JP4315756B2 - (Co) polymer, resist composition, and pattern forming method - Google Patents
(Co) polymer, resist composition, and pattern forming method Download PDFInfo
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- JP4315756B2 JP4315756B2 JP2003276560A JP2003276560A JP4315756B2 JP 4315756 B2 JP4315756 B2 JP 4315756B2 JP 2003276560 A JP2003276560 A JP 2003276560A JP 2003276560 A JP2003276560 A JP 2003276560A JP 4315756 B2 JP4315756 B2 JP 4315756B2
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- GQRTVVANIGOXRF-UHFFFAOYSA-N (2-methyl-1-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)C2(OC(=O)C=C)C3 GQRTVVANIGOXRF-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
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- MWMWRSCIFDZZGW-UHFFFAOYSA-N (2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC1=O MWMWRSCIFDZZGW-UHFFFAOYSA-N 0.000 description 2
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- WLZMKZGLQVILBX-UHFFFAOYSA-N 2-(1-adamantyl)propan-2-yl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(C(C)(C)OC(=O)C(=C)C)C3 WLZMKZGLQVILBX-UHFFFAOYSA-N 0.000 description 1
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical group CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
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- YYSDNLZCJQMZCZ-UHFFFAOYSA-N 5,5-dimethyl-3-methylenedihydrofuran-2-one Chemical compound CC1(C)CC(=C)C(=O)O1 YYSDNLZCJQMZCZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
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- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- UUMAFLKWOXKEID-UHFFFAOYSA-N diphenyliodanium;dodecyl benzenesulfonate Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 UUMAFLKWOXKEID-UHFFFAOYSA-N 0.000 description 1
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- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- LABYRQOOPPZWDG-UHFFFAOYSA-M naphthalene-1-sulfonate;triphenylsulfanium Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LABYRQOOPPZWDG-UHFFFAOYSA-M 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
本発明は、レジスト材料等に有用な（共）重合体、特に、エキシマレーザーあるいは電子線を使用する微細加工に好適なレジスト材料用（共）重合体、その製造方法、この（共）重合体を用いたレジスト組成物、およびパターン形成方法に関する。 The present invention relates to a (co) polymer useful for a resist material and the like, in particular, a (co) polymer for a resist material suitable for fine processing using an excimer laser or an electron beam, a method for producing the same, and the (co) polymer. The present invention relates to a resist composition and a pattern forming method.
近年、半導体素子あるいは液晶素子の製造における微細加工の分野においては、素子の高密度化、高集積化を実現するため、リソグラフィー技術の進歩を背景とした急速な微細化が進んでいる。その微細化の手法としては、一般に、露光光源の短波長化が用いられ、具体的には、従来のｇ線（波長：４３８ｎｍ）、ｉ線（波長：３６５ｎｍ）に代表される紫外光から遠紫外光へと露光光源が変化してきている。 In recent years, in the field of microfabrication in the manufacture of semiconductor devices or liquid crystal devices, rapid miniaturization has progressed against the backdrop of advances in lithography technology in order to realize higher density and higher integration of devices. As a method for miniaturization, generally, the exposure light source is shortened in wavelength. Specifically, it is far from ultraviolet light typified by conventional g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm). The exposure light source is changing to ultraviolet light.
現在では、ＫｒＦエキシマレーザー（波長：２４８ｎｍ）リソグラフィー技術が市場に導入され、さらに短波長化を図ったＡｒＦエキシマレーザー（波長：１９３ｎｍ）リソグラフィー技術も導入されようとしている。さらに、次世代の技術として、Ｆ2エキシマレーザー（波長：１５７ｎｍ）リソグラフィー技術が研究されている。また、これとは若干異なるタイプのリソグラフィー技術として、電子線リソグラフィー技術についても精力的に研究されている。 At present, a KrF excimer laser (wavelength: 248 nm) lithography technique is introduced into the market, and an ArF excimer laser (wavelength: 193 nm) lithography technique aiming for a shorter wavelength is also being introduced. Further, as a next-generation technique, an F 2 excimer laser (wavelength: 157 nm) lithography technique has been studied. Also, as a slightly different type of lithography technique, an electron beam lithography technique has been vigorously studied.
このような短波長の光源あるいは電子線に対する高感度のレジストとして、インターナショナル・ビジネス・マシーン（ＩＢＭ）社より「化学増幅型レジスト」が提唱され、現在、この化学増幅型レジストの改良および開発が精力的に進められている。 As a highly sensitive resist for such short-wavelength light sources or electron beams, International Business Machines (IBM) has proposed “Chemically Amplified Resist” and is currently energetically improving and developing this chemically amplified resist. Is underway.
光源の短波長化においては、レジストに使用される樹脂もその構造変化を余儀なくされる。例えば、ＫｒＦエキシマレーザーリソグラフィーにおいては、波長２４８ｎｍの光に対して透明性の高いポリヒドロキシスチレンや、その水酸基を酸解離性の溶解抑制基で保護したもの等が用いられる。しかし、ＡｒＦエキシマレーザーリソグラフィーにおいては、前記樹脂は波長１９３ｎｍの光に対する透明性が必ずしも十分とはいえず、使用できない場合が多い。 In order to shorten the wavelength of the light source, the resin used for the resist is forced to change its structure. For example, in KrF excimer laser lithography, polyhydroxystyrene having high transparency with respect to light having a wavelength of 248 nm, or a hydroxyl group protected with an acid dissociable, dissolution inhibiting group is used. However, in ArF excimer laser lithography, the resin is not necessarily sufficiently transparent with respect to light having a wavelength of 193 nm, and cannot be used in many cases.
そのため、１９３ｎｍにおいて透明なアクリル系樹脂が注目されている。このようなアクリル系樹脂としては、例えば、特許文献１にはメタクリル酸２−メチル−２−アダマンチルの（共）重合体が酸の作用により解裂してポジ型に作用するとともに、高いドライエッチング耐性、高感度および高解像性が得られることが報告されている。しかしながら、このような脂環式骨格を有する（共）重合体は、基板密着性がよくない、疎水性が高く現像液への濡れ性がよくないなどの問題を持つ。 Therefore, an acrylic resin that is transparent at 193 nm has attracted attention. As such an acrylic resin, for example, in Patent Document 1, a (co) polymer of 2-methyl-2-adamantyl methacrylate is cleaved by the action of an acid to act positively, and high dry etching It has been reported that tolerance, high sensitivity and high resolution can be obtained. However, such (co) polymers having an alicyclic skeleton have problems such as poor substrate adhesion, high hydrophobicity, and poor wettability to a developer.
これらの問題を改良すべく、ラクトン構造を有する化合物のメタクリル酸誘導体を使用する方法、脂環式構造に水酸基などの親水性基を導入した化合物のメタクリル酸エステル使用する方法などの数々の提案がなされた。例えば、特許文献２、特許文献３、特許文献４、特許文献５などには、ラクトン環を有する橋かけ環式飽和炭化水素のメタクリル酸エステルが記載されている。 In order to improve these problems, there are numerous proposals such as a method using a methacrylic acid derivative of a compound having a lactone structure, a method using a methacrylic acid ester of a compound in which a hydrophilic group such as a hydroxyl group is introduced into an alicyclic structure. Was made. For example, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and the like describe a methacrylic ester of a bridged cyclic saturated hydrocarbon having a lactone ring.
しかし、ラクトン構造を有するメタクリル酸誘導体や脂環式構造に水酸基などの親水性基を導入した化合物のメタクリル酸誘導体を（共）重合した場合は、分子中の炭素密度が小さくなることから必要性能の一つであるドライエッチング耐性が低下する現象が見られるようになった。 However, when a methacrylic acid derivative having a lactone structure or a methacrylic acid derivative of a compound in which a hydrophilic group such as a hydroxyl group is introduced into an alicyclic structure is (co) polymerized, the carbon density in the molecule is reduced, so the required performance The phenomenon that the dry etching resistance, which is one of the above, decreases.
本発明は、波長２５０ｎｍ以下の光、特にＡｒＦエキシマレーザー光に対して高感度で、ドライエッチング耐性に優れ、遠紫外光エキシマレーザーリソグラフィーや電子線リソグラフィー等に好適なレジスト組成物用樹脂およびレジスト組成物、レジスト組成物に適したこのような樹脂の製造方法、並びに、このレジスト組成物を用いた微細なパターン形成方法を提供することを目的とする。 The present invention relates to a resist composition resin and a resist composition which are highly sensitive to light having a wavelength of 250 nm or less, particularly ArF excimer laser light, excellent in dry etching resistance, and suitable for far ultraviolet excimer laser lithography, electron beam lithography and the like. It is an object of the present invention to provide a method for producing such a resin suitable for a resist and a resist composition, and a fine pattern forming method using the resist composition.
本発明者らは、前記目的を達成するため鋭意検討した結果、特定の構成単位を含む新規な（共）重合体、その製造方法、そのような（共）重合体を用いた高感度で、ドライエッチング耐性に極めて優れたレジスト組成物、およびこのレジスト組成物を用いたパターン形成方法を見出して本発明に到達した。 As a result of intensive studies to achieve the above object, the present inventors have found that a novel (co) polymer containing a specific structural unit, a production method thereof, and a high sensitivity using such a (co) polymer, The present inventors have found a resist composition having extremely excellent dry etching resistance and a pattern forming method using the resist composition, and have reached the present invention.
すなわち、本発明の第一の要旨は、下記式（２）〜（３）：
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位であり、ただし、上記式（２）で表される繰り返し単位が、下記式（２２）、（２３）、（２４）、（２５）、（２６）、（２７）、（２９）及び（３０）：
から選択されるものである繰り返し単位と、
下記式（Ａ）〜（Ｃ）：
で表される繰り返し単位から選ばれる１種又は２種以上とを含み、質量平均分子量が１，０００〜１００，０００である（共）重合体である。
That is, the first gist of the present invention is the following formulas (2) to (3):
Is a repeating unit represented by the following formulas (22), (23), (24), and the repeating unit represented by the above formula (2). (25), (26), (27), (29) and (30):
A repeating unit that is selected from:
The following formulas (A) to (C):
It is a (co) polymer which contains 1 type (s) or 2 or more types selected from the repeating unit represented by these, and whose weight average molecular weights are 1,000-100,000.
本発明の第二の要旨は、下記式（２）〜（３）：
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位となる単量体であり、ただし、上記式（２）で表される繰り返し単位が、下記式（２２）、（２３）、（２４）、（２５）、（２６）、（２７）、（２９）及び（３０）：
から選択されるものである単量体と、
下記式（Ａ）〜（Ｃ）：
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位となる単量体とを、有機溶剤に溶解させた溶液を、重合釜中に滴下しながら（共）重合を行う（共）重合体の製造方法である。
The second gist of the present invention is the following formulas (2) to (3):
A monomer that becomes one or more repeating units selected from the repeating units represented by the formula: wherein the repeating unit represented by the above formula (2) is represented by the following formulas (22), (23): , (24), (25), (26), (27), (29) and (30):
A monomer that is selected from
The following formulas (A) to (C):
(Co) polymerization is carried out while a solution prepared by dissolving one or more monomers selected from repeating units represented by the formula (1) is dissolved in an organic solvent into a polymerization vessel (co-polymerization). ) A method for producing a polymer.
本発明の第三の要旨は、前記（共）重合体を含有するレジスト組成物である。 The third gist of the present invention is a resist composition containing the (co) polymer.
本発明の第四の要旨は、前記レジスト組成物を被加工基板上に塗布する工程と、２５０ｎｍ以下の波長の光で露光する工程と、現像液を用いて現像する工程とを含むパターン形成方法である。 According to a fourth aspect of the present invention, there is provided a pattern forming method comprising: a step of applying the resist composition on a substrate to be processed; a step of exposing with light having a wavelength of 250 nm or less; and a step of developing using a developer. It is.
本発明第五の要旨は、前記レジスト組成物を被加工基板上に塗布する工程と、２５０ｎｍ以下の波長の光で露光する工程と、加熱処理した後現像液を用いて現像する工程とを含むパターン形成方法である。 The fifth gist of the present invention includes a step of applying the resist composition onto a substrate to be processed, a step of exposing with light having a wavelength of 250 nm or less, and a step of developing using a developer after heat treatment. This is a pattern forming method.
本発明第六の要旨は、前記レジスト組成物を被加工基板上に塗布する工程と、電子線で露光する工程と、現像液を用いて現像する工程とを含むパターン形成方法である。 The sixth aspect of the present invention is a pattern forming method including a step of applying the resist composition onto a substrate to be processed, a step of exposing with an electron beam, and a step of developing using a developer.
本発明第七の要旨は前記レジスト組成物を被加工基板上に塗布する工程と、電子線で露光する工程と、加熱処理した後現像液を用いて現像する工程とを含むパターン形成方法である。 The seventh gist of the present invention is a pattern forming method including a step of applying the resist composition onto a substrate to be processed, a step of exposing with an electron beam, and a step of developing using a developer after heat treatment. .
本発明のレジスト組成物用樹脂を用いたレジスト組成物は波長２５０ｎｍ以下の光、特にＡｒＦエキシマレーザー光に対して透明性が高く、高感度である。また、ドライエッチング耐性に優れており、遠紫外光エキシマレーザーリソグラフィーや電子線リソグラフィー等、特に特にＡｒＦエキシマレーザーを使用するリソグラフィーに好適に用いることが出来る。また、本発明の製造方法はレジスト組成物に適した樹脂を製造することが可能である。
このようなレジスト組成物を用いた本発明のパターン形成方法によれば、高精度の微細なレジストパターンを安定して形成することができる。このパターン形成方法は遠紫外光エキシマレーザーリソグラフィーや電子線リソグラフィー、特にＡｒＦエキシマレーザーを使用するリソグラフィーに好適である。
The resist composition using the resin for resist compositions of the present invention is highly transparent and highly sensitive to light having a wavelength of 250 nm or less, particularly ArF excimer laser light. Moreover, it is excellent in dry etching resistance, and can be suitably used for lithography using far-ultraviolet excimer laser lithography, electron beam lithography, etc., in particular, using ArF excimer laser. Further, the production method of the present invention can produce a resin suitable for the resist composition.
According to the pattern forming method of the present invention using such a resist composition, a highly accurate fine resist pattern can be stably formed. This pattern forming method is suitable for deep ultraviolet excimer laser lithography and electron beam lithography, particularly for lithography using an ArF excimer laser.
以下、本発明を詳しく説明する。 The present invention will be described in detail below.
本発明では、（共）重合とは単独重合または共重合を意味し、（共）重合体とは単独重合または共重合により得られた（共）重合体を意味する。
また、本発明では、「（メタ）アクリル酸」とは、アクリル酸とメタクリル酸の総称である。
In the present invention, (co) polymerization means homopolymerization or copolymerization, and (co) polymer means a (co) polymer obtained by homopolymerization or copolymerization.
In the present invention, “(meth) acrylic acid” is a general term for acrylic acid and methacrylic acid.
本発明の前記式（１）〜（３）で表される構成単位から選ばれる１種又は２種以上を含有する（共）重合体は下記式（４）〜（６） The (co) polymer containing one or more selected from the structural units represented by the formulas (1) to (3) of the present invention is represented by the following formulas (4) to (6).
で表される単量体から選ばれる１種又は２種以上を（共）重合させることにより得られる。
It is obtained by (co) polymerizing one or more selected from the monomers represented by
前記式（４）〜（６）で表される単量体は、前記式（４）〜（６）で表される単量体以外の単量体と（共）重合させてもよい。 The monomers represented by the formulas (4) to (6) may be (co) polymerized with monomers other than the monomers represented by the formulas (4) to (6).
なお、本発明において、単量体とはすべての幾何異性体、光学異性体などを含む概念であり、純粋な異性体として、またそれらの混合物として使用できる。また、中間体を含んでいても使用可能である。必要ならば、通常の蒸留、薄膜蒸留、再結晶、およびカラムクロマトグラフィー等の手段によって精製してもよい。 In the present invention, the monomer is a concept including all geometric isomers, optical isomers and the like, and can be used as a pure isomer or a mixture thereof. Moreover, it can be used even if it contains an intermediate. If necessary, it may be purified by means of ordinary distillation, thin film distillation, recrystallization, column chromatography and the like.
この（共）重合体をベース樹脂として配合したレジスト材料は、矩形性の良好なパターンを形成し、剥がれを起こさず、優れたドライエッチング耐性を有する。 A resist material blended with this (co) polymer as a base resin forms a pattern with good rectangularity, does not cause peeling, and has excellent dry etching resistance.
前記式（１）〜（３）中のＣａＨ２ａ〜ＣｆＨ２ｆの例としては、単結合、ＣＨ２、ＣＨ２−ＣＨ２などが挙げられる。（共）重合体をレジスト組成物材料に使用したときの感度の点からａ〜ｆは０または１が好ましい。 Examples of C a H 2a to C f H 2f in the formulas (1) to (3) include a single bond, CH 2 , and CH 2 —CH 2 . From the viewpoint of sensitivity when a (co) polymer is used as a resist composition material, a to f are preferably 0 or 1.
前記多環式炭化水素構造は、骨格中に−Ｏ−または−Ｓ−、−ＮＨ−を１つまたは複数個有していてもよい。 The polycyclic hydrocarbon structure may have one or more —O—, —S—, and —NH— in the skeleton.
（共）重合体をレジスト組成物材料に使用したときのドライエッチング耐性、光透過性等の点から骨格中に−Ｏ−を１つまたは複数個有していてものが好ましく、−Ｏ−を１つ有しているものがより好ましい。 From the viewpoints of dry etching resistance and light transmittance when a (co) polymer is used as a resist composition material, it may preferably have one or more —O— in the skeleton. What has one is more preferable.
前記多環式炭化水素構造は、（共）重合体をレジスト組成物材料に使用したときのドライエッチング耐性の点から、炭素数が１０〜２２である必要があり、１０〜１８が好ましく、さらに好ましくは、下記式（７）〜（１５） The polycyclic hydrocarbon structure needs to have 10 to 22 carbon atoms, preferably 10 to 18 carbon atoms, from the viewpoint of dry etching resistance when a (co) polymer is used as a resist composition material. Preferably, the following formulas (7) to (15)
本発明に使用される単量体の好ましい例示として、下記式（１６）〜（３３） Preferred examples of the monomer used in the present invention include the following formulas (16) to (33).
で表される単量体などが挙げられる。より好ましい単量体として前記式（２２）〜（３３）が挙げられる。
And the like. More preferable monomers include the above formulas (22) to (33).
（共）重合体をレジスト組成物材料に使用したときのドライエッチング耐性の点から、前記式（２）で表される構成単位が好ましい。また、（共）重合体をレジスト組成物材料に使用したときのラインエッジラフネス低減の点から、前記式（３）で表される構成単位が好ましい。 From the viewpoint of dry etching resistance when a (co) polymer is used for the resist composition material, the structural unit represented by the formula (2) is preferable. Moreover, the structural unit represented by said Formula (3) is preferable from the point of the line edge roughness reduction when a (co) polymer is used for resist composition material.
以上の多環式炭化水素構造の水素原子は、炭素数１〜６の直鎖もしくは分岐アルキル基で置換されていてもよく、さらにヒドロキシ基、カルボキシ基、炭素数１〜６のエステル基、炭素数１〜６のアルコキシ基、アミノ基、またはシアノ基のいずれかを有していてもよい。
直鎖もしくは分岐アルキル基の例としてはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、ｎ−ペンチル基、ｓｅｃ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｓｅｃ−ヘキシル基などが挙げられる。
炭素数１〜６のエステル基の例としては、−ＣＯＯＣＨ３、−ＣＯＯＣ２Ｈ５、−ＣＯＯＣ３Ｈ７、−ＣＯＯＣ４Ｈ９、−ＣＯＯＣ５Ｈ１０、−ＣＯＯＣ６Ｈ１３（ここで、Ｃ３Ｈ７はｎ−プロピル基、ｉｓｏ−プロピル基、Ｃ４Ｈ９はｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、Ｃ５Ｈ１０はｎ−ペンチル基、ｓｅｃ−ペンチル基、ネオペンチル基、Ｃ６Ｈ１３はｎ−ヘキシル基、ｓｅｃ−ヘキシル基等を示す）が挙げられる。
炭素数１〜６のアルコキシ基の例としては、−ＯＣＨ３、−ＯＣ２Ｈ５、−ＯＣ３Ｈ７、−ＯＣ４Ｈ９、−ＯＣ５Ｈ１０、−ＯＣ６Ｈ１３（ここで、Ｃ３Ｈ７はｎ−プロピル基、ｉｓｏ−プロピル基、Ｃ４Ｈ９はｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、Ｃ５Ｈ１０はｎ−ペンチル基、ｓｅｃ−ペンチル基、ネオペンチル基、Ｃ６Ｈ１３はｎ−ヘキシル基、ｓｅｃ−ヘキシル基等を示す）が挙げられる。
The hydrogen atom of the above polycyclic hydrocarbon structure may be substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and further, a hydroxy group, a carboxy group, an ester group having 1 to 6 carbon atoms, carbon You may have either the alkoxy group of number 1-6, an amino group, or a cyano group.
Examples of linear or branched alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, sec-pentyl. Group, neopentyl group, n-hexyl group, sec-hexyl group and the like.
Examples of the ester group having 1 to 6 carbon atoms include —COOCH 3 , —COOC 2 H 5 , —COOC 3 H 7 , —COOC 4 H 9 , —COOC 5 H 10 , —COOC 6 H 13 (where, C 3 H 7 is n-propyl group, iso-propyl group, C 4 H 9 is n-butyl group, sec-butyl group, tert-butyl group, C 5 H 10 is n-pentyl group, sec-pentyl group, Neopentyl group, C 6 H 13 represents n-hexyl group, sec-hexyl group, etc.).
Examples of the alkoxy group having 1 to 6 carbon atoms include —OCH 3 , —OC 2 H 5 , —OC 3 H 7 , —OC 4 H 9 , —OC 5 H 10 , —OC 6 H 13 (where, C 3 H 7 is n-propyl group, iso-propyl group, C 4 H 9 is n-butyl group, sec-butyl group, tert-butyl group, C 5 H 10 is n-pentyl group, sec-pentyl group, Neopentyl group, C 6 H 13 represents n-hexyl group, sec-hexyl group, etc.).
（共）重合体をレジスト組成物材料に使用したときのドライエッチング耐性の点から、前記多環式炭化水素構造は、炭素数１〜２のアルキル基を有していることが好ましい。レジスト組成物材料に使用したときの（共）重合体の基板に対する密着性の点で、前記多環式炭化水素構造および／またはその置換基がヒドロキシ基、カルボキシ基、炭素数１〜６のエステル基または炭素数１〜６のアルコキシ基のいずれかを有していることが好ましく、ヒドロキシ基、カルボキシ基、メトキシ基、エトキシ基を有していることがより好ましく、メトキシ基、エトキシ基を有していることがもっとも好ましい。これらの基は２種以上でも、複数でもよいが、１〜２個であることがレジスト組成物材料に使用したときのドライエッチング耐性の点から好ましい。 From the viewpoint of dry etching resistance when a (co) polymer is used as a resist composition material, the polycyclic hydrocarbon structure preferably has an alkyl group having 1 to 2 carbon atoms. The polycyclic hydrocarbon structure and / or its substituent is a hydroxy group, a carboxy group, or an ester having 1 to 6 carbon atoms in terms of adhesion of the (co) polymer to the substrate when used as a resist composition material. Group or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxy group, a carboxy group, a methoxy group or an ethoxy group, and a methoxy group or an ethoxy group. Most preferably. These groups may be two or more types or a plurality of groups, but one or two groups are preferable from the viewpoint of dry etching resistance when used as a resist composition material.
（共）重合体中の前記式（１）〜（３）で表される構成単位の比率（２種以上ある場合はその和）に関し、下限は、感度および解像度の点で、１５モル％以上が好ましく、３０モル％以上がより好ましい。上限は、基板表面等への密着性および有機溶剤への溶解性の点で、７０モル％以下が好ましく、６０モル％以下がより好ましい。 Regarding the ratio of the structural units represented by the above formulas (1) to (3) in the (co) polymer (sum of two or more types), the lower limit is 15 mol% or more in terms of sensitivity and resolution. Is preferable, and 30 mol% or more is more preferable. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less, from the viewpoint of adhesion to the substrate surface and the like and solubility in an organic solvent.
本発明で使用される単量体の製造は、一例として下記工程（Ｓｃｈｅｍｅ １〜４）にて行うことができるが、これに限定されるものではない。 As an example, the production of the monomer used in the present invention can be performed in the following steps (Schemes 1 to 4), but is not limited thereto.
前記原料に１，３−ブタジエン、シクロペンタジエン、シクロヘキサジエン、フランなどを付加させるディールス・アルダー反応は既知の方法にて、容易に進行するが、好ましくは無溶剤又はベンゼン等の溶剤中、必要に応じてルイス酸等の触媒を添加して行われる。 Diels-Alder reaction for adding 1,3-butadiene, cyclopentadiene, cyclohexadiene, furan, etc. to the raw material proceeds easily by a known method, but preferably in a solvent-free or solvent such as benzene. Accordingly, a catalyst such as Lewis acid is added.
水素化ホウ素ナトリウムを還元剤として、酸無水物からラクトンを得る方法は広く知られており、例えば、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，３５，３５７４（１９７０）には、テトラヒドロフラン（ＴＨＦ）またはＤＭＦ溶剤下、水素化ホウ素ナトリウムを還元剤としてラクトン化合物を合成する方法が記載され、また、Ｓｙｎｔｈｅｓｉｓ，４２（１９７４）エタノール溶剤下、水素化ホウ素ナトリウムにより還元する方法が記載されている。
反応剤と溶剤を兼ねてギ酸を使用し、過酸化水素酸化したのちラクトン環の巻直しを起こさせる反応はＪ．Ｃｈｅｍ．Ｓｏｃ．，２２１（１９５９）記載の方法などを応用することにより実施可能である。
A method for obtaining a lactone from an acid anhydride using sodium borohydride as a reducing agent is widely known. Org. Chem. , 35, 3574 (1970) describes a method of synthesizing a lactone compound using sodium borohydride as a reducing agent in tetrahydrofuran (THF) or DMF solvent, and Synthesis, 42 (1974) in ethanol solvent. A method of reduction with sodium borohydride is described.
The reaction that uses formic acid as a reactant and a solvent to cause lactone ring rewinding after oxidation with hydrogen peroxide is described in J. Am. Chem. Soc. , 221 (1959), and the like.
エステル化反応は既知の方法のいずれでも使用可能である。（メタ）アクリル酸クロリドなどのカルボン酸ハライドを使用する場合、塩化メチレン等の溶剤中、トリエチルアミン等の塩基を加えて反応を行う方法がある。 The esterification reaction can be used by any known method. When a carboxylic acid halide such as (meth) acrylic acid chloride is used, there is a method in which a reaction is carried out by adding a base such as triethylamine in a solvent such as methylene chloride.
ラクトン環を有する化合物の不飽和結合への（メタ）アクリル酸の付加反応は非常に起こりにくい。しかし、トリフロロメタンスルホン酸などの強い酸性を有する酸触媒を使用することにより、反応が進行する。反応は、室温〜還流温度で、無溶剤、過剰の（メタ）アクリル酸中、トルエンなどの不活性溶剤中などで行うことが可能である。また、不飽和結合に付加しやすいギ酸等のカルボン酸を付加させ、エステル交換反応する方法または加水分解して生成するヒドロキシ基とし、既知の方法でエステル化する方法も使用可能である。 The addition reaction of (meth) acrylic acid to an unsaturated bond of a compound having a lactone ring is very difficult to occur. However, the reaction proceeds by using an acid catalyst having strong acidity such as trifluoromethanesulfonic acid. The reaction can be carried out at room temperature to reflux temperature without solvent, in excess (meth) acrylic acid, or in an inert solvent such as toluene. In addition, a method of adding a carboxylic acid such as formic acid that is easily added to an unsaturated bond, and performing a transesterification reaction or a hydrolyzed hydroxy group, and esterifying by a known method can be used.
また、本発明においては、本発明に使用される前記単量体から選ばれる１種又は２種以上に、これまで化学増幅型のポジ型レジストとして公知の耐ドライエッチング性向上基や酸解離性の溶解抑制基を有する（メタ）アクリル酸誘導体、（メタ）アクリル酸、マレイン酸、フマル酸などのアルカリ可溶性とするためのエチレン性二重結合を有するカルボン酸およびその無水物、その他の単量体などを必要に応じ、適宜組み合わせ、（共）重合させて用いることができる。 In the present invention, one or two or more selected from the monomers used in the present invention can be used as a chemically amplified positive resist, a dry etching resistance improving group or an acid dissociation group. (Meth) acrylic acid derivatives having a dissolution inhibiting group, (meth) acrylic acid, maleic acid, carboxylic acid having an ethylenic double bond to make it soluble in alkali such as fumaric acid and its anhydride, and other single quantities The bodies and the like can be appropriately combined and (co) polymerized as necessary.
上記の（メタ）アクリル酸誘導体としては、例えば（メタ）アクリル酸の水素原子をメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、ｎ−ヘキシル、オクチル、２−エチルヘキシル、ラウリル、２−ヒドロキシエチル、２−ヒドロキシプロピル、シクロペンチル、シクロヘキシル、ノルボルニル、トリシクロデカニル、アダマンチル、１−メチルアダマンチル、２−メチル−２−アダマンチル、テトラヒドロピラニル、テトラヒドロフラニル、１−メチルシクロヘキシル、エトキシエチル、エトキシプロピル、および２−ヒドロキシ−３−ピナノン等の基で置換した（メタ）アクリル酸誘導体等を挙げることが出来る。 As the above (meth) acrylic acid derivative, for example, the hydrogen atom of (meth) acrylic acid is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, octyl, 2-ethylhexyl, lauryl. 2-hydroxyethyl, 2-hydroxypropyl, cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl, adamantyl, 1-methyladamantyl, 2-methyl-2-adamantyl, tetrahydropyranyl, tetrahydrofuranyl, 1-methylcyclohexyl, ethoxy Examples include (meth) acrylic acid derivatives substituted with groups such as ethyl, ethoxypropyl, and 2-hydroxy-3-pinanone.
エチレン性二重結合を有するカルボン酸およびその無水物としては、例えば（メタ）アクリル酸、マレイン酸、フマル酸及び無水マレイン酸等を挙げることができる。 Examples of the carboxylic acid having an ethylenic double bond and its anhydride include (meth) acrylic acid, maleic acid, fumaric acid, and maleic anhydride.
その他の単量体の例として、ノルボルネン又はその一部をアルキル基、アルキルオキシ基、水酸基、ヒドロキシアルキル基、カルボキシ基、アルキルオキシカルボニル基等で置換したノルボルネン誘導体；エチルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシエチルビニルエーテル等のビニルエーテル誘導体；スチレン、パラヒドロキシスチレン、パラメトキシスチレン、パラｔｅｒｔ−ブトキシスチレン等のスチレン誘導体等を挙げることができる。 Examples of other monomers include norbornene or a norbornene derivative in which a part thereof is substituted with an alkyl group, an alkyloxy group, a hydroxyl group, a hydroxyalkyl group, a carboxy group, an alkyloxycarbonyl group, etc .; ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl Examples thereof include vinyl ether derivatives such as vinyl ether; styrene derivatives such as styrene, parahydroxystyrene, paramethoxystyrene, and para tert-butoxystyrene.
本発明の（共）重合体は、前記式（１）〜（３）で表される構成単位から選ばれる１種又は２種以上と下記式（Ａ）〜（Ｃ） The (co) polymer of the present invention is one or more selected from the structural units represented by the above formulas (1) to (3) and the following formulas (A) to (C).
で表される構成単位から選ばれる１種又は２種以上を構成単位として含有する（共）重合体が好ましい。
(Co) polymers containing one or more selected from the structural units represented by the following structural units are preferred.
前記式（Ａ）に関する置換基の例としては、炭素数１〜６の直鎖もしくは分岐アルキル基等が挙げられる。 As an example of the substituent regarding the said formula (A), a C1-C6 linear or branched alkyl group etc. are mentioned.
前記式（Ｂ）に関する置換基の例としてはヒドロキシ基、カルボキシ基、または、炭素数１〜６のエステル基等が挙げられる。 Examples of the substituent relating to the formula (B) include a hydroxy group, a carboxy group, or an ester group having 1 to 6 carbon atoms.
前記式（Ａ）、（Ｂ）中の炭素数１〜６の直鎖もしくは分岐アルキル基の例としてはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、ｎ−ペンチル基、ｓｅｃ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｓｅｃ−ヘキシル基およびシクロペンチル基などが挙げられる。 Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in the formulas (A) and (B) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert. -Butyl group, tert-amyl group, n-pentyl group, sec-pentyl group, neopentyl group, n-hexyl group, sec-hexyl group and cyclopentyl group.
前記式（Ａ）、（Ｂ）中の環式飽和炭化水素基の例としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基およびこれらの置換基がスピロ構造を有しているものがあげられる。 Examples of the cyclic saturated hydrocarbon group in the formulas (A) and (B) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and those in which these substituents have a spiro structure. can give.
前記式（Ａ）、（Ｂ）中の橋かけ環式飽和炭化水素基とは、アダマンタン、ノルボルナンに代表される、一般式（１０） The bridged cyclic saturated hydrocarbon group in the formulas (A) and (B) is represented by the general formula (10) represented by adamantane and norbornane.
または一般式（１１）
Or general formula (11)
で表される構造を有すものである。
It has a structure represented by.
前記式（Ｂ）、（Ｃ）中の親水性官能基の例としては、ヒドロキシ基、カルボキシ基、アミノ基などの極性の高い基、およびケトン、酸無水物、エステル、エーテル、ラクトン、イミド、アミドなどの構造を有する直鎖もしくは分岐アルキル基、環状化合物等があげられる。親水性官能基を有する化合物には、骨格の一部がケトン、酸無水物、エステル、エーテル、ラクトン、イミド、アミドなどの構造に置換された炭素数４〜８の環式飽和炭化水素基、炭素数４〜１６の橋かけ環式飽和炭化水素基も含まれる。 Examples of the hydrophilic functional group in the formulas (B) and (C) include highly polar groups such as a hydroxy group, a carboxy group, and an amino group, and ketones, acid anhydrides, esters, ethers, lactones, imides, Examples thereof include a linear or branched alkyl group having a structure such as amide, and a cyclic compound. The compound having a hydrophilic functional group includes a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms in which a part of the skeleton is substituted with a structure such as ketone, acid anhydride, ester, ether, lactone, imide, amide, A bridged cyclic saturated hydrocarbon group having 4 to 16 carbon atoms is also included.
環式飽和炭化水素基および橋かけ環式飽和炭化水素基を有する構成単位は、これを含む（共）重合体に高いドライエッチング耐性を付与するものである。特に、酸により脱離する保護基（環式飽和炭化水素基が直接保護基になっていてもよい。）を含有するものは、波長１９３ｎｍのＡｒＦエキシマレーザーを用いたフォトリソグラフィーにおける高い感度も付与することができる。環式飽和炭化水素基を有する構成単位は、必要に応じて、１種としても、２種以上としてもよい。 The structural unit having a cyclic saturated hydrocarbon group and a bridged cyclic saturated hydrocarbon group imparts high dry etching resistance to a (co) polymer containing the structural unit. In particular, those containing a protecting group that can be eliminated by an acid (a cyclic saturated hydrocarbon group may be directly a protecting group) also provide high sensitivity in photolithography using an ArF excimer laser having a wavelength of 193 nm. can do. The structural unit having a cyclic saturated hydrocarbon group may be one type or two or more types as necessary.
親水性官能基を有する構成単位は、これを含む（共）重合体に基板に対する密着性を付与するものである。特に、酸により脱離する保護基を含有するものは、波長１９３ｎｍのＡｒＦエキシマレーザーを用いたフォトリソグラフィーにおける高い感度も付与することができる。親水性官能基としては、例えば、末端ヒドロキシ基、アルキル置換エーテル基、δ−バレロラクトニル基、γ−ブチロラクトニル基等を挙げることができる。なお、前記の親水性官能基には、通常、疎水性に含まれるものもあるが、本発明において必要な親水性が得られればよいので、前記のものが含まれる。親水性官能基を有する単量体単位は、必要に応じて、１種としても、２種以上としてもよい。親水性官能基を有する構成単位を（共）重合体に導入するためには、親水性官能基を有する単量体を（共）重合すればよい。 The structural unit having a hydrophilic functional group imparts adhesiveness to the substrate to the (co) polymer containing the structural unit. In particular, those containing a protecting group that is eliminated by an acid can impart high sensitivity in photolithography using an ArF excimer laser having a wavelength of 193 nm. Examples of the hydrophilic functional group include a terminal hydroxy group, an alkyl-substituted ether group, a δ-valerolactonyl group, and a γ-butyrolactonyl group. In addition, although the said hydrophilic functional group has some which are normally contained in hydrophobicity, since the hydrophilicity required in this invention should just be acquired, the said thing is contained. The monomer unit having a hydrophilic functional group may be one kind or two or more kinds as necessary. In order to introduce a structural unit having a hydrophilic functional group into a (co) polymer, a monomer having a hydrophilic functional group may be (co) polymerized.
前記式（Ａ）で表される構成単位を（共）重合体に導入するには、式（Ａ’）で表される単量体を共重合すればよい。
前記式（Ｂ）で表される構成単位を（共）重合体に導入するには、式（Ｂ’）で表される単量体を共重合すればよい。 In order to introduce the structural unit represented by the formula (B) into the (co) polymer, the monomer represented by the formula (B ′) may be copolymerized.
このような単量体として、具体的には、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル、（メタ）アクリル酸−４−ヒドロキシブチル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−２−エトキシエチル、１−メタクリロイルオキシ−３−ヒドロキシアダマンタン、β−（メタ）アクリロイルオキシ−β−メチル−δ−バレロラクトン、β−（メタ）アクリロイルオキシ−γ−ブチロラクトン、β−（メ
タ）アクリロイルオキシ−β−メチル−γ−ブチロラクトン、α−（メタ）アクリロイルオキシ−γ−ブチロラクトン、２−（１−（メタ）アクリロイルオキシ）エチル−４−ブタノリド、パントラクトン（メタ）アクリレート、８−メタクリロイルオキシ−３−オキサトリシクロ［５．２．１．０２,６］デカン−２−オン、９−メタクリロイルオキシ−３−オキサトリシクロ［５．２．１．０２,６］デカン−２−オン等を共重合することにより得られる（共）重合体が挙げられる。
Specific examples of such monomers include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, and (meth) acrylic. Acid-2-methoxyethyl, (meth) acrylic acid-2-ethoxyethyl, 1-methacryloyloxy-3-hydroxyadamantane, β- (meth) acryloyloxy-β-methyl-δ-valerolactone, β- (meth) Acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolactone, 2- (1- (meth) acryloyloxy) ethyl-4- Butanolide, pantolactone (meth) acrylate, 8-methacryloyloxy-3-oxatricycle [5.2.1.0 2, 6] decan-2-one, copolymerizing 9- methacryloyloxy-3-oxatricyclo [5.2.1.0 2, 6] decan-2-one, etc. (Co) polymer obtained by this is mentioned.
これらのなかで、１−メタクリロイルオキシ−３−ヒドロキシアダマンタン、８−メタクリロイルオキシ−３−オキサトリシクロ［５．２．１．０２,６］デカン−２−オン、９−メタクリロイルオキシ−３−オキサトリシクロ［５．２．１．０２,６］デカン−２−オン等がレジスト組成物材料に使用したときの（共）重合体の基板に対する密着性の点で好ましい。 Among these, 1-methacryloyloxy-3-hydroxyadamantane, 8-methacryloyloxy-3-oxatricyclo [5.2.1.0 2,6 ] decan-2-one, 9-methacryloyloxy-3- Oxatricyclo [5.2.1.0 2,6 ] decan-2-one or the like is preferable in terms of adhesion of the (co) polymer to the substrate when used as a resist composition material.
前記式（Ｃ）で表される構成単位を（共）重合体に導入するには、式（Ｃ’）で表される単量体を共重合すればよい。 In order to introduce the structural unit represented by the formula (C) into the (co) polymer, the monomer represented by the formula (C ′) may be copolymerized.
これらのなかで、α−メチレン−γ−ブチロラクトン、およびそのγ位炭素上にアルキル基、ヒドロキシ基、カルボキシ基等の置換基を有する誘導体、例えばα−メチレン−γ−ブチロラクトン、α−メチレン−γ−メチル−γ−ブチロラクトン、α−メチレン−γ−エチル−γ−ブチロラクトン、４，４−ジメチル−２−メチレン−４−ブタノライド等がレジスト組成物材料に使用したときの感度および解像度の点で好ましい。 Among these, α-methylene-γ-butyrolactone and derivatives having a substituent such as an alkyl group, a hydroxy group, and a carboxy group on the γ-position carbon, such as α-methylene-γ-butyrolactone, α-methylene-γ -Methyl-γ-butyrolactone, α-methylene-γ-ethyl-γ-butyrolactone, 4,4-dimethyl-2-methylene-4-butanolide and the like are preferable in terms of sensitivity and resolution when used as a resist composition material. .
（共）重合体中の前記式（Ａ）で示される構成単位の比率は、感度および解像度を高めるため３０モル％以上が好ましく、４０モル％以上がより好ましい。また、有機溶剤への溶解性を低下させないため７０モル％以下が好ましく、６０モル％以下がより好ましい。 The proportion of the structural unit represented by the formula (A) in the (co) polymer is preferably 30 mol% or more, more preferably 40 mol% or more in order to increase sensitivity and resolution. Moreover, 70 mol% or less is preferable and 60 mol% or less is more preferable in order not to reduce the solubility in an organic solvent.
（共）重合体の前記式（Ｂ）で示される構成単位の比率は、ドライエッチング耐性を低下させないため７０モル％以下が好ましく、６０モル％以下がより好ましい。（共）重合体の前記式（Ｃ）で示される構成単位の比率は、感度および解像度を低下させないため６０モル％以下が好ましい。
また、前記（１）〜（３）、（Ａ）〜（Ｃ）以外の単量体は、本発明の効果を大きく損なわない範囲内で用いることができる。通常、これらの単量体は、単量体成分全体に対して２０モル％以下の範囲で用いることが好ましい。
The ratio of the structural unit represented by the above formula (B) of the (co) polymer is preferably 70 mol% or less, more preferably 60 mol% or less in order not to reduce the dry etching resistance. The proportion of the structural unit represented by the formula (C) of the (co) polymer is preferably 60 mol% or less so as not to lower the sensitivity and resolution.
Moreover, monomers other than said (1)-(3) and (A)-(C) can be used within the range which does not impair the effect of this invention largely. Usually, it is preferable to use these monomers in the range of 20 mol% or less with respect to the whole monomer component.
なお、この（共）重合体において、各構成単位は任意のシーケンスを取り得る。したがって、この（共）重合体は、ランダム（共）重合体であっても、ブロック（共）重合体であっても、グラフト（共）重合体であってもよい。 In this (co) polymer, each structural unit can take an arbitrary sequence. Therefore, this (co) polymer may be a random (co) polymer, a block (co) polymer, or a graft (co) polymer.
本発明の（共）重合体の例としては、前記単量体と下記式（Ｄ）〜（Ｋ） Examples of the (co) polymer of the present invention include the monomer and the following formulas (D) to (K):
本発明の（共）重合体の好ましい例として、表１および２に示す単量体を（共）重合させたものが挙げられる。 Preferable examples of the (co) polymer of the present invention include (co) polymerized monomers shown in Tables 1 and 2.
以上の（共）重合体は、レジスト組成物材料、特に化学増幅型レジスト組成物材料に好適である。以下、本発明の（共）重合体が化学増幅型レジスト組成物用樹脂である場合について説明する。
化学増幅型レジスト組成物用樹脂には、高感度を実現するために酸によりアルカリ水溶液に可溶となる性質と、高いドライエッチング耐性とが要求される。
The above (co) polymers are suitable for resist composition materials, particularly chemically amplified resist composition materials. Hereinafter, the case where the (co) polymer of the present invention is a resin for a chemically amplified resist composition will be described.
The chemically amplified resist composition resin is required to have a property of being soluble in an alkaline aqueous solution by an acid and high dry etching resistance in order to realize high sensitivity.
酸によりアルカリ水溶液に可溶にするためには、前記式（７）〜（９）で表される単量体と、酸の作用で脱離しやすい官能基（例えば、アシル基、ｔ−ブチル基、テトラヒドロピラニル基、メチルアダマンチル基等によりヒドロキシ基やカルボキシ基を保護した基等）を有する単量体と
を共重合すればよい。
In order to make it soluble in an alkaline aqueous solution with an acid, the monomer represented by the above formulas (7) to (9) and a functional group that is easily released by the action of an acid (for example, an acyl group, a t-butyl group). And a monomer having a hydroxy group or a carboxy group protected by a tetrahydropyranyl group, a methyladamantyl group, or the like.
また、高いドライエッチング耐性を有する構造を導入するためには、前記式（７）〜（９）で表される単量体と炭素密度の高いアルキル基を有する単量体とを共重合すればよい。 In order to introduce a structure having high dry etching resistance, the monomer represented by the formulas (7) to (9) and a monomer having an alkyl group having a high carbon density may be copolymerized. Good.
このような構造を有する単量体としては、例えば、これまで化学増幅型レジスト組成物用樹脂の原料単量体として知られているものが使用可能である。本発明の（共）重合体に用いる原料単量体は、リソグラフィーに使用される光源によって任意に選択される。 As the monomer having such a structure, for example, those known so far as raw material monomers for resins for chemically amplified resist compositions can be used. The raw material monomer used in the (co) polymer of the present invention is arbitrarily selected depending on the light source used in lithography.
例えば、ＫｒＦエキシマレーザーや電子線を光源とする場合は、エッチング耐性を考慮して、前記式（４）〜（６）で表される単量体とｐ−ヒドロキシスチレンあるいはその誘導体を（共）重合した（共）重合体が好適に用いられる。この場合、（共）重合体中の前記式（４）〜（６）由来の構成単位の比率は、５モル％以上であることが好ましく、また、６０モル％以下であることが好ましい。 For example, when a KrF excimer laser or an electron beam is used as a light source, in consideration of etching resistance, the monomer represented by the above formulas (4) to (6) and p-hydroxystyrene or a derivative thereof are (co) A polymerized (co) polymer is preferably used. In this case, the ratio of the structural units derived from the above formulas (4) to (6) in the (co) polymer is preferably 5 mol% or more, and preferably 60 mol% or less.
ＡｒＦエキシマレーザーを光源とする場合は、前記式（１）〜（３）と前記式（Ａ）および／または前記式（Ｂ）および／または前記（Ｃ）を構成単位として含む（共）重合体が好適である。このような（共）重合体は、高感度、高解像度、感度、解像度および基板密着性、現像液への濡れ性といったレジスト性能を損なうことなく、ドライエッチング耐性を向上させることが可能になる。 When an ArF excimer laser is used as a light source, a (co) polymer containing the above formulas (1) to (3) and the above formula (A) and / or the above formula (B) and / or the above (C) as constituent units Is preferred. Such a (co) polymer can improve dry etching resistance without impairing resist performance such as high sensitivity, high resolution, sensitivity, resolution and substrate adhesion, and wettability to a developer.
化学増幅型レジスト組成物用樹脂として用いる場合、本発明の（共）重合体の質量平均分子量は特に限定されないが、下限は１，０００以上であることが好ましく、２，０００以上であることがより好ましく、４，０００以上であることがさらに好ましい。また、上限は１００，０００以下であることが好ましく、５０，０００以下であることがより好ましく、３０，０００以下であることがさらに好ましい。質量平均分子量がこれより大きいと、レジスト溶液に対する溶解性が低下して解像度が低下する。質量平均分子量がこれより小さいと、ドライエッチング耐性が低下してレジスト形状が悪化する傾向がある。 When used as a resin for a chemically amplified resist composition, the mass average molecular weight of the (co) polymer of the present invention is not particularly limited, but the lower limit is preferably 1,000 or more, and preferably 2,000 or more. More preferably, it is more preferably 4,000 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. If the mass average molecular weight is larger than this, the solubility in the resist solution is lowered and the resolution is lowered. If the mass average molecular weight is smaller than this, the dry etching resistance tends to decrease and the resist shape tends to deteriorate.
本発明の（共）重合体（化学増幅型レジスト組成物用樹脂）の製造方法は特に限定されないが、簡便に、組成分布および／または分子量分布の狭い（共）重合体が得られる点で、単量体を、重合釜内に滴下しながら重合を行う重合、いわゆる滴下重合法により製造することが好ましい。 The method for producing the (co) polymer (resin for chemically amplified resist composition) of the present invention is not particularly limited, but a (co) polymer having a narrow composition distribution and / or molecular weight distribution can be easily obtained. It is preferable to produce by a so-called dropping polymerization method in which the monomer is polymerized while being dropped into the polymerization vessel.
滴下溶液重合法においては、好ましい方法として例えば、有機溶剤をあらかじめ重合容器に仕込み、所定の重合温度まで加熱した後、単量体および重合開始剤、必要に応じて連鎖移動剤を有機溶剤に溶解させ、その溶液を、重合容器内の有機溶剤中に滴下する方法を挙げることが出来る。
滴下の方法は制限がなく、単量体、重合開始剤、および連鎖移動剤を必要に応じて溶剤に溶解し、それぞれ単独または複数を組み合わせて滴下する。また、１液を滴下しても２液以上を滴下しても構わない。２液以上滴下する場合、滴下はそれぞれ独立して行ってもよい。
In the dropping solution polymerization method, as a preferred method, for example, an organic solvent is previously charged in a polymerization vessel and heated to a predetermined polymerization temperature, and then a monomer, a polymerization initiator, and a chain transfer agent as required are dissolved in the organic solvent. And a method in which the solution is dropped into an organic solvent in the polymerization vessel.
There is no restriction | limiting in the method of dripping, a monomer, a polymerization initiator, and a chain transfer agent are melt | dissolved in a solvent as needed, and it drops, combining each individually or in combination. Moreover, 1 liquid may be dripped or 2 liquids or more may be dripped. When two or more liquids are dropped, the dropping may be performed independently.
本発明の（共）重合体の製造に用いられる有機溶剤としては特に限定されないが、単量体、重合開始剤および得られる（共）重合体、さらに連鎖移動剤を使用する場合はその連鎖移動剤のいずれも溶解できる溶剤が好ましく、例えば、１，４−ジオキサン、イソプロピルアルコール、アセトン、テトラヒドロフラン（以下「ＴＨＦ」とも言う。）、乳酸エチル等が挙げられる。なお、有機溶剤の使用量は特に限定されず、適宜決めればよい。 Although it does not specifically limit as an organic solvent used for manufacture of the (co) polymer of this invention, When using a monomer, a polymerization initiator, the obtained (co) polymer, and also a chain transfer agent, the chain transfer is carried out. A solvent that can dissolve any of the agents is preferable, and examples thereof include 1,4-dioxane, isopropyl alcohol, acetone, tetrahydrofuran (hereinafter also referred to as “THF”), ethyl lactate, and the like. In addition, the usage-amount of an organic solvent is not specifically limited, What is necessary is just to determine suitably.
本発明の（共）重合体の製造に用いられる重合開始剤としては特に限定されないが、例えば、アゾビスイソブチロニトリル（以下、ＡＩＢＮともいう）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物、過酸化ベンゾイル等の有機過酸化物等が挙げられる。また、ｎ−ブチルメルカプタン、ｎ−オクチルメルカプタン、２−メルカプトエタノール等のメルカプタン類を連鎖移動剤として用いてもよい。なお、重合開始剤および連鎖移動剤の使用量は特に限定されず、適宜決めればよい。 Although it does not specifically limit as a polymerization initiator used for manufacture of the (co) polymer of this invention, For example, azobisisobutyronitrile (henceforth AIBN), 2,2'-azobis (2,4- And azo compounds such as dimethylvaleronitrile) and organic peroxides such as benzoyl peroxide. Further, mercaptans such as n-butyl mercaptan, n-octyl mercaptan and 2-mercaptoethanol may be used as a chain transfer agent. In addition, the usage-amount of a polymerization initiator and a chain transfer agent is not specifically limited, What is necessary is just to determine suitably.
本発明の（共）重合体を製造する際の重合温度は特に限定はされないが、通常、５０〜１５０℃の範囲であることが好ましい。 The polymerization temperature for producing the (co) polymer of the present invention is not particularly limited, but it is usually preferably in the range of 50 to 150 ° C.
前記製造方法によって製造された（共）重合体溶液は、必要に応じてテトラヒドロフラン、１，４−ジオキサン等の良溶剤を単独または２種以上を混合して適当な溶液粘度に希釈した後、ヘプタン、メタノール、水等を単独または２種以上を混合した多量の貧溶剤中に滴下して（共）重合体を析出させる。その後、その析出物を濾別し、十分に乾燥して本発明の（共）重合体を得る。 The (co) polymer solution produced by the production method described above is prepared by mixing a good solvent such as tetrahydrofuran or 1,4-dioxane, if necessary, or a mixture of two or more kinds to dilute to an appropriate solution viscosity, and then heptane. Then, methanol, water or the like is added alone or in a large amount of a poor solvent in which two or more are mixed to precipitate a (co) polymer. Thereafter, the precipitate is filtered off and sufficiently dried to obtain the (co) polymer of the present invention.
重合溶液を多量の貧溶剤中に滴下して（共）重合体を析出させる工程は再沈殿と呼ばれ、重合溶液中に残存する単量体や重合開始剤等の未反応物を取り除くために非常に有効である。これらの未反応物等は、そのまま残存しているとレジスト性能に悪影響をおよぼす可能性があるため、できれば取り除くことが好ましい。この再沈殿工程は、場合により不要となることもある。 The step of dropping the polymerization solution into a large amount of poor solvent and precipitating the (co) polymer is called reprecipitation, in order to remove unreacted substances such as monomers and polymerization initiator remaining in the polymerization solution. It is very effective. If these unreacted substances remain as they are, there is a possibility of adversely affecting the resist performance. Therefore, it is preferable to remove them if possible. This reprecipitation step may be unnecessary in some cases.
本発明のレジスト組成物における、本発明の（共）重合体の含有量は、下限はレジスト性能が優れる点で１質量％以上が好ましく、５質量％以上がより好ましい。また、上限は粘性の低い点で、８０質量％以下が好ましく、５０質量％以下がより好ましい。 The lower limit of the content of the (co) polymer of the present invention in the resist composition of the present invention is preferably 1% by mass or more and more preferably 5% by mass or more in terms of excellent resist performance. Moreover, an upper limit is a point with low viscosity, 80 mass% or less is preferable and 50 mass% or less is more preferable.
本発明のレジスト組成物が化学増幅型レジスト用の場合は光酸発生剤を含有する。ここで、光酸発生剤とは、活性光線または放射線の照射により酸を発生する化合物である。光酸発生剤は、１種を用いても、２種以上を併用してもよい。 When the resist composition of the present invention is for a chemically amplified resist, it contains a photoacid generator. Here, the photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. A photo-acid generator may use 1 type or may use 2 or more types together.
このような光酸発生剤としては、例えば、オニウム塩化合物、スルホンイミド化合物、スルホン化合物、スルホン酸エステル化合物、キノンジアジド化合物、ジアゾメタン化合物等が挙げられる。中でも、スルホニウム塩、ヨードニウム塩、ホスホニウム塩、ジアゾニウム塩、ピリジニウム塩等のオニウム塩化合物を用いることが好ましい。具体的には、トリフェニルスルホニウムトリフレート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムナフタレンスルホネート、（ヒドロキシフェニル）ベンジルメチルスルホニウムトルエンスルホネート、ジフェニルヨードニウムトリフレート、ジフェニルヨードニウムピレンスルホネート、ジフェニルヨードニウムドデシルベンゼンスルホネート、ジフェニルヨードニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of such photoacid generators include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, diazomethane compounds, and the like. Among them, it is preferable to use an onium salt compound such as a sulfonium salt, an iodonium salt, a phosphonium salt, a diazonium salt, or a pyridinium salt. Specifically, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate And diphenyliodonium hexafluoroantimonate.
光酸発生剤の含有量は、用いる光酸発生剤の種類等により適宜決められるが、本発明の（共）重合体１００質量部に対して、０．１質量部以上であることが好ましく、０．５質量部以上であることがより好ましい。光酸発生剤の含有量をこの範囲にすることにより、露光により発生した酸の触媒作用による化学反応を十分に生起させることができる。また、光酸発生剤の含有量は、本発明の（共）重合体１００質量部に対して２０質量部以下であることが好ましく、１０質量部以下であることがより好ましい。光酸発生剤の含有量をこの範囲にすることにより、レジスト組成物の安定性が向上し、組成物を塗布する際の塗布むらや現像時のスカム等の発生が少なくなる。光酸発生剤は必要に応じ１種または２種以上が選ばれる。 The content of the photoacid generator is appropriately determined depending on the type of the photoacid generator used and the like, but is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the (co) polymer of the present invention, More preferably, it is 0.5 parts by mass or more. By setting the content of the photoacid generator within this range, a chemical reaction due to the catalytic action of the acid generated by exposure can be sufficiently caused. Moreover, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of (co) polymer of this invention, and, as for content of a photo-acid generator, it is more preferable that it is 10 mass parts or less. By setting the content of the photoacid generator within this range, the stability of the resist composition is improved, and the occurrence of uneven coating during application of the composition and scum during development is reduced. One or more photoacid generators are selected as necessary.
本発明のレジスト組成物に用いる溶剤は目的に応じて任意に選択されるが、溶剤の選択は樹脂の溶解性以外の理由、例えば、塗膜の均一性、外観あるいは安全性等からも制約を受けることがある。
本発明において通常使用される溶剤としては、メチルエチルケトン、２−ペンタノン、２−ヘキサノン等の直鎖状ケトン類、シクロペンタノン、シクロヘキサノン等の環状ケトン類、プロピレングリコールモノメチルエーテルアセテート（以下、ＰＧＭＥＡと略すことがある）、プロピレングリコールモノエチルエーテルアセテート等のプロピレングリコールモノアルキルアセテート類、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のプロピレングリコールモノアルキルエーテル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコ−ルモノイソプロピルエ−テル等のエチレングリコールモノアルキルエーテル類、ジエチレングリコールジメチルエーテル、ジエチレングリコ−ルモノメチルエ−テル、ジエチレングリコールジエチルエーテル等のジエチレングリコールアルキルエーテル類、酢酸エチル、乳酸エチル等のエステル類、ｎ−プロピルアルコ−ル、イソプロピルアルコ−ル、ｎ−ブチルアルコ−ル、ｔｅｒｔ−ブチルアルコ−ル、シクロヘキサノール、１−オクタノール等のアルコール類、１，４−ジオキサン、炭酸エチレン、γ−ブチロラクトン等が挙げられる。これらの溶剤は、１種を用いても、２種以上を併用してもよい。
The solvent used in the resist composition of the present invention is arbitrarily selected depending on the purpose, but the choice of the solvent is limited due to reasons other than the solubility of the resin, such as uniformity of the coating film, appearance, or safety. I may receive it.
Solvents usually used in the present invention include linear ketones such as methyl ethyl ketone, 2-pentanone and 2-hexanone, cyclic ketones such as cyclopentanone and cyclohexanone, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). Propylene glycol monoalkyl acetates such as propylene glycol monoethyl ether acetate, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono Propylene glycol monoalkyl ethers such as ethyl ether, ethylene glycol monomethyl ether, ethyl Ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and ethylene glycol monoisopropyl ether, diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol monomethyl ether and diethylene glycol diethyl ether, esters such as ethyl acetate and ethyl lactate , Alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclohexanol, 1-octanol, 1,4-dioxane, ethylene carbonate, γ-butyrolactone, etc. Is mentioned. These solvents may be used alone or in combination of two or more.
溶剤の使用量は、通常、レジスト用（共）重合体（本発明の（共）重合体）１００質量部に対して２００質量部以上であり、３００質量部以上であることがより好ましい。また、溶剤の使用量は、通常、レジスト用（共）重合体（本発明の（共）重合体）１００質量部に対して５０００質量部以下であり、２０００質量部以下であることがより好ましい。 The amount of the solvent used is usually 200 parts by mass or more and more preferably 300 parts by mass or more with respect to 100 parts by mass of the resist (co) polymer (the (co) polymer of the present invention). The amount of the solvent used is usually 5000 parts by mass or less and more preferably 2000 parts by mass or less with respect to 100 parts by mass of the resist (co) polymer (the (co) polymer of the present invention). .
さらに、本発明のレジスト組成物には、必要に応じて、界面活性剤、クエンチャー、増感剤、ハレーション防止剤、保存安定剤、消泡剤等の各種添加剤を配合することもできる。これらの添加剤は、当該分野で既知のものであればいずれも使用可能である。また、これらの添加剤の配合量は特に限定されず、適宜決めればよい。 Furthermore, various additives such as surfactants, quenchers, sensitizers, antihalation agents, storage stabilizers, antifoaming agents, and the like can be blended with the resist composition of the present invention as necessary. Any of these additives can be used as long as it is known in the art. Moreover, the compounding quantity of these additives is not specifically limited, What is necessary is just to determine suitably.
次に、本発明のパターン形成方法の一例について説明する。
最初に、パターンを形成するシリコンウエハー等の被加工基板の表面に、本発明の化学増幅型レジスト組成物をスピンコート等により塗布する。そして、この化学増幅型レジスト組成物が塗布された被加工基板は、ベーキング処理（プリベーク）等で乾燥し、被加工基板上にレジスト膜を形成する。
Next, an example of the pattern forming method of the present invention will be described.
First, the chemically amplified resist composition of the present invention is applied to the surface of a substrate to be processed such as a silicon wafer on which a pattern is formed by spin coating or the like. Then, the substrate to be processed coated with the chemically amplified resist composition is dried by baking (pre-baking) or the like, and a resist film is formed on the substrate to be processed.
次いで、このようにして得られたレジスト膜に、フォトマスクを介して、２５０ｎｍ以下の波長の光を照射する（露光）。露光に用いる光は、ＫｒＦエキシマレーザーまたはＡｒＦエキシマレーザーであることが好ましく、特にＡｒＦエキシマレーザーであることが好ましい。 Next, the resist film thus obtained is irradiated with light having a wavelength of 250 nm or less through a photomask (exposure). The light used for exposure is preferably a KrF excimer laser or an ArF excimer laser, and particularly preferably an ArF excimer laser.
光照射（露光）後、適宜ベーキング処理（ＰＥＢ）し、基板をアルカリ現像液に浸漬し、露光部分を現像液に溶解除去する（現像）。アルカリ現像液は公知のものいずれを用いてもよい。そして、現像後、基板を純水等で適宜リンス処理する。このようにして被加工基板上にレジストパターンが形成される。 After light irradiation (exposure), baking treatment (PEB) is appropriately performed, the substrate is immersed in an alkaline developer, and the exposed portion is dissolved and removed in the developer (development). Any known alkaline developer may be used. Then, after development, the substrate is appropriately rinsed with pure water or the like. In this way, a resist pattern is formed on the substrate to be processed.
通常、レジストパターンが形成された被加工基板は、適宜ベーキング処理（ポストベーク）してレジストを強化し、レジストのない部分を選択的にエッチングする。エッチングを行った後、レジストは、通常、剥離剤を用いて除去される。 Usually, a substrate to be processed on which a resist pattern is formed is appropriately baked (post-baked) to strengthen the resist and selectively etch a portion without the resist. After etching, the resist is usually removed using a release agent.
以下、本発明を実施例によって詳しく説明するが、本発明はこれらの記載に限定されるものではない。ここで、各実施例、比較例中「部」とあるのは、特に断りがない限り、「質量部」を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these description. Here, “part” in each example and comparative example means “part by mass” unless otherwise specified.
また、（共）重合体の物性測定およびレジストの評価は以下の方法で行った。 The physical properties of the (co) polymer and the resist were evaluated by the following methods.
＜質量平均分子量＞
ゲル・パーミエイション・クロマトグラフィー（以下ＧＰＣという。）により、ポリスチレン換算で求めた。溶剤には、クロロホルムあるいはＴＨＦを使用した。
<Mass average molecular weight>
It calculated | required in polystyrene conversion with the gel permeation chromatography (henceforth GPC). As the solvent, chloroform or THF was used.
＜平均（共）重合組成（モル％）＞
1Ｈ−ＮＭＲ、1３Ｃ−ＮＭＲの測定により求めた。溶剤には、重クロロホルムあるいは重ジメチルスルホキシドを使用した。
<Average (co) polymerization composition (mol%)>
It calculated | required by the measurement of < 1 > H-NMR and < 13 > C-NMR. As the solvent, heavy chloroform or heavy dimethyl sulfoxide was used.
＜レジスト組成物の調整＞
（共）重合体１００部と、トリフェニルスルホニウムトリフレート２部、ＰＧＭＥＡ６３０部とγ−ブチロラクトン７０部を混合して均一溶液とした後、テフロン（登録商標）フィルターを用いて濾過し、レジスト組成物溶液を調製した。シリコンウエハー上にレジスト組成物溶液をスピンコートし、ホットプレートを用いて、１２０℃、６０秒間プリベークを行い、膜厚４００ｎｍの薄膜を形成した。次いで、１９３ｎｍ光照射装置（ニコン製ＳＰ１９３）を用いて露光した後、直ちに１２０℃、６０秒間露光後ベークを行った。次いで、２．３８質量％水酸化テトラメチルアンモニウム水溶液を用いて室温で６０秒間現像し、純粋で水洗し、乾燥した。
<Preparation of resist composition>
100 parts of (co) polymer, 2 parts of triphenylsulfonium triflate, 630 parts of PGMEA and 70 parts of γ-butyrolactone were mixed to form a homogeneous solution, and then filtered using a Teflon (registered trademark) filter, and a resist composition A solution was prepared. A resist composition solution was spin-coated on a silicon wafer and pre-baked at 120 ° C. for 60 seconds using a hot plate to form a thin film having a thickness of 400 nm. Next, after exposure using a 193 nm light irradiation apparatus (SP193 manufactured by Nikon), post-exposure baking was performed immediately at 120 ° C. for 60 seconds. Subsequently, it was developed for 60 seconds at room temperature using a 2.38 mass% aqueous tetramethylammonium hydroxide solution, washed with pure water and dried.
＜感度＞
レジスト膜が完全に溶解し、シリコンウエハー表面が露出する最低露光量を感度とした。
<Sensitivity>
Sensitivity was defined as the minimum exposure amount at which the resist film was completely dissolved and the silicon wafer surface was exposed.
＜エッチング速度＞
膜厚４００ｎｍのレジスト膜が塗布されたシリコンウエハーを、昭和真空（株）製ＳＰＥ−２２０Ｔ型ドライエッチング装置にてドライエッチング処理した。ガスはＣＦ４／Ｏ２混合ガスとし、処理時間を２分間とした。ドライエッチング処理前後のレジスト膜の膜厚を、大日本スクリーン製造（株）製ラムダエースＶＭ−８０００Ｊ型光干渉式膜厚測定装置を用いて測定し、単位時間あたりの膜厚減少量をレジストのエッチング速度とした。なお、エッチング速度はノボラック樹脂のエッチング速度を１として規格化した。
このエッチング速度が小さいほどドライエッチング耐性が優れる。
＜合成例１＞
<Etching rate>
A silicon wafer coated with a resist film having a thickness of 400 nm was subjected to a dry etching process using an SPE-220T type dry etching apparatus manufactured by Showa Vacuum Co., Ltd. The gas was a CF 4 / O 2 mixed gas, and the treatment time was 2 minutes. The film thickness of the resist film before and after the dry etching process was measured using a Lambda Ace VM-8000J type optical interference type film thickness measuring device manufactured by Dainippon Screen Mfg. Co., Ltd. The etching rate was used. The etching rate was normalized with the novolac resin etching rate set to 1.
The smaller the etching rate, the better the dry etching resistance.
<Synthesis Example 1>
下記の式（３６）で示される（共）重合体Ｐ−１の合成 Synthesis of (co) polymer P-1 represented by the following formula (36)
各物性を測定したところ、ＧＰＣ分析による質量平均分子量（以下Ｍｗという。）は１２５００、分散度（以下、Ｍｗ／Ｍｎという。）は１．６６で、平均共重合組成比は1Ｈ−ＮＭＲの積分比からａ−１：ＭＡｄＭＡ＝５０：５０であった。
＜合成例２〜１０＞
When each physical property was measured, the mass average molecular weight (hereinafter referred to as Mw) by GPC analysis was 12500, the dispersity (hereinafter referred to as Mw / Mn) was 1.66, and the average copolymer composition ratio was 1 H-NMR. From the integration ratio, it was a-1: MAdMA = 50: 50.
<Synthesis Examples 2 to 10>
＜（共）重合体Ｐ−２〜Ｐ−１０の合成＞
合成例１と同様の方法で（共）重合体Ｐ−２〜Ｐ−１０を得た。得られた（共）重合体の平均共重合組成比、Ｍｗ、Ｍｗ／Ｍｎを表３に示す。
<Synthesis of (co) polymers P-2 to P-10>
(Co) polymers P-2 to P-10 were obtained in the same manner as in Synthesis Example 1. Table 3 shows the average copolymer composition ratio, Mw, and Mw / Mn of the obtained (co) polymer.
＜参考例１〜３、５、実施例４、６〜８、比較例１〜２＞
合成例１〜１０で得られた（共）重合体Ｐ−１〜Ｐ−１０をそれぞれ用いて調製したレジスト組成物の感度およびエッチング速度を測定して表４に示した。 Table 4 shows the sensitivity and etching rate of the resist compositions prepared using the (co) polymers P-1 to P-10 obtained in Synthesis Examples 1 to 10, respectively.
本発明のレジスト組成物用樹脂を用いたレジスト組成物は波長２５０ｎｍ以下の光、特にＡｒＦエキシマレーザー光に対して透明性が高く、高感度である。また、ドライエッチング耐性に優れており、遠紫外光エキシマレーザーリソグラフィーや電子線リソグラフィー等、特にＡｒＦエキシマレーザーを使用するリソグラフィーに好適に用いることが出来る。また、本発明の製造方法はレジスト組成物に適した樹脂を製造することが可能である。 The resist composition using the resin for resist compositions of the present invention is highly transparent and highly sensitive to light having a wavelength of 250 nm or less, particularly ArF excimer laser light. Moreover, it is excellent in dry etching resistance, and can be suitably used for lithography using far-ultraviolet excimer laser lithography, electron beam lithography, etc., particularly using ArF excimer laser. Further, the production method of the present invention can produce a resin suitable for the resist composition.
このレジスト組成物を用いた本発明のパターン形成方法によれば、高精度の微細なレジストパターンを安定して形成することができる。このパターン形成方法は遠紫外光エキシマレーザーリソグラフィーや電子線リソグラフィー、特にＡｒＦエキシマレーザーを使用するリソグラフィーに好適である。 According to the pattern forming method of the present invention using this resist composition, a highly accurate fine resist pattern can be stably formed. This pattern forming method is suitable for deep ultraviolet excimer laser lithography and electron beam lithography, particularly for lithography using an ArF excimer laser.
Claims (11)
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位であり、ただし、上記式（２）で表される繰り返し単位が、下記式（２２）、（２３）、（２４）、（２５）、（２６）、（２７）、（２９）及び（３０）：
から選択されるものである繰り返し単位と、
下記式（Ａ）〜（Ｃ）：
で表される繰り返し単位から選ばれる１種又は２種以上とを含み、質量平均分子量が１，０００〜１００，０００である（共）重合体。 The following formulas (2) to (3):
Is a repeating unit represented by the following formulas (22), (23), (24), and the repeating unit represented by the above formula (2). (25), (26), (27), (29) and (30):
Those and the unit returns to Ri Repetitive is to be selected from,
The following formulas (A) to (C):
(Co) polymer which contains 1 type, or 2 or more types chosen from the repeating unit represented by these, and whose weight average molecular weights are 1,000-100,000.
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位となる単量体であり、ただし、上記式（２）で表される繰り返し単位が、下記式（２２）、（２３）、（２４）、（２５）、（２６）、（２７）、（２９）及び（３０）：
から選択されるものである単量体と、
下記式（Ａ）〜（Ｃ）：
で表される繰り返し単位から選ばれる１種又は２種以上の繰り返し単位となる単量体とを、有機溶剤に溶解させた溶液を、重合釜中に滴下しながら（共）重合を行う（共）重合体の製造方法。 The following formulas (2) to (3):
A monomer that becomes one or more repeating units selected from the repeating units represented by the formula: wherein the repeating unit represented by the above formula (2) is represented by the following formulas (22), (23): , (24), (25), (26), (27), (29) and (30):
A monomer that is selected from
The following formulas (A) to (C):
(Co) polymerization is carried out while a solution prepared by dissolving one or more monomers selected from repeating units represented by the formula (1) is dissolved in an organic solvent into a polymerization vessel (co-polymerization). ) A method for producing a polymer.
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| US20060147832A1 (en) * | 2003-03-04 | 2006-07-06 | Hideo Hada | Polymer and positive type resist composition |
| JP4832019B2 (en) * | 2005-07-27 | 2011-12-07 | 株式会社ダイセル | Polycyclic ester containing cyclic carbonate skeleton |
| JP4796794B2 (en) * | 2005-07-27 | 2011-10-19 | ダイセル化学工業株式会社 | Polycyclic ester containing lactone skeleton |
| JP5005197B2 (en) * | 2005-07-27 | 2012-08-22 | 株式会社ダイセル | Polycyclic ester |
| JP4781086B2 (en) * | 2005-10-31 | 2011-09-28 | ダイセル化学工業株式会社 | Polymer compound having alicyclic skeleton |
| JP5285884B2 (en) * | 2007-09-07 | 2013-09-11 | 東京応化工業株式会社 | POLYMER COMPOUND, POSITIVE RESIST COMPOSITION AND METHOD FOR FORMING RESIST PATTERN |
| JP5418268B2 (en) * | 2010-02-10 | 2014-02-19 | Ｊｓｒ株式会社 | Radiation sensitive resin composition |
| JP5572127B2 (en) * | 2011-06-08 | 2014-08-13 | 株式会社ダイセル | Polymer compound having alicyclic skeleton |
| JP5793388B2 (en) * | 2011-09-30 | 2015-10-14 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film and pattern forming method using the same |
| JP6002378B2 (en) | 2011-11-24 | 2016-10-05 | 東京応化工業株式会社 | Method for producing polymer compound |
| JP5757851B2 (en) * | 2011-11-25 | 2015-08-05 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, resist film and pattern forming method using the composition, and electronic device manufacturing method |
| JP5775804B2 (en) * | 2011-12-06 | 2015-09-09 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film using the same, pattern formation method, electronic device manufacturing method, and electronic device |
| JP2013130654A (en) * | 2011-12-20 | 2013-07-04 | Fujifilm Corp | Actinic ray sensitive or radiation sensitive resin composition, resist film and pattern forming method using said composition, and method for manufacturing electronic device and electronic device |
| JP2013137338A (en) * | 2011-12-27 | 2013-07-11 | Fujifilm Corp | Actinic ray-sensitive or radiation-sensitive resin composition, resist film and pattern forming method using composition, and method for manufacturing electronic device and electronic device |
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