group having a bond group of 1 to 10 carbon atoms. -39 - a unit (FP). Or (the compound (.Q 2 ) is a hydrocarbon group of the formula 1 to 3, -C(0)0-rpl2 is a 2 hydroxy group, and the carbon group of the hydrocarbon group of the carboxyl group is a divalent group) alkoxy group, the above group 200809410 (36) The Rqp systems in the compounds (qllP) and (ql2P) are each independently a hydrogen atom, and the fluorine atom 'methyl or trifluoromethyl group is preferred' to be preferably a hydrogen atom or a methyl group. In the case where the photoresist (p) contains a repeating unit (Q1P), the exposed portion can be easily removed with an alkali solution after the immersion exposure step, and the developing step can be easily performed. The reason is not clear. We believe that the photoresist (P) containing a repeating unit (Qlp) has a -0-, -c(o)o- or -c(o) interposed between carbon atoms. - Therefore, the affinity with the alkali solution is high. The group inserted between the carbon atoms in Qqpll and QW12 is preferably -c(o)o- or -c(o)- from the viewpoint of developability, and -c(o)o- is particularly good. . The carbon atoms in QW21 and Qqp22 are copolymerized with other polymerizable compounds, and the adhesion between the other materials (the substrate coated with the polymer for immersion exposure of the present invention, etc.) It is preferred to bind a hydroxyl group or -OCH2OYp (however, Yp represents an alkyl group having 1 to 9 carbon atoms), preferably a hydroxyl group, -CH2OCH2CH3, -CH2OCH3 or -CH2OC(CH3)3, and a hydroxyl group is preferred. . Specific examples of the compound (q 1 1 P ) and the compound (q 1 2P ) are the same as those described in the specific examples of the compound (q 1 ) and the compound (q2). • When the photoresist (P) contains a repeating unit (Q1P), the photoresist (P) is preferably 20 to 60 mol% relative to the full repeat unit (Qlp). . In the case where the photoresist (P) contains a repeating unit (Q2P), the photoresist (P) contains 5 to 30 moles with respect to the full repeat unit (Q2P). /. It is better. -40- (37) (37) 200809410 The weight average molecular weight of the photoresist (P) of the present invention is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000. The preferred aspect of the photoresist (P) comprises a repeating unit (Fp) and a repeating unit (Rp), and the repeating unit (Fp) contains 2.5 to 30 moles relative to the full repeating unit. %, repeat unit (Rp) contains 30 to 60 mol% of polymer. The special aspect of the photoresist (P) is a polymer containing a repeating unit (Fp), a repeating unit (Rp) and a repeating unit (Qlp), and is heavy relative to the full repeating unit. The covering unit (Fp) contains 2·5 to 30 mol%, the repeating unit (RP) contains 30 to 60 mol%, and the repeating unit (Qlp) contains 20 to 60 mol% of the polymer. Further, the polymer preferably contains 5 to 30 mol% of the repeating unit (Q2P). In a preferred embodiment, the repeating unit (RP) is preferably a repeating unit formed by the polymerization of the compound (rlp), and the repeating unit formed by the polymerization of the compound (r 1 1 ) is particularly preferred. Further, the repeat unit (Q1P) is preferably a repeating unit formed by polymerization of the compound (q22), (q23), (q25) or (q26). The repeating unit (Q2P) is preferably a repeating unit formed by polymerization of the compound (ql2) or the compound (q1 3 ). The method for producing the photoresist (P) is not particularly limited, and a method of radically polymerizing the compound (fP) and the compound (〆) in the presence of a radical initiator can be exemplified. The radical initiator is not particularly limited, and examples thereof include phenylhydrazine peroxide, diisopropylperoxydicarbonate, di-tertiary butylperoxydicarbonate, and tertiary butylperoxytrimethylol. Acetate, perfluorobutanyl peroxide, perfluorophenylhydrazine peroxide, etc.; azobisbutyronitrile, etc., nitrite-41 - (38) (38) 200809410; persulfate Wait. The method of radical polymerization is not particularly limited, and it can be carried out according to a polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. The solvent in the case where the radical polymerization is carried out in the presence of a solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as pentane, hexane, and heptane; methanol, ethanol, n-propanol, and isopropanol. a hydrocarbon-based alcohol such as butanol; a hydrocarbon ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; dimethyl ether, diethyl ether, methyl ethyl ether, a hydrocarbon-based ether such as methyl tertiary butyl ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether; a cyclic aliphatic hydrocarbon ether such as tetrahydrofuran or 1,4-dioxane Nitriles such as acetonitrile; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, tertiary butyl acetate, butyl, methyl propionate, ethyl propionate, etc. Esters; aromatic hydrocarbons such as toluene, xylene; chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride; 1,1,2-trichlorotrifluoroethane, dichloropentafluoropropane Fluorinated chlorinated tobaccos such as hospitals; 1,1,1,2,2,3,3,4,4,5,5,6,6-trifluorohexane, 1,1,1,2, Fluorinated hydrocarbons such as 2,3,3,4,4-nonafluorohexane; methyl 2,2,3,3-tetrafluoroethyl a fluorinated hydrocarbon ether; 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoroisopropanol, 2,2,3,3-tetrafluoropropanol, Fluorinated hydrocarbon-based alcohols such as 2,2,3,3,4,4,5,5-octafluoropentanol. The reaction temperature in the radical polymerization is not particularly limited, and is preferably 〇 ° C to 200 ° C, and particularly preferably 25 ° C to 100 ° C. Further, the reaction pressure in the radical polymerization may be any of a reduced pressure condition, an atmospheric pressure condition, and a pressurization condition, preferably 1 kPa to 100 MPa, and 1 0 k P a 〜1 0 Μ P a particularly good ° -42 - (39) 200809410 In the immersion lithography method for photoresist (P), the photoresist (P) and photoacid generator are dissolved or dispersed in an organic solvent to become light-sensitive. Chemically enhanced photoresist is preferred. The present invention provides a photoresist composition for a liquid immersion exposure containing a photoresist polymer (P), a photoacid generator, and an organic solvent (hereinafter referred to as a photoresist forming composition (P)). The photo-acid generator and the organic solvent in the resist formation composition (P) are the same as those of the photoresist-forming composition (1). The photoresist forming composition (P) is preferably contained in an amount of 1 to 1% by mass based on the photopolymer generator (P). The photoresist forming composition (P) is preferably contained in an amount of from 1% by mass to 1% by mass based on the total amount of the organic solvent. The method for producing the photoresist-forming composition (P) is not particularly limited, and a method of dissolving or dispersing the photoresist polymer (P) and the photo-acid generator in an organic solvent can be exemplified. The method for forming the photoresist pattern by the liquid immersion lithography method using the photoresist forming composition (P) is not particularly limited, and is the same as the photoresist forming composition (1). Further, in the liquid immersion lithography method, the photoresist film may be formed on the outermost surface of the photoresist film from the viewpoint of suppressing the elution of the water in the photoresist film. The present invention provides a polymer (Rq) containing the following polymer (fq), which can increase alkali solubility by the action of an acid, and a polymer (Fq) of 0.1 to 30 with respect to the polymer (Rq) A photoresist composition for immersion exposure of mass% (hereinafter referred to as a photoresist composition (Q)). -43 - 200809410 (40) Polymer (fq): a polymer of repeating unit (fq) formed by polymerization of the following compound (fq), 'reset repeating unit (fq) with respect to full repeating unit Containing more than 10 mol% of the polymer. CH2 = CRfqC(0)0-Xq (fq). However, the symbol in the formula indicates the following meaning (the same applies hereinafter).

Rfq is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluorine-containing alkyl group having 1 to 3 carbon atoms. Xq : a fluorine-containing cyclic hydrocarbon group having 5 to 20 carbon atoms. Further, the carbon atom in xq is selected from a group consisting of a hydroxyl group, a carboxyl group, or an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group and an alkylcarbonyl group, and a group having one or more carbon atoms having a carbon number of 1 to 10; Combiner. The photoresist composition (Q) of the present invention is excellent in water repellency and excellent in water repellency. The reason for this is not clear, and it is considered that the polymer (Fq) has a polymer having a bulky fluorine-containing group (base represented by the formula _xq) derived from the compound (fq). Therefore, we believe that the photoresist composition (Q) containing the polymer (F q ) is highly resistant to water and difficult to be immersed in water, and is excellent in dynamic water repellency and water slidable photosensitive photoresist material. . Rfq in the compound (fq) is preferably a hydrogen atom or a methyl group. Xq is not particularly limited as long as it contains a monovalent fluorine-containing cyclic hydrocarbon group, and may be a fluorine-containing cyclic hydrocarbon group, or a fluorine-containing cyclic hydrocarbon group may be bonded to a formula CH2=CRfqC through a bond. 0) 0-based group. The fluorine-containing cyclic nicotyl group may be a fluorine-containing monocyclic hydrocarbon group, and may be a fluorine-containing polycyclic hydrocarbon group, and is a fluorine-containing polycyclic hydrocarbon group from the viewpoint of superior steric bulk dynamic water repellency. It is better. -44 - 200809410 (41) Further, the fluorine-containing cyclic hydrocarbon group in the compound (fq) may be an aliphatic group or an aromatic group, and it is preferably an aliphatic group from the viewpoint of water repellency. It is especially good for saturated aliphatic bases. The fluorine content of the fluorine-containing cyclic hydrocarbon group is preferably 30% by mass or more, and particularly preferably 50% by mass or more from the viewpoint of water repellency. The upper limit of the fluorine content is not particularly limited, and is preferably 76% by mass or less. Further, in the compound (fq), the carbon atom in the fluorine-containing cyclic hydrocarbon group is one or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, or an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group and an alkylcarbonyl group. In the case of a combination of a carbon number of 1 to 1 fluorene, it is preferred to have a hydroxyl group or a hydrazine CH2OXfqq (however, xfqq represents an alkyl group having 1 to 9 carbon atoms), preferably having a hydroxyl group, -0CH20CH2CH3, -OCH2OCH3 Or -OCH2OC(CH3)3 combination is particularly good. The fluorine-containing polycyclic hydrocarbon group in the compound (fq) is preferably a fluorine-containing condensed polycyclic hydrocarbon group having 5 to 20 carbon atoms, and is fluorine-containing having a carbon number of 5 to 20 from the viewpoint of a large volume of solidity. The bicyclic hydrocarbon group is particularly good. The fluorine-containing crosslinked cyclic hydrocarbon group is preferably a group containing a fluoroadamantyl group or a group containing a fluorine-containing primary group. From the viewpoint of a large volume on a solid surface, the former is preferred, and any of the following formulas is preferred. A base is good. [化31]

The compound (fq) is preferably the following compound (f 1 q ), and is particularly preferably the following compound (flGq) or (f 1 lq). -45- (42) 200809410 [Chem. 32]

However, the symbol in the formula indicates the following meaning (hereinafter, I Rflq : hydrogen atom 'fluorine atom, methyl group or trifluoromethyl 3 pq : 0 or 1.

Xflq : In the case where p is 0, it is a fluorine atom or a hydroxyl group, and the form is a fluorine atom or a hydroxymethyl group.

Rflq is preferably a hydrogen atom or a methyl group, and the methyl group is particularly preferred. Xflq is preferably a fluorine atom. Specific examples of the compound (fq) are the same as those described in the specific examples of the polymerizability. The polymer (Fq) may be a polymer which can be a repeating unit (Fq) and a repeating unit (Fq) or less, other than the repeating unit (Fq), and is referred to as another unit (Fq). also

Fq) may be one type or two or more types of total polymer (Fq), and may contain 1% by mole or more with respect to the total repeat unit (Fq), and may contain 5% by mole. In the case where the substance (Fq) contains other units (Fq), the other single iu (Fq) is aggregated with respect to the total repeat unit, and is preferably 9 or less, preferably 50% or less. The other unit (Fq) is not particularly limited to -46-I ° ° ° 〇pq is the compound of the compound (fm), the repeating unit (, repeat unit (〇, make repeat) Preferably, the polymer (Fq) is obtained by mol% or less from the compound (200809410 (43) rlp ) , ( r2p ), a compound (r l3q ), 〜(rl8q ) described later, the compound (qiip) Or a repeating unit formed by the polymerization of (qi2p), and one or more repeating units of the group of repeating units formed by the cyclization polymerization of the following compound (1). CF2 = CF-Qcq-CRcq = CH2 (cq) However, the symbol in the formula indicates the following meaning (the same below).

Req · · hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Qcq : -CF2C(CF3)(OXcq)(CH2)mcq-, -CH2CH((CH2)pcqC(CF3)2(OXcq))(CH2)ncq- or -CH2CH(C(0)0Ycq)(CH2)ncq -. Mcq, ncq and pcq: are independent, 〇, 1 or 2.

Req is preferably a hydrogen atom.

Xeq, a hydrogen atom, -CH2OZeql (however, Zeql represents an alkyl group having 1 to 9 carbon atoms, preferably -CH2OCH2CH3, -CH2OCH3, -CH2OC(CH3)3 or -c(o)oc(ch3)3) or - oc(o)ozeq2 (however, zeq2 represents an alkyl group having 1 to 9 carbon atoms, preferably -CH3, -CH2CH2 or -C(CH3)3 is preferred)

Yeq is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly preferably a hydrogen atom, -CH3, -CH2CH3 or -C(CH3)3. Mcq and ncq are preferably 1. Pq is preferably 0. The weight average molecular weight of the polymer (Fq) is preferably from 1000 to 30,000, and in terms of the preferred aspect of the polymer (Fq) of from 10,000 to 10,000, the following polymers are mentioned. 47- 200809410 (44) FHq), the following polymer (FCq). Polymer (FW): a polymer formed by repeating polymerization of a compound (flq) (hereinafter referred to as "unit" (Flq)), having a weight average molecular weight of 1000 to 30000 (1000 to 10,000 is preferred). .) Polymer. Polymer (ACq): containing unit (Flq) 'and the repeat unit (Rp), repeat unit (Q1P) or repeat unit (Q2P), with 10~50 relative to the full repeat unit 'Flq' The molar %, and the polymer having a repeating unit (Rlq), (Qlp) and (Q2P) of 50 to 90 mol%, has a weight average molecular weight of 1,000 to 30,000, preferably 1 〇〇 0 to 1. 000 〇 polymer. The preferred aspects of the repeating units (Rlq), (Qlp) and (Q2P) are the same as those of the photoresist polymer (P). The photoresist composition (Q) is a polymer (Rq) which can increase the alkali solubility by the action of an acid. The polymer (Rq) is not particularly limited, and is preferably a polymer containing a repeating unit formed by polymerization of a compound (rlp) or (r2p). In this case, the polymer (Rq)' is a carboxylate moiety in the repeating unit. The component is cleaved by the action of an acid to form a carboxyl group, so that alkali solubility can be increased by the action of an acid. Further, the polymer containing a repeating unit having a cyclic group in the repeating unit is excellent in dry etching resistance. The preferred aspect of the compound (rlP) and (r2p) in the polymer (Rq) is the same as that of the photoresist (P). The polymer (Rq) may also contain a repeating unit other than the repeating unit formed by the compound (rlP) or (r2P) poly-48 - 200809410 (45). The repeating unit is preferably a repeating unit formed by polymerization of a compound (qllp) or (q22p). The preferred form of the compound (ql 1P ) and (q22P ) in the polymer (Rq ) is the same as that of the photoresist (P). In the case of the other polymer (Rq), a polymer having a repeating unit formed by polymerization of one or more compounds (rq) selected from the group consisting of the following compounds (n3q) to (ri8q) (hereinafter referred to as polymerization) (RA) )° [化33] 〇r1q pr1q CH2=〇C λ CH2=C二"c=o ·::(:=0 n/C=0 ^C=0 〇rlqjhl _______W" R31q.^ _R33q CF3-C-CF3 CF3-C-CFj R32t* 0R4q 0R5q (M^) (r14q) (Π51») CH2 CF3-C-CF3 0R6q (r16q) CF3-C-CF3 cf3-c~cf3 〇R7q 0r81c> (r17q) (r18c*) cf3 C-OR82q cf3 However, the symbol in the formula indicates the following meaning (the same applies hereinafter.) R31q: an alkyl group having a carbon number of 1 to 6 which can be inserted between -0- Methyl is preferred. R32q and R33q are independent of each other, and an alkyl group having a carbon number of from 1 to 20 (preferably a methyl group) may be inserted between carbon atoms and carbon atoms, or together with a carbon atom in the formula Forming a cyclic hydrocarbon group having a carbon number of 4 to 20 valence groups. Further, each of the carbon atoms and carbon atoms in R31q, R32q and R33q may be inserted with -C(0)0- or -C(O)-. a carbon atom in R31q, R3 2q& R33q selected from a fluorine atom, a hydroxyl group, a carboxyl group or an alkoxy group, Alkoxyalkoxy, a group of more than one group of a group of oxycarbonyl groups and a group of oresines have a carbon number of -49- 200809410 (46) 1 to 1 0. R4q, R5q, R6q, R7q, R81q And R82q: each independently, in a group selected from the group consisting of an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group and an alkylcarbonyl group, a group having a carbon number of 1 to 10. Further, the carbon number is 1 to In the group of 10, a carbon atom-carbon atom may be intercalated with -〇-, -c(o)o- or -c(o)-. The group having 1 to 10 carbon atoms is represented by the formula -CH2ORbxq (but Rbxq is preferably an alkyl group having 1 to 9 carbon atoms, and particularly preferably -CH2OCH2CH3, -CH2OCH3 or -CH2OC(CH3)3. Specific examples of the compound () include the following compounds. ]

Ch3-c-ch3 cf3-c-cf3 CF3-C-CF3 cf3 c-cf3 CF3-C-CF3 CH3 OCH2OCH3 OCH2OCH2CH3 OCH2OCH3 0c(o)oc(ch3)3 I think polymer (Rfq) polymer (R The carboxylic acid ester moiety of 'q) is cleaved by the action of an acid to form a carboxyl group, or a part represented by the formula -C(CF3)20- is cleaved by the action of an acid to form -C(CF3)2OH. The alkali solubility increases due to the action of acid. Specific examples of the polymer (Rfq) include a repeating unit formed by polymerization of the compound (r'q) and a polymer of a repeating unit formed by polymerization of the following compound. [化35]

The weight average molecular weight of the polymer (Rq) is preferably from 1 000 to 10,000 -50 to 200809410 (47), preferably from 5,000 to 50,000. In a preferred aspect of the polymer (Rq) in the present invention, a repeating unit formed by polymerization of the compound (r 1 1 ) and a weight formed by polymerization of the compound (q ! 2 ) or (qi3) may be exemplified. A unit of a repeating unit formed by polymerization of a compound (ql4), (ql5) '(q22) or (q23). The polymer has a weight of 20 to 50 mol% in a repeating unit formed by polymerization of the compound (r11) relative to the total recoating unit, and the weight of the compound (ql2) or (ql3) is formed by polymerization. The covering unit contains 30 to 50 mol%, and the repeating unit formed by the polymerization of the compound (ql4) '(ql5), (q2 2) or (q23) preferably contains 20 to 30 mol%. The weight average molecular weight of the polymer is preferably from 1,000 to 50,000. 1〜30质量百分比%。 The polymer (Fq) with a polymer (Fq) containing 0. 1~30% by mass. More preferably, the polymer (Fq) is contained in an amount of from 1 to 1% by mass based on the polymer (Rq). In this case, the polymer (Fq) and the polymer (Rq) are easily compatible, and the film forming property of the liquid immersion resist is excellent. The photoresist composition (Q) may contain components other than the polymer (Fq) and the polymer (Rq). The photoresist composition (Q) is usually used as a photosensitive chemically enhanced photoresist, so that a photoacid generator is preferred. The photoresist composition (Q) is preferably 1 to 1% by mass based on the polymer (Rq) so that the photoacid generator is contained. Further, the photoacid generator may be used alone or in combination of two or more. Specific examples of the photoacid generator include the same photoacid generator as the photoresist forming composition (1). -51 - 200809410 (48) The photoresist composition (Q) is usually applied to a substrate (such as a wafer) to form a film. Therefore, in terms of film formation, liquid is used. ^ is better. The photoresist composition (Q) is preferably an organic solvent. The organic solvent is not particularly limited as long as it is a solvent having high compatibility with respect to the polymer (Fq) and the polymer (Rq). The organic solvent may be used alone or in combination of two or more. High compatibility with a polymer (Fq) having a high content ratio with respect to a repeating unit (Fq) (generally having a polymer content of 75 mol% or more with respect to a full repeat unit repeating unit (Fq)) In terms of the organic solvent, the fluorine-containing organic solvent is preferably a fluorine-containing compound, and the fluorine-containing compound having a carbon atom-hydrogen atom is contained in the viewpoint of high compatibility with the polymer (Rq). Fluorine organic solvents are particularly good. One type of the fluorine-containing organic solvent may be used, or one type or more may be used. Further, the polymer (Fq) having a low content ratio with respect to the repeating unit (Fq) (generally contains less than 75 mol% of the polymer relative to the total repeat unit repeating unit (Fq)). In the case of an organic solvent having a high compatibility, an organic solvent which is a compound having no fluorine atom is preferred. The specific organic solvent may, for example, be an organic solvent similar to the photoresist-forming composition (1). In the organic solvent of the present invention, in view of the compatibility of the photoresist composition (Q), it is preferred to use a fluorine-containing organic solvent as an essential organic solvent, and the fluorine-containing organic solvent is contained in an amount of 10 relative to the total mass of the organic solvent. ~70% by mass of organic solvents are particularly good. Further, the photoresist composition (Q)' is relative to the total amount of the polymer (Fq) and the polymer (Rq) so that the organic solvent contains 100% - 52 - 200809410 (49) % ~ 1 ο ο ο ο 〇 % by mass It is better. The method for producing the photoresist composition (Q) is not particularly limited, and examples thereof include a solution obtained by dissolving a polymer (Fq) in a fluorine-containing organic solvent (hereinafter referred to as a resin solution (F)). And a solution obtained by dissolving a polymer (Rq) in an organic solvent (hereinafter referred to as a resin solution (R)), followed by mixing the resin solution (F) with the resin solution (R) to polymerize (Fq) A method of mixing with a resin solution (R). It is preferred that the solution (F) is such that the polymer (Fq) contains 〜·1 to 10% by mass. Further, the resin solution (R) is preferably one by one to 20% by mass of the polymer (Rq). The liquid immersion photoresist of the present invention is used in liquid immersion lithography. The specific aspect of the liquid immersion lithography method is the same as before. The present invention provides a photoresist material for lithography (hereinafter, referred to as a photoresist material (W)), which contains a polymer containing a repeating unit (J?w), the repeating unit (Fw) A repeating unit (Fw) formed by polymerization of a polymerizable compound (fw) having a fluorine-containing two-ring crosslinked ring structure. The polymerizable compound (fw) is a compound having a polymerizable group and a fluorine-containing two-ring crosslinked ring structure, wherein a compound having a fluorine atom bonded to a carbon atom constituting the fluorine-containing two-ring crosslinked ring There is no particular limitation. The polymerizable group is preferably a group having a polymerizable carbon atom-carbon atom double bond. The fluorine-containing 2-ring crosslinked ring structure is preferably an aliphatic group and is preferably a saturated aliphatic group. Further, in the fluorine-containing two-ring crosslinked ring structure, a carbon atom_carbon atom may be inserted between -〇-, -C(0)0- or -C(O)-. Further, the fluorine atom in the fluorine-containing 2-ring type -53-(50) (50) 200809410 crosslinked ring structure may be bonded to a trans group or a mercapto group. The fluorine content of the polymerizable compound (fw) is preferably 3 〇 by mass or more, and more preferably 50% by mass or more. The upper limit of the fluorine content is preferably 76% by mass or less. The carbon number of the polymerizable compound (Π) is preferably from 8 to 20%. The polymerizable compound (fw) is preferably the following compound (flw) or (f2w).

The symbol in the formula indicates the following meaning. WFw: fluorine atom or trifluoromethyl group. RFw: In a fluorine atom or a perfluoroalkyl group having 1 to 16 carbon atoms, two rfws may be the same or different. QFw: -CF2- or -C(CF3)2-, two qFws may be the same or different 〇 RAw: a hydrogen atom, a fluorine atom, an alkyl group having a carbon number of 33 or a fluoroalkyl group having a carbon number of 3. JAw : an alkylene group having a carbon number i to 10 which may contain an etheric oxygen atom. The three-dimensional arrangement of the asymmetric center of the main ring of the compound (flw) or the compound (f2w) may be inward or outward. rAw is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group. Both rFw are fluorine atoms, but one of them is a fluorine atom and the other is a carbon number -54-200809410 (51). The perfluoroalkyl group of 1 to 16 is preferred, and both of them are fluorine atoms. JAw is preferably a methylene group. The specific example of the polymerizable compound (fw) is the same as the compound described in the specific example of the polymerizable compound (fm). The compound (flw) is a novel compound. The compound (fiw) is an esterification reaction of the following compound (fl51w) with RfPw-COF to obtain the following compound (fl41w), followed by liquid phase fluorination of the compound (fl41w) to obtain the following compound (fi3w), Next, the compound (fi3w) is thermally decomposed in the presence of KF to obtain the following compound (fl2w), followed by reduction of the compound (fl2w) to obtain a compound (fllw), followed by a compound (fllw) and CH2 = CRAwC(0) C1 can be produced by reaction. [化37]

However, the symbol in the formula indicates the following meaning. R • An all-gas base with a carbon number of 1 to 20 containing an enchanting oxygen atom. WPw : a hydrogen atom or a methyl group in the group corresponding to wFw. RPw: a hydrogen atom or an alkyl group having 1 to 16 carbon atoms in the group corresponding to RFw. The two RPws can be the same or different.

Qpw : -CH2- or -C(CH3)2- in the group corresponding to QFw. 2 Qpw can be the same or different. The compound (f 13 w ) is the same as the following compound (f丨5 2 w ) in place of the compound (π51 w ), and the same is obtained by the following -55-200809410 2 (5 11 f Γν The compound (f2w) is a novel compound, and the compound (f2w) is the following compound (f251w) and RfPw, which can be obtained by reacting the fluorinated phase liquid with CHF. -COF is subjected to an esterification reaction to obtain the following compound (f241w), followed by liquid phase fluorination of the compound (f241w) to obtain the following compound (f23w), followed by thermal decomposition of the compound (f23w) in the presence of KF The following compound (f22w) can be used for the production. [Chem. 39] ^ch2oh Human^ RPW-CH |, CH RPW-CH |, CH I Qpw| I Qpw| Rpw-0h /ipw Rpw-CH I ^QpVi ^ CH, CH (f251w) (f241w)

CH20C(0)R,p /C ^CF20C(0)Rrp ^COF

R _CF R^-CF XF Q^l I Q^l

R--CF, | R^-CF^I (f23w) (ff22w) For example, the compound (f22w) is reacted with methanol to obtain the following compound (f22Mw), followed by reduction of the compound (f22Mw) to obtain the following compound (f2i1Mw), followed by the reaction of the compound (m1Mw) with CH2 = CRwC(0)Cl, to give the following compound (f2Mw). WFw WFw WFw /C /C(0}0CH3 /9 /CH2OH /C ^CH20C(0)CRAw=CH2 R "?FJ^?F rFw-cf I^cf rFw-cf I^cf RFw (f22Mw) iFw rFw-cf I ^CF (f211Mw) I - Ί rFw-cf I ^ , CF (f2Mw) Compound f2 except for the following compound (f252 for -56- 200809410 (53) generation compound (f251w) The liquid phase fluorination reaction of the following compound (f242w) obtained in the same manner may be obtained. [Chem. 41]

The method of polymerizing the polymerizable compound (fw) may, for example, be a method of polymerizing the polymerizable compound (fw) in the presence of a polymerization initiator. The polymerization initiator may, for example, be an organic peroxide or an inorganic peroxide 'azo compound. The temperature, pressure, and time during the polymerization are not particularly limited. The photoresist material (W) is excellent in water repellency, especially dynamic water repellency. The reason for this is not clear, and it is considered that the photoresist (W) is a bulky fluoropolymer containing a fluorine-containing two-ring crosslinked ring structure derived from a polymerizable compound (fw). Therefore, the photoresist (w) can be easily immersed in the impregnation liquid, and the immersion liquid can be satisfactorily followed by the photoresist member. The present invention provides a repeating unit (F" and a group having the following group (r-lw), the following group (r-2w), -c(CF3)2(OZRw) (hereinafter referred to as ' The basis of the repeating unit (R) formed by the polymerization of the group (r-3w)) or - (hereinafter referred to as the group (r-4w)) polymerizable compound (,) increases the alkali solubility due to the action of the acid In the polymer, the repeating unit (Fw) contains 1 to 45 mol%, and the repeating unit (Rw) contains 10 mol% or more of the photoresist for immersion lithography ( Hereinafter, it is called a photoresist polymer (w). -57- (54) 200809410 [Chem. 42]

(Mw) (r-2w) The symbol in the formula indicates the following meaning (the same applies hereinafter). XRlw : an alkyl group having 1 to 6 carbon atoms. YRlw : a divalent group having 4 to 20 carbon atoms which forms a cyclic hydrocarbon group together with a carbon atom in the formula. XR2w: Among the alkyl groups having 1 to 20 carbon atoms, three XR2s may be the same or different. ZRw is a group having a carbon number of 1 to 20 in an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group. However, a carbon atom-carbon atom in XRlw, YRlw, XR2w or ZRw may be intercalated with -〇-, -C(0)0- or -C(O)-, and further, carbon in XRlw, YRlw, xR2w or ZRw The atom may bond to a fluorine atom, a hydroxyl group or a carboxyl group. The photoresist (W) is particularly excellent in dynamic water repellency because it contains a repeating unit (Fw). In the immersion lithography method using the photosensitive photoresist prepared by the photoresist (W), the projection lens immersion liquid which is moved at high speed on the photosensitive photoresist can follow well. Further, since the photoresist (W) contains a repeating unit (Rw), it is a polymer which increases alkali solubility due to the action of an acid. The exposed portion of the photosensitive photoresist prepared by the photoresist (W) can be easily removed by an alkali solution. Therefore, by means of the photoresist polymer (W), it is possible to realize a stable high-speed implementation of the immersion lithography method of the image mask of the high-58-(55) 200809410 resolution transfer. The polymerizable compound (wide) in the photoresist (W) is preferably a compound (flw) or (f2w). The polymerizable compound (,) in the photoresist (W) is preferably the following compound (rlw), (r2w) or (r3w). RRw pRw ch2=c[ ch2=< C=0 C=〇xR1w-方一\ xR2w - c —»xR2w Γ ) 丨Galter CF2=CF—QR1w_CH==CH2 (r^) (r2w) (r3w) The symbol in the formula indicates the following meaning (the same applies hereinafter). RRw • Hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms. XRlw : an alkyl group having 1 to 6 carbon atoms. YRlw : a divalent group having 4 to 20 carbon atoms which forms a cyclic hydrocarbon group together with a carbon atom in the formula. XR2w: Among the alkyl groups having 1 to 20 carbon atoms, three XR2w may be the same or different. Qriw : .CF2C(CF3)(〇ZRw)(CH2)mw., ^ -CH2CH((CH2)nwC(CF3)2(OZRw))(CH2)mw, -CH2CH(C(0)0ZRw)(CH2) Mw-. ZRw : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group having a carbon number of 1 to 20. Mw and nw: are independent of each other, 1 or 2. -59- (56) (56)200809410 However, in the carbon atom-carbon atom of xRlw, YRlw, xR2w or ZRw, -0, -c(0)0- or -C(O)- can be inserted, and, XR1W, The carbon atom in YRlw, xRh or ZRW may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. The preferred aspect of the radical (r-lw) is the same as the url. The preferred aspect of the radical (r-2w) is the same as the radical (ur2). The preferred aspect of the radical (r-3w) is the same as the radical (ur3). The preferred aspect of the radical (r-4w) is the same as the radical (ur4). The preferred aspect of the compound (r 1 w ) is the same as the compound (r 1 ). The preferred aspect of the compound (r2w) is the same as the compound (r2). The preferred aspect of the compound (r3w) is the same as the compound (r3). The photoresist polymer (W) is preferably one in which the repeating unit (Fw) contains 2 · 5 to 30 mol% with respect to the total repeat unit. In this case, the liquid composition which disperses or dissolves the photoresist polymer (W) in the organic solvent can be easily adjusted. The photoresist polymer (W) is preferably 20 to 90 mol% in terms of the repeating unit (Rw) with respect to the full recoating unit, and is preferably 30% to 60 mol%. In this case, in the immersion lithography method, the exposed portion of the photoresist (w) can be easily removed as an alkali solution. The photoresist (W) may contain a repeating unit other than the repeating unit (Fw) and the repeating unit (Rw) (hereinafter referred to as another unit (Fw)). In this case, the photoresist polymer (W) is preferably contained in an amount of 2 〇 to 6 〇 mol% with respect to the total repeat unit, other units (Fw). The other unit (Fw) is not particularly limited, and a repeating unit (qU) formed by polymerization of a polymerizable compound (qm) is preferred. -60- (57) 200809410 The weight average molecular weight of the photoresist polymer of the present invention is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000. In terms of preferred aspects of the photoresist (W), it can be exemplified that the repeat unit (Fw) contains 1 to 45 mol%, and the repeat unit (Rw) contains 30 to 60 mol. % of the polymer of the ear. In terms of a particularly good aspect, in a polymer containing a repeating unit (Fw), a repeating unit (Rw), and other units (Fw), the repeating unit (Fw) has 1 with respect to the full repeating unit. ~45 mol%, repeat unit (Rw) contains 30~60 mol%, and other units (Fw) contain 20~60 mol% of polymer. In this aspect, the repeating unit (Rw) is preferably a repeating unit formed by polymerization of the compound (r 1 ), and the repeating unit formed by the polymerization of the compound (r 1 1 ) is particularly preferable. The other unit (R) in this aspect is preferably a repeating unit formed by polymerization of the compound (q 1 2 ), (q22), (q23), (q25) or (q26). The weight average molecular weight of the polymer in this aspect is preferably from 1,000 to 30,000. The photoresist (W) is suitable for use in a immersion lithography process, usually in the form of a chemically enhanced photosensitive photoresist. It is preferred that the photoresist (W) is combined with a photoacid generator. Further, the photoresist (W), which is suitable for use in the immersion lithography method, is usually applied to a substrate. The photoresist (W) is preferably one which is prepared into a liquid composition. In the present invention, the photoacid generator is not particularly limited as long as it has a group which generates an acid by irradiation with active rays (however, the active light system is -61 - 200809410 (58) ). The compound may be a non-polymeric compound' or a polymer compound. Further, the photoacid generator _ may be used alone or in combination of two or more. Specific examples of the photoacid generator include the same photoacid generator as the photoresist-forming composition (1). The photoresist forming composition (W) is preferably contained in an amount of from 1 to 10% by mass based on the photoresist polymer (W). The organic solvent is not particularly limited as long as it has a high compatibility with the photoresist (W). Specific examples of the organic solvent include the same organic solvents as the photoresist-forming composition (1). The photoresist forming composition (w) is preferably such that the organic solvent contains 100% by mass to 1% by mass based on the resist polymer (w). The preferred aspect of the immersion lithography method using the photoresist forming composition (W) is the same as before. The present invention provides a polymer containing a repeating unit (Fw) comprising a polymer (FRW) and a polymer (Rw), the polymer (FRW) being relative to a full repeat unit, and a repeating unit (Fw) Containing more than 1% by mole, and polymer (Rw), the polymer (Rw) is made to have an alkali solubility due to the action of an acid, and the polymer (FRW) is 0.1 1 relative to the polymer (Rw). ～300% by mass of a photoresist composition for immersion lithography (hereinafter referred to as a photoresist composition (V)). The photoresist composition (V) is excellent in dynamic water repellency because it contains a polymer (FRW) containing a repeating unit (Fw). In the immersion lithography method using the photosensitive photoresist prepared by the photoresist composition (w), the projection lens immersion liquid which is moved at high speed on the photosensitive photoresist -62 - (59) 200809410 can be well resisted. The composition (V) contains a polymer (Rw), so that the alkali solubility is increased. The exposed portion of the photoresist composition (V) resist can be easily removed by an alkali solution. It is possible to make the pattern image of the photomask stable and high-speed implementation of the high-resolution lithography method. The polymerizable compound (fW flw) or (f2w) in the photoresist composition (V) is preferred. FRW ) can only be a repeating unit (Fw ). It can contain repeating units (Fw) and repeating units (Fw) (hereinafter, referred to as other units (FRW)) of polymer (FRW), relative to the total weight. It is preferable to cover the unit so that it is more than 20% by mole, and more than 20% by mole. If the group name 3 has other units (FRW), it is 90% or less with respect to the total weight unit (FRW). Preferably, the polymer (FRW) contains a polymerizable compound (qw) having the following group (group (q-2w)). The polymer of the polymerization site (Qw) is preferred. [Chem. 44] Follows. Further, the light is sensitized by the action of acid, so that the compound is formed by the transfer of light. 'Over the repeated unit. In short, the aggregated (F) contains 10 $ (FRW) in the covering unit, the other contains 8 〇 mol % q-1 w ) or the following repeated form

-63- (60) (60)200809410 The symbol in the formula represents the following meaning (the same applies hereinafter). Y^w: a carbon number of 4 to 2 0 which forms a crosslinked cyclic hydrocarbon group together with a carbon atom in the formula. . YQ2w: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula. However, a carbon atom-carbon atom in yq1w or yQ2w may be inserted between -〇_, -C(0)0- or -c(o)-, and further, a carbon atom in yq1w or yQ2w may be bonded to a fluorine atom, a hydroxyl group or carboxyl. The preferred aspect of the repeated unit (Qw) is formed by the polymerization of the repeating unit (Rw) or the repeating unit (Qw) which is better than the compound 'r 1 ' ( r2 ) ' ( ql ) or (q2) The repeating unit is particularly good. The weight average molecular weight of the polymer (FRW) is preferably from 1,000 to 10,000. As a preferable aspect of the polymer (FRW), the following polymer (FRHw) and the following polymer (FRew) can be exemplified. Polymer (FRHw): A polymer formed by repeating only the unit (Fw). Polymer (FRew): In a polymer containing a repeating unit (Fw) and other units (FRW), the repeating unit (Fw) contains 10 to 50 mol%, and other units (with respect to the full repeat unit) FRW) contains 50 to 90 mole % of polymer. Other units (FRW) in the polymer (FRCw) are preferably in units of repeats (Rw) and repeat units (Qw). The repeating unit (Rw) is preferably a repeating unit formed by polymerization of the compound (rl 1 ). The repeat unit (Qw) is particularly good for the repeated units formed by the combination of (Q12), (q22), (q23), (q25) or (q26) -64 - 200809410 (61). The weight average molecular weight of the polymer in this aspect is preferably from 1,000 to 30,000. The polymer (Rw) is not particularly limited, and a polymer having a repeating unit (R" formed by polymerization of a polymerizable compound (rm) is preferred, and a repeat unit is used with respect to a full repeat unit ( Rw) is particularly preferred as a polymer containing 10% by mole or more. The repeating unit (Rw) is preferably a repeating unit formed by polymerization of a polymerizable compound (rm), and is a compound (rl), (r2) or The repeating unit formed by the polymerization of (r3) is preferred, and the repeating unit formed by the polymerization of the compound (rl) is particularly preferable, and the repeating unit formed by the polymerization of the compound (r 1 1 ) is preferred. (Rw), preferably a repeating unit (Qu) formed by polymerization of a polymerizable compound (qm). A preferred aspect of the polymerizable compound (qm) in the polymer (Rw), in the light of the present invention The composition of the resist is the same as the polymer (R). The weight average molecular weight of the polymer (Rw) is preferably from 1,000 to 10,000. The preferred aspect of the polymer (Rw) can be exemplified in the unit containing the repeat (R", repeating unit (QB1U) and repeating unit (QB2U) in the polymer, repeating relative to the full repeat unit The unit (Rw) contains 20 to 50 mol%, the repeat unit (QB1U) contains 30 to 50 mol%, and the repeat unit (QB2U) contains 20 to 30 mol% of the polymer. In the preferred embodiment, The repeating unit (QB 1 U ) is preferably a repeating unit formed by the polymerization of the compound (qB 1 ) -65 - 200809410 (62), and is formed by polymerization of the compound (q 1 2 ) or (q 1 3 ). The repeating unit is particularly good. Further, the repeating unit (QB2u) is preferably a repeating unit formed by polymerization of the compound (qB2), and is a polymerization compound of the compound (q22), (q23), (q25) or (q26). The repeating unit formed is particularly preferred. The weight average molecular weight of the polymer in this aspect is preferably from 1000 to 100000, particularly preferably from 1 to 100 to 50,000. The photoresist composition (V) contains polymerization. The polymer (FRW) and the polymer (Rw) have a polymer (FRW) content of 0.1 to 30% by mass based on the polymer (Rw). Preferably, the polymer (FRw) is contained with respect to the polymer (Rw). 1 to 10% by mass. In this case, the polymer (FRw) and the polymer (Rw) are easily dissolved, and the film forming property of the photoresist composition (V) is excellent. The photoresist composition (V) is suitable. In the immersion lithography method, it is usually prepared by using a chemically enhanced photosensitive photoresist. It is preferable to use a photo-acid generator in the photoresist composition (V). Further, the photoresist composition (V) is in the pair. In the application of the immersion lithography method, it is usually applied to a substrate. The photoresist composition (V) is preferably prepared into a liquid composition. The photo-acid generator in the photoresist composition (V), A photoacid generator similar to the photoresist-forming composition (1) can be exemplified. The photoresist composition (V) is preferably an organic solvent containing 1 to 10% by mass of the photoacid generator relative to the polymer (Rw), and is highly compatible with respect to the polymer (Rw). The solvent is not particularly limited. Specific examples of the organic solvent include -66-200809410 (63) the same organic solvent as the photoresist-forming composition (1). The photoresist forming composition (V) is preferably one by mass to 10,000% by mass based on the total mass of the polymer (Fw) and the polymer (Rw). The method for producing the photoresist-forming composition (V) is not particularly limited, and a method of dissolving or dispersing the photoresist composition (V) and the photo-acid generator in an organic solvent can be exemplified. In the preferred embodiment of the immersion lithography method using the photoresist forming composition (V), it is the same as the photoresist forming composition (1). [Embodiment] The present invention can be specifically described by way of examples, but the invention is not limited thereto. In the examples, the gel permeation chromatography is represented by the GPC method, the weight average molecular weight is represented by Mw, the number average molecular weight is represented by Μη, and the glass transition temperature is represented by Tg. 1,1,2-trichloro-1,2,2-trifluoroethane is represented by R113, dichloropentafluoropropane. Alkane (mixture of CF3CF2CHC12 and CF2C1CF2CHFC1) is represented by R225, diisopropyl peroxydicarbonate The ester is represented by IPP and tetramethylnonane is represented by TMS. Tetrahydrofuran is represented by THF, propylene glycol methyl ether acetate is represented by PGMEA, 2-heptanone (methyl amyl ketone) is represented by MAK, methyl ethyl ketone is represented by MEK, cyclopentanone is represented by CP, 2-propane The alcohol is shown in IPA Table-67-200809410 (64), and ethyl lactate is represented by EL. The Mw and Μη of the polymer were determined by gel permeation chromatography (expansion: solvent: THF, internal standard: polystyrene). The Tg of the polymer was determined using differential scanning calorimetry. For the production of the polymer, the following compounds (f1)' (f2), (f3), (f4), (r1), (r2), (q1), (q2), (q3) are used. [化45]

Ϋ_3 accounted for. u (r1) (r2) (q1) (q2) (q3> The repeating unit formed by the polymerization of the compound (f1) is expressed in units (F1), and the unit of repetition formed by the polymerization of the compound (f2) is in units ( F2) means that the repeating unit formed by the polymerization of the compound (f3) is represented by a unit (F3), and the repeating unit formed by the polymerization of the compound (f4) is represented by a unit (F4). Further, the polymerization of the compound (r1) The repeating unit formed is expressed by the unit (R1), and the repeating unit formed by the polymerization of the compound (r2) is represented by the unit (R2), and the repeating of the compound (q1) is formed by repeating -68 - (65) ( 65) 200809410 The unit is expressed in units (Q1), and the repeating unit formed by the polymerization of the compound (q2) is represented by a unit (Q2), and the repeating unit formed by the polymerization of the compound (q3) is represented by a unit (Q3). Example 1 (Reference Synthesis Example)] Production Example of Compound (f) [Example 1-1] A production example of the compound (f2) was placed in a flask maintained at 〇 °c, and the following compound (pf2 ) ( 27.46 g ) was charged. NaF (3·78) and acetone (100 mL) were stirred. Then water (1 · 14 g) was dropped in the flask. The contents of the flask were sublimed and purified to obtain the following compound (qf2) (22.01 g), a mixture of the compound (qf2) (2.03 g) and diterpene sulfoxide (50 mL) in a flask, and potassium hydroxide (l. 〇g ) With formaldehyde aqueous solution (20 mL), the reaction was carried out at 75 ° C for 6.5 hours. After the reaction was completed, the reaction solution was extracted with R22 5 (40 mL), and then R225 was distilled off to obtain the following compound ( rf 2 ) ( 1.58 g Similarly, the obtained compound (rf2) (6.01 g) and R225 (10 〇3 g) were added to the flask, followed by triethylamine (1.68 g) and CH2 = C(CH3)COCl (1.58 g). Add a force to the well, and still stir in a flask at 2 5 ° C for 2 hours. The filtrate obtained by filtering the solution in the flask was washed twice with water (5 OmL). Then, the solution in the flask was dried over magnesium sulfate. After concentration, a pale yellow solid (6.19 g) was obtained. The solid was purified by column chromatography to give compound (f2). -69- (66) 200809410

The NMR data of the compound (f2) are shown below. iH-NMR (3 00_4MHz, solvent: CDC13, standard: Si(CH3)4) δ (ppm): 1.96 (s, 3H), 5.06 (s, 2H), 5.71 (s, 1H), 6.19 (s, 1H) ). 19F-NMR (2 82·7 ΜΗζ, solvent: CDC13, standard: CFC13) δ (ppm): -113.6 (6F), -121.1 (6F), -219.4 (3F). [Example 1-2] Production Example of Compound (f3) According to the production route shown by the following formula, the compound (f3) was produced from the following compound (nf3). However, Rfl shows F(CF2)3OCF(CF3)CF2OCF(CF3)-〇 [Chem. 47]

The flask was charged with a compound (nf3) (15 g) and -70-(67) (67) 200809410 chloroform (100 g) and NaF (7.02 g) under a nitrogen atmosphere, and Rfl-C0F was dropped while stirring in a flask. 79 g), after the completion of the dropwise addition, the mixture was further stirred in the flask. The insoluble solid of the contents of the flask was removed by filtration under pressure, and a saturated aqueous solution of sodium hydrogencarbonate (1,03 g) was placed in the flask, and the organic layer was collected and concentrated to give compound (of3) (74 g). At the gas outlet, R113 (313 g) was added to the autoclave provided with the NaF pellet filling layer, and stirred in an autoclave at 25 t, while nitrogen gas was blown in the autoclave for 1 hour, and then nitrogen gas was blown. Diluted into 20% by volume of fluorine gas. The 20% fluorine gas was blown in as it was, and introduced into a hot press at a pressure of O.IMPa to dissolve the compound (of3) (67 g) in a solution of R1 13 (299 g). After the introduction was completed, the contents of the autoclave were recovered and concentrated to obtain a compound (pf3). In a flask under a nitrogen atmosphere, a compound (pf3) (80 g) and a powdery KF (0.7 g) were charged and heated in a flask for 6 hours, and then the contents of the flask were purified to obtain a compound (qf3) (38 g). A round bottom flask under a nitrogen atmosphere was charged with NaBH4 (1.lg) and THF (30 g). While the flask was ice-cooled, the compound (qf3) was added dropwise to a 22 mass% R225 solution (48 g). After the completion of the dropwise addition, the mixture was further stirred in a flask, and the solution in the flask was neutralized with a hydrochloric acid aqueous solution (150 mL), and the mixture was washed with water and then purified by distillation to obtain compound (rf3). In the flask, a compound (rf3) (2.2 g), THF (10 g), an aluminum salt of N-nitrosophenylhydroxylamine (2 mg) and triethylamine (1.2 g) were charged. The flask was ice-cooled, stirred, and the solution obtained by dissolving CH2 = C(CH3)C(0)C1 -71 - (68) 200809410 (1.2 g) in T H F (7 · 3 g ) was dropped in the flask. After the completion of the dropwise addition, the mixture was further stirred in a flask, and then an aqueous sodium hydrogencarbonate solution was placed. The extract obtained by extracting the solution in the flask with R225 is dried and concentrated to obtain a compound (f3) (2.7 g). The NMR data of the compound (f3) is as follows. Show. iH-NMRC 300·4ΜΗζ, solvent: CDC13, standard: TMS) δ (ppm) : 6 · 3 1 ( 1 Η), 5 · 8 8 (1 Η), 5 · 84 (1 Η), 2 · 0 1 (3 Η). 19F-NMR ( 282·7ΜΗζ, dissolved ij : CDC13, benchmark: CFC13) δ (ppm): -104.6(1F)5 -120.5(1F)? -122.4(1F)? -124.2(1F), -124.6( 1F), -126.5 (1F), -132.7 to -132.8 (2F), -214.8 (1F), -223.2 (1F) ° [Example 1-3] The production example of the compound (f4) is produced according to the following formula: The compound (f4) was produced from the following compound (nf4) by a via. However, Rf2- shows F(CF2)3〇CF(CF3)-. [化48]

CF20C0Rf: CF2C^CF I .cf2 I -. CF, /CF2 \CF2 (pf4) (nf4) (of4)

CH2〇H (f4) CF; ^CF ΊI CF CF2, cf2 (rf4) In a flask under a nitrogen atmosphere, the compound (nf4) (26 g) and R225 (100 g) were charged, and the mixture was ice-cooled while stirring in a flask. Drip on one side

Rf2-COF (91 g), after completion of the dropwise addition, was further stirred in a flask. The contents of the flask were concentrated by filtration to give the compound (of 4) (88 g). -72- 200809410 (69) Add R113 (326g) to the autoclave of the NaF particle filling layer at the gas outlet, and stir it at 25 °C in the autoclave while blowing the nitrogen gas into the heat. After 1 hour, it was diluted to 20 °/ with nitrogen. Volume ^ of fluorine gas is blown in. A 20% fluorine gas was blown in as it was, and a solution of the compound (0 f 4 ) (75 g) dissolved in R 1 1 3 (346 g) was introduced into a hot press under a pressure of 0.1 MPa. After the introduction was completed, the contents of the autoclave were recovered and concentrated to obtain a compound (pf4). The compound (pf4) (10 〇 6 g) was dissolved in a solution of R225 (100 mL), and methanol (20 g) was dropped under ice-cooling to obtain a solution. After the completion of the dropwise addition, the solution was stirred at 25 ° C, and R225 and F(CF2)3OCF(CF3)COOCH3 were distilled off from the solution to obtain a reaction product (42 g). A solution containing a reaction product and THF (100 mL) was added dropwise ((CH3)2CHCH2)2A1H in a hexane solution (20 g) containing 79% by mass to obtain a solution. After the completion of the dropwise addition, after the solution was stirred, the solution was neutralized with a 〇.2 mo 1 /L aqueous hydrochloric acid solution to obtain a crude reaction liquid. The low-boiling component of the extract obtained by extracting the crude liquid in R225 was distilled off, and then the crude reaction liquid was recrystallized from hexane to obtain a compound (rf4). In the flask, the compound (rf4) (1. 63 g), tributylbutyl ether (82 mL), hydroquinone (5 mg), and triethylamine (8.1 g) were charged. The flask was ice-cooled while dropping CH2 = C(CH3)C(0)C1 (8.4 g) in a flask. After the completion of the dropwise addition, the mixture was stirred in a flask, and then the flask was charged with pure water (50 mL) to obtain a two-layer separation liquid. The upper layer of the two layers of the separation liquid was recovered, and dried and concentrated to obtain a concentrate. This concentrate was purified by cerium oxide gel column chromatography to obtain a compound (f4) (14 g). -73- (70) 200809410 The NMR data of the compound (f4) are shown below. H-NMR (300.4MHz, solvent CDC13, benchmark: TMS) δ ( • ppm): . 6 · 2 0 (1 Η), 5 · 7 0 (1 Η), 4 · 7 5 (2 Η), 1 · 9 8 (3 Η) 19F-NMR (282.7MHz, solvent = CDC13, benchmark: CFC13) δ (ppm): 19F-NMR (282.7MHz, solvent: CDC13, benchmark: CFC13) δ (ppm) ·· _118.6 (1F), -120.6(1F), -123.8(2F), -124.5(1F)? -124.9(1F)5 -128.6(1F)? -131.4(1F), -179.1(1F),-219.8(1F ), -227.0 (1 F). [Example 2] Production example of a photoresist for immersion lithography (i) [Example 2-1] A production example of the polymer (F1) was placed in a reactor (internal volume: 200 mL, made of glass), and charged with a compound. (f1) (4.8g), compound (r2) (12.0g), compound (q1) (9.0g), compound (q2) (2.5g) and MEK (7 7g). Next, IPP (1.59 g) containing 50% by mass of R225 solution was added as a polymerization initiator. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization reaction, the solid solution was recovered by dropping the solution in methanol in a reactor, and the solid matter was dried at 90 ° C for 24 hours, and dried under vacuum to obtain a polymer (F 1 ) (1 5 · 5 g ) ° Polymer (F1) is a non-crystalline polymer in the form of a white powder at 25 ° C. The polymer (F1) had a ηη of 3,700 and a Mw of 7,200. As a result of 13C-NMR analysis of the polymer (F1), the polymer (F1), relative to the total repeat unit, contains 1 1 mol% of the unit (F1) 'single-74- (71) 200809410 (R2) Containing 43 mol%, unit (Qi) contains 27 mol%, and unit (Q2) contains 19 mol% of polymer. Further, the polymers (F1) are each soluble in THF, CP, PGMEA. [Example 2-2] A production example of the polymer (F2) was placed in a reactor (internal volume: 30 mL, made of glass), and a compound (f1) (〇.17 g), a compound (r2) (1.0 g), a compound was charged. (q1) (0.46g) and MEK (2.7g). Next, IPP (0.65 g) containing 50% by mass of R225 solution was added as a polymerization initiator. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization reaction, the solution in the reactor was dropped in methanol to recover the aggregated solid matter. The solid matter was dried at 90 ° C for 24 hours, and vacuum-dried to obtain a polymer (F2) (1.2 g). The polymer (F2) was a non-crystalline polymer in the form of a white powder at 25t. The polymer (F2) had a Μη of 4500 and a Mw of 10,000. The polymer (F2) was analyzed by 13C-NMR. As a result, it was found that the polymer (F2) contained 54 mol% in units (F1) with respect to the total re-fraction unit, and the unit (R2) contained 54 mol%, and Unit (Q1) contains 41 mole % of polymer. Further, the polymer (F2) is each soluble in THF, CP, PGMEA. [Example 2-3] Production Example of Polymer (F3) In a reactor (inner volume 200 mL, made of glass), a compound (f2) (3.9 g), a compound (r 2 ) (1 0 · 0 g ), Compound (q 1 ) (-75-(72) (72) 200809410 6.7 g), Compound (q2) (1.7 g) and MEK (61 g). Next, IPP (12.5 g) containing 50% by mass of R225 solution was added as a polymerization initiator. After degassing in the reactor, the polymerization reaction was carried out at 4 (TC, i 8 hours. After the polymerization reaction, the solution in the reactor was dropped in methanol to recover the solidified aggregate, and the solid matter was at 90 ° C. The polymer (F3) (11.9 g) was obtained by vacuum drying over 24 hours. The polymer (F3) was a white powdery amorphous polymer at 25 ° C. The polymer (F3) had a η of 4,100 and Mw was 7800. The polymer (F3) was analyzed by 13C-NMR. As a result, it was found that the polymer (F3) contained 11 mol% per unit (F2) and 39 mol% per unit (R2) with respect to the total repeat unit. , unit (Q1) contains 4 2 mol%, and unit (Q2) contains 8 mol% of polymer. Further, polymer (F3), each soluble in THF, CP, PGMEA. [Example 2-4] The production example of the polymer (F4) was placed in a reactor (internal volume: 30 mL, made of glass), and the compound (f2) (〇.17 g), the compound (r2) (1〇g), and the compound (qi) (0.46 g) were charged. And MEK (2.7g). Then IP P (0.6 5 g) containing 50% by mass of R22 5 solution was added as a polymerization initiator. After degassing in the reactor, 'at 40 °C' for 18 hours. The polymerization reaction was carried out. After the polymerization reaction, the solid solution in the reactor was dropped in methanol to recover the solid matter, and the solid matter was dried at 90 ° C for 24 hours, and vacuum-dried to obtain a polymer (F4 ) (1 · 3 g ). The ruthenium polymer (F4) is a non-crystalline polymer in the form of a white powder at -25-(73) 200809410. The polymer (F4) has a Μη of 4100 and a Mw of 7800. The polymer (F4) is 13C- NMR analysis revealed that the polymer (F4) contained 4 mol per unit (F2) with respect to the full refraction unit, and the unit (R2) contained 54 mol%, and the unit (Q1) contained 42 mol% of the polymer. Further, the polymer (F4) is soluble in each of THF, CP, and PGMEA [Example 2-5 (Reference Example)] Polymer (R1) in the reactor (internal volume 200 mL) , made of glass), charged with compound (r2) (1 0.4g), compound (q1) (3.7g), compound (q2) (8.0g), and MEK (76.5g). Next, IP A (6 · 3 g ) As a chain transfer agent, IPP (U.Og) diluted to 50% by mass with R225 was used as a polymerization initiator, and each was charged. After degassing in the reactor, the temperature was 40. After 18 hours, the polymerization reaction was carried out, and the solution in the reactor was dropped in hexane to recover the aggregated solid matter, and the solid matter was vacuum dried at 90' for 24 hours to obtain a polymer (Ri) (1. 9 g). ). The polymer (R1) is a non-crystalline polymer in the form of a white powder at 25 °C. The polymer (R1) had a Μη of 2,870 and a Mw of 6,600. The results were measured by the 13c-nmr method. As a result, it was found that the polymer (R1) contained 40% by mol, the unit (Q1) 曰 2 0 旲%, and the unit (Q2) in terms of the unit (r2) with respect to the total repeat unit. 40 mole % of polymer. Further, the polymer (R1) is soluble in each of THF, PGMEA and CP. [Example 3] Evaluation example of photoresist for immersion lithography (1) -77- (74) (74) 200809410 [Example 3-1] Water repellency evaluation example Polymer (F1) (〇.9g) The solution obtained by dissolving in PGMEA (9.1 g) was further filtered through a filter (polytetrafluoroethylene) to obtain a resin solution. An antireflection film was formed on the surface (R0HM AHD HAAS Electr〇nic Materials, Inc., trade name AR26) The resin solution was spin-coated on the substrate of the following same). Next, the ruthenium substrate was heat-treated at 9 〇 ° C for 90 seconds to form a resin film (film thickness: 200 nm) of the polymer (F1) on the ruthenium substrate. Then, the static contact angles of the water relative to the resin film are measured as the drop angle and the receding angle. In addition, the polymers (F2) to (F4) and (R1) are used instead of the polymer (F). The same measurement was carried out except for 1). The results are summarized in Table 1. In addition, the drop angle measured by the slip method is expressed by the drop angle, and the back contact angle is measured by the slip method. The angle indicates (the same below). Static contact angle, drop angle and receding angle The unit is at the respective angle (°) (the same below). The static contact angle of the polymer forming the resin film is the fall angle of the falling angle _ Polymer (F1) 84 19 65 ^ Polymer (F2) 91 12 70 Polymer (F3) 85 18 69 ^ Polymer (F4) 84 14 69 One polymer (R1) 69 25 50 -78- (75) 200809410 [Example 3-2] Formation of photoresist pattern Polymer (F 1 ) ( 1 g) The triphenyl methanesulfonate (〇.〇5g) with the photoacid generator was dissolved in PGMEA (10 mL) and filtered through a filter to obtain a resist composition containing the polymer (F 1 ). The photoresist composition is spin-coated on the surface of the antireflection film and heat-treated to obtain a tantalum substrate formed of the photoresist film formed from the composition. ArF laser light (wavelength 193 nm) is used. As a light source interference exposure apparatus, a 90 nm/S immersion test of the ruthenium substrate was performed (immersion liquid: ultrapure water, developer: tetramethyl oxyhydroxide). As a result, it was confirmed by SEM image that the photoresist on the ruthenium substrate was good. From the above results, it is known that the polymerization of the repeating unit containing the compound (f) (Polymers (F1) to (F4). The polymer containing the repeating unit (Polymer (R1).) is superior in water repellency, especially dynamic water repellency. Therefore, by photo-resistance polymerization using immersion lithography The object is a shadow lens on a photosensitive photoresist, and the water can be well followed, so the immersion lithography method can be applied. [Example 4] Production example of a photoresist for immersion lithography (2) [Example 4 -1 ] Production Example of Polymer (F 5 ) Based on Solution of Trifluoron Photosensitive Light 矽 Substrate Photoresistive Two-beam Spot Exposure Test Solution) The film can be formed into a combination), and High rejection of the mobile stable of the present invention-79 - (76) 200809410 In a reactor (glass, internal volume 3 OmL), charged with compound (f3) (0.36 g), compound (r2) (1.0 g) , compound (q2) (• 21.21g), compound (q1) (〇.55g) and MEK ( 5.74g). Next, in the reactor, IPP (1.18 g) which is a polymerization initiator was charged with 50% by mass of R225 solution, and IPA (0.27 g) which is a chain transfer agent. After the atmosphere in the reactor was degassed by a nitrogen gas, the mixture was stirred in a reactor and polymerized at 40 ° C for 18 hours. After the polymerization, the agglomerate obtained by dropping the solution in the reactor in hexane was recovered, and dried under vacuum at 90 ° C for 24 hours to obtain a white powdery amorphous polymer (F5 ) at 25 ° C (1.56 g). ). The polymer (F5) had a Μη of 3,700 and a Mw of 8,800. The polymer (F5) was confirmed by 13C-NMR measurement, the unit (F3) contained 12 mol%, the unit (R2) contained 47 mol%, the unit (Q2) contained 30 mol%, and the unit (Q1) contained 21 Mole% of the polymer. Further, the polymer (F5), each soluble in THF, PGMEA, CP, MAK and EL. [Example 4-2] Production Example of Polymer (F6) In a reactor (made of glass, internal volume 30 mL), a compound (•f4) (〇.38 g), a compound (r2) (0.80 g), a compound was charged. (q2) (0.16 g), compound (q1) (〇.45 g) and MEK (4.88 g). Next, in the reactor, IPP (1.0 g) which is a polymerization initiator was charged with 50% by mass of R2 25 solution, and IPA (0.23 g) which is a chain transfer agent. After degassing the atmosphere into a nitrogen gas in the reactor, the mixture was stirred in a reactor and polymerized at 40 ° C for 18 hours. After the polymerization, the agglomerate obtained by dropping the solution in the reactor-80-(77) 200809410 in hexane was recovered, vacuum-dried at 90 ° C for 24 hours, and white powdery amorphous at 25 ° C. Polymer (F6) (l. 〇 3g). The polymer (F6) had a Μη of 5,500 and a Mw of 9,800. Further, the polymer (F6) was soluble in each of THF, PGMEA, CP, MAK and EL. [Example 5] Evaluation example of photoresist for immersion lithography (Part 2) [Example 5-1] Water repellency evaluation example A solution obtained by dissolving a polymer (F5) in PGMEA was filtered through a filter to obtain a polymerization. The material (F5) contains a 9% by mass resin solution. This resin solution was spin-coated on a crucible substrate having an antireflection film formed on its surface, and then heat-treated to form a resin film of the polymer (F5) on the crucible substrate. Next, the static contact angle, the falling angle, and the receding angle with respect to the water of the resin film were each measured. Further, the same measurement was carried out except that the polymer (F6) was used instead of the polymer (F5). The results are summarized in Table 2 as shown in Table 2. [Table 2] Material forming resin film Static contact angle Drop angle Back angle polymer (F5) 84 21 69 Polymer (F6) 88 21 75 [Example 5-2] Photoresist pattern Formation Example-81 - (78) (78) 200809410 The polymer (F5) (lg) and the triphenyllate triflate salt (0.05 g) which is a photoacid generator are dissolved in The solution obtained by PGMEA (10 mL) was filtered through a filter to obtain a photosensitive photoresist composition containing the polymer (F5). The photosensitive resist composition was spin-coated on a crucible substrate having an antireflection film formed on the surface thereof, and subjected to heat treatment to obtain a crucible substrate formed of the photoresist film formed of the photosensitive resist composition. An immersion exposure test of 90 nm/mL of the sand substrate (immersion liquid: ultrapure water, developing solution: tetramethylammonium hydroxide aqueous solution) was carried out using a two-beam interference exposure apparatus using ArF laser light (wavelength: 193 nm) as a light source. As a result, it was confirmed by the SEM screen that the photoresist film on the ruthenium substrate can form a good pattern. From the above results, it is understood that when the photoresist for immersion lithography of the present invention is used, a photoresist film excellent in photoresist characteristics and water repellency and excellent in dynamic water repellency can be formed. Therefore, in the immersion lithography method, the projection lens water that moves at high speed on the photoresist film can easily follow. [Example 6] Production example of the photoresist composition for immersion lithography (i) [Example 6-1] A production example of the polymer (F7) was used in a pressure-resistant reactor (internal volume 30 mL, made of glass). The compound (f1) (2.5 g) and CF3(CF2)5H (5.25 g) were charged. Next, IPP (1.17 g) containing 50% by mass of R225 solution was added as a polymerization initiator. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization reaction, the solution in the reactor was dropped in methanol to recover the solid matter of the coagulation-82-(79) (79) 200809410, and the solid matter was dried at 90 ° C for 24 hours under vacuum to obtain a polymer (F). ) (2.〇5g). The polymer (f7) was a white powdery amorphous polymer at 25 °C. The polymer (F7) had an Mn of 2,900 and a Mw of 6,300. [Example 6-2] Production Example of Polymer (F8) In a pressure-resistant reactor (internal volume: 30 mL, made of glass), a compound (f2) (0.8 g) and C3F(CF2)5H (1.06 g) were charged. Will then make ιρρ

(〇.28g) A 50% by mass solution of R225 was added as a polymerization initiator. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization, the solution in the reactor was dropped in methanol to recover the solid matter which was agglomerated, and the solid was vacuum dried at 90 ° C for 24 hours to obtain a polymer (F8 ) (0.62 g). The polymer (F8) was a non-crystalline polymer in the form of a white powder at 25 °C. The polymer (F8) had a Μη of 7000 and a Mw of 20,000. [Example 6-3] Production Example of Polymer (F9) In the same manner as in Example 6-1, a polymer (F9) of Mw9000 obtained by a repeating unit formed by polymerization of the compound (f1) was obtained. [Example 6-4] Production Example of Polymer (F1()) In the same manner as in Example 6-2, a polymer (FI()) of Mwll300 obtained by a repeating unit formed by polymerization of the compound (f2) was obtained. -83- (80) 200809410 [Example 6-5] Production example of polymer (F11) in a pressure resistant reactor (internal volume 30 mL, glass (f1) (〇.97 g), compound (r1) (〇· (0.34g) and MEK (4.7g). Then, 5〇% by mass of R225 solution was added as a polymerization bow to freeze and degas, and then reacted at 40 ° C for 18 hours, after the reaction, the reactor was placed. The solution was dropped into methanol 4 to make the solid at 90 ° C for 24 hours | (F11 ) ( 1.22 g). The polymer (F11 ) was a non-crystalline polymer. 3900, Mw is determined by 19F-NMR and W-NMR, and the unit is (F 1 ) 1 (R1 ) contains 38 mol%, and the unit (Q1) is contained. (F11) each soluble in THF, [Example 6-6] Polymer (F12) was produced in a pressure-resistant reactor (internal volume 30 mL, sputum (f1) (1.2 1 g), compound (r1) ( 〇 ·) (0.45g) and MEK (8.6g). Then, 50% by mass of R2 25 solution was added as a polymerization bow to freeze and degas, and after 40 hours at 40 ° C, the solution in the reactor was dropped. In methanol (made of glass), loaded with compound 42g) The compound (q1 contains IPP (0.97g) containing a hair styling agent. The polymerization is carried out in the reactor. The polymerization 1 is used to dry the agglomerated solids to obtain a polymerization of 25C as a white powder of 8200. F 11 ) $ 3 3 mole %, unit 2 9 mole % polymer PGMEA, CP, ΜΑΚ glass), loaded with compound 70g), compound (q2 makes IPP (1, 65g) contain hairpin. In the reactor, the polymerization reaction was carried out. The polymerization [received solids back-84-(81) (81) 200809410 was collected, and the solid matter was vacuum dried at 90 ° C for 24 hours to obtain a polymer (F12). (1.30g). Polymer (F12) is a non-crystalline polymer in the form of a white powder at 25 ° C. The polymer (F12) has a Μ η of 5000 and a Mw of 8800. 19F-NMR and 1 H-NMR As a result of the measurement, the polymer (F12) contains 37 mol%, the unit (R1) contains 34 mol%, and the unit (Q2) contains 29 mol% of the polymerization relative to the total repeat unit. Further, the polymer (F12) is each soluble in THF, PGMEA, CP, MAK. [Example 6-7] Production example of the polymer (F13) in a pressure resistant reactor (internal volume 30 mL, made of glass) ) Compound (f2) (1.42 g), compound (r1) (〇.70 g), compound (q1) (0.42 g) and MEK (6.9 g). Then, a R225 solution containing 50% by mass of IP P (1 · 4 2 g ) was added as a polymerization initiator, and IPA (0.24 g) was added as a chain transfer agent. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization reaction, the solid matter collected in the reactor was recovered in methanol under reduced pressure, and the solid matter was dried under vacuum at 90 ° C for 24 hours to obtain a polymer (F13) ( 1.18 g). The polymer (F13), which is a white powdery amorphous polymer at 25 ° C, has a Μη of 3700 and a Mw of 7,000. As a result of 19F-NMR and 1H-NMR measurement, the polymer (with respect to the total re-unit unit (F2) contains 28 mol%, the unit (Ri) contains 34 mol%, and the unit (Q1) contains 38 mole % of polymer. -85- (82) (82)200809410

Further, the polymers (F13) are each soluble in THF, PGMEA, CP, MAK

[Example 6-8] Production Example of Polymer (F14) In a pressure-resistant reactor (internal volume: 30 mL, made of glass), a compound (f1) (1*〇g), a compound (q3) (0.50 g), a compound were charged. (q1) (0.48g) and MEK (7.56g). Next, IPP (1.01 g) containing 50% by mass of R225 solution was added as a polymerization initiator. After degassing in the reactor, the polymerization was carried out at 40 ° C for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol, and the aggregated solid matter was recovered. The solid matter was vacuum dried at 90 ° C for 24 hours to obtain a polymer (F14) (1.64 g). Polymer (F14) at 25t: a non-crystalline polymer in the form of a white powder. The polymer (F14) had a Μη of 8400 and a Mw of 21600. As a result of 19F-NMR and 1 H-NMR measurement, the polymer (F14) contains 27 mol%, unit (Q3) contains 3 6 mol%, and unit per unit (F1) with respect to the full refraction unit. (Q 1 ) contains 37 mole % of polymer. Further, the polymer (F14) is each soluble in THF, PGMEA, CP, and ethylene glycol. [Example 6-9 (Comparative Example)] Production Example of Polymer (C)

In the same manner as in Example 6-2, the polymer (C) -86- obtained by the polymerization unit formed by the polymerization of CH2 = C(CH3)C(0) 〇CH2CH2(CF2)6F can be obtained. (83) (83) 200809410 [Example 6-10] The manufacturing example of the composition (;!) will contain 0.9 mass. / 〇 〇 polymer (F7) 1,3 - bis (difluoromethyl) benzene solution (1.09g), mixed with 7.3% by mass of polymer (R) CP solution (2.73g) to obtain transparent uniformity The solution. This solution was filtered through a filter having a pore size of 0.2 μm (manufactured by PTFE) to obtain a composition (1) containing 5.0% by mass of the polymer (F7) based on the total amount of the polymer (R1). [Example 6-1 1] The production examples of the compositions (2) to (4) were the same as those of [Example 6-10] except that the polymer (F8) was used instead of the polymer (F7), with respect to the polymer. The total amount of (Ri) is obtained as a composition (2) of a polymer (F8) containing 5 % by mass, except that the polymer (F9) is used instead of the polymer (f7), and [Example 1] Similarly, a composition (3) containing 5.0% by mass of the polymer (F9) was obtained with respect to the total amount of the polymer (R1), except that the polymer (ρ1()) was used instead of the polymer (F7). Then, in the same manner as in [Example 6-10], the composition (4) containing the polymer (f 1 G ) of 5% by mass was obtained with respect to the total amount of the polymer (R 1 ). [Example 6-12] Production Example of Composition (5)

113⁄4• 水 水 水 (F i) (2〇.〇mg), mixed with 9.57% by weight of polymer (R1) PGMEA solution (4.18g) to obtain a transparent and uniform solution. The solution was filtered through a filter of pore size 〇·2 μηη (manufactured by pTFE-87-(84) 200809410) to obtain a composition of a polymer (F11) containing 5.0 mass/〇 relative to the total amount of the polymer (R1). (5). [Example 6-13] The production examples of the compositions (6) to (8) were the same as those of [Example 6 - 1 2 ] except that the polymer (F 1 2 ) was used instead of the polymer (F 1 1 ). In the total amount of the polymer (R1), a composition (6) containing 0.5% by mass of the polymer (F 1 2 ) was obtained, except that the polymer (F13) was used instead of the polymer (F11), and the others were In the same manner as in [Example 6-12], a composition (7) containing 5 〇 mass% of the polymer (F 13 ) was obtained with respect to the total amount of the polymer (1^), except that the polymer (F14) was used instead. Other than the polymer (F 11 ), the composition of the polymer (1 4 ) containing 5.0 mass / 〇 was obtained with respect to the total amount of the polymer (R 1 ), in the same manner as in [Example 6 - 1 2 ]. (8 ). [Example 6 - 1 4 (Comparative Example)] The production example of the composition (C) was the same as [Example 6-10] except that the polymer (C) was used instead of the polymer (F7), with respect to the polymer. The total amount of (Ri) was obtained as a composition (C) of a polymer (C) containing 5.0% by mass. [Example 7] Evaluation example of the photosensitive photoresist composition for immersion lithography (the 〇 [stomach 7-1] water repellency evaluation example was carried out on the sand substrate on which the antireflection film was formed on the surface, and the composition (1 丨 spin coating) Then, the ruthenium substrate was heated at 100T for 90 seconds, and then heat treated at l3 〇 °C for 120 seconds to polymerize the polymer (F7) with the polymer -88-(85) 200809410 (R1). A film (film thickness: 50 nm) was formed on the ruthenium substrate. Next, the static contact angle with respect to the water of the resin film, the dynamic drop angle and the dynamic receding angle were measured. In addition to the composition (2) to the composition ( 8), the composition (C) was measured in the same manner as the composition (1), and the contact angle, the falling angle, and the receding angle of the resin film formed of only the polymer (R1) were measured. Table 3 shows the contact angle of the material forming the resin film, the falling angle, the receding angle composition (1), 107, 14 92, composition (2), 93, 25, 71, composition, (3) 105, 17, 86, composition (4) 103 20 84 Composition (5) 103 14 96 Composition (6) 100 15 93 Composition (7) 100 16 92 Composition (8) 99 14 94 Composition (C) 72 28 53 Polymer (R1) 69 25 50 From the above results, it is understood that the resin film formed of the composition containing the polymer (F) and the polymer (R), The resin film formed only of the polymer (R) and the resin film having the polymer (R) and the linear fluoroalkyl group (C) have a high backlash angle due to the resin film having a polymer (R) and a linear fluoroalkyl group (C). The water solubility is self-evident. [Example 7-2] Formation of a photoresist pattern-89- (86) (86) 200809410 Polymer (R1) (lg), polymer (F7) (0.05 g) and triphenyl A photosensitive uniform resist composition obtained by dissolving a triflate salt (0.05 g) in a transparent homogeneous solution obtained by dissolving PGMEA (10 mL) through a filter having a pore size of 0.2 μm (manufactured by PTFE). The photosensitive photoresist composition is spin-coated on a substrate on which an anti-reflection film is formed on the surface. Then, the germanium substrate is heat-treated at 100 ° C for 90 seconds, and further heated at 130 ° C for 120 seconds. A tantalum substrate of a resin film (film thickness: 150 nm) forming a photosensitive photoresist composition can be obtained. Two-beam interference is used. Exposure apparatus (light source: ArF laser light (wavelength 193 nm)), the 90 nm/S exposure test of the ruthenium substrate can be carried out by liquid immersion method and Dry method using ultrapure water as a liquid immersion medium. After exposure test, use The alkali aqueous solution was subjected to a development step, and the formation of a good pattern shape was confirmed when the surface of the ruthenium substrate was confirmed. From the above results, it is understood that the liquid crystal medium (water or the like) of the projection lens that moves on the photosensitive photoresist can be well followed by using the photoresist composition for liquid immersion exposure of the present invention, so that the immersion lithography method can be used. Implemented steadily. [Example 8] Production Example of Photoresist Composition for Impregnation Microshadow (Part 2) [Example 8-1] Production Example of Polymer (F15) In a reactor (made of glass, internal volume: 30 mL), a compound (f3) was charged. (〇.85g), compound (r2) (〇.50g), compound (q1) (0.40g) and MEK ( 4.75g). Next, IP P (0.98 g) which is a polymerization initiator was charged with a 50% by mass solution of R225. The reactor internal atmosphere -90-(87) 200809410 was placed in a nitrogen gas atmosphere, and after degassing, the polymerization reaction was carried out at 40 ° C for 18 hours while stirring in a reactor. After the polymerization, the agglomerate obtained by dropping the solution in the reactor in hexane was recovered, vacuum dried at 90 ° C for 24 hours, and a white powdery amorphous polymer was obtained at 25 ° C ( F15) (1.1 7g). The polymer (F15) had a Μη of 5,100 and a Mw of 14,300. The polymer (F15) was confirmed to have a polymer (F15) of 23 mol%, a unit (R2) of 34 mol%, and a unit (Q1) of 43 mol%, as measured by 13C-NMR. Further, the polymers (F15) are each soluble in THF, PGMEA, CP, MAK and EL. [Example 8-2] Production Example of Polymer (F16) In a reactor (made of glass, internal volume 30 mL), a compound (f4) (〇.64 g), a compound (r2) (0.35 g), and a compound (q1) were charged. (〇28g) and methyl isobutyl ketone (465g). Next, IPP (〇.89g) containing 50% by mass of R225 solution was charged as a polymerization initiator. After the atmosphere in the reactor was degassed by a nitrogen gas, the inside of the reactor was stirred, and polymerization was carried out at 40 ° C for 18 hours. • After polymerization, the solution in the reactor is dropped in hexane and the resulting agglomerate is recovered at 90. (: Vacuum drying was carried out for 24 hours to obtain a white powdery amorphous polymer (Fi6) (0.91 g) at 25 ° C. The polymer (F16) had a Μη of 6900 and a Mw of 13,000. By 19F-NMR and The iH-NMR measurement confirmed that the polymer (pl6) contained unit (F4) 2 9 mol%, unit (R2) 3 4 mol%, unit (q 1 ) 3 7 -91 - (88) ( 88) 200809410 Moer/〇 polymer. Further, the polymer (F16) is each soluble in τ HF, PGMEA, CP, MAK and EL. [Example 8 - 3] Composition of the composition (9) Polymer (R2) is a repeating unit of compound (r2) 4 〇 mol% 'recovery unit 40 mol% of compound (q1) and a repeating unit of compound (q2) 20 mol% of polymer (Mw6600, Mn2900). The polymer (F15) (20 mg) was mixed with the polymer (R2) and a 9.57 mass% PGMea solution (4.18 g) to obtain a transparent uniform resin solution, which was filtered through a filter to obtain a polymerization-free polymerization. The total mass of the substance (r2) is a composition (9) containing 5.0% by mass of the polymer (F 15 ). [Example 8-4] A production example of the composition (10) except for using a polymer ( F 1 6 ) other than the substitute polymer (F 15 ), the same as [Example 8-3], the polymer (F16) having a total mass of the polymer (R2) of 5.0% by mass is obtained. Composition (10) [Example 9] Evaluation example of photoresist composition for immersion lithography (Part 2) [Example 9-1] Water repellency evaluation example The composition (9) was formed on the surface of an antireflection film 矽 substrate Spin coating is applied thereto, and heat treatment is performed to form a resin film containing the polymer (r2) and the polymer (F 15 ) on the ruthenium substrate. Then, the static contact angle with respect to the water of the resin film is measured, Dynamic drop angle, dynamic -92- (89) 200809410 Retreat. Except for the composition (1 〇) instead of the composition (9), the same is measured. The results are summarized in Table 4. [Table 4] Material Forming Resin Film Static Contact Angle Drop Angle Backward Angle Composition (9) 97 17 88 Composition (10) 100 15 92 [Example 9-2] Formation Example of Photoresist Pattern Polymer (R2) (1 g), polymer (F 15 ) (〇·〇5 g ) and photoacid generator triphenylsulfonium trifluoromethanesulfonate (〇.〇5g) dissolved (10 mL) of the resultant PGMEA solution was filtered through a filter, comprising a polymer obtained (R2) and the polymer (F 15) is formed of the resist composition (1). This photosensitive resist composition was spin-coated on a crucible substrate having an antireflection film formed on its surface, and subjected to heat treatment to obtain a crucible substrate formed of a photoresist film formed of the photosensitive resist composition. An immersion exposure test of 90 nm/S of the ruthenium substrate was carried out using a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source (impregnation liquid: ultrapure water, developer: tetramethylammonium hydroxide aqueous solution) . As a result, it was confirmed by the SEM image that a good pattern can be formed on the resist film on the germanium substrate. [Example 9 - 3] Photoacid generator (PAG) dissolving amount of photoresist forming composition - 93- (90) 200809410 Price example Rotating light pj (1 ) on a crucible substrate on which an antireflection film is formed on the surface The cloth was further treated with a crucible substrate at 1 ° C, and a polymer (R2 ) and a polymer (F15) having a thickness of 15 5 nm were formed on the sand substrate. Next, the argon-based ArF laser light (wavelength: 193 nm) was used as a light source, and placed between the outer cover glass (made of synthetic quartz) and the ruthenium substrate (?50 μL), and then placed for 60 seconds. In addition, the wetted area of the pure water on the ruthenium substrate was 7 cm 2 . Next, the ultrapure water is recovered, using LC/MS/MS Quattro micro API, manufactured by Waters Co., Ltd. (detection boundary P mol/cm2), and the photoacid generated from the photoreceptor contained in the ultrapure water is formed. Agent (PAG) origin, cation (ion) dissolved amount and anion (phenyl fluorene trifluoromethanesulfonic acid (solubility measured) (dissociation amount: mol/cm2/60 again, in the photoresist forming composition ( 1) A photoresist forming composition made of a polymer (F 13 ) which is produced by using a polymerization-replacement polymer (F 15 ) to form a composition (F 13 ). Further, the comparative example uses only polymerization. The photo-resistance of the composition (C) was measured in the same manner. The results are summarized in Table 5. The L-formed composition was heated at a temperature of 90 seconds (the film was placed on the 干涉 interference exposure package [in ultra pure Water (f-fat film and super-analytical device (艮: 7.0xl〇_15 (1) dissolved in triphenylphosphonium triflate)))) (F 1 1 ) with (2), and 〇, proceed Manufactured in the same manner as Rl) -94- (91) 200809410 [Table 5] Material forming a resin film Ionizing photoresist forming composition (1) 7.0xl〇-14 3.8xl0'13 photoresist forming composition (2) 1.5xl〇·12 3.4xl0"12 photoresist forming composition (3) 6.8xl0'13 2.0xl (T12 photoresist forming composition (C) 3.0xl0'12 ^-two-__ 7.5xl0'12 From the above results, it can be seen that light can be formed when the photoresist composition for immersion lithography of the present invention is used. The resistive property and the water repellency are excellent, and the dynamic water repellency excellent photoresist film is self-evident. Therefore, in the immersion lithography method, the projection lens that moves at high speed on the photoresist film can easily follow the water. According to the present invention, it is possible to provide a photoresist material for immersion lithography which is excellent in photoresist characteristics and dynamic water repellency, and a photo resist material is used in the immersion lithography method of the present invention. It is possible to perform a high-speed and high-speed immersion lithography method with high-resolution transfer. It is also possible to apply Japanese Patent Application No. 2006-110971, filed on May 11, 2006, Japan, filed on May 11, 2006 Patent Application No. 2006-13 24 07, Japanese Patent Application No. 2 filed on June 27, 2006 Japanese Patent Application No. 006-176881, filed on Jul. 31, 2006, the entire disclosure of which is hereby incorporated by Disclosure of the description of the invention - 95-

Claims (1)

200809410 (1) X. Patent Application No. 1 · A photoresist material for immersion lithography, which contains a polymer (F , ) containing polymerizable property having a fluorine-containing crosslinked ring structure The repeating unit (Fu) formed by the polymerization of the compound (fm), and the alkali solubility is increased by the action of an acid. 2. The photoresist for immersion lithography according to claim 1, wherein the polymerizable compound (fm) is selected from the group consisting of the following formula (f 1 ), the following formula (f2), the following formula (f3), and the following formula (f) A compound (f) of a group of compounds shown in the group, [Chemical Formula 1] (&quot;&gt; (f2) (f3) (f4) The symbol in the formula indicates the following meaning, RF: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or chloroanthyl group having 1 to 3 carbon atoms XF: a fluorine atom, a hydroxyl group or a hydroxymethyl group, and the fluorine atom in the compound (f) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. - a photoresist for immersion lithography which increases alkali solubility due to the action of an acid, and is characterized by containing a weight formed by polymerization of a polymerizable compound (fm) having a fluorine-containing crosslinked ring structure Overlay unit (Fu) '------- (2) 200809410, a repeating unit (Ru) formed by polymerization of a polymerizable compound (rm) having a base which has an increase in alkali solubility due to an acid action. The photoresist compound for immersion lithography according to Item 3, wherein the polymerizable compound (fm) is selected from the following formula (Π), the following formula (f2), the following formula (〇), and the following formula (f*4). a compound (f) in which one or more of the compounds shown are grouped, The symbol in the formula means the following meaning, RF: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms: fluorine atom, hydroxyl group or hydroxymethyl group, and 'compound ( The fluorine atom in the crucible can be replaced by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. 5. For impregnation lithography according to claim 3 or 4 A photoresist polymer in which the polymerizable compound (rm) is a polymer of the formula (ur2), a group represented by the following formula (ur4), a formula (ur3) of the following formula (ur3) or a compound of the following formula -97- (3) 200809410 [Chemical 3] &gt;=〇0 x«2-c-~xR2 —c(cf3)2(〇ZR3&gt;—C(CF3)(OZft4)—(ur2&gt; (ur3) (ur4) The notation in the formula indicates the following meaning, : an alkyl group having a carbon number of 1 to 6, qr1: a divalent group having a carbon number of 4 to 2 Å together with a carbon atom of the formula: XR2: among the monovalent hydrocarbon groups having 1 to 20 carbon atoms, 3 XR2 may be the same or different, and the respective alkyl, alkoxyalkyl, alkoxycarbonyl or alkylcarbonyl groups of ZR4 are each a carbon number of 1 to 20, and further, XR1, QR1, XR2, ZR3 or In ZR4, a carbon atom-carbon atom can be inserted between a group of the formula - 〇-, a group of the formula - c(0)0 - or a group of the formula - C(O)-' XR1, QR1, xR2 The carbon atom in ZR3 or zR4 may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. 6. The photoresist for immersion lithography according to any one of claims 3 to 5, wherein the polymerizable compound (rm) One or more compounds (r) selected from the group consisting of the compounds represented by the following formula (r 1 ), the following formula (r2), and the following formula (r3) '-98- 200809410 (4) CH2==cCo (r2) cf2=cf~qR3—ch=ch2 (r3) The symbol in the formula indicates the following meaning 'rR: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms 'XR1: a hospital base having a carbon number of 1 to 6' qRI: a divalent group having a carbon number of 4 to 20 which forms a cyclic hydrocarbon group together with a carbon atom in the formula, XR2: in a monovalent hydrocarbon group having 1 to 20 carbon atoms, 3 XR2 may be the same or different, QR3: a group of the formula -CF2C(CF3)(OZR4)(CH2)m-, a formula -CH2CH((CH2)nC(CF3)2(OZR3))(CH2)m a group represented by the formula or the formula -CH2CH(C(0)0ZR3)(CH2)m-, ZR3 and ZR4: each independently, in an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group Is a group having a carbon number of 1 to 20, and a carbon atom in the QR1, XR2, ZR3 or ZR4, a group in which a carbon atom is interposable, and a group represented by the formula -C(0)0- The carbon atom in the group or the group represented by the formula _c(0)-, XR1, QR1, XR2, ZR3 or ZR4 may be bonded to a fluorine atom, a hydroxyl group or a thiol group. 7. The photoresist for immersion lithography according to any one of claims 3 to 6, wherein the repeat unit (Fu-99-(5) 200809410) is included with respect to the full repeat unit. 1 to 45 mol%, and the repeating unit (Ru) contains 10 mol% or more of a polymer. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> And organic solvents. 9 . A method for forming a photoresist pattern of a photoresist pattern on a substrate, which is a method for forming a photoresist pattern caused by immersion lithography, characterized in that, in accordance with the order, the patent application scope is The immersion lithography of the eighth item is applied to the substrate by the photoresist forming composition, the step of forming a photoresist film on the substrate, the immersion lithography step, and the developing step. 1 〇. A photoresist composition for immersion lithography which is characterized by an increase in alkali solubility due to the action of an acid, characterized by containing a polymer (F) and a polymer (R), wherein the polymer (F): a repeating unit (Fu) comprising a polymerization of a polymerizable compound (fm) having a fluorine-containing crosslinked ring structure, and a polymer (R) containing a polymerizability which increases alkali solubility by an action of an acid The repeating unit (Ru ) formed by the polymerization of the compound (rm). The immersion lithography photoresist composition according to the first aspect of the invention, wherein the polymerizable compound (fm) is selected from the following formula (f丨), the following formula (f2), and the following formula (f3) And a compound (f) of a group or a group of compounds represented by the following formula (f4), -100- 200809410 (6) [Chemical 5] CH2=C &gt;=〇CH2=C, o CH2 γ献 F献 g: ^ -CF-CF2 cf2_cf ~cf2 cf inside -. Bu cf2 ((1) (f2) , Rf &gt;=〇 CH : CF I /CF2 cf2 (f3) The symbol in the formula represents the following meaning, rf: a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, XF • a fluorine atom, a hydroxyl group or a hydroxymethyl group, The fluorine atom in the compound (f) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. i 2 . The photoresist composition for immersion lithography according to claim 1 or claim 1 wherein the polymerizable compound (rm) has the following formula (ur 1 ), the following formula (ur2 ), and the following formula ( a polymerizable compound of the formula ur3) or the formula (ur4), [Chem. 6] XR2』_XR2 XR2 (ur2)-C(CF3)2(〇ZR3)(ur3)-C(CF3)(OZR4(ur4) The symbol in the formula indicates the following meaning, XR1 ··carbon number 1~6 Base, qr1: a divalent group having a carbon number of 4 to 2 fluorene together with a carbon atom of the formula - 101 - 200809410 (7) xR2 : among the monovalent hydrocarbon groups having a carbon number of i to 20, 3 x R 2 It may be the same or different, and zR3 and zR4 are each independently, in the alkyl group, alkoxyalkyl group, alkoxycarbonyl group or alkylcarbonyl group, a carbon number of 1 to 20, and further, XR1, QR1, XR2, ZR3 Or a carbon atom-carbon atom in ZR4, a group represented by a formula, a group represented by the formula -c(0)0_ or a group represented by the formula -c(o)-, XR1, QR1, XR2, zR3 The carbon atom in zR4 may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. The photoresist composition for impregnation lithography of any one of claims 10 to 12, wherein the polymerizable compound (rm) is a compound (r) selected from the group consisting of the following formula ( rl ), the following formula (r2 ), and a compound represented by the following formula (r3) The symbol in the formula represents the following meaning, Rr: a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having a carbon number of 1 to 3 'XR1: an alkyl group having 1 to 6 carbon atoms, qr1: and Wherein the carbon atoms together form a cyclic hydrocarbon group having a carbon number of 4 to 2 fluorene of a valence group XR2: in a monovalent hydrocarbon group having 1 to 2 carbon atoms, 3 XR2 may be the same -102-(8) (8) ) 200809410 or different, QR3: the formula -CF2C(CF3)(OZR4)(CH2)m-, the formula -CH2CH((CH2)nC(CF3)2(OZR3))(CH2)m- a group or a group of the formula -CH2CH(C(0)0ZR3)(CH2)m-, ZR3 and ZR4: each independently, in an alkyl group, an alkoxyalkyl group, an alkoxy group or a ferrous group, a group having a carbon number of 1 to 20, and a carbon atom-carbon atom in the XR1, QR1, XR2, ZR3 or ZR4, which is intercalated by the formula -〇-, is represented by the formula -c(o)o- The carbon atom in XR1, QR1, XR2, ZR3 or ZR4 may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group, or a group represented by the formula -c(0)-. The photoresist composition for immersion lithography according to any one of claims 10 to 13, wherein the polymer (F) is contained in an amount of 0.1 to 30% by mass based on the polymer (R). By. The immersion lithography photoresist composition for immersion lithography, which comprises the photoresist composition for immersion lithography according to any one of claims 1 to 14, the photoacid generator, and Organic solvents. 16. A method for forming a photoresist pattern of a photoresist pattern formed on a substrate, which is a method for forming a photoresist pattern caused by immersion lithography, and is characterized in that 'sequentially' will be patented The immersion lithography photoresist composition for the immersion lithography is applied to the substrate, the step of forming a photoresist film on the substrate, the immersion lithography step, and the development step. -103- 200809410 无• · Ming said that there is no simple •• number as the map of the map. The map is representative of the table. The representative of the table is one or two. If there is a chemical formula in this case, please reveal the best invention. Chemical formula of the feature: none