JP5106911B2 - Polymer and antireflection film-forming composition using the same - Google Patents

Description

The present invention relates to a polymer and an antireflection film-forming composition, and in particular, uses various types of radiation such as deep ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. In a lithography process for manufacturing a semiconductor device, a composition used for forming an antireflection film that reduces reflection of exposure light on a photoresist layer coated on the substrate from the substrate, and a polymer that can be used in the composition About.

  In recent years, along with the improvement in the degree of integration of semiconductor elements, technology corresponding to microfabrication has been developed in the semiconductor element manufacturing process, and further microfabrication is required in the photolithography process of semiconductor element manufacturing. In connection with this, various methods for forming an extremely fine photoresist pattern using a photoresist material corresponding to irradiation light with a short wavelength such as KrF, ArF, F2 excimer laser, EUV, EB, and the like have been studied.

  In particular, recently, development of an ultrafine processing process using actinic rays having a wavelength of 200 nm or less, particularly ArF excimer laser light (wavelength 193 nm) has been energetically advanced. It is an important issue to form a highly accurate photoresist pattern.

  By the way, in the formation of a photoresist pattern by photolithography, a thin film interference effect or reflection notching caused by reflection of irradiated light from the substrate is caused. Therefore, in order to prevent this, reflection between the photoresist layer and the substrate is generally performed. A method of providing a prevention film has been widely studied.

Properties desired as an organic antireflection film include high absorbance to light and radiation, no intermixing with the photoresist layer (insoluble in the photoresist solvent), application or heat drying Sometimes there is no low molecular diffusion from the antireflective coating into the overcoated photoresist (does not contaminate the photoresist), and a higher dry etch rate than the photoresist.
In addition, with the increase in the degree of integration of semiconductor devices, the anti-reflection film is also required to have a characteristic that a rectangular resist pattern having a higher resolution, that is, a finer pattern size can be formed. ing.
By the way, when the pattern line width becomes narrower when the photoresist is removed by alkaline developer, that is, when the upper photoresist is exposed and developed, the pattern is collapsed due to the surface tension of the developer or linear water. Yes. In order to solve this problem, methods of copolymerizing monomers having various polarities to increase the elastic modulus of the upper layer photoresist and improve adhesion to the lower layer have been studied. There is no significant improvement effect.

In addition, in order to improve the adhesion of the antireflection film to the photoresist, a composition for forming an antireflection film using a polymer in which a polycyclic alicyclic structure is introduced in the side chain connected to the main chain is proposed. (For example, Patent Document 1). However, in this method, since a polycyclic alicyclic structure is introduced in the side chain, there is a problem that the etching speed is slow and the selectivity to the resist is low during etching.
Japanese Patent Application Laid-Open No. 2004-309561

Due to such circumstances, the present invention is effective when various kinds of irradiation light such as deep ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams are used for fine processing. In addition, it improves the adhesion to the photoresist that can prevent reflection and can suppress pattern collapse when developing and dissolving the photoresist, and is used to form an antireflection film with a high selectivity to the photoresist during etching. An object of the present invention is to provide a composition for forming an antireflection film and a polymer that can be used in the composition.

As a result of intensive studies to achieve the above object, the present inventors reflected a polymer containing a monomer unit having a monocyclic aliphatic ring structure that can be removed by an acid at least in a side chain bonded to the main chain. It has been found that when used as a polymer for forming a protective film, the balance between the adhesion to the photoresist and the selectivity with respect to the photoresist during dry etching is improved, and a fine pattern can be formed clearly and accurately, thus completing the present invention .

（式（１）において、Ｒ１，Ｒ２，Ｒ３は、それぞれ同一又は異なって、水素原子、フッ素原子、炭素数１から６で水素原子がフッ素原子で置換されていてもよいアルキル基を示し、Ｒ４，Ｒ５は炭素数１から６で水素原子がフッ素原子で置換されていてもよいアルキル基を示し、Ｘは炭素数１から５のアルキル基、ハロゲン原子、水酸基、炭素数１から５のアルコキシ基、アセチル基、又はシアノ基で置換されていてもよい単環式の脂肪族炭化水素基である。）
で表されるモノマー単位を少なくとも１つ有し、さらに、
（ii）下記式（２）

（式（２）において、Ｒ６，Ｒ７，Ｒ８は、それぞれ同一又は異なって、水素原子、フッ素原子、又は炭素数１から６で水素原子がフッ素原子で置換されていてもよいアルキル基を示し、Ａｒは置換又は非置換の芳香族炭化水素基である。）
で表されるモノマー単位、スチレン、メチルスチレン、ヒドロキシスチレン、メトキシスチレン、シアノスチレン、クロロスチレン、ブロモスチレン、アセチルスチレン、α−メチルスチレン、α−クロロスチレン、ビニルナフタレン、ビニルアントラセン、ベンジルアクリレート、アントリルメチルアクリレート、２−フェニルエチルアクリレート、ベンジルメタクリレート、アントリルメチルメタクリレート、２−フェニルエチルメタクリレートから選択されたモノマー成分由来のモノマー単位から選ばれる少なくとも１つのモノマー単位、及び、
（iii）１−（メタ）アクリロイルオキシ−３−［２−（トリメトキシシリル）エチル］アダマンタン、２−（トリメチルシリルメチル）アクリル酸アダマンチル、１−（１−（メタ）アクリロイルオキシ−１−メチルエチル）アダマンタン、１−ヒドロキシ−３−（１−（メタ）アクリロイルオキシ−１−メチルエチル）アダマンタン、１−（１−エチル−１−（メタ）アクリロイルオキシプロピル）アダマンタン、１−ヒドロキシ−３−（１−エチル−１−（メタ）アクリロイルオキシプロピル）アダマンタン、１−ヒドロキシ−３−（１−（メタ）アクリロイルオキシ−１−メチルプロピル）アダマンタン、１−（１−（メタ）アクリロイルオキシ−１，２−ジメチルプロピル）アダマンタン、１ − ヒドロキシ−３−（１−（メタ）アクリロイルオキシ−１，２−ジメチルプロピル）アダマンタン、１，３−ジヒドロキシ−５−（１−（メタ）アクリロイルオキシ−１−メチルエチル）アダマンタン、１−（１−エチル−１−（メタ）アクリロイルオキシプロピル）−３，５−ジヒドロキシアダマンタン、１，３−ジヒドロキシ−５−（１−（メタ）アクリロイルオキシ−１−メチルプロピル）アダマンタン、１，３−ジヒドロキシ−５−（１−（メタ）アクリロイルオキシ−１，２−ジメチルプロピル）アダマンタン、１−ｔ−ブトキシカルボニル−３−（メタ）アクリロイルオキシアダマンタン、１，３−ビス（ｔ−ブトキシカルボニル）−５−（メタ）アクリロイルオキシアダマンタン、１−ｔ−ブトキシカルボニル−３−ヒドロキシ−５−（メタ）アクリロイルオキシアダマンタン、１−（２−テトラヒドロピラニルオキシカルボニル）−３−（メタ）アクリロイルオキシアダマンタン、１，３−ビス（２−テトラヒドロピラニルオキシカルボニル）−５−（メタ）アクリロイルオキシアダマンタン、１−ヒドロキシ−３−（２−テトラヒドロピラニルオキシカルボニル）−５−（メタ）アクリロイルオキシアダマンタン、２−（メタ）アクリロイルオキシ−２−メチルアダマンタン、１−ヒドロキシ−２−（メタ）アクリロイルオキシ−２−メチルアダマンタン、５−ヒドロキシ−２−（メタ）アクリロイルオキシ−２−メチルアダマンタン、１，３−ジヒドロキシ−２−（メタ）アクリロイルオキシ−２−メチルアダマンタン、１，５−ジヒドロキシ−２−（メタ）アクリロイルオキシ−２−メチルアダマンタン、１，３−ジヒドロキシ−６−（メタ）アクリロイルオキシ−６−メチルアダマンタン、２−（メタ）アクリロイルオキシ−２−エチルアダマンタン、１−ヒドロキシ−２−（メタ）アクリロイルオキシ−２−エチルアダマンタン、５−ヒドロキシ−２−（メタ）アクリロイルオキシ−２−エチルアダマンタン、１，３−ジヒドロキシ−２−（メタ）アクリロイルオキシ−２−エチルアダマンタン、１，５−ジヒドロキシ−２−（メタ）アクリロイルオキシ−２−エチルアダマンタン、１，３−ジヒドロキシ−６−（メタ） アクリロイルオキシ−６−エチルアダマンタン、１−（アダマンタン−１−イルオキシ）エチル（メタ）アクリレート、１−（アダマンタン−１−イルメトキシ）エチル（メタ）アクリレート、１−［２−（アダマンタン−１−イル）エトキシ］エチル（メタ）アクリレート、１−（３−ヒドロキシアダマンタン−１−イルオキシ）エチル（メタ）アクリレート、１−（ノルボルナン−２−イルオキシ）エチル（メタ）アクリレート、１−（ノルボルナン−２−イルメトキシ）エチル（メタ）アクリレート、１−（２−メチルノルボルナン−２−イルオキシ）エチル（メタ）アクリレート、１−［１−（ノルボルナン−２−イル）−１−メチルエトキシ］エチル（メタ）アクリレート、１−（３−メチルノルボルナン−２−イルメトキシ）エチル（メタ）アクリレート、１−（ボルニルオキシ）エチル（メタ）アクリレート、１−（イソボルニルオキシ）エチル（メタ）アクリレート、１−［１−（メタ）アクリロイルオキシエトキシ］−４−オキサトリシクロ［４．３．１．１^3,8］ウンデカン−５−オン、２−［１−（メタ）アクリロイルオキシエトキシ］−４−オキサトリシクロ［４．２．１．０^3,7］ノナン−５−オン、８−［１−（メタ）アクリロイルオキシエトキシ］−４−オキサトリシクロ［５．２．１．０^2,6］デカン−５−オン、９−［１−（メタ）アクリロイルオキシエトキシ］−４−オキサトリシクロ［５．２．１．０^2,6］デカン−５−オン、１−ヒドロキシ−３−（メタ）アクリロイルオキシアダマンタン、１，３−ジヒドロキシ−５−（メタ）アクリロイルオキシアダマンタン、１−カルボキシ−３−（メタ）アクリロイルオキシアダマンタン、１，３−ジカルボキシ−５−（メタ）アクリロイルオキシアダマンタン、１−カルボキシ−３−ヒドロキシ−５−（メタ）アクリロイルオキシアダマンタン、１−（メタ）アクリロイルオキシ−４−オキソアダマンタン、３−ヒドロキシ−１−（メタ）アクリロイルオキシ−４−オキソアダマンタン、７−ヒドロキシ−１−（メタ）アクリロイルオキシ−４−オキソアダマンタン、１−（メタ）アクリロイルオキシ−４−オキサトリシクロ［４．３．１．１^3,8］ウンデカン−５−オン、１−（メタ）アクリロイルオキシ−４，７−ジオキサトリシクロ［４．４．１．１^3,9］ドデカン−５，８−ジオン、１−（メタ）アクリロイルオキシ−４，８−ジオキサトリシクロ［４．４．１．１^3,9］ドデカン−５，７−ジオン、１−（メタ）アクリロイルオキシ−５，７−ジオキサトリシクロ［４．４．１．１^3,9］ドデカン−４，８−ジオン、２−（メタ）アクリロイルオキシ−４−オキサトリシクロ［４．２．１．０^3,7］ノナン−５−オン、２−（メタ）アクリロイルオキシ−２−メチル−４−オキサトリシクロ［４．２．１．０^3,7］ノナン−５−オン、（メタ）アクリル酸デカヒドロナフチル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸ジメチルアダマンチル、（メタ）アクリル酸トリシクロ［５．２．１．０^2,6］デシル、（メタ）アクリル酸テトラシクロ［４．４．０．１^2,5．１^7,10］ドデシルから選ばれる少なくとも１つのモノマー単位を含む重合体であって、
前記式（１）で表される構造単位の割合が、該重合体を構成する全モノマー単位に対して、数の比率として、０．１〜０．７０である反射防止膜形成用重合体を提供する。
That is, the present invention provides (i) the following formula (1)

(In the formula (1), R1, R2, and R3 are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom; , R5 represents an alkyl group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and X represents an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 5 carbon atoms. , An acetyl group, or a monocyclic aliphatic hydrocarbon group which may be substituted with a cyano group.)
Having at least one monomer unit represented by:
(Ii) The following formula (2)

(In the formula (2), R6, R7 and R8 are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom; Ar is a substituted or unsubstituted aromatic hydrocarbon group.)
In represented by monomer units, scan styrene, methyl styrene, hydroxystyrene, methoxystyrene, cyanostyrene, chlorostyrene, bromostyrene, acetyl styrene, alpha-methyl styrene, alpha-chlorostyrene, vinyl naphthalene, vinyl anthracene, benzyl acrylate, At least one monomer unit selected from monomer units derived from monomer components selected from anthryl methyl acrylate, 2-phenylethyl acrylate, benzyl methacrylate, anthryl methyl methacrylate, 2-phenylethyl methacrylate, and
(Iii) 1- (meth) acryloyloxy-3- [2- (trimethoxysilyl) ethyl] adamantane, 2- (trimethylsilylmethyl) adamantyl acrylate, 1- (1- (meth) acryloyloxy-1-methylethyl ) Adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane, 1-hydroxy-3- ( 1-ethyl-1- (meth) acryloyloxypropyl) adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane, 1- (1- (meth) acryloyloxy-1, 2-Dimethylpropyl) adamantane, 1-hydroxy-3- (1- (meth) a Liloyloxy-1,2-dimethylpropyl) adamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) ) -3,5-dihydroxyadamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy- 1,2-dimethylpropyl) adamantane, 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane, 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-t- Butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxy Adamantane, 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane, 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-hydroxy -3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 2- (meth) acryloyloxy-2-methyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-methyl Adamantane, 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,5-dihydroxy-2- (meth) acryloyl Oxy-2-methylada 1,3-dihydroxy-6- (meth) acryloyloxy-6-methyladamantane, 2- (meth) acryloyloxy-2-ethyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane 5-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,5-dihydroxy-2- (meth) acryloyloxy 2-ethyladamantane, 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane, 1- (adamantan-1-yloxy) ethyl (meth) acrylate, 1- (adamantan-1-ylmethoxy) ethyl (Meth) acrylate, 1- [2- (a Mantan-1-yl) ethoxy] ethyl (meth) acrylate, 1- (3-hydroxyadamantan-1-yloxy) ethyl (meth) acrylate, 1- (norbornan-2-yloxy) ethyl (meth) acrylate, 1- ( Norbornan-2-ylmethoxy) ethyl (meth) acrylate, 1- (2-methylnorbornan-2-yloxy) ethyl (meth) acrylate, 1- [1- (norbornan-2-yl) -1-methylethoxy] ethyl ( (Meth) acrylate, 1- (3-methylnorbornan-2-ylmethoxy) ethyl (meth) acrylate, 1- (bornyloxy) ethyl (meth) acrylate, 1- (isobornyloxy) ethyl (meth) acrylate, 1- [ 1- (Meth) acryloyloxyethoxy] -4-oxa Rishikuro [4.3.1.1 ^{3, 8]} undecane-5-one, 2- [1- (meth) acryloyloxy ethoxy] -4-oxatricyclo [4.2.1.0 ^3,7] nonane -5-one, 8- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one, 9- [1- (meth) acryloyl Oxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one, 1-hydroxy-3- (meth) acryloyloxyadamantane, 1,3-dihydroxy-5- (meta ) Acryloyloxyadamantane, 1-carboxy-3- (meth) acryloyloxyadamantane, 1,3-dicarboxy-5- (meth) acryloyloxyadamantane, 1-carboxy-3-hydroxy-5- (me ) Acryloyloxyadamantane, 1- (meth) acryloyloxy-4-oxoadamantane, 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane, 7-hydroxy-1- (meth) acryloyloxy-4-oxo Adamantane, 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one, 1- (meth) acryloyloxy-4,7-dioxatricyclo [ 4.4.1.1 ^3,9 ] dodecane-5,8-dione, 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5 , 7-dione, 1- (meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-4,8-dione, 2- (meth) acrylo Yloxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 2- (meth) acryloyloxy-2-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, decahydronaphthyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, (meth ) Tricyclo [5.2.1.0 ^2,6 ] decyl acrylate, tetracyclo (meth) acrylate [4.4.0.1 ^2,5 . 1 ^7,10 ] a polymer comprising at least one monomer unit selected from dodecyl,
A polymer for forming an antireflection film in which the proportion of the structural unit represented by the formula (1) is 0.1 to 0.70 as a ratio of the number of all monomer units constituting the polymer. provide.

The present invention also provides an antireflection film material comprising at least the polymer for forming an antireflection film as described above, an organic solvent, and a crosslinking agent .

The antireflection film material may further contain at least one component selected from a crosslinking catalyst, a surfactant, and an acid generator.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer useful for the antireflection film for semiconductor manufacture can be provided. In addition, according to the present invention, it is possible to form a fine pattern with high accuracy in the manufacture of a semiconductor using an antireflection film.

The present invention provides at least a repeating unit having an optionally substituted monocyclic aliphatic hydrocarbon group that can be removed by an acid in a side chain connected to a main chain used in an antireflection film-forming composition for manufacturing a semiconductor device. A polymer having one or more.

  The molecular weight of the polymer is 1,000 to 1,000,000, preferably 5,000 to 20,000, and more preferably 7,000 to 10,000 as a weight average molecular weight. When the weight average molecular weight is less than 1000, the strength of the applied antireflection film is weak, and low molecular components diffuse into the resist layer, adversely affecting image formation. As a result, the solution viscosity increases too much and uniform coating cannot be formed.

  In the polymer of the present invention, the formula (1) is an essential structural unit. Reflection formed from the antireflection film-forming composition of the present invention by using a polymer component into which a structural unit having an optionally substituted monocyclic aliphatic hydrocarbon group that can be removed by an acid is used The adhesion of the prevention film to the substrate can be enhanced. In addition, the adhesion to the photoresist formed thereon can be improved, and a high selectivity with respect to the photoresist layer during dry etching can be obtained. As a result, a photoresist pattern, particularly a KrF excimer can be obtained. It becomes possible to prevent collapse, peeling, and the like of a fine photoresist pattern formed by a manufacturing process using laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EB, or EUV.

  The groups R1, R2, and R3 described in the formula (1) are the same or different and each is a hydrogen atom, a fluorine atom, or an alkyl group in which a hydrogen atom is substituted with a fluorine atom. R4 and R5 each represents an alkyl group having 1 to 6 carbon atoms, in which a hydrogen atom may be substituted with a fluorine atom. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl and hexyl groups. Of these, methyl and ethyl groups are preferred.

  X is a monocyclic aliphatic hydrocarbon which may be substituted with an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, an acetyl group, or a cyano group. Examples of the monocyclic aliphatic hydrocarbon group include a C3-15 cycloalkyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. The hydrogen of these cycloalkyl groups may be substituted with a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and the hydrogen atom may be substituted with a fluorine atom. A cyclohexyl group or a cyclohexyl group substituted with a methyl group is particularly preferable.

  Examples of preferable monomers include the following monomers. 1-methyl-1- (4-methylcyclohexyl) ethyl = (meth) acrylate, 1-methyl-1- (4-methylcyclohexyl) propyl = (meth) acrylate, 1-methyl-1-cyclohexylethyl = (Meth) acrylate, 1-methyl-1-cyclohexylpropyl = (meth) acrylate, and the like.

  In addition to the monomer component having a monocyclic aliphatic hydrocarbon structure that can be eliminated by the acid, the polymer of the present invention uses a polymer obtained by copolymerizing other monomer components as necessary. Can do.

  As structural units other than the monomer component having a monocyclic aliphatic hydrocarbon structure that can be eliminated by the acid, a monomer having a structure capable of absorbing an excimer laser such as KrF or ArF is copolymerized. The case is preferred. For example, vinyl compounds such as styrene, methyl styrene, hydroxy styrene, methoxy styrene, cyano styrene, chloro styrene, bromo styrene, acetyl styrene, α-methyl styrene, α-chloro styrene, vinyl naphthalene, vinyl anthracene, phenyl acrylate, benzyl acrylate Acrylate compounds such as naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, 2-phenylethyl acrylate, hydroxyphenyl acrylate, bromophenyl acrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate 2-phenylethyl methacrylate, hydroxyphenyl methacrylate Over DOO, methacrylic acid ester compounds such as bromophenyl methacrylate.

Other monomer components used for copolymerization include, for example, methyl acrylate, normal butyl acrylate, cyclohexyl acrylate, 2, 2, 2-trifluoroethyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, tetrahydrofurfuryl. Acrylate compounds such as acrylate, 3-methoxybutyl acrylate, 3-acryloxypropyltrimethoxysilane, methyl methacrylate, isobutyl methacrylate, normal octyl methacrylate, 2,2,2-tribromoethyl methacrylate, 2-chloroethyl methacrylate, 2-Ethoxyethyl methacrylate, methoxytriethylene glycol methacrylate, tetrahydrofurfurylme Methacrylate compounds such as acrylate, 2- (trimethylsiloxy) ethyl methacrylate, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, allyltrimethylsilane, allylamino Silane compounds such as trimethylsilane and allyldimethylpiperidinomethylsilane, acrylamide compounds such as N-methylacrylamide and N, N-diethylacrylamide, methacrylamide compounds such as N-propylmethacrylamide and N, N-dimethylacrylamide, vinyl Alcohol, methyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether Vinyl compounds such as tellurium, maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, maleic anhydride, acrylonitrile, 1- (meth) acryloyloxy-3- [2- (trimethoxysilyl) ethyl] adamantane (Meth) acrylic acid 2- (trimethoxysilyl) ethyl ester, (meth) acrylic acid 3- (trimethoxysilyl) propyl ester, (meth) acrylic acid 2- (trimethylsilyloxy) ethyl ester, (meth) acrylic acid 3- (trimethylsilyloxy) propyl ester 2- (trimethylsilylmethyl) ethyl acrylate, 2- (trimethylsilylmethyl) propyl acrylate, 2- (trimethylsilylmethyl) butyl acrylate, 2- (tri Tylsilylmethyl) hexyl acrylate, 2- (trimethylsilylmethyl) cyclohexyl acrylate, 2- (trimethylsilylmethyl) adamantyl acrylate 1- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1-hydroxy-3 -(1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane, 1-hydroxy-3- (1-ethyl-1- (meta) ) Acrylyloxypropyl) Adamantane, 1- (1- (meth) acryloyloxy-1-methylpropyl) Adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) Damantane, 1- (1- (meth) acryloyloxy-1,2-dimethylpropyl) Adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane, 1,3- Dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) -3,5-dihydroxyadamantane, 1,3-dihydroxy- 5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane 1-t-butoxycarbonyl- 3- (Me ) Acryloyloxyadamantane, 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane, 1- (2 -Tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane, 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-hydroxy-3- (2- (Tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane. 2- (meth) acryloyloxy-2-methyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1, 3 -Dihydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,5-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,3-dihydroxy-6- (meth) acryloyloxy-6 -Methyladamantane, 2- (meth) acryloyloxy-2-ethyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 5-hydroxy-2- (meth) acryloyloxy-2 Ethyladamantane, 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,3-dihydroxy-6- ( (Meth) acryloyloxy-6-ethyladamantane, 2-tetrahydropyranyl (meth) acrylate, 2-tetrahydrofuranyl (meth) acrylate. β- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone, β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone, β- (Meth) acryloyloxy-α, α, β-trimethyl-γ-butyrolactone, β- (meth) acryloyloxy-β, γ, γ-trimethyl-γ-butyrolactone, β- (meth) acryloyloxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone. 5-t-butoxycarbonylnorbornene, 9-t-butoxycarbonyltetracyclo [6. 2. 1. 1 ^{3, 6} . 0 ^{2, 7]} dodeca - 4 - ene, 5 - (2 - tetrahydropyranyloxy carbonyl) norbornene, 9 - (2 - tetrahydropyranyloxy carbonyl) tetracyclo [6. 2. 1. 1 ^{3, 6} . 0 ^{2, 7} ] Dodeca-4-en. 1- (adamantane-1-yloxy) ethyl (meth) acrylate, 1- (adamantane-1-ylmethoxy) ethyl (meth) acrylate, 1- [2- (adamantan-1-yl) ethoxy] ethyl (meth) acrylate, 1- (3-hydroxyadamantane-1-yloxy) ethyl (meth) acrylate, 1- (norbornane-2-yloxy) ethyl (meth) acrylate, 1- (norbornane-2-ylmethoxy) ethyl (meth) acrylate, 1- (2-Methylnorbornane-2-yloxy) ethyl (meth) acrylate, 1- [1- (norbornane-2-yl) -1-methylethoxy] ethyl (meth) acrylate, 1- (3-methylnorbornane-2 Ylmethoxy) ethyl (meth) acrylate, 1- (bornyloxy) ethyl (meth) acrylate, 1- (isobornyloxy) ethyl (meth) acrylate; 1- [1- (meth) acryloyloxyethoxy] -4-oxatri Cyclo [4. 3. 1. 1 ^{3, 8} ] undecan-5-one, 2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4. 2. 1. 0 ^{3, 7} ] nonan-5-one, 8- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [5. 2. 1. 0 ^{2, 6]} decane - 5 - one, 9 - [1 - (meth) acryloyloxy ethoxy] - 4 - oxatricyclo [5. 2. 1. 0 ^{2, 6} ] decan-5-one, α- [1- (meth) acryloyloxyethoxy] -γ, γ-dimethyl-γ-butyrolactone, 3- [1- (meth) acryloyloxyethoxy] -2-oxo -1-oxaspiro [4. 5] Decane, α- [1- (meth) acryloyloxyethoxy] -γ-butyrolactone, α- [1- (meth) acryloyloxyethoxy] -α, γ, γ-trimethyl-γ-butyrolactone, α- [1 -(Meth) acryloyloxyethoxy]-β, β-dimethyl-γ-butyrolactone. 1-hydroxy-3- (meth) acryloyloxyadamantane, 1,3-dihydroxy-5- (meth) acryloyloxyadamantane, 1-carboxy-3- (meth) acryloyloxyadamantane, 1,3-dicarboxy-5- (Meth) acryloyloxyadamantane, 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane, 1- (meth) acryloyloxy-4-oxoadamantane, 3-hydroxy-1- (meth) acryloyloxy-4 Oxoadamantane, 7-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane. 1- (meth) acryloyloxy-4-oxatricyclo [4. 3. 1. 1 ^{3, 8} ] undecan-5-one, 1- (meth) acryloyloxy-4,7-dioxatricyclo [4. 4. 1. 1 ^{3, 9} ] dodecane-5,8-dione, 1- (meth) acryloyloxy-4,8-dioxatricyclo [4. 4. 1. 1 ^{3, 9} ] dodecane-5,7-dione, 1- (meth) acryloyloxy-5,7-dioxatricyclo [4. 4. 1. 13, 9] dodecane-4,8-dione. 2- (meth) acryloyloxy-4-oxatricyclo [4. 2. 1. 0 ^{3, 7} ] nonan-5-one, 2- (meth) acryloyloxy-2-methyl-4-oxatricyclo [4. 2. 1. 0 3, 7] nonan-5-one α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-α-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β- Dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β-trimethyl-γ-butyrolactone, α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone, α- (meth) acryloyl Oxy-α, γ, γ-trimethyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β, γ, γ-tetramethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β , Γ, γ-pentamethyl-γ-butyrolactone, (meth) acrylic acid, (Meth) methyl acrylate, (meth) ethyl acrylate, (meth) isopropyl acrylate, (meth) n-butyl acrylate, (meth) cyclohexyl acrylate, (meth) decahydronaphthyl acrylate, (meth) acrylic Acid norvo



Lunyl, (meth) isobornyl acrylate, (meth) adamantyl acrylate, (meth) dimethyladamantyl acrylate, (meth) tricycloacrylate [5. 2. 1. 0 ^{2, 6} ] decyl, (meth) acrylic acid tetracyclo [4. 4. 0. 1 ^{2, 5} . 1 ^{7, 10} ] dodecyl, maleic anhydride 4-oxatricyclo [5. 2. 1. 0 ^{2, 6} ] decan-8-ene-5-one, 3-oxatricyclo [5. 2. 1. 0 ^{2, 6} ] decan-8-ene-4-one, 5-oxatricyclo [6. 2. 1. 0 ^{2, 7} ] Undecan-9-en-6-one, 4-oxatricyclo [6. 2. 1. 0 ^{2, 7]} undecane - 9 - ene - 5 - one, 4 - oxa penta cyclo [6. 5. 1. 1 ^{9, 1 2} . 0 ^{2, 6} . 0 ^{8, 1 3} ] pentadecane-10-en-5-one, 3-oxapentacyclo [6. 5. 1. 1 ^{9, 1 2} . 0 ^{2, 6} . 0 ^{8, 1 3} ] pentadecane-10-en-4-one, 5-oxapentacyclo [6. 6. 1. 1 ^{1 0, 1 3} . 0 ^{2, 7} . 0 ^{9, 14} ] hexadecan-11-en-6-one, 4-oxapentacyclo [6. 6. 1. 1 1 0, 1 3. 0 2, 7. 09,14] hexadecan-11-en-5-one, norbornene, 5-hydroxy-2-norbornene and the like.

  In obtaining the polymer of the present invention, the polymerization of the monomer mixture is carried out by a conventional method used for producing an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. Although it can be performed, solution polymerization is particularly preferred. Furthermore, drop polymerization is preferable among solution polymerization. Specifically, in the dropping polymerization, for example, (i) a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in the organic solvent are respectively prepared in an organic solvent kept at a constant temperature. A method in which the monomer solution and the polymerization initiator solution are respectively added dropwise; and (ii) a method in which a mixed solution in which the monomer and the polymerization initiator are dissolved in an organic solvent is added dropwise to an organic solvent maintained at a constant temperature. (Iii) A monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in the organic solvent are respectively prepared, and the polymerization initiator solution is dropped into the monomer solution maintained at a constant temperature. It is performed by a method or the like.

  As the polymerization solvent, a known solvent can be used. For example, ether (chain ether such as diethyl ether, propylene glycol monomethyl ether, etc., cyclic ether such as tetrahydrofuran, dioxane, etc.), ester (methyl acetate, ethyl acetate, Glycol ether esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.) ), Sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbon (benzene, toluene, xylene, etc.) Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane), and mixtures of these solvents. Moreover, a well-known polymerization initiator can be used as a polymerization initiator. The polymerization temperature can be appropriately selected within a range of, for example, about 30 to 150 ° C.

The polymer obtained by polymerization can be purified by precipitation or reprecipitation. The precipitation or reprecipitation solvent may be either an organic solvent or water, or a mixed solvent. Examples of organic solvents used as a precipitation or reprecipitation solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatics such as benzene, toluene, and xylene. Aromatic hydrocarbons), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.) , Nitrile (acetonitrile, benzonitrile, etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ether) Ruketone, diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (Acetic acid etc.), mixed solvents containing these solvents, and the like.

  Among these, as the organic solvent used as the precipitation or reprecipitation solvent, a solvent containing at least a hydrocarbon (particularly an aliphatic hydrocarbon such as hexane) is preferable. In such a solvent containing at least hydrocarbon, the ratio of hydrocarbon (for example, aliphatic hydrocarbon such as hexane) and other solvent is, for example, the former / the latter (volume ratio; 25 ° C.) = 10/90 to 99 / 1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = About 50/50 to 97/3. If the proportion of hydrocarbons increases, the removal efficiency of highly polar monomers may decrease, and if the proportion of hydrocarbons decreases, the polymer may dissolve depending on the combination of monomer units that make up the polymer, making it difficult to recover the polymer There is a risk of becoming.

  Moreover, as the organic solvent used as the precipitation or precipitation solvent, a solvent containing at least an alcohol (particularly a lower alcohol such as methanol) can be preferably used. In such a solvent containing at least an alcohol, the ratio of the alcohol to the other solvent is, for example, the former / the latter (volume ratio; 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = About 50/50 to 97/3.

  The proportion of the structural unit of the formula (1) in the polymer of the present invention is not particularly limited, and required performance as an antireflection film, that is, attenuation coefficient (k value), refractive index (n value) and dryness. It can be changed according to the etching rate or the like. The ratio of the structural unit of the formula (1) in the polymer is 0.01 to 0.95, preferably 0.1 to 0.70 as the ratio of the number of structural units in the polymer as the formula (1). It is. In addition, the attenuation coefficient (k value), refractive index (n value) and dry etching rate of the antireflection film formed from the antireflection film-forming composition of the present invention are copolymerized as necessary. It can be adjusted by the kind of the polymer, its ratio in the polymer and the like.

  The antireflective film-forming composition of the present invention comprises a polymer containing a monocyclic aliphatic hydrocarbon structure that can be eliminated by an acid at least in the side chain linked to the main chain, a crosslinking agent, and a solvent. Containing a crosslinking catalyst, a surfactant, an acid generator and the like. The solid content of the antireflection film-forming composition of the present invention is, for example, 0. 1 to 50% by mass, and for example, 0. 5 to 30% by mass. Here, the solid content is obtained by removing the solvent component from all components of the antireflection film-forming composition. If the solid content concentration is less than 0.1% by mass, the productivity may be reduced. If the solid content concentration exceeds 50% by mass, the viscosity of the liquid becomes high and handling becomes difficult. May also decrease.

  As a compounding quantity of such a polymer in the anti-reflective film formation composition of this invention, it is 50-99 mass% in solid content, for example, Moreover, it is 60-99 mass%, for example. Yes, or 60 to 95% by mass. If the blending amount of the polymer is less than 50% by mass, the strength after film formation may decrease, and if the blending amount of the polymer exceeds 99% by mass, crosslinking is insufficient and intermixing with the resist layer is performed. Etc. may occur.

  The antireflection film-forming composition of the present invention further contains a crosslinking agent. Examples of the crosslinking agent include melamine-based, substituted urea-based, and polymer systems containing an epoxy group. Preferably, it is a cross-linking agent having at least two cross-linking substituents, and is a compound such as methoxymethylated glycouril or methoxymethylated melamine, particularly preferably tetramethoxymethylglycoluril or hexamethoxymethylmelamine. is there. In addition, compounds such as tetramethoxymethylurea and tetrabutoxymethylurea are also included.

  The amount of the crosslinking agent added varies depending on the coating solvent used, the underlying substrate used, the performance required for the antireflective film, such as the refractive index and the attenuation coefficient, and the type of photoresist used as the upper layer. For example, it is 1 to 50% by mass, for example, 1 to 40% by mass, and 5 to 40% by mass. When the addition amount of the crosslinking agent is less than 1% by mass, a sufficient number of crosslinking points may not be generated, and intermixing with the resist layer may occur. Moreover, when the addition amount of a crosslinking agent exceeds 50 mass%, there exists a possibility that sufficient antireflection effect cannot be acquired.

  These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linkable substituent is present in the polymer, it can cause a cross-linking reaction with these cross-linkable substituents. Examples of the case where a crosslinkable substituent is present in the polymer include a case where X is substituted with a hydroxyl group, and a case where a hydroxyl group is present in another copolymerized monomer structure.

  The antireflective film-forming composition of the present invention contains a cross-linking agent, so that the antireflective film formed from the composition is a strong film. That is, a crosslinking reaction occurs during the formation of the antireflection film by baking the antireflection film-forming composition applied on the substrate, and as a result, the formed antireflection film is insoluble in organic solvents such as those used in photoresists. It becomes. Therefore, the antireflection film does not cause intermixing with the photoresist. Further, since the antireflection film thus formed is insoluble in an alkaline aqueous solution, the removal is performed by dry etching.

  In the antireflection film forming composition of the present invention, as a catalyst for promoting the crosslinking reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, Acids such as benzoic acid and hydroxybenzoic acid, or thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate and 2-nitrobenzyl tosylate can be added. The amount added was 0. 0 2 to 10% by mass, preferably 0. 0 4 to 5 mass%. If the addition amount is less than 0.04% by mass, a sufficient crosslinking reaction may not be obtained, and intermixing with the resist layer may occur. If the addition amount exceeds 10% by mass, the resist may bleed into the resist layer. There is a risk of deformation of the shape.

  In the antireflection film-forming composition of the present invention, a photoacid generator can be added in order to match the acidity with the photoresist coated on the upper layer in the lithography process. The shape of the photoresist pattern can be made rectangular by adjusting and matching the acidity with the photoresist.

  In the monomer unit of the present invention, an ester bond is dissociated by an acid to generate a carboxylic acid. Compared with the case where cyclic hydrocarbons exist in the side chain, the ester bond is cleaved by the acid generated by the decomposition of the photoacid generator added to the antireflection film upon exposure to carboxylic acid, It is possible to reduce the etching resistance and the etching ratio with respect to the resist. Furthermore, by controlling the degree of crosslinking of the antireflection film, only the exposed antireflection film can be removed with an alkali developer.

  Desirably, the photoacid generator is a photoacid generator that generates an acid with light in a range of 300 nm or less, preferably 220 nm or less, and the above-described mixture with the polymer or the like in the present invention is sufficient for an organic solvent. Any photoacid generator may be used as long as it dissolves in the solution and the solution can form a uniform coating film by a film forming method such as spin coating. Moreover, you may use individually and in mixture of 2 or more types, or in combination with a suitable sensitizer.

  Examples of usable photoacid generators include, for example, J described in Journal of the Organic Chemistry, Vol. 43, No. 15, pages 3055-3058 (1978). . V. Triphenylsulfonium salt derivatives of JV Crivello et al. And other onium salts typified by them (for example, compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts), 2, 6-Dinitrobenzyl esters [O. O. Nalamasu et al., SPIE Proceeding, 1262, 32 (1990)], 1,2,3-tri (methanesulfonyloxy) benzene [Takumi Ueno et al., Proceeding of PME'89, Kodansha, 413-424 (1990)].

Specifically, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate , Triphenylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, and the like, but are not limited thereto.
In the composition of the present invention, the photoacid generator may be used alone, but two or more kinds may be mixed and used. The content of the photoacid generator is usually 0.02 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of all components including itself.
The antireflection film-forming composition of the present invention may further contain a rheology adjusting agent, a surfactant and the like as necessary.

The rheology modifier is added mainly for the purpose of improving the fluidity of the antireflective film-forming composition, and particularly for improving the filling property of the antireflective film-forming composition into the hole in the firing step.
Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, Mention may be made of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. it can. These rheology modifiers are usually added in a proportion of less than 30% by mass based on the total composition of the antireflection film-forming composition.
The surfactant is added in order to suppress the occurrence of pinholes and installations, and to further improve the applicability to surface unevenness. Examples of the surfactant include nonionic surfactants, fluorine surfactants, and organosiloxane polymers. The blending amount of these surfactants is usually 0. 0 per total composition of the antireflection film-forming composition of the present invention. 2% by mass or less, preferably 0. 1% by mass or less. These surfactants may be added singly or in combination of two or more.

  In the present invention, the solvent for dissolving the solids such as the polymer is methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, decanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol. Monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, glycerol, glycerol monomethyl ether, glycerol dimethyl ether, glycerol monoethyl ether, glycerol diethyl ether Alcohols such as solvents, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, can be used methyl lactate, such as ester solvents ethyl lactate.

  These solvents can be used alone or as a mixture of two or more. Among these, alcohol solvents and mixed solvents of alcohol solvents and other polar solvents are preferable from the viewpoint of the solubility of each component and the stability of the composition.

  As the alcohol solvent, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether are preferable. The mixed solvent of the alcohol solvent and the other polar solvent is preferably a mixed solvent of an alcohol solvent / ether solvent and a mixed solvent of an alcohol solvent / ester solvent.

  Preferable specific examples of the mixed solvent of the alcohol solvent / ether solvent include at least one alcohol solvent of propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether, and bis (2- (Methoxyethyl) ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether include a mixed solvent with at least one ether solvent.

  Preferred examples of the mixed solvent of the alcohol solvent / ester solvent include at least one alcohol solvent of propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether, and propylene glycol monomethyl ether. Examples thereof include a mixed solvent with at least one ester solvent selected from acetate and propylene glycol monomethyl ether acetate.

  As the photoresist applied to the upper layer of the antireflection film in the present invention, either a negative type or a positive type can be used, and a positive type photoresist composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester is decomposed by an acid. Chemically amplified photoresist comprising a binder having a group that increases the alkali dissolution rate and a photoacid generator, an alkali-soluble binder, a low-molecular compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator Chemically amplified photoresist comprising a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator Type photoresist.

  As a developer for a positive photoresist having an antireflection film formed using the antireflection film-forming composition of the present invention, an appropriate organic solvent depending on the solubility of the polymer compound used in the present invention, or The mixed solvent, an alkali solution having an appropriate concentration, an aqueous solution or a mixture thereof may be selected. Examples of the organic solvent used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, Examples include alcohols such as tertiary-butyl alcohol, cyclopentanol and cyclohexanol, and organic solvents such as tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, isoamyl acetate, benzene, toluene, xylene and phenol. Examples of the alkaline solution used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia, and organic solvents such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine, and triethylamine. An aqueous solution containing an amine and an organic ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, or an organic solvent, and Examples thereof include, but are not limited to, mixtures thereof. Among these, a preferred developer is tetramethylammonium hydroxide.

  Next, the photoresist pattern forming method of the present invention will be described. Anti-reflective film forming composition by a suitable application method such as a spinner or coater on a substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, glass substrate, I T O substrate, etc.) used in the manufacture of a semiconductor device After applying the material, it is baked and cured to produce an antireflection film. Here, the film thickness of the antireflection film is 0. 0 1 to 3. 0 μm is preferred. If the film thickness is smaller than 0.01 μm, sufficient antireflection effect may not be obtained. If the film thickness is larger than 3.0 μm, the resist may be lost before the substrate etching when the substrate is etched. There is. Moreover, as conditions for baking after application | coating, as baking temperature, it is 80-250 degreeC, for example, Preferably it is 150-250 degreeC. The firing time is, for example, 0. 2 to 60 minutes, preferably 0. 5 to 30 minutes. Thereafter, a photoresist layer is formed, exposed through a predetermined mask, developed, rinsed, and dried to obtain a good resist pattern. The exposure can be performed using a K r F excimer laser (wavelength 2 48 nm), an Ar F excimer laser (wavelength 1 9 3 nm), EB, EUV, or the like used for manufacturing a semiconductor device. If necessary, post-exposure heating (PEB: PostexposureBake) can also be performed. Then, the portion of the antireflective film from which the photoresist has been developed and removed by the above process is removed by dry etching, and a desired pattern can be formed on the substrate.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.
Reference synthesis example 1
Preparation of resist solution

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、窒素雰囲気下、テトラヒドロフラン（ＴＨＦ）１０ｇを入れ、温度を６０℃に保ち、撹拌しながら、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン１．７ｇ（７．７ｍｍｏｌ）、２−メチル−２−メタクリロイルオキシアダマンタン１．７ｇ（７．３ｍｍｏｌ）、３−ヒドロキシ−１−メタクリロイルオキシアダマンタン１．７ｇ（７．２ｍｍｏｌ）、開始剤（和光純薬工業製、商品名「Ｖ−６５」）０．５０ｇ及びＴＨＦ１６ｇを混合したモノマー溶液を２時間かけて一定速度で滴下した。滴下終了後、さらに６時間撹拌を続けた。重合反応終了後、得られた反応液をヘキサンと酢酸エチルの９：１（体積比；２５℃）混合液５００ｍｌ中に撹拌しながら滴下した。生じた沈殿物を濾別し、減圧乾燥（２５℃）することによりすることにより、所望の樹脂３．６ｇを得た。回収したポリマーをＧＰＣ（ゲルパーミエーションクロマトグラフィー）分析したところ、重量平均分子量（Ｍｗ）が９５００、分子量分布（Ｍｗ／Ｍｎ）が２．０であった。また、得られた重合体の共重合比率はＮＭＲ分析によると、重合に供した比率とほぼ同じであった。
得られた重合体１００重量部とトリフェニルスルホニウムヘキサフルオロアンチモネート１０重量部とを溶媒である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）と混合して、ポリマー濃度１７重量％のフォトレジスト用樹脂組成物を調製した。
実施例１
１‐メチル−１−シクロへキシルエチル＝メタクリレート、ベンジルメタクリレート、１−メタクロイルオキシ−３−ヒドロキシアダマンタン共重合体（下記式）の合成

In a 100 ml round bottom flask equipped with a reflux tube, a stirring bar and a three-way cock, 10 g of tetrahydrofuran (THF) was placed under a nitrogen atmosphere, and the temperature was kept at 60 ° C., while stirring, 5-methacryloyloxy-2,6- Norbornane carbolactone 1.7 g (7.7 mmol), 2-methyl-2-methacryloyloxyadamantane 1.7 g (7.3 mmol), 3-hydroxy-1-methacryloyloxyadamantane 1.7 g (7.2 mmol), initiator A monomer solution in which 0.50 g (manufactured by Wako Pure Chemical Industries, trade name “V-65”) and 16 g of THF were mixed was dropped at a constant rate over 2 hours. After completion of the dropwise addition, stirring was continued for 6 hours. After completion of the polymerization reaction, the obtained reaction solution was added dropwise to 500 ml of a 9: 1 (volume ratio; 25 ° C.) mixture of hexane and ethyl acetate while stirring. The resulting precipitate was filtered off and dried under reduced pressure (25 ° C.) to obtain 3.6 g of the desired resin. When the collected polymer was analyzed by GPC (gel permeation chromatography), the weight average molecular weight (Mw) was 9500, and the molecular weight distribution (Mw / Mn) was 2.0. Further, the copolymerization ratio of the obtained polymer was almost the same as the ratio used for polymerization according to NMR analysis.
100 parts by weight of the obtained polymer and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a resin composition for photoresist having a polymer concentration of 17% by weight. Prepared.
Example 1
Synthesis of 1-methyl-1-cyclohexylethyl methacrylate, benzyl methacrylate, 1-methacryloyloxy-3-hydroxyadamantane copolymer (following formula)

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、窒素雰囲気下、テトラヒドロフラン（ＴＨＦ）１０ｇを入れ、温度を６０℃に保ち、撹拌しながら、１‐メチル−１−シクロへキシルエチル＝メタクリレート １．４３ｇ（６．８ｍｍｏｌ）、ベンジルメタクリレート０．８９ｇ（５．０ｍｍｏｌ）、１−メタクロイルオキシ−３−ヒドロキシアダマンタン２．８５ｇ（１２．１ｍｍｏｌ）、開始剤（和光純薬工業製、商品名「Ｖ−６５」）０．５０ｇ及びＴＨＦ１６ｇを混合したモノマー溶液を２時間かけて一定速度で滴下した。滴下終了後、さらに６時間撹拌を続けた。重合反応終了後、得られた反応液をヘキサンと酢酸エチルの９：１（体積比；２５℃）混合液５００ｍｌ中に撹拌しながら滴下した。生じた沈殿物を濾別し、減圧乾燥（２５℃）することによりすることにより、所望の樹脂３．６ｇを得た。回収したポリマーをＧＰＣ（ゲルパーミエーションクロマトグラフィー）分析したところ、重量平均分子量（Ｍｗ）が９０００、分子量分布（Ｍｗ／Ｍｎ）が２．０であった。また、得られたポリマーの共重合比率はＮＭＲ分析によると、重合に供した比率とほぼ同じであった。
実施例２
１−メチル−1−（４−メチルシクロへキシル）エチル＝メタクリレート、ベンジルメタクリレート、１−メタクロイルオキシ−３−ヒドロキシアダマンタン共重合体（下記式）の合成

In a 100 ml round bottom flask equipped with a reflux tube, a stirring bar and a three-way cock, 10 g of tetrahydrofuran (THF) was placed under a nitrogen atmosphere, and the temperature was kept at 60 ° C., while stirring, 1-methyl-1-cyclohexylethyl. = Methacrylate 1.43 g (6.8 mmol), benzyl methacrylate 0.89 g (5.0 mmol), 1-methacryloyloxy-3-hydroxyadamantane 2.85 g (12.1 mmol), initiator (manufactured by Wako Pure Chemical Industries, Ltd., A monomer solution obtained by mixing 0.50 g (trade name “V-65”) and 16 g of THF was added dropwise at a constant rate over 2 hours. After completion of the dropwise addition, stirring was continued for 6 hours. After completion of the polymerization reaction, the obtained reaction solution was added dropwise to 500 ml of a 9: 1 (volume ratio; 25 ° C.) mixture of hexane and ethyl acetate while stirring. The resulting precipitate was filtered off and dried under reduced pressure (25 ° C.) to obtain 3.6 g of the desired resin. When the collected polymer was analyzed by GPC (gel permeation chromatography), the weight average molecular weight (Mw) was 9000 and the molecular weight distribution (Mw / Mn) was 2.0. Moreover, the copolymerization ratio of the obtained polymer was almost the same as the ratio used for the polymerization according to NMR analysis.
Example 2
Synthesis of 1-methyl-1- (4-methylcyclohexyl) ethyl methacrylate, benzyl methacrylate, 1-methacryloyloxy-3-hydroxyadamantane copolymer (following formula)

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、窒素雰囲気下、テトラヒドロフラン（ＴＨＦ）１０ｇを入れ、温度を６０℃に保ち、撹拌しながら、１−メチル−1−（４−メチルシクロへキシル）エチル＝メタクリレート、１．９６ｇ（８．７ｍｍｏｌ）、ベンジルメタクリレート１．１４ｇ（６．５ｍｍｏｌ）、１−メタクロイルオキシ−３−ヒドロキシアダマンタン２．０７ｇ（８．７ｍｍｏｌ）、開始剤（和光純薬工業製、商品名「Ｖ−６５」）０．５０ｇ及びＴＨＦ１６ｇを混合したモノマー溶液を２時間かけて一定速度で滴下した。滴下終了後、さらに６時間撹拌を続けた。重合反応終了後、得られた反応液をヘキサンと酢酸エチルの９：１（体積比；２５℃）混合液５００ｍｌ中に撹拌しながら滴下した。生じた沈殿物を濾別し、減圧乾燥（２５℃）することによりすることにより、所望の樹脂３．３ｇを得た。回収したポリマーをＧＰＣ（ゲルパーミエーションクロマトグラフィー）分析したところ、重量平均分子量（Ｍｗ）が８０００、分子量分布（Ｍｗ／Ｍｎ）が２．１であった。また、得られたポリマーの共重合比率はＮＭＲ分析によると、重合に供した比率とほぼ同じであった。
比較例１
１−メチル−1−（1−アダマンチル）エチル＝メタクリレート、、ベンジルメタクリレート、１−メタクロイルオキシ−３−ヒドロキシアダマンタン共重合体（下記式）の合成

In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 10 g of tetrahydrofuran (THF) was placed under a nitrogen atmosphere, and the temperature was kept at 60 ° C., while stirring, 1-methyl-1- (4- Methylcyclohexyl) ethyl methacrylate, 1.96 g (8.7 mmol), benzyl methacrylate 1.14 g (6.5 mmol), 1-methacryloyloxy-3-hydroxyadamantane 2.07 g (8.7 mmol), initiator ( A monomer solution prepared by mixing 0.50 g of Wako Pure Chemical Industries, trade name “V-65”) and 16 g of THF was added dropwise at a constant rate over 2 hours. After completion of the dropwise addition, stirring was continued for 6 hours. After completion of the polymerization reaction, the obtained reaction solution was added dropwise to 500 ml of a 9: 1 (volume ratio; 25 ° C.) mixture of hexane and ethyl acetate while stirring. The resulting precipitate was filtered off and dried under reduced pressure (25 ° C.) to obtain 3.3 g of the desired resin. When the collected polymer was analyzed by GPC (gel permeation chromatography), the weight average molecular weight (Mw) was 8000, and the molecular weight distribution (Mw / Mn) was 2.1. Moreover, the copolymerization ratio of the obtained polymer was almost the same as the ratio used for the polymerization according to NMR analysis.
Comparative Example 1
Synthesis of 1-methyl-1- (1-adamantyl) ethyl methacrylate, benzyl methacrylate, 1-methacryloyloxy-3-hydroxyadamantane copolymer (the following formula)

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、窒素雰囲気下、テトラヒドロフラン（ＴＨＦ）１０ｇを入れ、温度を６０℃に保ち、撹拌しながら、１−メチル−1−（1−アダマンチル）エチル＝メタクリレート ２．２９ｇ（８．７ｍｍｏｌ）、ベンジルメタクリレート１．１４ｇ（６．５ｍｍｏｌ）、１−メタクロイルオキシ−３−ヒドロキシアダマンタン２．０７ｇ（８．７ｍｍｏｌ）、開始剤（和光純薬工業製、商品名「Ｖ−６５」）０．５０ｇ及びＴＨＦ１６ｇを混合したモノマー溶液を２時間かけて一定速度で滴下した。滴下終了後、さらに６時間撹拌を続けた。重合反応終了後、得られた反応液をヘキサンと酢酸エチルの９：１（体積比；２５℃）混合液５００ｍｌ中に撹拌しながら滴下した。生じた沈殿物を濾別し、減圧乾燥（２５℃）することによりすることにより、所望の樹脂３．０ｇを得た。回収したポリマーをＧＰＣ（ゲルパーミエーションクロマトグラフィー）分析したところ、重量平均分子量（Ｍｗ）が８０００、分子量分布（Ｍｗ／Ｍｎ）が２．０であった。また、得られたポリマーの共重合比率はＮＭＲ分析によると、重合に供した比率とほぼ同じであった。

In a 100 ml round bottom flask equipped with a reflux tube, a stirring bar and a three-way cock, 10 g of tetrahydrofuran (THF) was placed under a nitrogen atmosphere, and the temperature was kept at 60 ° C., while stirring, 1-methyl-1- (1- Adamantyl) ethyl methacrylate 2.29 g (8.7 mmol), benzyl methacrylate 1.14 g (6.5 mmol), 1-methacryloyloxy-3-hydroxyadamantane 2.07 g (8.7 mmol), initiator (Wako Pure Chemical Industries, Ltd.) A monomer solution obtained by mixing 0.50 g (trade name “V-65”, manufactured by Kogyo Co., Ltd.) and 16 g of THF was added dropwise at a constant rate over 2 hours. After completion of the dropwise addition, stirring was continued for 6 hours. After completion of the polymerization reaction, the obtained reaction solution was added dropwise to 500 ml of a 9: 1 (volume ratio; 25 ° C.) mixture of hexane and ethyl acetate while stirring. The resulting precipitate was filtered off and dried under reduced pressure (25 ° C.) to obtain 3.0 g of the desired resin. When the collected polymer was analyzed by GPC (gel permeation chromatography), the weight average molecular weight (Mw) was 8000, and the molecular weight distribution (Mw / Mn) was 2.0. Moreover, the copolymerization ratio of the obtained polymer was almost the same as the ratio used for the polymerization according to NMR analysis.

Evaluation test Polymers prepared in Examples 1 and 2 and Comparative Example 1 (0.8 g), hexamethoxymethylmelamine (0.3 g), pyridinium-p-toluenesulfonic acid (0.05 g), propylene glycol monomethyl ether acetate (9 g) and propylene glycol monomethyl ether (20 g) were mixed and filtered using a membrane filter having a pore size of 0.1 μm to obtain an antireflection film solution.

  A silicon wafer was first coated with the above anti-reflective coating solution to a thickness of 70 nm and then heat-treated at 200 ° C. for 60 seconds. Next, this coated wafer was coated with the resist solution prepared in Reference Example 1 to a film thickness of 500 nm, and baked at 110 ° C. for 60 seconds. This coated wafer was exposed through a mask at an irradiation dose of 30 mJ / cm 2 using an ArF excimer laser with a wavelength of 193 nm, and then post-exposure baking (PEB) at 1300 ° C. for 90 seconds. . This wafer was paddle developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 30 seconds. The state of the pattern was observed from a photograph taken with a scanning electron microscope (SEM). The results are shown in Table 1.

Claims (3)

(I) The following formula (1)

(In the formula (1), R1, R2, and R3 are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom; , R5 represents an alkyl group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and X represents an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 5 carbon atoms. , An acetyl group, or a monocyclic aliphatic hydrocarbon group which may be substituted with a cyano group.)
Having at least one monomer unit represented by:
(Ii) The following formula (2)

(In the formula (2), R6, R7 and R8 are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom; Ar is a substituted or unsubstituted aromatic hydrocarbon group.)
In represented by monomer units, scan styrene, methyl styrene, hydroxystyrene, methoxystyrene, cyanostyrene, chlorostyrene, bromostyrene, acetyl styrene, alpha-methyl styrene, alpha-chlorostyrene, vinyl naphthalene, vinyl anthracene, benzyl acrylate, At least one monomer unit selected from monomer units derived from monomer components selected from anthryl methyl acrylate, 2-phenylethyl acrylate, benzyl methacrylate, anthryl methyl methacrylate, 2-phenylethyl methacrylate, and
(Iii) 1- (meth) acryloyloxy-3- [2- (trimethoxysilyl) ethyl] adamantane, 2- (trimethylsilylmethyl) adamantyl acrylate, 1- (1- (meth) acryloyloxy-1-methylethyl ) Adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane, 1-hydroxy-3- ( 1-ethyl-1- (meth) acryloyloxypropyl) adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane, 1- (1- (meth) acryloyloxy-1, 2-Dimethylpropyl) adamantane, 1-hydroxy-3- (1- (meth) a Liloyloxy-1,2-dimethylpropyl) adamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- (meth) acryloyloxypropyl) ) -3,5-dihydroxyadamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane, 1,3-dihydroxy-5- (1- (meth) acryloyloxy- 1,2-dimethylpropyl) adamantane, 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane, 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-t- Butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxy Adamantane, 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane, 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-hydroxy -3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 2- (meth) acryloyloxy-2-methyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-methyl Adamantane, 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane, 1,5-dihydroxy-2- (meth) acryloyl Oxy-2-methylada 1,3-dihydroxy-6- (meth) acryloyloxy-6-methyladamantane, 2- (meth) acryloyloxy-2-ethyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane 5-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane, 1,5-dihydroxy-2- (meth) acryloyloxy 2-ethyladamantane, 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane, 1- (adamantan-1-yloxy) ethyl (meth) acrylate, 1- (adamantan-1-ylmethoxy) ethyl (Meth) acrylate, 1- [2- (a Mantan-1-yl) ethoxy] ethyl (meth) acrylate, 1- (3-hydroxyadamantan-1-yloxy) ethyl (meth) acrylate, 1- (norbornan-2-yloxy) ethyl (meth) acrylate, 1- ( Norbornan-2-ylmethoxy) ethyl (meth) acrylate, 1- (2-methylnorbornan-2-yloxy) ethyl (meth) acrylate, 1- [1- (norbornan-2-yl) -1-methylethoxy] ethyl ( (Meth) acrylate, 1- (3-methylnorbornan-2-ylmethoxy) ethyl (meth) acrylate, 1- (bornyloxy) ethyl (meth) acrylate, 1- (isobornyloxy) ethyl (meth) acrylate, 1- [ 1- (Meth) acryloyloxyethoxy] -4-oxa Rishikuro [4.3.1.1 ^{3, 8]} undecane-5-one, 2- [1- (meth) acryloyloxy ethoxy] -4-oxatricyclo [4.2.1.0 ^3,7] nonane -5-one, 8- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one, 9- [1- (meth) acryloyl Oxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one, 1-hydroxy-3- (meth) acryloyloxyadamantane, 1,3-dihydroxy-5- (meta ) Acryloyloxyadamantane, 1-carboxy-3- (meth) acryloyloxyadamantane, 1,3-dicarboxy-5- (meth) acryloyloxyadamantane, 1-carboxy-3-hydroxy-5- (me ) Acryloyloxyadamantane, 1- (meth) acryloyloxy-4-oxoadamantane, 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane, 7-hydroxy-1- (meth) acryloyloxy-4-oxo Adamantane, 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one, 1- (meth) acryloyloxy-4,7-dioxatricyclo [ 4.4.1.1 ^3,9 ] dodecane-5,8-dione, 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5 , 7-dione, 1- (meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-4,8-dione, 2- (meth) acrylo Yloxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 2- (meth) acryloyloxy-2-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, decahydronaphthyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, (meth ) Tricyclo [5.2.1.0 ^2,6 ] decyl acrylate, tetracyclo (meth) acrylate [4.4.0.1 ^2,5 . 1 ^7,10 ] a polymer comprising at least one monomer unit selected from dodecyl,
The polymer for antireflective film formation whose ratio of the structural unit represented by said Formula (1) is 0.1-0.70 as a ratio of the number with respect to all the monomer units which comprise this polymer.   An antireflection film material comprising at least the polymer for forming an antireflection film according to claim 1, an organic solvent, and a crosslinking agent.   The antireflection film material according to claim 2, further comprising at least one component selected from a crosslinking catalyst, a surfactant, and an acid generator.