JP5582316B2 - Resist underlayer film forming composition containing polymer-type photoacid generator and method for forming resist pattern using the same - Google Patents
Resist underlayer film forming composition containing polymer-type photoacid generator and method for forming resist pattern using the same Download PDFInfo
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- JP5582316B2 JP5582316B2 JP2011526706A JP2011526706A JP5582316B2 JP 5582316 B2 JP5582316 B2 JP 5582316B2 JP 2011526706 A JP2011526706 A JP 2011526706A JP 2011526706 A JP2011526706 A JP 2011526706A JP 5582316 B2 JP5582316 B2 JP 5582316B2
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- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
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- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
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- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
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- 239000001593 sorbitan monooleate Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本発明は、ポリマー型の光酸発生剤を含有するレジスト下層膜形成組成物及び該組成物から形成されるレジスト下層膜を用いたレジストパターンの形成方法に関し、より詳細には、レジストパターン形状の改良が可能な該組成物及び該パターン形成方法に関する。 The present invention relates to a resist underlayer film forming composition containing a polymer-type photoacid generator and a method of forming a resist pattern using a resist underlayer film formed from the composition. The present invention relates to the composition which can be improved and the pattern forming method.
従来より、低分子の光酸発生剤を含むレジスト下層膜形成組成物、例えば、酸官能基を有する、溶媒系に可溶なポリマーおよび／またはオリゴマーを架橋剤および光酸発生剤と共に含む、湿式現像性反射防止膜組成物（特許文献１）や光吸収をなす発色団（クロモフォア）を有する少なくとも一種の繰り返し単位と、ヒドロキシル及び／またはカルボキシル基を有する少なくとも一種の繰り返し単位とを含んでなるポリマー、末端ビニルエーテル基を有する架橋剤、場合によっては光酸発生剤及び／または酸及び／または熱酸発生剤を含む、反射防止膜形成組成物（特許文献２）が提案されて用いられている。 Conventionally, a resist underlayer film forming composition containing a low-molecular photoacid generator, for example, a wet polymer containing an acid functional group-soluble polymer and / or oligomer with a crosslinking agent and a photoacid generator. A polymer comprising a developable antireflection film composition (Patent Document 1) and at least one repeating unit having a light-absorbing chromophore (chromophore) and at least one repeating unit having a hydroxyl and / or carboxyl group An antireflective film forming composition (Patent Document 2) containing a crosslinking agent having a terminal vinyl ether group, and optionally a photoacid generator and / or an acid and / or a thermal acid generator has been proposed and used.
しかし、これら反射防止膜組成物では、光酸発生剤として単独の低分子化合物が使用されているため、光酸発生剤成分がレジストへ溶出（リーチング）することや焼成時に光酸発生剤成分に由来する昇華物が発生することが問題となる。レジストへの溶出は、液体のレジスト組成物を汚染し、これにより、光酸発生剤成分のリソグラフィー装置内部への残留や部品への付着を引き起こし、露光不足や現像不良など露光・現像に悪影響を及ぼす原因となる。また、昇華物は、その後反射防止膜上に異物として付着し、欠陥等の悪影響を与えるおそれがある。 However, since these anti-reflective coating compositions use a single low-molecular compound as the photoacid generator, the photoacid generator component can be eluted (leached) into the resist or used as a photoacid generator component during firing. The problem is that sublimates derived therefrom are generated. The elution into the resist contaminates the liquid resist composition, thereby causing the photoacid generator component to remain inside the lithography apparatus and adhere to the parts, and adversely affect exposure and development such as underexposure and development failure. Cause. In addition, the sublimate may subsequently adhere as a foreign matter on the antireflection film, and may cause adverse effects such as defects.
一方、ポリマー化された光酸発生剤をレジスト膜に取り入れる技術は既に知られており、例えば、光酸発生剤として重合性不飽和結合を有するスルホン酸のオニウム塩を重合した重合体を含むことを特徴とするレジスト材料が提案されている（特許文献３）。この文献には、前記重合体が、さらに、酸素脱離基を有する繰り返し単位と、密着性基を有する繰り返し単位とを有する構造をなすところのレジスト材料についても開示されている。しかし、当該レジスト材料は、液浸リソグラフィーに好適なレジスト材料を提供することを目的としており、またこの文献には、高精度なパターンを得るためのレジスト下層膜への適用について具体的な手段及び効果は示唆されていない。 On the other hand, a technique for incorporating a polymerized photoacid generator into a resist film is already known. For example, it contains a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond as a photoacid generator. A resist material characterized by the above has been proposed (Patent Document 3). This document also discloses a resist material in which the polymer further has a structure having a repeating unit having an oxygen leaving group and a repeating unit having an adhesive group. However, the resist material is intended to provide a resist material suitable for immersion lithography, and this document describes specific means for applying to a resist underlayer film for obtaining a highly accurate pattern, and No effect has been suggested.
また、光酸発生剤の重合体、上部反射防止膜の重合体、及び有機溶媒を含む上部反射防止膜組成物が提案されている（特許文献４）。当該上部反射防止膜組成物はフォトレジスト膜の上部に塗布し、上部反射防止膜を形成するものであり、この文献はイマージョンリソグラフィに適用可能な上部反射防止膜の組成物を提供することを目的としている。その上、この文献には、当該組成物のレジスト下層膜としてのドライリソグラフィへの適用の可能性については示唆されていない。 Further, an upper antireflection film composition containing a polymer of a photoacid generator, a polymer of an upper antireflection film, and an organic solvent has been proposed (Patent Document 4). The upper antireflective coating composition is applied on top of a photoresist film to form an upper antireflective coating. This document aims to provide a composition of an upper antireflective coating applicable to immersion lithography. It is said. Moreover, this document does not suggest the possibility of applying the composition to dry lithography as a resist underlayer film.
そこで、本発明は、上記の事情に基づきなされたものであり、その解決しようとする課題は、パターン底部においても容易にストレート形状のレジストパターンを形成できる等、レジストパターン形状のより一層の改良を達成することが可能なポリマー型の光酸発生剤を含有するレジスト下層膜形成組成物及び該組成物から形成されるレジスト下層膜を用いたレジストパターンの形成方法を提供することである。 Therefore, the present invention has been made based on the above circumstances, and the problem to be solved is to further improve the resist pattern shape, such as being able to easily form a straight resist pattern even at the bottom of the pattern. It is an object of the present invention to provide a resist underlayer film forming composition containing a polymer-type photoacid generator that can be achieved, and a resist pattern forming method using the resist underlayer film formed from the composition.
本発明者らは、上記の課題を解決するべく鋭意研究を行った結果、光酸発生剤をポリマーの構造単位として導入することで、レジスト下層膜からレジスト底部へ酸を効果的に供給することができ且つ光酸発生剤のレジストへの溶出及び昇華を抑制することができる構成とすることにより、ストレート形状のレジストパターンを容易に形成できる等、レジストパターン形状のより改良を図ることができ、その上、レジストへの溶出による悪影響及び昇華物の発生による問題の発生を無くすことができることを見出し、本発明を完成するに至った。また、ポリマー中に光酸発生剤成分以外に、第二成分、第三成分を導入して機能性ポリマーに仕上げることにより、その機能性ポリマーを含むレジスト下層膜形成組成物の機能・役割を多様化し、それから形成されるレジスト下層膜の機能性を向上させることが可能になることも見出した。 As a result of diligent research to solve the above problems, the present inventors have effectively supplied acid from the resist underlayer film to the resist bottom by introducing a photoacid generator as a structural unit of the polymer. It is possible to further improve the resist pattern shape, such as being able to easily form a straight resist pattern, by making it possible to suppress elution and sublimation of the photoacid generator into the resist. In addition, the inventors have found that it is possible to eliminate the adverse effects caused by elution into the resist and the problems caused by the generation of sublimates, and the present invention has been completed. In addition to the photoacid generator component, the second and third components are introduced into the polymer to finish it into a functional polymer, thereby diversifying the functions and roles of the resist underlayer film forming composition containing the functional polymer. It has also been found that the functionality of the resist underlayer film formed therefrom can be improved.
すなわち、第１観点として、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位を有する重合体を含むレジスト下層膜形成組成物。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）。｝That is, as a first aspect, a resist underlayer film forming composition comprising a polymer having a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2).
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.) }
第２観点として、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位、及び下記式（Ｂ）で表される構造単位を有する重合体を含むレジスト下層膜形成組成物。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
ｐ及びｑは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ及びｑはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ≦１を満たす。｝As a second aspect, a polymer having a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (B). A resist underlayer film forming composition.
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
p and q represent the charging ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p and q are in the range of 0.05 to 0.95, respectively. However, p + q ≦ 1 is satisfied. }
第３観点として、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位、下記式（Ｂ）で表される構造単位、及び下記式（Ｃ）で表される構造単位を有する重合体を含むレジスト下層膜形成組成物。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
式（Ｃ）中、Ｒ1は水素原子又はメチル基を表し、Ａ2は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ2は水素原子の一部又は全てがフッ素原子で置換された炭素原子数１乃至８のアルキル基を表す。
ｐ、ｑ及びｒは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ、ｑ及びｒはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ＋ｒ≦１を満たす。｝As a third aspect, a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2), a structural unit represented by the following formula (B), and the following formula (C The resist underlayer film forming composition containing the polymer which has a structural unit represented by this.
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
In the formula (C), R 1 represents a hydrogen atom or a methyl group, A 2 represents —C (═O) O—, —O— or a direct bond, and X 2 represents a part or all of the hydrogen atoms are fluorine. An alkyl group having 1 to 8 carbon atoms substituted with an atom is represented.
p, q, and r represent the charge ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p, q, and r are each in the range of 0.05 to 0.95. However, p + q + r ≦ 1 is satisfied. }
さらに、前記式（Ａ−１）、式（Ａ−２）で表されるような光酸発生剤を構造単位に有しない重合体を、第１観点乃至第３観点のいずれかに記載のレジスト下層膜形成組成物に含むことができる。このような重合体として、例えばアクリル系ポリマー、ポリエステル、ノボラックが挙げられる。 Furthermore, the resist which does not have a photoacid generator as a structural unit as represented by said Formula (A-1) and Formula (A-2) in any one of a 1st viewpoint thru | or a 3rd viewpoint. It can be included in the underlayer film forming composition. Examples of such polymers include acrylic polymers, polyesters, and novolacs.
第４観点として、さらに架橋剤、架橋触媒、及び有機溶剤を含む第１観点乃至第３観点のいずれかに記載のレジスト下層膜形成組成物。
第５観点として、
第１観点乃至第４観点のいずれかに記載のレジスト下層膜形成組成物を、パターンを形成する加工対象膜を有する基板上に、塗布しベークしてレジスト下層膜を形成する工程、
形成された前記レジスト下層膜上にレジスト膜を形成する工程、
前記レジスト膜が形成された基板に、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、極端紫外線（ＥＵＶ）及び電子線（ＥＢ）からなる群から選択される放射線を照射する工程、
照射後に前記レジスト膜を現像してレジストパターンを形成する工程、及び
形成された前記レジストパターンをマスクとしてドライエッチングにより前記基板上にパターンを転写する工程を含む、半導体素子を作製する方法。As a fourth aspect, the resist underlayer film forming composition according to any one of the first aspect to the third aspect, further including a crosslinking agent, a crosslinking catalyst, and an organic solvent.
As a fifth aspect,
Applying and baking the resist underlayer film forming composition according to any one of the first aspect to the fourth aspect on a substrate having a film to be processed for forming a pattern to form a resist underlayer film;
Forming a resist film on the formed resist underlayer film,
Irradiating the substrate on which the resist film is formed with radiation selected from the group consisting of KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV) and electron beam (EB);
A method for producing a semiconductor device, comprising: a step of developing the resist film after irradiation to form a resist pattern; and a step of transferring the pattern onto the substrate by dry etching using the formed resist pattern as a mask.
本発明のレジスト下層膜形成組成物は、光酸発生剤をポリマーの構造単位として導入したものを組成物中に配合していることから、当該組成物から形成されたレジスト下層膜において、露光時、光酸発生剤から効率的に酸が発生し、当該レジスト下層膜とレジスト膜の界面近傍に供給することで、とりわけレジストパターン底部におけるより正確なエッチングが可能となり、容易にストレート形状のレジストパターンを形成できる等、レジストパターン形状の著しい改良を図ることが可能である。また、従来の低分子光酸発生剤の適用の際に問題となる光酸発生剤成分の溶出（リーチング）を防止すること、及び焼成工程による光酸発生剤成分の昇華を抑制することが可能である。
また、本発明のレジスト下層膜形成組成物は、光酸発生剤成分以外に第二、第三成分として機能性モノマーを導入したポリマーを含有することにより、レジスト下層膜形成組成物から形成されるレジスト下層膜の機能性を向上させることが可能となる。
さらに、本発明のレジスト下層膜形成組成物から形成されたレジスト下層膜は、放射線、特にＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、ＥＵＶ、ＥＢ等に対して高感度、高解像度でラインエッジラフネスが小さく、レジスト材料とのインターミキシングの発生を低減できる。Since the resist underlayer film-forming composition of the present invention contains a photoacid generator introduced as a structural unit of a polymer in the composition, the resist underlayer film formed from the composition is exposed during exposure. By generating acid efficiently from the photoacid generator and supplying it to the vicinity of the interface between the resist underlayer film and the resist film, it is possible to perform more accurate etching, especially at the bottom of the resist pattern, and easily form a straight resist pattern Thus, the resist pattern shape can be remarkably improved. In addition, it is possible to prevent the elution (leaching) of the photoacid generator component, which is a problem when applying the conventional low molecular photoacid generator, and to suppress sublimation of the photoacid generator component during the baking process. It is.
The resist underlayer film forming composition of the present invention is formed from the resist underlayer film forming composition by containing a polymer in which a functional monomer is introduced as the second and third components in addition to the photoacid generator component. The functionality of the resist underlayer film can be improved.
Furthermore, the resist underlayer film formed from the resist underlayer film forming composition of the present invention has high sensitivity and high resolution with respect to radiation, particularly KrF excimer laser, ArF excimer laser, EUV, EB, etc., and low line edge roughness. Generation of intermixing with the resist material can be reduced.
以下、各成分の詳細を説明する。
本発明のレジスト下層膜形成組成物から有機溶剤を除いた固形分は、例えば０．５乃至１０質量％である。Hereinafter, details of each component will be described.
The solid content excluding the organic solvent from the resist underlayer film forming composition of the present invention is, for example, 0.5 to 10% by mass.
本発明のレジスト下層膜形成組成物に含まれる光酸発生剤の重合体としては、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位を有する。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）。｝The polymer of the photoacid generator contained in the resist underlayer film forming composition of the present invention includes a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2). Have.
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.) }
上記式（Ａ−１）は、重合性不飽和結合を有するスルホン酸のスルホニウム塩（カチオン遊離型）である光酸発生剤の重合体である。また、上記式（Ａ−２）は、重合性不飽和結合を有するスルホニウムのスルホン酸塩（アニオン遊離型）である光酸発生剤の重合体である。 The above formula (A-1) is a polymer of a photoacid generator that is a sulfonium salt of a sulfonic acid having a polymerizable unsaturated bond (cation free type). Further, the above formula (A-2) is a polymer of a photoacid generator which is a sulfonium sulfonate (anion free type) having a polymerizable unsaturated bond.
上述のような本発明のレジスト下層膜形成組成物に含まれる重合体を得るために必要な重合性不飽和結合を有するスルホン酸のスルホニウム塩及び重合性不飽和結合を有するスルホニウムのスルホン酸塩としては、下記一般式（Ｉ）及び（ＩＩ）が例示される。
一方、式（ＩＩ）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）。｝As a sulfonium salt of a sulfonic acid having a polymerizable unsaturated bond and a sulfonium salt of a sulfonium having a polymerizable unsaturated bond necessary for obtaining the polymer contained in the resist underlayer film forming composition of the present invention as described above The following general formulas (I) and (II) are exemplified.
On the other hand, in formula (II), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or 7 carbon atoms. To 10 alkylphenylene groups (wherein, some or all of the hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with fluorine atoms, 1 or more).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.) }
上記一般式（Ｉ）で表されるスルホン酸のスルホニウム塩におけるスルホン酸アニオンとしては、下記のものを例示することができる。
また、上記一般式（Ｉ）で表されるスルホニウム塩のカチオンとしては、下記のものを例示することができる。
上記一般式（ＩＩ）で表されるスルホニウムのスルホン酸塩におけるスルホニウムカチオンとしては、下記のものを例示することができる。
また、上記一般式（ＩＩ）で表されるスルホン酸塩のアニオンとしては、下記のものを例示することができる。
上記一般式（Ｉ）で表されるスルホン酸のスルホニウム塩の合成は既知であり、例えば、特開２００９−０９１３５０号公報及び特開２００９−０９１３５１号公報に開示されている。 The synthesis of sulfonium salts of sulfonic acids represented by the above general formula (I) is known and disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2009-091350 and 2009-091351.
また、上記一般式（ＩＩ）で表されるスルホニウムのスルホン酸塩の合成も既知であり、例えば、Ｈｅｎｇｐｅｎｇ Ｗｕ等 Ａｄｖ．Ｆｕｎｃｔ．Ｍａｔｅｒ．２００１，１１，Ｎｏ．４，Ａｕｇｕｓｔ等に開示されている。 The synthesis of sulfonium sulfonates represented by the above general formula (II) is also known, for example, Hengpeng Wu et al. Adv. Funct. Mater. 2001, 11, no. 4, August et al.
上記式（Ａ−１）又は上記式（Ａ−２）で表される構造単位を有する重合体の粘度は、通常、１乃至１００ｃＰである。
なお、粘度は、東機産業（株）製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０で測定した値である。The viscosity of the polymer having the structural unit represented by the above formula (A-1) or the above formula (A-2) is usually 1 to 100 cP.
In addition, a viscosity is the value measured by Toki Sangyo Co., Ltd. product and VISCOMETER TV-20.
本発明のレジスト下層膜形成組成物における上記式（Ａ−１）又は上記式（Ａ−２）で表される構造単位を有する重合体の含有量は、当該レジスト下層膜形成組成物の固形分の含有量に基づいて、例えば、０．１乃至１０質量％である。この重合体は、添加剤としてだけでなく前記固形分の主成分として本発明のレジスト下層膜形成組成物に含ませても良い。 The content of the polymer having the structural unit represented by the above formula (A-1) or the above formula (A-2) in the resist underlayer film forming composition of the present invention is the solid content of the resist underlayer film forming composition. For example, the content is 0.1 to 10% by mass. This polymer may be contained not only as an additive but also as a main component of the solid content in the resist underlayer film forming composition of the present invention.
また、本発明のレジスト下層膜形成組成物に含まれる重合体は、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位以外に、下記式（Ｂ）で表される構造単位を有することができる。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
ｐ及びｑは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ及びｑはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ≦１を満たす。｝Moreover, the polymer contained in the resist underlayer film forming composition of the present invention has the following formula in addition to the structural unit represented by the following formula (A-1) or the structural unit represented by the following formula (A-2). It can have a structural unit represented by (B).
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
p and q represent the charging ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p and q are in the range of 0.05 to 0.95, respectively. However, p + q ≦ 1 is satisfied. }
本発明のレジスト下層膜形成組成物は、ポリマー中に上記式（Ａ−１）又は上記式（Ａ−２）で表される光酸発生剤成分以外に、第二成分として上記式（Ｂ）で表される構造単位を導入したポリマーを含ませることにより、レジスト下層膜形成組成物から形成されるレジスト下層膜の機能性を向上させることが可能となる。 In addition to the photoacid generator component represented by the above formula (A-1) or the above formula (A-2) in the polymer, the resist underlayer film forming composition of the present invention has the above formula (B) as a second component. It is possible to improve the functionality of the resist underlayer film formed from the resist underlayer film forming composition by including a polymer having a structural unit represented by
上記式（Ｂ）で表される第二成分としては、例えば、下記式（ＩＩＩ）で表される架橋部位（−ＯＨ）を有する構造単位を導入することにより、本発明のレジスト下層膜形成組成物から形成されるレジスト下層膜に熱架橋膜としての性質を付与することが可能であり、かつ本発明のレジスト下層膜形成組成物に含まれる、光酸発生剤成分を構造単位に有するポリマーを添加剤として適用した場合にベースポリマーに固定化することが可能となるため、レジスト下層膜上にレジストを塗布する際に光酸発生成分のリーチング（溶出）を抑制したり、光酸発生剤成分の昇華を抑制することが可能となる。
上記式（Ｂ）で表される第二成分の原料モノマーとして、例えばアクリル酸、メタクリル酸、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレート、２，３−ジヒドロキシプロピルアクリレート、３−クロロ−２−ヒドロキシアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルメタクリレート、２，３−ジヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシメタクリレート、４−ヒドロキシスチレン、４−ヒドロキシフェニルアクリレート、４−ヒドロキシフェニルメタクリレート、グリシジルアクリレート、グリシジルメタクリレートが挙げられる。 As a raw material monomer of the second component represented by the above formula (B), for example, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 3-chloro-2-hydroxy acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, 3-chloro-2-hydroxy methacrylate, 4-hydroxystyrene, 4 -Hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, glycidyl acrylate, glycidyl methacrylate.
レジストパターン形状をストレート形状に改良し、第二成分を導入することでレジスト下層膜の機能性を向上させるためには、ｐは通常、０．０５乃至０．９５である。一方、ｑは通常、０．０５乃至０．９５である。 In order to improve the functionality of the resist underlayer film by improving the resist pattern shape to a straight shape and introducing the second component, p is usually 0.05 to 0.95. On the other hand, q is usually 0.05 to 0.95.
また、上記式（Ａ−１）又は上記式（Ａ−２）で表される構造単位、及び上記式（Ｂ）で表される構造単位を有する重合体の粘度は、１乃至１００ｃＰである。
なお、粘度は、東機産業（株）製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０で測定した値である。The viscosity of the polymer having the structural unit represented by the above formula (A-1) or the above formula (A-2) and the structural unit represented by the above formula (B) is 1 to 100 cP.
In addition, a viscosity is the value measured by Toki Sangyo Co., Ltd. product and VISCOMETER TV-20.
さらに、本発明のレジスト下層膜形成組成物に含まれる重合体は、下記式（Ａ−１）で表される構造単位又は下記式（Ａ−２）で表される構造単位、及び下記式（Ｂ）で表される構造単位以外に、下記式（Ｃ）で表される構造単位を有することができる。
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
式（Ｃ）中、Ｒ1は水素原子又はメチル基を表し、Ａ2は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ2は水素原子の一部又は全てがフッ素原子で置換された炭素原子数１乃至８のアルキル基を表す。
ｐ、ｑ及びｒは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ、ｑ及びｒはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ＋ｒ≦１を満たす。｝Furthermore, the polymer contained in the resist underlayer film forming composition of the present invention includes a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2), and the following formula ( In addition to the structural unit represented by B), it may have a structural unit represented by the following formula (C).
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
In the formula (C), R 1 represents a hydrogen atom or a methyl group, A 2 represents —C (═O) O—, —O— or a direct bond, and X 2 represents a part or all of the hydrogen atoms are fluorine. An alkyl group having 1 to 8 carbon atoms substituted with an atom is represented.
p, q, and r represent the charge ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p, q, and r are each in the range of 0.05 to 0.95. However, p + q + r ≦ 1 is satisfied. }
本発明のレジスト下層膜形成組成物は、ポリマー中に上記式（Ａ−１）又は上記式（Ａ−２）で表される光酸発生剤成分以外に、上述の第二成分同様、第三成分として上記式（Ｃ）で表される構造単位を導入したポリマーを含ませることにより、レジスト下層膜形成組成物から形成されるレジスト下層膜の機能性を向上させることが可能となる。 In addition to the photoacid generator component represented by the above formula (A-1) or the above formula (A-2) in the polymer, the resist underlayer film forming composition of the present invention is the same as the above-mentioned second component. By including a polymer into which the structural unit represented by the above formula (C) is introduced as a component, it is possible to improve the functionality of the resist underlayer film formed from the resist underlayer film forming composition.
上記式（Ｃ）で表される第三成分としては、例えば、下記式（ＩＶ）で表されるフッ素系の構造単位を導入することにより、表面エネルギーを低下させ、本発明のレジスト下層膜形成組成物に含まれる、光酸発生剤成分を構造単位に有するポリマーを添加剤として適用した場合に光酸発生剤成分を効果的にレジスト下層膜表面部位へ偏析可能となる。また、少量の添加量でも効果的に酸としての効能を示すことが可能となる。
上記式（Ｃ）で表される第三成分の原料モノマーとして、例えば２，２，２−トリフルオロエチルアクリレート、２，２，３，３−テトラフルオロプロピルアクリレート、２，２，３，３，３−ペンタフルオロプロピルアクリレート、２，２，３，３，４，４，４−ヘプタフルオロブチルアクリレート、２，２，３，３，４，４−ヘキサフルオロブチルアクリレート、ビス（２，２，２−トリフルオロメチル）イソプロピルアクリレート、４−フルオロフェニルアクリレート、２，３，４，５，６−ペンタフルオロフェニルアクリレート、２，２，２−トリフルオロエチルメタクリレート、２，２，３，３−テトラフルオロプロピルメタクリレート、２，２，３，３，３−ペンタフルオロプロピルメタクリレート、２，２，３，３，４，４，４−ヘプタフルオロブチルメタクリレート、２，２，３，３，４，４−ヘキサフルオロブチルメタクリレート、ビス（２，２，２−トリフルオロメチル）イソプロピルメタクリレート、４−フルオロフェニルメタクリレート、２，３，４，５，６−ペンタフルオロフェニルメタクリレート等が挙げられる。 As the raw material monomer of the third component represented by the above formula (C), for example, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3, 3-pentafluoropropyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4-hexafluorobutyl acrylate, bis (2,2,2 -Trifluoromethyl) isopropyl acrylate, 4-fluorophenyl acrylate, 2,3,4,5,6-pentafluorophenyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoro Propyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,4,4, -Heptafluorobutyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, bis (2,2,2-trifluoromethyl) isopropyl methacrylate, 4-fluorophenyl methacrylate, 2,3,4, Examples include 5,6-pentafluorophenyl methacrylate.
レジストパターン形状をストレート形状に改良し、第二成分及び第三成分を導入することでレジスト下層膜の機能性を向上させるためには、ｐは通常、０．０５乃至０．９５である。また、ｑは通常、０．０５乃至０．９５である。さらに、ｒは通常、０．０５乃至０．９５である。 In order to improve the functionality of the resist underlayer film by improving the resist pattern shape to a straight shape and introducing the second component and the third component, p is usually 0.05 to 0.95. Moreover, q is usually 0.05 to 0.95. Further, r is usually 0.05 to 0.95.
また、上記式（Ａ−１）又は上記式（Ａ−２）で表される構造単位、上記式（Ｂ）及び上記式（Ｃ）で表される構造単位を有する重合体の粘度は、１乃至１００ｃＰである。
なお、粘度は、東機産業（株）製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０で測定した値である。The viscosity of the polymer having the structural unit represented by the above formula (A-1) or the above formula (A-2), the structural unit represented by the above formula (B) and the above formula (C) is 1 To 100 cP.
In addition, a viscosity is the value measured by Toki Sangyo Co., Ltd. product and VISCOMETER TV-20.
本発明のレジスト下層膜形成組成物に含まれる重合体の合成方法としては、特に限定されないが、例えば、有機溶媒中で、上記式（Ｉ）で表されるスルホン酸のスルホニウム塩又は上記式（ＩＩ）で表されるスルホニウムのスルホン酸塩、上記式（Ｂ）で表される第二成分の原料モノマー、及び上記式（Ｃ）で表される第三成分の原料モノマーに重合開始剤を加えて加熱重合を行い合成することができる。 The method for synthesizing the polymer contained in the resist underlayer film forming composition of the present invention is not particularly limited. For example, in an organic solvent, the sulfonium salt of sulfonic acid represented by the above formula (I) or the above formula ( A polymerization initiator is added to the sulfonium sulfonate salt represented by II), the second component raw material monomer represented by the above formula (B), and the third component raw material monomer represented by the above formula (C). Can be synthesized by heat polymerization.
当該重合開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、ジメチル２，２’−アゾビス（２−メチルプロピオネート）、ベンゾイルパーオキシド、ラウロイルパーオキシド等を挙げることができ、通常５０乃至８０℃に加熱して重合できる。反応時間としては通常２乃至１００時間、または５乃至３０時間である。 Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropio). Nate), benzoyl peroxide, lauroyl peroxide, and the like, and can be polymerized by heating to 50 to 80 ° C. The reaction time is usually 2 to 100 hours, or 5 to 30 hours.
本発明のレジスト下層膜形成組成物はさらに架橋剤を含むことができる。
そのような架橋剤としては、特に制限はないが、少なくとも二つの架橋形成置換基を有する架橋性化合物が好ましく用いられる。当該架橋剤としては、例えば、メチロール基、メトキシメチル基といった架橋形成置換基を有するメラミン系化合物や置換尿素系化合物が挙げられる。具体的には、メトキシメチル化グリコールウリル又はメトキシメチル化メラミンなどの化合物であり、例えば、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル、及びヘキサメトキシメチルメラミンである。また、テトラメトキシメチル尿素、テトラブトキシメチル尿素などの化合物も挙げられる。The resist underlayer film forming composition of the present invention may further contain a crosslinking agent.
Such a crosslinking agent is not particularly limited, but a crosslinking compound having at least two crosslinking-forming substituents is preferably used. Examples of the crosslinking agent include melamine-based compounds and substituted urea-based compounds having a crosslinking-forming substituent such as a methylol group or a methoxymethyl group. Specifically, it is a compound such as methoxymethylated glycoluril or methoxymethylated melamine, for example, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and hexamethoxymethylmelamine. In addition, compounds such as tetramethoxymethylurea and tetrabutoxymethylurea are also included.
本発明のレジスト下層膜形成組成物における上記架橋剤の含有量は、当該レジスト下層膜形成組成物の固形分の含有量に基づいて、１乃至５０質量％である。 The content of the crosslinking agent in the resist underlayer film forming composition of the present invention is 1 to 50% by mass based on the solid content of the resist underlayer film forming composition.
また架橋反応を促進させるために、本発明のレジスト下層膜形成組成物は架橋触媒を含むことができる。
そのような架橋触媒としては、例えば、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸、及びピリジニウム−ｐ−トルエンスルホネート等のスルホン酸化合物、サリチル酸、スルホサリチル酸、クエン酸、安息香酸、及びヒドロキシ安息香酸等のカルボン酸化合物を挙げることができる。Moreover, in order to promote a crosslinking reaction, the resist underlayer film forming composition of this invention can contain a crosslinking catalyst.
Examples of such crosslinking catalysts include sulfonic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pyridinium-p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid. The carboxylic acid compound can be mentioned.
本発明のレジスト下層膜形成組成物における上記架橋触媒の含有量は、当該レジスト下層膜形成組成物の固形分の含有量に基づいて、０．０２乃至１０質量％である。 The content of the crosslinking catalyst in the resist underlayer film forming composition of the present invention is 0.02 to 10% by mass based on the solid content of the resist underlayer film forming composition.
本発明のレジスト下層膜形成組成物は、上述より、上記の各成分を有機溶剤に溶解させ、重合開始剤を加えて加熱重合させることによって調製できる。
そのような有機溶剤としては、例えば、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、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、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、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、メトキシブタノール類、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、及びＮ−メチルピロリドン等を挙げることができる。As described above, the resist underlayer film forming composition of the present invention can be prepared by dissolving the above-described components in an organic solvent, adding a polymerization initiator, and heating and polymerizing.
Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl. Ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methoxybutanols, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, hydroxyethyl acetate Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, acetic acid Examples thereof include butyl, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
上記有機溶剤は単独又は２種以上の組み合わせで使用することができる。 The said organic solvent can be used individually or in combination of 2 or more types.
また、本発明のレジスト下層膜形成組成物は、界面活性剤を含むこともできる。
当該界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ［登録商標］ＥＦ３０１、ＥＦ３０３、ＥＦ３５２（三菱マテリアル電子化成株式会社（旧（株）ジェムコ）製）、メガファック［登録商標］Ｆ１７１、Ｆ１７３、Ｒ３０（ＤＩＣ株式会社（旧大日本インキ化学工業（株））製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム（株）製）、アサヒガード［登録商標］ＡＧ７１０、サーフロン［登録商標］Ｓ−３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）等を挙げることができる。
Moreover, the resist underlayer film forming composition of this invention can also contain surfactant.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene polyoxyethylene alkylaryl over ethers such as oleyl ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tri Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Non-ionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as N-sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop [registered trademark] ] EF301, EF303, EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd. (formerly Gemco)), MegaFac [registered trademark] F171, F173, R30 (DIC Corporation (formerly Dainippon Ink and Chemicals)) ), FLORARD FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass) Fluorine-based surfactants such as Ltd.)), manufactured by organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and the like.
上記界面活性剤は、単独又は２種以上の組み合わせで使用することができる。 The said surfactant can be used individually or in combination of 2 or more types.
また、上記界面活性剤が使用される場合、本発明のレジスト下層膜形成組成物における含有量は、当該レジスト下層膜形成組成物の固形分中の含有量に基づいて、３質量％以下であり、好ましくは１質量％以下であり、より好ましくは０．５質量％以下である。 Moreover, when the said surfactant is used, content in the resist underlayer film forming composition of this invention is 3 mass% or less based on content in solid content of the said resist underlayer film forming composition. , Preferably it is 1 mass% or less, More preferably, it is 0.5 mass% or less.
また、本発明のレジスト下層膜形成組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、レオロジー調整剤、接着補助剤等も含むことができる。 Moreover, the resist underlayer film forming composition of this invention can also contain a rheology regulator, an adhesion adjuvant, etc. as needed, as long as the effect of this invention is not impaired.
以下、本発明のレジスト下層膜形成組成物の使用について説明する。 Hereinafter, the use of the resist underlayer film forming composition of the present invention will be described.
基板｛例えば、酸化珪素膜で被覆されたシリコン等の半導体基板、窒化珪素膜又は酸化窒化珪素膜で被覆されたシリコン等の半導体基板、窒化珪素基板、石英基板、ガラス基板（無アルカリガラス、低アルカリガラス、結晶化ガラスを含む）、ＩＴＯ膜が形成されたガラス基板等｝上に、スピナー、コーター等の適当な塗布方法により本発明のレジスト下層膜形成組成物が塗布され、その後、ホットプレート等の加熱手段を用いてベークすることにより、レジスト下層膜が形成される。 Substrate {for example, a semiconductor substrate such as silicon covered with a silicon oxide film, a semiconductor substrate such as silicon covered with a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (non-alkali glass, low (Including alkali glass, crystallized glass), glass substrate on which an ITO film is formed, etc.}, the resist underlayer film forming composition of the present invention is applied by an appropriate application method such as a spinner or coater, and then hot plate A resist underlayer film is formed by baking using a heating means such as the above.
ベーク条件としては、ベーク温度８０乃至２５０℃、ベーク時間０．３乃至６０分間の中から適宜選択され、好ましくは、ベーク温度１３０乃至２５０℃、ベーク時間０．５乃至５分間である。 Baking conditions are appropriately selected from a baking temperature of 80 to 250 ° C. and a baking time of 0.3 to 60 minutes, preferably a baking temperature of 130 to 250 ° C. and a baking time of 0.5 to 5 minutes.
また、本発明のレジスト下層膜の膜厚としては、０．００５乃至３．０μｍであり、好ましは０．０１乃至１．０μｍであり、より好ましくは０．０１乃至０．５μｍである。 The thickness of the resist underlayer film of the present invention is 0.005 to 3.0 μm, preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.5 μm.
次にレジスト下層膜上にフォトレジスト膜が形成される。フォトレジスト膜の形成は一般的な方法、すなわち、フォトレジスト溶液のレジスト下層膜上への塗布及びベークによって行うことができる。 Next, a photoresist film is formed on the resist underlayer film. The formation of the photoresist film can be performed by a general method, that is, by applying and baking a photoresist solution on the resist underlayer film.
本発明のレジスト下層膜形成組成物により得られるレジスト下層膜上に形成されるフォトレジストとしては、露光光に感光するものであれば、特に限定はない。当該フォトレジストとしては、例えば、ノボラック樹脂と１，２−ナフトキノンジアジドスルホン酸エステルとからなるポジ型フォトレジスト、酸により分解してアルカリ溶解速度を上昇させる基を有するバインダーと光酸発生剤とからなる化学増幅型フォトレジスト、酸により分解してフォトレジストのアルカリ溶解速度を上昇させる低分子化合物とアルカリ可溶性バインダーと光酸発生剤とからなる化学増幅型フォトレジスト、酸により分解してアルカリ溶解速度を上昇させる基を有するバインダーと酸により分解してフォトレジストのアルカリ溶解速度を上昇させる低分子化合物と光酸発生剤とからなる化学増幅型フォトレジスト等がある。 The photoresist formed on the resist underlayer film obtained by the resist underlayer film forming composition of the present invention is not particularly limited as long as it is sensitive to exposure light. Examples of the photoresist include a positive photoresist composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, and a photoacid generator. Chemically amplified photoresist, a chemically amplified photoresist consisting of a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, an alkali dissolution rate that decomposes with acid There are chemically amplified photoresists composed of a low molecular weight compound that decomposes with a binder having a group that raises the acid and an acid to increase the alkali dissolution rate of the photoresist and a photoacid generator.
具体的には、商品名：ＡＰＥＸ−Ｘ（ローム・アンド・ハース・エレクトロニック・マテリアルズ社（旧シプレイ社）製）、商品名：ＰＡＲ７１０（住友化学（株）製）、商品名：ＳＥＰＲ４３０（信越化学工業（株）製）等が挙げられる。 Specifically, product name: APEX-X (Rohm and Haas Electronic Materials (formerly Shipley)), product name: PAR710 (Sumitomo Chemical Co., Ltd.), product name: SEPR430 (Shin-Etsu) Chemical Industry Co., Ltd.).
本発明では、半導体製造装置の製造に用いるフォトレジストパターンの形成方法において、露光は所定のパターンを形成するためのマスク（レチクル）を通して露光が行われる。露光には、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー等を使用することができる。露光後、必要に応じて露光後加熱（Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｅ）が行われる。露光後加熱の条件としては、加熱温度８０乃至１５０℃、加熱時間０．３乃至６０分間の中から適宜選択される。レジスト下層膜とフォトレジスト膜で被覆された半導体基板を、フォトマスクを用いて露光を行い、その後に現像する工程により半導体装置を製造する。 In the present invention, in a method for forming a photoresist pattern used for manufacturing a semiconductor manufacturing apparatus, exposure is performed through a mask (reticle) for forming a predetermined pattern. For the exposure, a KrF excimer laser, an ArF excimer laser, or the like can be used. After exposure, post-exposure bake is performed as necessary. The conditions for the post-exposure heating are appropriately selected from heating temperatures of 80 to 150 ° C. and heating times of 0.3 to 60 minutes. A semiconductor device is manufactured by a process in which a semiconductor substrate covered with a resist underlayer film and a photoresist film is exposed using a photomask and then developed.
現像に用いる現像液としては、例えば、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリン等の水酸化四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミン等のアミン水溶液等のアルカリ性水溶液等が挙げることができる。 Examples of the developer used for development include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanol. Examples include alkaline aqueous solutions such as amine aqueous solutions such as amine, propylamine and ethylenediamine.
現像の条件としては、現像温度５乃至５０℃、現像時間１０乃至３００秒から適宜選択される。本発明のレジスト下層膜形成組成物から形成されるレジスト下層膜は、フォトレジストの現像に汎用されている２．３８質量％の水酸化テトラメチルアンモニウム水溶液を用いて、室温で容易に現像を行うことができる。 The development conditions are appropriately selected from a development temperature of 5 to 50 ° C. and a development time of 10 to 300 seconds. The resist underlayer film formed from the resist underlayer film forming composition of the present invention is easily developed at room temperature using a 2.38 mass% tetramethylammonium hydroxide aqueous solution that is widely used for developing photoresists. be able to.
以下、実施例及び比較例を挙げて、本発明を更に詳しく説明するが、本発明は、これら実施例に限定されるものでない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples.
＜合成例１＞
１００ｍＬのフラスコにトリフェニルスルホニウム２−メタクリロイルオキシ−１，１−ジフルオロエタンスルホネート（モノマー１）２．８０ｇ（特開２００９−０９１３５０号公報及び特開２００９−０９１３５１号公報参照）と２−ヒドロキシプロピルメタクリレート２．１０ｇ、２，２，２−トリフルオロエチルメタクリレート２．１０ｇにプロピレングリコールモノメチルエーテル２０．９３ｇを添加した。次に、この反応容器を遮光した後、７０℃に加熱し、窒素雰囲気下、プロピレングリコールモノメチルエーテル７．００ｇに２，２’−アゾビスイソブチロニトリル０．０７ｇを溶解させた溶液を少しずつ反応容器内に滴下した。滴下終了後、７０℃で２４時間反応させ、高分子化合物の溶液を得た。得られた溶液の粘度は５７．８ｃＰ（東機産業(株)製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０）であった。これをポリマー１とする。
In a 100 mL flask, 2.80 g of triphenylsulfonium 2-methacryloyloxy-1,1-difluoroethanesulfonate (monomer 1) (see Japanese Patent Application Laid-Open Nos. 2009-09350 and 2009-091351) and 2-hydroxypropyl methacrylate 2 .10 g, and 2.93 g of 2,2,2-trifluoroethyl methacrylate were added with 20.93 g of propylene glycol monomethyl ether. Next, the reaction vessel was shielded from light, and then heated to 70 ° C., and a solution obtained by dissolving 0.07 g of 2,2′-azobisisobutyronitrile in 7.00 g of propylene glycol monomethyl ether was slightly added under a nitrogen atmosphere. The solution was dropped into the reaction vessel. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer compound solution. The viscosity of the obtained solution was 57.8 cP (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-20). This is polymer 1.
＜合成例２＞
１００ｍＬのフラスコにトリフルオロメタンスルホニル４−ジメチルスルホニルフェニルメタクリレート（モノマー２）２．８０ｇ（Ｈｅｎｇｐｅｎｇ Ｗｕ等 Ａｄｖ．Ｆｕｎｃｔ．Ｍａｔｅｒ．２００１，１１，Ｎｏ．４，Ａｕｇｕｓｔ参照）と２−ヒドロキシプロピルメタクリレート２．１０ｇ、２，２，２−トリフルオロエチルメタクリレート２．１０ｇに乳酸エチル２０．９３ｇを添加した。次に、この反応容器を遮光した後、７０℃に加熱し、窒素雰囲気下、乳酸エチル７．００ｇに２，２’−アゾビスイソブチロニトリル０．０７ｇを溶解させた溶液を少しずつ反応容器内に滴下した。滴下終了後、７０℃で２４時間反応させ、高分子化合物の溶液を得た。得られた溶液の粘度は５５．０ｃＰ（東機産業(株)製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０）であった。これをポリマー２とする。
In a 100 mL flask, 2.80 g of trifluoromethanesulfonyl 4-dimethylsulfonylphenyl methacrylate (monomer 2) (see Hengpeng Wu et al. Adv. Funct. Mater. 2001, 11, No. 4, August) and 2.10 g of 2-hydroxypropyl methacrylate. Then, 20.93 g of ethyl lactate was added to 2.10 g of 2,2,2-trifluoroethyl methacrylate. Next, the reaction vessel was shielded from light, then heated to 70 ° C., and a solution of 0.02 g of 2,2′-azobisisobutyronitrile in 7.00 g of ethyl lactate was reacted little by little in a nitrogen atmosphere. It was dripped in the container. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer compound solution. The viscosity of the obtained solution was 55.0 cP (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-20). This is polymer 2.
＜合成例３＞
１００ｍＬのフラスコにノナフルオロブタンスルホニル４−ジメチルスルホニルフェニルメタクリレート（モノマー３）４．００ｇ（Ｈｅｎｇｐｅｎｇ Ｗｕ等 Ａｄｖ．Ｆｕｎｃｔ．Ｍａｔｅｒ．２００１，１１，Ｎｏ．４，Ａｕｇｕｓｔ参照）と２−ヒドロキシプロピルメタクリレート３．００ｇ、２，２，２−トリフルオロエチルメタクリレート３．００ｇに乳酸エチル２９．９０ｇを添加した。次に、この反応容器を遮光した後、７０℃に加熱し、窒素雰囲気下、乳酸エチル１０．００ｇに２，２’−アゾビスイソブチロニトリル０．１０ｇを溶解させた溶液を少しずつ反応容器内に滴下した。滴下終了後、７０℃で２４時間反応させ、高分子化合物の溶液を得た。得られた溶液の粘度は４２．４ｃＰ（東機産業(株)製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０）であった。これをポリマー３とする。
In a 100 mL flask, 4.00 g of nonafluorobutanesulfonyl 4-dimethylsulfonylphenyl methacrylate (monomer 3) (see Hengpeng Wu et al. Adv. Funct. Mater. 2001, 11, No. 4, August) and 2-hydroxypropyl methacrylate. To 3.0 g of 00 g and 2,2,2-trifluoroethyl methacrylate, 29.90 g of ethyl lactate was added. Next, the reaction vessel was shielded from light, then heated to 70 ° C., and a solution of 0.10 g of 2,2′-azobisisobutyronitrile dissolved in 10.00 g of ethyl lactate was reacted little by little in a nitrogen atmosphere. It was dripped in the container. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer compound solution. The viscosity of the obtained solution was 42.4 cP (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-20). This is polymer 3.
＜合成例４＞
１００ｍＬのフラスコにヘプタデカフルオロオクタンスルホニル４−ジメチルスルホニルフェニルメタクリレート（モノマー４）４．００ｇ（Ｈｅｎｇｐｅｎｇ Ｗｕ等 Ａｄｖ．Ｆｕｎｃｔ．Ｍａｔｅｒ．２００１，１１，Ｎｏ．４，Ａｕｇｕｓｔ参照）と２−ヒドロキシプロピルメタクリレート３．００ｇ、２，２，２−トリフルオロエチルメタクリレート３．００ｇに乳酸エチル２９．９０ｇを添加した。次に、この反応容器を遮光した後、７０℃に加熱し、窒素雰囲気下、乳酸エチル１０．００ｇに２，２’−アゾビスイソブチロニトリル０．１０ｇを溶解させた溶液を少しずつ反応容器内に滴下した。滴下終了後、７０℃で２４時間反応させ、高分子化合物の溶液を得た。得られた溶液の粘度は１８．１ｃＰ（東機産業(株)製、ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２０）であった。これをポリマー４とする。
In a 100 mL flask, 4.00 g of heptadecafluorooctanesulfonyl 4-dimethylsulfonylphenyl methacrylate (monomer 4) (see Hengpeng Wu et al. Adv. Funct. Mater. 2001, 11, No. 4, August) and 2-hydroxypropyl methacrylate 3 To 3.00 g of 0.000 g and 2,2,2-trifluoroethyl methacrylate, 29.90 g of ethyl lactate was added. Next, the reaction vessel was shielded from light, then heated to 70 ° C., and a solution of 0.10 g of 2,2′-azobisisobutyronitrile dissolved in 10.00 g of ethyl lactate was reacted little by little in a nitrogen atmosphere. It was dripped in the container. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer compound solution. The viscosity of the obtained solution was 18.1 cP (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-20). This is polymer 4.
＜合成例５＞
３００ｍＬのフラスコにベンジルメタクリレート１０．２０ｇと２−ヒドロキシプロピルメタクリレート９．９０ｇ、γ−ブチロラクトンメタクリレート９．９０ｇに乳酸エチル８９．７０ｇを添加した。次に、この反応容器を７０℃に加熱し、窒素雰囲気下、乳酸エチル３０．００ｇに２，２’−アゾビスイソブチロニトリル０．３０ｇを溶解させた溶液を少しずつ反応容器内に滴下した。滴下終了後、７０℃で２４時間反応させ、高分子化合物の溶液を得た。得られた溶液の重量平均分子量Ｍｗは２６０００（ポリスチレン換算）であった。これをポリマー５とする。
To a 300 mL flask was added 10.20 g of benzyl methacrylate, 9.90 g of 2-hydroxypropyl methacrylate, and 89.70 g of ethyl lactate to 9.90 g of γ-butyrolactone methacrylate. Next, this reaction vessel was heated to 70 ° C., and a solution prepared by dissolving 0.30 g of 2,2′-azobisisobutyronitrile in 30.00 g of ethyl lactate was gradually dropped into the reaction vessel in a nitrogen atmosphere. did. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer compound solution. The weight average molecular weight Mw of the obtained solution was 26000 (polystyrene conversion). This is designated as Polymer 5.
上記重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）による測定結果である。
測定には東ソー（株）製ＧＰＣ装置を用いた。
装置名：ＧＰＣ ＡＳ−８０２０
溶離液：Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）＋ＬｉＢｒ・Ｈ2Ｏ（１０ｍｍｏｌ）
使用カラム：Ａｓａｈｉｐａｋ[登録商標]（ＧＦ−７１０ＨＧ、ＧＦ−５１０ＨＱ、ＧＦ−３１０ＨＱ）
流量：０．６００ｍｌ／分
カラム温度：４０℃The weight average molecular weight is a measurement result by gel permeation chromatography (GPC).
A GPC apparatus manufactured by Tosoh Corporation was used for the measurement.
Device name: GPC AS-8020
Eluent: N, N-dimethylformamide (DMF) + LiBr.H 2 O (10 mmol)
Column used: Asahipak [registered trademark] (GF-710HG, GF-510HQ, GF-310HQ)
Flow rate: 0.600 ml / min Column temperature: 40 ° C
＜実施例１＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例１で得た高分子化合物（ポリマー１）０．０３ｇを有するプロピレングリコールモノメチルエーテル溶液０．１５ｇ（ポリマー５の固形分に対して５質量％）を混合し、プロピレングリコールモノメチルエーテル４．４ｇ、乳酸エチル１０．２ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 1>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.15 g of a propylene glycol monomethyl ether solution (0.05 g based on the solid content of polymer 5) having 0.03 g of the polymer compound (polymer 1) obtained in Example 1 was mixed to obtain 4.4 g of propylene glycol monomethyl ether, A solution was prepared by dissolving in 10.2 g of ethyl lactate. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例２＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例１で得た高分子化合物（ポリマー１）０．０９ｇを有するプロピレングリコールモノメチルエーテル溶液０．４５ｇ（ポリマー５の固形分に対して１５質量％）を混合し、プロピレングリコールモノメチルエーテル４．６ｇ、乳酸エチル１１．１ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 2>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.45 g of propylene glycol monomethyl ether solution (15% by mass based on the solid content of polymer 5) having 0.09 g of the polymer compound (polymer 1) obtained in Example 1 was mixed, and 4.6 g of propylene glycol monomethyl ether, A solution was prepared by dissolving in 11.1 g of ethyl lactate. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例３＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例２で得た高分子化合物（ポリマー２）０．０３ｇを有する乳酸エチル溶液０．１４ｇ（ポリマー５の固形分に対して５質量％）を混合し、プロピレングリコールモノメチルエーテル４．５ｇ、乳酸エチル１０．１ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 3>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.14 g of ethyl lactate solution (5% by mass based on the solid content of polymer 5) having 0.03 g of the polymer compound (polymer 2) obtained in Example 2 was mixed, 4.5 g of propylene glycol monomethyl ether, ethyl lactate A solution was prepared by dissolving in 10.1 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例４＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例３で得た高分子化合物（ポリマー３）０．０３ｇを有する乳酸エチル溶液０．１４ｇ（ポリマー５の固形分に対して５質量％）を混合し、プロピレングリコールモノメチルエーテルアセテート５．２ｇ、乳酸エチル８．７ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 4>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.14 g of ethyl lactate solution (5% by mass based on the solid content of polymer 5) having 0.03 g of the polymer compound (polymer 3) obtained in Example 3 was mixed, and 5.2 g of propylene glycol monomethyl ether acetate was added. A solution was prepared by dissolving in 8.7 g of ethyl. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例５＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例３で得た高分子化合物（ポリマー３）０．０９ｇを有する乳酸エチル溶液０．４３ｇ（ポリマー５の固形分に対して１５質量％）を混合し、プロピレングリコールモノメチルエーテルアセテート５．２ｇ、乳酸エチル８．５ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 5>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.43 g of ethyl lactate solution (15% by mass with respect to the solid content of polymer 5) having 0.09 g of the polymer compound (polymer 3) obtained in Example 3 was mixed, and 5.2 g of propylene glycol monomethyl ether acetate, A solution was prepared by dissolving in 8.5 g of ethyl. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例６＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例４で得た高分子化合物（ポリマー４）０．０３ｇを有する乳酸エチル溶液０．１４ｇ（ポリマー５の固形分に対して５質量％）を混合し、プロピレングリコールモノメチルエーテルアセテート５．２ｇ、乳酸エチル８．７ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 6>
To 3.00 g of ethyl lactate solution containing 0.57 g of the polymer compound (Polymer 5) obtained in Synthesis Example 5, 0.14 g of tetramethoxymethylglycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.14 g of ethyl lactate solution (5% by mass with respect to the solid content of polymer 5) having 0.03 g of the polymer compound (polymer 4) obtained in Example 4 was mixed, and 5.2 g of propylene glycol monomethyl ether acetate, A solution was prepared by dissolving in 8.7 g of ethyl. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜実施例７＞
上記合成例５で得た高分子化合物０．５７ｇ（ポリマー５）を有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例４で得た高分子化合物（ポリマー４）０．０９ｇを有する乳酸エチル溶液０．４３ｇ（ポリマー５の固形分に対して１５質量％）を混合し、プロピレングリコールモノメチルエーテルアセテート５．２ｇ、乳酸エチル８．５ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Example 7>
To 3.00 g of ethyl lactate solution containing 0.57 g (polymer 5) of the polymer compound obtained in Synthesis Example 5, 0.14 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.43 g of ethyl lactate solution (15% by mass with respect to the solid content of polymer 5) having 0.09 g of the polymer compound (polymer 4) obtained in Example 4 was mixed, and 5.2 g of propylene glycol monomethyl ether acetate, A solution was prepared by dissolving in 8.5 g of ethyl. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜比較例１＞
上記合成例５で得た高分子化合物（ポリマー５）０．５７ｇを有する乳酸エチル溶液３．００ｇにテトラメトキシメチルグリコールウリル０．１４ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇを混合し、プロピレングリコールモノメチルエーテルアセテート５．２ｇ、乳酸エチル８．８ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物溶液を調製した。<Comparative Example 1>
0.10 g of tetramethoxymethylglycoluril and 0.01 g of pyridinium-p-toluenesulfonate are mixed with 3.00 g of an ethyl lactate solution containing 0.57 g of the polymer compound (polymer 5) obtained in Synthesis Example 5, and propylene glycol. A solution was prepared by dissolving in 5.2 g of monomethyl ether acetate and 8.8 g of ethyl lactate. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist underlayer film forming composition solution.
＜比較例２＞
上記合成例５で得た高分子化合物（ポリマー５）０．５４ｇを有する乳酸エチル溶液２．７３ｇにテトラメトキシメチルグリコールウリル０．１３ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例１で得た高分子化合物（ポリマー１）の前駆体化合物であるトリフェニルスルホニウム２−メタクリロイルオキシ−１，１−ジフルオロエタンスルホネート（モノマー１）０．０１ｇを混合し、プロピレングリコールモノメチルエーテル５．７ｇ、乳酸エチル１１．０ｇに溶解させて溶液とした。その後、孔径０．１μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物を調製した。なお、モノマー１の添加量は、ポリマー５の固形分に対して２質量％とした。<Comparative example 2>
To 2.73 g of ethyl lactate solution containing 0.54 g of the polymer compound (polymer 5) obtained in Synthesis Example 5, 0.13 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.01 g of triphenylsulfonium 2-methacryloyloxy-1,1-difluoroethanesulfonate (monomer 1), which is a precursor compound of the polymer compound (polymer 1) obtained in Example 1, is mixed with 5.7 g of propylene glycol monomethyl ether. A solution was prepared by dissolving in 11.0 g of ethyl lactate. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.1 micrometer, and prepared the resist lower layer film forming composition. In addition, the addition amount of the monomer 1 was 2 mass% with respect to the solid content of the polymer 5.
＜比較例３＞
上記合成例５で得た高分子化合物（ポリマー５）０．５４ｇを有する乳酸エチル溶液２．７３ｇにテトラメトキシメチルグリコールウリル０．１３ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例１で得た高分子化合物（ポリマー１）の前駆体化合物であるトリフェニルスルホニウム２−メタクリロイルオキシ−１，１−ジフルオロエタンスルホネート（モノマー１）０．０３ｇを混合し、プロピレングリコールモノメチルエーテル５．７ｇ、乳酸エチル１１．１ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物を調製した。なお、モノマー１の添加量は、実施例１と同様にポリマー５の固形分に対して５質量％とした。<Comparative Example 3>
To 2.73 g of ethyl lactate solution containing 0.54 g of the polymer compound (polymer 5) obtained in Synthesis Example 5, 0.13 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.03 g of triphenylsulfonium 2-methacryloyloxy-1,1-difluoroethanesulfonate (monomer 1) which is a precursor compound of the polymer compound (polymer 1) obtained in Example 1 is mixed, and 5.7 g of propylene glycol monomethyl ether A solution was prepared by dissolving in 11.1 g of ethyl lactate. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist lower layer film forming composition. In addition, the addition amount of the monomer 1 was 5 mass% with respect to the solid content of the polymer 5 similarly to Example 1.
＜比較例４＞
上記合成例５で得た高分子化合物０．５４ｇ（ポリマー５）を有する乳酸エチル溶液２．７３ｇにテトラメトキシメチルグリコールウリル０．１３ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例２で得た高分子化合物（ポリマー２）の前駆体化合物であるトリフルオロメタンスルホニル４−ジメチルスルホニルフェニルメタクリレート（モノマー２）０．０１ｇを混合し、プロピレングリコールモノメチルエーテル５．７ｇ、乳酸エチル１１．０ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物を調製した。なお、モノマー２の添加量は、ポリマー５の固形分に対して２質量％とした。<Comparative example 4>
2.73 g of ethyl lactate solution containing 0.54 g of polymer compound (polymer 5) obtained in Synthesis Example 5 above, 0.13 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.01 g of trifluoromethanesulfonyl 4-dimethylsulfonylphenyl methacrylate (monomer 2), which is a precursor compound of the polymer compound (polymer 2) obtained in Example 2, was mixed, 5.7 g of propylene glycol monomethyl ether, and 11.10 ethyl acetate. A solution was prepared by dissolving in 0 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist lower layer film forming composition. In addition, the addition amount of the monomer 2 was 2 mass% with respect to the solid content of the polymer 5.
＜比較例５＞
上記合成例５で得た高分子化合物０．５４ｇ（ポリマー５）を有する乳酸エチル溶液２．７３ｇにテトラメトキシメチルグリコールウリル０．１３ｇ、ピリジニウム−ｐ−トルエンスルホネート０．０１ｇ、添加剤として上記合成例２で得た高分子化合物（ポリマー２）の前駆体化合物であるトリフルオロメタンスルホニル４−ジメチルスルホニルフェニルメタクリレート（モノマー２）０．０３ｇを混合し、プロピレングリコールモノメチルエーテル５．７ｇ、乳酸エチル１１．１ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、レジスト下層膜形成組成物を調製した。なお、モノマー２の添加量は、実施例３と同様にポリマー５の固形分に対して５質量％とした。<Comparative Example 5>
2.73 g of ethyl lactate solution containing 0.54 g of polymer compound (polymer 5) obtained in Synthesis Example 5 above, 0.13 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, and the above synthesis as an additive 0.03 g of trifluoromethanesulfonyl 4-dimethylsulfonylphenyl methacrylate (monomer 2), which is a precursor compound of the polymer compound (polymer 2) obtained in Example 2, was mixed, 5.7 g of propylene glycol monomethyl ether, and ethyl lactate 11. A solution was prepared by dissolving in 1 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the resist lower layer film forming composition. The amount of monomer 2 added was 5% by mass with respect to the solid content of polymer 5 as in Example 3.
［昇華物定量試験］
このように調製したレジスト下層膜形成組成物溶液（実施例１乃至４及び比較例２乃至５）をスピンコーターによりシリコンウエハー上に塗布し、国際公開第２００７／１１１１４７号に記載の昇華物定量装置を用いて、２０５℃のホットプレート上で６０秒間加熱した際に発生するレジスト下層膜形成組成物由来の昇華物量を定量した。その結果を表１及び表２にまとめる。[Sublimation quantification test]
The resist underlayer film forming composition solutions (Examples 1 to 4 and Comparative Examples 2 to 5) thus prepared were applied onto a silicon wafer by a spin coater, and the sublimate quantification apparatus described in International Publication No. 2007/111147 Was used to quantify the amount of sublimate derived from the resist underlayer film forming composition generated when heated on a hot plate at 205 ° C. for 60 seconds. The results are summarized in Tables 1 and 2.
表１及び表２の結果より、本発明のレジスト下層膜形成組成物は、ポリマー化した光酸発生剤を含むことにより、従来の低分子タイプの光酸発生剤を含むレジスト下層膜形成組成物と比較して、ベーク時に光酸発生剤成分の昇華を抑制することが可能であることを確認できた。 From the results of Tables 1 and 2, the resist underlayer film forming composition of the present invention contains a polymerized photoacid generator, so that a resist underlayer film forming composition containing a conventional low molecular type photoacid generator is included. It was confirmed that it was possible to suppress sublimation of the photoacid generator component at the time of baking.
［レジストパターン形成試験］
上記のように調製したレジスト下層膜形成組成物溶液（実施例１乃至８及び比較例１乃至５）をコーターデベロッパー（東京エレクトロン（株）製、ＣｌｅａｎＴｒａｃｋ−ＡＣＴ８）によりシリコンウエハー上に塗布し、ホットプレート上で２０５℃、６０秒間加熱することで、リソグラフィー用レジスト下層膜（膜厚０．０８μｍ）を形成した。このレジスト下層膜の上層に、ＡｒＦリソグラフィー用レジスト（東京応化工業（株）製、ＴＡｒＦ−Ｐ６１１１ＭＥ）溶液を塗布し、ホットプレート上で１３０℃、６０秒間加熱してレジスト膜を形成した。この膜に、ＡｒＦエキシマレーザー露光装置（（株）ニコン製、Ｓ３０７Ｅ、ＮＡ＝０．８５）を用いてレジストのライン幅が０．０８μｍ、スペース幅が０．１０μｍとなるようなラインアンドスペースが形成されるマスクを通して露光した後、１３０℃、６０秒間加熱（ＰＥＢ）し、テトラメチルアンモニウムヒドロキシドの２．３８質量％水溶液で６０秒間現像を行うことで、レジストパターン（実施例１乃至８及び比較例１乃至５）を得た。
得られたレジストパターンは、走査型電子顕微鏡（（株）日立ハイテクノロジーズ製、Ｓ−４８００）を用いてレジストのパターン形状を観察した。その結果を表３にまとめる。[Resist pattern formation test]
The resist underlayer film forming composition solutions (Examples 1 to 8 and Comparative Examples 1 to 5) prepared as described above were applied onto a silicon wafer by a coater developer (Tokyo Electron Co., Ltd., CleanTrack-ACT8), and hot By heating on the plate at 205 ° C. for 60 seconds, a resist underlayer film (film thickness: 0.08 μm) for lithography was formed. On top of this resist underlayer film, an ArF lithography resist (TARF-P6111ME, manufactured by Tokyo Ohka Kogyo Co., Ltd.) solution was applied and heated on a hot plate at 130 ° C. for 60 seconds to form a resist film. This film has a line and space such that the resist line width is 0.08 μm and the space width is 0.10 μm using an ArF excimer laser exposure apparatus (Nikon Corporation, S307E, NA = 0.85). After exposure through a mask to be formed, heating (PEB) at 130 ° C. for 60 seconds, and developing with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 60 seconds, a resist pattern (Examples 1 to 8 and Comparative examples 1 to 5) were obtained.
With respect to the obtained resist pattern, the pattern shape of the resist was observed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-4800). The results are summarized in Table 3.
表３の結果より、本発明のレジスト下層膜形成組成物は、光酸発生剤成分の昇華が抑制されるため、波長１９３ｎｍのＡｒＦエキシマレーザーにおける露光条件において、当該組成物から形成されたレジスト下層膜中に含まれる光酸発生剤成分から効率的に酸が発生することで、従来のレジスト下層膜と比較して、レジストパターン形状をストレート形状に改善することが可能であることが確認できた。 From the results of Table 3, the resist underlayer film forming composition of the present invention suppresses the sublimation of the photoacid generator component, and therefore the resist underlayer formed from the composition under the exposure conditions in an ArF excimer laser with a wavelength of 193 nm As a result of efficient generation of acid from the photoacid generator component contained in the film, it was confirmed that the resist pattern shape could be improved to a straight shape as compared with the conventional resist underlayer film. .
以上、本発明のリソグラフィー用レジスト下層膜形成組成物の実施形態を説明したが、本発明の技術的範囲は上記実施形態に記載された範囲には限定されない。上記実施形態に、多様な変更又は改良を加えることが可能である。 As mentioned above, although embodiment of the resist underlayer film forming composition for lithography of this invention was described, the technical scope of this invention is not limited to the range described in the said embodiment. Various modifications or improvements can be added to the above embodiment.
Claims (6)
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）。｝A resist underlayer film forming composition comprising a polymer having a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2).
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.) }
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
ｐ及びｑは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ及びｑはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ≦１を満たす。｝Formation of resist underlayer film comprising a polymer having a structural unit represented by the following formula (A-1) or a structural unit represented by the following formula (A-2) and a structural unit represented by the following formula (B) Composition.
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
p and q represent the charging ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p and q are in the range of 0.05 to 0.95, respectively. However, p + q ≦ 1 is satisfied. }
一方、式（Ａ−２）中、Ｒ1は水素原子又はメチル基を表し、Ｒ2は炭素原子数１乃至８のアルキレン基、炭素原子数４乃至８のシクロアルキレン基、フェニレン基又は炭素原子数７乃至１０のアルキルフェニレン基を表す（ここで、該アルキレン基、該シクロアルキレン基、該フェニレン基又は該アルキルフェニレン基の水素原子の一部又は全てがフッ素原子で置換されていてもよく、エーテル基を１つ以上有していてもよい。）。
Ｒ3、Ｒ4及びＲ5は同一又は異種の炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又は置換基を有してもよいフェニル基を表し、Ｒ3とＲ4、Ｒ3とＲ5、Ｒ4とＲ5はそれぞれ結合して環を形成していてもよい。
Ｒ6は炭素原子数１乃至８のアルキル基、炭素原子数４乃至８のシクロアルキル基又はフェニル基を表す（ここで、該アルキル基、該シクロアルキル基又は該フェニル基の水素原子の一部又は全てがフッ素原子で置換されていてもよい。）
式（Ｂ）中、Ｒ1は水素原子又はメチル基を表し、Ａ1は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ1は炭素原子数１乃至８のアルキル基、アリール基又はアリールアルキル基を表し、該アルキル基、該アリール基又は該アリールアルキル基はヒドロキシ基、カルボキシル基又はエポキシ基を少なくとも１つ有する。
式（Ｃ）中、Ｒ1は水素原子又はメチル基を表し、Ａ2は−Ｃ（＝Ｏ）Ｏ−、−Ｏ−又は直接結合を表し、Ｘ2は水素原子の一部又は全てがフッ素原子で置換された炭素原子数１乃至８のアルキル基を表す。
ｐ、ｑ及びｒは前記重合体に含まれる構造単位を得るための原料モノマーの仕込み比（質量％）を表し、ｐ、ｑ及びｒはそれぞれ０．０５乃至０．９５の範囲である。但し、ｐ＋ｑ＋ｒ≦１を満たす。｝The structural unit represented by the following formula (A-1) or the structural unit represented by the following formula (A-2), the structural unit represented by the following formula (B), and the following formula (C) A resist underlayer film forming composition comprising a polymer having a structural unit.
On the other hand, in formula (A-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a phenylene group, or a carbon atom. Represents an alkylphenylene group of formula 7 to 10 (wherein, a part or all of hydrogen atoms of the alkylene group, the cycloalkylene group, the phenylene group or the alkylphenylene group may be substituted with a fluorine atom, It may have one or more ether groups).
R 3, R 4 and R 5 represent the same or alkyl group having a carbon number of 1 to 8 heterologous, cycloalkyl group or phenyl group which may have a substituent group having a carbon number of 4 to 8, and R 3 R 4 , R 3 and R 5 , and R 4 and R 5 may be bonded to each other to form a ring.
R 6 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a phenyl group (wherein the alkyl group, the cycloalkyl group, or a part of hydrogen atoms of the phenyl group). Alternatively, all may be substituted with fluorine atoms.)
In formula (B), R 1 represents a hydrogen atom or a methyl group, A 1 represents —C (═O) O—, —O— or a direct bond, and X 1 represents an alkyl group having 1 to 8 carbon atoms. Represents an aryl group or an arylalkyl group, and the alkyl group, the aryl group or the arylalkyl group has at least one hydroxy group, carboxyl group or epoxy group.
In the formula (C), R 1 represents a hydrogen atom or a methyl group, A 2 represents —C (═O) O—, —O— or a direct bond, and X 2 represents a part or all of the hydrogen atoms are fluorine. An alkyl group having 1 to 8 carbon atoms substituted with an atom is represented.
p, q, and r represent the charge ratio (mass%) of the raw material monomer for obtaining the structural unit contained in the polymer, and p, q, and r are each in the range of 0.05 to 0.95. However, p + q + r ≦ 1 is satisfied. }
形成された前記レジスト下層膜上にレジスト膜を形成する工程、
前記レジスト膜が形成された基板に、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、極端紫外線（ＥＵＶ）及び電子線（ＥＢ）からなる群から選択される放射線を照射する工程、
照射後に前記レジスト膜を現像してレジストパターンを形成する工程、及び
形成された前記レジストパターンをマスクとしてドライエッチングにより前記基板上にパターンを転写する工程を含む、半導体素子を作製する方法。Applying and baking the resist underlayer film forming composition according to any one of claims 1 to 5 on a substrate having a processing target film for forming a pattern to form a resist underlayer film;
Forming a resist film on the formed resist underlayer film,
Irradiating the substrate on which the resist film is formed with radiation selected from the group consisting of KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV) and electron beam (EB);
A method for producing a semiconductor device, comprising: a step of developing the resist film after irradiation to form a resist pattern; and a step of transferring the pattern onto the substrate by dry etching using the formed resist pattern as a mask.
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| JP2004309561A (en) * | 2003-04-02 | 2004-11-04 | Nissan Chem Ind Ltd | Composition for formation of antireflection film containing polymer having polycyclic alicyclic structure |
| JP2005084365A (en) * | 2003-09-09 | 2005-03-31 | Jsr Corp | Radiation-sensitive resin composition |
| JP2006045311A (en) * | 2004-08-03 | 2006-02-16 | Tokyo Ohka Kogyo Co Ltd | Polymeric compound, acid generator, positive type resist composition and resist pattern-forming method |
| JP2006178317A (en) * | 2004-12-24 | 2006-07-06 | Shin Etsu Chem Co Ltd | Resist material and pattern forming method using the same |
| JP2006301145A (en) * | 2005-04-19 | 2006-11-02 | Shin Etsu Chem Co Ltd | Resist undercoat film material, and patternning method using same |
| JP2007316600A (en) * | 2006-04-25 | 2007-12-06 | Shin Etsu Chem Co Ltd | Resist material and pattern forming method |
| WO2008056796A1 (en) * | 2006-11-10 | 2008-05-15 | Jsr Corporation | Radiation-sensitive resin composition |
| JP2008133448A (en) * | 2006-10-27 | 2008-06-12 | Shin Etsu Chem Co Ltd | Sulfonium salt having polymerizable anion and polymer compound, resist material and method for pattern formation |
| JP2008158308A (en) * | 2006-12-25 | 2008-07-10 | Matsushita Electric Ind Co Ltd | Pattern forming material and pattern forming method using the same |
| JP2011164345A (en) * | 2010-02-09 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | Resist underlayer film material and pattern forming method |
-
2010
- 2010-07-14 JP JP2011526706A patent/JP5582316B2/en not_active Expired - Fee Related
- 2010-07-14 KR KR1020127004763A patent/KR101541440B1/en not_active IP Right Cessation
- 2010-07-14 WO PCT/JP2010/061903 patent/WO2011018928A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004309561A (en) * | 2003-04-02 | 2004-11-04 | Nissan Chem Ind Ltd | Composition for formation of antireflection film containing polymer having polycyclic alicyclic structure |
| JP2005084365A (en) * | 2003-09-09 | 2005-03-31 | Jsr Corp | Radiation-sensitive resin composition |
| JP2006045311A (en) * | 2004-08-03 | 2006-02-16 | Tokyo Ohka Kogyo Co Ltd | Polymeric compound, acid generator, positive type resist composition and resist pattern-forming method |
| JP2006178317A (en) * | 2004-12-24 | 2006-07-06 | Shin Etsu Chem Co Ltd | Resist material and pattern forming method using the same |
| JP2006301145A (en) * | 2005-04-19 | 2006-11-02 | Shin Etsu Chem Co Ltd | Resist undercoat film material, and patternning method using same |
| JP2007316600A (en) * | 2006-04-25 | 2007-12-06 | Shin Etsu Chem Co Ltd | Resist material and pattern forming method |
| JP2008133448A (en) * | 2006-10-27 | 2008-06-12 | Shin Etsu Chem Co Ltd | Sulfonium salt having polymerizable anion and polymer compound, resist material and method for pattern formation |
| WO2008056796A1 (en) * | 2006-11-10 | 2008-05-15 | Jsr Corporation | Radiation-sensitive resin composition |
| JP2008158308A (en) * | 2006-12-25 | 2008-07-10 | Matsushita Electric Ind Co Ltd | Pattern forming material and pattern forming method using the same |
| JP2011164345A (en) * | 2010-02-09 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | Resist underlayer film material and pattern forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4202548A1 (en) * | 2021-12-23 | 2023-06-28 | Shin-Etsu Chemical Co., Ltd. | Material for forming adhesive film, patterning process, and method for forming adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011018928A1 (en) | 2013-01-17 |
| KR101541440B1 (en) | 2015-08-03 |
| KR20120045028A (en) | 2012-05-08 |
| WO2011018928A1 (en) | 2011-02-17 |
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