JP2010139518A - Resist polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist polymer excellent in photosensitive resist properties or resist protective film properties and in dynamic liquid repellency. <P>SOLUTION: The resist polymer has a repeating unit (A) which is formed by polymerizing a compound represented by formula: CF<SB>2</SB>=CFCF<SB>2</SB>C(X<SP>A</SP>)(C(O)OZ<SP>A</SP>)(CH<SB>2</SB>)<SB>na</SB>CR<SP>A</SP>=CHR<SP>A</SP>, wherein X<SP>A</SP>represents H, cyano or a group represented by the formula -C(O)Z<SP>A</SP>; Z<SP>A</SP>represents H or a 1-20C monovalent organic group; na represents 0, 1 or 2; and R<SP>A</SP>represents H or a 1-20C monovalent organic group, and two R<SP>A</SP>'s may be the same as or different from each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resist polymer, a resist polymer for immersion lithography, a resist composition for immersion lithography, a resist protective film polymer for immersion lithography, and a resist protective film composition for immersion lithography.

  In the manufacture of integrated circuits such as semiconductors, the mask pattern image obtained by irradiating the light from the exposure light source onto the mask is projected onto the photosensitive resist layer on the substrate, and the pattern image is transferred to the photosensitive resist layer. A lithography method is used. Usually, the projection of the pattern image is performed by a scanning method. That is, the pattern image is projected by projecting the pattern image onto the photosensitive resist layer via a projection lens that moves relatively on the photosensitive resist layer.

The present applicant has proposed a cyclized polymer of a fluorodiene having a functional group as a resist polymer. For example, the applicant of the present invention uses 1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene (CF ₂ ═CFCH ₂ CH (C (O) OC (CH ₃ ) ₃ ) as the fluorodiene. CH ₂ CH = CH ₂ etc.) is proposed (see Patent Document 1).

By the way, in recent years, the immersion lithography method, that is, the space between the lower part of the projection lens and the upper part of the photosensitive resist layer is filled with a liquid medium having a high refractive index (liquid medium such as ultrapure water) (hereinafter also referred to as an immersion liquid). However, a method of projecting a mask pattern image onto a photosensitive resist layer through a projection lens has been studied.
In the immersion lithography method, since the space between the projection lens and the photosensitive resist layer is filled with the immersion liquid, a photosensitive resist layer in which components of the photosensitive resist layer (such as a photoacid generator) are eluted into the immersion liquid. There are problems such as swelling by immersion liquid. In order to solve this problem, resist materials for immersion lithography have been studied.
As a photosensitive resist material for immersion lithography, a resist composition containing a copolymer of three kinds of compounds represented by the following formula and a fluorosurfactant is known (see Patent Document 2).

In addition, in the immersion lithography method, an attempt has been made to suppress elution and swelling of the photosensitive resist layer by providing a resist protective film layer on the photosensitive resist layer.
As a resist protective film material for immersion lithography, a composition containing an alkali-soluble polymer containing a repeating unit of a polymerizable compound having a polar group such as the following compound and a fluorosurfactant is known (patent document). 3).

Further, as a resist protective film polymer for immersion lithography, Patent Document 4 discloses that CF ₂ = CFCF ₂ C (CF ₃ ) (OR ^g ) CH ₂ CH = CH ₂ (b ^g is a hydrogen atom or a carbon number of 1 to 15 represents an alkyloxy group or an alkyloxyalkyl group.) And a polymer containing the following repeating unit (p1) formed by cyclopolymerization is described. Patent Document 5 describes CF ₂ ═CFCH ₂ CH (C A polymer composed of the following repeating unit (p2) formed by cyclopolymerization of (CF ₃ ) ₂ OH) CH ₂ CH═CH ₂ is described.

JP 2005-298707 A JP 2005-234178 A JP 2005-352384 A JP 2005-264131 A JP 2007-072336 A

The cyclopolymerizable fluorodiene having a functional group is preferably studied for various structures in order to improve the properties of the polymer. However, even if it actually tried to carry out such a study, it was difficult to obtain the raw material compound and it was difficult to carry out.
Regarding the fluorodiene having an analogous group of carboxy group, only 1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene described in Patent Document 1 is known, and other compounds are known. It wasn't.

On the other hand, the photosensitive resist material for immersion lithography is preferably excellent in dynamic liquid repellency so that the immersion liquid follows the projection lens moving on the photosensitive resist layer. For example, when the immersion liquid is water, it is desirable that the photosensitive resist material for immersion lithography is excellent in dynamic water repellency. However, such a resist material is not known.
For example, the fluorosurfactant described in Patent Document 2 is merely a polymer of a non-polymeric fluorine-containing compound and an acyclic fluoroalkyl (meth) acrylate, and the dynamic repellent property of the resist composition of Patent Document 2 Aqueous was low. Therefore, in the immersion lithography method using the photosensitive resist material prepared from the resist composition, it is considered that it is not easy to cause the immersion liquid to follow the projection lens that moves at high speed.

It is desirable that the resist protective film provided in the immersion lithography method is also excellent in dynamic liquid repellency. However, such a resist protective film material is not known.
For example, the fluorosurfactant described in Patent Document 3 is only a polymer of a non-polymeric fluorine-containing compound and an acyclic fluoroalkyl (meth) acrylate. The water repellency was low.

  Further, the polymer described in Patent Document 4 or 5 does not have sufficient dynamic water repellency and developer solubility. Therefore, it is considered that it is not easy to cause the immersion liquid to follow the projection lens that moves at high speed on the resist protective film layer in the immersion lithography method using these resist protective film materials.

  The present invention is an invention intended to provide a resist material excellent in characteristics as a photosensitive resist material or a resist protective film material and dynamic liquid repellency (particularly dynamic water repellency).

That is, the present invention provides the following inventions.
<1> A resist polymer containing a repeating unit (A) formed by polymerization of a compound represented by the following formula (a).
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different.

<2> The resist polymer according to <1>, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 .

<3> A resist polymer for immersion lithography, which contains a repeating unit (A) formed by polymerization of a compound represented by formula (a) and has increased alkali solubility by the action of an acid.
<4> The resist polymer for immersion lithography according to <3>, wherein the compound represented by formula (a) is a compound represented by formula (a1) or formula (a2).

<5> The immersion lithography according to <3> or <4>, wherein the resist polymer for immersion lithography further comprises a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. Resist polymer.
<6> The polymerizable compound (f) is a compound represented by the following formula (f1), the following formula (f2), the following formula (f3), the following formula (f4), or the following formula (f5). A resist polymer for immersion lithography as described in 1. above.

The symbols in the formula have the following meanings.
R ^F : 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.
In addition, the fluorine atom in the compounds (f1) to (f5) may be substituted with a C 1-6 perfluoroalkyl group or a C 1-6 perfluoroalkoxy group.

  <7> Polymerization of a polymerizable compound (b) in which the resist polymer for immersion lithography further has a group represented by the following formula (b1), the following formula (b2), the following formula (b3), or the following formula (b4) The resist polymer for immersion lithography according to any one of <3> to <6>, comprising a repeating unit formed by

The symbols in the formula have the following meanings.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group together with the carbon atom in the formula.
X ^B2 : a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Z ^B : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, a group having 1 to 20 carbon atoms, or a hydrogen atom.
In addition, a group represented by the formula -O-, a group represented by the formula -C (O) O-, or a formula -C between the carbon atom and the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B A group represented by (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B.

  <8> The resist polymer for immersion lithography according to <7>, wherein the polymerizable compound (b) is a compound represented by the following formula (b1), the following formula (b2), or the following formula (b3).

The symbols in the formula have the following meanings.
R ^B : 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.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with the carbon atom in the formula.
X ^{B2 is} an alkyl group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Q ^B3 : Formula —CF ₂ C (CF ₃ ) (OZ ^B ) (CH ₂ ) _nb —, or Formula —CH ₂ CH ((CH ₂ ) _mb C (CF ₃ ) ₂ (OZ ^B )) (CH ₂ ) a group represented by _nb- .
Z ^B : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, a group having 1 to 20 carbon atoms, or a hydrogen atom.
mb and nb: each independently 0, 1, or 2.
^However, X ^B1, Q ^B1, carbon atoms ^{X B2} or ^{Z B} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, also, A fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom of X ^B1 , Q ^B1 , X ^B2 or Z ^B.

  <9> A resist forming composition for immersion lithography, comprising the resist polymer for immersion lithography according to any one of <3> to <8>, a photoacid generator, and an organic solvent.

  <10> A method of forming a resist pattern by an immersion lithography method, the step of applying a resist formation composition for immersion lithography according to <9> on a substrate to form a resist film on the substrate, an immersion lithography step, And a developing method for forming a resist pattern on a substrate, wherein the developing steps are performed in this order.

<11> A polymer (A) containing a repeating unit (A) formed by polymerization of a compound represented by the formula (a) and a polymer (B) whose alkali solubility is increased by the action of an acid. A resist composition for immersion lithography.
<12> The resist composition for immersion lithography according to <11>, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).

<13> The polymer (A) is a polymer (AF) including a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. <11> or <12> A resist composition for immersion lithography as described in 1. above.
<14> The immersion lithography according to <13>, wherein the polymerizable compound (f) is a compound represented by the formula (f1), the formula (f2), the formula (f3), the formula (f4), or the formula (f5). Resist composition.

<15> The polymer (B) is a polymerizable compound (b) having a group represented by the formula (b1), formula (b2), formula (b3) or formula (b4) <11> to <14 > The resist composition for immersion lithography according to any one of the above.
<16> The resist composition for immersion lithography according to <15>, wherein the polymerizable compound (b) is a compound represented by the formula (b1), the formula (b2), or the formula (b3).

  <17> The resist composition for immersion lithography according to any one of <11> to <16>, comprising 0.1 to 30% by mass of the polymer (A) with respect to the polymer (B).

  <18> A resist forming composition for immersion lithography comprising the resist composition for immersion lithography according to any one of <11> to <17>, a photoacid generator and an organic solvent.

  <19> A method of forming a resist pattern by an immersion lithography method, the step of applying a resist formation composition for immersion lithography according to <18> on a substrate to form a resist film on the substrate, an immersion lithography step, And a developing method for forming a resist pattern on a substrate, wherein the developing steps are performed in this order.

<20> An alkali-soluble resist protective film polymer for immersion lithography, comprising a repeating unit (A) formed by polymerization of a compound represented by formula (a).
<21> The resist protective film polymer for immersion lithography according to claim 20, wherein the compound represented by the formula (a) is a compound represented by the formula (a1) or the formula (a2).

<22> The resist protective film polymer for immersion lithography further includes a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure, described in <20> or <21> A resist protective film polymer for immersion lithography.
<23> The immersion lithography according to <22>, wherein the polymerizable compound (f) is a compound represented by the formula (f1), the formula (f2), the formula (f3), the formula (f4), or the formula (f5). Resist protective film polymer.

  <24> A resist protective film forming composition for immersion lithography comprising the resist protective film polymer for immersion lithography according to any one of <20> to <23> and an organic solvent.

  <25> A step of applying a photosensitive resist material onto a substrate to form a resist film on the substrate, and applying the resist protective film forming composition for immersion lithography according to <24> onto the resist film. A resist pattern forming method for forming a resist pattern on a substrate, wherein a resist protective film forming step, an immersion lithography step, and a developing step are performed in this order.

<26> formed by polymerization of a polymer (A) containing a repeating unit (A) formed by polymerization of a compound represented by formula (a) and a polymerizable compound (f) having a fluorine-containing ring structure A resist protective film composition for immersion lithography, comprising a polymer (F) containing a repeating unit (F).
<27> The resist protective film composition for immersion lithography according to <26>, wherein the compound represented by the formula (a) is a compound represented by the formula (a1) or the formula (a2).

<28> The resist protective film composition for immersion lithography according to <26> or <27>, wherein the polymer (F) is a polymer (FA) containing the repeating unit (A) and the repeating unit (F).
<29> The polymerizable compound (f) is a compound represented by the formula (f1), the formula (f2), the formula (f3), the formula (f4), or the formula (f5). The resist protective film composition for immersion lithography according to any one of the above.

  <30> The resist protective film composition for immersion lithography according to any one of <26> to <29>, comprising 0.1 to 200% by mass of the polymer (F) with respect to the polymer (A).

  <31> A resist protective film forming composition for immersion lithography comprising the resist protective film composition for immersion lithography according to any one of <26> to <30> and an organic solvent.

  <32> A step of applying a photosensitive resist material on a substrate to form a resist film on the substrate, and applying the resist protective film-forming composition for immersion lithography according to <31> onto the resist film. A resist pattern forming method for forming a resist pattern on a substrate, wherein a resist protective film forming step, an immersion lithography step, and a developing step are performed in this order.

  According to the present invention, photosensitive resist properties (transparency to short wavelength light, etching resistance, etc.) or resist protective film properties (suppression of swelling and elution of photosensitive resist, etc.) And a resist polymer excellent in dynamic water repellency. By using the resist polymer of the present invention, it is possible to stably carry out an immersion lithography method capable of transferring a mask pattern image with high resolution.

In the present specification, a compound represented by the formula (a) is referred to as a compound (a), and a group represented by the formula —C (O) OZ ^A is referred to as —C (O) OZ ^A. Other compounds and other groups are also described in the same manner.
Further, symbols in the group are as defined above unless otherwise specified.

The present invention provides a resist polymer containing a repeating unit (A) formed by polymerization of the following compound (a).
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).

X ^A is preferably a hydrogen atom or —C (O) OZ ^A.
na is preferably 1.
R ^A is preferably a hydrogen atom.

Z ^A is a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ (hereinafter also referred to as group (G1)), a group represented by the formula —CH ₂ OZ ^A12 (hereinafter referred to as group (G2)). Or a group represented by the following formula (hereinafter also referred to as group (G3)) is preferable.

When Z ^A11 in the group (G1) is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, Z ^A11 may be an acyclic group or a group containing a cyclic group. Good. The acyclic group may be a linear group or a branched group. The group containing a cyclic group may be a group containing a polycyclic group or a group containing a monocyclic group. The group containing a polycyclic group may be a group containing a bridged cyclic group or a group containing a condensed cyclic group.

  Specific examples of the group containing a cyclic group include a group containing any group represented by the following formula, and a group containing a group in which a hydrogen atom in the group is substituted with a fluorine atom.

  Specific examples of the group in which a hydrogen atom in a group containing a cyclic group is substituted with a fluorine atom include the following groups.

Three Z ^A11 in the group (G1) may be the same or different.
Three Z ^A11 in the group (G1) are two monovalent saturated hydrocarbon groups having 1 to 6 carbon atoms and one is a monovalent cyclic saturated hydrocarbon group having 1 to 12 carbon atoms, Preferably two are hydrogen atoms and one is a polyfluoroalkyl group having 1 to 12 carbon atoms, or three are monovalent saturated hydrocarbon groups having 1 to 6 carbon atoms, and two are carbon atoms. 1 to 6 alkyl groups (preferably a methyl group) and one is a 1-adamantyl group, or a polyfluoroalkyl group represented by the formula —CH ₂ R ^FZ (wherein R ^FZ represents 1 to 10 is a perfluoroalkyl group.) Or 3 are preferably an alkyl group having 1 to 6 carbon atoms (preferably a methyl group).

  Specific examples of the group (G1) include a group represented by the following formula.

^ZA12 in the group (G2) is a saturated hydrocarbon group having 1 to 12 carbon atoms, a saturated hydrocarbon group containing -O- having 1 to 12 carbon atoms, a fluorine-containing saturated hydrocarbon group having 1 to 12 carbon atoms, or A fluorine-containing saturated hydrocarbon group containing -O- having 1 to 12 carbon atoms is preferred.

  Specific examples of the group (G2) include any group represented by the following formula.

Z ^A13 is preferably a saturated hydrocarbon group containing 1 to 6 carbon atoms or a saturated hydrocarbon group containing 1 to 6 carbon atoms —O—.
Q ^A13 represents a saturated hydrocarbon group having 4 to 12 carbon atoms, 4 to 12 carbon atoms in which —O—, —C (O) —, or —C (O) O— is inserted between carbon atoms. Saturated hydrocarbon group, a fluorine-containing saturated hydrocarbon group having 4 to 12 carbon atoms, or —O—, —C (O) — or —C (O) O— is inserted between the carbon atom and the carbon atom. A fluorine-containing saturated hydrocarbon group having 4 to 12 carbon atoms is preferred.

  Specific examples of the group (G3) include any group represented by the following formula.

The compound (a) is preferably the following compound (a1) or (a2).
^{_{CF 2 = CFCF 2 -CH (C}} (O) OZ A1) CH 2 CH = CH 2 (a1).
^{_{CF 2 = CFCF 2 -C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).

  Specific examples of the compound (a) include the following compounds.

Compound (a) is obtained by reacting CH ₂ ═C (C (O) OZ ^P ) ₂ and CH ₂ ═CH (CH ₂ ) _na Br in the presence of a basic compound to obtain CH (C (O) OZ ^P ). ₂ ((CH ₂ ) _na CH═CH ₂ ), then base CH (C (O) OZ ^P ) ₂ ((CH ₂ ) _na CH═CH ₂ ) and CF ₂ = CFCF ₂ OSO ₂ F CF ₂ ═CFCF ₂ C (C (O) OZ ^P ) ₂ (CH ₂ ) _na CH═CH ₂ (hereinafter also referred to as compound (p1)) obtained by reacting in the presence of the active compound. preferably produced (although, ^{Z P} is .Z ^P to a monovalent organic group having 1 to 20 carbon atoms is preferably the same as ^{Z a.).}
For example, CF ₂ ═CFCF ₂ C (C (O) OH) ₂ (CH ₂ ) _na CH═CH ₂ is preferably produced by hydrolyzing the compound (p1).
CF ₂ ═CFCF ₂ CH (C (O) OH) (CH ₂ ) _na CH═CH ₂ is preferably produced by decarboxylation of the compound (p1).

  The weight average molecular weight of the resist polymer of the present invention is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000.

  The resist polymer of the present invention is excellent in dynamic liquid repellency, particularly dynamic water repellency. The reason is not necessarily clear, but the compound (a) is a cyclopolymerizable compound, and a polymer containing any one of the following repeating units (A) formed by cyclopolymerization of the compound (a) is used. Usually formed.

The polymer is a polymer containing a repeating unit having a bulky fluorine-containing ring structure in the main chain, and is a conventionally known compound (1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene. ) Is higher than the polymer containing a repeating unit formed by cyclopolymerization, and is considered to be excellent in dynamic liquid repellency, particularly dynamic water repellency.
Therefore, by using the resist polymer of the present invention, it is easy to prepare an immersion lithography material that hardly penetrates into the immersion liquid and that slides well.

  The present invention provides a resist polymer for immersion lithography (hereinafter, also referred to as an Im resist polymer) that includes the repeating unit (A) formed by polymerization of the compound (a) and that increases alkali solubility by the action of an acid. provide.

The Im resist polymer of the present invention is particularly excellent in dynamic water repellency because it contains the repeating unit (A). In the immersion lithography method using a photosensitive resist material prepared from an Im resist polymer, the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist layer.
The Im resist polymer of the present invention is a polymer whose alkali solubility is increased by the action of an acid, and the exposed portion of the photosensitive resist layer prepared from the Im resist polymer can be easily removed with an alkaline solution. Therefore, by using the Im resist polymer of the present invention, an immersion lithography method capable of transferring a mask pattern image with high resolution can be performed at high speed.

  The compound (a) in the Im resist polymer of the present invention is preferably the compound (a1) or (a2). Further, the repeating unit (A) in the Im resist polymer may be composed of only one type, or may be composed of two or more types.

  The Im resist polymer of the present invention preferably contains a repeating unit whose alkali solubility is increased by the action of an acid. The repeating unit may be a repeating unit derived from the repeating unit (A), or may be a repeating unit formed by polymerization of another polymerizable compound whose alkali solubility is increased by the action of an acid.

The repeating unit of the former, Z ^A is a group (G1), include groups (G2) or repeating units formed by polymerization of group (G3), Compound (a).
As the latter repeating unit, the polymerizable compound (b) having the following group (b1), (b2), (b3) or (b4) is preferable, and the following compound (b1), (b2) or (b3) is particularly preferable. preferable.

X ^B1 is preferably an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms containing an etheric oxygen atom, and particularly preferably a methyl group or an ethyl group.

The divalent group formed by Q ^B1 and 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 monocyclic hydrocarbon group. The divalent group is preferably a monocyclic hydrocarbon group, particularly preferably a bridged cyclic hydrocarbon group.
Carbon atom in Q ^B1 - -O between carbon atoms -, - the case where is inserted, -C (O) O-is inserted - C (O) O-or -C (O) Is preferred. Fluorine atom to carbon atom in Q ^R1, if hydroxy or carboxy group is bonded, the hydroxy group or carboxy group is bonded is preferred.

X ^B2 is an alkyl group having 1 to 3 carbon atoms, or two are alkyl groups having 1 to 3 carbon atoms and one is a monovalent cyclic hydrocarbon group having 4 to 20 carbon atoms ( 1-adamantyl group, etc.).

Z ^B is —C (Z ^B11 ) ₃ (where Z ^B11 represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms; the same shall apply hereinafter) or —CH ₂ OZ ^B11 is preferred, and —C (CH ₃ ) ₃ , —CH ₂ OCH ₃ , —CH ₂ OCH ₂ CH ₃ ), —CH ₂ OC (CH ₃ ) ₃ or any of the following groups is particularly preferred.

R ^B is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

^Nb in Q ^B3 is preferably 1.
Mb in Q ^B3, 0 is preferable.
Q ^{B3 _{is, -CF 2 C (CF 3)}} (OC (Z B11) 3) CH 2 -, - CF 2 C (CF 3) (OCH 2 OZ B11) CH 2 -, - CH 2 CH (C (CF ^{_{3) 2 (OCH 2 OZ B11}} )) CH 2 - or _{-CH 2 CH (C (CF 3} ) 2 (OC (Z B11) 3)) CH 2 - is preferred.

  Specific examples of the group (b1) include any group represented by the following formula.

  Specific examples of the group (b2) include any group represented by the following formula.

  The compound (b1) is preferably the following compound (b11), (b12), (b13), (b14) or (b15), particularly preferably the compound (b11).

  The compound (b2) is preferably the following compound (b21) or (b22).

The compound (b3) contains CF ₂ ═CFCF ₂ C (CF ₃ ) (OC (Z ^B11 ) ₃ ) CH ₂ CH═CH ₂ , CF ₂ ═CFCF ₂ C (CF ₃ ) (OCH ₂ OZ ^B11 ) CH ₂ CH ═CH ₂ , CF ₂ ═CFCH ₂ CH (C (CF ₃ ) ₂ (OCH ₂ OZ ^B11 )) CH ₂ CH═CH ₂ , or CF ₂ ═CFCH ₂ CH (C (CF ₃ ) ₂ (OC (Z ^B11 ₃ )) CH ₂ CH═CH ₂ is preferred.

  Specific examples of the compound (b1) include the following compounds.

  Specific examples of the compound (b2) include the following compounds.

  Specific examples of the compound (b3) include the following compounds.

In order to further improve the dynamic liquid repellency of the Im polymer of the present invention, the Im resist polymer of the present invention further comprises a repeating unit formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure ( F) is preferably included.
The polymerizable compound (f) is preferably a compound having a monovalent polymerizable group and a monovalent fluorine-containing cyclic hydrocarbon group.
The monovalent polymerizable group is preferably a vinyl group, a (meth) acryloyloxy group, a 2-fluoro-acryloyloxy group, or a 2-fluoroalkyl-acryloyloxy group, and a (meth) acryloyloxy group is particularly preferable. However, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group (the same applies hereinafter).

The monovalent fluorine-containing cyclic hydrocarbon group is preferably a monovalent fluorine-containing monocyclic hydrocarbon group or a monovalent fluorine-containing polycyclic hydrocarbon group. The monovalent fluorine-containing polycyclic hydrocarbon group may be a monovalent fluorine-containing condensed ring hydrocarbon group or a monovalent fluorine-containing bridged cyclic hydrocarbon group.
The monovalent fluorine-containing cyclic hydrocarbon group is a monovalent group obtained by removing one hydrogen atom of a cyclic saturated hydrocarbon compound, and a group in which 50% or more of the remaining hydrogen atoms are substituted with fluorine atoms. Preferably there is. It is more preferable that 80% or more of the remaining hydrogen atoms are substituted with fluorine atoms, and it is particularly preferable that all the hydrogen atoms are substituted with fluorine atoms.
The cyclic saturated hydrocarbon compound is preferably any compound represented by the following formula.

  The following compound (f1), (f2), (f3), (f4) or (f5) is particularly preferable as the polymerizable compound (f).

  In the compound (f3) or (f4), the configuration of the asymmetric center may be endo or exo.

R ^F is preferably a hydrogen atom or a methyl group.

Compound (f2), compound (f3) and compound (f4) are novel compounds.
Compound (f2) is obtained by reacting the following compound (pf2) with H—CHO in the presence of a basic compound to obtain the following compound (qf2), and then compound (qf2) and CH ₂ ═CR ^F C (O It is preferably produced by reacting Cl).

The compound (f3) is reacted with the following compound (mf3) and Rf-COF (where Rf represents an alkyl group which may contain an etheric oxygen atom having 1 to 20 carbon atoms) to react with the following compound (nf3 Then, the compound (nf3) is fluorinated by a liquid phase fluorination method to obtain the following compound (of3), and then the compound (of3) is decomposed in the presence of KF to give the following compound (pf3) Next, the following compound (pf3) is subjected to a reduction reaction to obtain the following compound (qf3), and then the compound (qf2) is reacted with CH ₂ = CR ^F C (O) Cl. Is preferred.

  Compound (f4) is preferably produced in the same manner except that the following compound (mf4) is used in place of compound (mf3).

  The Im resist polymer of the present invention preferably contains 1 to 100 mol% of the repeating unit (A) with respect to all repeating units.

In addition, when the Im resist polymer of the present invention includes a repeating unit (B) formed by polymerization of the polymerizable compound (b), the Im resist polymer of the present invention has a repeating unit ( It is preferable to contain 10 to 60 mol% of B).
When the Im resist polymer of the present invention includes a repeating unit (F) formed by polymerization of the polymerizable compound (f), the Im resist polymer of the present invention has a repeating unit (B) with respect to all repeating units. 1 to 45 mol% is preferable.

The Im resist polymer of the present invention may further contain other units.
The other unit is preferably a repeating unit formed by polymerization of a polymerizable compound (c) having the following group (c1) or (c2), and a repeating unit formed by polymerization of the following compound (c1) or (c2) Is particularly preferred.

The symbols in the formula have the following meanings (the same applies hereinafter).
Q ^C1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group together with the carbon atom in the formula.
Q ^C2 : a trivalent group having 4 to 20 carbon atoms that forms a bridged cyclic hydrocarbon group in combination with a carbon atom in the formula.
^However, the carbon atoms in ^{Q C1} or ^{Q C2} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, ^{also, Q C1} or ^{Q C2} A group containing a hydroxy group or a carboxy group may be bonded to the carbon atom therein.
R ^C : 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 ( ^RC is preferably a hydrogen atom or a methyl group).

  The group (c1) is preferably any group represented by the following formula.

  The group (c2) is preferably any group represented by the following formula.

  The compound (c1) is preferably any one of the following compounds.

  The compound (c2) is preferably any one of the following compounds.

  The weight average molecular weight of the Im resist polymer of the present invention is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000.

  The Im resist polymer of the present invention is usually prepared and used as a chemically amplified photosensitive resist in application to the immersion lithography method. The Im resist polymer of the present invention preferably contains a photoacid generator. In addition, the Im resist polymer is usually used by being applied onto a substrate in application to the immersion lithography method. The Im resist polymer is preferably prepared into a liquid composition.

The present invention provides a resist forming composition for immersion lithography (hereinafter also referred to as resist forming composition (1)) comprising the Im resist polymer of the present invention, a photoacid generator and an organic solvent.
The resist-forming composition (1) preferably contains 1 to 10% by mass of a photoacid generator with respect to the Im resist polymer. The resist forming composition (1) preferably contains 100% by mass to 10,000% by mass of an organic solvent with respect to the Im resist polymer.

  A photo-acid generator will not be specifically limited if it is a compound which has the group which generate | occur | produces an acid by irradiation of actinic light (Actinic light means the wide concept including radiation). The compound may be a non-polymer compound or a polymer compound. Moreover, 1 type may be used for a photo-acid generator, and 2 or more types may be used for it.

  The photoacid generator is a photoacid generator selected from the group consisting of onium salts, halogen-containing compounds, diazoketones, sulfone compounds, sulfonic acid compounds, diazodisulfones, diazoketosulfones, iminosulfonates, and disulfones. Agents are preferred.

  Specific examples of the photoacid generator include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium dodecylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium triflate, bis (4- tert-butylphenyl) iodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium nonanate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium trifluoromethanesulfone Nato, triphenylsulfonium carbonate Fursulfonium, 1- (naphthylacetomethyl) thiolanium triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium triflate, dicyclohexyl (2-oxocyclohexyl) sulfonium triflate, dimethyl (4-hydroxynaphthyl) sulfonium tosylate, dimethyl (4-hydroxynaphthyl) sulfonium dodecylbenzenesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium naphthalenesulfonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, (4-methoxyphenyl) phenyliodonium trifluoromethane Sulfonate, bis (t-butylphenyl) iodonium trif Oromethanesulfonate, phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, 1,1-bis (4-chlorophenyl) ) -2,2,2-trichloroethane, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, benzoin tosylate, 1,8-naphthalenedicarboxylic acid imide triflate.

  The organic solvent is not particularly limited as long as it is a highly compatible solvent for the Im resist polymer. The organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent.

Specific examples of the fluorine-based organic solvent include hydrochlorofluorocarbons such as CCl ₂ FCH ₃ , CF ₃ CF ₂ CHCl ₂ , and CClF ₂ CF ₂ CHClF; CF ₃ CHFCHFCF ₂ CF ₃ , CF ₃ (CF ₂ ) ₅ H, Hydrofluorocarbons such as CF ₃ (CF ₂ ) ₃ C ₂ H ₅ , CF ₃ (CF ₂ ) ₅ C ₂ H ₅ , CF ₃ (CF ₂ ) ₇ C ₂ H ₅ ; 1,3-bis (trifluoromethyl) ) Hydrofluorobenzenes such as benzene and metaxylene hexafluoride; Hydrofluoroketones; Hydrofluoroalkylbenzenes; CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF (CF ₃ ) CF ₂ OCH ₃ , CF ₃ CH ₂ OCF ₂ CHF _{2 and} other hydrofluoroethers And hydrofluoroalcohols such as CHF ₂ CF ₂ CH ₂ OH.

  Specific examples of the non-fluorinated organic solvent include methyl alcohol, ethyl alcohol, diacetone alcohol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethylbutanol, pentanol, and hexanol. , Alcohols such as heptanol, acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, ketones such as N-methylpyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, Propylene glycol monoethyl ether acetate, carbitol acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, butyric acid Ethyl, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate, esters such as ethyl lactate, aromatic hydrocarbons such as toluene and xylene, propylene glycol monomethyl ether, propylene glycol methyl ether Glycol mono or dialkyl ethers such as acetate, propylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide and the like It is done.

  The resist forming composition (1) of the present invention is used in an immersion lithography method. As the immersion lithography method, a resist forming composition (1) is applied on a substrate (silicon wafer or the like) to form a resist film on the substrate, an immersion lithography step, a developing step, an etching step, and a resist film peeling step. There is an immersion lithography method in which the steps are performed in this order.

  As an immersion lithography process, a projection lens that relatively moves on a resist film while filling a pattern image of the mask obtained by irradiating light from an exposure light source onto the mask with an immersion liquid between the projection lens and the resist film. And a step of projecting to a desired position of the resist film through the step.

The exposure light source is preferably g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm) or F ₂ excimer laser light (wavelength 157 nm), and ArF excimer Laser light or F ₂ excimer laser light is more preferable, and ArF excimer laser light is particularly preferable.
The immersion liquid may be an oily liquid medium (such as decalin) or an aqueous liquid medium (such as ultrapure water), preferably a liquid medium containing water as a main component, particularly ultrapure water. preferable.

  Examples of the development step include a step of removing the exposed portion of the resist film with an alkaline solution. The alkali solution is not particularly limited, and examples thereof include an aqueous alkali solution containing an alkali compound selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine.

  The present invention relates to a resist for immersion lithography comprising a polymer (A) containing a repeating unit (A) formed by polymerization of a compound (a) and a polymer (B) whose alkali solubility is increased by the action of an acid. A composition (hereinafter also referred to as an Im resist composition) is provided.

The Im resist composition of the present invention is particularly excellent in dynamic water repellency since it contains the polymer (A). In the immersion lithography method using the photosensitive resist material prepared from the Im resist composition, the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist layer.
Further, the Im resist composition of the present invention contains a polymer (B) whose alkali solubility is increased by the action of an acid, and the exposed portion of the photosensitive resist layer prepared from the Im resist composition is easily removed with an alkaline solution. it can. Therefore, an immersion lithography method capable of transferring a mask pattern image with high resolution can be performed at high speed by using the Im resist composition of the present invention.

The compound (a) in the polymer (A) is preferably the compound (a1) or (a2).
The polymer (A) preferably contains 10% by mole or more of the repeating unit (A), and particularly preferably comprises only the repeating unit (A). Moreover, the repeating unit (A) may consist of only one type or may consist of two or more types.

  In order to further improve the dynamic liquid repellency of the Im resist composition, the polymer (A) includes a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. May be. It is preferable that a polymer (A) contains 1 to 45 mol% of repeating units (F) with respect to all repeating units. Preferred embodiments of the polymerizable compound (f) are the same as those described for the Im resist polymer.

  The polymer (A) may further contain other units. The other unit is preferably a repeating unit formed by polymerization of the polymerizable compound (c), and particularly preferably a repeating unit formed by polymerization of the compound (c1) or the compound (c2).

  1000-100000 are preferable and, as for the weight average molecular weight of a polymer (A), 1000-50000 are especially preferable.

  As a preferred embodiment of the polymer (A), a polymer (AF) containing the repeating unit (A) and the repeating unit (F) can be mentioned. The polymer (F) in this case preferably contains 80 to 99 mol% of the repeating unit (A) and 1 to 20 mol% of the repeating unit (F) with respect to all repeating units. In addition, the weight average molecular weight of the polymer (F) in this case is preferably 1000 to 30000.

The polymer (B) preferably contains a repeating unit formed by polymerization of a polymerizable compound other than the compound (a) whose alkali solubility is increased by the action of an acid. It is particularly preferable that the unit contains 25 mol% or more.
The polymerizable compound is preferably a polymerizable compound (b), particularly preferably a compound (b1), a compound (b2) or a compound (b3).

  1000-100000 are preferable and, as for the weight average molecular weight of a polymer (B), 1000-50000 are especially preferable.

  The Im resist composition of the present invention preferably contains 0.1 to 30% by mass, particularly 0.1 to 10% by mass of the polymer (A) with respect to the total mass of the polymer (B). preferable.

  The Im resist composition of the present invention is usually prepared and used as a chemically amplified photosensitive resist for application to immersion lithography. It is preferable that a photoacid generator is blended in the Im resist composition. In addition, the Im resist composition of the present invention is usually used by being applied onto a substrate in application to the immersion lithography method. The resist composition of the present invention is preferably prepared as a liquid composition.

The present invention provides a resist forming composition for immersion lithography (hereinafter, also referred to as resist forming composition (2)) comprising the Im resist composition of the present invention, a photoacid generator and an organic solvent.
The resist-forming composition (2) preferably contains 1 to 10% by mass of a photoacid generator with respect to the polymer (B). It is preferable that a resist formation composition (2) contains 100 mass%-10000 mass% of organic solvents with respect to a polymer (B).
Specific examples of the photoacid generator are the same as the photoacid generator described in the resist forming composition (1). Specific examples of the organic solvent are the same as the organic solvent described in the resist forming composition (1).

  The resist forming composition (2) is used in an immersion lithography method. The specific aspect of the immersion lithography method is the same as the aspect described in the resist forming composition (1).

The present invention provides an alkali-soluble resist protective film polymer for immersion lithography (hereinafter also referred to as an Im protective film polymer) containing the repeating unit (A) formed by polymerization of the compound (a).
Since the Im protective film polymer of the present invention is an alkali-soluble polymer, it can be easily removed with an alkaline solution. Therefore, the Im protective film polymer of the present invention enables high-speed execution of an immersion lithography method capable of transferring a mask pattern image with high resolution.

The Im protective film polymer of the present invention preferably contains alkali-soluble repeating units. The repeating unit is preferably a repeating unit derived from the repeating unit (A) or a repeating unit formed by polymerization of another polymerizable compound having alkali solubility, and a repeating unit derived from the repeating unit (A) is particularly preferable. .
Repeating units of the former repeating units formed by polymerization of the compound Z ^A is a hydrogen atom (a) is preferred.
Examples of the latter repeating unit include a repeating unit formed by polymerization of a polymerizable compound other than the compound (a) having a hydroxy group, a carboxy group, a sulfonic acid group, a sulfonylamide group, an amino group or a phosphoric acid group. .

  The polymerizable compound other than the compound (a) is preferably the following compound (oa1), (oa2), (oa3) or (oa4).

The symbols in the formula have the following meanings.
Q ^OA1 : —CF ₂ C (CF ₃ ) (OH) (CH ₂ ) — or —CH ₂ CH (C (CF ₃ ) ₂ (OH)) CH ₂ —.
R ^OA2 : 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.
Q ^OA2 and Q ^OA3 : each independently an (ab + 1) ^-valent hydrocarbon group having 1 to 20 carbon atoms.
ab: 1 or 2.
Q ^OA4 : A single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
In addition, a fluorine atom may be bonded to the carbon atom in Q ^OA2 , Q ^OA3, or Q ^OA4 .

  Specific examples of the polymerizable compound other than the compound (a) include the following compounds.

The compound (a) in the Im protective film polymer is preferably the compound (a1) or (a2). The repeating unit (A) in the Im protective film polymer may consist of only one type, or may consist of two or more types.
The Im protective film polymer of the present invention preferably contains 50 to 99 mol% of the repeating unit (A) with respect to all repeating units.

The Im protective film polymer of the present invention preferably contains a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure in order to further improve dynamic liquid repellency. . Preferred embodiments of the polymerizable compound (f) are the same as those described for the Im resist polymer.
When the Im protective film polymer of the present invention includes a repeating unit (F) formed by polymerization of the polymerizable compound (f), the Im protective film polymer of the present invention has a repeating unit ( F) is preferably contained in an amount of 1 to 50 mol%.

  1000-100000 are preferable and, as for the weight average molecular weight of the Im protective film polymer of this invention, 1000-50000 are especially preferable.

The Im protective film polymer of the present invention is preferably applied to the surface of a photosensitive resist film formed on a substrate for use in an immersion lithography method, and is therefore preferably prepared as a liquid composition. .
The present invention provides a resist protective film-forming composition for immersion lithography (hereinafter also referred to as protective film-forming composition (1)) comprising the Im protective film polymer of the present invention and an organic solvent.
It is preferable that a protective film formation composition (1) contains 100 mass%-10000 mass% of organic solvents with respect to the gross mass of the Im protective film polymer of this invention.

The organic solvent is not particularly limited as long as it is a highly compatible solvent for the Im protective film polymer of the present invention. Specific examples of the organic solvent include the same solvents as the organic solvent described in the resist forming composition (1). Among them, alcohols, ketones, esters (particularly monoalkyl ether esters), fluoroethers. (Especially perfluoroethers), fluoroalcohols, fluorobenzenes (especially hydrofluorobenzenes), or fluoroketones are preferred.
Further, the protective film-forming composition (1) is usually used by being applied on the photosensitive resist layer by a spin coating method or the like. The organic solvent is more preferably a solvent that does not dissolve the photosensitive resist layer, and alcohols, fluoroethers, fluoroalcohols, fluoroketones, or fluorobenzenes are particularly preferable.

The alcohol is preferably isopropyl alcohol, 1-butyl alcohol, 1-hexanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, or 2-octanol, and 2-methyl-1-propanol, 4- Methyl-2-pentanol is particularly preferred.
The fluoroalcohol is preferably C ₃ H ₇ CH ₂ OH or C ₄ H ₉ CH ₂ CH ₂ OH.
The fluorobenzene is preferably 1,3-bis (trifluoromethyl) benzene.

  The protective film-forming composition (1) may contain components other than the Im protective film polymer of the present invention and an organic solvent. Specific examples of the component include a plasticizer, a stabilizer, a colorant, and an antihalation agent.

  The protective film-forming composition (1) is used as a protective film material for a photosensitive resist layer in the immersion lithography method. As an immersion lithography method, a photosensitive resist material is applied on a substrate to form a photosensitive resist film on the substrate, and a protective film forming composition (1) is applied on the surface of the photosensitive resist film to make it photosensitive. There is a method of forming a resist pattern on a substrate, in which a step of forming a resist protective film on the resist film surface, an immersion lithography step, and a development step are performed in this order.

  The photosensitive resist material is not particularly limited as long as it is a composition containing a polymer whose alkali solubility is increased by the action of an acid and a photoacid generator. Specific examples of the photosensitive resist material include photosensitive resist materials described in JP-A-2005-234178. More specifically, a composition containing triphenylsulfonium triflate as a photoacid generator and a copolymer of the following three compounds as the polymer may be mentioned.

  The specific aspect of the immersion lithography method is the same as the aspect described in the resist forming composition (1).

  The present invention relates to a polymer (A) containing a repeating unit (A) formed by polymerization of a compound (a) and a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. ) -Containing polymer (F) and an alkali-soluble resist protective film composition for immersion lithography (hereinafter also referred to as an Im protective film composition).

  Since the Im protective film composition of the present invention contains the polymer (F), it is particularly excellent in dynamic water repellency. In the immersion lithography method provided with the resist protective film prepared from the Im protective film composition, the immersion liquid follows the projection lens that moves at high speed on the resist protective film. Moreover, since the Im protective film composition of the present invention is an alkali-soluble polymer, the resist protective film can be easily removed with an alkaline solution. Therefore, the Im protective film polymer of the present invention enables high-speed execution of an immersion lithography method capable of transferring a mask pattern image with high resolution.

  The polymer (A) in the Im protective film composition preferably contains an alkali-soluble repeating unit. The repeating unit is preferably a repeating unit derived from the repeating unit (A) or a repeating unit formed by polymerization of another polymerizable compound having alkali solubility, and a repeating unit derived from the repeating unit (A) is particularly preferable. .

Repeating units of the former repeating units formed by polymerization of the compound Z ^A is a hydrogen atom (a) is preferred.
Examples of the latter repeating unit include a repeating unit formed by polymerization of a polymerizable compound other than the compound (a) having a hydroxy group, a carboxy group, a sulfonic acid group, a sulfonylamide group, an amino group or a phosphoric acid group. .
Preferred embodiments and specific examples of the polymerizable compound other than the compound (a) are the same as the embodiments and specific examples described in the Im protective film polymer.

The compound (a) in the polymer (A) is preferably the compound (a1) or (a2). The repeating unit (A) in the polymer (A) may be composed of only one type or may be composed of two or more types.
It is preferable that a polymer (A) contains 50-100 mol% of repeating units (A) with respect to all the repeating units.
1000-100000 are preferable and, as for the weight average molecular weight of a polymer (A), 1000-50000 are especially preferable.

  As a preferable aspect of the polymer (A), a polymer having a weight average molecular weight of 1000 to 30000 consisting only of the repeating unit (A) can be mentioned.

The preferred embodiment of the polymerizable compound (f) of the polymer (F) in the Im protective film composition is the same as that of the Im protective film polymer.
It is preferable that a polymer (F) contains 1-100 mol% of repeating units (F) with respect to all the repeating units.
1000-100000 are preferable and, as for the weight average molecular weight of a polymer (F), 1000-50000 are especially preferable.

  As a preferable aspect of the polymer (F), a polymer (FA) containing the repeating unit (A) and the repeating unit (F) can be mentioned. The polymer (F) in this case preferably contains 80 to 99 mol% of the repeating unit (A) and 1 to 20 mol% of the repeating unit (F) with respect to all repeating units. In addition, the weight average molecular weight of the polymer (F) in this case is preferably 1000 to 30000.

  The Im protective film composition of the present invention preferably contains 0.1 to 200% by mass of the polymer (F) with respect to the total mass of the polymer (A). In particular, when the polymer (F) is a polymer (FA), it is preferable to contain 25 to 200% by mass of the polymer (F) with respect to the total mass of the polymer (A).

  The Im protective film composition of the present invention is preferably applied to the surface of a photosensitive resist film formed on a substrate in application to an immersion lithography method, and thus is preferably prepared as a liquid composition. . The present invention provides a resist protective film forming composition for immersion lithography (hereinafter, also referred to as protective film forming composition (2)) comprising the protective film composition of the present invention and an organic solvent.

  It is preferable that a protective film formation composition (2) contains 100 mass%-10000 mass% of organic solvents with respect to the gross mass of the Im protective film composition of this invention.

The organic solvent is not particularly limited as long as it is a highly compatible solvent for the Im protective film composition of the present invention. Specific examples of the organic solvent include the same solvents as the organic solvent described in the resist forming composition (1). Among them, alcohols, ketones, esters (particularly monoalkyl ether esters), fluoroethers. (Especially perfluoroethers), fluoroalcohols, fluorobenzenes (especially hydrofluorobenzenes), or fluoroketones are preferred.
Further, the protective film-forming composition (2) is usually used by being applied on the photosensitive resist layer by a spin coating method or the like. The organic solvent is more preferably a solvent that does not dissolve the photosensitive resist layer, and alcohols, fluoroethers, fluoroalcohols, fluoroketones, or fluorobenzenes are particularly preferable.

The alcohol is preferably isopropyl alcohol, 1-butyl alcohol, 1-hexanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, or 2-octanol, and 2-methyl-1-propanol, 4- Methyl-2-pentanol is particularly preferred.
The fluoroalcohol is preferably C ₃ H ₇ CH ₂ OH or C ₄ H ₉ CH ₂ CH ₂ OH.
The fluorobenzene is preferably 1,3-bis (trifluoromethyl) benzene.

  The protective film-forming composition (2) may contain components other than the Im protective film composition of the present invention and an organic solvent. Specific examples of the component include a plasticizer, a stabilizer, a colorant, and an antihalation agent.

  The protective film-forming composition (2) is used as a protective film material for a photosensitive resist layer in the immersion lithography method. The aspect of the immersion lithography method and the photosensitive resist material is the same as that of the protective film forming composition (1).

Next, examples of the present invention will be specifically described, but the present invention is not limited thereto.
In the examples, tetrahydrofuran is THF, 1,1,2-trichloro-1,2,2-trifluoroethane is R113, dichloropentafluoropropane is R225, diisopropyl peroxydicarbonate is IPP, and isopropyl alcohol is used. IPA, propylene glycol monomethyl ether acetate is PGMEA, weight average molecular weight is Mw, number average molecular weight is Mn, and glass transition temperature is Tg. Mw and Mn of the polymer were measured by gel permeation chromatography (developing solvent: THF, internal standard: polystyrene, the same applies hereinafter).

[Example 1] Compound Preparation of (a) [Example _{1-1] CF 2 = CFCF 2 C} (C (O) OC (CH 3) 3) 2 CH 2 CH = CH 2 ( hereinafter, compound ^(a2 1) In addition, 60% pure NaH (2.1 g) and THF (100 mL) were added to the reactor, mixed and stirred, and then CH ₂ (C (O) OC (CH ₃ ) ₃ ) ₂ (11 g) was added dropwise over 20 minutes. After completion of the dropwise addition, the inside of the reactor was stirred as it was at 25 ° C. for 100 minutes. Further, CH ₂ ═CHCH ₂ Br (6.0 g) was added to the reactor over 10 minutes, and the inside of the reactor was stirred at 65 ° C. for 5 hours. Next, water (100 mL) was added to the reactor to quench the reaction, and then the reactor contents were extracted three times with 50 mL t-butyl methyl ether. The extract was washed with brine and dried over sodium sulfate. The extract was further concentrated and distilled under reduced pressure to obtain CH ₂ ═CHCH ₂ CH (C (O) OC (CH ₃ ) ₃ ) ₂ (9.4 g) having an NMR purity of 90%.

The reactor was charged with NaH (1.8 g) having a purity of 60% and THF (80 mL), and then mixed and stirred. Next, CH (C (O) OC (CH ₃ ) ₃ ) ₂ (CH ₂ CH═CH ₂ ) (9.4 g) was added dropwise to the reactor over 15 minutes. During the dropping, the internal temperature of the reactor was kept at 20 ° C. or lower. The reactor was stirred for 75 minutes at 25 ° C.
Next, when CF ₂ = CFCF ₂ OSO ₂ F (8.5 g) is added to the reactor at a reactor internal temperature of 0 ° C. over 25 minutes, the reactor content liquid turns yellow and solid (FSO ₃ Na). Precipitated. The reactor was stirred as it was for 20 hours, and then quenched by adding water (150 mL) to the reactor.

The solution in the reactor was extracted 3 times with t-butyl methyl ether (50 mL). The extract was washed with an aqueous sodium chloride solution, dried over sodium sulfate and then concentrated to obtain a crude product. The crude product was purified by column to obtain compound (a2 ¹ ) (5.3 g).

The NMR data of the compound (a2 ¹ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.47 (18H), 2.85 (2H), 5.11 (1H), 5.18 (1H) , 5.90 (1H).
¹⁹ F-NMR (282.7 MHz; CDCl ₃ , CFCl ₃ ) δ (ppm): −95.2 (1F), −103.2 (2F), −106.2 (1F), −181.32 (1F) ).

[Example 1-2] Production example of CF ₂ ═CFCF ₂ C (C (O) OH) ₂ CH ₂ CH═CH ₂ (hereinafter also referred to as compound (a2 ^H )) Trifluoroacetic acid while stirring with ice cooling Compound (a2 ¹ ) (6.4 g) was added dropwise to (60 mL) over 5 minutes, and after completion of the addition, the mixture was stirred as it was for 2 hours. Then at 25 ° C., the trifluoroacetic acid was evaporated under reduced pressure to give compound ^(a2 H) ^(4.6g).

Compound NMR data of (a2 ^H) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.97 (2H), 5.20 (1H), 5.26 (1H), 5.89 (1H) , 11.29 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −92.4 (1F), −102.6 (2F), −105.1 (1F), −183 0.0 (1F).

[Example 1-3] Production example of CF ₂ ═CFCF ₂ CH (C (O) OH) CH ₂ CH═CH ₂ (hereinafter also referred to as compound (a1 ^H )) Compound (a2 ^H ) (2.6 g) Was mixed with toluene (15 mL), and the toluene was distilled off as it was, followed by heating at 112 to 139 ° C. for 1 hour. Furthermore, it was dried under reduced pressure to obtain compound (a1 ^H ) (1.8 g).

The NMR data of the compound (a1 ^H ) are shown below.

¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.55 (1H), 2.67 (1H), 3.28 (1H), 5.15 (1H) , 5.20 (1H) 5.79 (1H), 11.72 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −93.6 (1F), −105.4 (2F), −108.0 (1F), −186 .7 (1F).

[Example 1-4] Production example of CF ₂ = CFCF ₂ CH (C (O) OC (CH ₃ ) ₃ ) CH ₂ CH = CH ₂ (hereinafter also referred to as compound (a1 ¹ )) (A1 ^H ) (1.77 g) was dissolved in dichloromethane (10 mL), and 3 drops (about 0.04 g) of sulfuric acid was added. While stirring and bubbling inside the reactor at 25 ° C., CH ₂ ═C (CH ₃ ) ₂ (0.51 g) was added to the reactor. The reaction was stirred for 5.5 hours in the reactor as it was, and then the reactor was quenched by adding 5% aqueous sodium hydrogen carbonate solution (20 mL). The solution in the reactor was extracted four times with t-butyl methyl ether (50 mL), and the resulting extract was washed with an aqueous sodium chloride solution, dried over sodium sulfate, and concentrated. The obtained concentrate was purified by silica gel column chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate (mixing ratio 10: 1)) to obtain compound (a1 ¹ ) (1.31 g). It was.

The NMR data of the compound (a1 ¹ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.45 (9H), 2.47 (1H), 2.62 (1H), 3.11 (1H) , 5.10 (1H), 5.16 (1H) 5.76 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −95.0 (1F), −104.1 (1F), −107.7 (1F), −108 .9 (1F), -186.0 (1F).

[Example _{1-5] CF 2 = CFCF 2 CH} (C (O) OCH 2 OCH 3) CH 2 CH = CH 2 ( hereinafter, compound (a1 ²⁾ and referred to.) In Production Example reactor, compound (a1 ^H ) (2.30 g) was dissolved in t-butyl methyl ether (20 mL), and then diisopropylethylamine (1.29 g) was slowly added. Further, chloromethyl methyl ether (0.79 g, 10 mmol) was added, and the reaction was stirred for 2 hours in the reactor. Next, water (30 mL) was added to the reactor to quench the reaction, and the organic layer was separated. The aqueous layer was extracted twice with t-butyl methyl ether (10 mL), the extract was dried over sodium sulfate and concentrated, and the resulting concentrate was subjected to silica gel column chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate ( The compound (a1 ² ) (1.97 g) was obtained.

The NMR data of the compound (a1 ² ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.53 (1H), 2.69 (1H), 3.28 (1H), 3.47 (3H) , 5.13 (1H), 5.19 (1H), 5.28 (1H), 5.31 (1H), 5.77 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −93.8 (1F), −104.9 (1F), −106.0 (1F), −108 .2 (1F), -186.6 (1F).

[Example 1-6] Production Example of Compound (a1 ³ ) Diisopropylethylamine (1.15 g) was added to a solution containing the compound (a1 ^H ) (2.05 g) and tert-butyl methyl ether (20 mL) under ice-cooling. ) Was slowly added dropwise, and the following compound (w ³ ) (1.91 g) was further added dropwise. The solution was stirred as it was for 5 hours to carry out the reaction. Next, water was added to the solution to quench the reaction, and the organic layer was recovered. The organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 10: 1) to obtain the following compound (a1 ³ ) (2.1 g).

The NMR data and IR data of the compound (a1 ³ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 1.51-1.97 (15H), 2.48-2.73 (2H), 3.22 (2H ), 3.27 (1H) 5.13 (2H), 5.32 (2H), 5.76 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −94.1 (1F), −105.3 (2F), −108.2 (1F), −186 .4 (1F).

Example 1-7 Production Example of Compound (a1 ⁴ ) To a solution containing the compound (a1 ^H ) (2.35 g) and toluene (3 mL), 2 drops of sulfuric acid were added. Next, a toluene solution (3 mL) containing the following compound (w ⁴ ) (2.04 g) was added dropwise to the solution under ice cooling to carry out the reaction. The solution was stirred as it was for 12 hours, and then an aqueous sodium hydrogen carbonate solution was added to the solution to quench the reaction and the organic layer was recovered. The organic layer was washed with water, dried over sodium sulfate and concentrated to obtain a crude product. The crude product was purified by a silica gel column chromatography method (developing solvent hexane) to obtain the following compound (a1 ⁴ ) (2.11 g).

The NMR data and IR data of the compound (a1 ⁴ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.57 (2H), 1.59 (3H), 1.69-1.92 (8H), 2. 02 (2H), 2.29 (2H), 2.49 (1H), 2.66 (1H), 3.19 (1H), 5.11 (1H), 5.18 (1H), 5.79 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −94.6 (1F), −104.4 (1F), −106.2 (1F), −108 .6 (1F), -185.9 (1F).

Example 1-8 Production Example of Compound (a1 ⁵ ) To a solution containing the compound (a1 ^H ) (2.0 g) and tert-butyl methyl ether (20 mL) was added diisopropylethylamine (1.12 g) under ice-cooling. ) Was slowly added dropwise, and the following compound (w ⁵ ) (1.83 g) was further added dropwise. The solution was stirred as it was for 5 hours to carry out the reaction. Next, water was added to the solution to quench the reaction, and the organic layer was recovered. The organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 10: 1) to obtain the following compound (a1 ⁵ ) (2.7 g).

The NMR data of the compound (a1 ⁵ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 1.48-2.05 (15H), 2.47-2.73 (2H), 3.17-3 .32 (1H), 5.08-5.21 (2H), 5.43 (2H), 5.69-5.83 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −94.1 (1F), −105.9 (2F), −108.3 (1F), −186 .4 (1F).

[Example 1-9] Production example of compound (a1 ⁶ ) Compound (a1 ^H ) (5.0 g), compound (W ⁶ ) (9.9 g), dimethylaminopyridine (0.2 g) and dichloromethane were charged in a reactor. (30 g) was added and cooled to 0 ° C. Next, a solution of dicyclohexylcarbodiimide (4.7 g) dissolved in dichloromethane (15 g) was slowly added dropwise to the reactor. The reaction was carried out by stirring the solution in the reactor as it was for 1 hour, and then the reaction was further stirred at 25 ° C. for 1 hour. The solution in the reactor was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 20: 1) to obtain the following compound (a1 ⁶ ) (10.5 g).

The NMR data of the compound (a1 ⁶ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 2.64 to 2.70 (2H), 3.44 to 3.48 (1H), 5.16 to 5 .21 (2H), 5.68 to -5.80 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −92.3 (1F), −105.2 (2F), −107.2 (1F), −123 .6 (6F), -132.6 (2F), -187.3 (1F), -214.7 (m, 1F), -223.0 (1F).

Compound (w ⁶ ) was synthesized according to the following synthesis scheme (where R ^f1 − represents F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) —).

That is, compound (aw ⁶ ) (15 g), chloroform (100 g) and NaF (7.02 g) were placed in a flask under a nitrogen gas atmosphere, and R ^f1 -COF (79 g) was added dropwise while stirring the flask with ice. Further, the inside of the flask was stirred. After removing insoluble solids in the flask contents by pressure filtration, a saturated aqueous sodium hydrogen carbonate solution (103 g) was added to the flask, and the organic layer was recovered and concentrated to obtain compound (bw ⁶ ) (74 g).

R113 (313 g) was added to an autoclave in which a NaF pellet packed bed was installed at the gas outlet, and nitrogen gas was blown into the autoclave for 1 hour while stirring the autoclave at 25 ° C., and then diluted to 20% volume with nitrogen gas. Fluorine gas was blown. While the 20% fluorine gas was blown as it was, a solution in which the compound (bw ⁶ ) (67 g) was dissolved in R113 (299 g) was introduced into the autoclave under a pressure of 0.1 MPa. After completion of the introduction, the autoclave contents were collected and concentrated to obtain a compound (cw ⁶ ).

A compound (cw ⁶ ) (80 g) and powdered KF (0.7 g) were placed in a flask under a nitrogen gas atmosphere, and after heating the flask for 6 hours, the flask contents were purified to obtain compound (dw ⁶ ) ( 38 g) was obtained.

NaBH ₄ (1.1 g) and THF (30 g) were placed in a round bottom flask under a nitrogen gas atmosphere. While the flask was stirred with ice cooling, an R225 solution (48 g) containing 22% by mass of the compound (dw ⁶ ) was added dropwise to the flask. After completion of the dropwise addition, the inside of the flask was further stirred, and then the solution obtained by neutralizing the flask contents with an aqueous hydrochloric acid solution (150 mL) was washed with water and purified by distillation to obtain the compound (w ⁶ ).

The NMR data of the compound (w ⁶ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.89 to 4.57 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −105.0 (1F), −119.7 (1F), −124.0 (1F), −124 .3 (1F), -125.7 (1F), -126.8 (1F), -133.2 (2F), -216.6 (1F), -223.5 (1F).

[Example 1-10] Production example of CF ₂ ═CFCF ₂ CH (C (O) OCH ₂ CF ₂ CF ₃ ) CH ₂ CH═CH ₂ (hereinafter, also referred to as compound (a1 ⁷ )) (A1 ^H ) (5.0 g), CF ₃ CF ₂ CH ₂ OH (3.6 g), dimethylaminopyridine (0.23 g) and dichloromethane (15 mL) were added and cooled to 0 ° C. Next, a solution of dicyclohexylcarbodiimide (4.9 g) dissolved in dichloromethane (35 mL) was slowly added dropwise to the reactor. The reaction was carried out by stirring the solution in the reactor as it was for 1 hour, and then the reaction was further stirred at 25 ° C. for 1 hour.

Next, water was added to the reactor to quench the reaction, and the organic layer was recovered. The organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 10: 1) to obtain compound (a1 ⁷ ) (4.0 g).

The NMR data of the compound (a1 ⁷ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 2.51 to 2.73 (2H), 3.30 to 3.44 (1H), 4.50 to 4 .69 (2H), 5.07-5.23 (2H), 5.66-5.84 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −84.4 (3F), −94.2 (1F), −105.3 (2F), −107 .8 (1F), -124.0 (2F), -187.0 (1F).

Example 1-11 Production Example of Compound (a1 ⁸ ) To a solution containing the compound (a1 ^H ) (7.6 g) and toluene (30 mL), 3 drops of sulfuric acid was added. Next, under ice-cooling, the following compound (w ⁸ ) (4.1 g) was added dropwise to the solution for reaction. After the temperature was raised to 25 ° C., the solution was stirred as it was for 7 hours, and then an aqueous sodium hydrogen carbonate solution was added to the solution to quench the reaction, and the organic layer was recovered. The organic layer was washed with water, dried over sodium sulfate and concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent hexane) to obtain the following compound (a1 ⁸ ) (1.78 g).

The NMR data of the compound (a1 ⁸ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.57 (2H), 1.59 (3H), 1.69-1.92 (8H), 2. 02 (2H), 2.29 (2H), 2.49 (1H), 2.66 (1H), 3.19 (1H), 5.11 (1H), 5.18 (1H), 5.79 (1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −94.6 (1F), −104.4 (1F), −106.2 (1F), −108 .6 (1F), -185.9 (1F).

[Example 2] Production example of polymer [Example 2-1] Production example of polymer (A ¹ ) In a pressure resistant reactor (internal volume 30 mL, made of glass), compound (a2 ¹ ) (1.51 g) and Ethyl acetate (3.41 g) was charged. Next, R225 solution (0.20g) containing 50 mass% of IPP was added to the pressure | voltage resistant reactor as a polymerization initiator. After freezing and degassing the inside of the reactor, polymerization was carried out for 18 hours while maintaining the reactor at 40 ° C. The solution in the reactor was added dropwise to methanol, and the resulting solid was collected and vacuum dried at 80 ° C. for 20 hours. As a result, a white powdery polymer (A ¹ ) (0.84 g) was obtained at 25 ° C. It was.

Mw of the polymer (A ¹ ) was 6300, and Mn was 4600.
As a result of analyzing the polymer (A ¹ ) by ¹⁹ F-NMR and ¹ H-NMR, the polymer (A ¹ ) was obtained from the following formula (U1-A2 ¹ ), the following formula (U2-A2 ¹ ), and the following formula ( It was confirmed that at least one repeating unit (A2 ¹ ) selected from the group consisting of repeating units represented by U3-A2 ¹ ) was included.

The polymer (A ¹ ) is soluble in acetone, THF, ethyl acetate, methanol, 2-perfluorohexylethanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), perfluoro-n-octane. It was.

[Example 2-2] Production example of polymer (A ² ) Compound (a2 ¹ ) (1.51 g) and R225 (8.56 g) were charged into a pressure resistant reactor (internal volume 30 mL, made of glass). It is. Next, R225 solution (0.20g) containing 50 mass% of IPP was added to the pressure | voltage resistant reactor as a polymerization initiator. After freezing and degassing the inside of the reactor, polymerization was carried out for 18 hours while maintaining the reactor at 40 ° C. The solution in the reactor was dropped into methanol, and the generated solid was recovered and vacuum-dried at 80 ° C. for 20 hours. As a result, a white powdery polymer (A ² ) (0.81 g) was obtained at 25 ° C. It was.

Mw of the polymer (A ² ) was 30000, and Mn was 18000. Further, the polymer ^{(A 2)} was confirmed to contain the repeating unit (A2 ^1).

[Example 2-3] Production example of polymer (A ³ ) Compound (a2 ^H ) (1.00 g), R225 (5.41 g) and IPP ( 0.10 g) was charged. Next, R225 solution (0.28g) containing 50 mass% of IPP was added to the pressure | voltage resistant reactor as a polymerization initiator. After freezing and degassing the inside of the reactor, polymerization was carried out for 18 hours while maintaining the reactor at 40 ° C. After the solvent in the reactor was converted to THF, the solution was added dropwise to hexane, and the resulting solid was collected and vacuum-dried at 80 ° C. for 20 hours. As a result, the polymer (A ³ ) (0 .82 g) was obtained.

Mw of the polymer (A ³ ) was 22100, and Mn was 8700.
As a result of analyzing the polymer (A ³ ) by ¹⁹ F-NMR and ¹ H-NMR, the polymer (A2) was obtained by the following formula (U1-A2 ^H ), the following formula (U2-A2 ^H ) and the following formula (U3 -A2 ^H) was confirmed to contain the repeating unit (A2 ^H) 1 or more selected from the group consisting of repeating units represented by.

[Example 2-4] Production example of polymer (A ⁴ ) In the presence of a polymerization initiator (an R-225 solution containing 50% by mass of IPP) in R225 and a 2-propanol solvent, compound (a2 ^H ) and the compound (f ¹ ) are polymerized. The solid obtained was dropped into the reaction solution by hexane were collected and is vacuum dried for 24 hours at 100 ° C., the repeating unit (U-A2 ^H) and repeating units formed by polymerization of the compound (f ¹⁾ A polymer (A ⁴ ) containing (F ¹ ) is obtained.

[Example 2-5] Production example of polymer (A ⁵ ) A reactor (inner volume 200 mL, glass) was charged with compound (a1 ^H ) (16.0 g) and ethyl acetate (129.8 g), and As a polymerization initiator, IPP (5.95 g) was added as a 50 mass% R225 solution. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was collected and dried in vacuo at 120 ° C. for 40 hours. As a result, a white powdery polymer (A ⁵ ) (15.5 g) was obtained at 25 ° C.

Mw of the polymer (A ⁵ ) was 9700, Mn was 4600, and Tg of the polymer (A ⁵ ) measured by differential scanning calorimetry was 178 ° C.
As a result of analyzing the polymer (A ⁵ ) by ¹⁹ F-NMR and ¹ H-NMR, the polymer (A ⁵ ) was obtained by the following formula (U1-A1 ^H ), the following formula (U2-A1 ^H ) and the following formula ( It was confirmed that at least one repeating unit (A1 ^H ) selected from the group consisting of repeating units represented by U3-A1 ^H ) was included.

The polymer (A ⁵ ) was soluble in acetone, THF, ethyl acetate, methanol, and PGMEA, and was insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.

[Example 2-6] Production example of polymer (A ⁶ ) Compound (a1 ¹ ) (0.8 g), R225 (8.0 g) and IPA (0. 06 g) was added, and IPP (1.0 g) was added as a 50 mass% R225 solution as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane (90 g) was collected and vacuum-dried at 90 ° C. for 40 hours. As a result, a white powdery polymer (A ⁶ ) (0.56 g) was obtained at 25 ° C.

Mw of the polymer (A ⁶ ) was 16000, Mn was 11000, and Tg of the polymer (A ⁶ ) measured by differential scanning calorimetry was 118 ° C.

From the NMR analysis, the polymer (A ⁶ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ¹ ), the following formula (U2-A1 ¹ ) and the following formula (U3-A1 ¹ ). It was confirmed that at least one type of repeating unit (A1 ¹ ) was contained.

The polymer (A ⁶ ) was soluble in acetone, THF, ethyl acetate, and PGMEA, and was insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.

[Example 2-7] Production example of polymer (A ⁷ ) Compound (a1 ² ) (0.8 g), R225 (4.3 g) and IPA (0. 07g), and IPP (0.53g) as a 50 mass% R225 solution was added as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane (60 g) was collected and vacuum-dried at 90 ° C. for 40 hours. As a result, a white powdery polymer (A ⁷ ) (0.6 g) was obtained at 25 ° C.

Mw of the polymer (A ⁷ ) was 15800, and Mn was 8900.
From the NMR analysis, the polymer (A ⁷ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ² ), the following formula (U2-A1 ² ) and the following formula (U3-A1 ² ). It was confirmed that at least one type of repeating unit (A1 ² ) was contained.

The polymer (A ⁷ ) was soluble in acetone, THF, ethyl acetate, and PGMEA, and was insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.

[Example 2-8] Production example of polymer (A ⁸ ) Compound (a1 ³ ) (2.0 g) and ethyl acetate (15.8 g) were charged into a reactor (internal volume 30 mL, glass), and 50 masses. IPP (0.73 g) was charged as a% R225 solution and polymerized at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into hexane was collected and vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (A ⁸ ) (1.40 g).

Mw of the polymer (A ⁸ ) was 12600, Mn was 6100, and Tg of the polymer (A ⁸ ) measured by differential scanning calorimetry was 90 ° C.
From the NMR analysis, the polymer (A ⁸ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ³ ), the following formula (U2-A1 ³ ) and the following formula (U3-A1 ³ ). It was confirmed that the polymer contained one or more repeating units (A1 ³ ).

The polymer (A ⁸ ) was in the form of a white powder at 25 ° C. and was soluble in acetone, tetrahydrofuran and ethyl acetate, respectively.

[Example 2-9] Production example of polymer (A ⁹ ) Compound (a1 ⁴ ) (2.0 g) and ethyl acetate (11.0 g) were charged into a reactor (internal volume 30 mL), and 50% by mass of R225 IPP (0.53 g) was charged as a solution, and a polymerization reaction was performed at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into hexane was collected and vacuum-dried at 110 ° C. for 24 hours to obtain a polymer (A ⁹ ) (1.90 g).

Mw of the polymer (A ⁹ ) was 23500, Mn was 9600, and Tg of the polymer (A ⁹ ) measured by differential scanning calorimetry was 107 ° C.
From the NMR analysis, the polymer (A ⁹ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ⁴ ), the following formula (U2-A1 ⁴ ) and the following formula (U3-A1 ⁴ ). It was confirmed that the polymer contained one or more repeating units (A1 ⁴ ).

The polymer (A ⁹ ) was a white powder at 25 ° C. and was soluble in tetrahydrofuran and ethyl acetate, respectively.

[Example 2-10] Production example of polymer (A ¹⁰ ) Compound (a1 ⁵ ) (1.0 g) and ethyl acetate (8.8 g) were charged into a reactor (internal volume 30 mL), and 50% by mass of R225. IPP (0.40 g) was charged as a solution, and a polymerization reaction was performed at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into methanol was collected and vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (A ¹⁰ ) (0.62 g).

Mn of the polymer (A ¹⁰ ) was 6100, Mw was 10200, and Tg of the polymer (A ¹⁰ ) measured by differential scanning calorimetry was 107 ° C.
From the NMR analysis, the polymer (A ¹⁰ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ⁵ ), the following formula (U2-A1 ⁵ ), and the following formula (U3-A1 ⁵ ). It was confirmed that at least one type of repeating unit (A1 ⁵ ) was contained.

[Example 2-11] Production example of polymer (A ¹¹ ) A reactor (internal volume 30 mL) was charged with compound (a1 ⁶ ) (0.5 g) and R225 (1.93 g), and a 50% by mass R225 solution As an IPP (0.15 g), a polymerization reaction was carried out at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into hexane was collected and vacuum dried at 100 ° C. for 24 hours to obtain a polymer (A ¹¹ ) (0.42 g).

Mn of the polymer (A ¹¹ ) was 9900, and Mw was 15100.
From the NMR analysis, the polymer (A ¹¹ ) is 1 selected from the group consisting of repeating units represented by the following formula (U1-A1 ⁶ ), the following formula (U2-A1 ⁶ ) and the following formula (U3-A1 ⁶ ). It was confirmed that a repeating unit (A1 ⁶ ) of at least species was included.

The polymer (A ¹¹ ) was in the form of a white powder at 25 ° C. and was soluble in acetone, THF, ethyl acetate, methanol, and R225, respectively.

[Example 2-12] Production example of polymer (A ¹² ) Compound (a1 ⁷ ) (0.81 g) and R225 (7.2 g) were charged into a reactor (internal volume 30 mL), and 50% by mass of R225 solution As an IPP (0.81 g), a polymerization reaction was carried out at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into hexane was collected and vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (A ¹² ) (0.66 g).

Mn of the polymer (A ¹² ) was 4300, and Mw was 6000.
From the NMR analysis, the polymer (A ¹² ) is 1 selected from the group consisting of repeating units represented by the following formula (U1-A1 ⁷ ), the following formula (U2-A1 ⁷ ) and the following formula (U3-A1 ⁷ ). It was confirmed that a repeating unit (A1 ⁷ ) of at least species was included.

[Example 2-13] Production example of polymer (A ¹³ ) A reactor (internal volume: 30 mL) was charged with compound (a1 ⁸ ) (0.89 g) and ethyl acetate (7.8 g), and 50% by mass of R225 IPP (0.35 g) was charged as a solution, and a polymerization reaction was performed at 40 ° C. for 18 hours. The solid substance obtained by dropping the solution in the reactor into hexane was collected and dried in vacuo at 100 ° C. for 24 hours to obtain a polymer (A ¹³ ) (0.80 g).

Mn of the polymer (A ¹³ ) was 7500, and Mw was 16000.
From the NMR analysis, the polymer (A ¹³ ) is selected from the group consisting of repeating units represented by the following formula (U1-A1 ⁸ ), the following formula (U2-A1 ⁸ ) and the following formula (U3-A1 ⁸ ). It was confirmed that at least one type of repeating unit (A1 ⁸ ) was contained.

The polymer (A ¹³ ) was in the form of a white powder at 25 ° C. and was soluble in tetrahydrofuran and ethyl acetate, respectively.

[Example 2-14] Production example of polymer (A ¹⁴ ) In a reactor (internal volume 30 mL, made of glass), compound (a1 ^H ) (0.07 g), compound (a1 ¹ ) (0.75 g) and Ethyl acetate (1.85 g) was charged, and IPP (0.11 g) was added as a 50 mass% R225 solution as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was recovered and vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (A ¹⁴ ) (0.67 g).

Mw of the polymer (A ¹⁴ ) was 28000 and Mn was 14500.
From the NMR analysis, the polymer (A ¹⁴ ) is a polymer containing repeating units (A1 ^H ) and repeating units (A1 ¹ ), and contains 12 mol% of repeating units (A1 ^H ) with respect to all repeating units. The polymer was confirmed to be a polymer containing 88 mol% of the repeating unit (A1 ¹ ).

[Example 2-15] Production example of polymer (A ¹⁵ ) In a reactor (internal volume 30 mL, made of glass), compound (a1 ⁴ ) (0.75 g), compound (a1 ⁷ ) (0.18 g) and Ethyl acetate (6.7 g) was charged, and IPP (0.31 g) was added as a 50 mass% R225 solution as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was collected and vacuum dried at 90 ° C. for 24 hours to obtain a polymer (A ¹⁵ ) (0.61 g).

Mw of the polymer (A ¹⁵ ) was 18900 and Mn was 10600.
From the NMR analysis, the polymer (A ¹⁵ ) is a polymer containing the repeating unit (A 1 ⁴ ) and the repeating unit (A 1 ⁷ ), and contains 77 mol% of the repeating unit (A 1 ⁴ ) with respect to all the repeating units. And a polymer containing 23 mol% of the repeating unit (A1 ⁷ ).

[Example 2-16] Production example of polymer (A ¹⁶ ) In a reactor (internal volume 30 mL, made of glass), compound (a1 ^H ) (0.02 g), compound (a1 ⁶ ) (0.41 g) and Ethyl acetate (3.8 g) was charged, and IPP (0.17 g) was added as a 50 mass% R225 solution as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was collected and vacuum dried at 100 ° C. for 24 hours to obtain a polymer (A ¹⁶ ) (0.29 g).

Mw of the polymer (A ¹⁶ ) was 8700, and Mn was 6300.
From the NMR analysis, the polymer (A ¹⁶ ) is a polymer containing repeating units (A1 ^H ) and repeating units (A1 ⁶ ), and contains 10 mol% of repeating units (A1 ^H ) with respect to all repeating units. And a polymer containing 90 mol% of the repeating unit (A1 ⁶ ). Further, the polymer (A ¹⁶ ) was soluble in each of acetone, THF, ethyl acetate and methanol.

[Example 2-17] Production example of polymer (A ¹⁷ ) CF ₂ = CFCH ₂ CH (C (CF ₃ ) ₂ (OH)) CH ₂ CH = CH was charged into a reactor (internal volume 30 mL, glass). ₂ , 0.5 g of compound (a1 ⁶ ) (0.15 g) and R225 (2.5 g) were charged, and IPP (0.10 g) was added as a 50 mass% R225 solution as a polymerization initiator. After degassing the inside of the reactor under reduced pressure, a polymerization reaction was carried out at a reactor internal temperature of 40 ° C. for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was collected and vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (A ¹⁷ ) (0.57 g).

Mn of the polymer (A ¹⁷ ) was 9200 and Mw was 14200.
As a result of analyzing the polymer (A ¹⁷ ) by NMR analysis, the polymer (A ¹⁷ ) was formed by polymerization of CF ₂ ═CFCH ₂ (C (CF ₃ ) ₂ OH) CH ₂ CH═CH _2. A polymer containing a unit (OA ¹ ) and a repeating unit (A1 ⁶ ), and a polymer containing 87 mol% of the repeating unit (OA ¹ ) and 13 mol% of the repeating unit (A1 ⁶ ) with respect to all the repeating units. It was confirmed that they were coalesced. The polymer (A ¹⁷ ) was soluble in each of acetone, THF, ethyl acetate, and methanol.

  The physical properties of the polymer (A) produced in Example 2 are collectively shown in Table 1. The numerical value in parentheses in the “Repeating unit type” column in Table 1 indicates the ratio (mol%) of the repeating unit to the total repeating unit.

[Example 3] Production example of other polymer [Example 3-1] Production example of polymer (B ¹ ) The following compound (b ¹ ) (10.4 g) was added to a reactor (internal volume 200 mL, glass), The following compound (c2 ¹ ) (8.0 g), the following compound (c1 ¹ ) (3.7 g) and methyl ethyl ketone (76.5 g) were added, and isopropanol (6.3 g) as a chain transfer agent and IPP as a polymerization initiator. R225 solution (11.0 g) containing 50% by mass of was added. After depressurizing and depressurizing the inside of the pressure resistant reactor, a polymerization reaction was performed at a reactor internal temperature of 40 ° C. for 18 hours.

Next, the solution in the reactor was dropped into hexane to recover the solid content, and the solid content was vacuum-dried at 90 ° C. for 24 hours, and a white powdery polymer (B ¹ ) at 25 ° C. ) (15.9 g) was obtained. Mn of the polymer (B ¹ ) was 2870, and Mw was 6600.

According to ¹³ C-NMR method analysis, the polymer (B ¹ ) has a repeating unit of compound (b ¹ ) of 40 mol%, a repeating unit of compound (c2 ¹ ) of 40 mol%, based on all repeating units. And a polymer containing 20 mol% of the repeating unit of the compound (c1 ¹ ). Further, the polymer (B ¹ ) was soluble in THF, PGMEA and cyclopentanone, respectively.

[Example 4] Production Example of Composition [Example 4-1] Production Example of Composition (1) Polymer (A ¹ ) (0.3 g) was dissolved in PGMEA (3.74 g) to obtain a uniform solution. It was. The solution was filtered through a filter to obtain a composition containing a polymer (A ^{1) (1).}
[Example 4-2] Production example of composition (2) Polymer (A ² ) (0.3 g) was dissolved in PGMEA (3.74 g) to obtain a uniform solution. The solution was filtered through a filter to obtain a composition containing a polymer (A ^{2) (2).}

[Example 4-3] Production Example of Composition (3) The polymer (B ¹ ) was dissolved in a mixed solvent of PGMEA (90% by mass) and cyclopentanone (10% by mass), and the polymer (B ¹ ) was dissolved. A solution containing 4.63% by mass (4.46 g) was prepared. Polymer (A ¹ ) (0.017 g) was added to the solution and dissolved to obtain a uniform solution. The solution was filtered and a composition (3) containing the polymer (B ¹ ) and the polymer (A ¹ ) was obtained.
[Example 4-4] except for using Production Example Polymer composition (4) polymers in place of ^{(A 1) (A 2)} in the same manner as in Example 4-3, and the polymer ^{(B 1)} weight A composition (4) containing the coalescence (A ² ) was obtained.

[Example 4-5] Production Example of Composition (5) A uniform solution obtained by dissolving the polymer (A ³ ) in 2-methyl-1-propanol was filtered and the polymer (A ³ ) Was obtained.
[Example 4-6] Production Example of Composition (6) When a uniform solution obtained by dissolving the polymer (A ⁴ ) in 2-methyl-1-propanol was filtered, the polymer (A ⁴ ) A composition (6) containing is obtained.

[Example 4-7] Production example of composition (7) When a polymer (A ³ ) and a polymer (A ⁴ ) were dissolved in 4-methyl-2-pentanol, a uniform solution was filtered. A composition (7) containing 50% by mass of the polymer (A ⁴ ) with respect to the total mass of the polymer (A ³ ) is obtained.

[Example 4-8] Production Example of Composition (C) The polymer (B ¹ ) (0.3 g) was dissolved in PGMEA (3.74 g) to obtain a uniform solution. The solution was filtered and a composition (C) was obtained.

  In the same manner, the polymer produced in Example 2 or 3 and the solvent were appropriately selected to prepare a composition. Each prepared composition and its composition are summarized in Table 2. In addition, the numerical value in the parenthesis in Table 2 shows the mixing ratio (mass ratio) of the polymer when a plurality of polymers are included.

[Example 5] Production example of resist-forming composition [Example 5-1] Production example of resist-forming composition (1) To the composition (1), photoacid generator triphenylsulfonium triflate (0.013 g) was added. The transparent uniform solution obtained by dissolution was filtered and a resist-forming composition (1) was obtained.

[Example 5-2] Production Example of Resist Forming Composition (2) A transparent and uniform solution obtained by dissolving triphenylsulfonium triflate (0.014 g) in the composition (2) was filtered and filtered. A resist-forming composition (2) was obtained.

[Example 5-3] Production Example of Resist Forming Composition (3) A transparent uniform solution obtained by dissolving triphenylsulfonium triflate (0.014 g) in the composition (3) was filtered and filtered. A resist-forming composition (3) was obtained.

[Example 5-4] Production Example of Resist Forming Composition (4) Transparent uniform obtained by dissolving triphenylsulfonium nonafluorobutanesulfonate (0.014 g) as a photoacid generator in composition (3) The solution was filtered and a resist-forming composition (4) was obtained.

[Example 5-5] Production Example of Resist Forming Composition (5) A transparent uniform solution obtained by dissolving triphenylsulfonium nonafluorobutanesulfonate (0.014 g) in composition (4) was filtered. Thus, a resist-forming composition (5) was obtained.

Example 5-7 (Comparative Example) Production Example of Resist Forming Composition (C) Polymer (B ¹ ) (0.3 g) and triphenylsulfonium triflate (0.014 g) were added to PGMEA (3.74 g). Dissolved to obtain a homogeneous solution. The solution was filtered and a resist-forming composition (C) was obtained.

Example 5-8 (Comparative Example) Production Example of Resist Forming Composition (D) Polymer (B ¹ ) (0.3 g) and triphenylsulfonium nonafluorobutane sulfonate (0.014 g) were mixed with PGMEA (3.74 g). ) To obtain a uniform solution. The solution was filtered and a resist-forming composition (D) was obtained.

  Hereinafter, similarly, the composition produced in Example 4 and the photoacid generator were appropriately selected to prepare a resist-forming composition. Table 3 summarizes the components contained in each prepared resist forming composition. The photoacid generator triphenylsulfonium triflate is referred to as TPS, and triphenylsulfonium nonafluorobutanesulfonate as TPSF.

[Example 6] Evaluation of water repellency of composition or resist-forming composition A composition (2) on a silicon substrate on which an antireflection film (trade name AR26, manufactured by ROHM AHD HAAS Electronic Materials) was formed. ) Was spin-coated. Next, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to form a resin thin film (film thickness 50 nm) made of the polymer (A ² ) on the silicon substrate. Subsequently, the static contact angle, the falling angle, the advancing angle, and the receding angle of the resin thin film with respect to water were measured (measured by the sliding method, the falling angle was the falling angle, the advancing contact angle was the advancing angle, and the receding angle The contact angle is referred to as the receding angle.) The unit of the static contact angle, the falling angle, the advancing angle, and the receding angle is an angle (°) (the same applies hereinafter).

  A resin thin film was formed on a silicon substrate in the same manner except that the composition produced in Example 4 and the resist-forming composition produced in Example 5 were used instead of the composition (2), and a static contact angle with water. The falling angle, advancing angle and receding angle were measured. The results are summarized in Table 3.

  As is clear from the above results, it can be seen that the polymer containing the repeating unit (a) is excellent in water repellency, particularly dynamic water repellency. Therefore, in the immersion lithography method, the immersion liquid can easily follow the projection lens that moves at high speed on the layer containing the resist polymer of the present invention.

Example 7 Evaluation Example of Liquid Repellency of Resist Forming Composition to Developer The resist forming composition (1) was spin-coated on a silicon substrate having an antireflection film formed on the surface. Next, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to form a thin film (thickness 50 nm) made of the polymer (A ¹ ) on the silicon substrate. Next, the silicon wafer was exposed by irradiating the silicon wafer with an ArF excimer laser (intensity 50 mJ / cm ² ). Further, the silicon wafer was heat-treated at 130 ° C. for 60 seconds with a hot plate.
The static contact angle with respect to the aqueous | water-based alkaline developing solution (made by Tama Chemicals, brand name AD-10) of the thin film of the silicon wafer in each after thin film formation, exposure, and heat processing was measured.

  Further, the other resist forming compositions produced in Example 5 were measured in the same manner. The results are summarized in Table 5.

  As is clear from the above results, the resist polymer containing the repeating unit (a) is a material having an increased affinity for an alkaline aqueous solution after the lithography process.

[Example 8] PAG elution amount evaluation example of resist forming composition The resist forming composition (4) was spin-coated on a silicon substrate having an antireflection film formed on the surface. Next, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to form a resin thin film (thickness 150 nm) made of the polymer (A ¹ ) and the polymer (B ¹ ) on the silicon substrate. Next, the silicon substrate is set in a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, and ultrapure water (450 μL) is sealed between the cover glass (made of synthetic quartz) and the silicon substrate, and then for 60 seconds. I left it alone. The wetted area of the resin thin film on the silicon substrate and ultrapure water is 7 cm ² .

Next, ultrapure water is collected and converted into ultrapure water using an LC / MS / MS (Quatromicro API, manufactured by Waters) method (detection limit: 7.0 × 10 ⁻¹⁵ mol / cm ² ). The elution amount of the cation (triphenylsulfonium cation) and the anion (nonafluorobutanesulfonate anion), which are derived from the photoacid generator (PAG) eluted from the contained resist forming composition (4), was measured (elution) the amount of the unit: mol / ^cm 2/60 seconds).. It measured similarly about another resist formation composition. The results are summarized in Table 6.

[Example 9] Photosensitivity evaluation example of resist-forming composition A resist-forming composition (3) was spin-coated on a silicon substrate having an antireflection film formed on the surface. Next, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to form a resin thin film (thickness: 200 nm) made of the polymer (A ¹ ) and the polymer (B ¹ ) on the silicon substrate. The silicon substrate was exposed by irradiating the silicon substrate with an ArF excimer laser. In the irradiation with the ArF excimer laser, the number of irradiations was controlled to change the exposure amount. Subsequently, the silicon substrate was heat-treated at 130 ° C. for 60 seconds with a hot plate, and further developed, and the film thickness (unit: nm) of the resin thin film was measured. The film thickness according to exposure amount is collectively shown in FIG.

  Moreover, it measured similarly about the resin thin film at the time of using resist forming composition (6)-(9) instead of resist forming composition (3). The film thickness according to exposure amount is collectively shown in FIG.

[Example 10] Example of forming resist pattern using resist forming composition A resist forming composition (1) was spin-coated on a silicon substrate having an antireflection film formed on the surface thereof. The silicon substrate was heat-treated at 100 ° C. for 90 seconds to obtain a silicon substrate on which a resin thin film (thickness 150 nm) formed from the resist forming composition (1) was formed.

Using a two-beam interference exposure apparatus using ArF laser light as a light source, a 90 nm L / S exposure test of the silicon substrate was performed by an immersion exposure method using an ultrapure water as an immersion medium and a Dry method. In any case, it was confirmed by the SEM image that a good pattern was formed on the resin thin film on the silicon substrate.
Further, even when the resist forming composition (6) is used in place of the resist forming composition (1), it can be confirmed from the SEM image that a good pattern is formed on the resin thin film on the silicon substrate. It was.

[Example 11] Evaluation Example of Alkali Solubility of Composition After spin coating the composition (5) on a crystal resonator, the composition was heat-treated at 130 ° C for 90 seconds to form a polymer (A ³ ) on the crystal resonator. A thin film was formed. Next, the crystal resonator is immersed in an aqueous solution containing 2.38% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH), and the TMAH of the thin film is formed using a crystal resonator microbalance (QCM) method. The film reduction rate (unit: nm / s) in the aqueous solution was measured as the development rate (unit: nm / s) of the thin film. Moreover, it measured similarly using the composition (18). The results are summarized in Table 4. The refractive index of the resin thin film formed from the composition (18) was 1.575.

[Example 12] Resist protective film characteristic evaluation example of composition (part 1)
A resist-forming composition (C) is spin-coated on a silicon substrate having an antireflection film formed on the surface. Next, when the silicon substrate is heat-treated at 100 ° C. for 90 seconds, a silicon substrate (A) on which a resist film containing the polymer (B ¹ ) is formed is obtained. Next, the composition (7) is spin-coated on the resist film of the silicon substrate (A), and the silicon substrate is subjected to heat treatment at 100 ° C. for 90 seconds, whereby the polymer (A ³ ) and the polymer ( A silicon substrate (B) on which a resin thin film made of A ⁴ ) is formed is obtained.

After setting the silicon substrates (A) and (B) in a two-beam interference exposure apparatus using ArF laser light as a light source and enclosing ultrapure water (450 μL) between the cover glass (made of synthetic quartz) and the silicon substrate, respectively. Leave for 60 seconds. The wetted area of the resin thin film on the silicon substrate and ultrapure water is 7 cm ² .

  Next, ultrapure water was recovered, and in the same manner as in Example 7, when the elution amount of the photoacid generator-derived material eluted from the resist-forming composition (C) contained in the ultrapure water was measured, a silicon substrate (A It can be seen that the elution of the photoacid generator-derived material is suppressed in the silicon substrate (B) as compared with ().

[Example 13] Photosensitivity evaluation example of the composition Using a two-beam interference exposure apparatus using ArF laser light as a light source, a 90 nm L / S exposure test of a silicon substrate (B) was performed using ultrapure water as an immersion medium. When the immersion exposure method and the Dry method are used, it can be confirmed from the SEM image that a good pattern is formed on the resin thin film on the silicon substrate (B).

[Example 14] Evaluation example of resist protective film characteristics of composition (part 2)
A resist forming composition (C) was spin-coated on a silicon substrate having an antireflection film formed on the surface. Next, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to obtain a silicon substrate (A) on which a resist film containing the polymer (B ¹ ) was formed. Next, the composition (24) is spin-coated on the resist film of the silicon substrate (A), and the silicon substrate is heat-treated at 100 ° C. for 90 seconds, so that the polymer (A ⁵ ) and the polymer are formed on the resist film. A silicon substrate (C) on which a resin thin film (film thickness 100 nm) made of (A ¹⁶ ) was formed was obtained.
Next, using a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, a 90 nm L / S immersion exposure test (immersion solution: ultrapure water, developer: tetramethylammonium) of the silicon substrate (C). As a result of performing the aqueous solution of hydroxide.), It was confirmed by the SEM image that a good pattern was formed on the resist film on the silicon substrate (C).

  As is clear from the above results, the polymer (A) is used in the immersion lithography method, the polymer whose alkali solubility is increased by the action of an acid, or the alkali-soluble polymer used in the immersion lithography method. Suitable as a resist protective film polymer. Therefore, the use of the polymer (A) enables stable and high-speed implementation of the immersion lithography method.

  According to the present invention, resist characteristics (transparency to short-wavelength light, etching resistance, etc.) or resist protective film characteristics for immersion lithography (inhibition of swelling of photosensitive resist due to penetration of immersion liquid, photosensitive resist component in immersion liquid) And a resist material excellent in dynamic liquid repellency (particularly dynamic water repellency), which slides well in an immersion liquid. By using the resist material of the present invention, it is possible to stably carry out the immersion lithography method capable of transferring a mask pattern image with high resolution.

The graph which showed the film thickness (unit: nm) of the resin thin film after image development processing according to the exposure amount. The photosensitivity evaluation result of the resist formation composition which used resist formation composition (6)-(9) instead of resist formation composition (3). The vertical axis represents the film thickness of the resin thin film formed from each resist forming composition, and the horizontal axis represents the exposure amount.

Claims (32)

A resist polymer containing a repeating unit (A) formed by polymerization of a compound represented by the following formula (a).
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different. The resist polymer according to claim 1, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 . A resist polymer for immersion lithography, comprising a repeating unit (A) formed by polymerization of a compound represented by the following formula (a), wherein alkali solubility is increased by the action of an acid.
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different. The resist polymer for immersion lithography according to claim 3, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 .   The resist polymer for immersion lithography according to claim 3 or 4, wherein the resist polymer for immersion lithography further comprises a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. The polymerizable compound (f) is a compound represented by the following formula (f1), the following formula (f2), the following formula (f3), the following formula (f4), or the following formula (f5). Resist polymer for immersion lithography.

The symbols in the formula have the following meanings.
R ^F : 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, and the fluorine atom in the compounds (f1) to (f5) is a perfluoro having 1 to 6 carbon atoms. It may be substituted with an alkyl group or a C 1-6 perfluoroalkoxy group. A resist polymer for immersion lithography is further formed by polymerization of a polymerizable compound (b) having a group represented by the following formula (b1), the following formula (b2), the following formula (b3), or the following formula (b4). The resist polymer for immersion lithography according to any one of claims 3 to 6, comprising a repeating unit.

The symbols in the formula have the following meanings.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group together with the carbon atom in the formula.
X ^B2 : a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Z ^B : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
In addition, a group represented by the formula -O-, a group represented by the formula -C (O) O-, or a formula -C between the carbon atom and the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B A group represented by (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B. The resist polymer for immersion lithography according to claim 7, wherein the polymerizable compound (b) is a compound represented by the following formula (b1), the following formula (b2), or the following formula (b3).

The symbols in the formula have the following meanings.
R ^B : 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.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with the carbon atom in the formula.
X ^{B2 is} an alkyl group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Q ^B3 : Formula —CF ₂ C (CF ₃ ) (OZ ^B ) (CH ₂ ) _nb —, or Formula —CH ₂ CH ((CH ₂ ) _mb C (CF ₃ ) ₂ (OZ ^B )) (CH ₂ ) a group represented by _nb- .
Z ^B : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, a group having 1 to 20 carbon atoms, or a hydrogen atom.
mb and nb: each independently 0, 1, or 2.
^However, X ^B1, Q ^B1, carbon atoms ^{X B2} or ^{Z B} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, also, A fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom of X ^B1 , Q ^B1 , X ^B2 or Z ^B.   The resist formation composition for immersion lithography containing the resist polymer for immersion lithography in any one of Claims 3-8, a photo-acid generator, and an organic solvent.   A method for forming a resist pattern by an immersion lithography method, the step of applying the resist formation composition for immersion lithography according to claim 9 on a substrate to form a resist film on the substrate, an immersion lithography step, and a development step The resist pattern formation method which forms a resist pattern on a board | substrate which performs this in this order. Immersion lithography comprising a polymer (A) containing a repeating unit (A) formed by polymerization of a compound represented by the following formula (a) and a polymer (B) whose alkali solubility is increased by the action of an acid Resist composition.
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different. The resist composition for immersion lithography according to claim 11, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 .   The immersion lithography according to claim 11 or 12, wherein the polymer (A) is a polymer (AF) comprising a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. Resist composition. The polymerizable compound (f) is a compound represented by the following formula (f1), the following formula (f2), the following formula (f3), the following formula (f4), or the following formula (f5). A resist composition for immersion lithography.

The symbols in the formula have the following meanings.
R ^F : 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.
In addition, the fluorine atom in the compounds (f1) to (f5) may be substituted with a C 1-6 perfluoroalkyl group or a C 1-6 perfluoroalkoxy group. The polymer (B) is a polymerizable compound (b) having a group represented by the following formula (b1), the following formula (b2), the following formula (b3), or the following formula (b4). The resist composition for immersion lithography according to any one of the above.

The symbols in the formula have the following meanings.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group together with the carbon atom in the formula.
X ^B2 : a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Z ^B : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, a group having 1 to 20 carbon atoms, or a hydrogen atom.
In addition, a group represented by the formula -O-, a group represented by the formula -C (O) O-, or a formula -C between the carbon atom and the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B A group represented by (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in X ^B1 , Q ^B1 , X ^B2 or Z ^B. The resist composition for immersion lithography according to claim 15, wherein the polymerizable compound (b) is a compound represented by the following formula (b1), the following formula (b2), or the following formula (b3).

The symbols in the formula have the following meanings.
R ^B : 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.
X ^B1 : an alkyl group having 1 to 6 carbon atoms.
Q ^B1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with the carbon atom in the formula.
X ^{B2 is} an alkyl group having 1 to 20 carbon atoms, and three X ^B2s may be the same or different.
Q ^B3 : Formula —CF ₂ C (CF ₃ ) (OZ ^B ) (CH ₂ ) _nb —, or Formula —CH ₂ CH ((CH ₂ ) _mb C (CF ₃ ) ₂ (OZ ^B )) (CH ₂ ) a group represented by _nb- .
Z ^B : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, a group having 1 to 20 carbon atoms, or a hydrogen atom.
mb and nb: each independently 0, 1, or 2.
^However, X ^B1, Q ^B1, carbon atoms ^{X B2} or ^{Z B} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, also, A fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom of X ^B1 , Q ^B1 , X ^B2 or Z ^B.   The resist composition for immersion lithography according to any one of claims 11 to 16, comprising 0.1 to 30% by mass of the polymer (A) with respect to the polymer (B).   The resist formation composition for immersion lithography containing the resist composition for immersion lithography in any one of Claims 11-17, a photo-acid generator, and an organic solvent.   A method for forming a resist pattern by an immersion lithography method, the step of applying a resist formation composition for immersion lithography according to claim 18 on a substrate to form a resist film on the substrate, an immersion lithography step, and a development step The resist pattern formation method which forms a resist pattern on a board | substrate which performs this in this order. An alkali-soluble resist protective film polymer for immersion lithography, comprising a repeating unit (A) formed by polymerization of a compound represented by the following formula (a).
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different. The resist protective film polymer for immersion lithography according to claim 20, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 .   The resist for immersion lithography according to claim 20 or 21, wherein the resist protective film polymer for immersion lithography further comprises a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. Protective film polymer. The polymerizable compound (f) is a compound represented by the following formula (f1), the following formula (f2), the following formula (f3), the following formula (f4), or the following formula (f5). Resist protective film polymer for immersion lithography.

The symbols in the formula have the following meanings.
R ^F : 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, and the fluorine atom in the compounds (f1) to (f5) is a perfluoro having 1 to 6 carbon atoms. It may be substituted with an alkyl group or a C 1-6 perfluoroalkoxy group.   A resist protective film forming composition for immersion lithography comprising the resist protective film polymer for immersion lithography according to any one of claims 20 to 23 and an organic solvent.   A step of forming a resist film on the substrate by applying a photosensitive resist material on the substrate, and applying the resist protective film forming composition for immersion lithography on the resist film to form a resist on the resist film. A resist pattern forming method for forming a resist pattern on a substrate, wherein a protective film forming step, an immersion lithography step, and a developing step are performed in this order. A polymer (A) containing a repeating unit (A) formed by polymerization of a compound represented by the following formula (a), and a repeating unit formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure A resist protective film composition for immersion lithography, comprising a polymer (F) containing (F).
CF ₂ = CFCF ₂ C (X ^A ) (C (O) OZ ^A ) (CH ₂ ) _na CR ^A = CHR ^A (a).
The symbols in the formula have the following meanings.
X ^A : a hydrogen atom, a cyano group or a group represented by the formula —C (O) OZ ^A.
Z ^A : a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
na: 0, 1 or 2.
R ^{A is a} hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and two R ^A may be the same or different. 27. The resist protective film composition for immersion lithography according to claim 26, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2).
CF ₂ = CFCF ₂ CH (C (O) OZ ^A1 ) CH ₂ CH = CH ₂ (a1),
^{_{CF 2 = CFCF 2 C (C}} (O) OZ A1) 2 CH 2 CH = CH 2 (a2).
The symbols in the formula have the following meanings.
Z ^A1 : a hydrogen atom, a group represented by the formula —C (Z ^A11 ) ₃ , a group represented by the formula —CH ₂ OZ ^A12 , or a group represented by the following formula.

Z ^A11 , Z ^A12 and Z ^A13 : each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Q ^A13 : a group having 3 to 20 carbon atoms that forms a divalent cyclic hydrocarbon group in combination with a carbon atom in the formula.
However, Z ^A11 , Z ^A12 or Z ^A13 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom in Q ^A13 , a group represented by the formula —O—, a formula —C (O) — Or a group represented by the formula —C (O) O— may be inserted. In addition, a fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom in Z ^A11 , Z ^A12 , Z ^A13 or Q ^A13 .   28. The resist protective film composition for immersion lithography according to claim 26 or 27, wherein the polymer (F) is a polymer (FA) comprising a repeating unit (A) and a repeating unit (F). The polymerizable compound (f) is a compound represented by the following formula (f1), the following formula (f2), the following formula (f3), the following formula (f4) or the following formula (f5): The resist protective film composition for immersion lithography according to any one of the above.

The symbols in the formula have the following meanings.
R ^F : 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, and the fluorine atom in the compounds (f1) to (f5) is a perfluoro having 1 to 6 carbon atoms. It may be substituted with an alkyl group or a C 1-6 perfluoroalkoxy group.   The resist protective film composition for immersion lithography according to any one of claims 26 to 29, wherein the polymer (F) is contained in an amount of 0.1 to 200% by mass relative to the polymer (A).   A resist protective film composition for immersion lithography comprising the resist protective film composition for immersion lithography according to any one of claims 26 to 30 and an organic solvent.   32. A step of applying a photosensitive resist material on a substrate to form a resist film on the substrate, and applying the resist protective film forming composition for immersion lithography according to claim 31 on the resist film to form a resist on the resist film. A resist pattern forming method for forming a resist pattern on a substrate, wherein a protective film forming step, an immersion lithography step, and a developing step are performed in this order.

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