JP2021070749A - Material liquid set for pattern formation comprising first liquid for pattern formation by self-organizing material and second liquid for base film formation, base agent as the second liquid for base film formation and method for forming pattern by self-organizing material by using these materials - Google Patents
Material liquid set for pattern formation comprising first liquid for pattern formation by self-organizing material and second liquid for base film formation, base agent as the second liquid for base film formation and method for forming pattern by self-organizing material by using these materials Download PDFInfo
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
Description
本発明は、自己組織化材料によるパターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セット、下地膜形成用第二の液である下地剤及びそれらを用いた自己組織化材料によるパターン形成方法に関する。 The present invention uses a pattern-forming material liquid set consisting of a pattern-forming first liquid and a base film-forming second liquid using a self-assembling material, a base material which is a base film-forming second liquid, and the like. It relates to a pattern forming method using a self-assembling material.
近年、ブロックコポリマーの誘導自己組織化技術（ＤＳＡ：Ｄｉｒｅｃｔｅｄ Ｓｅｌｆ―Ａｓｓｅｍｂｌｙ）を用いた微細なパターンの形成が脚光を浴びている（例えば、特許文献１〜４参照）。
ところで、例えばフォトニクス結晶、有機薄膜太陽電池のドメインサイズ制御方法、薬物送達用高分子ミセル及びバイオマテリアルの分野では、ハーフピッチが１０ｎｍ以下程度の極めて微細な凹凸パターンの形成が望まれている。
用途に応じた目的の機能を発現するためには、ブロックコポリマーの自己組織化の配向制御が必須である。この要求に対し、ブロックコポリマー層の下部に隣接して、ブロックコポリマーの各ドメインの中間の表面自由エネルギーを有する下地膜を形成することで、基板上に良好なパターンを形成することが提案されている。
In recent years, the formation of fine patterns using the induced self-assembly technique (DSA: Directed Self-Assembly) of block copolymers has been in the limelight (see, for example, Patent Documents 1 to 4).
By the way, for example, in the fields of photonics crystals, domain size control methods for organic thin-film solar cells, polymer micelles for drug delivery, and biomaterials, it is desired to form extremely fine uneven patterns having a half pitch of about 10 nm or less.
In order to exhibit the desired function according to the application, it is essential to control the orientation of the self-assembly of the block copolymer. In response to this requirement, it has been proposed to form a good pattern on the substrate by forming a base film with surface free energy in the middle of each domain of the block copolymer adjacent to the bottom of the block copolymer layer. There is.
しかし、１０ｎｍ以下程度の微細なドメインを含むミクロ相分離構造を形成するブロックコポリマーは、一般に各ドメイン間の表面自由エネルギー差が大きく、配向制御が困難である。そのため、１０ｎｍ以下程度の微細なパターンを形成するための十分に実用的な方法は、未だ確立されていないというのが実情であった。
本発明は、自己組織化による相分離構造を良好に形成させ、１０ｎｍ以下程度の微細なパターンを形成することのできる自己組織化材料によるパターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セット、下地膜形成用第二の液である下地剤及びそれらを用いた自己組織化材料によるパターン形成方法を提供するものである。
However, block copolymers that form a microphase-separated structure containing fine domains of about 10 nm or less generally have a large difference in surface free energy between the domains, making orientation control difficult. Therefore, the fact is that a sufficiently practical method for forming a fine pattern of about 10 nm or less has not yet been established.
In the present invention, the first liquid for pattern formation and the second liquid for forming a base film using a self-assembling material capable of forming a phase-separated structure by self-assembly well and forming a fine pattern of about 10 nm or less can be formed. It provides a pattern forming material liquid set composed of a liquid, a base material which is a second liquid for forming a base film, and a pattern forming method using a self-assembling material using them.
本発明は、［１］ 自己組織化材料によるパターンを形成するために用いられるブロックコポリマーを含むパターン形成用第一の液と、前記パターンを形成する際に用いられる下地膜を形成するために用いられるポリマーを含む下地膜形成用第二の液とを備え、パターン形成用第一の液が、下記式（１）： The present invention is used to form [1] a first liquid for pattern formation containing a block copolymer used for forming a pattern made of a self-assembling material, and a base film used for forming the pattern. The first liquid for pattern formation includes the second liquid for forming the base film containing the polymer to be obtained, and the following formula (1):
下記式（２）：
The following formula (2):
前記第１ブロックが、下記式（１Ｓ）：
The first block is the following formula (1S):
前記第２ブロックが、下記式（２Ｓ）：
The second block is the following formula (2S):
下地膜形成用第二の液が、上記式（１）及び上記式（２）を構造単位として少なくとも一つ有するランダムコポリマーを含むことを特徴とする、パターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セットに関する。
また、本発明は、［２］ 上記［１］に記載の下地膜形成用第二の液が、上記式（１）におけるＲ１、又は上記式（２）におけるＲ３がヒドロキシ基を含む構造単位を少なくとも一つ有するランダムコポリマーを含むことを特徴とする、パターン形成用材料液セットに関する。
また、本発明は、［３］ 上記［１］又は［２］に記載のパターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セットのパターン形成用第一の液であるブロックコポリマーを用いてパターンを形成する際に用いられる下地膜形成用第二の液である下地膜を形成するためのポリマーを含む下地剤であって、前記下地剤が、上記［１］に記載の式（１）及び式（２）を構造単位として少なくとも一つ有するランダムコポリマーを含むことを特徴とする、下地剤に関する。
また、本発明は、［４］ 上記［３］に記載の下地剤が、上記［１］に記載の式（１）におけるＲ１、又は上記式（２）におけるＲ３がヒドロキシ基を有する構造単位を少なくとも一つ有するランダムコポリマーを含むことを特徴とする、下地剤に関する。
また、本発明は、［５］ 前記パターン形成用第一の液であるブロックコポリマーが、上記［１］に記載の式（１）で表されるスチレン系モノマー単位であって、Ｒ１が水素原子、ヒドロキシ基、フッ素原子、Ｃ１−６アルキル基、Ｃ１−６フッ化アルキル基、Ｃ６−１４アリール基、Ｃ７−１６アリールアルキル基、又はヘテロアリール基を示す、スチレン系モノマー単位を１種以上含む第１ブロックと、式（２）で表されるアクリル系モノマー単位であって、Ｒ２が水素原子又は直鎖状のＣ１−６アルキル基を示し、Ｒ３が水素原子、又は置換基を有していてもよいＣ１−２０アルキル基を示す、アクリル系モノマー単位を１種以上含む第２ブロックと、を有し、前記第１ブロックが、上記式（１Ｓ）で表され、Ｚ１がＳｉ原子を含む基であるＳｉ含有スチレン系モノマー単位を１種以上更に含む、Ｓｉ含有スチレン系ランダムコポリマー鎖である、又は、前記第２ブロックが、上記式（２Ｓ）で表され、Ｒ２が水素原子又は直鎖状のＣ１−６アルキル基を示し、Ｚ２がＳｉ原子を含む基であるＳｉ含有アクリル系モノマー単位を１種以上更に含む、Ｓｉ含有アクリル系ランダムコポリマー鎖である、ブロックコポリマーである、下地剤に関する。
更に、本発明は、［６］ 上記［３］〜［５］のいずれか一項に記載の下地剤を基板に塗布する下地膜形成工程、前記下地膜上で上記［１］又は［２］に記載のパターン形成用第一の液のブロックコポリマーを含む層の形成工程、及び前記ブロックコポリマーを含む層の相分離工程を有することを特徴とする、パターン形成方法に関する。
The first liquid for pattern formation and the base film formation are characterized in that the second liquid for forming the base film contains a random copolymer having at least one of the above formula (1) and the above formula (2) as a structural unit. The present invention relates to a material liquid set for pattern formation consisting of a second liquid for use.
Further, in the present invention, [2] the second liquid for forming an undercoat film according to the above [1] has a structure in which R 1 in the above formula (1) or R 3 in the above formula (2) contains a hydroxy group. The present invention relates to a material liquid set for pattern formation, which comprises a random copolymer having at least one unit.
Further, in the present invention, [3] the first pattern-forming material liquid set comprising the first pattern-forming liquid and the second base film-forming liquid according to the above [1] or [2]. A base material containing a polymer for forming a base film, which is a second liquid for forming a base film used when forming a pattern using a block copolymer which is the liquid of the above. 1] The present invention relates to a base material, which comprises a random copolymer having at least one of the formulas (1) and (2) as a structural unit.
Further, in the present invention, [4] the base material described in the above [3] has a structure in which R 1 in the formula (1) described in the above [1] or R 3 in the above formula (2) has a hydroxy group. The present invention relates to a base material, which comprises a random copolymer having at least one unit.
Further, in the present invention, [5] the block copolymer, which is the first liquid for pattern formation, is a styrene-based monomer unit represented by the formula (1) described in the above [1], and R 1 is hydrogen. A styrene-based monomer unit indicating an atom, a hydroxy group, a fluorine atom, a C 1-6 alkyl group, a C 1-6 fluoride alkyl group, a C 6-14 aryl group, a C 7-16 aryl alkyl group, or a heteroaryl group. 1 block containing one or more of the above, and an acrylic monomer unit represented by the formula (2), where R 2 represents a hydrogen atom or a linear C 1-6 alkyl group, and R 3 is a hydrogen atom. , Or a second block containing one or more acrylic monomer units showing a C 1-20 alkyl group which may have a substituent, and the first block is represented by the above formula (1S). Represented, a Si-containing styrene-based random copolymer chain further containing one or more Si-containing styrene-based monomer units in which Z 1 is a group containing a Si atom, or the second block is represented by the above formula (2S). Represented, R 2 represents a hydrogen atom or a linear C 1-6 alkyl group, and Z 2 further contains one or more Si-containing acrylic monomer units which are groups containing a Si atom, and is a Si-containing acrylic random. It relates to a base material, which is a block copolymer, which is a copolymer chain.
Further, the present invention relates to [6] a step of forming a base film for applying the base material according to any one of the above [3] to [5] to a substrate, and the above [1] or [2] on the base film. The present invention relates to a pattern forming method, which comprises a step of forming a layer containing a block copolymer of the first liquid for pattern forming according to the above, and a step of phase separation of the layer containing the block copolymer.
本発明のパターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セットによれば、下地膜形成用第二の液により下地膜を形成し、その表面に自己組織化材料によるパターン形成用第一の液を設け、微細なパターンを高い選択性のエッチングにより形成することが可能なブロックコポリマーを用いて、基板上で良好なパターンを形成させることができる。 According to the pattern-forming material liquid set consisting of the first liquid for pattern formation and the second liquid for forming the base film of the present invention, the base film is formed by the second liquid for forming the base film, and self on the surface thereof. A good pattern can be formed on the substrate by using a block copolymer capable of forming a fine pattern by highly selective etching by providing a first liquid for pattern formation with an assembling material.
本発明のパターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セットは、自己組織化材料によるパターンを形成するために用いられるブロックコポリマーを含むパターン形成用第一の液と、前記パターンを形成する際に用いられる下地膜を形成するために用いられるポリマーを含む下地膜形成用第二の液とを備え、パターン形成用第一の液が、下記式（１）で表されるスチレン系モノマー単位でスチレン系モノマー単位を１種以上含む第１ブロックと、下記式（２）で表されるアクリル系モノマー単位でアクリル系モノマー単位を１種以上含む第２ブロックと、を有し、前記第１ブロックが、下記式（１Ｓ）で表される、Ｓｉ含有スチレン系モノマー単位を１種以上更に含む、Ｓｉ含有スチレン系ランダムコポリマー鎖である、又は、前記第２ブロックが、下記式（２Ｓ）で表されるＳｉ含有アクリル系ランダムコポリマー鎖である、ブロックコポリマーを含み、下地膜形成用第二の液が、上記式（１）及び上記式（２）を構造単位として少なくとも一つ有するランダムコポリマーを含むことを特徴とする。 The pattern-forming material liquid set comprising the pattern-forming first liquid and the base film-forming second liquid of the present invention is a pattern-forming first liquid containing a block copolymer used for forming a pattern with a self-assembling material. The first liquid for pattern formation includes the first liquid and the second liquid for forming the base film containing the polymer used for forming the base film used when forming the pattern, and the first liquid for pattern formation has the following formula ( The first block containing one or more styrene-based monomer units in the styrene-based monomer unit represented by 1) and the second block containing one or more acrylic-based monomer units in the acrylic monomer unit represented by the following formula (2). The first block is a Si-containing styrene-based random copolymer chain, which further comprises one or more Si-containing styrene-based monomer units represented by the following formula (1S), or the first block. The second liquid for forming the base film contains the block copolymer, in which the two blocks are Si-containing acrylic random copolymer chains represented by the following formula (2S), and the above formula (1) and the above formula (2) are used. It is characterized by containing a random copolymer having at least one structural unit.
式（１）のスチレン系モノマー単位のＲ１が水素原子、フッ素原子、ヒドロキシ基、Ｃ１−６アルキル基、Ｃ１−６フッ化アルキル基、Ｃ６−１４アリール基、Ｃ７−１６アリールアルキル基、又はヘテロアリール基を示す。
Ｃ１−６アルキル基は、炭素原子数が１〜６のアルキル基であり、「アルキル基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の１価の飽和炭化水素基を包含するものとする。
直鎖状、分岐鎖状のアルキル基として、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基等が挙げられる。環状の１価の飽和炭化水素基として、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
Ｃ１−６フッ化アルキル基は、炭素原子数が１〜６のフッ化アルキル基であり、「フッ化アルキル基」は、アルキル基（直鎖状、分岐鎖状、環状の１価の飽和炭化水素基）の水素原子の一部又は全部がフッ素原子で置換された基をいう。
Ｃ６−１４アリール基は、炭素原子数が６〜１４のアリール基であり、「アリール基」は、芳香族炭化水素の芳香環から水素１原子を除いた残りの原子団の総称で、フェニル基、トリル基、キシリル基、メシチル基、ナフチル基、アントリル基などである。
Ｃ７−１６アリールアルキル基は、アリール基とアルキル基の炭素原子数の和が７〜１６で、芳香環の水素原子の１つがアルキレン基で置換された基で、ベンジル基、フェネチル基、フェニルメチル基、１−ナフチルメチル基、２−ナフチルメチル基、１−ナフチルエチル基、２−ナフチルエチル基、アントリルメチル基等が挙げられ、上記芳香族基は置換基を有していてもよい。
ヘテロアリール基は、芳香族複素環から水素原子を１個除いた原子団であり、芳香族複素環の例としては、ピリジン、ピラジン、キノリン、イソキノリン、アクリジン、フェナントロリン、フラン、ピロール、チオフェン、カルバゾール、オキサゾール、オキサジアゾール、チアジアゾール、トリアゾール、ベンゾオキサゾール、ベンゾオキサジアゾール、ベンゾチアジアゾール、ベンゾトリアゾール、ベンゾチオフェン等が挙げられる。
式（１）で表されるスチレン系モノマー単位としては、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、４−ｔ−ブチルスチレン、４−ｎ−オクチルスチレン、ｐ-ヒドロキシスチレン等が挙げられ、原料モノマーの入手性、合成の容易性の観点から、スチレンが好ましい。
R 1 of the styrene-based monomer unit of the formula (1) is a hydrogen atom, a fluorine atom, a hydroxy group, a C 1-6 alkyl group, a C 1-6 alkyl fluoride group, a C 6-14 aryl group, and a C 7-16 aryl. Indicates an alkyl group or a heteroaryl group.
The C 1-6 alkyl group is an alkyl group having 1 to 6 carbon atoms, and the "alkyl group" is a linear, branched, or cyclic monovalent saturated hydrocarbon group unless otherwise specified. Shall be included.
Examples of the linear and branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like. Be done. Examples of the cyclic monovalent saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
The C 1-6 alkyl fluoride group is an alkyl fluoride group having 1 to 6 carbon atoms, and the "alkyl fluoride group" is a monovalent saturated alkyl group (linear, branched chain, cyclic monovalent). A group in which a part or all of the hydrogen atom of the hydrocarbon group) is replaced with a fluorine atom.
The C 6-14 aryl group is an aryl group having 6 to 14 carbon atoms, and the "aryl group" is a general term for the remaining atomic group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon, and is phenyl. Group, tolyl group, xsilyl group, mesityl group, naphthyl group, anthryl group and the like.
A C 7-16 arylalkyl group is a group in which the sum of the carbon atoms of the aryl group and the alkyl group is 7 to 16, and one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group. A benzyl group, a phenethyl group, or a phenyl group. Examples thereof include a methyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, an anthrylmethyl group and the like, and the aromatic group may have a substituent. ..
A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle, and examples of the aromatic heterocycle include pyridine, pyrazine, quinoline, isoquinoline, aclysine, phenanthroline, furan, pyrrole, thiophene, and carbazole. , Oxazole, oxaziazole, thiadiazol, triazole, benzoxazole, benzoxaziazole, benzothiazol, benzotriazole, benzothiophene and the like.
Examples of the styrene-based monomer unit represented by the formula (1) include 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, p-hydroxystyrene and the like. Styrene is preferable from the viewpoint of availability of raw material monomer and ease of synthesis.
式（２）で表されるアクリル系モノマー単位のＲ２が水素原子又は直鎖状のＣ１−６アルキル基を示し、Ｒ３が水素原子、又は置換基を有していてもよいＣ１−２０アルキル基を示す。
Ｒ２は、水素原子又は炭素原子数１〜６の直鎖状のアルキル基を示し、水素原子、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ-ペンチル基、ｎ-ヘキシル基等が挙げられ、水素原子、メチル基が好ましい。
Ｒ３は、水素原子、又は置換基を有していてもよい炭素原子数１〜２０アルキル基を示す。「置換基を有していてもよい」と記載する場合、水素原子（−Ｈ）を１価の基で置換する場合と、メチレン基（−ＣＨ２−）を２価の基で置換する場合の両方を含む。置換基がヒドロキシ基を含むとヒドロキシ基を含む構造単位となり好ましい。
Ｒ２が水素原子の場合、式（２）で表されるアクリル系モノマー単位は、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸ｔ−ブチル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸ノニル、アクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、アクリル酸ベンジル、アクリル酸アントラセン等のアクリル酸エステルが挙げられる。
Ｒ２がメチル基の場合、式（２）で表されるアクリル系モノマー単位は、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸シクロヘキシル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ベンジル、メタクリル酸アントラセン等のメタクリル酸エステル等が挙げられる。
R 2 of the acrylic monomer unit represented by the formula (2) represents a hydrogen atom or a linear C 1-6 alkyl group, and R 3 may have a hydrogen atom or a substituent C 1 Shows a -20 alkyl group.
R 2 represents a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or an n-hexyl group. Examples thereof include a hydrogen atom and a methyl group.
R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. When describing "may have a substituent", when the hydrogen atom (-H) is replaced with a monovalent group and when the methylene group (-CH 2- ) is replaced with a divalent group. Including both. When the substituent contains a hydroxy group, it becomes a structural unit containing a hydroxy group, which is preferable.
When R 2 is a hydrogen atom, the acrylic monomer unit represented by the formula (2) is acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylic. Examples thereof include acrylic acid esters such as cyclohexyl acid, octyl acrylate, nonyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, and anthracene acrylate.
When R 2 is a methyl group, the acrylic monomer unit represented by the formula (2) is methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacrylic acid. Examples thereof include methacrylic acid esters such as cyclohexyl acid, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, benzyl methacrylate and anthracene methacrylate.
式（１Ｓ）のＳｉ含有スチレン系モノマー単位は、Ｚ１がＳｉ原子を含む基である。例えば、アルキルシリル基、アルキルシリルオキシ基が挙げられる。アルキルシリル基としては、トリアルキルシリル基、トリアルキルシリルアルキル基が好ましい。
トリアルキルシリル基又はトリアルキルシリルアルキル基としては、例えばトリメチルシリル基、トリメチルシリルメチル基、トリメチルシリルエチル基、トリメチルシリル−ｎ−プロピル基等が挙げられる。
アルキルシリルオキシ基としては、トリアルキルシリルオキシ基又はトリアルキルシリルオキシアルキル基が好ましく、例えばトリメチルシリルオキシ基、トリメチルシリルオキシメチル基、トリメチルシリルオキシエチル基、トリメチルシリルオキシ−ｎ−プロピル基等が挙げられる。
The Si-containing styrene-based monomer unit of the formula (1S) is a group in which Z 1 contains a Si atom. For example, an alkylsilyl group and an alkylsilyloxy group can be mentioned. As the alkylsilyl group, a trialkylsilyl group and a trialkylsilylalkyl group are preferable.
Examples of the trialkylsilyl group or the trialkylsilylalkyl group include a trimethylsilyl group, a trimethylsilylmethyl group, a trimethylsilylethyl group, a trimethylsilyl-n-propyl group and the like.
The alkylsilyloxy group is preferably a trialkylsilyloxy group or a trialkylsilyloxyalkyl group, and examples thereof include a trimethylsilyloxy group, a trimethylsilyloxymethyl group, a trimethylsilyloxyethyl group, and a trimethylsilyloxy-n-propyl group.
式（２Ｓ）で表されるＳｉ含有アクリル系モノマー単位は、Ｒ２が水素原子又は直鎖状のＣ１−６アルキル基を示し、Ｚ２がＳｉ原子を含む。
Ｒ２は、水素原子又は炭素原子数１〜６の直鎖状のアルキル基を示し、水素原子、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ-ペンチル基、ｎ-ヘキシル基等が挙げられ、水素原子、メチル基が好ましい。
Ｚ２はＳｉ原子を含む１価の基であり、アルキルシリル基、アルキルシリルオキシ基が挙げられる。アルキルシリル基としては、トリアルキルシリル基、トリアルキルシリルアルキル基が好ましい。
トリアルキルシリル基又はトリアルキルシリルアルキル基としては、例えばトリメチルシリル基、トリメチルシリルメチル基、トリメチルシリルエチル基、トリメチルシリル−ｎ−プロピル基等が挙げられる。
アルキルシリルオキシ基としては、トリアルキルシリルオキシ基又はトリアルキルシリルオキシアルキル基が好ましく、例えばトリメチルシリルオキシ基、トリメチルシリルオキシメチル基、トリメチルシリルオキシエチル基、トリメチルシリルオキシ−ｎ−プロピル基等が挙げられる。
In the Si-containing acrylic monomer unit represented by the formula (2S), R 2 represents a hydrogen atom or a linear C 1-6 alkyl group, and Z 2 contains a Si atom.
R 2 represents a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or an n-hexyl group. Examples thereof include a hydrogen atom and a methyl group.
Z 2 is a monovalent group containing a Si atom, and examples thereof include an alkylsilyl group and an alkylsilyloxy group. As the alkylsilyl group, a trialkylsilyl group and a trialkylsilylalkyl group are preferable.
Examples of the trialkylsilyl group or the trialkylsilylalkyl group include a trimethylsilyl group, a trimethylsilylmethyl group, a trimethylsilylethyl group, a trimethylsilyl-n-propyl group and the like.
The alkylsilyloxy group is preferably a trialkylsilyloxy group or a trialkylsilyloxyalkyl group, and examples thereof include a trimethylsilyloxy group, a trimethylsilyloxymethyl group, a trimethylsilyloxyethyl group, and a trimethylsilyloxy-n-propyl group.
ランダムコポリマー、ブロックコポリマーは、アニオン重合、ラジカル重合等公知の方法で製造することができる。 Random copolymers and block copolymers can be produced by known methods such as anionic polymerization and radical polymerization.
以下、実施例及び比較例を挙げて本発明についてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。
＜１．測定装置＞
［１−１．分子量］
ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によってジブロックポリマーのＴＨＦ溶液を分析し、ジブロックコポリマーの重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。ＧＰＣ装置として株式会社日立ハイテクサイエンス製のＣｈｒｏｍａｓｔｅｒを用いた。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.
<1. Measuring device>
[1-1. Molecular weight]
The THF solution of the diblock polymer was analyzed by gel permeation chromatography (GPC) to determine the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the diblock copolymer. A Chromaster manufactured by Hitachi High-Tech Science Corporation was used as the GPC device.
［１−２．モノマー組成比］
ジブロックコポリマー及びランダムコポリマーを、以下の条件の１Ｈ ＮＭＲで分析した。
・装置：Ｂｒｕｋｅｒ社製Ａｖａｎｃｅ３００
・溶媒：ＣＤＣｌ３
・共鳴周波数：３００ＭＨｚ
・測定温度：２５℃
・基準物質：テトラメチルシラン
１Ｈ ＮＭＲチャートにおいて、ベンゼン環由来のシグナル（６．０ｐｐｍ−７．１ｐｐｍ）、メトキシ基由来のシグナル（３．６ｐｐｍ）、及びトリメチルシリルスチレンのトリメチルシリル基由来のシグナル（０．２３ｐｐｍ）などのシグナルの面積比を求め、それらに基づいてジブロックコポリマーを構成する各モノマー単位の組成比（モル％）を求めた。ここからさらに、各モノマーの体積比を、求めた組成比に各モノマーの分子量をかけ、得られた値を各モノマーのホモポリマーのポリマー密度で割ることにより算出した。
[1-2. Monomer composition ratio]
The diblock copolymer and the random copolymer were analyzed by 1 H NMR under the following conditions.
-Device: Bruker Avance 300
-Solvent: CDCl 3
・ Resonance frequency: 300MHz
・ Measurement temperature: 25 ° C
・ Reference substance: Tetramethylsilane
1 In the H NMR chart, signals such as a signal derived from a benzene ring (6.0 ppm-7.1 ppm), a signal derived from a methoxy group (3.6 ppm), and a signal derived from a trimethylsilyl group of trimethylsilylstyrene (0.23 ppm). The area ratio was determined, and the composition ratio (mol%) of each monomer unit constituting the diblock copolymer was determined based on them. Further, the volume ratio of each monomer was calculated by multiplying the obtained composition ratio by the molecular weight of each monomer and dividing the obtained value by the polymer density of the homopolymer of each monomer.
＜２．ジブロックコポリマーの合成＞
（合成例１）
容量５Ｌのアニオン重合反応装置を減圧乾燥した。反応装置内を減圧した状態で、脱水処理されたテトラヒドロフラン（ＴＨＦ）３７５０ｇを投入し、−７０℃まで冷却した。
冷却したＴＨＦに、ｓｅｃ−ブチルリチウム（シクロヘキサン溶液：１．２８ｍｏｌ／Ｌ）７．８ｍＬをヘキサン８５ｇに希釈して調製した溶液を注入した。反応装置内の反応液に、脱水処理されたスチレン（Ｓｔ）８２．６ｇと、脱水処理されたｐ−（トリメチルシリル）スチレン（ＴＭＳＳｔ）４０．０gとの混合物を滴下した。反応液の内温が−６０℃以上にならないように滴下速度を調整した。滴下終了後、更に３０分間かけて重合反応を進行させた。続いて、脱水処理された１，１−ジフェニルエチレン９．１ｇを滴下し、さらに３０分間、重合反応を進行させた。次に、脱水処理されたメタクリル酸メチル（ＭＭＡ）１４０．０ｇを滴下し、１時間かけて重合反応を進行させた。脱水処理されたメタノール５.０ｇを注入することで重合反応を停止させた。室温（２５℃）まで昇温した後、反応液にメタノールを加えて、生成したポリマーを再沈殿させた。沈殿物を濾過により回収し、回収した沈殿物を４５℃で８時間かけて減圧乾燥して、Ｓｔ及びＴＭＳＳｔのランダム共重合体からなる第１ブロックと、ＭＭＡの単独重合体からなる第２ブロックとを有するパターン形成用第一の液であるジブロックコポリマーの白色粉末２８８．６ｇを得た。
<2. Synthesis of diblock copolymers>
(Synthesis Example 1)
An anionic polymerization reactor having a capacity of 5 L was dried under reduced pressure. With the inside of the reactor depressurized, 3750 g of dehydrated tetrahydrofuran (THF) was added and cooled to −70 ° C.
A solution prepared by diluting 7.8 mL of sec-butyllithium (cyclohexane solution: 1.28 mol / L) with 85 g of hexane was injected into the cooled THF. A mixture of 82.6 g of dehydrated styrene (St) and 40.0 g of dehydrated p- (trimethylsilyl) styrene (TMSSt) was added dropwise to the reaction solution in the reaction apparatus. The dropping rate was adjusted so that the internal temperature of the reaction solution did not exceed -60 ° C. After completion of the dropping, the polymerization reaction was allowed to proceed for another 30 minutes. Subsequently, 9.1 g of dehydrated 1,1-diphenylethylene was added dropwise, and the polymerization reaction was further allowed to proceed for 30 minutes. Next, 140.0 g of dehydrated methyl methacrylate (MMA) was added dropwise, and the polymerization reaction was allowed to proceed over 1 hour. The polymerization reaction was stopped by injecting 5.0 g of dehydrated methanol. After raising the temperature to room temperature (25 ° C.), methanol was added to the reaction solution to reprecipitate the produced polymer. The precipitate was collected by filtration, and the collected precipitate was dried under reduced pressure at 45 ° C. for 8 hours to form a first block composed of a random copolymer of St and TMSSt and a second block composed of a homopolymer of MMA. 288.6 g of white powder of diblock copolymer, which is the first liquid for pattern formation having and, was obtained.
＜３．ランダムコポリマーの合成＞
（合成例２）
容量２５ｍｌのラジカル重合反応装置にＳｔ１０．４ｇ、ＭＭＡ１０．０ｇ、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）０．２１ｇ、アゾビスイソブチロニトリル３．３ｍｇ、２−フェニル−２−プロピルベンゾジチオエート０．０３２ｇを投入し、窒素置換した。１００℃に加熱し、同温度で５時間加熱後、氷浴で冷却し重合反応を停止させた。室温まで昇温した後、反応液をメタノールに滴下し、生成したポリマーを再沈殿させた。沈殿物を濾過により回収し、回収した沈殿物を減圧乾燥して、Ｓｔ、ＭＭＡ、及びＨＥＭＡのランダムコポリマー（共重合体）の桃色粉末を得た。
<3. Random copolymer synthesis>
(Synthesis Example 2)
St 10.4 g, MMA 10.0 g, 2-hydroxyethyl methacrylate (HEMA) 0.21 g, azobisisobutyronitrile 3.3 mg, 2-phenyl-2-propylbenzodithioate 0 in a radical polymerization reactor with a capacity of 25 ml. .032 g was added and replaced with nitrogen. The mixture was heated to 100 ° C., heated at the same temperature for 5 hours, and then cooled in an ice bath to stop the polymerization reaction. After raising the temperature to room temperature, the reaction solution was added dropwise to methanol to reprecipitate the produced polymer. The precipitate was collected by filtration, and the collected precipitate was dried under reduced pressure to obtain a pink powder of a random copolymer of St, MMA, and HEMA.
（合成例３）
各モノマーの仕込み量を、Ｓｔ１２．０ｇ、ＭＭＡ８．５ｇ、ＨＥＭＡ０．２１ｇに変更したこと以外は合成例２と同様にして、ランダムコポリマーの桃色粉末を得た。
(Synthesis Example 3)
A pink powder of a random copolymer was obtained in the same manner as in Synthesis Example 2 except that the amount of each monomer charged was changed to St 12.0 g, MMA 8.5 g, and HEMA 0.21 g.
（合成例４）
各モノマーの仕込み量を、Ｓｔ１６．７ｇ、ＭＭＡ４．０ｇ、ＨＥＭＡ０．２１ｇに変更したこと以外は合成例２と同様にして、ランダムコポリマーの桃色粉末を得た。
(Synthesis Example 4)
A pink powder of a random copolymer was obtained in the same manner as in Synthesis Example 2 except that the amount of each monomer charged was changed to St16.7 g, MMA 4.0 g, and HEMA 0.21 g.
（合成例５）
各モノマーの仕込み量を、Ｓｔ１８．８ｇ、ＭＭＡ２．０ｇ、ＨＥＭＡ０．２１ｇに変更したこと以外は合成例２と同様にして、ランダムコポリマーの桃色粉末を得た。
(Synthesis Example 5)
A pink powder of a random copolymer was obtained in the same manner as in Synthesis Example 2 except that the amount of each monomer charged was changed to St18.8 g, MMA 2.0 g, and HEMA 0.21 g.
（合成例６）
各モノマーの仕込み量を、Ｓｔ２０．９ｇ、ＭＭＡ０ｇ、ＨＥＭＡ０．２１ｇに変更したこと以外は合成例２と同様にして、ランダムコポリマーの桃色粉末を得た。
(Synthesis Example 6)
A pink powder of a random copolymer was obtained in the same manner as in Synthesis Example 2 except that the amount of each monomer charged was changed to St 20.9 g, MMA 0 g, and HEMA 0.21 g.
＜４．下地剤の調製＞
合成例２〜６で得た化合物をプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）にそれぞれ１．０質量％溶解させ、下地膜形成用第二の液である下地剤１〜５をそれぞれ調製した。
<4. Preparation of base material>
The compounds obtained in Synthesis Examples 2 to 6 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) in an amount of 1.0% by mass, respectively, to prepare base materials 1 to 5, which are second liquids for forming a base film.
＜５．下地膜の作製＞
［５−１．下地膜形成］
下地剤１〜５をシリコンウエハ上にスピンコートし、２５０℃で５分間ベークした。次いで、５０℃のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）に浸漬し超音波洗浄を２回行うことで、未反応ランダムコポリマーを除去した。
<5. Preparation of base film>
[5-1. Base film formation]
Base agents 1 to 5 were spin-coated on a silicon wafer and baked at 250 ° C. for 5 minutes. Then, the unreacted random copolymer was removed by immersing it in propylene glycol monomethyl ether acetate (PGMEA) at 50 ° C. and performing ultrasonic cleaning twice.
＜５−２．水の接触角の測定＞
作製した下地膜の表面に、自動接触角計（ＤＭ−５０１、協和界面科学株式会社製）を用いて水を２μｌ滴下し、接触角の測定を行った。各下地膜について１０回測定し平均値を算出して接触角とした。
<5-2. Measurement of water contact angle>
2 μl of water was dropped onto the surface of the prepared base film using an automatic contact angle meter (DM-501, manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle was measured. Each base film was measured 10 times and the average value was calculated to obtain the contact angle.
＜６．アイランド／ホール試験＞
上記下地膜上に、パターン形成用第一の液である合成例１のジブロックコポリマーを２質量％ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）に溶かした液をスピンコートした。次いで、１７０℃で３０分間熱アニールすることによりミクロ相分離させた。表面の凹凸構造を確認するために原子間力顕微鏡（ＡＦＭ）観察を行った。
相対的に凹部が広い場合を「アイランド」構造、凸部が広い場合を「ホール」構造と呼ぶ。試験結果を表1に示した。
<6. Island / Hall test>
A solution prepared by dissolving the diblock copolymer of Synthesis Example 1, which is the first solution for pattern formation, in 2% by mass PGMEA (propylene glycol monomethyl ether acetate) was spin-coated on the base film. Then, microphase separation was performed by thermal annealing at 170 ° C. for 30 minutes. Atomic force microscope (AFM) observation was performed to confirm the uneven structure of the surface.
The case where the concave portion is relatively wide is called an "island" structure, and the case where the convex portion is wide is called a "hole" structure. The test results are shown in Table 1.
膜厚を一定とし下地膜組成を変化させていったとき、表面構造が変化した領域にジブロックコポリマーの垂直配向を誘導する組成が存在する。表１の結果から、Ｓｔ／ＭＭＡ（スチレン／メタクリル酸メチル）比が１２．０／８．５から１６．７／４．０の間に目的の組成領域があることが分かる。
本発明の下地膜によれば、微細なパターンを高い選択性のエッチングにより形成することが可能なブロックコポリマーを用いて、基板上で良好なパターンを形成させることができる。
When the film thickness is kept constant and the composition of the underlying film is changed, there is a composition that induces the vertical orientation of the diblock copolymer in the region where the surface structure has changed. From the results in Table 1, it can be seen that the desired composition region has a St / MMA (styrene / methyl methacrylate) ratio between 12.0 / 8.5 and 16.7 / 4.0.
According to the undercoat of the present invention, a good pattern can be formed on a substrate by using a block copolymer capable of forming a fine pattern by highly selective etching.
Claims (6)
下記式（２）：
前記第１ブロックが、下記式（１Ｓ）：
前記第２ブロックが、下記式（２Ｓ）：
下地膜形成用第二の液が、上記式（１）及び上記式（２）を構造単位として少なくとも一つ有するランダムコポリマーを含むことを特徴とする、パターン形成用第一の液と下地膜形成用第二の液からなるパターン形成用材料液セット。 Formation of a base film containing a first liquid for pattern formation containing a block copolymer used for forming a pattern with a self-assembling material and a polymer used for forming a base film used for forming the pattern. The first liquid for pattern formation includes the second liquid for pattern formation, and the following formula (1):
The following formula (2):
The first block is the following formula (1S):
The second block is the following formula (2S):
The first liquid for pattern formation and the base film formation are characterized in that the second liquid for forming the base film contains a random copolymer having at least one of the above formula (1) and the above formula (2) as a structural unit. A material liquid set for pattern formation consisting of a second liquid for use.
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