JPWO2007119803A1 - Resist material for immersion lithography - Google Patents

Abstract

A resist material for immersion lithography is provided. Immersion lithography comprising a polymer (F) containing a repeating unit (FU) formed by polymerization of a polymerizable compound (fm) having a fluorine-containing bridged ring structure, and having increased alkali solubility by the action of an acid Resist material. For example, the polymerizable compound (fm) is one or more compounds selected from the group consisting of compounds represented by the following formula (f1), the following formula (f2), the following formula (f3), and the following formula (f4) (f ) Is a repeating unit formed by polymerization (RF is —H, —F, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, XF is —F, —OH or —CH 2 OH). Is shown.)

Description

  The present invention relates to a resist material for immersion lithography, a resist polymer for immersion lithography, a resist composition for immersion lithography, a resist forming composition for immersion lithography, and a method for forming a resist pattern.

  In the manufacture of integrated circuits such as semiconductors, lithography is performed by projecting a mask pattern image obtained by irradiating light from an exposure light source onto a mask onto a photosensitive resist on a substrate and transferring the pattern image to the photosensitive resist. The method is used. Usually, the pattern image is projected onto a desired position of the photosensitive resist through a projection lens that moves relatively on the photosensitive resist.

Since the resolution of the pattern image transferred to the photosensitive resist improves as the light from the exposure light source becomes shorter, light having a wavelength shorter than 220 nm (ArF excimer laser light, F ₂ laser light, etc.) is considered as the exposure light source. Has been. A resist material used in a lithography method using the short wavelength light is also actively studied. For example, Patent Document 1 discloses a polymer of polyfluoroadamantyl (meth) acrylate (a copolymer of the following three types of compounds) as a photosensitive resist material used in a lithography method using an F ₂ laser beam as an exposure light source. ) Resist materials are described.

In recent years, an exposure process using a phenomenon in which the wavelength of light in a liquid medium is a reciprocal of the refractive index of the liquid medium, that is, a liquid medium having a high refractive index (between the lower part of the projection lens and the upper part of the photosensitive resist). An immersion lithography method including a step of projecting a mask pattern image onto a photosensitive resist through a projection lens while being filled with ultrapure water or the like (hereinafter also referred to as an immersion liquid) has been studied (Patent Document 2). Etc.)
As a photosensitive resist material used in the immersion lithography method, Patent Document 3 describes a resist composition for immersion lithography containing a copolymer of the following three types of compounds and a fluorosurfactant.

JP 2004-182796 A International Publication No. 99/049504 Pamphlet JP 2005-234178 A

In the immersion lithography method, since the space between the projection lens and the photosensitive resist is filled with the immersion liquid, components (photoacid generator, etc.) in the photosensitive resist are eluted into the immersion liquid or the photosensitive resist is immersed in the immersion liquid. There is a concern of swelling by the liquid.
Further, in the immersion lithography method, it is desirable to use a resist material having excellent dynamic liquid repellency so that the immersion liquid follows the projection lens moving on the photosensitive resist well. For example, in the immersion lithography method in which the immersion liquid is water, it is desirable to use a resist material having excellent dynamic water repellency.

However, such a resist material excellent in dynamic water repellency is not known. For example, the fluorosurfactant described in Patent Document 3 is merely a polymer of a non-polymeric fluorine-containing compound and an acyclic fluoroalkyl (meth) acrylate, and the dynamics of the resist composition of Patent Document 3 The water repellency was low. Therefore, in the immersion lithography method using the resist composition of Patent Document 3, it is not easy to cause the immersion liquid to follow the projection lens moving on the photosensitive resist.
Therefore, there is a demand for a resist material for immersion lithography that has a high dynamic water repellency and can easily follow an immersion liquid to a moving projection lens.

  The present inventors have excellent resist characteristics (transparency to short-wavelength light, etching resistance, etc.) and are also excellent in liquid repellency with respect to immersion liquid (water, etc.), particularly with excellent dynamic liquid repellency. In order to obtain a resist material, intensive studies were conducted. As a result, a resist material for immersion lithography having excellent physical properties was found.

That is, the present invention has the following gist.
<1> A polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and alkali-soluble by the action of an acid Increasing resist material for immersion lithography.
<2> The polymerizable compound ^{(f m)} is the following formula (f1), the following equation (f2), the following formula (f3) and one or more compounds selected from the group consisting of compounds represented by the following formula (f4) The resist material for immersion lithography according to <1>, which is (f).

式中の記号は下記の意味を示す。
Ｒ^Ｆ：水素原子、フッ素原子、炭素数１〜３のアルキル基または炭素数１〜３のフルオロアルキル基。
Ｘ^Ｆ：フッ素原子、ヒドロキシ基またはヒドロキシメチル基。
また、化合物（ｆ）中のフッ素原子は、炭素数１〜６のペルフルオロアルキル基または炭素数１〜６のペルフルオロアルコキシ基に置換されていてもよい。

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.
X ^F : fluorine atom, hydroxy group or hydroxymethyl group.
Moreover, the fluorine atom in a compound (f) may be substituted by the C1-C6 perfluoroalkyl group or C1-C6 perfluoroalkoxy group.

<3> A polymerizable compound (r) having a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure and a group whose alkali solubility is increased by the action of an acid ^m ) a resist polymer for immersion lithography which includes a repeating unit (R ^U ) formed by polymerization and has an alkali solubility increased by the action of an acid.
<4> The polymerizable compound ^{(f m)} is, immersion lithography resist polymer according to the compound (f) <3>.
<5> The polymerizable compound (r ^m ) is a polymerizable compound having a group represented by the following formula (ur1), the following formula (ur2), the following formula (ur3), or the following formula (ur4) <3> Or the resist polymer for immersion lithography as described in <4>.

式中の記号は下記の意味を示す。
Ｘ^Ｒ１：炭素数１〜６のアルキル基。
Ｑ^Ｒ１：式中の炭素原子と共同して環式炭化水素基を形成する炭素数４〜２０の２価の基。
Ｘ^Ｒ２：炭素数１〜２０の１価炭化水素基であって、３個のＸ^Ｒ２は同一であってもよく異なっていてもよい。
Ｚ^Ｒ３およびＺ^Ｒ４：それぞれ独立に、アルキル基、アルコキシアルキル基、アルコキシカルボニル基またはアルキルカルボニル基であって、炭素数１〜２０の基。
また、Ｘ^Ｒ１、Ｑ^Ｒ１、Ｘ^Ｒ２、Ｚ^Ｒ３またはＺ^Ｒ４中の炭素原子−炭素原子間には式−Ｏ−で表される基、式−Ｃ（Ｏ）Ｏ−で表される基または式−Ｃ（Ｏ）−で表される基が挿入されていてもよく、Ｘ^Ｒ１、Ｑ^Ｒ１、Ｘ^Ｒ２、Ｚ^Ｒ３またはＺ^Ｒ４中の炭素原子にはフッ素原子、ヒドロキシ基またはカルボキシ基が結合していてもよい。

The symbols in the formula have the following meanings.
X ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it.

<6> The polymerizable compound (r ^m ) is one or more compounds (r) selected from the group consisting of compounds represented by the following formula (r1), the following formula (r2), and the following formula (r3) < The resist polymer for immersion lithography according to any one of 3> to <5>.

式中の記号は下記の意味を示す。
Ｒ^Ｒ：水素原子、フッ素原子、炭素数１〜３のアルキル基または炭素数１〜３のフルオロアルキル基。
Ｘ^Ｒ１：炭素数１〜６のアルキル基。
Ｑ^Ｒ１：式中の炭素原子と共同して環式炭化水素基を形成する炭素数４〜２０の２価の基。
Ｘ^Ｒ２：炭素数１〜２０の１価炭化水素基であって、３個のＸ^Ｒ２は同一であってもよく異なっていてもよい。
Ｑ^Ｒ３：式−ＣＦ_２Ｃ（ＣＦ_３）（ＯＺ^Ｒ４）（ＣＨ_２）_ｍ−で表される基、式−ＣＨ_２ＣＨ（（ＣＨ_２）_ｎＣ（ＣＦ_３）_２（ＯＺ^Ｒ３））（ＣＨ_２）_ｍ−で表される基または式−ＣＨ_２ＣＨ（Ｃ（Ｏ）ＯＺ^Ｒ３）（ＣＨ_２）_ｍ−で表される基。
Ｚ^Ｒ３およびＺ^Ｒ４：それぞれ独立に、アルキル基、アルコキシアルキル基、アルコキシカルボニル基またはアルキルカルボニル基であって、炭素数１〜２０の基。
また、Ｘ^Ｒ１、Ｑ^Ｒ１、Ｘ^Ｒ２、Ｚ^Ｒ３またはＺ^Ｒ４中の炭素原子−炭素原子間には式−Ｏ−で表される基、式−Ｃ（Ｏ）Ｏ−で表される基または式−Ｃ（Ｏ）−で表される基が挿入されていてもよく、Ｘ^Ｒ１、Ｑ^Ｒ１、Ｘ^Ｒ２、Ｚ^Ｒ３またはＺ^Ｒ４中の炭素原子にはフッ素原子、ヒドロキシ基またはカルボキシ基が結合していてもよい。

The symbols in the formula have the following meanings.
R ^R : 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 ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Q ^R3: the formula ^{_{-CF 2 C (CF 3) (}} OZ R4) (CH 2) m - , a group represented by formula _{-CH 2 CH ((CH 2)} n C (CF 3) 2 (OZ R3)) _{(CH 2) m} -, a group represented by or formula ^{_{-CH 2 CH (C (O)}} OZ R3) (CH 2) m - group represented by the.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it.

Against <7> total repeating units include repeating units ^{(F U)} 1 to 45 mol%, either a polymer containing repeating units ^{(R U)} of 10 mol% or more <3> to <6> A resist polymer for immersion lithography as described in 1. above.
<8> A resist forming composition for immersion lithography comprising the resist polymer for immersion lithography according to any one of <3> to <7>, a photoacid generator, and an organic solvent.
<9> 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 <8> 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.
<10> Polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and polymerization in which alkali solubility is increased by the action of an acid And a polymer (R) containing a repeating unit (R ^U ) formed by polymerization of a functional compound (r ^m ), and a resist composition for immersion lithography having increased alkali solubility by the action of an acid.
<11> The polymerizable compound ^{(f m)} is a compound (f) for immersion lithography resist composition as described in <10>.
<12> The polymerizable compound (r ^m ) is a polymerizable compound having a group represented by the formula (ur1), the formula (ur2), the formula (ur3) or the formula (ur4) <10> or <11> A resist composition for immersion lithography as described in 1. above.
<13> The resist composition for immersion lithography according to any one of <10> to <12>, wherein the polymerizable compound (r ^m ) is the compound (r).
<14> The resist composition for immersion lithography according to any one of <10> to <13>, comprising 0.1 to 30% by mass of the polymer (F) with respect to the polymer (R).
<15> A resist forming composition for immersion lithography comprising the resist composition for immersion lithography according to any one of <10> to <14>, a photoacid generator, and an organic solvent.
<16> 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 <15> 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.

  According to the present invention, there is provided a resist material for immersion lithography that is excellent in resist characteristics and particularly excellent in dynamic water repellency. By using the resist material for immersion lithography of the present invention, stable and high-speed implementation of the immersion lithography method capable of transferring a mask pattern image with high resolution becomes possible.

In this specification, the compound represented by the formula (f1) is the compound (f1), the group represented by the formula (ur1) is the group (ur1), and the formula —CF ₂ C (CF ₃ ) (OZ), respectively. ^{_{R3) (CH 2) m -}} -CF 2 C (CF 3 groups represented _{^{by) (OZ R3) (CH 2}} ) m - and referred. The same applies to other compounds and other groups.
Further, symbols in the group are as defined above unless otherwise specified.

The present invention includes a polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and is alkali-soluble by the action of an acid. The resist material for immersion lithography (hereinafter also referred to as the resist material of the present invention) is provided.

  The resist material of the present invention is excellent in liquid repellency, particularly dynamic liquid repellency, and particularly excellent in water repellency, particularly dynamic water repellency. Although the reason is not necessarily clear, the polymer (F) contained in the resist material of the present invention is a polymer having a bulky structure derived from a fluorine-containing bridged ring structure, and has a non-cyclic fluorine-containing structure. This is thought to be because the film is more easily oriented to the outermost surface when the coating film is formed as compared with the fluorine-containing polymer. Therefore, according to the present invention, it is easy to prepare a resist material that hardly penetrates into the immersion liquid and slides well in the immersion liquid.

Polymerizable compound in the present invention (f ^m) is a monovalent polymerizable group, compounds having a monovalent fluorinated bridged cyclic hydrocarbon group.
The monovalent polymerizable group is preferably a monovalent group having a polymerizable carbon atom-carbon atom double bond, and is a vinyl group, a (meth) acryloyloxy group, a 2-fluoro-acryloyloxy group, or a 2-fluoro group. Alkyl-acryloyloxy groups are preferred, and (meth) acryloyloxy groups are particularly preferred. However, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyl group (the same applies hereinafter).

The monovalent fluorine-containing bridged cyclic hydrocarbon group is preferably an aliphatic group, particularly preferably a saturated aliphatic group. In addition, —O—, —C (O) O—, or —C (O) — may be inserted between carbon atoms in the monovalent fluorine-containing bridged cyclic hydrocarbon group. . In addition, a group containing a hydroxy group or a carboxy group may be bonded to the carbon atom of the monovalent fluorine-containing bridged cyclic hydrocarbon group.
The monovalent fluorine-containing bridged cyclic hydrocarbon group is a monovalent group obtained by removing one hydrogen atom of the bridged cyclic saturated hydrocarbon compound, and 50% or more of the remaining hydrogen atoms are converted into fluorine atoms. A substituted group is preferred. 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 bridged cyclic saturated hydrocarbon compound is preferably at least one bridged cyclic saturated hydrocarbon compound selected from the group consisting of the following compound (1) and the following compound (2).

本発明における重合性化合物（ｆ^ｍ）は、下記化合物（ｆ１）、（ｆ２）、（ｆ３）および（ｆ４）からなる群から選ばれる一種以上の化合物（ｆ）が好ましい。

The polymerizable compound (f ^m ) in the present invention is preferably one or more compounds (f) selected from the group consisting of the following compounds (f1), (f2), (f3) and (f4).

また、化合物（ｆ）中のフッ素原子は、炭素数１〜６のペルフルオロアルキル基または炭素数１〜６のペルフルオロアルコキシ基に置換されていてもよい。また、不斉炭素を有する化合物（ｆ）において、不斉中心の立体配置は、ｅｎｄｏであってもよくｅｘｏであってもよい。
Ｒ^Ｆは、水素原子またはメチル基が好ましい。
Ｘ^Ｆは、フッ素原子が好ましい。
重合性化合物（ｆ^ｍ）の具体例としては、下記化合物が挙げられる。

Moreover, the fluorine atom in a compound (f) may be substituted by the C1-C6 perfluoroalkyl group or C1-C6 perfluoroalkoxy group. In the compound (f) having an asymmetric carbon, the configuration of the asymmetric center may be endo or exo.
R ^F is preferably a hydrogen atom or a methyl group.
X ^F is a fluorine atom is preferable.
Specific examples of the polymerizable compound (f ^m ) include the following compounds.

Compounds (f2), (f3) and (f4) are novel compounds. The manufacturing method will be described later.
1000-100000 are preferable and, as for the weight average molecular weight of the polymer (F) in this invention, 1000-50000 are especially preferable.
The present invention relates to a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure and a repeating unit (R ^U) having a group whose alkali solubility is increased by the action of an acid. And a resist polymer for immersion lithography that increases alkali solubility by the action of an acid (hereinafter referred to as the resist polymer of the present invention).

The resist polymer of the present invention is excellent in liquid repellency, particularly dynamic liquid repellency, and particularly excellent in water repellency, particularly dynamic water repellency. The reason for this is not necessarily clear, but the resist polymer of the present invention comprises a polymer having a bulky structure derived from a fluorine-containing bridged ring structure, and is compared with a fluorine-containing polymer having an acyclic fluorine-containing structure. This is considered to be because the film is easily oriented on the outermost surface during the formation of the coating film. Therefore, in the immersion lithography method using the photosensitive resist prepared from the resist polymer of the present invention, the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist. Moreover, since the resist polymer of the present invention contains a repeating unit (R ^U ), the alkali solubility is increased by the action of an acid. The exposed portion of the photosensitive resist prepared from the resist polymer of the present invention can be easily removed with an alkaline solution. Therefore, the resist polymer of the present invention enables stable and high-speed execution of an immersion lithography method capable of transferring a mask pattern image with high resolution.

The repeating unit (R ^U ) is preferably a repeating unit formed by polymerization of a polymerizable compound having the following groups (ur1), (ur2), (ur3) or (ur4), and the following compounds (r1), (r2) And a repeating unit formed by polymerization of one or more compounds (r) selected from the group consisting of the compounds (r3).
The symbols in the formula have the same meaning as described above unless otherwise specified.

X ^R1 is preferably a C 1-6 alkyl group or a C 1-6 alkyl group containing an etheric oxygen atom, and particularly preferably a methyl group or an ethyl group.
The divalent group formed by ^QR1 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 polycyclic hydrocarbon group. The divalent group is preferably a polycyclic hydrocarbon group, particularly preferably a bridged cyclic hydrocarbon group.
X ^R2 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. Preferably there is.
Z ^R3 and Z ^R4 are preferably each independently an alkyl group having 1 to 12 carbon atoms or an alkoxymethyl group having 1 to 12 carbon atoms.
R ^R is a hydrogen atom or a methyl group is particularly preferred.
As for m in ^QR3 , 1 is preferable.
N in Q ^R3, 0 is preferable.
The group (ur1) is preferably any group represented by the following formula.

基（ｕｒ２）は、下式で表されるいずれかの基が好ましい。

The group (ur2) is preferably any group represented by the following formula.

基（ｕｒ３）は、−Ｃ（ＣＦ_３）_２（ＯＣ（Ｚ^Ｒ１１）_３）または−Ｃ（ＣＦ_３）_２（ＯＣＨ_２ＯＺ^Ｒ１１）が好ましく、−Ｃ（ＣＦ_３）_２（ＯＣ（ＣＨ_３）_３）、−Ｃ（ＣＦ_３）_２（ＯＣＨ_２ＯＣＨ_３）、−Ｃ（ＣＦ_３）_２（ＯＣＨ_２ＯＣＨ_２ＣＨ_３）、−Ｃ（ＣＦ_３）_２（ＯＣＨ_２ＯＣ（ＣＨ_３）_３）、または下記基のいずれかが特に好ましい（ただし、Ｚ^Ｒ１１は炭素数１〜１２のアルキル基または炭素数１〜１２のアルコキシメチル基を示す。以下同様。）。

The group (ur3) is preferably —C (CF ₃ ) ₂ (OC (Z ^R11 ) ₃ ) or —C (CF ₃ ) ₂ (OCH ₂ OZ ^R11 ), and —C (CF ₃ ) ₂ (OC (CH _{3) ) 3), - C (CF} 3) 2 (OCH 2 OCH 3), - C (CF 3) 2 (OCH 2 OCH 2 CH 3), - C (CF 3) 2 (OCH 2 OC (CH 3) 3 ) Or any of the following groups is particularly preferable (wherein Z ^R11 represents an alkyl group having 1 to 12 carbon atoms or an alkoxymethyl group having 1 to 12 carbon atoms; the same shall apply hereinafter).

基（ｕｒ４）は、−Ｃ（ＣＦ_３）（ＯＣ（Ｚ^Ｒ１１）_３）−または−Ｃ（ＣＦ_３）（ＯＣＨ_２ＯＺ^Ｒ１１）−が好ましく、−Ｃ（ＣＦ_３）（ＯＣ（ＣＨ_３）_３）−、−Ｃ（ＣＦ_３）（ＯＣＨ_２ＯＣＨ_３）−、−Ｃ（ＣＦ_３）（ＯＣＨ_２ＯＣＨ_２ＣＨ_３）−、−Ｃ（ＣＦ_３）（ＯＣＨ_２ＯＣ（ＣＨ_３）_３）−または下記基のいずれかが特に好ましい。

The group (ur4) is preferably —C (CF ₃ ) (OC (Z ^R11 ) ₃ ) — or —C (CF ₃ ) (OCH ₂ OZ ^R11 ) —, and —C (CF ₃ ) (OC (CH ₃ )) _{3) -, - C (CF} 3) (OCH 2 OCH 3) -, - C (CF 3) (OCH 2 OCH 2 CH 3) -, - C (CF 3) (OCH 2 OC (CH 3) 3) -Or any of the following groups is particularly preferred:

化合物（ｒ１）は、下記化合物（ｒ１１）、（ｒ１２）、（ｒ１３）、（ｒ１４）、（ｒ１５）または（ｒ１６）が好ましく、化合物（ｒ１１）が特に好ましい。

The compound (r1) is preferably the following compound (r11), (r12), (r13), (r14), (r15) or (r16), and particularly preferably the compound (r11).

化合物（ｒ２）は、下記化合物（ｒ２１）または（ｒ２２）が好ましい。

The compound (r2) is preferably the following compound (r21) or (r22).

化合物（ｒ３）は、ＣＦ_２＝ＣＦＣＨ_２ＣＨ（Ｃ（ＣＦ_３）_２（ＯＣ（Ｚ^Ｒ１１）_３））ＣＨ_２ＣＨ＝ＣＨ_２、ＣＦ_２＝ＣＦＣＨ_２ＣＨ（Ｃ（ＣＦ_３）_２（ＯＣＨ_２ＯＺ^Ｒ１１））ＣＨ_２ＣＨ＝ＣＨ_２、ＣＦ_２＝ＣＦＣＦ_２Ｃ（ＣＦ_３）（ＯＣ（Ｚ^Ｒ１１）_３）ＣＨ_２ＣＨ＝ＣＨ_２、またはＣＦ_２＝ＣＦＣＦ_２Ｃ（ＣＦ_３）（ＯＣＨ_２ＯＺ^Ｒ１１）ＣＨ_２ＣＨ＝ＣＨ_２が好ましい。
化合物（ｒ１）の具体例としては、下記化合物が挙げられる。

The compound (r3) contains CF ₂ ═CFCH ₂ CH (C (CF ₃ ) ₂ (OC (Z ^R11 ) ₃ )) CH ₂ CH═CH ₂ , CF ₂ ═CFCH ₂ CH (C (CF ₃ ) ₂ (OCH ^{_{2 OZ R11)) CH 2 CH}} = CH 2, CF 2 = CFCF 2 C (CF 3) (OC (Z R11) 3) CH 2 CH = CH 2 or _{CF 2 = CFCF 2 C (CF} 3,) (OCH ₂ OZ ^R11 ) CH ₂ CH═CH ₂ is preferred.
Specific examples of the compound (r1) include the following compounds.

化合物（ｒ２）の具体例としては、下記化合物が挙げられる。

Specific examples of the compound (r2) include the following compounds.

化合物（ｒ３）の具体例としては、下記化合物が挙げられる。

Specific examples of the compound (r3) include the following compounds.

Resist polymer of the present invention, based on all repeating units include repeating units ^{(F U)} 1 to 45 mole%, of recurring units ^{(R U)} preferably contains 10 mol% or more.
The resist polymer of the present invention further preferably contains 2.5 to 30 mol% of repeating units (F ^U ) with respect to all repeating units. In this case, it is easy to prepare a liquid composition in which the resist polymer of the present invention is dispersed or dissolved in an organic solvent.
The resist polymer of the present invention further preferably contains 20 to 90 mol%, particularly preferably 30 to 60 mol% of repeating units (R ^U ) with respect to all repeating units. In this case, the exposed portion of the resist polymer is easily removed with an alkaline solution.

The resist polymer of the present invention may contain a repeating unit other than the repeating unit (F ^U ) and the repeating unit (R ^U ) (hereinafter also referred to as other unit (FR ^U )). In this case, the resist polymers of the present invention, based on all repeating units, other units (FR ^U) preferably contains 20 to 60 mol%.
The other unit (FR ^U ) is not particularly limited, and a repeating unit (Q ^U ) formed by polymerization of a polymerizable compound (q ^m ) having the following group (uq1) or (uq2) is preferable, and the following compound ( A repeating unit formed by polymerization of one or more compounds (q) selected from the group consisting of q1) and (q2) is particularly preferred.

式中の記号は下記の意味を示す（以下同様。）。
Ｑ^Ｑ１：式中の炭素原子と共同して橋かけ環式炭化水素基を形成する炭素数４〜２０の３価の基。
Ｑ^Ｑ２：式中の炭素原子と共同して環式炭化水素基を形成する炭素数４〜２０の２価の基。
ただし、Ｑ^Ｑ１またはＱ^Ｑ２中の炭素原子−炭素原子間には−Ｏ−、−Ｃ（Ｏ）Ｏ−または−Ｃ（Ｏ）−が挿入されていてもよく、また、Ｑ^Ｑ１またはＱ^Ｑ２中の炭素原子にはフッ素原子、ヒドロキシ基またはカルボキシ基が結合していてもよい。
Ｒ^Ｑ：水素原子、フッ素原子、炭素数１〜３のアルキル基または炭素数１〜３のフルオロアルキル基。
Ｑ^Ｑ１と式中の炭素原子により形成される３価の基は、脂肪族の基が好ましく、飽和脂肪族の基が特に好ましい。
Ｑ^Ｑ２と式中の炭素原子により形成される２価の基は、脂肪族の基が好ましく、飽和脂肪族の基が特に好ましい。前記２価の基は、単環式炭化水素基であってもよく、多環式炭化水素基であってもよい。

The symbols in the formula have the following meanings (the same applies hereinafter).
Q ^Q1 : a trivalent group having 4 to 20 carbon atoms that forms a bridged cyclic hydrocarbon group in cooperation with a carbon atom in the formula.
Q ^Q2 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
^However, the carbon atoms in ^{Q Q1} or ^{Q Q2} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, ^{also, Q Q1} or ^{Q Q2} A fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom therein.
R ^Q : 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.
The trivalent group formed by Q ^Q1 and the carbon atom in the formula is preferably an aliphatic group, particularly preferably a saturated aliphatic group.
The divalent group formed by Q ^Q2 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 polycyclic hydrocarbon group.

Between carbon atoms, -O - - carbon atom in Q ^Q1 or ^{Q Q2, - C (O)} O- or -C (O) - is -C (O) O-is inserted when it is inserted It is preferable. When a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in Q ^Q1 or Q ^Q2 , it is preferable that a hydroxy group or a carboxy group is bonded.
^RQ is preferably a hydrogen atom or a methyl group.
The group (uq1) is preferably the following group (uq11), (uq12), (uq13), (uq14) or (uq15).

基（ｕｑ２）は、は、下記基（ｕｑ２１）、（ｕｑ２２）、（ｕｑ２３）、（ｕｑ２４）、（ｕｑ２５）、（ｕｑ２６）、（ｕｑ２７）、（ｕｑ２８）または（ｕｑ２９）が好ましい。

The group (uq2) is preferably the following group (uq21), (uq22), (uq23), (uq24), (uq25), (uq26), (uq27), (uq28) or (uq29).

化合物（ｑ１）は、下記化合物（ｑ１１）、（ｑ１２）、（ｑ１３）、（ｑ１４）または（ｑ１５）が好ましい。

The compound (q1) is preferably the following compound (q11), (q12), (q13), (q14) or (q15).

化合物（ｑ２）は、下記化合物（ｑ２１）、（ｑ２２）、（ｑ２３）、（ｑ２４）、（ｑ２５）、（ｑ２７）、（ｑ２８）または（ｑ２９）が好ましい。

The compound (q2) is preferably the following compound (q21), (q22), (q23), (q24), (q25), (q27), (q28) or (q29).

化合物（ｑ１）の具体例としては、下記化合物が挙げられる。

Specific examples of the compound (q1) include the following compounds.

化合物（ｑ２）の具体例としては、下記化合物が挙げられる。

Specific examples of the compound (q2) include the following compounds.

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.
A preferred embodiment of the resist polymer of the present invention, based on all repeating units include repeating units ^{(F U)} 1 to 45 mol%, polymer thereof comprising a repeating unit ^{(R U)} 30 to 60 mol% It is done.
A particularly preferred embodiment is a polymer containing a repeating unit (F ^U ), a repeating unit (R ^U ), and another unit (FR ^U ), wherein the repeating unit (F ^U ) is 1 for all repeating units. Examples include polymers containing ˜45 mol%, repeating units (R ^U ) of 30 to 60 mol%, and other units (FR ^U ) of 20 to 60 mol%.
The repeating unit (R ^U ) in the above embodiment is preferably a repeating unit formed by polymerization of the compound (r1), particularly preferably a repeating unit formed by polymerization of the compound (r11).

The other unit (FR ^U ) in the above embodiment is preferably a repeating unit formed by polymerization of the compound (q12), (q22), (q23), (q25) or (q26).
As for the weight average molecular weight of the polymer in the said aspect, 1000-30000 are preferable.
In application to the immersion lithography method, the resist polymer of the present invention is usually prepared and used as a chemically amplified photosensitive resist. The resist polymer of the present invention preferably contains a photoacid generator. In addition, the resist polymer of the present invention is usually used by being applied onto a substrate in application to the immersion lithography method. The resist polymer of the present invention 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 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 resist polymer of the present invention. The resist-forming composition (1) preferably contains 100% by mass to 10000% by mass of an organic solvent with respect to the resist polymer of the present invention.

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 an actinic ray (however, an actinic ray means the wide concept including a radiation. The same hereafter). 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 at least one selected from the group consisting of onium salts, halogen-containing compounds, diazoketones, sulfone compounds, sulfonic acid compounds, diazodisulfones, diazoketosulfones, iminosulfonates and disulfones. A photoacid generator is 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.

An organic solvent will not be specifically limited if it is a solvent with high compatibility with the resist polymer of this invention. 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; 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 hydrofluoroethers such as _{2 CHF 2; CHF 2 CF 2} CH 2 OH And the like.

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; ketones such as acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrolidone, and 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 Esters such as ethyl, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate and 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 present invention relates to a polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and alkali solubility is increased by the action of an acid. A resist composition for immersion lithography (hereinafter referred to as the present invention) comprising a polymer (R) containing a repeating unit (R ^U ) formed by polymerization of a polymerizable compound (r ^m ) and having increased alkali solubility by the action of an acid. The resist composition of the invention).

  The resist composition of the present invention is excellent in liquid repellency, particularly dynamic liquid repellency, and particularly excellent in water repellency, particularly dynamic water repellency. The reason for this is not necessarily clear, but the polymer (F) contained in the resist composition of the present invention is a polymer having a bulky structure derived from a fluorine-containing bridged ring structure, and an acyclic fluorine-containing structure. This is considered to be because the film is more easily oriented to the outermost surface when the coating film is formed as compared with the fluorine-containing polymer having. Therefore, in the immersion lithography method using the photosensitive resist prepared from the resist composition of the present invention, the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist. Moreover, since the resist composition of this invention contains a polymer (R), it is a composition which alkali solubility increases by the effect | action of an acid. The exposed portion of the photosensitive resist prepared from the resist composition of the present invention can be easily removed with an alkaline solution. Therefore, the resist composition of the present invention enables stable and high-speed execution of an immersion lithography method capable of transferring a mask pattern image with high resolution.

Polymer in the resist composition of the present invention (F) (hereinafter also referred to as polymer (FS).) May be a polymer consisting of a repeating unit (F ^U), and the repeating units (F ^U) It may be a polymer containing a repeating unit other than the repeating unit (F ^U ) (hereinafter also referred to as another unit (FS ^U )). In any case, the polymer (FS) contains 10 mol% or more and preferably 20 mol% or more of the repeating unit (F ^U ) with respect to all repeating units. When the polymer (FS) comprises other units (FS ^U), preferably contains other units (FS ^U) 90 mol% or less based on all repeating units, particularly preferably contains 80 mol% or less.

The other unit (FS ^U ) is preferably a repeating unit (R ^U ) or a repeating unit (Q ^U ), and the repeating unit formed by polymerization of the compound (r1), (r2), (q1) or (q2) Particularly preferred.
The weight average molecular weight of the polymer (FS) is preferably from 1,000 to 100,000, and particularly preferably from 1,000 to 30,000 from the viewpoint of compatibility with the polymer (R) and developability.

Preferable embodiments of the polymer (FS) include the following polymer (FS ^H ) and the following polymer (FS ^C ).
Polymer (FS ^H ): A polymer consisting only of repeating units (F ^U ).
Polymer (FS ^C ): A polymer containing repeating units (F ^U ) and other units (FS ^U ), and containing 10 to 50 mol% of repeating units (F ^U ) with respect to all repeating units. and polymers containing other units (FS ^U) 50 to 90 mol%.
The other unit (FS ^U ) in the polymer (FS ^C ) is preferably a repeating unit (R ^U ) or a repeating unit (Q ^U ). The repeating unit (R ^U ) is preferably a repeating unit formed by polymerization of the compound (r11). The repeating unit (Q ^U ) is particularly preferably a repeating unit formed by polymerization of the compound (q12), (q22), (q23), (q25) or (q26).
As for the weight average molecular weight of the polymer in the said aspect, 1000-30000 are preferable.

The polymer (R) in the present invention is preferably a polymer containing 10 mol% or more of repeating units (R ^U ) with respect to all repeating units.
The repeating unit (R ^U ) is more preferably a repeating unit formed by polymerization of the compound (r), particularly preferably a repeating unit formed by polymerization of the compound (r1), and formed by polymerization of the compound (r11). Repeat units are most preferred.
The polymer (R) preferably contains a repeating unit (Q ^U ).
The repeating unit (Q ^U ) is a repeating unit (QB1 ^U ) formed by polymerization of a polymerizable compound having the following group (uqB1) or a repeating unit formed by polymerization of a polymerizable compound having the following group (uqB2) ( QB2 ^U) is preferably the following compound (QB1) or (QB2) repeating units formed by polymerization are particularly preferred.

The symbols in the formula have the following meanings (the same applies hereinafter).
Q ^QB1 : a trivalent group having 5 to 20 carbon atoms that forms a bridged cyclic hydrocarbon group in cooperation with a carbon atom in the formula, and the carbon atom in the group is a fluorine atom, a hydroxy group or a carboxy group Is a group to which Further, —C (O) O— or —C (O) — may be inserted between the carbon atom and the carbon atom in ^QQB1 .
Q ^QB2 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula, and —C (O) O between the carbon atom and the carbon atom in the group. A group in which-or -C (O)-is inserted. In addition, a fluorine atom, a hydroxy group, or a carboxy group may be bonded to the carbon atom in ^QQB2 .

The trivalent group formed by ^QQB1 and the carbon atom in the formula is preferably an aliphatic group, particularly preferably a saturated aliphatic group. In addition, when -C (O) O- or -C (O)-is inserted between the carbon atom and the carbon atom in ^QQB1 , -C (O) O- is inserted. preferable.
The divalent group formed by ^QQB2 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 polycyclic hydrocarbon group.

The group (uqB1) is preferably a group (uq12) or (uq13).
The group (uqB2) is preferably the group (uq22), (uq23), (uq25) or (uq26).
The compound (qB1) is preferably the compound (q12) or (q13).
The compound (qB2) is preferably the compound (q22), (q23), (q25) or (q26).
The weight average molecular weight of the polymer (R) is preferably 1000 to 100,000.
A preferred embodiment of the polymer (R) is a polymer containing a repeating unit (R ^U ), a repeating unit (QB1 ^U ) and a repeating unit (QB2 ^U ), wherein the repeating unit (R the ^U) 20 to 50 mol%, the repeating units (QB1 ^U) 30-50 mol% and the repeating units (QB2 ^U) a polymer containing 20 to 30 mol% are exemplified.

In the preferred embodiment, the repeating unit (QB1 ^U ) is preferably a repeating unit formed by polymerization of the compound (q12) or (q13). The repeating unit (QB2 ^U ) is particularly preferably a repeating unit formed by polymerization of the compound (q22), (q23), (q25) or (q26).
The weight average molecular weight of the polymer in the above embodiment is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000.
The resist composition of the present invention contains a polymer (FS) and a polymer (R), and preferably contains 0.1 to 30% by mass of the polymer (FS) with respect to the polymer (R). It is particularly preferable to contain 1 to 10% by mass. In this case, the polymer (FS) and the polymer (R) are easily compatible with each other, and there is an effect that the film forming property of the resist composition of the present invention is excellent.

The resist composition of the present invention is usually prepared and used as a chemically amplified photosensitive resist in application to the immersion lithography method. The resist composition of the present invention preferably contains a photoacid generator. In addition, the 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 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 (R). It is preferable that a resist formation composition (2) contains 100 mass%-10000 mass% of organic solvents with respect to a polymer (R).
As the photoacid generator, the same photoacid generator as in the resist-forming composition (1) can be used. The same organic solvent as the resist forming composition (1) can be used as the organic solvent.
The resist forming composition of the present invention (meaning the resist composition (1) or the resist composition (2)) is used in an immersion lithography method. As the immersion lithography method, a step of coating the resist-forming composition of the present invention on a substrate (silicon wafer or the like) to form a resist film on the substrate, an immersion lithography step, a development 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 one or more alkali compounds selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine.
The present invention includes a repeating unit (F ^p ) formed by polymerization of the following compound (f ^p ) and a repeating unit (R ^p ) formed by polymerization of the following compound (r1 ^p ) or (r2 ^p ). and, based on all repeating units, immersion exposure resist polymer containing repeating units ^{(F p)} 1 to 40 mol% (hereinafter, referred resist polymer (P) and also.) provides.

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
R ^fp , R ^rp : each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms.
pp: 0 or 1.
X ^fp : When pp is 0, it is a fluorine atom or a hydroxy group, and when pp is 1, it is a fluorine atom or a hydroxymethyl group.
X ^r1p : a ^C 1-6 alkyl group in which —O— may be inserted between the carbon atom and the carbon atom.
Q ^rp : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula. Between carbon atoms, -O - - Q carbon atoms in the ^rp, - C (O) O- or -C (O) - is may be inserted, ^also to a carbon atom in ^{Q rp} is A fluorine atom, a hydroxy group, a carboxy group, or one or more groups selected from the group consisting of an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an alkylcarbonyl group, and a group having 1 to 10 carbon atoms bonded thereto Also good.

^Xr2p , ^Xr3p and ^Xr4p : each independently a hydrocarbon group having 1 to 20 carbon atoms. -O-, -C (O) O- or -C (O)-may be inserted between carbon atoms in the hydrocarbon group, and carbon in the hydrocarbon group. The atom is a fluorine atom, a hydroxy group, a carboxy group, or a group having 1 to 10 carbon atoms that is one or more groups selected from the group consisting of an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an alkylcarbonyl group. It may be bonded.

Since the resist polymer (P) of the present invention contains a repeating unit (F ^p ) formed by polymerization of the compound (f ^p ), it is excellent in water repellency and particularly excellent in dynamic water repellency. The reason is not necessarily clear, but it is considered that the resist polymer (P) has a bulky polyfluoroadamantyl group in the side chain in the repeating unit (F ^p ). Therefore, it is considered that the resist polymer (P) containing the repeating unit (F ^p ) is excellent in water repellency and hardly penetrates into water, is excellent in dynamic water repellency, and slides well in water.

The resist polymer (P) contains 1 to 40 mol% of repeating units (F ^p ) with respect to all repeating units. More preferably, 2.5 to 30 mole percent of repeating units ^{(F p)} with respect to the total repeating units. In this case, not only is the water repellency of the resist polymer (P) excellent, but it is easy to prepare a resist composition for immersion exposure because the resist polymer (P) is easily dispersed or dissolved in a general-purpose organic solvent. .
The compound (f ^p ) is preferably the following compound (f0 ^p ) or the following compound (f1 ^p ).

ただし、式中の記号は下記の意味を示す（以下同様。）。

However, the symbols in the formulas have the following meanings (the same applies hereinafter).

R ^{f1p represents} 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, more preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and a methyl group Is particularly preferred.
X ^f0p in the compound (f0 ^p ) represents a fluorine atom or a hydroxy group.
X ^f1p in the compound (f1 ^p ) ^represents a fluorine atom or a hydroxymethyl group.
Compound (f1 ^p ) is a novel compound. Compound (f1 ^p) is the following compound (f1-3 ^p) is reacted with water to give the following compound (f1-2 ^p), it was then compound (f1-2 ^p) reacting the H-CHO to give the following compound (f1-1 ^p), it can then compound (f1-1 ^p) produced by reacting ^{_{CH 2 = CR f1p C (O}} ) Cl.

ただし、Ｘ^ｂｐはＸ^ｆ１ｐがフッ素原子である場合にはフッ素原子を、Ｘ^ｆ１ｐがヒドロキシメチル基である場合にはフルオロカルボニル基を示し、Ｘ^ａｐはＸ^ｆ１ｐがフッ素原子である場合にはフッ素原子を、Ｘ^ｆ１ｐがヒドロキシメチル基である場合には水素原子を示す。

X ^{bp represents a} fluorine atom when X ^f1p is a fluorine atom, X fluoro ^{represents a} fluorocarbonyl group when X ^f1p is a hydroxymethyl group, and X ^{ap represents a} fluorine atom when X ^f1p is a fluorine atom. An atom ^{represents a} hydrogen atom when X ^f1p is a hydroxymethyl group.

Specific examples of the compound (f ^p ) are the same as the compounds described in the specific examples of the polymerizable compound (f ^m ).
Further, in the resist polymer (P) of the present invention, the carboxylate portion in the repeating unit (R ^p ) is cleaved by the action of an acid to form a carboxy group, so that the alkali solubility is considered to increase by the action of the acid. . Therefore, the exposed portion of the resist composition for immersion exposure according to the present invention after the immersion exposure step can be easily removed with an alkaline solution.
R ^rp in the compound (r1 ^p ) is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
X ^r1p is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group or an ethyl group.
The ring formed by Q ^rp and the carbon atom in the formula may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group, preferably a polycyclic hydrocarbon group, and a bridge. A cyclic hydrocarbon group is particularly preferred. These cyclic groups are preferably aliphatic groups, and particularly preferably saturated aliphatic groups.
Between carbon atoms, -O - - carbon atom in ^{Q rp, - C (O)} O- or -C (O) - when is inserted, -C (O) O- is inserted It is preferable.
The carbon atom in Q ^rp is a fluorine atom, a hydroxy group, a carboxy group, or one or more groups selected from the group consisting of an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an acyloxy group, having 1 to 10 carbon atoms. ^Are bonded, a hydroxy group or —OCH ₂ OX ^b1pp (where X ^b1pp represents an alkyl group having 1 to 9 carbon atoms) is preferably bonded to the hydroxy group, — It is particularly preferable that OCH ₂ OCH ₂ CH ₃ , —OCH ₂ OCH ₃ or —OCH ₂ OC (CH ₃ ) ₃ is bonded.

X ^{r2p to} X ^r4p in the compound (r2 ^p ) are each independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms. X ^R2P Preferred embodiments of ^{~X r4p, X} r2p ~X r4p a mode are each an alkyl group having 1 to 3 carbon atoms (preferably a methyl group.) Or ^{X R2P} is an alkyl group having 1 to 3 carbon atoms, ( A methyl group is preferred), and ^Xr3p and ^Xr4p are 1-adamantyl groups.
The repeating unit (R ^p ) is preferably a repeating unit formed by polymerization of the compound (r1 ^p ).
Specific examples of the compounds (r1 ^p ) and (r2 ^p ) are the same as the compounds described in the specific examples of the compound (r1) and the compound (r2).
The resist polymer (P) preferably contains 20 to 90 mol%, particularly preferably 30 to 60 mol% of the repeating unit (R ^p ) with respect to all repeating units. In this case, the resist polymer (P) is excellent in water repellency and easily removes the exposed portion by alkali solubility after immersion exposure.
The resist polymer (P) may contain a repeating unit other than the repeating unit (F ^p ) and the repeating unit (R ^p ) (hereinafter also referred to as other unit (F ^p )). Other units ^{(F p)} is not particularly limited, Compound (q11 ^p) or (q12 ^p) repeating units formed by polymerization of ^(Q1 p), or compound (q21 ^p) or the (q22 ^p) The repeating unit (Q2 ^p ) formed by polymerization is preferred.

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
R ^qp : each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms.
Q ^qp11 , Q ^qp12 : a group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula, and —O—, —C (O ) A group in which O- or -C (O) ^-is inserted (where Q ^qp11 is a trivalent group and Q ^qp12 is a divalent group). The carbon atom in the group is a fluorine atom, a hydroxy group, a carboxy group, or one or more groups selected from the group consisting of an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an alkylcarbonyl group. The group of several 1-10 may be couple | bonded.

Q ^qp21 , Q ^qp22 : a group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula (where Q ^qp21 is a trivalent group, and Q ^qp22 is a divalent group And the carbon atom in the group is a hydroxy group, a carboxy group, or one or more groups selected from the group consisting of an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an alkylcarbonyl group. A group to which a group having 1 to 10 carbon atoms is bonded.
R ^qp in the compounds (q11 ^p ) and (q12 ^p ) is each independently preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

When the resist polymer (P) contains a repeating unit (Q1 ^p ), the exposed portion can be easily removed with an alkaline solution after the immersion exposure step, and the development step can be easily performed. The reason is not necessarily clear, but the resist polymer (P) containing the repeating unit (Q1 ^p ) is —O—, —C (O) O— or —C inserted between carbon atoms. This is considered to be due to the high affinity with the alkaline solution because of having (O)-.

The group inserted between the carbon atom and the carbon atom in Q ^qp11 and Q ^qp12 is preferably —C (O) O— or —C (O) — from the viewpoint of developability, and —C (O) O— Is particularly preferred.
The carbon atoms in Q ^qp21 and Q ^qp22 include copolymerizability with other polymerizable compounds, adhesion to other materials (substrate to which the immersion exposure polymer of the present invention is applied, etc.), and the like. From the viewpoint, it is preferable that a hydroxy group or —OCH ₂ OY ^p (wherein Y ^p represents an alkyl group having 1 to 9 carbon atoms) is bonded to each other, and a hydroxy group, —CH ₂ OCH ₂ CH ₃ , —CH ₂ OCH ₃ or —CH ₂ OC (CH ₃ ) ₃ are preferably bonded, and it is particularly preferable that a hydroxy group is bonded.

Specific examples of the compound (q11 ^p ) and the compound (q12 ^p ) are the same as the compounds described in the specific examples of the compound (q1) and the compound (q2).
When the resist polymer (P) contains the repeating units (Q1 ^p), the resist polymer (P) is, repeating units (Q1 ^p) preferably contains 20 to 60 mol% based on all repeating units.

When the resist polymer (P) contains the repeating units (Q2 ^p), the resist polymer (P) is, repeating units (Q2 ^p) preferably contains 5 to 30 mol% based on all repeating units.
1000-100,000 are preferable and, as for the weight average molecular weight of the resist polymer (P) of this invention, 5000-50000 are especially preferable.
As a preferable aspect of the resist polymer (P), it contains a repeating unit (F ^p ) and a repeating unit (R ^p ), and the repeating unit (F ^p ) is 2.5 to 30 with respect to all repeating units. A polymer containing 30% by mole of the repeating unit (R ^p ) is included. A particularly preferred embodiment of the resist polymer (P) is a polymer containing a repeating unit (F ^p ), a repeating unit (R ^p ), and a repeating unit (Q1 ^p ), and is repeated with respect to all repeating units. Examples include a polymer containing 2.5 to 30 mol% of the unit (F ^p ), 30 to 60 mol% of the repeating unit (R ^p ), and 20 to 60 mol% of the repeating unit (Q1 ^p ). Further, the polymer repeating units (Q2 ^p) may comprise 5 to 30 mole%.

The repeating unit (R ^p ) in a preferred embodiment is preferably a repeating unit formed by polymerization of the compound (r1 ^p ), and particularly preferably a repeating unit formed by polymerization of the compound (r11). The repeating unit (Q1 ^p ) is preferably a repeating unit formed by polymerization of the compound (q22), (q23), (q25) or (q26). The repeating unit (Q2 ^p ) is preferably a repeating unit formed by polymerization of the compound (q12) or the compound (q13).

The method for producing the resist polymer (P) is not particularly limited, and examples thereof include a method in which the compound (f ^p ) and the compound (r ^p ) are radically polymerized in the presence of a radical initiator.
The radical initiator is not particularly limited, and is peroxidized such as benzoyl peroxide, diisopropyl peroxydicarbonate, di-t-butyl peroxydicarbonate, t-butyl peroxypivalate, perfluorobutyryl peroxide, perfluorobenzoyl peroxide. Products; azo compounds such as azoisobisbutyronitrile; and persulfates.
The method of radical polymerization is not particularly limited, and can be carried out according to a polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method.

  The solvent for radical polymerization in the presence of a solvent is not particularly limited, and aliphatic hydrocarbons such as pentane, hexane, and heptane; hydrocarbon alcohols such as methanol, ethanol, n-propanol, isopropanol, and t-butanol Hydrocarbon hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbon ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, methyl t-butyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; tetrahydrofuran, Cyclic aliphatic hydrocarbon ethers such as 1,4-dioxane; nitriles such as acetonitrile; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, Hydrocarbon esters such as t-butyl acid, methyl propionate and ethyl propionate; aromatic hydrocarbons such as toluene and xylene; chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; 1,1, Fluorinated chlorinated hydrocarbons such as 2-trichlorotrifluoroethane and dichloropentafluoropropane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane Fluorinated hydrocarbons such as 1,1,1,2,2,3,3,4,4-nonafluorohexane; Fluorinated hydrocarbons such as methyl 2,2,3,3-tetrafluoroethyl ether Ethers; 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoroisopropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,4 , 4, 5, - fluorinated hydrocarbon alcohols such as octa fluorosilicone pentanol.

The reaction temperature in radical polymerization is not particularly limited and is preferably 0 ° C to 200 ° C, particularly preferably 25 ° C to 100 ° C. Further, the reaction pressure in radical polymerization may be any of reduced pressure conditions, atmospheric pressure conditions, and pressurized conditions, preferably 1 kPa to 100 MPa, particularly preferably 10 kPa to 10 MPa.
In application of the resist polymer (P) to the immersion lithography method, the resist polymer (P) and the photoacid generator are dissolved or dispersed in an organic solvent to form a photosensitive chemical amplification resist. Is preferred. The present invention provides a resist composition for immersion exposure (hereinafter also referred to as resist-forming composition (P)) containing a resist polymer (P), a photoacid generator, and an organic solvent.
Specific examples of the photoacid generator and the organic solvent in the resist forming composition (P) are the same as those in the resist forming composition (1).
The resist-forming composition (P) preferably contains 1 to 10% by mass of a photoacid generator with respect to the resist polymer (P). The resist forming composition (P) preferably contains 100% by mass to 10,000% by mass of an organic solvent with respect to the resist polymer (P).
The method for producing the resist-forming composition (P) is not particularly limited, and examples thereof include a method in which the resist polymer (P) and the photoacid generator are dissolved or dispersed in an organic solvent.
A method for forming a resist pattern by an immersion lithography method using the resist forming composition (P) is not particularly limited, and is the same as the resist forming composition (1).

In the immersion lithography method, a resist protective film may be formed on the outermost surface of the resist film from the viewpoint of suppressing elution of additives in the resist film into water.
The present invention includes the following polymer (F ^q ) and a polymer (R ^q ) whose alkali solubility is increased by the action of an acid, and the polymer (F ^q ) is 0 with respect to the polymer (R ^q ). 1. A resist composition for immersion exposure containing 1 to 30% by mass (hereinafter also referred to as resist composition (Q)) is provided.
Polymer (F ^q ): A polymer containing a repeating unit (F ^q ) formed by polymerization of the following compound (f ^q ), wherein the repeating unit (F ^q ) is 10 mol% or more based on all repeating units. Containing polymer.
^{_{CH 2 = CR fq C (O}} ) O-X q (f q).
However, the symbols in the formulas have the following meanings (the same applies hereinafter).
R ^fq : a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms.
^Xq : a group containing a fluorine-containing cyclic hydrocarbon group having 5 to 20 carbon atoms. Further, the carbon atoms in X ^q, hydroxy group, carboxy group, or an alkoxy group, alkoxyalkoxy group, a one or more groups selected from the group consisting of alkoxycarbonyl group and an alkylcarbonyl group 1 carbon atoms Ten groups may be bonded.

The resist composition (Q) of the present invention is excellent in water repellency and particularly excellent in dynamic water repellency. The reason is not necessarily clear, but the polymer (F ^q ) is a polymer having a bulky fluorine-containing group (group represented by the formula -X ^q ) derived from the compound (f ^q ) in the side chain. It is thought that there is. Therefore, the resist composition (Q) containing the polymer (F ^q ) is considered to be a photosensitive resist material that has high water repellency and is difficult to enter water, is particularly excellent in dynamic water repellency, and is well slidable.
R ^fq in the compound (f ^q ) is preferably a hydrogen atom or a methyl group.
X ^q is not particularly limited as long as it is a group containing a monovalent fluorine-containing cyclic hydrocarbon group, and may be a group consisting of only a fluorine-containing cyclic hydrocarbon group, or a fluorine-containing cyclic hydrocarbon group ^May be a group bonded to a group represented by the formula CH ₂ ^{═CR fq} C (O) O— through a linking group. The fluorine-containing cyclic hydrocarbon group may be a fluorine-containing monocyclic hydrocarbon group or a fluorine-containing polycyclic hydrocarbon group, and is sterically bulky and more excellent in dynamic water repellency. In view of the above, a fluorine-containing polycyclic hydrocarbon group is preferable.

In addition, the fluorine-containing cyclic hydrocarbon group in the compound (f ^q ) may be an aliphatic group or an aromatic group. From the viewpoint of water repellency, an aliphatic group is preferable, and a saturated fat A group of groups is particularly preferred. From the viewpoint of water repellency, the fluorine content of the fluorine-containing cyclic hydrocarbon group is preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the fluorine content is not particularly limited, and is preferably 76% by mass or less.
Further, the carbon atom in the fluorine-containing cyclic hydrocarbon group in the compound (f ^q ) is at least one selected from the group consisting of a hydroxy group, a carboxy group, or an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, and an alkylcarbonyl group. When a group having 1 to 10 carbon atoms is bonded, a hydroxy group or —OCH ₂ OX ^fqq (where X ^fqq represents an alkyl group having 1 to 9 carbon atoms) is bonded. It is particularly preferable that a hydroxy group, —OCH ₂ OCH ₂ CH ₃ , —OCH ₂ OCH ₃ or —OCH ₂ OC (CH ₃ ) ₃ is bonded.

The fluorine-containing polycyclic hydrocarbon group in the compound (f ^q ) is preferably a fluorine-containing condensed polycyclic hydrocarbon group having 5 to 20 carbon atoms, and from the viewpoint of sterically bulky fluorine-containing fluorine atoms having 5 to 20 carbon atoms Bridged ring hydrocarbon groups are particularly preferred.
The fluorine-containing bridged cyclic hydrocarbon group is preferably a group containing a fluoroadamantyl group or a group containing a fluoronorbornyl group. From the viewpoint of steric bulk, the former is more preferred, and any of the groups represented by Such groups are particularly preferred.

化合物（ｆ^ｑ）は、下記化合物（ｆ１^ｑ）が好ましく、下記化合物（ｆ１^０ｑ）または（ｆ１^１ｑ）が特に好ましい。

Compound ^{(f q)} is the following compound (f1 ^q) is preferably the following compound ^{(f1 0q)} or ^{(f1 1q)} is particularly preferred.

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
R ^f1q : a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
pq: 0 or 1.
X ^f1q : When p is 0, it is a fluorine atom or a hydroxy group, and when pq is 1, it is a fluorine atom or a hydroxymethyl group.
R ^f1q is preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
X ^f1q is preferably a fluorine atom.
Specific examples of the compound (f ^q ) are the same as the compounds described in the specific examples of the polymerizable compound (f ^m ).

Polymer ^{(F q)} is the repeating unit ^{(F q)} may be a polymer consisting only of repeating units ^{(F q)} the repeating unit ^{(F q)} other than the repeating units (hereinafter, other units (F ^q )))). Further, the repeating unit (F ^q ) may be composed of only one type, or may be composed of two or more types.
In any case, the polymer (F ^q ) contains 10 mol% or more and preferably 50 mol% or more of the repeating unit (F ^q ) with respect to all repeating units. When the polymer (F ^q ) contains other units (F ^q ), the polymer (F ^q ) preferably contains 90 mol% or less of the other units (F ^q ) with respect to all repeating units. It is particularly preferred to contain 50 mol% or less.

The other unit (F ^q ) is not particularly limited, and the compound (r1 ^p ), (r2 ^p ), the compound (r1 ^3q ), to (r1 ^8q ) described later, the compound (q11 ^p ) or ( One or more repeating units selected from the group consisting of repeating units formed by polymerization of q12 ^p ) and repeating units formed by cyclopolymerization of the following compound (c ^q ) are preferred.
_{^{CF 2 = CF-Q cq -CR}} cq = CH 2 (c q)
However, the symbols in the formulas have the following meanings (the same applies hereinafter).
R ^cq : a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
_{^{Q cq: -CF 2 C (CF}} 3) (OX cq) (CH 2) mcq -, - CH 2 CH ((CH 2) pcq C (CF 3) 2 (OX cq)) (CH 2) ncq - or ^{_{-CH 2 CH (C (O)}} OY cq) (CH 2) ncq -.
mcq, ncq and pcq: each independently 0, 1 or 2.
R ^cq is preferably a hydrogen atom.
X ^cq represents a hydrogen atom, —CH ₂ OZ ^cq1 (where Z ^cq1 represents an alkyl group having 1 to 9 carbon atoms, —CH ₂ OCH ₂ CH ₃ , —CH ₂ OCH ₃ , —CH ₂ OC (CH ₃ ) ₃ or —C (O) OC (CH ₃ ) ₃ is preferable.) Or —OC (O) OZ ^cq2 (where Z ^cq2 represents an alkyl group having 1 to 9 carbon atoms, and —CH ₃ , —CH ₂ CH ₃ or —C (CH ₃ ) ₃ is preferred).

Y ^cq is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly preferably a hydrogen atom, —CH ₃ , —CH ₂ CH ₃ or —C (CH ₃ ) ₃ .
As for mcq and ncq, 1 is preferable.
pcq is preferably 0.
The weight average molecular weight of the polymer ^{(F q)} is preferably from 1,000 to 30,000, particularly preferably 1,000 to 10,000.
Preferred embodiments of the polymer (F ^q ) include the following polymer (FH ^q ) and the following polymer (FC ^q ).
Polymer (FH ^q ): A polymer consisting only of repeating units (hereinafter also simply referred to as units (F1 ^q )) formed by polymerization of the compound (f1 ^q ), and having a weight average molecular weight of 1000 to 30000 ( 1000 to 10,000 is preferred.).
Polymer (AC ^q ): comprising unit (F1 ^q ) and the above repeating unit (R ^p ), repeating unit (Q1 ^p ) or repeating unit (Q2 ^p ), with respect to all repeating units, unit (F1 ^q ) And a repeating unit (R1 ^q ), (Q1 ^p ), and (Q2 ^p ) in a total of 50 to 90 mol%, and a weight average molecular weight of 1000 to 30000, preferably A polymer that is 1000-10000.

Preferred embodiments of the repeating units (R1 ^q ), (Q1 ^p ) and (Q2 ^p ) are the same as those of the resist polymer (P).
The resist composition (Q) contains a polymer (R ^q ) whose alkali solubility is increased by the action of an acid. The polymer (R ^q ) is not particularly limited, and a polymer including a repeating unit formed by polymerization of the compound (r1 ^p ) or (r2 ^p ) is preferable.
In this case, the polymer (R ^q ) is considered to have increased alkali solubility by the action of the acid because the carboxylate moiety in the repeating unit is cleaved by the action of the acid to form a carboxy group. Furthermore, the polymer containing the repeating unit which has a cyclic group among the said repeating units is excellent in dry etching tolerance.

The preferred embodiments of the compounds (r1 ^p ) and (r2 ^p ) in the polymer (R ^q ) are the same as those of the resist polymer (P).
The polymer (R ^q ) may contain a repeating unit other than the repeating unit formed by polymerization of the compound (r1 ^p ) or (r2 ^p ). The repeating unit is preferably a repeating unit formed by polymerization of the compound (q11 ^p ) or (q22 ^p ).
The preferred embodiments of the compounds (q11 ^p ) and (q22 ^p ) in the polymer (R ^q ) are the same as those of the resist polymer (P).
As the other polymer (R ^q ), a polymer containing a repeating unit formed by polymerization of one or more compounds (r ′ ^q ) selected from the group consisting of the following compounds (r1 ^3q ) to (r1 ^8q ) ( Hereinafter, the polymer (also referred to as R ′ ^q )) may be mentioned.

However, the symbols in the formula have the following meanings (the same applies hereinafter).
R ^31q : a carbon atom-alkyl group having 1 to 6 carbon atoms in which —O— may be inserted between carbon atoms (a methyl group is preferred).
R ^32q and R ^33q : each independently an alkyl group having 1 to 20 carbon atoms in which —O— may be inserted between carbon atoms and carbon atoms (preferably a methyl group), or a carbon atom in the formula And a divalent group having 4 to 20 carbon atoms which forms a cyclic hydrocarbon group in combination with.
In addition, —O—, —C (O) O—, or —C (O) — may be inserted between carbon atoms and carbon atoms in R ^31q , R ^32q, and R ^33q , respectively. The carbon atoms in R ^31q , R ^32q and R ^33q are one or more selected from the group consisting of a fluorine atom, a hydroxy group, a carboxy group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group and an alkylcarbonyl group. And a group having 1 to 10 carbon atoms may be bonded.

R ^4q , R ^5q , R ^6q , R ^7q , R ^81q and R ^82q : each independently one or more groups selected from the group consisting of an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group and an alkylcarbonyl group, Number 1-10 groups. Further, —O—, —C (O) O—, or —C (O) — may be inserted between carbon atoms in the group having 1 to 10 carbon atoms.
The group having 1 to 10 carbon atoms is preferably a group represented by the formula —CH ₂ OR ^bxq (where R ^bxq represents an alkyl group having 1 to 9 carbon atoms), —CH ₂ OCH ₂ CH ₃ , -CH ₂ OCH ₃ or _-CH 2 OC _{(CH 3)} 3 is particularly preferred.
Specific examples of the compound (r ′ ^q ) include the following compounds.

In the polymer (R ′ ^q ), the carboxylate part of the polymer (R ′ ^q ) is cleaved by the action of an acid to form a carboxy group, or represented by the formula —C (CF ₃ ) ₂ O—. Is cleaved by the action of an acid to form —C (CF ₃ ) ₂ OH, and it is considered that the alkali solubility is increased by the action of the acid.
Specific examples of the polymer (R ′ ^q ) include a polymer containing a repeating unit formed by polymerization of the compound (r ′ ^q ) and a repeating unit formed by polymerization of the following compound.

The weight average molecular weight of the polymer ^{(R q)} is preferably from 1,000 to 100,000, particularly preferably 5,000 to 50,000.
In a preferred embodiment of the polymer (R ^q ) in the present invention, a repeating unit formed by polymerization of the compound (r11), a repeating unit formed by polymerization of the compound (q12) or (q13), and a compound (q14 ), (Q15), (q22) or a polymer containing a repeating unit formed by polymerization of (q23). The polymer comprises 20 to 50 mol% of a repeating unit formed by polymerization of the compound (r11) and 30 to 30 units of repeating unit formed by the polymerization of the compound (q12) or (q13) with respect to all repeating units. It is preferable to contain 20 to 30 mol% of a repeating unit formed by polymerization of 50 mol%, compound (q14), (q15), (q22) or (q23). The weight average molecular weight of the polymer is preferably 1000 to 50000.

The resist composition (Q) includes a polymer (F ^q ) and a polymer (R ^q ), and 0.1 to 30% by mass of the polymer (F ^q ) with respect to the polymer (R ^q ). More preferably, 1 to 10% by weight of polymer relative to the polymer ^{(R q) (F q)} . In this case, there is an effect that the polymer (F ^q ) and the polymer (R ^q ) are easily compatible and the film forming property of the immersion resist is excellent.
The resist composition (Q) may contain components other than the polymer (F ^q ) and the polymer (R ^q ).
Since the resist composition (Q) is usually used as a photosensitive chemically amplified resist, it preferably contains a photoacid generator. The resist composition (Q) preferably contains 1 to 10% by mass of a photoacid generator based on the polymer (R ^q ). Moreover, 1 type may be used for a photo-acid generator, and 2 or more types may be used for it.
Specific examples of the photoacid generator include the same photoacid generator as the resist forming composition (1).
Since the resist composition (Q) is usually applied on a substrate (silicon wafer or the like) and formed into a film, the resist composition (Q) is preferably liquid from the viewpoint of film forming properties. The resist composition (Q) preferably contains an organic solvent.

An organic solvent will not be specifically limited if it is a solvent with high compatibility with respect to a polymer ( ^Fq ) and a polymer ( ^Rq ). 1 type may be used for an organic solvent and 2 or more types may be used for it.
Compatibility with a polymer (F ^q ) having a high content of repeating units (F ^q ) (usually a polymer containing 75 mol% or more of repeating units (F ^q ) with respect to all repeating units). As the high organic solvent, a fluorine-containing organic solvent composed of a fluorine-containing compound is preferable. From the viewpoint of high compatibility with the polymer (R ^q ), a fluorine-containing organic solvent composed of a fluorine-containing compound having a carbon atom-hydrogen atom bond is used. Particularly preferred. 1 type may be used for a fluorine-containing organic solvent, and 1 or more types may be used for it.
Further, the phase with respect to low content polymer of the repeating units ^{(F q) (F q)} ( usually refers to a polymer comprising repeating units (F ^q) less than 75 mol% based on all repeating units.) The organic solvent having high solubility is preferably an organic solvent composed of a compound not containing a fluorine atom.

Specific examples of the organic solvent include the same organic solvent as the resist forming composition (1).
From the viewpoint of the compatibility of the resist composition (Q), the organic solvent in the present invention is preferably an organic solvent in which a fluorinated organic solvent is essential, and the fluorinated organic solvent is contained in an amount of 10 to 70 mass relative to the total mass of the organic solvent. % Of organic solvent is particularly preferred. Furthermore, it is preferable that resist composition (Q) contains 100 mass%-10000 mass% of organic solvents with respect to the total amount of a polymer ( ^Fq ) and a polymer ( ^Rq ).

The method for producing the resist composition (Q) is not particularly limited, and a solution obtained by dissolving the polymer (F ^q ) in a fluorine-containing organic solvent (hereinafter referred to as a resin solution (F)), and the polymer. A solution prepared by dissolving (R ^q ) in an organic solvent (hereinafter referred to as a resin solution (R)), and then mixing the resin solution (F) and the resin solution (R); The method of mixing a polymer ( ^Fq ) and a resin solution (R) is mentioned. The resin solution (F) preferably contains 0.1 to 10% by mass of the polymer (F ^q ). The resin solution (R) is the polymer ^{(R q)} the preferably contains 0.1 to 20 mass%.
The immersion resist of the present invention is used in an immersion lithography method. The specific aspect of the immersion lithography method is the same as described above.

The present invention relates to a resist material for lithography (hereinafter referred to as resist material (hereinafter referred to as resist material)) containing a polymer containing a repeating unit (F ^w ) formed by polymerization of a polymerizable compound (f ^w ) having a fluorine-containing bicyclic bridged ring structure. W))).
The polymerizable compound (f ^w ) is a compound having a polymerizable group and a fluorine-containing bicyclic bridged ring structure, and a fluorine atom is bonded to a carbon atom constituting the fluorine-containing bicyclic bridged ring structure. If it is the compound which is doing, it will not specifically limit.
The polymerizable group is preferably a group having a polymerizable carbon atom-carbon atom double bond.
The fluorine-containing bicyclic bridged ring structure is preferably an aliphatic group, particularly preferably a saturated aliphatic group. In addition, —O—, —C (O) O—, or —C (O) — may be inserted between carbon atoms in the fluorine-containing bicyclic bridged ring structure. In addition, a hydroxy group or a carboxy group may be bonded to a carbon atom in the fluorine-containing bicyclic bridged ring structure.
The fluorine content of the polymerizable compound (f ^w ) is preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the fluorine content is preferably 76% by mass or less. The number of carbon atoms of the polymerizable compound ^{(f w)} is 8 to 20 are preferred.
The following compound (f1 ^w ) or (f2 ^w ) is preferable as the polymerizable compound (f ^w ).

The symbols in the formula have the following meanings.
W ^Fw : a fluorine atom or a trifluoromethyl group.
R ^Fw : a fluorine atom or a C 1-16 perfluoroalkyl group, and two R ^{Fw s} may be the same or different.
Q ^Fw : —CF ₂ — or —C (CF ₃ ) ₂ —, and two Q ^Fw may be the same or different.
R ^Aw : 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.
J ^Aw : an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom.
The configuration of the asymmetric center on the main ring of the compound (f1 ^w ) or the compound (f2 ^w ) may be endo or exo.
R ^Aw is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
It is preferable that both of R ^Fw are fluorine atoms, or one is a fluorine atom and the other is a C 1-16 perfluoroalkyl group, and it is particularly preferable that both are fluorine atoms.
J ^Aw is preferably a methylene group.

Specific examples of the polymerizable compound (f ^w ) are the same as the compounds described in the specific examples of the polymerizable compound (f ^m ).
Compound (f1 ^w ) is a novel compound. The compound (f1 ^w ) is obtained by subjecting the following compound (f1 ^51w ) and R ^fPw -COF to an esterification reaction to obtain the following compound (f1 ^41w ), followed by a liquid phase fluorination reaction of the compound (f1 ^41w ). ^{(f1 3w)} was obtained, and then the compound ^{(f1 3w)} and by the thermal decomposition reaction in the presence of KF to obtain the following compound ^{(f1 2w),} then compound ^{(f1 2w)} a reduction reaction to the compound (f1 ^1w ) and then reacting the compound (f1 ^1w ) with CH ₂ = CR ^Aw C (O) Cl.

However, the symbol in a formula shows the following meaning.
R ^fPw : a C 1-20 perfluoroalkyl group which may contain an etheric oxygen atom.
W ^Pw : a group corresponding to W ^Fw and a hydrogen atom or a methyl group.
R ^Pw : a group corresponding to R ^Fw and a hydrogen atom or an alkyl group having 1 to 16 carbon atoms. Two R ^Pw may be the same or different.
Q ^Pw : a group corresponding to Q ^Fw and —CH ₂ — or —C (CH ₃ ) ₂ —. Two ^QPw may be the same or different.
The compound (f1 ^3w ) may be obtained by a liquid phase fluorination reaction of the following compound (f1 ^42w ) obtained in the same manner except that the ^following compound (f1 ^52w ) is used instead of the compound (f1 ^51w ).

化合物（ｆ２^ｗ）は新規化合物である。化合物（ｆ２^ｗ）は、下記化合物（ｆ２^５１ｗ）とＲ^ｆＰｗ−ＣＯＦをエステル化反応して下記化合物（ｆ２^４１ｗ）を得て、つぎに化合物（ｆ２^４１ｗ）の液相フッ素化反応により下記化合物（ｆ２^３ｗ）を得て、つぎに化合物（ｆ２^３ｗ）をＫＦ存在下に熱分解反応して得られる下記化合物（ｆ２^２ｗ）を用いて製造できる。

Compound (f2 ^w ) is a novel compound. Compound (f2 ^w) is obtained the following compound and ^{(f2 51w)} by esterifying the ^R FPW -COF following compound ^{(f2 41w),} then the compound ^{(f2 41w)} following compounds by liquid-phase fluorination reaction of (F2 ^3w ) is obtained, and then the compound (f2 ^3w ) can be produced using the following compound (f2 ^2w ) obtained by thermal decomposition reaction in the presence of KF.

たとえば、化合物（ｆ２^２ｗ）とメタノールを反応させて下記化合物（ｆ２^２Ｍｗ）を得て、つぎに化合物（ｆ２^２Ｍｗ）を還元反応して下記化合物（ｆ２１^１Ｍｗ）を得て、つぎに化合物（ｆ２１^１Ｍｗ）とＣＨ_２＝ＣＲ^ｗＣ（Ｏ）Ｃｌを反応させることにより、下記化合物（ｆ２^Ｍｗ）を製造できる。

For example, the compound (f2 ^2w ) and methanol are reacted to obtain the following compound (f2 ^2Mw ), then the compound (f2 ^2Mw ) is reduced to obtain the following compound (f21 ^1Mw ), and then the compound (f21 by reacting ^{1 mw)} and a ^{_{CH 2 = CR w C (O}} ) Cl, can be prepared the following compounds ^{(f2 Mw).}

化合物（ｆ２^３ｗ）は、化合物（ｆ２^５１ｗ）のかわりに下記化合物（ｆ２^５２ｗ）を用いる以外は同様にして得た下記化合物（ｆ２^４２ｗ）の液相フッ素化反応により得てもよい。

The compound (f2 ^3w ) may be obtained by a liquid phase fluorination reaction of the following compound (f2 ^42w ) obtained in the same manner except that the ^following compound (f2 ^52w ) is used instead of the compound (f2 ^51w ).

As a method for polymerizing compound (f ^w) is polymerized, methods exist polymerizable compound (f ^w) is polymerized under the polymerization initiator. Examples of the polymerization initiator include organic peroxides, inorganic peroxides, and azo compounds. The temperature, pressure, and time in the polymerization are not particularly limited.
The resist material (W) is excellent in water repellency, particularly dynamic water repellency. The reason is not necessarily clear, but it is considered that the resist material (W) contains a bulky fluorine-containing polymer derived from the fluorine-containing bicyclic bridged ring structure of the polymerizable compound (f ^w ). . Therefore, a resist member that hardly penetrates into the immersion liquid and that follows the immersion liquid can be easily prepared by the resist material (W).

The present invention relates to a repeating unit (F ^w ), a group represented by the following group (r-1 ^w ), the following group (r-2 ^w ), —C (CF ₃ ) ₂ (OZ ^Rw ) (hereinafter referred to as group ( r-3 ^w )) or -C (CF ₃ ) (OZ ^Rw )-(hereinafter also referred to as group (r-4 ^w )), and formed by polymerization of a polymerizable compound (r ^w ). and a repeating unit (R ^w), a polymer exhibits increased alkali solubility under action of acid, based on the total repeating units, wherein 1 to 45 mol% of the repeating units (F ^w), the repeating units ( A resist polymer for immersion lithography (hereinafter, also referred to as resist polymer (W)) containing 10 mol% or more of R ^w ) is provided.

The symbols in the formula have the following meanings (the same applies hereinafter).
X ^R1w : an alkyl group having 1 to 6 carbon atoms.
Y ^R1w : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula.
X ^R2w : an alkyl group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Z ^Rw : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group having 1 to 20 carbon atoms.
^However, X ^R1W, Y ^R1W, carbon atoms in ^{X R2w} or ^{Z Rw} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, also , X ^R1w , Y ^R1w , X ^R2w or Z ^Rw may be bonded to a fluorine atom, a hydroxy group or a carboxy group.
Since the resist polymer (W) contains a repeating unit (F ^w ), the resist polymer (W) is particularly excellent in dynamic water repellency. In the immersion lithography method using the photosensitive resist prepared from the resist polymer (W), the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist.

Further, the resist polymer (W) is a polymer whose alkali solubility is increased by the action of an acid because it contains a repeating unit (R ^w ). The exposed portion of the photosensitive resist prepared from the resist polymer (W) can be easily removed with an alkaline solution. Therefore, the resist polymer (W) enables stable and high-speed execution of an immersion lithography method that can transfer a mask pattern image with high resolution.
The polymerizable compound (f ^w ) in the resist polymer (W) is preferably the compound (f1 ^w ) or (f2 ^w ).
The polymerizable compound (r ^w ) in the resist polymer (W) is preferably the following compound (r1 ^w ), (r2 ^w ) or (r3 ^w ).

The symbols in the formula have the following meanings (the same applies hereinafter).
R ^Rw : 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 ^R1w : an alkyl group having 1 to 6 carbon atoms.
Y ^R1w : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula.
X ^R2w : an alkyl group having 1 to 20 carbon atoms, and three X ^{R2w s} may be the same or different.
_{^{Q R1w: -CF 2 C (CF}} 3) (OZ Rw) (CH 2) mw -, - CH 2 CH ((CH 2) nw C (CF 3) 2 (OZ Rw)) (CH 2) mw - or ^{_{-CH 2 CH (C (O)}} OZ Rw) (CH 2) mw -.
Z ^Rw : an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group having 1 to 20 carbon atoms.
mw and nw: each independently 0, 1 or 2.
^However, X ^R1W, Y ^R1W, carbon atoms in ^{X R2w} or ^{Z Rw} - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, also , X ^R1w , Y ^R1w , X ^R2w or Z ^Rw may be bonded to a fluorine atom, a hydroxy group or a carboxy group.

A preferred embodiment of the group (r-1 ^w ) is the same as the group (ur1).
A preferred embodiment of the group (r-2 ^w ) is the same as the group (ur2).
A preferred embodiment of the group (r-3 ^w ) is the same as the group (ur3).
A preferred embodiment of the group (r-4 ^w ) is the same as the group (ur4).
A preferred embodiment of the compound (r1 ^w ) is the same as that of the compound (r1).
A preferred embodiment of the compound (r2 ^w ) is the same as that of the compound (r2).
A preferred embodiment of the compound (r3 ^w ) is the same as that of the compound (r3).

Resist polymer (W), based on all repeating units, the repeating units ^{(F w)} preferably contains 2.5 to 30 mol%. In this case, it is easy to prepare a liquid composition in which the resist polymer (W) is dispersed or dissolved in an organic solvent.
Resist polymer (W), based on all repeating units, preferably comprises 20 to 90 mole% of recurring units ^{(R w),} particularly preferably contains 30 to 60 mol%. In this case, it is easy to remove the exposed portion of the resist polymer (W) with an alkaline solution in the immersion lithography method.
The resist polymer (W) may contain a repeating unit (hereinafter, also referred to as other unit (F ^w )) other than the repeating unit (F ^w ) and the repeating unit (R ^w ). In this case, the resist polymer (W), based on all repeating units, other units ^{(F w)} preferably contains 20 to 60 mol%.
The other unit (F ^w ) is not particularly limited, and a repeating unit (Q ^U ) formed by polymerization of the polymerizable compound (q ^m ) is preferable.

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.
A preferred embodiment of the resist polymer (W), based on all repeating units, wherein 1 to 45 mol% of the repeating units ^{(F w),} polymer thereof comprising a repeating unit ^{(R w)} 30 to 60 mol% It is done.
A particularly preferred embodiment is a polymer containing a repeating unit (F ^w ), a repeating unit (R ^w ) and another unit (F ^w ), wherein the repeating unit (F ^w ) is 1 for all repeating units. wherein 45 mol%, wherein the repeating units ^{(R w)} 30 to 60 mol%, the polymer containing other units ^{(F w)} 20 to 60 mol% are exemplified.

The repeating unit (R ^w ) in the above embodiment is preferably a repeating unit formed by polymerization of the compound (r1), particularly preferably a repeating unit formed by polymerization of the compound (r11). The other unit (R) in the above embodiment is preferably a repeating unit formed by polymerization of the compound (q12), (q22), (q23), (q25) or (q26).
As for the weight average molecular weight of the polymer in the said aspect, 1000-30000 are preferable.
The resist polymer (W) is usually prepared and used as a chemically amplified photosensitive resist for application to the immersion lithography method. The resist polymer (W) preferably contains a photoacid generator. In addition, the resist polymer (W) is usually used by being applied onto a substrate in application to the immersion lithography method. The resist polymer (W) is preferably prepared into a liquid composition.

The photoacid generator in the present invention is not particularly limited as long as it is a compound having a group capable of generating an acid upon irradiation with active light (however, active light means a broad 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.
Specific examples of the photoacid generator include the same photoacid generator as the resist forming composition (1). The resist-forming composition (W) preferably contains 1 to 10% by mass of a photoacid generator with respect to the resist polymer (W).
The organic solvent is not particularly limited as long as it is a solvent having high compatibility with the resist polymer (W). Specific examples of the organic solvent include the same organic solvent as the resist forming composition (1). It is preferable that a resist formation composition (W) contains 100 mass%-10000 mass% of organic solvents with respect to a resist polymer (W).
The preferable aspect of the immersion lithography method using the resist forming composition (W) is the same as described above.

The present invention is a polymer containing repeating units (F ^w), and repeating units based on all repeating units (F ^w) a polymer containing 10 mol% or more (FR ^w), alkali dissolution by the action of an acid includes polymers sex increases the ^{(R w),} and polymer ^{(R w)} polymer (FR ^w) for immersion lithography resist composition containing 0.1 to 30 wt% with respect to (or less, the resist Composition (V)).
Since the resist composition (V) contains a polymer (FR ^w ) containing a repeating unit (F ^w ), the resist composition (V) is particularly excellent in dynamic water repellency. In the immersion lithography method using the photosensitive resist prepared from the resist composition (W), the immersion liquid follows the projection lens that moves at high speed on the photosensitive resist. Moreover, since the resist composition (V) contains a polymer (R ^w ), the alkali solubility is increased by the action of an acid. The exposed portion of the photosensitive resist prepared from the resist composition (V) can be easily removed with an alkaline solution. Therefore, the resist composition (V) enables stable and high-speed execution of an immersion lithography method that can transfer a mask pattern image with high resolution.
The polymerizable compound (f ^w ) in the resist composition (V) is preferably the compound (f1 ^w ) or (f2 ^w ).

Polymer (FR ^w) are recurring units ^{(F w)} may be a polymer consisting only of repeating units ^{(F w)} and the repeating units ^{(F w)} other than the repeating units (hereinafter, the other units (FR ^w ))))). In any case, the polymer (FR ^w ) contains 10 mol% or more and preferably 20 mol% or more of the repeating unit (F ^w ) with respect to all repeating units. When the polymer (FR ^w) comprises another unit (FR ^w), preferably contains other units (FR ^w) 90 mol% or less based on all repeating units, particularly preferably contains 80 mol% or less .
The polymer (FR ^w ) is a polymer containing a repeating unit (Q ^w ) formed by polymerization of a polymerizable compound (q ^w ) having the following group (q-1 ^w ) or the following group (q-2 ^w ). Is preferred.

The symbols in the formula have the following meanings (the same applies hereinafter).
Y ^Q1w : a trivalent group having 4 to 20 carbon atoms that forms a bridged cyclic hydrocarbon group in cooperation with a carbon atom in the formula.
Y ^Q2w : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in cooperation with a carbon atom in the formula.
^{However, Y Q1w} or ^Y carbon atoms in ^Q2w - is between the carbon atoms -O -, - C (O) O- or -C (O) - is may be inserted, ^{also, Y Q1w} or ^{Y Q2w} A fluorine atom, a hydroxy group or a carboxy group may be bonded to the carbon atom therein.
A preferred embodiment of the repeating unit ^{(Q w)} are recurring units ^{(R w)} or repeating units ^{(Q w)} are preferred, Compounds (r1), (r2), repeatedly formed by polymerization of the (q1) or (q2) Units are particularly preferred.
The weight average molecular weight of the polymer (FR ^w ) is preferably 1000 to 100,000.
Preferable embodiments of the polymer (FR ^w ) include the following polymer (FR ^Hw ) and the following polymer (FR ^Cw ).
Polymer (FR ^Hw ): A polymer consisting only of repeating units (F ^w ).
Polymer (FR ^Cw ): A polymer containing repeating units (F ^w ) and other units (FR ^w ), and containing 10 to 50 mol% of repeating units (F ^w ) with respect to all repeating units. And a polymer containing 50 to 90 mol% of other units (FR ^w ).
The other units (FR ^w ) in the polymer (FR ^Cw ) are preferably a repeating unit (R ^w ) and a repeating unit (Q ^w ). The repeating unit (R ^w ) is preferably a repeating unit formed by polymerization of the compound (r11). The repeating unit (Q ^w ) is particularly preferably a repeating unit formed by polymerization of (q12), (q22), (q23), (q25) or (q26).

As for the weight average molecular weight of the polymer in the said aspect, 1000-30000 are preferable.
Polymer (R ^w) is not particularly limited, the polymerizable compound repeating unit polymer containing a (R ^w) which is formed by polymerization of (r ^m) is preferably a repeating unit based on all repeating units (R ^w ) Is particularly preferred.
The repeating unit (R ^w ) is preferably a repeating unit formed by polymerization of the polymerizable compound (r ^m ), more preferably a repeating unit formed by polymerization of the compound (r1), (r2) or (r3), The repeating unit formed by polymerization of the compound (r1) is particularly preferable, and the repeating unit formed by polymerization of the compound (r11) is most preferable.

The polymer (R ^w ) preferably contains a repeating unit (Q ^U ) formed by polymerization of the polymerizable compound (q ^m ). A preferred embodiment of the polymer polymerizable compound in (R ^w) (q ^m) is the same as the polymer in the resist composition of the present invention (R).
The weight average molecular weight of the polymer (R ^w ) is preferably 1000 to 100,000.
A preferred embodiment of the polymer (R ^w ) is a polymer containing a repeating unit (R ^w ), a repeating unit (QB1 ^U ), and a repeating unit (QB2 ^U ), wherein the repeating unit (R R ^w) 20 to 50 mol%, the repeating units (QB1 ^U) 30 to 50 mol% and the repeating units (QB2 ^U) a polymer containing 20 to 30 mol% are exemplified.
In the preferred embodiment, the repeating unit (QB1 ^U ) is preferably a repeating unit formed by polymerization of the compound (qB1), and particularly preferably a repeating unit formed by polymerization of the compound (q12) or (q13). The repeating unit (QB2 ^U ) is preferably a repeating unit formed by polymerization of the compound (qB2), and the repeating unit formed by polymerization of the compound (q22), (q23), (q25) or (q26) Particularly preferred.
The weight average molecular weight of the polymer in the above embodiment is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000.

The resist composition (V) includes a polymer (FR ^w ) and a polymer (R ^w ), and 0.1 to 30% by mass of the polymer (FR ^w ) with respect to the polymer (R ^w ). Preferably comprises 1 to 10 wt% of polymer relative to the polymer ^{(R w) (FR w)} . In this case, there is an effect that the polymer (FR ^w ) and the polymer (R ^w ) are easily compatible with each other and the film forming property of the resist composition (V) is excellent.
In application to the immersion lithography method, the resist composition (V) is usually prepared and used as a chemically amplified photosensitive resist. It is preferable that a photoacid generator is blended in the resist composition (V). Further, the resist composition (V) is usually used by being applied onto a substrate in application to the immersion lithography method. The resist composition (V) is preferably prepared as a liquid composition.
Examples of the photoacid generator in the resist composition (V) include the same photoacid generator as that in the resist forming composition (1). The resist composition (V) preferably contains 1 to 10% by mass of a photoacid generator with respect to the polymer (R ^w ).

An organic solvent will not be specifically limited if it is a solvent with high compatibility with a polymer ( ^Rw ). Specific examples of the organic solvent include the same organic solvent as the resist forming composition (1).
The resist-forming composition (V) preferably contains 100% by mass to 10,000% by mass of an organic solvent with respect to the total mass of the polymer (F ^w ) and the polymer (R ^w ).
The method for producing the resist forming composition (V) is not particularly limited, and examples thereof include a method in which the resist composition (V) and the photoacid generator are dissolved or dispersed in an organic solvent.
A preferred embodiment of the immersion lithography method using the resist forming composition (V) is the same as that of the resist forming composition (1).

The present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In the examples, the gel permeation chromatography method is described as GPC, the weight average molecular weight is Mw, the number average molecular weight is Mn, and the glass transition temperature is Tg.
1,1,2-trichloro-1,2,2-trifluoroethane is R113, dichloropentafluoropropane (mixture of CF ₃ CF ₂ CHCl ₂ and CF ₂ ClCF ₂ CHFCl) is R225, and diisopropyl par Oxydicarbonate is referred to as IPP, and tetramethylsilane is referred to as TMS.
Tetrahydrofuran in THF, propylene glycol methyl ether acetate in PGMEA, 2-heptanone (methyl amyl ketone) in MAK, methyl ethyl ketone in MEK, cyclopentanone in CP, 2-propanol in IPA, ethyl lactate in EL I write.
Mw and Mn of the polymer were measured using a gel permeation chromatography method (developing solvent: THF, internal standard: polystyrene). The Tg of the polymer was measured using differential scanning calorimetry.
In order to produce a polymer, the following compounds (f ¹ ), (f ² ), (f ³ ), (f ⁴ ), (r ¹ ), (r ² ), (q ¹ ), (q ² ), (Q ³ ) was used.

The repeating unit formed by the polymerization of the compound (f ¹ ) is the unit (F ¹ ), the repeating unit formed by the polymerization of the compound (f ² ) is the unit (F ² ), and the polymerization of the compound (f ³ ). The formed repeating unit is referred to as a unit (F ³ ), and the repeating unit formed by polymerization of the compound (f ⁴ ) is referred to as a unit (F ⁴ ). Further, a repeating unit formed by polymerization of the compound (r ¹ ) is represented by the unit (R ¹ ), a repeating unit formed by polymerization of the compound (r ² ) is represented by the unit (R ² ), and the compound (q ¹ ). A repeating unit formed by polymerization is a unit (Q ¹ ), a repeating unit formed by polymerization of the compound (q ² ) is a unit (Q ² ), and a repeating unit formed by polymerization of the compound (q ³ ) is The unit (Q ³ ) is described.

[Example 1 (Reference Synthesis Example)] Production Example of Compound (f) [Example 1-1] Production Example of Compound (f ² ) The following compound (pf ² ) (27.46 g) was placed in a flask maintained at 0 ° C. NaF (3.78) and acetone (100 mL) were added and stirred. Next, water (1.14g) was dripped at the flask, and the inside of a flask was fully stirred. The contents of the flask were purified by sublimation to obtain the following compound (qf ² ) (22.01 g).
To a mixture of the compound (qf ² ) (2.03 g) and dimethyl sulfoxide (50 mL) in the flask, potassium hydroxide (1.00 g) and an aqueous formalin solution (20 mL) were added, and reacted at 75 ° C. for 6.5 hours. I let you. After completion of the reaction, the reaction solution was extracted with R225 (40 mL), and further R225 was distilled off to obtain the following compound (rf ² ) (1.58 g).
Compound (rf ² ) (6.01 g) and R225 (103 g) obtained in the same manner were added to the flask, and then triethylamine (1.68 g) and CH ₂ ═C (CH ₃ ) COCl (1.58 g) Were added little by little, and the inside of the flask was stirred at 25 ° C. for 2 hours. The filtrate obtained by filtering the solution in the flask was washed twice with water (50 mL). Next, the solution in the flask was dried over magnesium sulfate and then concentrated to obtain a pale yellow solid (6.19 g). The solid was purified by column chromatography to obtain compound (f ² ).

化合物（ｆ^２）のＮＭＲデータを以下に示す。
^１Ｈ−ＮＭＲ（３００．４ＭＨｚ，溶媒：ＣＤＣｌ_３，基準：Ｓｉ（ＣＨ_３）_４）δ（ｐｐｍ）：１．９６（ｓ，３Ｈ），５．０６（ｓ，２Ｈ），５．７１（ｓ，１Ｈ），６．１９（ｓ，１Ｈ）。
^１９Ｆ−ＮＭＲ（２８２．７ＭＨｚ，溶媒：ＣＤＣｌ_３，基準：ＣＦＣｌ_３）δ（ｐｐｍ）：−１１３．６（６Ｆ），−１２１．１（６Ｆ），−２１９．４（３Ｆ）。

The NMR data of the compound (f ² ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: Si (CH ₃ ) ₄ ) δ (ppm): 1.96 (s, 3H), 5.06 (s, 2H), 5.71 ( s, 1H), 6.19 (s, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −113.6 (6F), −121.1 (6F), −219.4 (3F).

[Example 1-2] Production Example of Compound (f ³ ) According to the production route represented by the following formula, the compound (f ³ ) was produced from the following compound (nf ³ ). However, R ^f1 − represents F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) —.

A compound (nf ³ ) (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. After the dropping, the flask was further stirred. After removing the insoluble solid 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 (of ³ ) (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 compound (of ³ ) (67 g) was dissolved in R113 (299 g) was introduced into an autoclave under a pressure of 0.1 MPa. After the introduction, the autoclave contents were collected and concentrated to obtain a compound (pf ³ ).

A compound (pf ³ ) (80 g) and powdered KF (0.7 g) were placed in a flask under a nitrogen gas atmosphere. After heating the flask for 6 hours, the contents of the flask were purified to obtain compound (qf ³ ) ( 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 on ice, an R225 solution (48 g) containing 22% by mass of the compound (qf ³ ) was added dropwise to the flask. After completion of dropping, the inside of the flask was further stirred, and then the solution obtained by neutralizing the solution in the flask with an aqueous hydrochloric acid solution (150 mL) was washed with water and purified by distillation to obtain a compound (rf ³ ).

The flask was charged with compound (rf ³ ) (2.2 g), THF (10 g), N-nitrosophenylhydroxyamine aluminum salt (2 mg) and triethylamine (1.2 g). While the flask was ice-cooled and stirred, a solution obtained by dissolving CH ₂ ═C (CH ₃ ) C (O) Cl (1.2 g) in THF (7.3 g) was added dropwise to the flask. After completion of the dropwise addition, the flask was further stirred, and then an aqueous sodium hydrogen carbonate solution was added. The concentrate obtained by drying and concentrating the extract obtained by extracting the solution in the flask with R225 was purified by silica gel column chromatography to obtain compound (f ³ ) (2.7 g).

The NMR data of the compound (f ³ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 6.31 (1H), 5.88 (1H), 5.84 (1H), 2.01 (3H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −104.6 (1F), −120.5 (1F), −122.4 (1F), −124 .2 (1F), -124.6 (1F), -126.5 (1F), -132.7 to -132.8 (2F), -214.8 (1F), -223.2 (1F) .

[Example 1-3] Production Example of Compound (f ⁴ ) According to the production route represented by the following formula, the compound (f ⁴ ) was produced from the following compound (nf ⁴ ). However, R ^f2 − represents F (CF ₂ ) ₃ OCF (CF ₃ ) —.

Compound (nf ⁴ ) (26 g) and R225 (100 g) were placed in a flask under a nitrogen gas atmosphere, and R ^f2 -COF (91 g) was added dropwise with stirring in the flask while cooling with ice. Was stirred. The flask contents were concentrated and filtered to obtain compound (of ⁴ ) (88 g).
R113 (326 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 blowing 20% fluorine gas as it was, a solution in which compound (of ⁴ ) (75 g) was dissolved in R113 (346 g) was introduced into an autoclave under a pressure of 0.1 MPa. After the introduction, the autoclave contents were collected and concentrated to obtain a compound (pf ⁴ ).

Methanol (20 g) was added dropwise to a solution obtained by dissolving the compound (pf ⁴ ) (106 g) in R225 (100 mL) under ice cooling to obtain a solution. After completion of the dropwise addition, the solution was stirred at 25 ° C., and then R225 and F (CF ₂ ) ₃ OCF (CF ₃ ) COOCH ₃ were distilled off from the solution to obtain a reaction product (42 g). To a solution containing the reaction product and THF (100 mL), a hexane solution (20 g) containing 79% by mass of ((CH ₃ ) ₂ CHCH ₂ ) ₂ AlH was added dropwise to obtain a solution. After completion of the dropwise addition, the solution was stirred and then neutralized with 0.2 mol / L hydrochloric acid aqueous solution to obtain a reaction crude liquid. After distilling off low boiling components of the extract obtained by extracting the reaction crude liquid with R225, the reaction crude liquid was recrystallized in hexane to obtain a compound (rf ⁴ ).

The flask compound ^{(rf 4) (16.3g),} tert- butyl methyl ether (82 mL), was charged with hydroquinone (5 mg), and triethylamine (8.1 g). While the flask was stirred on ice, CH ₂ ═C (CH ₃ ) C (O) Cl (8.4 g) was added dropwise to the flask. After completion of dropping, the inside of the flask was stirred, and then pure water (50 mL) was added to the flask to obtain a two-layer separated liquid. The upper layer of the two-layer separated liquid was collected, dried and concentrated to obtain a concentrated liquid. The concentrated solution was purified by silica gel column chromatography to obtain compound (f ⁴ ) (14 g).

The NMR data of the compound (f ⁴ ) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm):
6.20 (1H), 5.70 (1H), 4.75 (2H), 1.98 (3H)
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −118 .6 (1F), -120.6 (1F), -123.8 (2F), -124.5 (1F), -124.9 (1F), -128.6 (1F), -131.4 (1F), -179.1 (1F), -219.8 (1F), -227.0 (1F).

[Example 2] Production example of resist polymer for immersion lithography (part 1)
[Example 2-1] Production example of polymer (F ¹ ) In a reactor (internal volume 200 mL, glass), compound (f ¹ ) (4.8 g), compound (r ² ) (12.0 g), Compound (q ¹ ) (9.0 g), compound (q ² ) (2.5 g) and MEK (77 g) were charged. Next, an R225 solution containing 50% by mass of IPP (15.9 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the agglomerated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ¹ ) (15.5 g). Got.
The polymer (F ¹ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ¹ ) was 3700, and Mw was 7200.
Polymer ^{(F 1)} of ¹³ C-NMR analysis result, the polymer ^{(F 1),} based on all repeating units, the units ^{(F 1)} of 11 mol%, units ^{(R 2)} 43 mol%, unit ^{(Q 1)} to 27 mol%, and unit ^{(Q 2)} was a polymer containing 19 mol%. The polymer (F ¹ ) was soluble in THF, CP, and PGMEA, respectively.

[Example 2-2] Production example of polymer (F ² ) In a reactor (internal volume 30 mL, glass), compound (f ¹ ) (0.17 g), compound (r ² ) (1.0 g), Compound (q ¹ ) (0.46 g) and MEK (2.7 g) were charged. Next, an R225 solution containing 50% by mass of IPP (0.65 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ² ) (1.2 g). Got.
The polymer (F ² ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ² ) was 4500, and Mw was 10,000.
Polymer ^{(F 2)} a ¹³ C-NMR analysis result, the polymer ^{(F 2),} based on the total repeating units, units ^{(F 1)} 5 mol%, the unit ^{(R 2)} 54 mol%, And a polymer containing 41 mol% of the unit (Q ¹ ). The polymer (F ² ) was soluble in THF, CP, and PGMEA, respectively.

[Example 2-3] Production example of polymer (F ³ ) Compound (f ² ) (3.9 g), compound (r ² ) (10.0 g), compound in reactor (internal volume 200 mL, glass) (Q ¹ ) (6.7 g), compound (q ² ) (1.7 g) and MEK (61 g) were charged. Next, an R225 solution containing 50% by mass of IPP (12.5 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ³ ) (11.9 g). Got.
The polymer (F ³ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ³ ) was 4100, and Mw was 7800.
Polymer ^{(F 3)} the ¹³ C-NMR analysis result, the polymer ^{(F 3),} based on the total repeating units, units ^{(F 2)} 11 mol%, units ^{(R 2)} 39 mol%, unit ^{(Q 1)} to 42 mol%, and unit ^{(Q 2)} was a polymer containing 8 mol%. Further, the polymer (F ³ ) was soluble in THF, CP and PGMEA, respectively.

[Example 2-4] Production example of polymer (F ⁴ ) In a reactor (internal volume 30 mL, glass), compound (f ² ) (0.17 g), compound (r ² ) (1.0 g), compound (Q ¹ ) (0.46 g) and MEK (2.7 g) were charged. Next, an R225 solution containing 50% by mass of IPP (0.65 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ⁴ ) (1.3 g). Got.
The polymer (F ⁴ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ⁴ ) was 4100, and Mw was 7800.
Polymer ^{(F 4)} the ¹³ C-NMR analysis result, the polymer ^{(F 4),} based on the total repeating units, units ^{(F 2)} 4 mol%, the unit ^{(R 2)} 54 mol%, And a polymer containing 42 mol% of the unit (Q ¹ ). Further, the polymer (F ⁴ ) was soluble in THF, CP, and PGMEA, respectively.

[Example 2-5 (reference example)] Production example of polymer (R ¹ ) Compound (r ² ) (10.4 g), compound (q ¹ ) (3. 7g), compound (q ² ) (8.0 g), and MEK (76.5 g) were charged. Next, IPA (6.3 g) was used as a chain transfer agent, and IPP (11.0 g) diluted to 50% by mass with R225 was used as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into hexane to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (R ¹ ) (15.9 g). Got.
The polymer (R ¹ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (R ¹ ) was 2870, and Mw was 6600.
As a result of measurement by ¹³ C-NMR method, the polymer (R ¹ ) was found to have 40 mol% of units (R ² ), 20 mol% of units (Q ¹ ) and units (Q ² ) with respect to all repeating units. Was a polymer containing 40 mol%. Further, the polymer (R ¹ ) was soluble in THF, PGMEA, and CP, respectively.

[Example 3] Evaluation example of resist polymer for immersion lithography (Part 1)
[Example 3-1] Evaluation example of water repellency A solution obtained by dissolving polymer (F ¹ ) (0.9 g) in PGMEA (9.1 g) was further filtered (made of polytetrafluoroethylene, pore size 0. 2 μm) to obtain a resin solution.
A resin solution was spin-coated on a silicon substrate on which an antireflection film (trade name AR26 manufactured by ROHM AHD HAAS Electronic Materials) was formed on the surface. Next, the silicon substrate was heat-treated at 90 ° C. for 90 seconds to form a polymer (F ¹ ) resin thin film (thickness: 200 nm) on the silicon substrate. Subsequently, the static contact angle, the falling angle, and the receding angle of the resin thin film with respect to water were measured.

Further, in place of the polymer ^{(F 1),} except for using the polymer ^{(F 2) ~ (F 4} ) and the ^{(R 1),} respectively it was measured in the same manner. The results are summarized in Table 1.
In addition, the falling angle measured by the sliding method is referred to as a falling angle, and the receding contact angle measured by the sliding method is referred to as a receding angle (the same applies hereinafter). The unit of the static contact angle, the falling angle and the receding angle is an angle (°) (the same applies hereinafter).

[Example 3-2] Formation example of resist pattern Obtained by dissolving polymer (F ¹ ) (1 g) and triphenylsulfonium triflate (0.05 g) as a photoacid generator in PGMEA (10 mL). The solution is filtered through a filter to obtain a photosensitive resist composition containing the polymer (F ¹ ).
The photosensitive resist composition is spin-coated on a silicon substrate having an antireflection film formed on the surface and heat-treated to obtain a silicon substrate on which a resist film formed from the photosensitive resist composition is formed.
Using a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, an immersion exposure test of 90 nm L / S of the silicon substrate (immersion solution: ultrapure water, developer: tetramethylammonium hydroxide aqueous solution). I do. As a result, it can be confirmed from the SEM image that a good pattern is formed on the resist film on the silicon substrate.
As is clear from the above results, the polymer (polymers (F ¹ ) to (F ⁴ )) containing a repeating unit formed by polymerization of the compound (f) is a polymer containing no repeating unit. Compared to a polymer (polymer (R ¹ )), it has a high water repellency, particularly a dynamic water repellency. Therefore, by using the resist polymer for immersion lithography of the present invention, water follows the projection lens moving on the photosensitive resist well, so that the immersion lithography method can be stably performed.

[Example 4] Example of production of resist polymer for immersion lithography (part 2)
[Example 4-1] Production example of polymer (F ⁵ ) In a reactor (made of glass, internal volume 30 mL), compound (f ³ ) (0.36 g), compound (r ² ) (1.0 g), compound (Q ² ) (0.21 g), compound (q ¹ ) (0.55 g) and MEK (5.74 g) were charged. Next, an R225 solution containing 50% by mass of IPP (1.18 g) as a polymerization initiator and IPA (0.27 g) as a chain transfer agent were charged into the reactor. After degassing the atmosphere in the reactor with nitrogen gas, the polymerization reaction was carried out at 40 ° C. for 18 hours while stirring the inside of the reactor.
After the polymerization, the agglomerates obtained by dropping the solution in the reactor into hexane were collected, vacuum-dried at 90 ° C. for 24 hours, and a white powdery amorphous polymer (F ⁵ ) (1.56 g) was obtained.
Mn of the polymer (F ⁵ ) was 3700, and Mw was 8800. ^{From the 13} C-NMR measurement, the polymer (F ⁵ ) has the unit (F ³ ) 12 mol%, the unit (R ² ) 47 mol%, the unit (Q ² ) 30 mol%, and the unit (Q ¹ ). Was confirmed to be a polymer containing 21 mol%. Further, the polymer (F ⁵ ) was soluble in THF, PGMEA, CP, MAK and EL, respectively.

[Example 4-2] Production example of polymer (F ⁶ ) In a reactor (made of glass, internal volume 30 mL), compound (f ⁴ ) (0.38 g), compound (r ² ) (0.80 g), compound (Q ² ) (0.16 g), compound (q ¹ ) (0.45 g) and MEK (4.88 g) were charged. Next, an R225 solution containing 50% by mass of IPP (1.00 g) as a polymerization initiator and IPA (0.23 g) as a chain transfer agent were charged into the reactor. After degassing the atmosphere in the reactor with nitrogen gas, the polymerization reaction was carried out at 40 ° C. for 18 hours while stirring the inside of the reactor. After the polymerization, the agglomerates obtained by dropping the solution in the reactor into hexane were collected, vacuum-dried at 90 ° C. for 24 hours, and a white powdery amorphous polymer (F ⁶ ) (1.03 g) was obtained.
Mn of the polymer (F ⁶ ) was 5500, and Mw was 9800. Further, the polymer (F ⁶ ) was soluble in THF, PGMEA, CP, MAK and EL, respectively.

[Example 5] Evaluation example of resist polymer for immersion lithography (part 2)
[Example 5-1] Evaluation example of water repellency A solution obtained by dissolving the polymer (F ⁵ ) in PGMEA is filtered through a filter to obtain a resin solution containing 9% by mass of the polymer (F ⁵ ). It was.
The resin solution was spin-coated on a silicon substrate having an antireflection film formed on the surface, and then heat-treated to form a polymer (F ⁵ ) resin thin film on the silicon substrate.
Subsequently, the static contact angle, the falling angle, and the receding angle of the resin thin film with respect to water were measured. Further, except for using the polymer in place of the polymer (F ⁵⁾ (F ⁶⁾ was measured in the same manner. The results are summarized in Table 2.

Example 5-2 Formation Example of Resist Pattern Obtained by dissolving polymer (F ⁵ ) (1 g) and triphenylsulfonium triflate (0.05 g) as a photoacid generator in PGMEA (10 mL). The solution is filtered through a filter to obtain a photosensitive resist composition containing the polymer (F ⁵ ).
The photosensitive resist composition is spin-coated on a silicon substrate having an antireflection film formed on the surface and heat-treated to obtain a silicon substrate on which a resist film formed from the photosensitive resist composition is formed.
Using a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, an immersion exposure test of 90 nm L / S of the silicon substrate (immersion solution: ultrapure water, developer: tetramethylammonium hydroxide aqueous solution). I do. As a result, it can be confirmed from the SEM image that a good pattern is formed on the resist film on the silicon substrate.
As is apparent from the above results, it can be seen that by using the resist polymer for immersion lithography of the present invention, a resist film excellent in resist characteristics and water repellency and particularly excellent in dynamic water repellency can be formed. Therefore, in the immersion lithography method, water can easily follow the projection lens that moves on the resist film at a high speed.

[Example 6] Production example of resist composition for immersion lithography (Part 1)
[Example 6-1] Production example of polymer (F ⁷ ) Compound (f ¹ ) (2.5 g) and CF ₃ (CF ₂ ) ₅ H (5) were added to a pressure resistant reactor (internal volume 30 mL, made of glass). .25 g). Next, an R225 solution containing 50% by mass of IPP (1.17 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to collect the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ⁷ ) (2.05 g). Got. The polymer (F ⁷ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ⁷ ) was 2900, and Mw was 6300.

[Example 6-2] Production example of polymer (F ⁸ ) Compound (f ² ) (0.8 g) and CF ₃ (CF ₂ ) ₅ H (1. 06g). Next, an R225 solution containing 50% by mass of IPP (0.28 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ⁸ ) (0.62 g). Got. The polymer (F ⁸ ) was a white powdery amorphous polymer at 25 ° C. Mn of the polymer (F ⁸ ) was 7000, and Mw was 20000.

[Example 6-3] Production example of polymer (F ⁹ ) In the same manner as in Example 6-1, a polymer (F ⁹ ) having an Mw of 9000 consisting of repeating units formed by polymerization of the compound (f ¹ ) was obtained. It was.

[Example 6-4] Production example of polymer (F ¹⁰ ) In the same manner as in Example 6-2, a polymer (F ¹⁰ ) of Mw11300 comprising a repeating unit formed by polymerization of the compound (f ² ) was obtained. It was.

[Example 6-5] Production example of polymer (F ¹¹ ) In a pressure resistant reactor (internal volume 30 mL, glass), compound (f ¹ ) (0.97 g), compound (r ¹ ) (0.42 g), Compound (q ¹ ) (0.34 g) and MEK (4.7 g) were charged. Next, an R225 solution containing 50% by mass of IPP (0.97 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the agglomerated solid, and the solid was vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (F ¹¹ ) (1.22 g). Got. The polymer (F ¹¹ ) was a white powdery amorphous polymer at 25 ° C.
Mn of the polymer (F ¹¹ ) was 3900, and Mw was 8200.
¹⁹ F-NMR and ¹ H-NMR result of the measurement, the polymer ^{(F 11),} based on all repeating units, the units ^{(F 1)} of 33 mol%, units ^{(R 1)} 38 mol%, and units It was a polymer containing 29 mol% of (Q ¹ ). Further, the polymer (F ¹¹ ) was soluble in THF, PGMEA, CP and MAK.

[Example 6-6] Production example of polymer (F ¹² ) In a pressure resistant reactor (internal volume 30 mL, glass), compound (f ¹ ) (1.21 g), compound (r ¹ ) (0.70 g), Compound (q ² ) (0.45 g) and MEK (8.6 g) were charged. Next, an R225 solution containing 50% by mass of IPP (1.65 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ¹² ) (1.30 g). Got. The polymer (F ¹² ) was a white powdery amorphous polymer at 25 ° C.
Mn of the polymer (F ¹² ) was 5000, and Mw was 8800.
¹⁹ F-NMR and ¹ H-NMR result of the measurement, the polymer ^{(F 12),} based on all repeating units, the units ^{(F 1)} of 37 mol%, units ^{(R 1)} 34 mol%, and units It was a polymer containing 29 mol% of (Q ² ). Further, the polymer (F ¹² ) was soluble in THF, PGMEA, CP and MAK.

[Example 6-7] Production example of polymer (F ¹³ ) In a pressure resistant reactor (inner volume 30 mL, glass), compound (f ² ) (1.42 g), compound (r ¹ ) (0.70 g), Compound (q ¹ ) (0.42 g) and MEK (6.9 g) were charged. Next, an R225 solution containing 50% by mass of IPP (1.42 g) was added as a polymerization initiator, and IPA (0.24 g) was added as a chain transfer agent. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum-dried at 90 ° C. for 24 hours to obtain a polymer (F ¹³ ) (1.18 g). Got. The polymer (F ¹³ ) was a white powdery amorphous polymer at 25 ° C.
Mn of the polymer (F ¹³ ) was 3700, and Mw was 7000.
^{As a result of 19} F-NMR and ¹ H-NMR measurements, the polymer (F ¹³ ) was 28 mol% in units (F ² ), 34 mol% in units (R ¹ ), and units with respect to all repeating units. This was a polymer containing 38 mol% of (Q ¹ ). Further, the polymer (F ¹³ ) was soluble in THF, PGMEA, CP and MAK.

[Example 6-8] Production example of polymer (F ¹⁴ ) In a pressure resistant reactor (internal volume 30 mL, glass), compound (f ¹ ) (1.0 g), compound (q ³ ) (0.50 g), Compound (q ¹ ) (0.48 g) and MEK (7.56 g) were charged. Next, an R225 solution containing 50% by mass of IPP (1.01 g) was added as a polymerization initiator. After freezing and degassing the inside of the reactor, a polymerization reaction was carried out at 40 ° C. for 18 hours. After the polymerization reaction, the solution in the reactor was dropped into methanol to recover the aggregated solid, and the solid was vacuum dried at 90 ° C. for 24 hours to obtain a polymer (F ¹⁴ ) (1.64 g). Got. The polymer (F ¹⁴ ) was a white powdery amorphous polymer at 25 ° C.
Mn of the polymer (F ¹⁴ ) was 8400, and Mw was 21600.
^{As a result of 19} F-NMR and ¹ H-NMR measurements, the polymer (F ¹⁴ ) was found to contain 27 mol% of units (F ¹ ), 36 mol% of units (Q ³ ), and units based on all repeating units. It was a polymer containing 37 mol% of (Q ¹ ). Further, the polymer (F ¹⁴ ) was soluble in THF, PGMEA, CP and ethylene glycol, respectively.

Example 6-9 (Comparative Example) Production Example of Polymer (C) In the same manner as in Example 6-2, CH ₂ ═C (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ F A polymer (C) having a Mw of 100,000 consisting of repeating units formed by polymerization was obtained.

Example 6-10 Production Example of Composition (1) 1,3-bis (trifluoromethyl) benzene solution (1.09 g) containing 0.9% by mass of polymer (F ⁷ ), 7.3 A transparent uniform solution was obtained by mixing with a CP solution (2.73 g) containing a polymer (R ¹ ) by mass. The solution was filtered through a filter (made of PTFE) having a pore diameter of 0.2 μm, and a composition (1) containing 5.0% by mass of the polymer (F ⁷ ) with respect to the total amount of the polymer (R ¹ ). )

[Example 6-11] Production example of compositions (2) to (4) A polymer (in the same manner as in [Example 6-10] except that the polymer (F ⁸ ) is used instead of the polymer (F ⁷ ). 5.0 wt% of the polymer based on the total amount of R ^{1) (F 8)} composition comprising a (2), except for using the polymer in place of the polymer ^{(F 7) (F 9)} is example 6-10], the composition (3) containing 5.0% by mass of the polymer (F ⁹ ) with respect to the total amount of the polymer (R ¹ ) is weighted in place of the polymer (F ⁷ ). A composition (4) containing 5.0% by mass of the polymer (F ¹⁰ ) with respect to the total amount of the polymer (R ¹ ) in the same manner as in [Example 6-10] except that the coalescence (F ¹⁰ ) is used. ,Obtained.

[Example 6-12] Production Example of Composition (5) Polymer (F ¹¹ ) (20.0 mg) and PGMEA solution (4.18 g) containing 9.57% by mass of polymer (R ¹ ) Mixing gave a clear and homogeneous solution. The solution was filtered through a filter (made of PTFE) having a pore diameter of 0.2 μm, and a composition (5) containing 5.0% by mass of the polymer (F ¹¹ ) with respect to the total amount of the polymer (R ¹ ). )

[Example 6-13] Production example of compositions (6) to (8) A polymer (in the same manner as in [Example 6-12]) except that the polymer (F ¹² ) is used instead of the polymer (F ¹¹ ). Except that the composition (6) containing 5.0% by mass of the polymer (F ¹² ) with respect to the total amount of R ¹ ) is replaced with the polymer (F ¹³ ) instead of the polymer (F ¹¹ ) [Example 6-12], the composition (7) containing 5.0% by mass of the polymer (F ¹³ ) with respect to the total amount of the polymer (R ¹ ) is weighted in place of the polymer (F ¹¹ ). A composition (8) containing 5.0% by mass of the polymer (F ¹⁴ ) with respect to the total amount of the polymer (R ¹ ) in the same manner as in [Example 6-12] except that the coalesced (F ¹⁴ ) is used. ,Obtained.

[Example 6-14 (Comparative Example)] Production Example of Composition (C) A polymer (C) was prepared in the same manner as in [Example 6-10] except that the polymer (C) was used instead of the polymer (F ⁷ ). A composition (C) containing 5.0% by mass of the polymer (C) with respect to the total amount of R ¹ ) was obtained.

[Example 7] Evaluation example of photosensitive resist composition for immersion lithography (part 1)
[Example 7-1] Water-repellent evaluation example The 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, and further heat-treated at 130 ° C. for 120 seconds to obtain a resin thin film (film thickness 50 nm) containing the polymer (F ⁷ ) and the polymer (R ¹ ). Was formed on a silicon substrate. Subsequently, the static contact angle, dynamic falling angle and dynamic receding angle of the resin thin film with respect to water were measured.
Measurement was performed in the same manner except that the composition (2) to the composition (8) and the composition (C) were used instead of the composition (1). Further, the contact angle, the falling angle, and the receding angle of the resin thin film consisting only of the polymer (R1) were measured. The results are summarized in Table 3.

  As is clear from the above results, the resin thin film formed from the composition containing the polymer (F) and the polymer (R) is composed of a resin thin film formed only from the polymer (R), and a heavy film. Compared to the resin thin film containing the polymer (R) and the polymer (C) having a linear fluoroalkyl group, the water repellency is high and the receding angle is particularly high, so that the dynamic water repellency is excellent.

[Example 7-2] Example of resist pattern formation Polymer (R ¹ ) (1 g), polymer (F ⁷ ) (0.05 g) and triphenylsulfonium triflate (0.05 g) were added to PGMEA (10 mL). When the transparent and uniform solution obtained by dissolving is filtered through a filter (manufactured by PTFE) having a pore size of 0.2 μm, a photosensitive resist composition is obtained.
The photosensitive resist composition 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 and further heat-treated at 130 ° C. for 120 seconds, a silicon substrate on which a resin thin film (thickness 150 nm) of the photosensitive resist composition is formed is obtained.
Using a two-beam interference exposure apparatus (light source: ArF laser light (wavelength: 193 nm)), a 90 nm L / S exposure test of the silicon substrate was performed using an immersion method and a Dry method using ultrapure water as an immersion medium, respectively. Do. After the exposure test, a development process is performed using an alkaline aqueous solution, and when the surface of the silicon substrate is confirmed, it can be confirmed that a good pattern shape is formed.
As is clear from the above results, by using the resist composition for immersion exposure according to the present invention, the liquid medium (water or the like) follows the projection lens moving on the photosensitive resist well. Lithography can be performed stably.

[Example 8] Production example of resist composition for immersion lithography (part 2)
[Example 8-1] Production example of polymer (F ¹⁵ ) Compound (f ³ ) (0.85 g), compound (r ² ) (0.50 g), compound in reactor (glass, internal volume 30 mL) (Q ¹ ) (0.40 g) and MEK (4.75 g) were charged. Next, an R225 solution containing 50% by mass of IPP (0.98 g) as a polymerization initiator was charged. After degassing the atmosphere in the reactor with nitrogen gas, the polymerization reaction was carried out at 40 ° C. for 18 hours while stirring the inside of the reactor.
After the polymerization, the agglomerates obtained by dropping the solution in the reactor into hexane were collected, vacuum-dried at 90 ° C. for 24 hours, and a white powdery amorphous polymer (F ¹⁵ ) (1.17 g).
Mn of the polymer (F ¹⁵ ) was 5100, and Mw was 14300. ^{From 13} C-NMR measurement, the polymer (F ¹⁵ ) is a polymer containing 23 mol% of units (F ³ ), 34 mol% of units (R ² ), and 43 mol% of units (Q ¹ ). confirmed. Further, the polymer (F ¹⁵ ) was soluble in THF, PGMEA, CP, MAK and EL.

[Example 8-2] Production example of polymer (F ¹⁶ ) In a reactor (made of glass, internal volume 30 mL), compound (f ⁴ ) (0.64 g), compound (r ² ) (0.35 g), compound (Q ¹ ) (0.28 g) and methyl isobutyl ketone (4.65 g) were charged. Next, an R225 solution containing 50% by mass of IPP (0.89 g) as a polymerization initiator was charged. After degassing the atmosphere in the reactor with nitrogen gas, the polymerization reaction was carried out at 40 ° C. for 18 hours while stirring the inside of the reactor.
After the polymerization, the agglomerates obtained by dropping the solution in the reactor into hexane were collected, vacuum-dried at 90 ° C. for 24 hours, and a white powdery amorphous polymer (F ¹⁶ ) (0.91 g) was obtained.
Mn of the polymer (F ¹⁶ ) was 6900, and Mw was 13000. ^{From 19} F-NMR and ¹ H-NMR measurements, the polymer (F ¹⁶ ) was a polymer containing 29 mol% of units (F ⁴ ), 34 mol% of units (R ² ), and 37 mol% of units (Q ¹ ). It was confirmed that they were coalesced. Further, the polymer (F ¹⁶ ) was soluble in THF, PGMEA, CP, MAK and EL, respectively.

[Example 8-3] Production Example of Composition (9) As the polymer (R ² ), 40 mol% of the repeating unit of the compound (r ² ), 40 mol% of the repeating unit of the compound (q ¹ ) and the compound ( A polymer (Mw6600, Mn2900) containing 20 mol% of q ² ) repeating units was used.
A transparent uniform resin solution obtained by mixing the polymer (F ¹⁵ ) (20 mg) and the PGMEA solution (4.18 g) containing 9.57% by mass of the polymer (R ² ) is filtered through a filter. Then, a composition (9) containing 5.0% by mass of the polymer (F ¹⁵ ) with respect to the total mass of the polymer (R ² ) was obtained.

[Example 8-4] Production example of composition (10) Polymer (R ² ) was prepared in the same manner as in [Example 8-3] except that polymer (F ¹⁶ ) was used instead of polymer (F ¹⁵ ). A composition (10) containing 5.0% by mass of the polymer (F ¹⁶ ) with respect to the total mass of was obtained.

[Example 9] Evaluation example of resist composition for immersion lithography (part 2)
[Example 9-1] Evaluation example of water repellency The composition (9) is spin-coated on a silicon substrate having an antireflection film formed on the surface, and heat-treated to polymer (R ² ) and polymer (F ¹⁵ ). A resin thin film containing was formed on a silicon substrate. Subsequently, the static contact angle, dynamic falling angle, and dynamic receding angle of the resin thin film with respect to water were measured.
Measurement was carried out in the same manner except that the composition (10) was used instead of the composition (9). The results are summarized in Table 4.

[Example 9-2] Formation example of resist pattern Polymer (R ² ) (1 g), polymer (F ¹⁵ ) (0.05 g) and photoacid generator triphenylsulfonium triflate (0.05 g) The solution obtained by dissolving in PGMEA (10 mL) was filtered through a filter to obtain a resist forming composition (1) containing a polymer (R ² ) and a polymer (F ¹⁵ ).
The photosensitive resist composition is spin-coated on a silicon substrate having an antireflection film formed on the surface and heat-treated to obtain a silicon substrate on which a resist film formed from the photosensitive resist composition is formed.
Using a two-beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, an immersion exposure test of 90 nm L / S of the silicon substrate (immersion solution: ultrapure water, developer: tetramethylammonium hydroxide aqueous solution). I do. As a result, it can be confirmed from the SEM image that a good pattern is formed on the resist film on the silicon substrate.

[Example 9-3] Example of evaluation of elution amount of photoacid generator (PAG) in resist-forming composition A resist-forming composition (1) is spin-coated on a silicon substrate having an antireflection film formed on the surface, and silicon The substrate was heat-treated at 100 ° C. for 90 seconds to form a resin thin film (thickness 150 nm) composed of the polymer (R ² ) and the polymer (F ¹⁵ ) 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. Left for a second. 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 ultrapure water was obtained using an LC / MS / MS analyzer (Quattro micro API, manufactured by Waters) (detection limit: 7.0 × 10 ⁻¹⁵ mol / cm ² ). Cation (triphenylsulfonium cation) elution amount and anion (phenylsulfonium triflate) elution amount, which are derived from the photoacid generator (PAG) eluted from the resist-forming composition (1) contained in the amount of the unit: mol / ^cm 2/60 seconds)..
Further, instead of the polymer (F ¹⁵ ) in the resist forming composition (1), the resist forming composition (2) manufactured using the polymer (F ¹¹ ) and the polymer (F ¹³ ) are used. The same measurement was performed using the resist-forming composition (3). Further, as a comparative example, the same measurement was performed using a resist forming composition (C) produced using only the polymer (R ¹ ).
The results are summarized in Table 5.

  As is clear from the above results, it can be seen that by using the resist composition for immersion lithography of the present invention, a resist film having excellent resist characteristics and water repellency and particularly excellent in dynamic water repellency can be formed. Therefore, in the immersion lithography method, water can easily follow the projection lens that moves on the resist film at a high speed.

According to the present invention, there is provided a resist material for immersion lithography that is excellent in resist characteristics and particularly excellent in dynamic water repellency. By using the resist material for immersion lithography of the present invention, it is possible to perform stable and high-speed execution of the immersion lithography method capable of transferring a mask pattern image to a high resolution.

Japanese Patent Application No. 2006-110971 filed on April 13, 2006, Japanese Patent Application No. 2006-132407 filed on May 11, 2006, Japanese Patent Application filed on June 27, 2006 The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2006-176881 and Japanese Patent Application No. 2006-207392 filed on July 31, 2006 are incorporated herein by reference. It is incorporated as a disclosure.

Claims (16)

A polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and the alkali solubility is increased by the action of an acid; Resist material for immersion lithography. The polymerizable compound (f ^m ) is one or more compounds (f) selected from the group consisting of compounds represented by the following formula (f1), the following formula (f2), the following formula (f3), and the following formula (f4). The resist material for immersion lithography according to claim 1.

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.
X ^F : fluorine atom, hydroxy group or hydroxymethyl group.
Moreover, the fluorine atom in a compound (f) may be substituted by the C1-C6 perfluoroalkyl group or C1-C6 perfluoroalkoxy group. A repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and a polymerizable compound (r ^m ) having a group whose alkali solubility is increased by the action of an acid A resist polymer for immersion lithography, comprising a repeating unit (R ^U ) formed by polymerization and having increased alkali solubility by the action of an acid. The polymerizable compound (f ^m ) is one or more compounds (f) selected from the group consisting of compounds represented by the following formula (f1), the following formula (f2), the following formula (f3), and the following formula (f4). The resist polymer for immersion lithography according to claim 3.

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 X ^F : A fluorine atom, a hydroxy group or a hydroxymethyl group.
Moreover, the fluorine atom in a compound (f) may be substituted by the C1-C6 perfluoroalkyl group or C1-C6 perfluoroalkoxy group. The polymerizable compound (r ^m ) is a polymerizable compound having a group represented by the following formula (ur1), the following formula (ur2), the following formula (ur3), or the following formula (ur4): The resist polymer for immersion lithography as described.

The symbols in the formula have the following meanings.
X ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it. The polymerizable compound (r ^m ) is one or more compounds (r) selected from the group consisting of compounds represented by the following formula (r1), the following formula (r2) and the following formula (r3): 6. The resist polymer for immersion lithography according to any one of 5 above.

The symbols in the formula have the following meanings.
R ^R : 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 ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Q ^R3: the formula ^{_{-CF 2 C (CF 3) (}} OZ R4) (CH 2) m - , a group represented by formula _{-CH 2 CH ((CH 2)} n C (CF 3) 2 (OZ R3)) _{(CH 2) m} -, a group represented by or formula ^{_{-CH 2 CH (C (O)}} OZ R3) (CH 2) m - group represented by the.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it. The immersion lithography according to any one of claims 3 to 6, which is a polymer containing 1 to 45 mol% of repeating units (F ^U ) and 10 mol% or more of repeating units (R ^U ) with respect to all repeating units. Resist polymer.   A resist forming composition for immersion lithography comprising the resist polymer for immersion lithography according to claim 3, a photoacid generator, and an organic solvent.   A method for forming a resist pattern by an immersion lithography method, the step of applying a resist forming composition for immersion lithography according to claim 8 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. A polymer (F) containing a repeating unit (F ^U ) formed by polymerization of a polymerizable compound (f ^m ) having a fluorine-containing bridged ring structure, and a polymerizable compound (alkali solubility increased by the action of an acid ( and a polymer (R) containing a repeating unit (R ^U ) formed by polymerization of r ^m ), and a resist composition for immersion lithography having increased alkali solubility by the action of an acid. The polymerizable compound (f ^m ) is one or more compounds (f) selected from the group consisting of compounds represented by the following formula (f1), the following formula (f2), the following formula (f3), and the following formula (f4). The resist composition for immersion lithography according to claim 10.

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 X ^F : A fluorine atom, a hydroxy group or a hydroxymethyl group.
Moreover, the fluorine atom in a compound (f) may be substituted by the C1-C6 perfluoroalkyl group or C1-C6 perfluoroalkoxy group. The polymerizable compound (r ^m ) is a polymerizable compound having a group represented by the following formula (ur1), the following formula (ur2), the following formula (ur3), or the following formula (ur4): The resist composition for immersion lithography as described.

The symbols in the formula have the following meanings.
X ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it. The polymerizable compound (r ^m ) is one or more compounds (r) selected from the group consisting of compounds represented by the following formula (r1), the following formula (r2), and the following formula (r3): 12. The resist composition for immersion lithography according to any one of 12 above.

The symbols in the formula have the following meanings.
R ^R : 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 ^R1 : an alkyl group having 1 to 6 carbon atoms.
Q ^R1 : a divalent group having 4 to 20 carbon atoms that forms a cyclic hydrocarbon group in combination with a carbon atom in the formula.
X ^{R2 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, and three X ^R2 groups may be the same or different.
Q ^R3: the formula ^{_{-CF 2 C (CF 3) (}} OZ R4) (CH 2) m - , a group represented by formula _{-CH 2 CH ((CH 2)} n C (CF 3) 2 (OZ R3)) _{(CH 2) m} -, a group represented by or formula ^{_{-CH 2 CH (C (O)}} OZ R3) (CH 2) m - group represented by the.
Z ^R3 and Z ^R4 : each independently an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group, and a group having 1 to 20 carbon atoms.
^{Further, X R1, Q R1, X} R2, the carbon atoms in ^{Z R3} or ^{Z R4} - group between the carbon atoms of the formula -O-, a group represented by the formula -C (O) O-or A group represented by the formula -C (O)-may be inserted, and a fluorine atom, a hydroxy group or a carboxy group is bonded to a carbon atom in X ^R1 , ^{QR 1} , X ^R2 , Z ^R3 or Z ^R4. You may do it.   The resist composition for immersion lithography according to any one of claims 10 to 13, comprising 0.1 to 30% by mass of the polymer (F) with respect to the polymer (R).   The resist formation composition for immersion lithography containing the resist composition for immersion lithography in any one of Claims 10-14, a photo-acid generator, and an organic solvent.   A resist pattern forming method using an immersion lithography method, the step of applying the resist forming composition for immersion lithography according to claim 15 on a substrate to form a resist film on the substrate, an immersion lithography step, and a developing step The resist pattern formation method which forms a resist pattern on a board | substrate which performs this in this order.