JP2010285375A - Cyclic compound, photoresist base material and photoresist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoresist material exhibiting high sensitivity and high resolution. <P>SOLUTION: A cyclic compound is represented by formula (I). In the formula, R is a cyclic alkoxycarbonylalkoxycarbonyl group or the like and R<SP>1</SP>is a cyclic alkoxycarbonylalkoxy group or the like. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to novel cyclic compounds, particularly radiation-sensitive compounds. The present invention also relates to a photoresist base material used in the electrical / electronic field such as a semiconductor and the optical field, and more particularly to a photoresist base material for ultrafine processing.

  Lithography using extreme ultraviolet light (hereinafter sometimes referred to as EUVL) or electron beam is useful as a high-performance, high-resolution fine processing method in the manufacture of semiconductors and the like. There is a need for photoresists with high sensitivity and high resolution. It is indispensable to improve the sensitivity of the photoresist from the viewpoint of the productivity and resolution of the desired fine pattern.

  As a photoresist used in the ultrafine processing by EUVL, for example, a method using a chemically amplified positive photoresist having a higher concentration of photoacid generator than other resist compounds has been proposed (for example, Patent Document 1). However, the photoresists of the examples are considered to be limited in processing up to 100 nm exemplified in the case of using an electron beam from the viewpoint of line edge roughness. It is presumed that the main cause of this is that the aggregate of the polymer compounds used as the base material or the three-dimensional shape of each polymer compound molecule is large and affects the production line width and the surface roughness.

  The inventor has already proposed a calix resorcinarene compound as a photoresist material with high sensitivity and high resolution (see Patent Documents 2 and 3). Patent Document 4 discloses a calix resorcinarene compound.

JP 2002-055557 A JP 2004-191913 A Japanese Patent Laying-Open No. 2005-075757 US Pat. No. 6,093,517

  However, higher sensitivity and higher resolution are required as an ultra-fine processing technique using EUVL. There is also a need for improvements in the adhesion between the photoresist base and the substrate. An object of the present invention is to provide a photoresist material with high sensitivity and high resolution.

［式中、Ａｒは炭素数の６〜１０のアリーレン基；炭素数６〜１０のアリーレン基を２つ以上組み合わせた基；又は炭素数６〜１０のアリーレン基と、アルキレン基及びエーテル結合の少なくとも一方を、それぞれ一つ以上組み合わせた基である。
Ｒはそれぞれ下記式（ＩＩ）で表される基である。

（式中、Ａ^１は単結合、アリーレン基、アルキレン基、エーテル結合、又は、アリーレン基、アルキレン基、エーテル結合のいずれかをそれぞれ２つ以上組み合わせた基である。
Ｒ^３は水素、置換もしくは無置換の炭素数１〜２０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１２の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、置換もしくは無置換の炭素数６〜１０の芳香族基、アルコキシアルキル基、シリル基、又はこれらの基と二価の基（置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、置換もしくは無置換のシリレン基、これらの基が２以上結合した基、又はこれらの基１以上と、エステル結合、炭酸エステル結合又はエーテル結合から選択される１以上の基）が結合した基である。
ｘは１〜５の整数、ｙは０〜３の整数である。
複数のＲ^３、Ａｒ及びＡ^１はそれぞれ同じでも異なってもよい。
Ｒ^１はそれぞれ、式（II）で表される基、前記Ｒ^３で表される基と同様な基又は溶解性調整基であり、
同一の芳香環上に存在する２つのＲ^１のうち、一方のＲ^１は、式（II）で表される基又はＲ^３で表される基と同様な基であり、他方が溶解性調整基であり、Ｒ^１の少なくとも１つは、式（II）で表される基である。
Ｒ^２はそれぞれ水素、水酸基、ＯＲ^３で表される基、ＯＲ^４（Ｒ^４は溶解性調整基である）で表される基、炭素数１〜２０の直鎖状脂肪族炭化水素基、炭素数３〜１２の分岐脂肪族炭化水素基、炭素数３〜２０の環状脂肪族炭化水素基、炭素数６〜１０の芳香族基又は酸素原子を含む基である。］
２．前記Ｒ^２が水素である１記載の環状化合物。
３．前記ＯＲ^３が酸解離性溶解抑止基である１又は２記載の環状化合物。
４．前記酸解離性溶解抑止基が、三級脂肪族構造、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する分子量が１５以上２０００以下の置換基である３記載の環状化合物。
５．ＯＲ^３が、下記式（ＩＩＩ）〜（ＶＩ）のいずれかである１又は２記載の環状
化合物。

（上記式（ＩＩＩ）〜（ＶＩ）において、
αは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。
βは、三級脂肪族構造、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基である。
γは、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基、又は芳香族構造、単環状脂肪族構造、複環状脂肪族構造のうち１以上の構造と、炭素数１〜１０の直鎖状脂肪族炭化水素基を組み合わせた基が置換したアルコキシ基である。
δは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。）
６．前記ＯＲ^３が、下記式に示される基のいずれかである１又は２記載の環状化合物。

（式中、ｒはそれぞれ上記式で表される置換基の内、ｒを有さない置換基のいずれかを表す。）
７．前記Ｒ^１及びＲ^４の溶解性調整基が、置換もしくは無置換の炭素数１〜２０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１２の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、置換もしくは無置換の炭素数６〜１０の芳香族基、アルコキシアルキル基、シリル基、又はこれらの基と二価の基（置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、置換もしくは無置換のシリレン基、これらの基が２以上結合してなる基、又はこれらの基とエステル結合、炭酸エステル結合又はエーテル結合がそれぞれ一つ以上結合してなる基）が結合した基である１〜６のいずれか記載の環状化合物。
８．上記１〜７のいずれか記載の環状化合物を含有するフォトレジスト基材。９．下記式（Ｉ’）で表される環状化合物を含有し、前記環状化合物１分子が有する、下記式（II）で表わされる基の個数の平均が、４よりも多く８以下であるフォトレジスト基材。

［式中、Ａｒは炭素数の６〜１０のアリーレン基；炭素数６〜１０のアリーレン基を２つ以上組み合わせた基；又は炭素数６〜１０のアリーレン基と、アルキレン基及びエーテル結合の少なくとも一方を、それぞれ一つ以上組み合わせた基である。
Ｒはそれぞれ下記式（ＩＩ）で表される基である。

（式中、Ａ^１は単結合、アリーレン基、アルキレン基、エーテル結合、又は、アリーレン基、アルキレン基、エーテル結合のいずれかをそれぞれ２つ以上組み合わせた基である。
Ｒ^３は水素、置換もしくは無置換の炭素数１〜２０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１２の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、置換もしくは無置換の炭素数６〜１０の芳香族基、アルコキシアルキル基、シリル基、又はこれらの基と二価の基（置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、置換もしくは無置換のシリレン基、これらの基が２以上結合した基、又はこれらの基１以上と、エステル結合、炭酸エステル結合又はエーテル結合から選択される１以上の基）が結合した基である。
ｘは１〜５の整数、ｙは０〜３の整数である。
複数のＲ^３、Ａｒ及びＡ^１はそれぞれ同じでも異なってもよい。
Ｒ^１はそれぞれ、式（II）で表される基、前記Ｒ^３で表される基と同様な基又は溶解性調整基であり、
同一の芳香環上に存在する２つのＲ^１のうち、一方のＲ^１は、式（II）で表される基又はＲ^３で表される基と同様な基であり、他方が溶解性調整基である。
Ｒ^２はそれぞれ水素、水酸基、ＯＲ^３で表される基、ＯＲ^４（Ｒ^４は溶解性調整基である）で表される基、炭素数１〜２０の直鎖状脂肪族炭化水素基、炭素数３〜１２の分岐脂肪族炭化水素基、炭素数３〜２０の環状脂肪族炭化水素基、炭素数６〜１０の芳香族基又は酸素原子を含む基である。］
１０．上記８又は９記載のフォトレジスト基材及び溶剤を含有するフォトレジスト組成物。
１１．さらに光酸発生剤を含有する１０記載のフォトレジスト組成物。
１２．さらに塩基性有機化合物をクエンチャーとして含有する１０又は１１記載のフォトレジスト組成物。
１３．上記１０〜１２のいずれか記載のフォトレジスト組成物を用いた微細加工方法。
１４．上記１３記載の微細加工方法により作製した半導体装置。
１５．上記１４に記載の半導体装置を備えた装置。 According to the present invention, the following cyclic compounds, photoresist base materials and the like are provided.
1. The cyclic compound represented by the following formula (I).

[In the formula, Ar is an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms and at least an alkylene group and an ether bond. A group in which one or more of them are combined.
Each R is a group represented by the following formula (II).

(In the formula, A ¹ is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
R ³ represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) , A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and one or more selected from an ester bond, a carbonate ester bond or an ether bond Group).
x is an integer of 1 to 5, and y is an integer of 0 to 3.
A plurality of R ³ , Ar and A ¹ may be the same or different.
R ¹ is a group represented by the formula (II), a group similar to the group represented by R ³ or a solubility adjusting group,
Of the two R ¹ existing on the same aromatic ring, one R ¹ is the same group as the group represented by the formula (II) or the group represented by R ³ , and the other is the solubility control. And at least one of R ¹ is a group represented by the formula (II).
R ² is hydrogen, a hydroxyl group, a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ]
2. ^2. The cyclic compound according to 1, wherein R ² is hydrogen.
3. The cyclic compound according to 1 or 2, wherein the OR ³ is an acid dissociable, dissolution inhibiting group.
4). 4. The cyclic compound according to 3, wherein the acid dissociable, dissolution inhibiting group is a substituent having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure and having a molecular weight of 15 to 2,000.
5). The cyclic compound according to 1 or 2, wherein OR ³ is any one of the following formulas (III) to (VI).

(In the above formulas (III) to (VI),
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
6). The cyclic compound according to 1 or 2, wherein the OR ³ is any of the groups represented by the following formulae.

(In the formula, r represents any of the substituents having no r among the substituents represented by the above formula.)
7). The solubility adjusting group for R ¹ and R ⁴ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. Substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, alkoxyalkyl group, silyl group, or these groups and divalent groups (Substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or an ester bond, a carbonate ester bond or an ether of these groups. The cyclic compound according to any one of 1 to 6, which is a group to which one or more bonds are bonded.
8). 8. A photoresist substrate containing the cyclic compound according to any one of 1 to 7 above. 9. A photoresist group containing a cyclic compound represented by the following formula (I ′) and having an average number of groups represented by the following formula (II) of more than 4 and 8 or less, which one molecule of the cyclic compound has Wood.

[In the formula, Ar is an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms and at least an alkylene group and an ether bond. A group in which one or more of them are combined.
Each R is a group represented by the following formula (II).

(In the formula, A ¹ is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
R ³ represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) , A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and one or more selected from an ester bond, a carbonate ester bond or an ether bond Group).
x is an integer of 1 to 5, and y is an integer of 0 to 3.
A plurality of R ³ , Ar and A ¹ may be the same or different.
R ¹ is a group represented by the formula (II), a group similar to the group represented by R ³ or a solubility adjusting group,
Of the two R ¹ existing on the same aromatic ring, one R ¹ is the same group as the group represented by the formula (II) or the group represented by R ³ , and the other is the solubility control. It is a group.
R ² is hydrogen, a hydroxyl group, a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ]
10. 10. A photoresist composition comprising the photoresist base material according to 8 or 9 and a solvent.
11. The photoresist composition according to 10, further comprising a photoacid generator.
12 The photoresist composition according to 10 or 11, further comprising a basic organic compound as a quencher.
13. A fine processing method using the photoresist composition according to any one of 10 to 12 above.
14 14. A semiconductor device manufactured by the microfabrication method according to the above 13.
15. 15. An apparatus comprising the semiconductor device according to 14 above.

  When the cyclic compound of the present invention is used for a photoresist, higher sensitivity and higher resolution can be obtained.

It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (A) obtained by manufacture example 1. 2 is a diagram showing the results of ¹ H-NMR measurement of the cyclic compound (B) obtained in Example 1. FIG. 2 is a diagram showing the results of ¹ H-NMR measurement of a cyclic compound (C) obtained in Example 2. FIG. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (D) obtained by the comparative example 1. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (E) obtained in Example 3. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (F) obtained by the comparative example 2.

The cyclic compound of the present invention has a structure represented by the following formula (I).

In the formula (I), Ar is an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms, an alkylene group, and an ether It is a group in which at least one of the bonds (—O—) is combined. For example, phenylene group, methylphenylene group, dimethylphenylene group, trimethylphenylene group, tetramethylphenylene group, naphthylene group, biphenylene group, and oxydiphenylene group are preferable.
Of these, a phenylene group, a biphenylene group, and an oxydiphenylene group are preferable.

Each R is a group represented by the following formula (II).

A ^{1 in the} formula (II) is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining two or more of an arylene group, an alkylene group, and an ether bond. An alkylene group, an ether bond, or a group in which two or more alkylene groups and ether bonds are combined is preferable.
Examples of the arylene group include the same groups as the above Ar.
As the alkylene group, those having 1 to 4 carbon atoms such as a methylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a butylene group are preferable.
The group in which two or more alkylene groups and ether bonds are combined is preferably an oxymethylene group, an oxydimethylmethylene group, an oxyethylene group, an oxypropylene group, or an oxybutylene group.

A ¹ is preferably a single bond or an oxymethylene group (—O—CH ₂ —).

R ³ represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon, respectively. A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a group in which these groups and a divalent group are bonded.

As the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable.
As the branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group, and the like are preferable.
As the cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, diamantyl group, and the like are preferable.
As the aromatic group having 6 to 10 carbon atoms, a phenyl group, a naphthyl group, and the like are preferable.
As the alkoxyalkyl group, a methoxymethyl group, an ethoxymethyl group, an adamantyloxymethyl group and the like are preferable.
As the silyl group, a trimethylsilyl group, a t-butyldimethylsilyl group and the like are preferable.
In addition, each of the above groups may have a substituent, specifically, an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group. Can be mentioned.

R ³ may be a group having a structure in which each of the above groups and a divalent group are bonded.
Examples of the divalent group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups. , A group in which one or more groups selected from an ester bond (—CO ₂ —), a carbonate ester bond (—CO ₃ —) and an ether bond (—O—) are bonded.
The alkylene group is preferably a methylene group, a methylmethylene group or the like, and the arylene group is preferably a phenylene group.

（式中、Ｒ’はそれぞれＨ又はアルキル基を示す。） As the group formed by bonding two or more divalent groups, the following structures are preferable.

(In the formula, each R ′ represents H or an alkyl group.)

OR ³ is preferably an acid dissociable, dissolution inhibiting group, and more preferably a substituent having an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure and having a molecular weight of 15 or more and 2000 or less.

Furthermore, a cyclic compound in which OR ³ is any one of the following formulas (III) to (VI) is preferable.

In the formulas (III) to (VI), α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms. , A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.

In addition, it is preferable that y of Formula (I) is 1. It is also preferred that x in the formula (II) is 1.
Furthermore, Ar is preferably a phenyl group. A ¹ is preferably a single bond.

（式中、ｒはそれぞれ上記式で表される置換基の内、ｒを有さない置換基のいずれかを表す。） Specific examples of the acid dissociable, dissolution inhibiting group (OR ³ ) include groups represented by the following formulae.

(In the formula, r represents any of the substituents having no r among the substituents represented by the above formula.)

x is an integer of 1 to 5, and preferably an integer of 1 to 3.
y is an integer of 0 to 3, and is preferably 1 or 2.
In formula (I), there are a plurality of R, but each R ³ , Ar, A ¹ , x and y constituting R may be the same or different.

（式中、Ｒ^３は式（II）と同様な基を表し、ｘは１〜５の整数である。） In the present invention, the formula (II) is preferably any one of the following formulas.

(In the formula, R ³ represents the same group as in formula (II), and x is an integer of 1 to 5.)

In the formula (I), R ¹ is a group represented by the formula (II), a group similar to the group represented by the R ³ or a solubility adjusting group. Of the two R ¹ existing on the same aromatic ring, one R ¹ is a group similar to the group represented by the formula (II) or the group represented by R ³ described above, Is a solubility adjusting group, and at least one of R ¹ is a group represented by the formula (II).
Specifically, when all four R ¹ except for the solubility adjusting group are formula (II), three are formula (II), two are formula (II), one is formula (II) II).
Preferably, two of the four R ¹ are of formula (II), and one of the four R ¹ is of formula (II). Thereby, hydrophilicity becomes high and adhesiveness with a photoresist substrate improves.
More preferably, only ^one of the four R ¹ is formula (II).

When R ¹ is a group similar to the group represented by R ³ , preferred examples of R ¹ are the same as the preferred examples of R ³ . Particularly preferred are the case where all R ³ present in R ¹ is hydrogen and the case where R ³ present in R ¹ coexists with hydrogen and an acid dissociable, dissolution inhibiting group. Specific examples of the acid dissociable, dissolution inhibiting group are the same as described above.

The solubility adjusting group is preferably a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted group. A substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group (substituted or unsubstituted). A substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group formed by bonding two or more of these groups, or one of these groups with an ester bond, a carbonate ester bond, and an ether bond. A group formed by bonding two or more groups).
Preferred examples of each group of dissolution controlling group is the same as R ³ as described above.

R ² is hydrogen, a hydroxyl group, a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.

A linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic group having 6 to 10 carbon atoms A preferred example of is the same as R ³ described above. Suitable examples of the solubility adjusting group are the same as those for R ¹ described above.
The group containing an oxygen atom is preferably a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), an alkoxy group, an alkoxycarbonyl group, or the like.
Preferably R ² is hydrogen.

A plurality of R, R ¹ and R ² in the formula (I) may be the same or different.

  Since the acid dissociable, dissolution inhibiting group has high reactivity with EUVL and electron beam, it is excellent in terms of sensitivity and etching resistance. Therefore, when the cyclic compound contains an acid dissociable, dissolution inhibiting group, it can be suitably used as a photoresist substrate for ultrafine processing.

The cyclic compound according to the present invention can be obtained by, for example, a calix resorcinol reaction by a condensation cyclization reaction between an aldehyde compound having a corresponding structure and an aromatic compound having both a solubility adjusting group and a hydroxyl group in the presence of an acid catalyst by a known method. It can be synthesized by synthesizing a len derivative (precursor) and introducing a compound corresponding to a group such as R ³ into the precursor by esterification reaction, etherification reaction, acetalization reaction or the like. Specific examples will be described in the embodiments described later.

  The cyclic compound according to the present invention is useful as a photoresist base material, particularly as a photoresist base material used in ultra-fine processing by lithography such as extreme ultraviolet light (wavelength 15 nm or less) or electron beam.

  When the cyclic compound according to the present invention is used for a photoresist substrate, it is refined and basic impurities (for example, alkali metal ions such as ammonia, Li, Na and K, alkaline earth metal ions such as Ca and Ba, etc.), etc. Is preferably removed. Specifically, the content of basic impurities is preferably 10 ppm or less, more preferably 2 ppm or less.

  Examples of the purification method include a method of treating by reprecipitation using acidic aqueous solution washing, ion exchange resin, or ultrapure water. You may refine | purify combining these washing | cleaning methods. For example, after washing with an aqueous acetic acid solution as an acidic aqueous solution, an ion exchange resin treatment or a reprecipitation treatment with ultrapure water is performed.

  The cyclic compound of the present invention preferably contains an alkali-soluble group because the solubility in an alkali developer is increased by the action of an acid.

Examples of the alkali-soluble group include a hydroxyl group, a sulfonic acid group, a phenol group, a carboxyl group, and a hexafluoroisopropanol group [—C (CF ₃ ) ₂ OH]. Preferred are a phenol group, a carboxyl group, and a hexafluoroisopropanol group, and more preferred are a phenol group and a carboxyl group.

［式中、Ｒはそれぞれ下記式（ＩＩ）で表される基である。

The cyclic compound of the present invention can be used as a photoresist base material used in ultra-fine processing by lithography such as extreme ultraviolet light or an electron beam.
Moreover, the photoresist base material of other embodiment of this invention contains the cyclic compound represented by following formula (I '), and the number of group represented by the following formula (II) which 1 molecule of cyclic compounds has. Is more than 4 and 8 or less.

[Wherein, R is a group represented by the following formula (II).

In the formulas (I ′) and (II), R ^{1 to} R ³ , Ar, A ¹ , x, y represent the same groups as in the examples of the above formulas (I) and (II).
Of the two R ¹ existing on the same aromatic ring, one R ¹ is the same group as the group represented by the formula (II) or the group represented by R ³ , and the other is the solubility control. It is a group.

The average number of groups represented by the following formula (II) contained in one molecule of the cyclic compound is more than 4 and 8 or less. That is, in addition to the four Rs that the compound of formula (I) has, at least a part of R ¹ has a group represented by formula (II). Preferably, it is more than 4 and 6 or less, and particularly preferably more than 4 and 5 or less.
When the average number of the formula (II) is 6.0 or less, the hydrophilicity becomes high and the adhesion with the photoresist substrate is improved.
If R ¹ of the cyclic compound in the composition is the formula (II), the sensitivity is improved, but the above range is preferable from the viewpoint of adhesion to the substrate. Accordingly, in the compound of the formula (I ′), it is preferable that two or one of the four R ¹ excluding the solubility-controlling group is a group of the formula (II), and in particular, of the four R ¹ , Preferred is the case where only one is of formula (II).
In addition, the average number of groups represented by the formula (II) contained in one molecule of the cyclic compound is calculated from an NMR spectrum and liquid chromatography.

The photoresist composition of this invention contains said photoresist base material and a solvent.
The compounding amount of the cyclic compound is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the entire composition excluding the solvent. When a cyclic compound is used as a photoresist base material, it may be used alone or in combination of two or more, as long as the effects of the present invention are not impaired.

  Examples of the solvent used in the photoresist composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycols such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Monoalkyl ethers; methyl lactate, ethyl lactate (E Lactic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Other esters such as methyl ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; tetrahydrofuran, dioxane Examples thereof include cyclic ethers such as lactones and lactones such as γ-butyrolactone, but are not particularly limited. These solvents can be used alone or in combination of two or more.

  The components other than the solvent in the composition, that is, the amount of the photoresist solid content, is preferably set to an amount suitable for forming a desired film thickness of the photoresist layer. Specifically, it is generally 0.1 to 50% by weight of the total weight of the photoresist composition, but it can be defined according to the type of base material and solvent used, or the desired film thickness of the photoresist layer. . The solvent is preferably blended in an amount of 50 to 99.9% by weight in the entire composition.

  The photoresist composition of the present invention may consist essentially of a photoresist base material comprising the cyclic compound of the present invention and a solvent, or may comprise only these components. “Substantially” means that the composition consists only of a photoresist base material and a solvent and can contain the following additives in addition to these components.

  The photoresist composition of the present invention does not require an additive particularly when the substrate molecule contains a chromophore active against EUV and / or electron beam and exhibits the ability as a photoresist alone. When it is necessary to enhance the performance (sensitivity) as a photoresist, a photoacid generator (PAG) or the like is generally included as a chromophore as necessary.

The photoacid generator is not particularly limited, and those proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. There are various known acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

［式中、Ｒ^５１は、直鎖、分岐鎖又は環状のアルキル基、又は直鎖、分岐鎖又は環状のフッ素化アルキル基を表し；Ｒ^５２は、水素原子、水酸基、ハロゲン原子、直鎖又は分岐鎖状のアルキル基、直鎖又は分岐鎖状のハロゲン化アルキル基、又は直鎖又は分岐鎖状のアルコキシ基であり；Ｒ^５３は置換基を有していてもよいアリール基であり；ｕ’’は１〜３の整数である。］ Examples of the onium salt acid generator include acid generators represented by the following formula (b-0).

Wherein, R ⁵¹ represents a linear, branched or cyclic alkyl group or a linear, represents branched or cyclic fluorinated alkyl group,; R ⁵² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or A branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R ⁵³ is an optionally substituted aryl group; u '' Is an integer of 1 to 3. ]

In the formula (b-0), R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, particularly hydrogen. Those in which all atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
R ⁵¹ is most preferably a linear alkyl group or a fluorinated alkyl group.

R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group.
In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
In R ^52, the alkyl group is a straight or branched chain, the number of carbon atoms is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
In R ⁵² , the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Examples of the alkyl group herein are the same as the “alkyl group” in R ⁵² . Examples of the halogen atom to be substituted include the same as those described above for the “halogen atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
In R ⁵² , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
Of these, R ⁵² is preferably a hydrogen atom.

R ⁵³ is an aryl group which may have a substituent, and examples of the structure of the basic ring (matrix ring) excluding the substituent include a naphthyl group, a phenyl group, an anthracenyl group, and the like. From the viewpoint of absorption of exposure light such as ArF excimer laser or the like, a phenyl group is desirable.
Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
As the aryl group for R ^53, an aryl group having no substituent is more preferable.

  u ″ is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

Preferable examples of the acid generator represented by the formula (b-0) include those represented by the following chemical formula.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”，Ｒ^６”は、それぞれ独立に、置換又は無置換のアリール基又はアルキル基を表し；Ｒ^４”は、直鎖、分岐又は環状のアルキル基又はフッ素化アルキル基を表し；Ｒ^１”〜Ｒ^３”のうち少なくとも１つはアリール基を表し、Ｒ^５”及びＲ^６”のうち少なくとも１つはアリール基を表す。］ The acid generator represented by the formula (b-0) can be used alone or in combination.
Examples of other onium salt-based acid generators represented by the formula (b-0) include compounds represented by the following formula (b-1) or (b-2).

[Wherein, R ¹ ″ to R ³ ″, R ⁵ ″, R ⁶ ″ each independently represents a substituted or unsubstituted aryl group or an alkyl group; R ⁴ ″ represents linear, branched or cyclic Represents an alkyl group or a fluorinated alkyl group; at least one of R ¹ ″ to R ³ ″ represents an aryl group, and at least one of R ⁵ ″ and R ⁶ ″ represents an aryl group.]

In formula (b-1), R ¹ ″ to R ³ ″ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R ¹ ″ to R ³ ″ represents a substituted or unsubstituted aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably substituted or unsubstituted aryl groups, and most preferably all of R ¹ ″ to R ³ ″ are substituted or unsubstituted aryl groups.

The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl or alkoxy. It may or may not be substituted with a group, a halogen atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.

The alkyl group that is a substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group that is a substituent of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
The halogen atom that is a substituent of the aryl group is preferably a fluorine atom.

The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, a straight, include branched or cyclic alkyl group. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
Among these, it is most preferable that all of R ¹ ″ to R ³ ″ are phenyl groups.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group is a cyclic group as indicated by R ¹ ″ and preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 carbon atoms. Most preferably, it is -10.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Also. The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and in particular, all hydrogen atoms are substituted with fluorine atoms. Since the strength of the acid is increased, it is preferable.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In formula (b-2), R ⁵ ″ and R ⁶ ″ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R ⁵ ″ and R ⁶ ″ represents a substituted or unsubstituted aryl group. All of R ⁵ ″ and R ⁶ ″ are preferably substituted or unsubstituted aryl groups.
Examples of the substituted or unsubstituted aryl group for R ⁵ ″ to R ⁶ ″ include the same as the substituted or unsubstituted aryl group for R ¹ ″ to R ³ ″.
Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″.
Among these, it is most preferable that all of R ⁵ ″ to R ⁶ ″ are phenyl groups.
"As ^{R 4} in the formula (b-1)" ^{R 4} in the In the formula (b-2) include the same as.

  Specific examples of the onium salt acid generators represented by the formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or the same Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropro Sulfonate or its nonafluorobutane sulfonate, trifluoromethane sulfonate of monophenyldimethylsulfonium, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, trifluoromethane sulfonate of diphenylmonomethylsulfonium, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, Bird (4 tert-butyl) phenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane Examples include sulfonates. In addition, onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”，Ｚ”は、それぞれ独立に、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０のアルキル基を表す。］ Moreover, the onium salt type acid generator which replaced the anion part by the anion part represented by the following formula (b-3) or (b-4) in the said formula (b-1) or (b-2) is also used. (The cation moiety is the same as (b-1) or (b-2)).

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Preferably it is C3.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.

  The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible within the range of the above carbon number for reasons such as good solubility in a resist solvent.

  In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, the strength of the acid increases as the number of hydrogen atoms substituted by fluorine atoms increases, and high-energy light or electron beam of 200 nm or less The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all. Are a perfluoroalkylene group or a perfluoroalkyl group in which a hydrogen atom is substituted with a fluorine atom.

In the present invention, compounds represented by the following formulas (30) to (35) can also be used as a photoacid generator.

In the formula (30), Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

The compound represented by the formula (30) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from the group consisting of to-5-ene-2,3-dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide.

In formula (31), R ¹⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

The compound represented by the formula (31) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It must be at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.

In formula (32), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

The compound represented by the formula (32) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α It is preferably at least one selected from the group consisting of-(methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (33), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

In the formulas (34) and (35), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group, a cyclopentyl group, or a cyclohexyl group. A cycloalkyl group such as methoxy group, ethoxy group, propoxy group or the like, or an aryl group such as phenyl group, toluyl group or naphthyl group, preferably 6 to 10 carbon atoms. An aryl group.
L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable.
p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5.
J ¹⁹ is a group having a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (34a), a carbonyl bond, an ester bond, an amide bond or an ether bond.
Y ¹⁹ is each independently a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is each independently a group represented by the following formula (35a).

式（３５ａ）中、Ｚ^２２はそれぞれ独立に、アルキル基、シクロアルキル基又はアリール基であり、Ｒ^２２はそれぞれ独立に、アルキル基、シクロアルキル基又はアルコキシ基であり、ｒは０〜３の整数である。

In the formula (35a), Z ²² each independently represents an alkyl group, a cycloalkyl group, or an aryl group, each R ²² independently represents an alkyl group, a cycloalkyl group, or an alkoxy group, and r is 0 to 3 It is an integer.

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1,4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfo) Bissulfonyldiazomethanes such as (ruazomethylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 , 6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate And triazine derivatives.

  Of these photoacid generators, compounds that generate an organic sulfonic acid by the action of actinic rays or radiation are particularly preferred.

  The blending amount of PAG is 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight in the total composition excluding the solvent.

  In the present invention, an acid diffusion control agent (quencher) having an action of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. May be blended in the photoresist composition. By using such an acid diffusion controller, the storage stability of the photoresist composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent.

  Examples of such acid diffusion control agents include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, and the like; diethanolamine, triethanolamine, diisopropanolamine, tri Isopropanol Electron beam radiation-decomposable basic compounds such as nitrogen-containing basic compounds such as amines, alkyl alcohol amines such as di-n-octanolamine and tri-n-octanolamine, basic sulfonium compounds and basic iodonium compounds Can be mentioned. The acid diffusion controller can be used alone or in combination of two or more.

  The blending amount of the quencher is 0 to 40% by weight, preferably 0.01 to 15% by weight in the total composition excluding the solvent.

  In the present invention, if desired, further miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving coating properties, dissolution control agents, sensitizers, plasticizers. Stabilizers, colorants, antihalation agents, dyes, pigments, and the like can be appropriately added and contained.

  The dissolution control agent is a component having an action of reducing the solubility of the cyclic compound in an alkaline developer so as to moderate the dissolution rate during development.

  Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. Furthermore, for example, bisphenols into which an acid dissociable functional group has been introduced, tris (hydroxyphenyl) methane into which a t-butylcarbonyl group has been introduced, and the like can also be mentioned. These dissolution control agents can be used alone or in combination of two or more. The blending amount of the dissolution control agent is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and more preferably 0 to 30% by weight based on the total weight of the solid component. Is more preferable.

  The sensitizer is a component that absorbs the energy of the irradiated radiation and transmits the energy to the acid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. is there. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, even more preferably 0 to 10% by weight based on the total weight of the solid component.

  The surfactant is a component having an action of improving the coating property and striation of the photoresist composition of the present invention, the developing property as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, nonionic surfactants are preferred. Nonionic surfactants have better affinity with the solvent used in the photoresist composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) The series products such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like can be mentioned, but are not particularly limited. The blending amount of the surfactant is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and still more preferably 0 to 0.1% by weight based on the total weight of the solid components.

  Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid.

  An organic carboxylic acid or phosphorus oxo acid or a derivative thereof is added as an optional component for the purpose of preventing sensitivity deterioration when an acid diffusion control agent is added and improving the resist pattern shape, retention stability, etc. be able to. These compounds can be used in combination with an acid diffusion controller or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Examples include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acid such as phosphinic acid and phenylphosphinic acid, and derivatives such as esters thereof. Of these, phosphonic acid is particularly preferred.

  In order to form a resist pattern, first, the photoresist composition of the present invention is applied onto a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum, by spin coating, cast coating, roll coating, or other coating means. Then, a resist film is formed by coating.

  If necessary, a surface treatment agent may be applied in advance on the substrate. Examples of the surface treatment agent include a silane coupling agent such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group), an anchor coating agent or a base agent (polyvinyl acetal, acrylic resin, vinyl acetate). Based resins, epoxy resins, urethane resins, etc.), and coating agents obtained by mixing these base agents and inorganic fine particles.

  If necessary, a protective film may be formed on the resist film in order to prevent an amine or the like floating in the atmosphere from entering. By forming a protective film, the acid generated in the resist film due to radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity. Can be prevented from decreasing. As the material for the protective film, a water-soluble and acidic polymer is preferable. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  In order to obtain a high-precision fine pattern and to reduce outgas during exposure, it is preferable to heat before irradiation (before exposure). The heating temperature varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The exposure conditions and the like are appropriately selected according to the composition of the photoresist composition. In the present invention, in order to stably form a high-precision fine pattern, it is preferable to heat after irradiation (after exposure). The post-exposure heating temperature (PEB) varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, a predetermined resist pattern can be formed by developing the exposed resist film with an alkaline developer. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution of preferably 1 to 10% by weight, more preferably 1 to 5% by weight, in which one or more compounds are dissolved is used. An appropriate amount of an alcohol such as methanol, ethanol, isopropyl alcohol, or the above-mentioned surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by weight of isopropyl alcohol. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  When a cyclic compound having an acid dissociable, dissolution inhibiting group is used as a photoresist base material, the resist film is exposed to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, thereby generating an acid. When the dissociable dissolution inhibiting group is eliminated or the structure is changed, the dissociable dissolution inhibiting group is dissolved in the alkaline developer. On the other hand, it is preferable that the unexposed portion of the pattern is not dissolved in the alkaline developer.

  The non-solubility in the alkali developer cannot be generally defined because the preferred non-solubility differs depending on the development conditions such as the size of the pattern to be formed and the type of the alkali developer to be used. When an aqueous methylammonium hydroxide solution is used as an alkaline developer, the insolubility expressed by the developer dissolution rate of a thin film made of a photoresist substrate is preferably less than 1 nanometer / second, preferably 0.5 nanometer / second. Less than a second is particularly preferred.

  In some cases, post-baking treatment may be included after the alkali development, and an organic or inorganic antireflection film may be provided between the resist film and the substrate.

  After forming the resist pattern, the pattern wiring board is obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas, wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. After the resist pattern is formed, a plating process such as copper plating, solder plating, nickel plating, or gold plating can be performed.

  The residual resist pattern after etching can be peeled off with an aqueous solution that is stronger than an organic solvent or an alkaline developer. Examples of the organic solvent include PGMEA, PGME, EL, acetone, tetrahydrofuran, and the like. Examples of the strong alkaline aqueous solution include 1 to 20% by weight sodium hydroxide aqueous solution and 1 to 20% by weight potassium hydroxide aqueous solution. Is mentioned. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  After forming a resist pattern using the photoresist composition of the present invention, a wiring substrate can be formed by a method in which a metal is vacuum-deposited and then the resist pattern is eluted with a solution, that is, a lift-off method.

  The photoresist composition according to the present invention can be used for ultra-fine processing by lithography of extreme ultraviolet light or electron beam. By the microfabrication method of the present invention, for example, semiconductor devices such as ULSIs, large-capacity memory devices, and ultrahigh-speed logic devices can be manufactured.

  With the microfabrication method of the present invention, the performance of the above-described ULSI, large-capacity memory device, ultrahigh-speed logic device, etc. can be dramatically improved. Furthermore, by incorporating semiconductor devices manufactured using the photoresist composition of the present invention as parts, the performance of semiconductor embedded products such as information home appliances, computer devices, memory devices such as USB memory, display devices, etc. Can be improved.

Production Example 1
Under a nitrogen stream, 50.0 g (402.8 mmol) of 3-methoxyphenol, 60.5 g (402.8 mmol) of 4-formylbenzoic acid, and 500 ml of dehydrated dichloromethane were added to a round bottom flask having a capacity of 200 ml. It was immersed in an ice water bath and cooled to 5 ° C. or lower. To this mixture, 60.8 ml (483.6 mmol) of boron trifluoride diethyl ether adduct was added dropwise so that the internal temperature did not exceed 15 ° C., and then the mixture was warmed to room temperature and stirred for 8 hours. The reaction solution was cooled in an ice water bath, quenched slowly by dropwise addition of water, and the precipitated solid was filtered off. The filtered precipitate was washed with water until neutral, then dissolved in NMP, reprecipitated with ethyl acetate, and the precipitated solid was filtered to obtain cyclic compound A (94.4 g, 91%). It was.
The structure of the cyclic compound A was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Example 1 [Synthesis of Compound B]

After adding the cyclic compound (A) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, ethyl adamantyl bromoacetate (1.50 g, 5.00 mmol) diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml). ) And 1,8-diazabicyclo [5,4,0] -7-undecene (0.37 ml, 2.5 mmol) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. To the solution obtained by concentrating the obtained organic layer, ion-exchanged water and a small amount of salt were added, and then the precipitate was filtered off to obtain cyclic compound C (1.9 g).
The structure of the cyclic compound C was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.
In ¹ H-NMR, the degree of protection is determined by protons of methylene sandwiched between the benzene ring on the side where no ring is formed around 6.6 ppm and 7.5 ppm, and both esters in the protecting group near 4.8 ppm. It calculated from the integrated value, and also calculated by analyzing by liquid chromatography.
The average number of groups represented by the formula (II) was 4.24 (protection rate × 8).

Example 2 [Synthesis of Compound C]
Under a nitrogen stream, ethyl adamantyl bromoacetate 4 was added to a mixture of 3.0 g (2.93 mmol) of the cyclic compound (A) prepared in Production Example 1, 1.64 g (15.5 mmol) of sodium carbonate and 100 ml of dimethylformamide. After dropwise addition of .65 g (15.5 mmol), the mixture was stirred with heating at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and the white precipitate precipitated by adding water was filtered off to obtain 2.0 g of cyclic compound C, and the results of ¹ H-NMR measurement are shown in FIG. It was confirmed that the structure was as follows.
The average number of groups represented by the formula (II) was 5.2.

Comparative Example 1 [Synthesis of Compound D]

After adding cyclic compound A prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) was added. Further, the mixture was stirred at room temperature, triethylamine (0.7 ml, 5.00 mmol), ethyl adamantyl bromoacetate (1.50 g, 5.00 mmol) diluted with anhydrous N-methyl-2-pyrrolidone (1 ml), And 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) was added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. To the solution obtained by concentrating the obtained organic layer, ion-exchanged water and a small amount of salt were added, and then the precipitate was filtered off to obtain cyclic compound D (1.8 g).
The structure of the cyclic compound D was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Example 3 [Synthesis of Compound E]
After adding the cyclic compound (1) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, 1-ethylcyclohexyl 2-bromoacetate (1.25 g, diluted with triethylamine (0.7 ml, 5.00 mmol), anhydrous N-methyl-2-pyrrolidone (1 ml)). 5.00 mmol) and 1,8-diazabicyclo [5,4,0] -7-undecene (0.37 ml, 2.5 mmol) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. To the solution obtained by concentrating the obtained organic layer, ion-exchanged water and a small amount of salt were added, and then the precipitate was filtered off to obtain cyclic compound E (1.8 g).
The structure of the cyclic compound E was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.
The average number of groups represented by the formula (II) was 4.48.

Comparative Example 2 [Synthesis of Compound F]

After adding the cyclic compound (A) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, 1-ethylcyclohexyl 2-bromoacetate (1.25 g, diluted with triethylamine (0.7 ml, 5.00 mmol), anhydrous N-methyl-2-pyrrolidone (1 ml)). 5.00 mmol) and 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. To the solution obtained by concentrating the obtained organic layer, ion-exchanged water and a small amount of salt were added, and then the precipitate was filtered off to obtain cyclic compound F (1.7 g).
The structure of the cyclic compound F was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

[Evaluation]
A photoresist solution composed of a substrate, PAG, quencher, and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
As a base material, 77 parts by weight of each of the compounds obtained in Example 1-3 and Comparative Examples 1 and 2 were used, and triphenylsulfonium nonafluorobutanesulfonate was used as the PAG, as shown in Table 1, respectively. 4 parts by weight of 4-diazabicyclo (2,2,2) octane was used. These solid components were dissolved in propylene glycol monomethyl ether so as to have a concentration of 2.5% by weight.
The photoresist solutions containing the compounds obtained in Example 1-3 and Comparative Examples 1 and 2 are each spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment and pre-baked (pre-exposure baking). As a result, a thin film was formed. Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), PEB (post-exposure baking), and then a 60% aqueous solution of tetrabutylammonium hydroxide having a concentration of 2.38 wt%. The film was developed for 2 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream.
Table 1 shows the resolution (half pitch) and sensitivity (necessary electron beam dose) obtained when a line / space pattern having a size of 1/1 was obtained from the observation result by a scanning electron microscope. The results were the same even when tri-n-octylamine was used in place of 1,4-diazabicyclo (2,2,2) octane as the quencher.
The substrate having the photoresist thin film was irradiated with EUV light (wavelength: 13.5 nm) using an EUV exposure apparatus instead of the electron beam drawing apparatus. Thereafter, a post-processing operation similar to that at the time of electron beam drawing was performed. When observed with a scanning electron microscope, it was observed that the resolution was the same as in the case of electron beam drawing.

  The cyclic compound of the present invention can be suitably used for a photoresist substrate or composition, particularly for an extreme ultraviolet light and / or a photoresist substrate or composition for an electron beam. The cyclic compound of the present invention can also be used as an additive for adjusting the solubility. The photoresist base material and the composition thereof of the present invention are suitably used in the electrical / electronic field and the optical field of semiconductor devices and the like.

Claims (15)

The cyclic compound represented by the following formula (I).

[In the formula, Ar is an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms and at least an alkylene group and an ether bond. A group in which one or more of them are combined.
Each R is a group represented by the following formula (II).

(In the formula, A ¹ is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
R ³ represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) , A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and one or more selected from an ester bond, a carbonate ester bond or an ether bond Group).
x is an integer of 1 to 5, and y is an integer of 0 to 3.
A plurality of R ³ , Ar and A ¹ may be the same or different.
R ¹ is a group represented by the formula (II), a group similar to the group represented by R ³ or a solubility adjusting group,
Of the two R ¹ existing on the same aromatic ring, one R ¹ is the same group as the group represented by the formula (II) or the group represented by R ³ , and the other is the solubility control. And at least one of R ¹ is a group represented by the formula (II).
R ² is hydrogen, a hydroxyl group, a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ] The cyclic compound according to claim 1, wherein R ² is hydrogen. The cyclic compound according to claim 1, wherein the OR ³ is an acid dissociable, dissolution inhibiting group.   The cyclic compound according to claim 3, wherein the acid dissociable, dissolution inhibiting group is a substituent having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure and having a molecular weight of 15 to 2,000. . The cyclic compound according to claim 1 or 2, wherein the OR ³ is any one of the following formulas (III) to (VI).

(In the above formulas (III) to (VI),
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. ) The cyclic compound according to claim 1, wherein the OR ³ is any one of groups represented by the following formulae.

(In the formula, r represents any of the substituents having no r among the substituents represented by the above formula.) The solubility adjusting group for R ¹ and R ⁴ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. Substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, alkoxyalkyl group, silyl group, or these groups and divalent groups (Substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or an ester bond, a carbonate ester bond or an ether of these groups. The cyclic compound according to any one of claims 1 to 6, which is a group in which one or more bonds are bonded to each other.   The photoresist base material containing the cyclic compound in any one of Claims 1-7. A photoresist group containing a cyclic compound represented by the following formula (I ′) and having an average number of groups represented by the following formula (II) of more than 4 and 8 or less, which one molecule of the cyclic compound has Wood.

[In the formula, Ar is an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms and at least an alkylene group and an ether bond. A group in which one or more of them are combined.
Each R is a group represented by the following formula (II).

(In the formula, A ¹ is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
R ³ represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) , A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and one or more selected from an ester bond, a carbonate ester bond or an ether bond Group).
x is an integer of 1 to 5, and y is an integer of 0 to 3.
A plurality of R ³ , Ar and A ¹ may be the same or different.
R ¹ is a group represented by the formula (II), a group similar to the group represented by R ³ or a solubility adjusting group,
Of the two R ¹ existing on the same aromatic ring, one R ¹ is the same group as the group represented by the formula (II) or the group represented by R ³ , and the other is the solubility control. It is a group.
R ² is hydrogen, a hydroxyl group, a group represented by OR ³ , a group represented by OR ⁴ (R ⁴ is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ]   A photoresist composition comprising the photoresist base material according to claim 8 or 9 and a solvent.   The photoresist composition according to claim 10, further comprising a photoacid generator.   The photoresist composition according to claim 10 or 11, further comprising a basic organic compound as a quencher.   The fine processing method using the photoresist composition in any one of Claims 10-12.   A semiconductor device manufactured by the microfabrication method according to claim 13.   An apparatus comprising the semiconductor device according to claim 14.

Images