JP5965971B2 - Pattern formation method - Google Patents

Description

  The present invention relates to a pattern forming method used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes, and multiple development used in the pattern forming method. The present invention relates to a positive resist composition, a negative developing developer used in the pattern forming method, and a negative developing rinse used in the pattern forming method. Particularly, a pattern forming method suitable for exposure with an ArF exposure apparatus and an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a positive resist composition for multiple development used in the pattern forming method The present invention relates to a negative developing solution used in the pattern forming method and a negative developing rinse solution used in the pattern forming method.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. When exposed, the acid generator in the exposed area decomposes to generate an acid, and the acid generated in the exposure bake (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

With the miniaturization of semiconductor elements, the wavelength of an exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. These can be expressed by the following equations as is generally well known.
(Resolving power) = k ₁ · (λ / NA)
(Depth of focus) = ± k ₂ · λ / NA ²
Where λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

As a technique for increasing the resolving power, a so-called immersion method in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between the projection lens and the sample has been proposed.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The above-described resolving power and depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

Further, as a technique for further increasing the resolution, a double exposure technology and a double patterning technology have been proposed. This is to reduce k ₁ in the above-described resolving power formula, and is positioned as a technique for increasing the resolving power.

Conventionally, pattern formation of an electronic device such as a semiconductor element is performed by reducing and transferring a mask or reticle pattern, which is 4-5 times the size of the pattern to be formed, to an object to be exposed such as a wafer using a reduction projection exposure apparatus. It was.
However, with the miniaturization of dimensions, the conventional exposure method has a problem in that the light irradiated to adjacent patterns interferes with each other and the optical contrast is reduced. The design is divided into two or more, each mask is exposed independently, and an image is synthesized. In these double exposure methods, it is necessary to divide the design of the exposure mask, re-synthesize the image on the object to be exposed (wafer), and the pattern on the reticle faithfully adheres to the object to be exposed. It is necessary to devise the division of the mask design so that it can be reproduced.
An example in which the effect of these double exposure methods is studied for transferring a fine image pattern of a semiconductor element is introduced in Patent Document 1 and the like.
Recent double exposure technology progress is reported in Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3, and the like.

However, if the conventional resist composition is simply applied to the conventional resist process for pattern formation, these double exposure methods require pattern formation near the resolution limit of the resist. The problem is that a large exposure margin and depth of focus cannot be obtained.
That is, a pattern forming process in which a positive resist composition is applied to a substrate, exposure, and development with an alkaline developer as introduced in Patent Document 2 or the like, or a negative as in Patent Document 3 or the like is introduced. If the pattern formation process in which the resist composition is applied to a substrate, exposed, and developed with an alkaline developer is applied to the double exposure process, sufficient resolution performance cannot be obtained.

Currently, as a developer for g-line, I-line, KrF, ArF, EB, EUV lithography, 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous alkaline developer is used as a positive resist developer and a negative type developer. Used as a resist developer.
As a developer other than the above, for example, Patent Document 4 discloses an aliphatic linear ether series for developing a resist material containing a copolymer of a styrene monomer and an acrylic monomer. A positive resist developer containing a solvent or an aromatic ether solvent and a ketone solvent having 5 or more carbon atoms is described. Patent Document 5 discloses an acetic acid group, a ketone group, an ether group, and a phenyl group for a resist material that dissolves in a solvent by cutting a polymer chain and reducing the molecular weight by irradiation with radiation. A positive resist developer characterized by having at least two and having a molecular weight of 150 or more is described. Patent Document 6 discloses that a negative photoresist mainly composed of a photosensitive polyhydroxy ether resin obtained by a reaction between a polyhydroxy ether resin and glycidyl (meth) acrylate is used to develop a negative photoresist having 6 to 6 carbon atoms. A negative photoresist developer characterized by using as a developer a mixed solvent containing 12 aromatic compounds or 50 mass% or more of an aromatic compound having 6 to 12 carbon atoms is described.
Patent Document 7 describes a positive resist developer containing an organic solvent, particularly a halogenated organic solvent, for developing a resist composition containing a specific resin containing fluorine. Yes. Further, Patent Document 8 is selected from the group consisting of propylene glycol methyl ether acetate, cyclohexanone, butyrolactate, and ethyl lactate for developing a negative photoresist composition containing a specific polycyclic olefin polymer. Negative resist developers containing one or more solvents are described.
Patent Document 9 discloses a method of improving the resolution by a factor of 2 using a normal positive resist.
However, in the combination of the resist composition and the developer described above, a specific resist composition is combined with either a positive developer or a negative developer to provide a system for pattern formation. I'm just there.
That is, as shown in FIG. 1, in a positive system (combination of a resist composition and a positive developer), a region having a high light irradiation intensity in an optical aerial image (light intensity distribution) is selectively dissolved and dissolved. Only the material to be removed and patterned is provided. On the other hand, the negative system (resist composition and negative developer) only provides a material system that selectively dissolves and removes areas with low light irradiation intensity to form a pattern. .

JP 2006-156422 A Japanese Patent Laid-Open No. 2001-109154 JP 2003-76019 A JP 2001-215731 A JP 2006-227174 A Japanese Patent Laid-Open No. 6-194847 Special Table 2002-525683 Special Table 2006-518779 Japanese Unexamined Patent Publication No. 2000-199953

SPIE Proc 5754,1508 (2005) SPIE Proc 5377,1315 (2004) SPIE Proc 61531K-1 (2006)

  SUMMARY OF THE INVENTION An object of the present invention is to provide a method for stably forming a highly accurate fine pattern in order to solve the above-described problems and to manufacture a highly integrated and highly accurate electronic device.

＜２＞
上記＜１＞に記載のパターン形成方法（但し、主鎖の少なくとも一部にビニルアルコール系化合物を重合して得られる骨格を含み、該骨格の水酸基の少なくとも一部が酸脱離性保護基で保護されている物質と、光酸発生剤とを含有することを特徴とする感光性組成物を用いて被露光材上にネガ・パターン形成を行う際に、アルコール又はケトン類で現像を行うことを特徴とするパターン形成方法を除く）。
＜３＞
前記樹脂組成物が、前記活性光線又は放射線の照射、及び、前記活性光線又は放射線の照射後の加熱により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物であり、
露光後に前記レジスト膜を加熱し、
前記現像する工程において、加熱後の前記レジスト膜を現像する、上記＜１＞又は＜２＞に記載のパターン形成方法。
＜４＞
前記ネガ型現像液における有機溶剤が、エステル系溶剤である、上記＜１＞〜＜３＞のいずれか１項に記載のパターン形成方法。
＜５＞
酸の作用によりアルカリ現像液であるポジ型現像液に対する溶解度が増大し、有機溶剤を含有するネガ型現像液に対する溶解度が減少する樹脂（但し、下記一般式（Ｉ）の三元重合体を除く）を含有し、活性光線又は放射線の照射により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物（但し、含有する水酸基の１０％、１５％〜２５％、又は、３０％を、下記式Ｉのターシャルブチルオキシカルボニルオキシ基で置換されたポリヒドロキシスチレンから成る樹脂成分１００重量部および露光により酸を発生する酸発生剤１〜３０重量部を含んでなるレジスト組成物を除く）を、基板上に塗布することで、レジスト膜を形成し、
前記レジスト膜をＥＵＶ光により露光し、
露光後のレジスト膜を現像する工程を
含むパターン形成方法であって、
前記現像する工程が、有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程を含み、
前記現像する工程が、前記有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程のみからなり、
前記パターン形成方法が、前記ネガ型現像液を用いて現像する工程の後に、有機溶剤を含むリンス液を用いて洗浄する工程を含み、
前記リンス液における有機溶剤が炭化水素系溶剤である、パターン形成方法。

［上式において、ｎは５ないし１０００の正の整数、Ｒ^１，Ｒ^２およびＲ^３は夫々独立して水素原子またはメチル基を表わし、Ｒ^４はトリシクロデカニル基、ジシクロペンテニル基、ジシクロペンテニルオキシエチル基、シクロヘキシル基、ノルボニル基、ノルボルナンエポキシ基、ノルボルナンエポキシメチル基、あるいはアダマンチル基、Ｒ^５はテトラヒドロピラニル基、テトラヒドロフラニル基、メチル基、エチル基、プロピル基、ｔｅｒｔ−ブチル基、あるいは３−オキソシクロヘキシル基、ｘ＋ｙ＋ｚ＝１、ｘは０．１ないし０．９、ｙは０．１ないし０．７、ｚは０．０１ないし０．７を表す。］
式Ｉ：

＜６＞
＜５＞に記載のパターン形成方法（但し、主鎖の少なくとも一部にビニルアルコール系化合物を重合して得られる骨格を含み、該骨格の水酸基の少なくとも一部が酸脱離性保護基で保護されている物質と、光酸発生剤とを含有することを特徴とする感光性組成物を用いて被露光材上にネガ・パターン形成を行う際に、アルコール又はケトン類で現像を行うことを特徴とするパターン形成方法を除く）。
＜７＞
前記樹脂組成物が、前記活性光線又は放射線の照射、及び、前記活性光線又は放射線の照射後の加熱により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物であり、
露光後に前記レジスト膜を加熱し、
前記現像する工程において、加熱後の前記レジスト膜を現像する、上記＜５＞又は＜６＞に記載のパターン形成方法。
＜８＞
前記ネガ型現像液における有機溶剤が、エステル系溶剤である、上記＜５＞〜＜７＞のいずれか１項に記載のパターン形成方法。
＜９＞
酸の作用によりアルカリ現像液であるポジ型現像液に対する溶解度が増大し、有機溶剤を含有するネガ型現像液に対する溶解度が減少する樹脂を含有し、活性光線又は放射線の照射により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物（但し、含有する水酸基の１０％、１５％〜２５％、又は、３０％を、下記式Ｉのターシャルブチルオキシカルボニルオキシ基で置換されたポリヒドロキシスチレンから成る樹脂成分１００重量部および露光により酸を発生する酸発生剤１〜３０重量部を含んでなるレジスト組成物を除く）を、基板上に塗布することで、レジスト膜を形成し、
前記レジスト膜をＥＵＶ光により露光し、
露光後のレジスト膜を現像する工程を
含むパターン形成方法であって、
前記現像する工程が、有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程を含み、
前記現像する工程が、前記有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程のみからなり、
前記パターン形成方法が、前記ネガ型現像液を用いて現像する工程の後に、有機溶剤を含むリンス液を用いて洗浄する工程を含み、
前記リンス液における有機溶剤が炭化水素系溶剤であり、
前記樹脂組成物が、下記一般式（ＺＩ）で表される化合物（ＺＩ−１）を含有する、パターン形成方法。
式Ｉ：

上記一般式（ＺＩ）において、Ｒ_２０１、Ｒ_２０２及びＲ_２０３は、各々独立に有機基を表す。Ｒ_２０１〜Ｒ_２０３のうち２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、カルボニル基を含んでいてもよい。但し、Ｒ_２０１〜Ｒ_２０３の少なくとも１つがアリール基である。
Ｘ⁻は、非求核性アニオンを表す。
＜１０＞
＜９＞に記載のパターン形成方法（但し、主鎖の少なくとも一部にビニルアルコール系化合物を重合して得られる骨格を含み、該骨格の水酸基の少なくとも一部が酸脱離性保護基で保護されている物質と、光酸発生剤とを含有することを特徴とする感光性組成物を用いて被露光材上にネガ・パターン形成を行う際に、アルコール又はケトン類で現像を行うことを特徴とするパターン形成方法を除く）。
＜１１＞
前記樹脂組成物が、前記活性光線又は放射線の照射、及び、前記活性光線又は放射線の照射後の加熱により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物であり、
露光後に前記レジスト膜を加熱し、
前記現像する工程において、加熱後の前記レジスト膜を現像する、上記＜９＞又は＜１０＞に記載のパターン形成方法。
＜１２＞
前記ネガ型現像液における有機溶剤が、エステル系溶剤である、上記＜９＞〜＜１１＞のいずれか１項に記載のパターン形成方法。
＜１３＞
酸の作用によりアルカリ現像液であるポジ型現像液に対する溶解度が増大し、有機溶剤を含有するネガ型現像液に対する溶解度が減少する樹脂を含有し、活性光線又は放射線の照射により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物（但し、含有する水酸基の１０％、１５％〜２５％、又は、３０％を、下記式Ｉのターシャルブチルオキシカルボニルオキシ基で置換されたポリヒドロキシスチレンから成る樹脂成分１００重量部および露光により酸を発生する酸発生剤１〜３０重量部を含んでなるレジスト組成物を除く）を、基板上に塗布することで、レジスト膜を形成し、
前記レジスト膜をＥＵＶ光により露光し、
露光後のレジスト膜を現像する工程を
含むパターン形成方法であって、
前記現像する工程が、有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程を含み、
前記現像する工程が、前記有機溶剤を含有するネガ型現像液を用いてネガ型現像する工程のみからなり、
前記パターン形成方法が、前記ネガ型現像液を用いて現像する工程の後に、有機溶剤を含むリンス液を用いて洗浄する工程を含み、
前記リンス液における有機溶剤が炭化水素系溶剤であり、
前記樹脂組成物が、下記式（Ａ）〜（Ｅ）のいずれかで示される構造を有する化合物を含有する、パターン形成方法。
式Ｉ：

一般式（Ａ）及び（Ｅ）中、
Ｒ^２００、Ｒ^２０１及びＲ^２０２は、同一でも異なってもよく、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、ここで、Ｒ^２０１とＲ^２０２は、互いに結合して環を形成してもよい。
Ｒ^２０３、Ｒ^２０４、Ｒ^２０５及びＲ^２０６は、同一でも異なってもよく、炭素数１〜２０個のアルキル基を表す。
＜１４＞
上記＜１３＞に記載のパターン形成方法（但し、主鎖の少なくとも一部にビニルアルコール系化合物を重合して得られる骨格を含み、該骨格の水酸基の少なくとも一部が酸脱離性保護基で保護されている物質と、光酸発生剤とを含有することを特徴とする感光性組成物を用いて被露光材上にネガ・パターン形成を行う際に、アルコール又はケトン類で現像を行うことを特徴とするパターン形成方法を除く）。
＜１５＞
前記樹脂組成物が、前記活性光線又は放射線の照射、及び、前記活性光線又は放射線の照射後の加熱により、前記ポジ型現像液に対する溶解度が増大し、前記ネガ型現像液に対する溶解度が減少するレジスト膜を形成する樹脂組成物であり、
露光後に前記レジスト膜を加熱し、
前記現像する工程において、加熱後の前記レジスト膜を現像する、上記＜１３＞又は＜１４＞に記載のパターン形成方法。
＜１６＞
前記ネガ型現像液における有機溶剤が、エステル系溶剤である、上記＜１３＞〜＜１５＞のいずれか１項に記載のパターン形成方法。
尚、本発明は、上記＜１＞〜＜１６＞に係る発明であるが、以下、その他についても参考のため記載した。
The present invention has the following configuration, whereby the above object of the present invention is achieved.
<1>
It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The pattern formation method whose organic solvent in the said rinse liquid is a hydrocarbon type solvent (however, except n-hexane).
Formula I:

<2>
The pattern forming method according to <1> above (provided that at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is an acid-eliminating protecting group. When a negative pattern is formed on an exposed material using a photosensitive composition containing a protected substance and a photoacid generator, development is performed with an alcohol or a ketone. Except for a pattern forming method characterized by
<3>
Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to <1> or <2>, wherein the resist film after heating is developed in the developing step.
<4>
The pattern forming method according to any one of <1> to <3>, wherein the organic solvent in the negative developer is an ester solvent.
<5>
Resin (excluding terpolymers represented by the following general formula (I) below) whose solubility in a positive developer, which is an alkaline developer, increases due to the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. ), And increases the solubility in the positive developer by irradiation with actinic rays or radiation, and forms a resist film in which the solubility in the negative developer decreases (however, 10 of the hydroxyl groups contained) %, 15% to 25%, or 30% of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of the following formula I and an acid generator 1 that generates an acid upon exposure: A resist film is formed by applying on a substrate except a resist composition comprising ˜30 parts by weight ,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The pattern formation method whose organic solvent in the said rinse liquid is a hydrocarbon type solvent.

[In the above formula, n is a positive integer of 5 to 1000, R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, R ⁴ represents a tricyclodecanyl group, a dicyclopentenyl group, dicyclopentenyl oxyethyl group, a cyclohexyl group, a norbornyl group, norbornane epoxy group, norbornane epoxy methyl group or an adamantyl group,, R ⁵ is a tetrahydropyranyl group, tetrahydrofuranyl group, a methyl group, an ethyl group, a propyl group, tert- butyl Group, or 3-oxocyclohexyl group, x + y + z = 1, x is 0.1 to 0.9, y is 0.1 to 0.7, and z is 0.01 to 0.7. ]
Formula I:

<6>
<5> The pattern formation method according to the above (provided that at least a part of the main chain contains a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is protected with an acid-eliminating protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method).
<7>
Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to <5> or <6>, wherein the resist film after heating is developed in the developing step.
<8>
The pattern forming method according to any one of <5> to <7>, wherein the organic solvent in the negative developer is an ester solvent.
<9>
It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The organic solvent in the rinse liquid is a hydrocarbon solvent,
The pattern formation method in which the said resin composition contains the compound (ZI-1) represented by the following general formula (ZI).
Formula I:

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. However, at least one of R _{201 to} R ₂₀₃ is an aryl group.
X ⁻ represents a non-nucleophilic anion.
<10>
<9> The pattern forming method according to the above (however, at least a part of the main chain contains a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is protected with an acid-eliminating protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method).
<11>
Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to <9> or <10>, wherein the resist film after heating is developed in the developing step.
<12>
The pattern forming method according to any one of <9> to <11>, wherein the organic solvent in the negative developer is an ester solvent.
<13>
It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The organic solvent in the rinse liquid is a hydrocarbon solvent,
The pattern formation method in which the said resin composition contains the compound which has a structure shown by either of following formula (A)-(E).
Formula I:

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, wherein R ²⁰¹ and R ²⁰² are bonded to each other to form a ring. May be.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
<14>
The pattern forming method according to <13> above (provided that at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is an acid-eliminating protecting group. When a negative pattern is formed on an exposed material using a photosensitive composition containing a protected substance and a photoacid generator, development is performed with an alcohol or a ketone. Except for a pattern forming method characterized by
<15>
Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to <13> or <14>, wherein the resist film after heating is developed in the developing step.
<16>
The pattern forming method according to any one of <13> to <15>, wherein the organic solvent in the negative developer is an ester solvent.
In addition, although this invention is invention which concerns on said <1>-<16>, below, it described for reference also.

(1) (a) A step of applying a positive resist composition on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation;
(A) An exposure step, and (d) a pattern forming method comprising a step of developing using a negative developer.

(2) The pattern forming method as described in (1), further comprising (c) a step of developing using a positive developer.

(3) (a) A step of applying a positive resist composition on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation.
(A) exposure process,
(D) A pattern forming method comprising: developing with a negative developer; and (c) developing with a positive developer in this order.

  (4) Further, (b) After the exposure step, (e) a heating (also referred to as a bake or PEB (post exposure bake)) step is included, according to any one of (1) to (3) Pattern forming method.

  (5) (a) The pattern forming method according to any one of (1) to (4), wherein the exposure step is performed a plurality of times.

  (6) The pattern forming method as described in (4) or (5), wherein (e) the step of heating (also referred to as baking or PEB (post exposure bake)) is performed a plurality of times.

(7) (a) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. ,
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(C) developing with a positive developer,
(I-2) Second exposure step,
(E-2) a pattern forming method comprising a second heating (also referred to as PEB (post exposure bake)) step, and (d) a step of developing with a negative developer in this order. .

(8) (a) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. ,
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(D) developing with a negative developer,
(I-2) Second exposure step,
(E-2) a second heating (also called bake, PEB (post exposure bake)) step, and (c) a step of developing using a positive developer,
The pattern formation method characterized by including these in this order.

  (9) A positive resist composition for multiple development that has an alicyclic hydrocarbon structure in which the solubility in a positive developer increases and the solubility in a negative developer decreases by irradiation with actinic rays or radiation. The pattern forming method as described in (7) or (8) above, which contains a resin whose solubility in an alkali developing solution is increased by the action of an acid and whose solubility in an organic solvent is reduced.

  (10) (D) Development in which the step of developing with a negative developer contains at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents The pattern forming method according to any one of (1) to (9), which is a step performed using a liquid.

  (11) (d) The step of developing using a negative developer is a step of developing using a developer containing a solvent represented by the following general formula (1) (1 ) To (10).

In general formula (1),
R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may be bonded to each other to form a ring.

  (12) (D) The step of developing using a negative developer is a step of developing using a developer containing a solvent represented by the following general formula (2) (1) ) To (11).

In general formula (2),
R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R ″ and R ″ ″ may be bonded to each other to form a ring.
R ′ ″ represents an alkylene group or a cycloalkylene group.

  (13) The pattern formation according to any one of (1) to (11), wherein the step of developing using a negative developer is a step of using a developer containing butyl acetate. Method.

  (14) (c) The step of developing using positive development is a step of selectively dissolving and removing a film having an exposure amount equal to or greater than a predetermined threshold (a), and (d) using a negative developer. The pattern forming method according to any one of (2) to (13), wherein the developing step is a step of selectively dissolving and removing a film having an exposure amount equal to or less than a predetermined threshold (b) .

  (15) Further, (d) after the step of developing with a negative developer, (f) a step of washing with a rinsing solution containing an organic solvent is included (1) to (14) The pattern formation method in any one of.

  (16) A resin containing (a) a side chain that decomposes to increase solubility in an alkali developer and decrease solubility in an organic solvent, (b) a photoacid generator, and (c) a solvent. And a positive resist composition for multiple development.

  (17) Negative development for use in a positive resist composition comprising at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents liquid.

  (18) A positive resist composition comprising at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. Rinse solution for negative development used in products.

  The preferred embodiments of the present invention will be further described below.

  (19) The pattern forming method as described in (14), wherein threshold value (a)> threshold value (b).

(20) (A-1) Exposure amount in the first exposure step (Eo1 [mJ / cm ² ]) and (A-2) Exposure amount in the second exposure step (Eo2 [mJ / cm ² ]. ² ]) satisfies the following equation: (7) or (8).
Eo1 <Eo2-5

  (21) The rinsing liquid containing an organic solvent contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. The pattern forming method as described in (15), which is characterized in that

(22) The pattern forming method as described in any one of (1) to (15) and (19) to (21), wherein the positive resist composition contains the following components.
(A) a resin whose solubility in an alkaline developer is increased by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.

  (23) The pattern forming method as described in (22), wherein the component (A) of the positive resist composition has an alicyclic hydrocarbon structure.

  (24) The pattern forming method as described in (22) or (23), wherein the weight average molecular weight of the component (A) of the positive resist composition is 1,000 to 100,000.

  (25) The pattern forming method as described in any one of (22) to (24), wherein the (A) component of the positive resist composition is a (meth) acrylic resin having a lactone structure.

  (26) The pattern forming method according to any one of (22) to (25), wherein the positive resist composition further contains a basic compound.

  (27) The pattern forming method as described in any one of (22) to (26) above, wherein the positive resist composition further contains a fluorine-based and / or silicon-based surfactant.

  (28) The pattern forming method as described in any one of (22) to (27), wherein the positive resist composition further contains a resin having at least one of a fluorine atom and a silicon atom.

  (29) The rinse liquid containing an organic solvent contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents ( The pattern formation method as described in 15) or (21).

  (30) The rinsing liquid containing an organic solvent contains at least one organic solvent selected from alcohol solvents and ester solvents, (15), (21) or (29) Pattern forming method.

  (31) The pattern according to any one of (15), (21), (29) and (30), wherein the rinse liquid containing an organic solvent contains a monohydric alcohol having 1 to 8 carbon atoms. Forming method.

(32) (a) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. ,
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(C) developing with a positive developer,
(I-2) Second exposure step,
(E-2) Second heating (also called bake, PEB (post exposure bake)) step,
(D) a step of developing with a negative developer, and (f) a step of washing with a rinse solution containing an organic solvent,
The pattern formation method characterized by including these in this order.

(33) (a) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. ,
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(D) developing with a negative developer,
(F) a step of washing with a rinse solution containing an organic solvent,
(I-2) Second exposure step,
(E-2) a second heating (also called bake, PEB (post exposure bake)) step and (c) a step of developing using a positive developer,
The pattern formation method characterized by including these in this order.

  (34) The pattern forming method as described in any one of (1) to (15) and (19) to (33), wherein exposure is performed using a wavelength of 200 nm or less.

  (35) The pattern forming method as described in any one of (1) to (15) and (19) to (34), wherein exposure is performed at a wavelength of 193 nm.

  (36) The pattern forming method as described in any one of (1) to (15) and (19) to (35), wherein immersion exposure is performed at a wavelength of 193 nm.

  (37) In any one of (2) to (15) and (19) to (36), the step of developing using a positive developer is a step of using an alkali developer. The pattern formation method as described.

  (38) The temperature in the first heating (bake, also referred to as PEB (post exposure bake)) step (e-1) is the same as that in the second heating (also referred to as bake, PEB (post exposure bake)) step ( -The method for forming a pattern according to (7) or (8), wherein the temperature is higher than that in (2).

  (39) The multiple development positive resist composition as described in (16), wherein the component (a) is a resin having an alicyclic hydrocarbon structure.

  (40) The positive resist composition for multiple development according to (16) or (39), wherein the component (a) is an acrylic resin and / or a methacrylic resin having an alicyclic hydrocarbon structure object.

  (41) The multiple development positive resist according to any one of (16), (39) and (40), wherein the weight average molecular weight of the component (a) is 1,000 to 100,000 Composition.

  (42) The positive resist composition for multiple development according to any one of (16) and (39) to (41), wherein the component (a) is a (meth) acrylic resin having a lactone structure object.

  (43) The positive resist composition for multiple development according to any one of (16) and (39) to (42), further comprising a basic compound.

  (44) The positive resist composition for multiple development according to any one of (16) and (39) to (43), further comprising a fluorine-based and / or silicon-based surfactant.

  (45) The positive resist composition for multiple development according to any one of (16) and (39) to (44), further comprising a resin having at least one of a fluorine atom and a silicon atom .

  (46) A negative developing solution for use in a positive resist composition as described in (17), which contains a solvent represented by the following general formula (1).

In general formula (1),
R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may be bonded to each other to form a ring.

  (47) A negative developing solution used for a positive resist composition as described in (17) or (46), which contains a solvent represented by the following general formula (2).

In general formula (2),
R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R ″ and R ″ ″ may be bonded to each other to form a ring.
R ′ ″ represents an alkylene group or a cycloalkylene group.

  (48) A negative developing solution for use in a positive resist composition as described in any of (17) and (46), which contains butyl acetate.

  (49) The negative developing developer as described in any one of (17) and (46) to (48), which comprises two or more kinds of solvents.

  (50) The positive type according to (18), which contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents. A rinsing solution for negative development used in a resist composition.

  (51) A negative developing rinse for use in a positive resist composition as described in (17) or (50), which comprises an alcohol solvent or an ester solvent.

  (52) A negative developing rinse solution for use in the positive resist composition as described in any one of (17), (50) and (51), which contains a monohydric alcohol having 6 to 8 carbon atoms.

  (53) The rinsing solution for negative development according to any one of (17) and (50) to (52), comprising two or more kinds of solvents.

  (54) The rinsing solution for negative development according to any one of (17) and (50) to (53), comprising at least one developer component used in the step of performing negative development.

  According to the present invention, a method for stably forming a high-precision fine pattern, a positive resist composition for multiple development used in the method, a developer for negative development used in the method, and a negative development used in the method A rinse solution can be provided.

It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the conventional method. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is the graph which showed the relationship between the exposure amount at the time of using a positive developing solution or a negative developing solution, and a residual film curve. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is drawing which shows the spatial intensity distribution of an optical image. It is a schematic diagram which shows the relationship between positive image development, threshold value (a), and light intensity. It is a schematic diagram which shows the spatial intensity distribution of an optical image. It is a schematic diagram which shows the relationship between negative image development, a threshold value (b), and light intensity. It is a schematic diagram which shows the state which forms a pattern by twice exposure.

Hereinafter, the best mode for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present invention, as a technique for increasing the resolving power, a negative developing solution can be obtained by irradiating an actinic ray or radiation with a developing solution (negative developing solution) that selectively dissolves and removes an exposed portion having a predetermined threshold value (b) or less. A new pattern formation method is presented that combines a positive resist composition that forms a film with reduced solubility in (preferably an organic developer).
In the present invention, as a technique for increasing the resolving power, more preferably, a developer (positive developer) that selectively dissolves and removes an exposed portion having a predetermined threshold value (a) or higher, and a predetermined threshold value (b) or lower. A developer (negative developer) that selectively dissolves and removes the exposed area and irradiation with actinic rays or radiation increase the solubility in a positive developer (preferably an alkali developer). A new pattern forming method is proposed, which is combined with a positive resist composition which forms a film having a reduced solubility in an organic developer).
That is, as shown in FIG. 2, when a pattern element on an exposure mask is projected onto a wafer by light irradiation, a region having a high light irradiation intensity (an exposed portion having a predetermined threshold (a) or more) is positively positioned. An optical aerial image (light) is obtained by dissolving / removing with a mold developer and dissolving / removing an area with a low light irradiation intensity (exposed portion below a predetermined threshold (b)) with a negative developer. A pattern having a resolution twice the frequency of the intensity distribution can be obtained. Further, in the method of the present invention, it is not necessary to divide the design of the exposure mask.

A pattern forming process necessary for carrying out the present invention includes the following steps.
(A) a step of applying a positive resist composition on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation;
(A) an exposure step; and (d) a step of developing using a negative developer.

  The pattern forming method of the present invention preferably further includes (c) a step of developing using a positive developer.

  The pattern forming method of the present invention preferably further includes (f) a step of washing with a rinsing solution containing an organic solvent after the step of (e) developing with a negative developer.

  The pattern forming method of the present invention preferably has (i) a heating (also called post exposure bake (PEB)) step after the exposure step.

  The pattern formation method of this invention can have (b) exposure process in multiple times.

  The pattern forming method of the present invention can include (e) a heating (also referred to as baking, PEB (post exposure bake)) process a plurality of times.

In carrying out the present invention, (a) a positive resist composition in which the solubility in a positive developer increases and the solubility in a negative developer decreases by irradiation with actinic rays or radiation, and (b) a negative resist. A developer (preferably an organic developer) is required.
In order to carry out the present invention, it is further preferable to use (c) a positive developer (preferably an alkali developer).
In order to carry out the present invention, it is preferable to further use (d) a rinsing liquid containing an organic solvent.

  There are two types of pattern formation methods: positive and negative. Both use the fact that the solubility of the resist film in the developer changes due to a chemical reaction triggered by light irradiation. The case where the part is dissolved in the developer is called a positive type, and the case where the non-irradiated part is dissolved in the developer is called a negative type. A positive resist uses a chemical reaction such as polarity conversion in order to improve solubility in a developer, and a negative resist uses a bond formation between molecules such as a crosslinking reaction or a polymerization reaction.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. When exposed, the acid generator in the exposed area decomposes to generate an acid, and the acid generated in the exposure bake (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

In the present invention, one positive resist composition (a) simultaneously acts as a positive type for a positive developer, and acts as a negative type for a negative developer.
In the present invention, an alkaline developer (aqueous) can be used as the positive developer, and an organic developer containing an organic solvent can be used as the negative developer.
Further, the positive resist composition (a) is “a resin composition that forms a film in which the solubility in an alkali developer increases as a result of a chemical reaction triggered by exposure irradiation and the solubility in a developer containing an organic solvent decreases. Things ".
In the negative type image forming system (negative type resist + negative type developer) that has been used in the past, there is a material system that utilizes a mechanism that increases the molecular weight due to intermolecular bonding and reduces the solubility in the developer. Has been proposed. However, in the image forming mechanism using the change in molecular weight, a system in which one resist material system acts positively for one developer and negatively for another developer. It was difficult to build.
In the present invention, the positive resist composition (a) not only reduces the solubility in the negative developer by the polarity conversion reaction of the polymer side chain, but also has a specific chemical reaction (of the polymer side chain). The polarity conversion reaction) simultaneously increases the solubility in an alkali developer and decreases the solubility in an organic developer.

  In the present invention, a combination of a positive resist composition and a negative developer, or a combination of a positive resist composition, a negative developer and a positive developer does not generate a resist residue and generates a fine pattern. Can be formed.

  In another preferred embodiment of the present invention, first development is performed using a negative developer (preferably an organic developer), and then a positive developer (preferably an alkali developer) is used. The second development is performed. Thereby, the chipping of the resist pattern can be further suppressed. By suppressing the chipping of the resist pattern, it is possible to suppress a defect in the circuit pattern transferred onto the substrate.

  Macromolecules, vol38, 1882-1898 (2005), J. Photopolymer Science and Technology, vol12, 545-551 (1999), etc. In this case, it is important to make the penetration of the developer into the resist film smoother. In the development process, it is not clear why the resist pattern chipping can be suppressed by performing the first development using a negative developer and then the second development using a positive developer. However, the combination of the positive resist composition, the positive developer and the negative developer of the present invention is considered important. That is, by performing two developments using a negative developer and a positive developer in combination, and setting the development sequence of the two times in the above order, the developer (positive type) is developed in the second development step. It is considered that the developer) penetrated into the resist film more smoothly, and as a result, the uniformity of development was improved and the pattern could be formed without causing the resist pattern to be chipped.

In the present invention, it is important to control the “threshold value” of the exposure amount (the exposure amount at which the film is solubilized or insolubilized in the developer in the light irradiation region). That is, when performing pattern formation, the minimum exposure amount solubilized in a positive developer and the minimum exposure amount insolubilized in a negative developer so that a desired line width can be obtained are “threshold values”. It is.
The “threshold value” can be obtained as follows.
That is, when performing pattern formation, the minimum exposure amount solubilized in the positive developer and the minimum exposure amount insoluble in the negative developer are threshold values so that a desired line width can be obtained. .
More precisely, the threshold value is defined as follows.
As shown in FIG. 3, when the remaining film ratio with respect to the exposure amount of the resist film is measured, the exposure amount at which the remaining film ratio becomes 0% with respect to the positive developer, the threshold value (a), and the negative developer. On the other hand, an exposure amount at which the remaining film rate becomes 100% is defined as a threshold value (b).
For example, as shown in FIG. 4, the threshold value (a) of the minimum exposure amount solubilized in the positive developer is set higher than the threshold value (b) of the minimum exposure amount insolubilized in the negative developer. Thus, the pattern can be formed by one exposure.

As a method of controlling the threshold value, there are a method of controlling material-related parameters of the positive resist composition (a) and the developer, and parameters related to the process.
As material-related parameters, it is effective to control various physical properties related to the solubility of the positive resist composition (a) in the developer and organic solvent, that is, SP value (solubility parameter), LogP value, etc. It is. Specifically, in the positive resist composition (a), the polymer weight average molecular weight, molecular weight dispersity, monomer composition ratio, monomer polarity, monomer sequence, polymer blend, addition of low molecular additives, As for the developer, there are developer concentration, addition of a low molecular additive, addition of a surfactant, and the like.
Process-related parameters include film formation temperature, film formation time, post-exposure post-heating temperature, time, development temperature, development time, developing device nozzle method (liquid filling method), post-development rinsing method Etc.

  The pattern formation process using two types of developer, a positive developer and a negative developer, may be performed by a single exposure as described above, or by performing the exposure by performing the following process twice or more. It may be done in a process. That is, after the first exposure, development is performed using a positive developer or a negative developer, and then, after the second exposure, with a developer different from the first development, Perform negative or positive development.

(A) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation;
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(C) developing with a positive developer,
(I-2) Second exposure step,
(E-2) a pattern forming method comprising: a second heating (also called bake, PEB (post exposure bake)) step; and (d) a step of developing with a negative developer in this order. .

As shown in FIG.
(A) A step of applying a positive resist composition for multiple development on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation;
(A-1) First exposure step,
(E-1) a first heating (also called bake, PEB (post exposure bake)) step,
(D) developing with a negative developer,
(I-2) Second exposure step,
(E-2) a second heating (also called bake, PEB (post exposure bake)) step, and (c) a step of developing using a positive developer,
The pattern formation method characterized by including these in this order.

  As the multiple development positive resist composition, a positive resist composition to be described later can be used.

As an advantage of performing exposure twice or more, there is an advantage that the degree of freedom in controlling the threshold value in the development after the first exposure and the control of the threshold value in the development after the second exposure is increased. When performing the exposure twice or more, it is desirable to make the second exposure amount larger than the first exposure amount. In the second development, the threshold value is determined based on the sum of the first and second exposure amount histories. If the second exposure amount is sufficiently larger than the first exposure amount, This is because the influence of the exposure amount of the second time becomes small and can be ignored in some cases.
The exposure amount (Eo1 [mJ / cm ² ]) in the first exposure process is 5 [mJ / cm ² ] or more from the exposure amount (Eo2 [mJ / cm ² ]) in the ^second exposure process. Smaller is desirable. This can reduce the influence of the history of the first exposure on the pattern forming process by the second exposure.

  In the case where the exposure is performed twice, the first development is not limited to the positive type, and the development may be performed using a negative developer first.

  In order to change the exposure amount for the first time and the exposure amount for the second time, the method of adjusting various parameters of the above-mentioned materials and processes is effective. In particular, the first heating (baking, PEB (post exposure bake) It is effective to control the temperature of the step of performing the second heating (also referred to as baking or PEB (post exposure bake)). That is, in order to make the first exposure amount smaller than the second exposure amount, it is effective to set the temperature of the first heating step higher than the temperature of the second heating step.

The threshold value (a) in the positive development corresponds to the following in the actual lithography process.
On the substrate, after forming a film with a positive resist composition, the solubility in a positive developer increases by irradiation with actinic rays or radiation, and the solubility in a negative developer decreases. Exposure is performed through a photomask having a desired pattern size. At this time, exposure is performed while swinging the focus of exposure (focus) by 0.05 [μm] and the exposure amount by 0.5 [mJ / cm ² ]. After exposure, heating is performed at a desired temperature for a desired time (also called baking or PEB (post exposure bake)), and development is performed for a desired time with an alkaline developer having a desired concentration. After development, the line width of the pattern is measured using a CD-SEM, and an exposure amount A [mJ / cm ² ] and a focus position for forming a desired line width are determined. Next, the intensity distribution of the optical image when the previous photomask is irradiated at a specific exposure amount A [mJ / cm ² ] and a specific focus position is calculated. The calculation can be performed using simulation software (Prolithver.9.2.0.15 manufactured by KLA). Details of the calculation method are described in Inside PROLITH (Chris. A. Mack, FINLE Technologies, Inc., Cahpter2 Aerial Image Formation).
As an example of the calculation result, a spatial intensity distribution of an optical image as shown in FIG. 7 is obtained.

  Here, as shown in FIG. 8, the light intensity at the position where the spatial position is shifted from the minimum value of the spatial intensity distribution of the optical image by 1/2 of the obtained pattern line width becomes the threshold value (a). Correspond.

The threshold value (b) in the negative development corresponds to the following in the actual lithography process.
On the substrate, after forming a film with a positive resist composition, the solubility in a positive developer increases by irradiation with actinic rays or radiation, and the solubility in a negative developer decreases. Exposure is performed through a photomask having a desired pattern size. At this time, exposure is performed while swinging the focus of exposure (focus) by 0.05 [μm] and the exposure amount by 0.5 [mJ / cm ² ]. After the exposure, heating is performed at a desired temperature for a desired time (also referred to as baking or PEB (post exposure bake)), and development is performed for a desired time with an organic developer having a desired concentration. After development, the line width of the pattern is measured using a CD-SEM, and an exposure amount A [mJ / cm ² ] and a focus position for forming a desired line width are determined. Next, the intensity distribution of the optical image when the previous photomask is irradiated at a specific exposure amount A [mJ / cm ² ] and a specific focus position is calculated. The calculation is performed using simulation software (Prolith manufactured by KLA).
For example, a spatial intensity distribution of an optical image as shown in FIG. 9 is obtained.

  Here, as shown in FIG. 10, the light intensity at the position where the spatial position is shifted from the maximum value of the spatial intensity distribution of the optical image by 1/2 of the obtained pattern line width is the threshold value (b). And

The threshold (a) is preferably 0.1 to 100 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], and still more preferably 1 to 30 [mJ / cm ² ]. The threshold (b) is preferably 0.1 to 100 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], and still more preferably 1 to 30 [mJ / cm ² ]. The difference between the threshold values (a) and (b) is preferably 0.1 to 80 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], still more preferably 1 to 30 [mJ / cm ² ].

In the present invention, the film formed on the substrate is a film made of a positive resist composition that increases its solubility in a positive developer and decreases its solubility in a negative developer by irradiation with actinic rays or radiation. is there.
The positive resist composition that can be used in the present invention will be described below.

(A) Resin in which the solubility in an alkali developer increases due to the action of an acid and the solubility in an organic solvent decreases. The solubility in an alkali developer increases due to the action of an acid used in the positive resist composition of the present invention. Resins whose solubility in a solvent is reduced are groups (hereinafter referred to as “acid-decomposable groups”) that are decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin, or in both the main chain and the side chain. (Also referred to as “acid-decomposable resin”, “acid-decomposable resin (A)” or “resin (A)”) having a monocyclic or polycyclic alicyclic hydrocarbon structure More preferably, the resin increases the solubility in an alkali developer by the action of an acid and decreases the solubility in an organic solvent. The reason is that the polarity of the resin changes greatly before and after irradiation with actinic rays or radiation, and development is performed using a positive developer (preferably an alkali developer) and a negative developer (preferably an organic solvent). This is because the dissolution contrast is improved. Furthermore, a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure is generally highly hydrophobic, and a negative developing solution (preferably an organic solvent) is used to develop a region with low light irradiation intensity of a resist film. The development speed is fast and the developability when using a negative developer is improved.
Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) Imido group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group A group having
Preferred alkali-soluble groups include carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferred group as an acid-decomposable group (acid-decomposable group) is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The positive resist composition of the present invention containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which increases the solubility in an alkali developer by the action of an acid and decreases the solubility in an organic solvent. It can be suitably used when irradiating excimer laser light.

  Resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, increases its solubility in an alkaline developer by the action of an acid, and decreases its solubility in an organic solvent (hereinafter referred to as “alicyclic hydrocarbon-based acid-decomposable resin”) As a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pV) and a group of repeating units represented by the following general formula (II-AB) It is preferable that it is resin containing at least 1 sort (s) selected from these.

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In the formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA′—R. ₁₇ ′ represents an alkyl group or a cycloalkyl group. At least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring.
Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure.
X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A ′ represents a single bond or a divalent linking group.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyl groups may have a substituent.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group.

  As further substituents of these alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (carbon numbers) 2-6). Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The structures represented by the general formulas (pI) to (pV) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (pI) to (pV), preferably a carboxylic acid Group, a hydrogen atom of a sulfonic acid group is substituted with a structure represented by general formulas (pI) to (pV).

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

Here, R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Represents. A single bond is preferable.
Rp ₁ represents any group of the above formulas (pI) to (pV).

  The repeating unit represented by the general formula (pA) is particularly preferably a repeating unit composed of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Hereinafter, although the specific example of the repeating unit shown by general formula (pA) is shown, this invention is not limited to this.

Examples of the halogen atom in the general formula (II-AB), R ₁₁ ′, and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Examples of the alkyl group in R ₁₁ ′ and R ₁₂ ′ include a linear or branched alkyl group having 1 to 10 carbon atoms.

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include the same alicyclic hydrocarbon groups as R _{12 to} R _{25 in} the general formulas (pI) to (pV).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2).

  In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid has a partial structure containing the alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV). It can be contained in at least one kind of repeating unit among the repeating unit having, the repeating unit represented by formula (II-AB), and the repeating unit of the copolymerization component described later. The group capable of decomposing by the action of an acid is preferably contained in a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by general formula (pI) to general formula (pV).

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or the general formula (II-AB2) are atomic groups for forming an alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z ′ for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, but the present invention is not limited to these specific examples.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a lactone group. As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure, and a bicyclo structure in the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), By using a specific lactone structure, line edge roughness and development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

As the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16), R _{13 in the} above general formula (II-AB1) or (II-AB2) may be used. Wherein at least one of 'to R ₁₆ ' has a group represented by the general formulas (LC1-1) to (LC1-16) (for example, R _{5 of} -COOR ₅ is represented by the general formulas (LC1-1) to (LC1) -16) or a repeating unit represented by the following general formula (AI).

In general formula (AI),
Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represent. A linking group represented by a single bond or —Ab ₁ —CO ₂ — is preferable. Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

  The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention has a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. preferable. This improves the substrate adhesion and developer compatibility. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.
As the alicyclic hydrocarbon structure substituted with a polar group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In general formulas (VIIa) to (VIIc),
R _{2c to} R _4c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R _{2c to} R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _{2c to} R _4c are a hydroxyl group and the rest are hydrogen atoms.
In general formula (VIIa), it is more preferable that two members out of R _{2c to} R _4c are a hydroxyl group and the remaining is a hydrogen atom.

As the repeating unit having a group represented by the general formulas (VIIa) to (VIId), at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2) is the above. has a group represented by the general formula (VII) (e.g., represents a group R ₅ in -COOR ₅ is a represented by the general formula (VIIa) ~ (VIId)) , or the following general formula (AIIa) ~ ( A repeating unit represented by AId) can be mentioned.

In general formulas (AIIa) to (AIId),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _2c to R _4c have the same meanings as R _2c to R _4c in formulas (VIIa) ~ (VIIc).

  Although the specific example of the repeating unit which has a structure represented by general formula (AIIa)-(AIId) is given to the following, this invention is not limited to these.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may have a repeating unit represented by the following general formula (VIII).

In the above general formula (VIII),
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alkali-soluble group, and more preferably has a repeating unit having a carboxyl group. By containing this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a carboxyl group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is introduced at the end of the polymer chain at the time of polymerization, and the linking group is a monocyclic or polycyclic hydrocarbon. You may have a structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may further have a repeating unit having 1 to 3 groups represented by the general formula (F1). This improves line edge roughness performance.

In general formula (F1),
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

  The repeating unit having a group represented by the general formula (F1) is preferably a repeating unit represented by the following general formula (F2).

In general formula (F2),
Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group (preferably a single bond).
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group (preferably a single bond or a methylene group).
F ₁ represents a group represented by the general formula (F1).
p ₁ is an integer of 1 to 3.
The cyclic hydrocarbon group for Fb is preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

  Specific examples of the repeating unit having a group represented by the general formula (F1) are shown below, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may further contain a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power that is a general necessary characteristic of resist. Various repeating structural units can be contained for the purpose of adjusting heat resistance, sensitivity, and the like.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition temperature),
(3) Solubility in positive developer and negative developer,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

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

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In alicyclic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is the resist's dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required performance of resists. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention include the following.
(1) What contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type).
Preferably those containing (meth) acrylate repeating units having a structure of (pI) to (pV).
(2) One containing a repeating unit represented by the general formula (II-AB) (main chain type).
However, in (2), for example, the following can be further mentioned.
(3) A repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 in all repeating structural units. -40 mol%.

  In the acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 to 40 mol% in all repeating structural units. is there.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 20 to 70 in all the repeating structural units. The mol% is preferable, more preferably 20 to 50 mol%, still more preferably 25 to 40 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol% in all repeating structural units. More preferably, it is 20-50 mol%.

In the acid-decomposable resin, the content of the repeating unit having a lactone ring is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 25 to 40 mol% in all repeating structural units.
In the acid-decomposable resin, the content of the repeating unit having an organic group having a polar group is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 5 to 20 mol in all repeating structural units. %.

  In addition, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can also be appropriately set according to the performance of the desired resist. ) To 99 p% with respect to the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by (pV) and the repeating unit represented by the general formula (II-AB). The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

  When the positive resist composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.

  The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units may be methacrylate repeating units, all of the repeating units may be acrylate repeating units, and all of the repeating units may be any mixture of methacrylate repeating units / acrylate repeating units, It is preferable that the acrylate repeating unit is 50 mol% or less of the entire repeating unit.

  The alicyclic hydrocarbon-based acid-decomposable resin includes at least a (meth) acrylate-based repeating unit having a lactone ring, a (meth) acrylate-based repeating unit having an organic group substituted with at least one of a hydroxyl group and a cyano group, and A copolymer having three types of repeating units of a (meth) acrylate-based repeating unit having an acid-decomposable group is preferable.

  Preferably, 20 to 50 mol% of repeating units having a partial structure containing an alicyclic hydrocarbon represented by general formulas (pI) to (pV), 20 to 50 mol% of repeating units having a lactone structure, substituted with a polar group It is a ternary copolymer containing 5 to 30% of repeating units having an alicyclic hydrocarbon structure, or a quaternary copolymer containing 0 to 20% of other repeating units.

  Particularly preferable resins include 20 to 50 mol% of repeating units having an acid-decomposable group represented by the following general formulas (ARA-1) to (ARA-7), and the following general formulas (ARL-1) to (ARL- 6) 50 to 50 mol% of a repeating unit having a lactone group represented by formula (6), and a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group represented by the following general formulas (ARH-1) to (ARH-3) A ternary copolymer containing 5 to 30 mol% of units, or a carboxyl group, or a repeating unit having a structure represented by the general formula (F1), having an alicyclic hydrocarbon structure and not exhibiting acid decomposability It is a quaternary copolymer containing 5 to 20 mol% of repeating units.

(In the formula, Rxy ₁ represents a hydrogen atom or a methyl group, Rxa ₁ and Rxb ₁ each independently represent a methyl group or an ethyl group, and Rxc ₁ represents a hydrogen atom or a methyl group.)

When the acid-decomposable resin (A) is used in a positive resist composition that irradiates KrF excimer laser light, electron beam, X-ray, high energy light (EUV, etc.) having a wavelength of 50 nm or less, the acid-decomposable resin is It is preferable to have a hydroxystyrene-based repeating unit such as a repeating unit based on hydroxystyrene. More preferably, it is a resin having a hydroxystyrene-based repeating unit and a repeating unit having an acid-decomposable group (hereinafter also referred to as “hydroxystyrene-based acid-decomposable resin”). The repeating unit having an acid-decomposable group is preferably a hydroxystyrene-based repeating unit protected with an acid-eliminable group or an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit.
The hydroxystyrene-based repeating unit protected with an acid leaving group is preferably a repeating unit of 1-alkoxyethoxystyrene, t-butylcarbonyloxystyrene or the like. Examples of the alkyl group in the acid-decomposable (meth) acrylic acid tertiary alkyl ester repeating unit include a chain alkyl group or a monocyclic or polycyclic alkyl group. The acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit is preferably t-butyl (meth) acrylate, 2-alkyl-2-adamantyl (meth) acrylate, 2- (1-adamantyl) -2. Examples of the repeating unit include -propyl (meth) acrylate, 1-alkyl-1-cyclohexyl (meth) acrylate, 1-alkyl-1-cyclopentyl (meth) acrylate, and the like.

  Hereinafter, although the specific example of a hydroxy styrene-type acid-decomposable resin is shown, this invention is not limited to this.

  In the above specific example, tBu represents a t-butyl group.

  The content of the acid-decomposable group is determined by the number of acid-decomposable groups (B) in the hydroxystyrene-based acid-decomposable resin and the number of alkali-soluble groups (S) that are not protected by an acid-eliminating group. / (B + S). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  The acid-decomposable resin (A) used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.
For purification, the same method as that for the resin (D) described later can be used, and a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, only those having a specific molecular weight or less. A purification method in a solution state such as ultrafiltration to extract and remove the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, A usual method such as a purification method in a solid state, such as washing the filtered resin slurry with a poor solvent, can be applied.

The weight average molecular weight of the acid-decomposable resin (A) according to the present invention is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, most preferably as a polystyrene-converted value by the GPC method. Is 5,000 to 15,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
Another particularly preferable form of the weight average molecular weight of the acid-decomposable resin (A) according to the present invention is 3,000 to 9,500 in terms of polystyrene by GPC method. By setting the weight average molecular weight to 3,000 to 9,500, resist residues (hereinafter also referred to as “scum”) are particularly suppressed, and a better pattern can be formed.
The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

In the positive resist composition of the present invention, the blending amount of all the acid-decomposable resins (A) according to the present invention in the whole composition is preferably 50 to 99.9% by mass, more preferably in the total solid content. It is 60-99.0 mass%.
In the present invention, the resins may be used alone or in combination.

  The acid-decomposable resin (A) of the present invention preferably contains no fluorine atom or silicon atom from the viewpoint of compatibility with the resin (D).

(B) Compound that generates acid upon irradiation with actinic ray or radiation The positive resist composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation ("photoacid generator" or "component (B)") (Also called).
Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like. Preferably, it is an organic anion containing a carbon atom.

  Preferable organic anions include organic anions represented by the following formula.

Where
Rc ₁ represents an organic group.
Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, —CO ₂ —, — Examples include groups linked by a linking group such as S-, -SO _3- , -SO ₂ N (Rd ₁ )-. Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group. Preferred examples of the organic group for Rc ₃ , Rc ₄ , and Rc ₅ include the same organic groups as those for Rc _1, and a perfluoroalkyl group having 1 to 4 carbon atoms is most preferred.
Rc ₃ and Rc ₄ may combine to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is particularly preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, when Rc ₃ and Rc ₄ are combined to form a ring, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and particularly preferable. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched 2-oxoalkyl group is preferably an alkoxycarbonyl methyl group.
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl). The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cyclic 2-oxoalkyl group.
Linear as R ₂₀₁ to R _203, branched or cyclic 2-oxoalkyl group may preferably be a group having a 2-position> C = O in the above-described alkyl or cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Any two or more of R _1c to R _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y include a butylene group and a pentylene group.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Or a linear or branched alkyl group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, or a linear or branched pentyl group).
The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group or a cyclohexyl group).
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
The cycloalkyl group as R _x and R _y may be the same as the cycloalkyl group as R _1c to R _7c. The cycloalkyl group as R _x and R _y is preferably a cyclic 2-oxoalkyl group.
Examples of the linear, branched, or cyclic 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .
R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
R ₂₀₄ to R ₂₀₇ may have a substituent. The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZIV), (ZV), and (ZVI) can be further exemplified.

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ represents an alkyl group or an aryl group.
_R207 and _R208 each independently represents an alkyl group, an aryl group, or an electron-withdrawing group. R ₂₀₇ is preferably an aryl group.
R ₂₀₈ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  As the compound that generates an acid upon irradiation with actinic rays or radiation, compounds represented by general formulas (ZI) to (ZIII) are preferable.

  The compound (B) is preferably a compound that generates an aliphatic sulfonic acid having a fluorine atom or a benzenesulfonic acid having a fluorine atom upon irradiation with actinic rays or radiation.

  The compound (B) preferably has a triphenylsulfonium structure.

  The compound (B) is preferably a triphenylsulfonium salt compound having an alkyl group or a cycloalkyl group not substituted with fluorine in the cation moiety.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, examples of particularly preferable compounds are listed below.

A photo-acid generator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 7% by mass, based on the total solid content of the positive resist composition. It is.

(C) Solvent Examples of the solvent that can be used when preparing the positive resist composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, Examples thereof include organic solvents such as alkyl alkoxypropionates, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds having 4 to 10 carbon atoms, which may contain a ring, alkylene carbonate, alkyl alkoxyacetates, and alkyl pyruvates. .

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ- Caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone are preferred.

  Examples of the monoketone compound having 4 to 10 carbon atoms which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4- Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4 -Heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5- Xen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopenta Non, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcyclo Preferred are heptanone and 3-methylcycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.
Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

(D) Resin having at least one of fluorine atom and silicon atom The positive resist composition of the present invention preferably contains a resin (D) having at least one of a fluorine atom and a silicon atom.
The fluorine atom or silicon atom in the resin (D) may be present in the main chain of the resin or may be substituted with a side chain.

The resin (D) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

  Specific examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom are shown below, but the present invention is not limited thereto.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{57 to} R ₆₁ , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoroethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH are preferred.

The resin (D) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

  Examples of the resin (D) include resins having at least one selected from the group of repeating units represented by the following general formulas (CI) to (CV).

In the general formulas (CI) to (CV),
R _{1 to} R ₃ each independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group.
W _{1 to} W ₂ represent an organic group having at least one of a fluorine atom and a silicon atom.
R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group. However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
R ₈ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
R ₉ represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
L < ₁ > -L < ₂ > represents a single bond or a bivalent coupling group, and is the same as said L < ₃ > -L < ₅ >.
Q represents a monocyclic or polycyclic cyclic aliphatic group. That is, it represents an atomic group that contains two bonded carbon atoms (C—C) and forms an alicyclic structure.
R ₃₀ and R ₃₁ each independently represents a hydrogen atom or a fluorine atom.
R ₃₂ and R ₃₃ each independently represents an alkyl group, a cycloalkyl group, a fluorinated alkyl group or a fluorinated cycloalkyl group.
However, the repeating unit represented by formula (CV) has at least one fluorine atom in at least one of R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ .

  The resin (D) preferably has a repeating unit represented by the general formula (CI), and further has a repeating unit represented by the following general formulas (C-Ia) to (C-Id). preferable.

In the general formulas (C-Ia) to (C-Id),
R ₁₀ and R ₁₁ represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
W _{3 to} W ₆ represent an organic group having at least one of a fluorine atom and a silicon atom.

When W _{1 to} W ₆ are organic groups having a fluorine atom, they are fluorinated, straight chain, branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, or fluorinated having 1 to 20 carbon atoms. It is preferably a linear, branched, or cyclic alkyl ether group.

Examples of the fluorinated alkyl group for W _{1 to} W ₆ include trifluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, heptafluorobutyl group, heptafluoroisopropyl group, octafluoro Examples thereof include an isobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, a perfluoroisopentyl group, a perfluorooctyl group, and a perfluoro (trimethyl) hexyl group.

When W _{1 to} W ₆ are an organic group having a silicon atom, an alkylsilyl structure or a cyclic siloxane structure is preferable. Specific examples include groups represented by the general formulas (CS-1) to (CS-3).

Specific examples of the repeating unit represented by the general formula (CI) are shown below. X represents a hydrogen atom, —CH ₃ , —F, or —CF ₃ .

The resin (D) is preferably any resin selected from the following (D-1) to (D-6).
(D-1) A resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a resin having only a repeating unit (a).
(D-2) A resin having a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, more preferably a resin having only a repeating unit (b).
(D-3) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 carbon atoms) To 20), a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms). More preferably, a copolymer resin of the repeating unit (a) and the repeating unit (c).
(D-4) a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 to 20 carbon atoms), Resin having a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms) More preferably, a copolymer resin of the repeating unit (b) and the repeating unit (c).
(D-5) A resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms) and a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, more preferably a repeating unit Copolymer resin of unit (a) and repeating unit (b).
(D-6) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, and a branched alkyl group (preferably Is a C4-20), cycloalkyl group (preferably C4-20), branched alkenyl group (preferably C4-20), cycloalkenyl group (preferably C4-20) or aryl. A resin having a repeating unit (c) having a group (preferably having 4 to 20 carbon atoms), more preferably a copolymer resin of repeating unit (a), repeating unit (b) and repeating unit (c).
Repeating unit (c) having a branched alkyl group, cycloalkyl group, branched alkenyl group, cycloalkenyl group, or aryl group in resins (D-3), (D-4), and (D-6) In consideration of hydrophilicity / hydrophobicity, interaction, etc., appropriate functional groups can be introduced, but from the viewpoint of immersion liquid follow-up and receding contact angle, functional groups that do not have polar groups Is preferred.
In the resins (D-3), (D-4), and (D-6), the repeating unit (a) having a fluoroalkyl group and / or the repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure is It is preferable that it is 20-99 mol%.
The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known that In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method. In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  The resin (D) is preferably a resin having a repeating unit represented by the following general formula (Ia).

In general formula (Ia):
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₁ represents an alkyl group.
R ₂ represents a hydrogen atom or an alkyl group.

In general formula (Ia), the alkyl group in which at least one hydrogen atom of Rf is substituted with a fluorine atom preferably has 1 to 3 carbon atoms, and more preferably a trifluoromethyl group.
The alkyl group represented by R ₁ is preferably a linear or branched alkyl group having 3 to 10 carbon atoms, and more preferably a branched alkyl group having 3 to 10 carbon atoms.
R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 10 carbon atoms.

  Hereinafter, although the specific example of the repeating unit represented by general formula (Ia) is given, this invention is not limited to this.

  The repeating unit represented by the general formula (Ia) can be formed by polymerizing a compound represented by the following general formula (I).

In general formula (I),
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₁ represents an alkyl group.
R ₂ represents a hydrogen atom or an alkyl group.

In the general formula (I), Rf, R ₁ and R ₂ are in the general formula (Ia), Rf, R ₁ and R ₂ synonymous.
The compound represented by the general formula (I) is a novel compound.
As the compound represented by the general formula (I), a commercially available product may be used, or a synthesized product may be used. In the case of synthesis, 2-trifluoromethylmethacrylic acid can be obtained by acidification and then esterification.

  The resin (D) having a repeating unit represented by the general formula (Ia) preferably further has a repeating unit represented by the following general formula (III).

In general formula (III):
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, or a group having a cyclic siloxane structure.
L ₆ represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.
The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.
The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

  Hereinafter, although the specific example of resin (D) which has a repeating unit represented by general formula (Ia) is given, this invention is not limited to this.

  The resin (D) is preferably a resin having a repeating unit represented by the following general formula (II) and a repeating unit represented by the following general formula (III).

In general formulas (II) and (III):
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or a group formed by combining two or more thereof.
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, a group having a cyclic siloxane structure, or a group formed by combining two or more thereof.
The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, and trialkylsilyl group of R ₃ and R ₄ can introduce a functional group, but have a polar group from the viewpoint of immersion liquid followability. The functional group is preferably not substituted, and more preferably unsubstituted.
L ₆ represents a single bond or a divalent linking group.
0 <m <100.
0 <n <100.

Rf in the general formula (II) is the same as Rf in the general formula (Ia).
The alkyl group represented by R ₃ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
L ₆ is preferably a single bond, a methylene group, an ethylene group or an ether group.
m = 30 to 70 and n = 30 to 70 are preferable, and m = 40 to 60 and n = 40 to 60 are more preferable.

  Hereinafter, specific examples of the resin (D) having the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) will be described, but the present invention is not limited thereto. .

  Resin (D) may have a repeating unit represented by the following general formula (VIII).

In general formula (VIII):
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  The resin (D) is preferably solid at room temperature (25 ° C.). Furthermore, it is preferable that glass transition temperature (Tg) is 50-200 degreeC, and 80-160 degreeC is more preferable.

Being solid at 25 ° C. means that the melting point is 25 ° C. or higher.
The glass transition temperature (Tg) can be measured by differential scanning calorimeter. For example, the specific volume changed when the sample was heated once, cooled and then heated again at 5 ° C./min. It can be measured by analyzing the value.

  The resin (D) is preferably stable to an acid and insoluble in an alkaline developer.

Resin (D) is decomposed by the action of (x) an alkali-soluble group, (y) an alkali (alkaline developer), a group that increases the solubility in the alkali developer and (z) an acid, From the viewpoint of the followability of the immersion liquid, it is preferable not to have a group that increases the solubility in the developer.
The total amount of repeating units having an alkali-soluble group in the resin (D) or a group whose solubility in a developer is increased by the action of an acid or an alkali is preferably 20 with respect to all the repeating units constituting the resin (D). It is not more than mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5 mol%.
In addition, unlike the surfactant generally used in resists, the resin (D) does not have an ionic bond or a hydrophilic group such as a (poly (oxyalkylene)) group. When the resin (D) contains a hydrophilic polar group, the followability of immersion water tends to decrease, and therefore it is more preferable that the resin (D) does not have a polar group selected from a hydroxyl group, an alkylene glycol, and a sulfone group. . In addition, it is preferable not to have an ether group bonded to a carbon atom of the main chain through a linking group because hydrophilicity increases and immersion liquid followability deteriorates. On the other hand, an ether group directly bonded to a carbon atom of the main chain as shown in the general formula (III) is preferable because it may express a hydrophobic group.

  (X) Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, and (alkylsulfonyl). ) (Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris ( And a group having an alkylsulfonyl) methylene group.

  (Y) Examples of the group that decomposes by the action of an alkali (alkaline developer) and increases the solubility in the alkali developer include a lactone group, an ester group, a sulfonamide group, an acid anhydride, and an acid imide group. Can be mentioned.

  (Z) Examples of the group that decomposes by the action of an acid and increases the solubility in a developer include the same groups as the acid-decomposable groups in the acid-decomposable resin (A).

  However, the repeating unit represented by the following general formula (pA-C) has no or very little decomposability due to the action of acid as compared with the acid-decomposable group of the resin (A), and is substantially non-acid-decomposable. Considered equivalent to gender.

In the general formula (pA-c),
Rp ₂ represents a hydrocarbon group having a tertiary carbon atom bonded to the oxygen atom in the formula.

  When the resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (D). Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mass% in resin (D), and it is more preferable that it is 20-100 mass%.

  When resin (D) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of resin (D). Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in resin (D), and it is more preferable that it is 30-100 mass%.

  The weight average molecular weight in terms of standard polystyrene of the resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000, and particularly preferably. Is 3,000 to 15,000.

  The resin (D) preferably has a residual monomer amount of 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 in terms of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of ~ 1.5.

  The addition amount of the resin (D) in the positive resist composition is preferably 0.1 to 20% by mass, and preferably 0.1 to 10% by mass based on the total solid content of the resist composition. Is more preferable. Furthermore, it is preferable that it is 0.1-5 mass%, More preferably, it is 0.2-3.0 mass%, More preferably, it is 0.3-2.0 mass%.

  Resin (D), like acid-decomposable resin (A), naturally has few impurities such as metals, but the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by mass by HPLC. It is preferable that not only the sensitivity, resolution, process stability, pattern shape and the like as a resist can be further improved, but also a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained.

  As the resin (D), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. A chain transfer agent can also be used as needed. The density | concentration of reaction is 5-50 mass% normally, Preferably it is 20-50 mass%, More preferably, it is 30-50 mass%. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer. For example, hydrocarbon (pentane, hexane, Aliphatic hydrocarbons such as heptane and octane; Cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.) Halogenated aliphatic hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, diisopropyl ether, dimethoxyethane) Chain A Cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols ( (Methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.), water, a mixed solvent containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable. In such a solvent containing at least hydrocarbon, the ratio of alcohol (particularly methanol) and other solvent (for example, ester such as ethyl acetate, ethers such as tetrahydrofuran) is, for example, the former / the latter (volume ratio). 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = 50 / It is about 50 to 97/3.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The nozzle diameter at the time of supplying the polymer solution to the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mmφ or less (for example, 0.2 to 4 mmφ). Moreover, the supply speed (dropping speed) of the polymer solution into the poor solvent is, for example, about 0.1 to 10 m / second, preferably about 0.3 to 5 m / second, as the linear speed.

  The precipitation or reprecipitation operation is preferably performed with stirring. As a stirring blade used for stirring, for example, a desk turbine, a fan turbine (including a paddle), a curved blade turbine, an arrow blade turbine, a fiddler type, a bull margin type, an angled blade fan turbine, a propeller, a multistage type, an anchor type (or Horseshoe type), gate type, double ribbon, screw, etc. can be used. Stirring is preferably further performed for 10 minutes or more, particularly 20 minutes or more after the supply of the polymer solution. When the stirring time is short, the monomer content in the polymer particles may not be sufficiently reduced. Further, the polymer solution and the poor solvent can be mixed and stirred using a line mixer instead of the stirring blade.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

The resin may be once deposited and separated, and then dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent.
That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
The solvent used in the preparation of the resin solution A can be the same solvent as the solvent that dissolves the monomer in the polymerization reaction, and may be the same as or different from the solvent used in the polymerization reaction.

(E) Basic compound The positive resist composition of the present invention preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably Represents a carbon number of 6 to 20, and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom.
The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.
Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

  These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a positive resist composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(F) Surfactant The positive resist composition of the present invention preferably further contains (F) a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based interface). It is more preferable to contain any one or two or more of an activator and a surfactant having both a fluorine atom and a silicon atom.

When the positive resist composition of the present invention contains the surfactant (F), a resist having good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. A pattern can be given.
Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.
Examples of commercially available surfactants that can be used include EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176 and F189. , F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, 352, EF801, EF802, EF 01 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group and (poly (oxy) And a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

  In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, may be mentioned polyoxyethylene sorbitan tristearate nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as such.

  These surfactants may be used alone or in several combinations.

  (F) The usage-amount of surfactant becomes like this. Preferably it is 0.01-10 mass% with respect to positive resist composition whole quantity (except a solvent), More preferably, it is 0.1-5 mass%.

(G) Carboxylic acid onium salt The positive resist composition in the present invention may contain (G) a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, the (G) carboxylic acid onium salt is preferably an iodonium salt or a sulfonium salt. Furthermore, it is preferable that the carboxylate residue of the (G) carboxylic acid onium salt of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluoro-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

  These (G) carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1%, based on the total solid content of the composition. -7% by mass.

(H) Other Additives The positive resist composition of the present invention further has solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and developers as necessary. (For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

  In the pattern formation method of the present invention, a step of forming a film of a resin composition on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. The step of exposing the film, the step of heating the film (also referred to as baking or PEB (post exposure bake)) and the step of developing the film positively can be performed by a generally known method.

The light source wavelength limit is not used for the exposure apparatus in the present invention, KrF excimer laser wavelength (248 nm), ArF excimer laser wavelength (193nm), F ₂ excimer laser wavelength (157 nm), EUV light (13.5 nm), etc. Applicable.

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention.
The immersion exposure method is a technology for filling and exposing a projection lens and a sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) as a technique for increasing the resolving power.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The resolution and the depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

  When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

  On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process such as the photolithographic lithography process can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

  As the organic antireflection film, any one of a light absorber and an organic film made of a polymer material can be used. For example, DUV30 series, DUV-40 series, Brewer Science Co., Ltd. AR-2, AR- 3, AR-5, ARC series such as ARC29A manufactured by Nissan Chemical Co., Ltd., and other commercially available organic antireflection films can be used. Further, as the antireflection film, an inorganic antireflection film can be used. For example, an antireflection film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or the like can be used.

When performing positive development, an alkali developer is preferably used.
Examples of the alkali developer used for positive development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine and the like. Primary amines, diethylamine, secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, Alkaline aqueous solutions such as quaternary ammonium salts such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

  As the rinsing liquid in the rinsing treatment performed after the positive development, pure water can be used and an appropriate amount of a surfactant can be added.

When performing negative development, it is preferable to use an organic developer containing an organic solvent.
As an organic developer that can be used in negative development, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used. .
In the present invention, the ketone solvent is a solvent having a ketone group in the molecule, the ester solvent is a solvent having an ester group in the molecule, and the alcohol solvent is alcoholic in the molecule. It is a solvent having a hydroxyl group, an amide solvent is a solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule, and in that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. And methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and γ-butyrolactone.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxy acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Propyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene group Coal monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl Cetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.
As the ester solvent, a solvent represented by general formula (1) described later or a solvent represented by general formula (2) described later is preferably used, and a solvent represented by general formula (1) is used. Is more preferable, alkyl acetate is more preferably used, and butyl acetate is most preferably used.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol, n-decanol, 3-methoxy-1-butanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol Propyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, may be mentioned glycol ether solvents such as containing a hydroxyl group such as propylene glycol monomethyl ether. Among these, it is preferable to use a glycol ether solvent.
Examples of the ether solvent include, in addition to the above-described glycol ether solvent containing a hydroxyl group, a glycol ether solvent not containing a hydroxyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, Anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like can be mentioned. Preferably, a glycol ether solvent is used.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, and perfluoro. Aliphatic hydrocarbon solvents such as hexane and perfluoroheptane, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene And aromatic hydrocarbon solvents such as dipropylbenzene. Among these, aromatic hydrocarbon solvents are preferable.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.

  As a developer that can be used in negative development, a solvent represented by the following general formula (1) is preferably used.

In general formula (1),
R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may be bonded to each other to form a ring. R and R ′ are preferably a hydrogen atom or an alkyl group, and the alkyl group of R and R ′ may be substituted with a hydroxyl group, a carbonyl group, a cyano group, or the like.

  Examples of the solvent represented by the general formula (1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate. , Propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, propion Examples include isopropyl acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and the like.

  Among these, in the solvent represented by the general formula (1), R and R ′ are preferably unsubstituted alkyl groups, more preferably alkyl acetates, and particularly preferably butyl acetate.

  The solvent represented by the general formula (1) may be used in combination with one or more other solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (1), and the solvents represented by the general formula (1) may be used in combination. The solvent represented by the general formula (1) may be used by mixing with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. good. One or more solvents can be used in combination, but it is preferably one solvent in order to obtain stable performance. The mixing ratio of the solvent represented by the general formula (1) and the combined solvent when the combined solvent is used is usually 20:80 to 99: 1, preferably 50:50 to 97: 3. Preferably it is 60: 40-95: 5, Most preferably, it is 60: 40-90: 10.

  As a developer that can be used in negative development, a solvent represented by the following general formula (2) is preferably used.

In general formula (2),
R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R ″ and R ″ ″ may be bonded to each other to form a ring. R ″ and R ″ ″ are preferably a hydrogen atom or an alkyl group.
R ′ ″ represents an alkylene group or a cycloalkylene group. R ′ ″ is preferably a hydrogen atom or an alkyl group. The alkyl group that R ″, R ′ ″, and R ″ ″ have may be substituted with a hydroxyl group, a carbonyl group, a cyano group, or the like.

  In the general formula (2), the alkylene group represented by R ″ ″ may have an ether bond in the alkylene chain.

  Examples of the solvent represented by the general formula (2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl. Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol model Propyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2- Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4- Propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl -4-methoxy-pentyl acetate, 4-methyl-4-methoxy pentyl acetate, and the like.

  The solvent represented by the general formula (2) may be used in combination with one or more other solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (2), and the solvents represented by the general formula (2) may be used in combination. The solvent represented by the general formula (2) may be used by mixing with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. good. One or more solvents can be used in combination, but it is preferably one solvent in order to obtain stable performance. The mixing ratio of the solvent represented by the general formula (2) and the combined solvent when the combined solvent is used is usually 20:80 to 99: 1, preferably 50:50 to 97: 3. Preferably it is 60: 40-95: 5, Most preferably, it is 60: 40-90: 10.

  As the solvent used in the negative development, an organic solvent containing no halogen atom is preferably used from the viewpoint of cost reduction of the solvent used for the development. The content of the organic solvent not containing halogen atoms in the total weight of all the solvents used in the negative development is usually 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, Especially preferably, it is 97 mass% or more.

The boiling point of the solvent used in the negative development is desirably 50 ° C. or higher and lower than 250 ° C.
The ignition point of the solvent used in the negative development is preferably 200 ° C. or higher.

An appropriate amount of a surfactant can be added to the developer that can be used for negative development, if necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  As a negative development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a developer is raised on the surface of the substrate by surface tension, and is developed for a certain period of time for development. Method (paddle method), Method of spraying developer on substrate surface (spray method), Method of continuing to apply developer while scanning developer application nozzle at constant speed on substrate rotating at constant speed ( Dynamic dispensing method) can be applied.

  Further, after the step of performing the negative development, a step of stopping the development may be performed while substituting with another solvent.

After the step of performing negative development, it is preferable to include a step of washing with a rinse solution containing an organic solvent.
In the washing step after negative development, a rinsing solution containing at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is usually used. Can be used.
In the present invention, the hydrocarbon solvent is a hydrocarbon solvent having no substituent. A ketone solvent is a solvent having a ketone group in the molecule, an ester solvent is a solvent having an ester group in the molecule, and an alcohol solvent is an alcoholic hydroxyl group in the molecule. The amide solvent is a solvent having an amide group in the molecule, and the ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule, and in that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification.
For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone , Ketone solvents such as acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Esters such as teracetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate System solvents can be used.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n- Alcohols such as octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol mono Examples include glycol ether solvents such as ethyl ether and methoxymethylbutanol.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
As the amide solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, etc. can be used. .
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  The rinsing liquid containing an organic solvent preferably uses at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents. More preferably, at least one solvent selected from alcohol solvents and ester solvents can be used as the rinsing liquid. Most preferably, a rinse liquid containing a monohydric alcohol having 6 to 8 carbon atoms can be used as the rinse liquid. Here, examples of the monohydric alcohol having 6 to 8 carbon atoms contained in the rinse liquid used in the washing step after the negative development include linear, branched, and cyclic monohydric alcohols. 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like can be used. 1-hexanol, 2-heptanol, and 2-hexanol are preferable. More preferably, it is 1-hexanol or 2-hexanol.

A plurality of the above solvents may be mixed, or may be used by mixing with an organic solvent other than the above.
The solvent may be mixed with water, but the water content in the rinsing liquid is usually 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. is there. By setting the water content to 30% by mass or less, good development characteristics can be obtained.

An appropriate amount of a surfactant can be added to the rinsing liquid as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  In the step of cleaning with the rinse solution, the resist after the negative development is cleaned with the rinse solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied.

Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
Furthermore, after the development processing, the rinsing processing or the processing with the supercritical fluid, a heat processing can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 ° C to 160 ° C. The heat treatment may be performed a plurality of times.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
Examples 1 to 15, 17 to 20, and 22 to 26 are reference examples.

Example 1
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. On top of that, a commercial product FAiRS-9101A12 (ArF positive resist composition manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. did. The obtained wafer was subjected to pattern exposure at 25 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with butyl acetate (negative developer) for 30 seconds (negative development) and rinsing with decane for 30 seconds to obtain a pattern having a pitch of 200 nm and a line width of 100 nm.

Synthesis Example 1 (Synthesis of Resin (A1))
Under a nitrogen stream, 8.4 g of methyl isobutyl ketone was placed in a three-necked flask and heated to 80 ° C. To this, 9.4 g of 2-cyclohexylpropan-2-yl methacrylate, 4.7 g of 3-hydroxy-1-adamantyl methacrylate, 6.8 g of β-methacryloyloxy-γ-butyrolactone and azobisisobutyronitrile were added. A solution prepared by dissolving 6 mol% of methyl isobutyl ketone in 75.3 g of the total monomer amount was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 720 ml of heptane / 80 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 18.3 g of Resin (A1). The obtained resin had a weight average molecular weight of 9,300 and a dispersity (Mw / Mn) of 1.98.

Positive resist composition (A)
A positive resist composition obtained by dissolving the following components in a mixed solvent of polyethylene glycol monomethyl ether acetate / polyethylene glycol monomethyl ether (60:40) and filtering the solution with a solid content concentration of 5.8% by mass through a 0.1 μm polyethylene filter. A product (A) was prepared.
(Resin A1) 1.83 g, triphenylsulfonium nonaflate 69.6 mg, diphenylaniline 8.7 mg, PF6320 (fluorine surfactant manufactured by OMNOVA) 1.7 mg.

Positive resist composition (B)
Instead of the resin (A1), the following resin (A2) was prepared to prepare a positive resist composition (B).

Positive resist composition (C)
Instead of the resin (A1), the following resin (B) was prepared to prepare a positive resist composition (C).

Positive resist composition (D)
Instead of the resin (A1), the following resin (C) was prepared to prepare a positive resist composition (D).

Example 2
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). Then, after heating at 120 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) (positive developer) for 30 seconds (positive development), rinsed with pure water for 30 seconds, and pitched. A pattern having a thickness of 1000 nm and a line width of 750 nm was obtained. Next, a 250-nm (1: 1) resist pattern was obtained by performing development (negative development) for 30 seconds with a 2: 3 mass solution (negative developer) of butyl acetate / 2-hexanol.

Example 3
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. A positive resist composition (A) prepared thereon was applied using a spin coater, and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 20 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). Then, after heating at 130 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) (positive developer) for 30 seconds (positive development), rinsed with pure water for 30 seconds, As shown in FIG. 11, a pattern having a pitch of 600 nm and a line width of 450 nm was obtained. Next, a second exposure is performed at 56 [mJ / cm ² ] through the same pattern forming mask used in the first exposure, and heating is performed at 120 ° C. for 60 seconds. Then, butyl acetate / A 150 nm (1: 1) resist pattern was obtained by performing development (negative development) with a solution of 2-hexanol in a mass ratio of 1: 2 (negative developer) for 30 seconds.

Example 4
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 18 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). After heating at 135 ° C. for 60 seconds, the film was developed with a butyl acetate / 2-hexanol mass ratio 2: 3 solution (negative developer) for 30 seconds (negative development), and a pattern with a pitch of 600 nm and a line width of 450 nm. Got. Further, the second exposure is performed at 45 [mJ / cm ² ] through the same mask for pattern formation as that used in the first exposure, and the film is heated at 90 ° C. for 60 seconds. The resist pattern of 150 nm (1: 1) was obtained by developing for 30 second (positive type development) with oxide aqueous solution (2.38 mass%) (positive type developing solution), and rinsing with pure water for 30 seconds.

Example 5
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 30 seconds and rinsing with pure water for 30 seconds to obtain a pattern with a pitch of 920 nm and a line width of 690 nm. Next, development was carried out with a solution of butyl acetate / 2-hexanol in a mass ratio of 2: 3 for 30 seconds, followed by rinsing with 2-hexanol for 30 seconds to obtain a 230 nm (1: 1) resist pattern.

Example 6
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (C) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds and rinsing with pure water for 30 seconds to obtain a pattern having a pitch of 880 nm and a line width of 660 nm. Next, development was carried out with a solution of butyl acetate / 2-hexanol in a mass ratio of 2: 3 for 30 seconds, followed by rinsing with 2-hexanol for 30 seconds to obtain a 220 nm (1: 1) resist pattern.

Example 7
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (A) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 20 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 130 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds and rinsing with pure water for 30 seconds to obtain a pattern with a pitch of 560 nm and a line width of 420 nm. Next, the second exposure is carried out at 56 [mJ / cm ² ] through the same pattern forming mask used in the first exposure, heated at 120 ° C. for 60 seconds, and then butyl acetate is used. Development was performed for 30 seconds, followed by rinsing with 1-hexanol for 30 seconds to obtain a 140 nm (1: 1) resist pattern.

Example 8
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 18 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). After heating at 135 ° C. for 60 seconds, development with a 2: 3 solution of butyl acetate / 2-hexanol is performed for 30 seconds, followed by rinsing with 2-hexanol for 30 seconds to obtain a pattern with a pitch of 560 nm and a line width of 420 nm. It was. Further, the second exposure is performed at 45 [mJ / cm ² ] through the same mask for pattern formation as that used in the first exposure, and the film is heated at 90 ° C. for 60 seconds. The resist pattern of 140 nm (1: 1) was obtained by developing for 30 second with oxide aqueous solution (2.38 mass%), and rinsing with pure water for 30 second.

Example 9
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). After heating at 120 ° C. for 60 seconds, development was performed with a solution of butyl acetate / 2-hexanol in a mass ratio of 2: 3 for 30 seconds to obtain a pattern having a pitch of 1000 nm and a line width of 750 nm. Next, the resist film was developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 30 seconds and rinsed with pure water for 30 seconds to obtain a 250 nm (1: 1) resist pattern.

Example 10
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (B) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds and rinsing with pure water for 30 seconds to obtain a pattern having a pitch of 1200 nm and a line width of 900 nm. Next, a 300 nm (1: 1) resist pattern was obtained by developing for 30 seconds with a solution of butyl acetate / 2-hexanol in a mass ratio of 2: 3.

Example 11
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (D) prepared thereon was applied using a spin coater, and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using a KrF excimer laser scanner (NA 0.75). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds and rinsing with pure water for 30 seconds to obtain a pattern having a pitch of 1280 nm and a line width of 960 nm. Next, the resist pattern of 320 nm (1: 1) was obtained by developing for 30 second with the solution of mass ratio 2: 3 of butyl acetate / 2-hexanol.

Example 12
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. On top of that, a commercial product FAiRS-9101A12 (ArF positive resist composition manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. did. The obtained wafer was subjected to pattern exposure at 25 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75). After heating at 120 ° C. for 60 seconds, development with butyl acetate (negative developer) for 30 seconds (negative development) and rinsing with 1-hexanol for 30 seconds gave a pattern with a pitch of 180 nm and a line width of 90 nm. .

  Hereinafter, the structures of the resins (E) to (R) used in Examples 13 to 26 are shown.

  Table 1 below shows the composition ratios of resins (E) to (R) (molar ratio, corresponding to each repeating unit in order from the left), weight average molecular weight, and degree of dispersion.

Positive resist compositions (E) to (R)
A positive resist composition (E) to (R) was prepared by filtering a solution having the composition shown in Table 2 below through a 0.1 μm polyethylene filter.

  Hereinafter, abbreviations in the table are shown.

  [Acid generator]

  [Basic compounds]

〔solvent〕
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: PF6320 (manufactured by OMNOVA) (fluorine-based)

Example 13
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (E) prepared thereon was applied using a spin coater and baked at 90 ° C. for 80 seconds to form an 80 nm resist film. The obtained wafer was exposed at 18 [mJ / cm ² ] through a mask for pattern formation using a PAS5500 / 1250i manufactured by ASML equipped with a lens of NA 0.85 as an ArF excimer laser scanner. . After heating at 120 ° C. for 60 seconds, development with butyl acetate (negative developer) for 30 seconds (negative development), followed by rinsing with 1-hexanol for 30 seconds, a pattern with a pitch of 320 nm and a line width of 240 nm Got. Next, development is carried out for 30 seconds (positive development) with an aqueous tetramethylammonium hydroxide solution (0.05% by mass) (positive developer), followed by rinsing with pure water for 30 seconds to obtain 80 nm (1: 1). A resist pattern was obtained.

Example 14
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (F) prepared thereon was applied using a spin coater and baked at 120 ° C. for 60 seconds to form a 120 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Thereafter, heating at 120 ° C. for 60 seconds, developing with methyl isobutyl ketone (negative developer) for 30 seconds (negative development), rinsing with 2-heptanol for 30 seconds, and a pattern having a pitch of 200 nm and a line width of 120 nm is obtained. It was.

Example 15
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (G) prepared thereon was applied using a spin coater and baked at 110 ° C. for 60 seconds to form a 100 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Then, after heating at 100 ° C. for 80 seconds, the film was developed with ethyl lactate (negative developer) for 30 seconds (negative development) and rinsed with 2-heptanol for 60 seconds to obtain a pattern with a pitch of 200 nm and a line width of 120 nm. .

Example 16
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (H) prepared thereon was applied using a spin coater and baked at 105 ° C. for 60 seconds to form a 220 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Then, after heating at 90 ° C. for 60 seconds, develop with a 1: 1 ratio of butyl acetate / 2-hexanone (negative developer) (negative development), rinse with decane for 30 seconds, and pitch A pattern of 200 nm and a line width of 100 nm was obtained.

Example 17
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (I) prepared thereon was applied using a spin coater and baked at 95 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Thereafter, heating at 110 ° C. for 60 seconds, developing with a solution of butyl acetate / dihexyl ether in a mass ratio of 7: 3 (negative developing solution) for 30 seconds (negative developing), rinsing with 1-hexanol for 30 seconds, A pattern having a pitch of 240 nm and a line width of 100 nm was obtained.

Example 18
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. A positive resist composition (J) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Thereafter, the film was heated at 105 ° C. for 60 seconds, developed with methyl ethyl ketone (negative developer) for 30 seconds (negative development), rinsed with 1-hexanol for 30 seconds, and a pattern having a pitch of 260 nm and a line width of 130 nm was obtained.

Example 19
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (K) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. After heating at 120 ° C. for 60 seconds, development with ethyl-3-ethoxypropionate (negative developer) for 30 seconds (negative development), rinsing with 1-hexanol for 30 seconds, pitch 240 nm, line width A 120 nm pattern was obtained.

Example 20
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (L) prepared thereon was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 17 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask. After heating at 120 ° C. for 60 seconds, development is carried out for 60 seconds (negative development) with a 95: 5 mass ratio of isoamyl acetate / decane (negative development solution), rinsing with 1-hexanol for 15 seconds, pitch A pattern with 400 nm and a line width of 300 nm was obtained. Further, after the second exposure was performed at 3 [mJ / cm ² ] without using a mask for pattern formation, 20% was added with an aqueous tetramethylammonium hydroxide solution (0.238% by mass) (positive developer). Development for 1 second (positive development) and rinsing with pure water for 30 seconds gave a 100 nm (1: 1) resist pattern.

Example 21
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (M) prepared thereon was applied using a spin coater and baked at 130 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Then, after heating at 100 ° C. for 60 seconds, development was performed for 15 seconds (negative development) with a solution (negative developer) having a mass ratio of cyclohexanone / 1-hexanol of 3: 2, and a mass ratio of 2-heptanol / decane of 1 : 1 rinse for 40 seconds to obtain a pattern with a pitch of 240 nm and a line width of 120 nm.

Example 22
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (N) prepared thereon was applied using a spin coater and baked at 105 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. Thereafter, the mixture is heated at 90 ° C. for 60 seconds, then developed for 10 seconds (negative development) with a 1: 3 mass solution of diethylene glycol monoethyl ether acetate / methyl isobutyl ketone (negative development), and 1-hexanol / 2 -Rinse with a solution of heptanol in a mass ratio of 1: 1 for 60 seconds to obtain a pattern having a pitch of 240 nm and a line width of 120 nm.

Example 23
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (O) prepared thereon was applied using a spin coater and baked at 120 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask at 25 [mJ / cm ² ]. After heating at 110 ° C. for 60 seconds, development was performed with a 95: 5 solution of amyl acetate / isopropanol (negative developer) for 30 seconds (negative development), rinsed with 1-hexanol for 30 seconds, and pitch A pattern of 200 nm and a line width of 100 nm was obtained.

Example 24
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition (P) prepared thereon was applied using a spin coater and baked at 90 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure at 17 [mJ / cm ² ] using an ArF excimer laser scanner (NA 0.75) through a pattern forming mask. Then, after heating at 120 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (0.238 mass%) (positive developer) for 30 seconds (positive development), rinsed with pure water for 30 seconds, and pitched. A pattern of 480 nm and a line width of 360 nm was obtained. Further, after the second exposure was performed at 3 [mJ / cm ² ] without using a mask for pattern formation, development was performed with butyl acetate (negative developer) for 30 seconds (negative development). After rinsing with hexanol for 20 seconds, heating was performed at 90 ° C. for 90 seconds to obtain a 120 nm (1: 1) resist pattern.

The pattern dimensions formed in Examples 1 to 24 are shown in Table 3 below. A smaller value indicates better performance.
After pattern formation, the upper surface of the line pattern and the space portion were observed using a length-measuring scanning electron microscope (S9380II manufactured by Hitachi, Ltd.). The case where there is a little is represented by Δ. The results are shown in Table 3.
When the resist pattern profile is observed with a scanning electron microscope, in each resolution line width, a part of the resist pattern disappears from the middle or upper part of the pattern and Δ ○. The results are shown in Table 3.

From the above examples, good pattern resolution performance can be obtained by the combination of the negative development of the present invention and the positive resist composition, or the combination of the positive development of the present invention, the negative development and the positive resist composition. It is clear that the problem of resist residue is solved. In particular, when a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure is used as a positive resist composition, it is clear that particularly good pattern resolution performance is obtained and the generation of residues is further suppressed. It is.
Further, it is apparent that resist pattern chipping can be suppressed by performing development twice and performing negative development first and then positive development in the two development sequences.

Example 25
A positive resist composition (Q) prepared on a silicon wafer subjected to hexamethyldisilazane treatment was applied using a spin coater and baked at 90 ° C. for 60 seconds to form a 100 nm resist film. The obtained wafer was subjected to surface exposure using EUV light (wavelength 13.5 nm) while changing the exposure amount in a range of 0 to 10.0 mJ by 0.5 mJ, and further heated at 120 ° C. for 60 seconds. Thereafter, the dissolution rate at each exposure amount was measured using butyl acetate (negative developer) to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast. These results are shown in Table 4 below.

Example 26
A positive resist composition (R) prepared on a silicon wafer subjected to hexamethyldisilazane treatment was applied using a spin coater and baked at 100 ° C. for 60 seconds to form a 50 nm resist film. The obtained wafer was subjected to surface exposure using EUV light (wavelength: 13.5 nm) while changing by 0.5 mJ in an exposure amount range of 0 to 10.0 mJ, and further heated at 100 ° C. for 60 seconds. Thereafter, the dissolution rate at each exposure amount was measured using butyl acetate (negative developer) to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast. These results are shown in Table 4.

  From the results of Table 4, it is clear that the combination of the negative development of the present invention and the positive resist composition provides a good dissolution contrast and high sensitivity even in the property evaluation by EUV light irradiation. is there.

Claims (16)

It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The pattern formation method whose organic solvent in the said rinse liquid is a hydrocarbon type solvent (however, except n-hexane).
Formula I:

  2. The pattern forming method according to claim 1, wherein at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is protected with an acid-eliminable protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method). Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to claim 1, wherein, in the developing step, the resist film after heating is developed.   The pattern forming method according to claim 1, wherein the organic solvent in the negative developer is an ester solvent. Resin (excluding terpolymers represented by the following general formula (I) below) whose solubility in a positive developer, which is an alkaline developer, increases due to the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. ), And increases the solubility in the positive developer by irradiation with actinic rays or radiation, and forms a resist film in which the solubility in the negative developer decreases (however, 10 of the hydroxyl groups contained) %, 15% to 25%, or 30% of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of the following formula I and an acid generator 1 that generates an acid upon exposure: A resist film is formed by applying on a substrate except a resist composition comprising ˜30 parts by weight ,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The pattern formation method whose organic solvent in the said rinse liquid is a hydrocarbon type solvent.

[In the above formula, n is a positive integer of 5 to 1000, R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, R ⁴ represents a tricyclodecanyl group, a dicyclopentenyl group, dicyclopentenyl oxyethyl group, a cyclohexyl group, a norbornyl group, norbornane epoxy group, norbornane epoxy methyl group or an adamantyl group,, R ⁵ is a tetrahydropyranyl group, tetrahydrofuranyl group, a methyl group, an ethyl group, a propyl group, tert- butyl Group, or 3-oxocyclohexyl group, x + y + z = 1, x is 0.1 to 0.9, y is 0.1 to 0.7, and z is 0.01 to 0.7. ]
Formula I:

  6. The pattern forming method according to claim 5, wherein at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is protected with an acid-eliminable protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method). Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern forming method according to claim 5, wherein, in the developing step, the heated resist film is developed.   The pattern forming method according to claim 5, wherein the organic solvent in the negative developer is an ester solvent. It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The organic solvent in the rinse liquid is a hydrocarbon solvent,
The pattern formation method in which the said resin composition contains the compound (ZI-1) represented by the following general formula (ZI).
Formula I:

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. However, at least one of R _{201 to} R ₂₀₃ is an aryl group.
X ⁻ represents a non-nucleophilic anion.   10. The pattern forming method according to claim 9, wherein at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of hydroxyl groups of the skeleton is protected with an acid-eliminable protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method). Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
The pattern formation method according to claim 9 or 10, wherein, in the developing step, the heated resist film is developed.   The pattern forming method according to claim 9, wherein the organic solvent in the negative developer is an ester solvent. It contains a resin whose solubility in a positive developer, which is an alkaline developer, is increased by the action of an acid, and which decreases in solubility in a negative developer containing an organic solvent. A resin composition that forms a resist film with increased solubility in the solution and decreased solubility in the negative developer (however, 10%, 15% to 25%, or 30% of the hydroxyl group contained is represented by the following formula I: Except for a resist composition comprising 100 parts by weight of a resin component composed of polyhydroxystyrene substituted with a tertiary butyloxycarbonyloxy group of 1 and 30 parts by weight of an acid generator that generates an acid upon exposure) . By applying on top, form a resist film,
Exposing the resist film with EUV light;
A pattern forming method including a step of developing a resist film after exposure,
The step of developing includes a step of negative development using a negative developer containing an organic solvent,
The developing step consists only of a negative developing process using a negative developing solution containing the organic solvent,
The pattern forming method includes a step of washing with a rinsing solution containing an organic solvent after the step of developing with the negative developer,
The organic solvent in the rinse liquid is a hydrocarbon solvent,
The pattern formation method in which the said resin composition contains the compound which has a structure shown by either of following formula (A)-(E).
Formula I:

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, wherein R ²⁰¹ and R ²⁰² are bonded to each other to form a ring. May be.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.   14. The pattern forming method according to claim 13, wherein at least a part of the main chain includes a skeleton obtained by polymerizing a vinyl alcohol compound, and at least a part of the hydroxyl groups of the skeleton is protected by an acid-eliminating protecting group. When a negative pattern is formed on a material to be exposed using a photosensitive composition characterized by containing a photosensitive material and a photoacid generator, development with alcohol or ketones is performed. Except for the characteristic pattern formation method). Resist in which the resin composition increases in solubility in the positive developer and decreases in solubility in the negative developer by irradiation with the actinic ray or radiation and heating after irradiation with the actinic ray or radiation. A resin composition for forming a film;
Heating the resist film after exposure,
15. The pattern forming method according to claim 13, wherein the resist film after heating is developed in the developing step. The pattern formation method according to claim 13, wherein the organic solvent in the negative developer is an ester solvent.

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