JPWO2009119784A1 - CYCLIC COMPOUND, PROCESS FOR PRODUCING CYCLIC COMPOUND, PHOTORESIST BASE COMPRISING CYCLIC COMPOUND, PHOTORESIST COMPOSITION, FINE PROCESSING METHOD, SEMICONDUCTOR DEVICE AND DEVICE - Google Patents

Abstract

A cyclic compound represented by any one of the following formulas (A-1) to (A-3), wherein a plurality of Rs are each an acid-dissociable, dissolution-inhibiting group or a hydroxyl group, and an acid-dissociable, dissolution-inhibiting group A photoresist base material comprising a cyclic compound having an average substitution rate of 55 to 90 percent.

Description

  The present invention relates to a photoresist base material used in the electrical / electronic field such as a semiconductor, an optical field, etc., and more particularly to a photoresist base material for ultrafine processing. The present invention also 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-productivity, high-resolution microfabrication 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). Further, Patent Document 4 discloses calix resorcinarene compounds, but these compounds are considered to be partially insoluble and are not composed of a photoresist base material but are made of a known polymer. It is only described as an additive to the photoresist substrate. On the other hand, in the current semiconductor manufacturing process, a photoresist substrate is required to have high solubility in a coating solvent because it is dissolved in a solvent and proceeds to a film forming process. Therefore, the inventor has also proposed a calix resorcinarene compound having improved coating solvent solubility (see Patent Document 5).

According to Non-Patent Document 1, in formulas (B-1) and (B-4) described later, R ′ is a methyl group, a phenyl group, or a 4-isopropylphenyl group, and all R A cyclic compound in which is a tert-butoxycarbonylmethoxy group, a tert-butoxycarbonyloxy group, or an acetoxy group is disclosed. When this compound is used as a photoresist, it is disclosed that it can be used as a dissolution inhibitor in a photoresist composition comprising a known polymer substrate, and fine processing with a half pitch of 40 nm width is possible. Yes. However, microfabrication requires application of extremely high energy of 115 microcoulomb / cm ² as sensitivity, and it cannot be said that the performance is sufficient as a photoresist base material.
JP 2002-055557 A JP 2004-191913 A Japanese Patent Laying-Open No. 2005-075757 US Pat. No. 6,093,517 JP 2007-197389 A Chemistry of Materials, Vol. 20, 341-356 (2008)

The calixresorcinarene compound is a developer (generally an aqueous 2.38% tetramethylammonium hydroxide solution) when it is easily dissolved in a solvent and a photoresist thin film is formed by spin coating or the like. It does not satisfy the two conditions that the dissolution resistance is sufficient.
An object of the present invention is to provide a photoresist base material that is excellent in solubility in a coating solvent and has a dissolution resistance to a developer.
Another object of the present invention is to obtain a photoresist base material that can be finely processed and has excellent sensitivity.

The present inventors have introduced the acid dissociable dissolution inhibiting group in the calix resorcinarene compound, that is, when the average substitution rate by the acid dissociable dissolution inhibiting group is a specific value, while easily dissolving in the solvent, In addition, the present invention was completed by finding that the developer has a dissolution resistance.
In addition, the present inventors specify the introduction rate of acid dissociable dissolution inhibiting groups containing an alicyclic structure in the calix resorcinalene compound, that is, the average substitution rate by acid dissociable dissolution inhibiting groups containing an alicyclic structure. In the case of this value, the present invention was completed by finding that the developer is easily dissolved in a solvent and the developer has a dissolution resistance.

［式中、Ｒ’はそれぞれ水素、水酸基、アルコキシル基、アリーロキシ基、炭素数１〜１２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３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、式（Ａ−４）で表される芳香族基、式（Ａ−５）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基を表す。

（式中、Ｒはそれぞれ酸解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。ｘが２以上のときＲは同一でも異なっていてもよい。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、又は式（Ａ−４）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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６〜１２の芳香族基、又はこれら基のうち２種以上を組み合わせて構成される基である。
ｙは１〜４の整数を表す。ｙが２以上のときＲ^１、Ｒ^２は同一でも異なっていてもよい。）］
２．前記酸解離性溶解抑止基が、下記式（Ａ−６）〜（Ａ−１０）から選択される基である１記載のフォトレジスト基材。

（式（Ａ−９），（Ａ−１０）中、ｒは下記のいずれかの置換基を表す。式（Ａ−９）のｒは同一でも異なっていてもよい。）

３．前記環状化合物が下記式（Ａ−１１）で表され、式中、Ｒはそれぞれ式（Ａ−１２）で表される置換基又は水酸基であり、式（Ａ−１２）で表される置換基の平均置換率が６０〜９０パーセントである環状化合物である２記載のフォトレジスト基材。

４．前記環状化合物が下記式（Ａ−１３）で表され、式中、Ｒはそれぞれ式（Ａ−１４）で表される置換基又は水酸基であり、式（Ａ−１４）で表される置換基の平均置換率が５５〜８０パーセントである環状化合物である２記載のフォトレジスト基材。

５．１〜４のいずれか記載のフォトレジスト基材と溶剤を含有するフォトレジスト組成物。
６．５記載のフォトレジスト組成物を用いた微細加工方法。
７．６記載の微細加工方法により作製した半導体装置。
８．７記載の半導体装置を備えた装置。
９．下記式（Ｂ−１）〜（Ｂ−６）のいずれかで表される立体的相対配置を有する環状化合物であって、前記環状化合物の立体異性体全体に対する比率が９０モル％以上である環状化合物。

〔式中、Ｒはそれぞれ酸解離性溶解抑止基又は水酸基であり、
Ｒ’はそれぞれ水酸基、エーテル基（−ＯＲ^ａ、Ｒ^ａは炭素数１〜１０の直鎖状脂肪族炭化水素基、炭素数３〜８の分岐を有する脂肪族炭化水素基、炭素数３〜８の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ナフチル基である。）、炭素数１〜１２の直鎖状脂肪族炭化水素基、炭素数３〜１２の分岐を有する脂肪族炭化水素基、炭素数３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、下記式（Ｂ−７）で表される芳香族基、下記式（Ｂ−８）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基である。

（式中、Ｒは酸解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、前記式（Ｂ−７）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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の分岐を有する脂肪族炭化水素基、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６〜１２の芳香族基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基である。
ｙは１〜４の整数である。）
Ｒは互いに同一でも異なっていても良く、Ｒ’は互いに同一でも異なっていても良い。
但し、前記式（Ｂ−１）及び（Ｂ−４）において、Ｒ’がメチル基、フェニル基、又は４−イソプロピルフェニル基であり、かつ、Ｒの全てが下記式（Ｂ−９）である場合を除く。〕

１０．前記酸解離性溶解抑止基が、前記式（Ｂ−９）、又は、下記式（Ｂ−１０）〜（Ｂ−３６）から選択される基である９に記載の環状化合物。

（式中、ｒはそれぞれ上記式（Ｂ−９）〜（Ｂ−３４）、下記式（ｒ−１）、（ｒ−２）で表される置換基のいずれかを表す。）

１１．下記式（Ｂ−１）〜（Ｂ−６）のいずれかで表される立体的相対配置を有する環状化合物からなり、前記環状化合物の立体異性体全体に対する比率が９０モル％以上であるフォトレジスト基材。

[式中、Ｒはそれぞれ酸解離性溶解抑止基又は水酸基であり、
Ｒ’はそれぞれ水酸基、エーテル基（−ＯＲ^ａ、Ｒ^ａは炭素数１〜１０の直鎖状脂肪族炭化水素基、炭素数３〜８の分岐を有する脂肪族炭化水素基、炭素数３〜８の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ナフチル基である。）、炭素数１〜１２の直鎖状脂肪族炭化水素基、炭素数３〜１２の分岐を有する脂肪族炭化水素基、炭素数３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、下記式（Ｂ−７）で表される芳香族基、下記式（Ｂ−８）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基である。

（式中、Ｒは酸解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、前記式（Ｂ−７）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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の分岐を有する脂肪族炭化水素基、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６〜１２の芳香族基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基である。
ｙは１〜４の整数である。）
Ｒは互いに同一でも異なっていても良く、Ｒ’は互いに同一でも異なっていても良い。]
１２．前記酸解離性溶解抑止基が、下記式（Ｂ−９）〜（Ｂ−３６）から選択される基である１１に記載のフォトレジスト基材。

（式中、ｒはそれぞれ上記式（Ｂ−９）〜（Ｂ−３４）、下記式（ｒ−１）、（ｒ−２）で表される置換基のいずれかを表す。）

１３．前記Ｒ’が、それぞれ炭素数３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、前記式（Ｂ−７）で表される芳香族基、前記式（Ｂ−８）で表される置換基、又はこれら基のうち２種以上を組み合わせて構成される置換基である１１又は１２に記載のフォトレジスト基材。
１４．前記式（Ｂ−１）又は（Ｂ−４）で表され、Ｒがすべて下記式（Ｂ−９）で表される基であり、Ｒ’がそれぞれ、メチル基、フェニル基、又は４−イソプロピルフェニル基である１１に記載のフォトレジスト基材。

１５．１１〜１４いずれかに記載のフォトレジスト基材と溶剤を含有するフォトレジスト組成物。
１６．１５に記載のフォトレジスト組成物を用いた微細加工方法。
１７．１６記載の微細加工方法により作製した半導体装置。
１８．１７記載の半導体装置を備えた装置。
１９．レゾルシノール、ピロガロール、１，２，３，５−テトラヒドロベンゼンから選ばれる多価フェノール化合物と酸触媒である固体状の有機スルホン酸の混合物に、沸点が９０℃以上であるアルコール類を溶媒として加え、
その後、下記式（Ｂ−２４）で表されるアルデヒド化合物を加えて反応溶液として、９０℃以上１５０℃以下の温度で環化縮合反応させ、下記式（Ｂ−１’）〜（Ｂ−３’）で表される環状化合物を製造し、
次いで、式（Ｂ−１’）〜（Ｂ−３’）で表される環状化合物上の水酸基の少なくとも１つに酸解離性溶解抑止基を導入する、
９に記載の式（Ｂ−１）〜（Ｂ−３）で表される環状化合物の製造方法。

（式中、Ｒ’は請求項９に示すＲ’と同じ基を示す。）
２０．下記式（Ｃ−１）〜（Ｃ−３）のいずれかで表される環状化合物であって、式中の複数Ｒはそれぞれ脂環式構造を含む酸解離性溶解抑止基又は水酸基であり、前記酸解離性溶解抑止基の平均置換率が２０〜６０パーセントである環状化合物からなるフォトレジスト基材。

〔式中、Ｒ’はそれぞれ水素、水酸基、アルコキシ基、アリーロキシ基、炭素数１〜１２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３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、式（Ｃ−４）で表される芳香族基、式（Ｃ−５）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基を表す。

（式中、Ｒはそれぞれ脂環式構造を含む酸解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。ｘが２以上のときＲは同一でも異なっていてもよい。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、又は式（Ｃ−４）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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６〜１２の芳香族基、又はこれら基のうち２種以上を組み合わせて構成される基である。
ｙは１〜４の整数を表す。ｙが２以上のときＲ^１、Ｒ^２は同一でも異なっていてもよい。）］
２１．前記酸解離性溶解抑止基が、下記式（Ｃ−６）〜（Ｃ−３１）から選択される基である２０記載のフォトレジスト基材。

（式中、ｒはそれぞれ上記式（Ｃ−６）〜（Ｃ−２９）で表される置換基のいずれかを表す。）
２２．前記環状化合物が下記式（Ｃ−３３）で表され、式中、Ｒはそれぞれ式（Ｃ−３４）で表される置換基又は水酸基であり、式（Ｃ−３４）で表される置換基の平均置換率が３５〜５０パーセントである環状化合物である２１記載のフォトレジスト基材。

２３．前記環状化合物が下記式（Ｃ−３３）で表され、式中、Ｒはそれぞれ式（Ｃ−３４’）で表される置換基又は水酸基であり、式（Ｃ−３４’）で表される置換基の平均置換率が２０〜６０パーセントである環状化合物である２１記載のフォトレジスト基材。

２４．２０〜２３のいずれか記載のフォトレジスト基材と溶剤を含有するフォトレジスト組成物。
２５．２４記載のフォトレジスト組成物を用いた微細加工方法。
２６．２５記載の微細加工方法により作製した半導体装置。
２７．２６記載の半導体装置を備えた装置。According to the present invention, the following photoresist base materials, cyclic compounds and the like are provided.
1. A cyclic compound represented by any one of the following formulas (A-1) to (A-3), wherein a plurality of Rs are each an acid dissociable, dissolution inhibiting group or a hydroxyl group, and an acid dissociable, dissolution inhibiting group A photoresist base material comprising a cyclic compound having an average substitution rate of 55 to 90 percent.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxyl group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( A-4) represents an aromatic group represented by formula (A-5), a substituent represented by formula (A-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, each R is an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (A-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]]
2. 2. The photoresist base material according to 1, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (A-6) to (A-10).

(In formulas (A-9) and (A-10), r represents one of the following substituents. R in formula (A-9) may be the same or different.)

3. The cyclic compound is represented by the following formula (A-11), wherein R is a substituent or a hydroxyl group represented by the formula (A-12), and a substituent represented by the formula (A-12). 3. The photoresist substrate according to 2, which is a cyclic compound having an average substitution rate of 60 to 90 percent.

4). The cyclic compound is represented by the following formula (A-13), wherein R is a substituent represented by the formula (A-14) or a hydroxyl group, and a substituent represented by the formula (A-14). 3. The photoresist substrate according to 2, which is a cyclic compound having an average substitution rate of 55 to 80 percent.

The photoresist composition containing the photoresist base material and solvent in any one of 5.1-4.
A fine processing method using the photoresist composition according to 6.5.
A semiconductor device manufactured by the microfabrication method according to 7.6.
A device comprising the semiconductor device according to 8.7.
9. A cyclic compound having a steric relative configuration represented by any of the following formulas (B-1) to (B-6), wherein the ratio of the cyclic compound to the total stereoisomer is 90 mol% or more Compound.

[Wherein R is an acid dissociable, dissolution inhibiting group or hydroxyl group,
R ′ is a hydroxyl group, an ether group (—OR ^a , R ^a is ^a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and 3 to 3 carbon atoms, respectively. 8 monocyclic cycloaliphatic hydrocarbon group, C4-C10 bicyclic cycloaliphatic hydrocarbon group, phenyl group, naphthyl group.), C1-C12 linear aliphatic carbonization A hydrogen group, a C3-C12 branched aliphatic hydrocarbon group, a C3-C12 monocyclic cycloaliphatic hydrocarbon group, a C4-C10 bicyclic cycloaliphatic hydrocarbon group, A phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B-8), or It is a substituent constituted by combining two or more of these substituents.

(In the formula, R represents an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (B-7).
R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a substituent formed by combining two or more of these substituents It is.
y is an integer of 1-4. )
R may be the same or different, and R ′ may be the same or different.
However, in said Formula (B-1) and (B-4), R 'is a methyl group, a phenyl group, or 4-isopropylphenyl group, and all of R is following formula (B-9). Except cases. ]

10. The cyclic compound according to 9, wherein the acid dissociable, dissolution inhibiting group is a group selected from the formula (B-9) or the following formulas (B-10) to (B-36).

(Wherein, r represents one of the substituents represented by the above formulas (B-9) to (B-34), the following formulas (r-1) and (r-2)).

11. A photoresist comprising a cyclic compound having a steric relative configuration represented by any of the following formulas (B-1) to (B-6), wherein the ratio of the cyclic compound to the total stereoisomer is 90 mol% or more Base material.

Wherein R is an acid dissociable, dissolution inhibiting group or a hydroxyl group,
R ′ is a hydroxyl group, an ether group (—OR ^a , R ^a is ^a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and 3 to 3 carbon atoms, respectively. 8 monocyclic cycloaliphatic hydrocarbon group, C4-C10 bicyclic cycloaliphatic hydrocarbon group, phenyl group, naphthyl group.), C1-C12 linear aliphatic carbonization A hydrogen group, a C3-C12 branched aliphatic hydrocarbon group, a C3-C12 monocyclic cycloaliphatic hydrocarbon group, a C4-C10 bicyclic cycloaliphatic hydrocarbon group, A phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B-8), or It is a substituent constituted by combining two or more of these substituents.

(In the formula, R represents an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (B-7).
R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a substituent formed by combining two or more of these substituents It is.
y is an integer of 1-4. )
R may be the same or different, and R ′ may be the same or different. ]
12 12. The photoresist base material according to 11, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (B-9) to (B-36).

(Wherein, r represents one of the substituents represented by the above formulas (B-9) to (B-34), the following formulas (r-1) and (r-2)).

13. R ′ is a monocyclic cycloaliphatic hydrocarbon group having 3 to 12 carbon atoms, a polycyclic cycloaliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a p-phenylphenyl group, a p-tert. -A butylphenyl group, a naphthyl group, an aromatic group represented by the formula (B-7), a substituent represented by the formula (B-8), or a combination of two or more of these groups. The photoresist base material of 11 or 12 which is a substituent.
14 It is represented by the formula (B-1) or (B-4), R is a group represented by the following formula (B-9), and R ′ is a methyl group, a phenyl group, or 4-isopropyl, respectively. 12. The photoresist base material according to 11, which is a phenyl group.

15. A photoresist composition comprising the photoresist substrate according to any one of 11 to 14 and a solvent.
16. A fine processing method using the photoresist composition according to 16.15.
A semiconductor device manufactured by the microfabrication method according to 17.16.
A device comprising the semiconductor device according to 18.17.
19. To a mixture of a polyphenol compound selected from resorcinol, pyrogallol, 1,2,3,5-tetrahydrobenzene and a solid organic sulfonic acid as an acid catalyst, an alcohol having a boiling point of 90 ° C. or more is added as a solvent,
Thereafter, an aldehyde compound represented by the following formula (B-24) is added to form a cyclization condensation reaction as a reaction solution at a temperature of 90 ° C. or higher and 150 ° C. or lower, and the following formulas (B-1 ′) to (B-3) ') To produce a cyclic compound represented by
Next, an acid dissociable, dissolution inhibiting group is introduced into at least one of the hydroxyl groups on the cyclic compound represented by the formulas (B-1 ′) to (B-3 ′).
A method for producing a cyclic compound represented by formulas (B-1) to (B-3) according to claim 9.

(Wherein R ′ represents the same group as R ′ shown in claim 9).
20. A cyclic compound represented by any one of the following formulas (C-1) to (C-3), wherein a plurality of Rs are acid dissociable, dissolution inhibiting groups or hydroxyl groups each containing an alicyclic structure, A photoresist base material comprising a cyclic compound having an average substitution rate of the acid dissociable, dissolution inhibiting group of 20 to 60 percent.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( An aromatic group represented by C-4), a substituent represented by formula (C-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, R is an acid dissociable, dissolution inhibiting group or a hydroxyl group each having an alicyclic structure, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different. )

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (C-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]]
21. 21. The photoresist base material according to 20, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (C-6) to (C-31).

(Wherein, r represents any of the substituents represented by the above formulas (C-6) to (C-29)).
22. The cyclic compound is represented by the following formula (C-33), wherein R is a substituent represented by the formula (C-34) or a hydroxyl group, and a substituent represented by the formula (C-34). 22. The photoresist substrate according to 21, which is a cyclic compound having an average substitution rate of 35 to 50 percent.

23. The cyclic compound is represented by the following formula (C-33), wherein R is a substituent or a hydroxyl group represented by the formula (C-34 ′), and is represented by the formula (C-34 ′). 22. The photoresist substrate according to 21, which is a cyclic compound having an average substitution rate of substituents of 20 to 60 percent.

24. A photoresist composition comprising the photoresist base material according to any one of 20 to 23 and a solvent.
A fine processing method using the photoresist composition according to 25.24.
A semiconductor device manufactured by the microfabrication method described in 26.25.
A device comprising the semiconductor device according to 27.26.

  According to the present invention, when a photoresist thin film is formed by spin coating or the like while being easily dissolved in a solvent, it is dissolved in a developer (generally, 2.38% tetramethylammonium hydroxide aqueous solution). A photoresist substrate having high resistance can be provided.

Since the cyclic compound and the photoresist base material of the present invention have a predetermined steric relative arrangement, the dissolution resistance to a developer (generally an aqueous 2.38% tetramethylammonium hydroxide solution) is sufficiently high, and It is easy to dissolve in a solvent for producing a photoresist composition.
Moreover, according to the manufacturing method of the cyclic compound of this invention, the cyclic compound which has a specific three-dimensional relative configuration can be manufactured. For this reason, since the three-dimensional relative arrangement | positioning of a cyclic compound is controllable, when it uses as a photoresist, it becomes easy to control the reactivity with respect to irradiation of EUVL or an electron beam. As a result, the performance of the photoresist, such as resolution and sensitivity, can be dramatically improved.

1 is a ¹ H-NMR chart of a cyclic compound produced in Example 1. FIG. 2 is a ¹ H-NMR chart of a crude product solid produced in Example 2. FIG. 2 is a ¹ H-NMR chart of a cyclic compound produced in Example 2. FIG. 2 is a ¹ H-NMR chart of a cyclic compound produced in Example 3. FIG. 4 is a ¹ H-NMR chart of a cyclic compound produced in Example 4. FIG. 2 is a ¹ H-NMR chart of a cyclic compound produced in Comparative Example 1. FIG. 2 is a ¹ H-NMR chart of a cyclic compound produced in Example 7. FIG. 2 is a ¹ H-NMR chart of a cyclic compound produced in Example 8. FIG.

［式中、Ｒ’はそれぞれ水素、水酸基、アルコキシル基、アリーロキシ基、炭素数１〜１２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３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、式（Ａ−４）で表される芳香族基、式（Ａ−５）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基を表す。

（式中、Ｒはそれぞれ酸解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。ｘが２以上のときＲは同一でも異なっていてもよい。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、又は式（Ａ−４）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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６〜１２の芳香族基、又はこれら基のうち２種以上を組み合わせて構成される基である。
ｙは１〜４の整数を表す。ｙが２以上のときＲ^１、Ｒ^２は同一でも異なっていてもよい。）］Hereinafter, the first aspect of the present invention will be described.
The photoresist base material of the first aspect of the present invention (hereinafter sometimes referred to as the first photoresist base material) is represented by any of the following formulas (A-1) to (A-3). It is a cyclic compound, and a plurality of R in the formula is an acid dissociable, dissolution inhibiting group or a hydroxyl group, and the acid dissociable, dissolution inhibiting group has an average substitution rate of 55 to 90 percent.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxyl group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( A-4) represents an aromatic group represented by formula (A-5), a substituent represented by formula (A-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, each R is an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (A-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]]

The “average substitution rate” in the first aspect of the present invention is defined as follows.
An acid dissociable, dissolution inhibiting group precursor is condensed with a cyclic compound in which all of R is a hydroxyl group by a conventionally known method to produce an acid dissociable, dissolution inhibiting group precursor of the cyclic compound. Depending on the reaction conditions, the number of substitutions 0 to [the number of R in the cyclic compound] (8 in the case of the cyclic compound (A-1), 12 in the case of the cyclic compound (A-2), and the cyclic compound (A-3) In this case, a mixture of a plurality of substitution number isomers selected from 16) is obtained, and the mixture has a certain distribution.
In the first aspect of the present invention, the average substitution rate is calculated from the distribution by the following formula and expressed as “average substitution rate X percent”.
{(Abundance of substitution isomers with 0 substitutions) × 0 + (Abundance of substitution isomers with 1 substitutions) × 1 + (Abundance of substitution isomers with 2 substitutions) × 2 +... + ( Substitution number [number of R in the cyclic compound] abundance of substitution number isomers) × [number of R in the cyclic compound]} ÷ (abundance of all substitution isomers) = average substitution rate (percent)

In general, this distribution shows a normal distribution, but depending on the structure of the cyclic compound, the stereoisomer configuration, and the combination of the acid dissociable, dissolution inhibiting group precursor, there are combinations that react easily, and combinations that do not react easily In some cases, it deviates from the normal distribution. Moreover, it becomes a specific distribution by the combination of the raw material to be used and reaction conditions.
The abundance of each substituted number isomer is measured by liquid chromatography (hereinafter referred to as LC) after separating and identifying each structure with a liquid chromatograph mass spectrometer (hereinafter referred to as LC / MS). It is determined by the peak area ratio indicating each substitution number isomer.

  The average substitution rate can be arbitrarily adjusted depending on the reaction conditions. For example, increasing the amount of the acid dissociable dissolution inhibiting group precursor charged, increasing the amount of the condensing agent added to condense the acid dissociable dissolution inhibiting group precursor, extending the reaction time, increasing the reaction temperature Increasing the average substitution rate increases, reducing the amount of the acid dissociable dissolution inhibiting group precursor charged, reducing the amount of the condensing agent added to condense the acid dissociable dissolution inhibiting group precursor, reaction The average substitution rate is lowered by shortening the time and lowering the reaction temperature. When a cyclic compound having an average substitution rate of 55 to 90% is easily dissolved in a solvent for preparing a photoresist composition and a photoresist thin film is formed by spin coating or the like, a developing solution (general Has a sufficiently high solubility in 2.38% tetramethylammonium hydroxide aqueous solution) and can be suitably used as a photoresist substrate.

  When the photoresist substrate is a cyclic compound of the general formula (A-11) and R is an acid dissociable, dissolution inhibiting group or hydroxyl group represented by the formula (A-12), the formula (A-12) When the average substitution rate of the acid dissociable, dissolution inhibiting group represented by () is 60 to 75 percent, a small amount of the acid dissociable, dissolution inhibiting group is eliminated upon exposure, so that the solubility in the developer is increased. As a result, the sensitivity as a photoresist increases. On the other hand, if the average substitution rate is 75 to 90%, the fine pattern to be formed becomes difficult to dissolve in the alkali developer, so that the smoothness of the desired fine pattern side wall surface is disturbed, the wall surface height is not lowered, and the like. This is preferable in terms of resolution. That is, although the most preferable range differs depending on whether the proposed photoresist emphasizes sensitivity, resolution, or the balance between them, the average substitution rate is 55 to 90%. If so, both sensitivity and resolution show practically satisfactory performance, preferably 60 to 90%.

  Similarly to the above, when it is a cyclic compound of the general formula (A-13) and R is a substituent or a hydroxyl group represented by the formula (A-14), it is represented by the formula (A-14). When the average substitution rate of the substituent is 55 to 70 percent, the sensitivity as a photoresist is increased, and when it is 70 to 80 percent, the resolution is preferable. In the case of this photoresist base material, if the average substitution rate is 55 to 90%, both sensitivity and resolution exhibit performance that is practically satisfactory, and preferably 55 to 80%.

  The cyclic compound of the first aspect of the present invention (hereinafter sometimes referred to as the first cyclic compound) 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.

The acid dissociable, dissolution inhibiting group is a substituent that replaces the hydrogen atom of OH in the alkali-soluble groups listed above, and is —C (R _11a ) (R _12a ) (R _13a ), —C (R _14a ) ( R _15a ) (OR _16a ) and —CO—OC (R _11a ) (R _12a ) (R _13a ) are preferred.

Here, R _{11a to} R _13a each independently represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group. R _14a and R _15a each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _16a represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group. Two of R _11a , R _12a and R _13a , or two of R _14a , R _15a and R _16a may be bonded to form a ring.

The alkyl group, cycloalkyl group and aralkyl group in R _{11a to} R _16a are cycloalkyl groups, hydroxy groups, alkoxy groups, oxo groups, alkylcarbonyl groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, alkylaminocarbonyls as substituents. Group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The aryl group and alkenyl group in R _{11a to} R _13a and R _16a are, as substituents, an alkyl group, a cycloalkyl group, a hydroxy group, an alkoxy group, an oxo group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an alkyl group. An aminocarbonyl group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The alkyl group, cycloalkyl group, alkenyl group, and aralkyl group of R _{11a to} R _16a each have an ether group, thioether group, carbonyl group, ester group, amide group, urethane group, ureido group, sulfonyl group, and sulfone group in the middle. You may have.

The acid dissociable, dissolution inhibiting group preferably has a total carbon number of 4 or more, more preferably 6 or more, and still more preferably 8 or more.
The acid dissociable, dissolution inhibiting group preferably contains an alicyclic structure or an aromatic ring structure. Examples of the alicyclic structure include a cyclopentane residue, a cyclohexane residue, a norbornane residue, and an adamantane residue. Examples of the aromatic ring structure include a benzene residue, a naphthalene residue, and an anthracene residue.
These alicyclic structures and aromatic ring structures may have a substituent at any position.

（式（Ａ−９），（Ａ−１０）中、ｒは下記のいずれかの置換基を表す。式（Ａ−９）のｒは同一でも異なっていてもよい。）

Although the preferable specific example of an acid dissociable dissolution inhibiting group is shown below, the 1st aspect of this invention is not limited to these.

(In formulas (A-9) and (A-10), r represents one of the following substituents. R in formula (A-9) may be the same or different.)

In the above formulas (A-1) to (A-3), R ′ is preferably a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, A phenyl group, a naphthyl group, an aromatic group represented by the formula (A-4), or a substituent represented by the formula (A-5), more preferably a linear fatty acid having 1 to 4 carbon atoms. An aromatic hydrocarbon group, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a phenyl group.
In the above formula (A-4), preferred acid dissociable, dissolution inhibiting groups for R are the same as R in formulas (A-1) to (A-3). x is preferably an integer of 1 to 2.
In the above formula (A-5), Ar is preferably a phenyl group or a naphthyl group. R ¹ and R ² are preferably a hydrogen atom, a methyl group, or an ethyl group. y is preferably an integer of 1 to 2.

A preferable cyclic compound used for the first photoresist base material of the present invention is represented by the following formula (A-11), wherein R is a substituent or a hydroxyl group represented by the formula (A-12), respectively. The cyclic compound whose average substitution rate of the substituent represented by Formula (A-12) is 60 to 90 percent.

Moreover, the preferable cyclic compound used for the 1st photoresist base material of this invention is represented by a following formula (A-13), and R is a substituent or a hydroxyl group each represented by a formula (A-14). It is a cyclic compound whose average substitution rate of the substituent represented by the formula (A-14) is 55 to 80 percent.

  Said cyclic compound can be used as a photoresist base material used in the ultrafine processing by lithography such as extreme ultraviolet light or electron beam.

The photoresist composition of the first aspect of the present invention (hereinafter sometimes referred to as the first photoresist composition) contains the above-mentioned photoresist base material and 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 first 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 mono Ethylene glycol monoalkyl ethers such as ethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; Propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Propylene glycol monoalkyl ethers; methyl lactate, ethyl lactate Lactate esters such as (EL); aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Other esters such as methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; tetrahydrofuran And cyclic ethers such as dioxane, 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 first photoresist composition of the present invention requires 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. However, 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, branched or cyclic fluorinated alkyl group; R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, 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 ^R52 , the alkyl 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.
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 , those having no substituent are 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 ″} and R ^{6 ″} each independently represents a substituted or unsubstituted aryl group or an alkyl group; R ^{4 ″} represents a linear, branched or cyclic group; 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 groups, alkoxy groups 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.

There is no restriction | limiting in particular as an alkyl group of R1 ^" -R3 ^" , For example, a C1-C10 linear, branched or cyclic alkyl group etc. are mentioned. 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 R ^{1 ″ to} R ^{3 ″} are all 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. It is preferable that all of R ^{5 ″} and R ^{6 ″} are 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 ″} .
As the alkyl group for R ^{5 ″ to} R ^{6 ″, the same as} the alkyl group for R ^{1 ″ to} R ^{3 ″} can be used.
Of these, it is most preferable that R ^{5 ″ to} R ^{6 ″} are all 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. Trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-methylphenyl) sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropro Sulfonate or its nonafluorobutane sulfonate, monophenyldimethylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenylmonomethylsulfonium trifluoromethane sulfonate, 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 heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate 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 first embodiment of 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.

式（３１）中、Ｒ^１６は、同一でも異なっていてもよく、それぞれ独立に、任意に置換された直鎖、分枝又は環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基又は任意に置換されたアラルキル基である。

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.

式（３２）中、Ｒ^１７は、同一でも異なっていてもよく、それぞれ独立に、任意に置換された直鎖、分枝又は環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基又は任意に置換されたアラルキル基である。

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.

式（３３）中、Ｒ^１８は、同一でも異なっていてもよく、それぞれ独立に、１以上の塩素原子及び１以上の臭素原子を有するハロゲン化アルキル基である。ハロゲン化アルキル基の炭素原子数は１〜５が好ましい。

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ル基であり、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 alkoxyl 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 first aspect of the present invention, an acid diffusion control 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. An agent (quencher) may be added to 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 first aspect of the present invention, if desired, further miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, a dissolution inhibitor, an increase 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 first 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 oxo acids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof 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 first aspect of the present invention, it is preferable to heat after irradiation (after exposure) in order to stably form a high-precision fine pattern. 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.

  In the case of the first photoresist base material of the present invention, an acid dissociable, dissolution inhibiting group is formed by exposing the resist film to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Desorption or change in structure causes dissolution in an alkaline developer. On the other hand, the non-exposed portion of the pattern is not dissolved in the alkaline developer, and as a result, a fine pattern is formed, thereby achieving the purpose as a photoresist substrate. That is, it is desirable that a photoresist base material having an acid dissociable, dissolution inhibiting group with an average substitution rate specified in the first aspect of the present invention or a thin film made of a photoresist base material is not dissolved in an alkali 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 first photoresist composition of the present invention, a wiring substrate can also 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.

  A semiconductor device can be produced by a microfabrication method using the first photoresist composition of the present invention. This semiconductor device can be provided in various devices such as an electric product (electronic device) such as a television receiver, a mobile phone, and a computer, a display, and a car controlled by a computer.

Hereinafter, the second aspect of the present invention will be described.
Hereinafter, the cyclic compound and the photoresist substrate of the second aspect of the present invention will be specifically described.
The cyclic compound of the second aspect of the present invention (hereinafter sometimes referred to as the second cyclic compound) and the photoresist base (hereinafter sometimes referred to as the second photoresist base) are represented by the following formula (B -1) to a cyclic compound represented by any one of (B-6). These compounds are characterized in that R ′ has a predetermined steric relative configuration.

Formulas (B-1) and (B-4) are isomers having different steric relative configurations of R ′. The same applies to Formula (B-2) and Formula (B-5), and Formula (B-3) and Formula (B-6).
The cyclic compound having the above three-dimensional relative arrangement has high solubility in a coating solvent and a developer.
In the second aspect of the present invention, the compounds represented by the formulas (B-1) to (B-3) or the formulas (B-4) to (B-6) rather than the isomer mixture in which the steric relative configuration is mixed. The higher the purity of one of the steric relative configurations of the isomer represented by the formula is preferred because the solubility in a coating solvent or a developer is higher. This improves the performance when used as a photoresist substrate. Preferably, the ratio of one of the isomers represented by the formulas (B-1) to (B-3) or the formulas (B-4) to (B-6) is 90 mol%. That's it.
In addition, the abundance ratio of isomers can be determined by ¹ H-NMR measurement.

In the above formulas (B-1) to (B-6), R is an acid dissociable, dissolution inhibiting group or a hydroxyl group.
The second cyclic compound of the present invention preferably contains at least two acid dissociable, dissolution inhibiting groups in one molecule of the compound. Since the 2nd cyclic compound of this invention increases the solubility with respect to an alkali developing solution by the effect | action of an acid, it is preferable to contain an alkali-soluble group.

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.

The acid dissociable, dissolution inhibiting group is a substituent that replaces the hydrogen atom of OH in the alkali-soluble groups listed above, and is —C (R _11a ) (R _12a ) (R _13a ), —C (R _14a ) ( R _15a ) (OR _16a ) and —CO—OC (R _11a ) (R _12a ) (R _13a ) are preferred.

Here, R _{11a to} R _13a each independently represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group. R _14a and R _15a each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _16a represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group. Two of R _11a , R _12a and R _13a , or two of R _14a , R _15a and R _16a may be bonded to form a ring.

The alkyl group, cycloalkyl group and aralkyl group in R _{11a to} R _16a are cycloalkyl groups, hydroxy groups, alkoxy groups, oxo groups, alkylcarbonyl groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, alkylaminocarbonyls as substituents. Group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The aryl group and alkenyl group in R _{11a to} R _13a and R _16a are, as substituents, an alkyl group, a cycloalkyl group, a hydroxy group, an alkoxy group, an oxo group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an alkyl group. An aminocarbonyl group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The alkyl group, cycloalkyl group, alkenyl group, and aralkyl group of R _{11a to} R _16a each have an ether group, thioether group, carbonyl group, ester group, amide group, urethane group, ureido group, sulfonyl group, and sulfone group in the middle. You may have.

The acid dissociable, dissolution inhibiting group preferably has a total carbon number of 4 or more, more preferably 6 or more, and still more preferably 8 or more.
The acid dissociable, dissolution inhibiting group preferably contains an alicyclic structure or an aromatic ring structure. Examples of the alicyclic structure include a cyclopentane residue, a cyclohexane residue, a norbornane residue, and an adamantane residue. Examples of the aromatic ring structure include a benzene residue, a naphthalene residue, and an anthracene residue.
These alicyclic structures and aromatic ring structures may have a substituent at any position.

Although the preferable specific example of an acid dissociable dissolution inhibiting group is shown, the 2nd aspect of this invention is not limited to these.

(In the formulas (B-35) and (B-36), r represents a substituent represented by the above formulas (B-9) to (B-34), the following formulas (r-1) and (r-2)). Represents either one.)

R ′ in formulas (B-1) to (B-6) is a hydroxyl group and an ether group (—OR ^a , R ^a is ^a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, and 3 to 8 carbon atoms, respectively. An aliphatic hydrocarbon group having a branched structure, a monocyclic cycloaliphatic hydrocarbon group having 3 to 8 carbon atoms, a polycyclic cycloaliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, and a naphthyl group. ), A linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aliphatic hydrocarbon group having 3 to 12 carbon atoms, a monocyclic cycloaliphatic hydrocarbon group having 3 to 12 carbon atoms, and a carbon number 4-10 polycyclic cycloaliphatic hydrocarbon group, phenyl group, p-phenylphenyl group, p-tert-butylphenyl group, naphthyl group, aromatic group represented by the following formula (B-7), A substituent represented by the formula (B-8), or a substituent constituted by combining two or more of these substituents It is.

  In formula (B-7), R represents an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5. Examples of the acid dissociable, dissolution inhibiting group are the same as R in the above formula (B-1) and the like.

In formula (B-8), Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (B-7).
R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a substituent formed by combining two or more of these substituents It is.
y is an integer of 1-4.

  R ′ represents a monocyclic cycloaliphatic hydrocarbon group having 3 to 12 carbon atoms, a polycyclic cycloaliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a p-phenylphenyl group, p-tert- A butylphenyl group, a naphthyl group, an aromatic group represented by the above formula (B-7), a substituent represented by the above formula (B-8), or a combination of two or more of these substituents. It is preferably a substituent.

  In addition, several R in each formula (B-1)-(B-6) may mutually be same or different. The same applies to R ′.

  In the above formulas (B-1) and (B-4), R ′ is a methyl group, a phenyl group, or a 4-isopropylphenyl group, and all of R are the above formula (B-9) This is not the second cyclic compound of the present invention. However, it corresponds to the second photoresist base material of the present invention.

  Of the isomers of the above formulas (B-1) to (B-3) and the isomers of the formulas (B-4) to (B-6), which isomer has a steric relative configuration showing superior performance. Is different depending on the combination of R and R ′ and cannot be defined unconditionally. However, when R is the above formula (B-9) and R ′ is a phenyl group, the isomer having the steric relative configuration of (B-1) to (B-3) is preferred. Compared with the isomers (B-4) to (B-6), sensitivity and resolution as a photoresist base material are further increased.

  In the second aspect of the present invention, it is represented by the above formula (B-1) or (B-4), R is a group represented by the formula (B-9), and R ′ is a methyl group. , Phenyl groups, or cyclic compounds that are 4-isopropylphenyl groups are particularly preferred as the photoresist substrate.

The second cyclic compound (second photoresist base material) of the present invention is, for example, the compound of the above (B-1) or (B-4), in which all Rs are hydroxyl groups, as described in the literature (Journal of Organic). Chemistry, Vol. 54, 1305-1312 (1989)). However, in order to synthesize the compound of formula (B-1) by this method, a long reaction time of 68 hours to 21 days is required. In addition, in order to synthesize the compound of formula (B-4), it is necessary to use different recrystallization solvents such as methanol and ethanol depending on the type of R ′. It is necessary and cannot be said to be a method that can be widely and generally adopted.
Therefore, it is preferable to manufacture by the method of the 2nd aspect of this invention demonstrated below.

  In the production method according to the second aspect of the present invention, a mixture of a polyhydric phenol compound selected from resorcinol, pyrogallol, and 1,2,3,5-tetrahydrobenzene and a solid organic sulfonic acid as an acid catalyst has a boiling point. An alcohol having a temperature of 90 ° C. or higher is added as a solvent, and then an aldehyde compound represented by the following formula (B-24) is added to form a reaction solution to cause a cyclization condensation reaction at a temperature of 90 ° C. or higher and 150 ° C. or lower. Thereby, the cyclic compounds represented by the following formulas (B-1 ′) to (B-3 ′) can be produced.

（式中、Ｒ’は上記本発明の第２の環状化合物に示すＲ’と同じ基を示す。）

(In the formula, R ′ represents the same group as R ′ shown in the second cyclic compound of the present invention.)

  In this production method, stereoisomers in which R ′ is all present on the same side (upper side of the paper in the formula (B-1 ′) etc.) are selectively obtained. Therefore, the cyclic compounds represented by the formulas (B-1) to (B-3) can be produced by introducing an acid dissociable, dissolution inhibiting group into the hydroxyl group of each formula by a known method.

In the second aspect of the present invention, the preferred acid catalyst includes solid organic sulfonic acid. Specifically, p-toluenesulfonic acid is mentioned.
Examples of alcohols having a boiling point of 90 ° C. or higher as a solvent include ethylene glycol, propylene glycol, glycerin, and cyclohexanol.
The reaction temperature is 90 ° C or higher and 150 ° C or lower. If it is less than 90 degreeC, the ratio of the isomer of a formula (B-4)-(B-6) will become high compared with the isomer of a formula (B-1)-(B-3). On the other hand, when it exceeds 150 degreeC, a by-product will increase.
The reaction time may be appropriately adjusted depending on the reaction system, but in general, it can be produced in an extremely short time of 1 hour to 24 hours.

The introduction of the acid dissociable, dissolution inhibiting group into the cyclic compounds represented by the above formulas (B-1 ′) to (B-3 ′) is performed, for example, by using a halide having an acid dissociable, dissolution inhibiting group. it can. Specific examples of the halide include bromide, chlorinated product, and fluorinated product.
As a reaction example, the same catalyst and conditions as those conventionally known, such as a condensation reaction in the presence of a base reactant and a coupling reaction in the presence of a transition metal catalyst and a base reactant, can be employed.

  In addition, in the manufacturing method of the 2nd aspect of this invention mentioned above, by making reaction temperature less than 90 degreeC, the isomer shown to Formula (B-1 ')-(B-3'), and Formula (B) -4) to (B-6), an isomer mixture in which R is a hydroxyl group is obtained. By separating this by recrystallization or the like, intermediates of the formulas (B-4) to (B-6) are obtained. In this case, the catalyst and alcohol are not limited to those described above, and an inorganic acid such as hydrochloric acid or a lower boiling alcohol can be used.

Subsequently, the photoresist composition of the second aspect of the present invention (hereinafter sometimes referred to as the second photoresist composition) will be described.
The second photoresist composition of the present invention contains the above-described second photoresist base material of the present invention and a solvent.
The solvent used in the second composition of the present invention is as described in the first embodiment.

  Components other than the solvent in the composition, that is, the amount of photoresist solids, are as described in the first embodiment.

  In the second photoresist composition of the present invention, when it is necessary to enhance the sensitivity, it is common to include a photoacid generator (PAG) or the like as a chromophore as needed.

The photoacid generator is not particularly limited, and those proposed as acid generators for chemically amplified resists can be used.
Such an acid generator is as described in the first embodiment.

  In the second aspect of the present invention, the acid diffusion control has the function of controlling the diffusion of the acid generated from the acid generator by irradiation in the resist film to prevent an undesirable chemical reaction in the unexposed area. You may mix | blend an agent (quencher) with a radiation sensitive composition. By using such an acid diffusion controller, the storage stability of the radiation-sensitive 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.

  Such an acid diffusion controller is as described in the first embodiment.

  In the second aspect of the present invention, if desired, there are further miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, a dissolution inhibitor, and an increase. Sensitizers, plasticizers, stabilizers, colorants, antihalation agents, dyes, pigments and the like can be appropriately added and contained.

  The dissolution control agent is as described in the first aspect.

  The sensitizer is as described in the first embodiment.

  The surfactant is as described in the first aspect.

  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. The organic carboxylic acid is as described in the first aspect.

  In order to form a resist pattern using the second photoresist composition of the present invention, first, the second photo of the present invention is formed on a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum. A resist film is formed by applying the resist composition by a coating means such as spin coating, cast coating, roll coating or the like.

  If necessary, a surface treatment agent may be applied in advance on the substrate. The surface treatment agent is as described in the first aspect.

  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 radiation 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 second aspect of the present invention, it is preferable to heat after irradiation (after exposure) in order to stably form a high-precision fine pattern. 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. The alkaline developer is as described in the first aspect.

  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 second photoresist composition of the present invention, a wiring substrate can also 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.

If ultrafine processing by lithography such as extreme ultraviolet light or electron beam is performed using the second composition of the present invention, a fine pattern can be formed with high sensitivity, high contrast, and low line edge roughness. Become.
By the microfabrication method according to the second aspect of the present invention, for example, a semiconductor device such as a ULSI, a large-capacity memory device, or an ultrahigh-speed logic device can be manufactured.

〔式中、Ｒ’はそれぞれ水素、水酸基、アルコキシ基、アリーロキシ基、炭素数１〜１２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３〜１２の単環式環状脂肪族炭化水素基、炭素数４〜１０の複環式環状脂肪族炭化水素基、フェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、式（Ｃ−４）で表される芳香族基、式（Ｃ−５）で表される置換基、又はこれら置換基のうち２種以上を組み合わせて構成される置換基を表す。

（式中、Ｒはそれぞれ脂環式構造を含む解離性溶解抑止基又は水酸基であり、ｘは１〜５の整数を表す。ｘが２以上のときＲは同一でも異なっていてもよい。）

（式中、Ａｒはフェニル基、ｐ−フェニルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ナフチル基、又は式（Ｃ−４）で表される芳香族基を表す。
Ｒ^１、Ｒ^２はそれぞれ水素原子、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６〜１２の芳香族基、又はこれら基のうち２種以上を組み合わせて構成される基である。
ｙは１〜４の整数を表す。ｙが２以上のときＲ^１、Ｒ^２は同一でも異なっていてもよい。）］The third aspect of the present invention will be described below.
The photoresist base material of the third aspect of the present invention (hereinafter sometimes simply referred to as a third photoresist base material) is represented by any of the following formulas (C-1) to (C-3). A plurality of R in the formula is an acid dissociable, dissolution inhibiting group or hydroxyl group each having an alicyclic structure, and the average substitution rate of the acid dissociable, dissolution inhibiting group is 20 to 60 percent. Consists of.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( An aromatic group represented by C-4), a substituent represented by formula (C-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, R is a dissociable dissolution inhibiting group or a hydroxyl group each containing an alicyclic structure, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (C-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]]

  The “average substitution rate” in the present invention is as described in the first aspect.

  When the photoresist substrate is a cyclic compound of the general formula (C-33) and R is an acid dissociable, dissolution inhibiting group or a hydroxyl group represented by the formula (C-34), respectively, the formula (C-34) When the average substitution rate of the acid dissociable, dissolution inhibiting group represented by 35) is 35 to 45%, a small amount of the acid dissociable, dissolution inhibiting group is eliminated upon exposure, so that the solubility in the developer is increased. As a result, the sensitivity as a photoresist increases. On the other hand, if the average substitution rate is 45 to 50%, the fine pattern to be formed is difficult to dissolve in the alkali developer, so that the smoothness of the desired fine pattern side wall surface is disturbed and the wall surface height is less likely to be lowered. This is preferable in terms of resolution. That is, although the most preferable range differs depending on whether the proposed photoresist emphasizes sensitivity, resolution, or the balance between them, the average substitution rate is 20 to 60%. If so, both sensitivity and resolution exhibit practically satisfactory performance, preferably 35 to 50%.

  The cyclic compound of the third aspect of the present invention (hereinafter sometimes simply referred to as the third cyclic compound) 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.

The acid dissociable, dissolution inhibiting group is a substituent that replaces the hydrogen atom of OH in the alkali-soluble groups listed above, and is —C (R _11a ) (R _12a ) (R _13a ), —C (R _14a ) ( R _15a ) (OR _16a ) and —CO—OC (R _11a ) (R _12a ) (R _13a ) are preferred.
In addition, the acid dissociable, dissolution inhibiting group for R in the above formulas (C-1) to (C-4) includes an alicyclic structure.

Here, R _{11a to} R _13a each independently represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group, and any one of R _{11a to} R _13a One contains a cycloalkyl group. R _14a and R _15a each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group or cycloalkyl group. R _16a represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group, and any one of R _{14a to} R _16a includes a cycloalkyl group. Two or more of R _11a , R _12a and R _13a , or two or more of R _14a , R _15a and R _16a may be bonded to form a monocyclic structure or a multicyclic structure. Good.

The alkyl group, cycloalkyl group and aralkyl group in R _{11a to} R _16a are cycloalkyl groups, hydroxy groups, alkoxy groups, oxo groups, alkylcarbonyl groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, alkylaminocarbonyls as substituents. Group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The aryl group and alkenyl group in R _{11a to} R _13a and R _16a are, as substituents, an alkyl group, a cycloalkyl group, a hydroxy group, an alkoxy group, an oxo group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an alkyl group. An aminocarbonyl group, alkylcarbonylamino group, alkylsulfonyl group, alkylsulfonyloxy group, alkylsulfonylamino group, alkylaminosulfonyl group, aminosulfonyl group, halogen atom, cyano group and the like may be contained.

The alkyl group, cycloalkyl group, alkenyl group, and aralkyl group of R _{11a to} R _16a each have an ether group, thioether group, carbonyl group, ester group, amide group, urethane group, ureido group, sulfonyl group, and sulfone group in the middle. You may have.

  The acid dissociable, dissolution inhibiting group preferably has a total carbon number of 4 or more, more preferably 6 or more, and still more preferably 8 or more.

The cycloaliphatic structure, cyclohexane residue, norbornane residue, adamantane residue and the like are exemplified as the alicyclic structure contained in the R acid dissociable, dissolution inhibiting group of the above formulas (C-1) to (C-4). . The acid dissociable, dissolution inhibiting group may contain an aromatic ring structure. Examples of the aromatic ring structure include a benzene residue, a naphthalene residue, and an anthracene residue.
These alicyclic structures and aromatic ring structures may have a substituent at any position.

（式中、ｒはそれぞれ上記式（Ｃ−６）〜（Ｃ−２９）で表される置換基のいずれかを表す。）Although the preferable specific example of an acid dissociable dissolution inhibiting group is shown below, the 3rd aspect of this invention is not limited to these.

(Wherein, r represents any of the substituents represented by the above formulas (C-6) to (C-29)).

In the above formulas (C-1) to (C-3), R ′ is preferably a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, A phenyl group, a naphthyl group, an aromatic group represented by the formula (C-4), or a substituent represented by the formula (C-5), more preferably a linear fatty acid having 1 to 4 carbon atoms. An aromatic hydrocarbon group, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a phenyl group.
In the above formula (C-4), preferred acid dissociable, dissolution inhibiting groups for R are the same as R in formulas (C-1) to (C-3). x is preferably an integer of 1 to 2.
In the above formula (C-5), Ar is preferably a phenyl group or a naphthyl group. R ¹ and R ² are preferably a hydrogen atom, a methyl group, or an ethyl group. y is preferably an integer of 1 to 2.

A preferable cyclic compound used for the third photoresist base material of the present invention is represented by the following formula (C-33), wherein R is a substituent or a hydroxyl group represented by the formula (C-34), respectively. The cyclic compound whose average substitution rate of the substituent represented by the formula (C-34) is 35 to 50 percent.

Moreover, the preferable cyclic compound used for the 3rd photoresist base material of this invention is represented by a following formula (C-33), and R is a substituent represented by a formula (C-34 ') respectively in the formula, or It is a cyclic compound having a hydroxyl group and an average substitution rate of the substituent represented by the formula (C-34 ′) of 20 to 60 percent.

  Said cyclic compound can be used as a photoresist base material used in the ultrafine processing by lithography such as extreme ultraviolet light or electron beam.

The photoresist composition of the third aspect of the present invention (hereinafter sometimes simply referred to as the third photoresist composition) contains the above-mentioned photoresist base material and 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.

  The solvent used in the third photoresist composition of the present invention is as described in the first embodiment.

  Components other than the solvent in the composition, that is, the amount of photoresist solids, are as described in the first embodiment.

  The third photoresist composition of the present invention requires an additive particularly when the substrate molecule contains a chromophore active against EUV and / or electron beam and exhibits its ability as a photoresist alone. However, 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 as described in the first embodiment.

  In the third aspect of the present invention, the acid diffusion control has a function of controlling an undesired chemical reaction in an unexposed region by controlling the diffusion in the resist film of the acid generated from the acid generator by irradiation. An agent (quencher) may be added to 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.

  Such an acid diffusion controller is as described in the first embodiment.

  In the third aspect of the present invention, if desired, there are further miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, a dissolution inhibitor, an increasing agent. Sensitizers, plasticizers, stabilizers, colorants, antihalation agents, dyes, pigments and the like can be appropriately added and contained.

  The dissolution control agent is as described in the first aspect.

  The sensitizer is as described in the first embodiment.

  The surfactant is as described in the first aspect.

  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. The organic carboxylic acid is as described in the first aspect.

  In order to form a resist pattern, first, the third photoresist composition of the present invention is applied onto a substrate such as a silicon wafer, a gallium arsenide wafer, or an aluminum-coated wafer by spin coating, casting coating, roll coating, etc. A resist film is formed by application by the application means.

  If necessary, a surface treatment agent may be applied in advance on the substrate. The surface treatment agent is as described in the first aspect.

  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 3rd aspect of this invention, in order to form a highly accurate fine pattern stably, it is preferable to heat after radiation 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. The alkaline developer is as described in the first aspect.

  In the case of the third photoresist base material of the present invention, an acid dissociable, dissolution inhibiting group is formed by exposing the resist film to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Desorption or change in structure causes dissolution in an alkaline developer. On the other hand, the non-exposed portion of the pattern is not dissolved in the alkaline developer, and as a result, a fine pattern is formed, thereby achieving the purpose as a photoresist substrate. That is, it is desirable that a photoresist base material having an acid dissociable, dissolution inhibiting group with an average substitution rate defined in the third aspect of the present invention or a thin film made of a photoresist base material is not dissolved in an alkali 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 third photoresist composition of the present invention, a wiring substrate can also 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.

A semiconductor device can be produced by a microfabrication method using the third photoresist composition of the present invention. This semiconductor device can be provided in various devices such as an electric product (electronic device) such as a television receiver, a mobile phone, and a computer, a display, and a car controlled by a computer.
[Example]

[Experimental Example 1]
To a three-necked flask (capacity 500 ml) equipped with a dropping funnel sufficiently substituted with nitrogen gas, Jim Roth condenser, thermometer, resorcinol (33 g, 300 mmol) and acetaldehyde (17 ml, 300 millimoles) was encapsulated, and distilled methanol (300 milliliters) was added under slightly pressurized nitrogen to prepare a methanol solution. The methanol solution was heated to 75 ° C. with stirring in an oil bath. Subsequently, 75 ml of concentrated hydrochloric acid was gradually added dropwise from the dropping funnel, and then the heating and stirring were continued at 75 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and then cooled in an ice bath. After standing for 1 hour, white target crude crystals were produced, which were filtered off. This crude crystal was washed twice with pure water (100 ml), then recrystallized from a mixed solution of ethanol and water, purified, and dried under reduced pressure to give a cyclic compound of the following formula (A-20) (16 g, Yield 40.2%) was synthesized. The structure of this cyclic compound was confirmed by ¹ H-NMR and the like.

[Experiment 2]
A cyclic compound (A-20) produced in Experimental Example 1 (135 g, 249.7 mmol) was added to a four-necked flask (capacity: 3000 ml) equipped with a nitrogen-introduced bowl, a thermometer, a mechanical stirrer, and a Jim Roth cooling bowl. , N, N-dimethylformamide (1557 ml) and sodium carbonate (294.29 g, 2776.48 mmol) were sealed and purged with nitrogen. Subsequently, tert-butyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., 444.96 g, 2280.68 mmol) was added, and heating and refluxing were started in an oil bath at 65 ° C. under stirring in a nitrogen atmosphere. Ten milliliters of each reaction solution was withdrawn for each reaction time shown in Table 1, and for each reaction solution, the reaction solution was filtered. Diethyl ether was added to the obtained filtrate to obtain a homogeneous solution, and 0. Washed with 5M aqueous acetic acid. Further, the ether solution was washed with ion exchange water until the aqueous layer became neutral, and the washed ether solution was treated with anhydrous magnesium sulfate to remove moisture. The ether solution from which water has been removed is concentrated under reduced pressure using a rotary evaporator, and the concentrated solution is poured into hexane to obtain a solid. The solid is filtered off and dried at 50 ° C. for 8 hours under vacuum. The cyclic compound represented by -21) was obtained. About each cyclic compound (A-21-1)-(A-21-11), while confirming a structure by < ¹ > H-NMR, the substitution number isomer contained by LC / MS was identified, and LC was used. The average substitution rate of acid dissociable, dissolution inhibiting groups was calculated. The results are shown in Table 1.

[Experiment 3]
In Experimental Example 1, a cyclic compound (A-22) was produced in the same manner as in Experimental Example 1, except that benzaldehyde was used instead of acetaldehyde. The structure of this cyclic compound was confirmed by ¹ H-NMR and the like.

[Experimental Example 4]
Using the cyclic compound (A-22) obtained in Experimental Example 3, a cyclic compound represented by the following formula (A-23) was obtained by the same method as in Experimental Example 2. About each cyclic compound (A-23-1)-(A-23-12), while confirming a structure by < ¹ > H-NMR, similarly to Experimental Example 2, the average substitution rate of the acid dissociable dissolution inhibiting group is determined. Calculated. The results are shown in Table 1.

[Evaluation Example 1]
About the cyclic compounds (A-21-1) to (A-21-11) produced in Experimental Example 2 and the cyclic compounds (A-23-1) to (A-23-12) produced in Experimental Example 4 The solubility test was conducted using propylene glycol methyl ether acetate (PGMEA), which is a typical coating solvent generally used in photoresist. The evaluation criteria of solubility were as follows.
(Double-circle): Immediately after pouring powder into a solvent at room temperature, it became a uniform solution without stirring operation.
○: The powder was put into a solvent at room temperature, and after stirring vigorously for 1 minute, a uniform solution was obtained.
(Triangle | delta): The powder was thrown into the solvent at room temperature, and became a uniform solution after vigorous stirring for 3 minutes.
X: The powder was put into a solvent at room temperature, and insoluble matter remained even after vigorous stirring for 3 minutes.

  In addition, a solution obtained by the solubility test was spin-coated on a silicon wafer subjected to HMDS treatment and heated at 100 ° C. for 180 seconds to form a thin film, and an alkali developer (2.38% tetramethyl) (Ammonium hydroxide aqueous solution) was immersed for 60 seconds. After the immersion, the state of the thin film was visually observed, the film thickness was measured, and the dissolution rate in the alkali developer was calculated from the difference from the film thickness before immersion.

  The results are shown in Table 2. As a result, (A-21-1) to (A-21-5) and (A-23-1) to (A-23-4) are 0.5 nanometer / second or more and the developer dissolution rate. In addition, (A-23-5) and (A-23-6) are partially peeled off, and (A-21-11) and (A-23-12) are used as coating solvents. On the other hand, it cannot be used as a photoresist because an insoluble material is generated. Although (A-23-11) cannot be said to have good coating solvent solubility, it can be used as a photoresist because it does not produce insolubles in the coating solvent. From the above, (A-21-6) to (A-21-10) and (A-23-7) to (A-23-11) (that is, when the average substitution rate is 55 to 90%) are photoresists. Confirming that it can be used satisfactorily as a substrate, (A-21-6) to (A-21-10) (that is, when the average substitution rate is 60% to 90%), and (A-23-7) -(A-23-10) (that is, when the average substitution rate is 55% to 80%) was confirmed to be particularly favorable as a photoresist substrate.

[Production of cyclic compounds]
Example 1
A cyclic compound having the structure of the following formula (B-1-1) was produced.

A 1-liter flask was charged with 100 g (0.91 mol) of resorcinol and 86.2 g (0.45 mol) of p-toluenesulfonic acid monohydrate, followed by nitrogen substitution, and then charged with 490 ml of ethylene glycol. And stirred with a mechanical stirrer to obtain a uniform solution. Next, 96.4 g (0.91 mmol) of benzaldehyde was added with a syringe at room temperature, and then the mixture was heated and stirred in an oil bath heated to 120 ° C. for 2 hours.
After the reaction, the reaction mixture was cooled to room temperature, 950 ml of ion-exchanged water was added to the reaction solution and stirred for 30 minutes, and then the crude product solid was filtered off. After vacuum drying at 80 ° C. for 8 hours, the crude product solid was put into tetrahydrofuran (1.5 liters), washed by stirring at 65 ° C. for 1 hour and heating to reflux.
The washed solid was separated by filtration and vacuum dried at 80 ° C. for 8 hours to obtain a product. It was confirmed by ¹ H-NMR (FIG. 1) that the product consisted only of the isomer having the steric relative configuration shown in (B-1-1) (175.3 g, yield 97%).

Example 2
A cyclic compound having the structure of the following formula (B-4-1) was produced.

A 1-liter flask equipped with a dropping funnel was charged with 100 g (0.91 mol) of resorcinol and 96.4 g (0.91 mmol) of benzaldehyde, purged with nitrogen, and then charged with 490 ml of 2-propanol. The mixture was stirred with a stirrer to obtain a uniform solution.
Next, after the flask was cooled to 5 ° C. in an ice bath, a 2-propanol solution of concentrated hydrochloric acid (concentrated hydrochloric acid / 2-propanol = 40 ml / 40 ml) was stirred and the internal temperature did not exceed 15 ° C. The solution was slowly dropped through a dropping funnel. After completion of the dropping, the reactor was removed from the ice bath, stirred at room temperature for 40 minutes, and then heated and stirred in an oil bath heated to 65 ° C. for 2 hours. After the reaction, it was cooled to room temperature.
After adding 950 milliliters of ion exchange water to the reaction solution and stirring for 30 minutes, the crude product solid was filtered off. The solid was washed with ion-exchanged water until the filtrate became neutral and dried in vacuo at 80 ° C. for 8 hours to obtain a crude product solid (144.9 g, yield 81%).
The crude product solid was determined by ¹ H-NMR (FIG. 2) to be a mixture of the above formula (B-4-1) and formula (B-1-1) ((B-4-1) / (B-1-1). ) = 73% / 27%).

A mixture of this crude product solid (144.9 g) and N, N-dimethylformamide (2.0 liters) was heated to 65 ° C. to make a homogeneous solution, allowed to stand still for 12 hours, and the precipitated solid was filtered off. . The precipitated solid was washed with N, N-dimethylformamide (30 ml) cooled in an ice bath and then washed with water. The washed precipitated solid was collected by filtration and vacuum dried at 80 ° C. for 8 hours to recover a recrystallized product. The obtained compound was confirmed by ¹ H-NMR (FIG. 3) to be a cyclic compound of the formula (B-4-1) (76.3 g, 53% as the recrystallization recovery rate, standard yield of preparation) 42%).

Example 3
A cyclic compound having the structure of the following formula (B-1-2) was produced.

In a 100 ml flask, the cyclic compound of formula (B-1-1) prepared in Example 1 (2.0 g, 2.5 mmol), NMP (23 ml), sodium carbonate (3.0 g, 28. 2 mmol) was enclosed and purged with nitrogen.
Subsequently, tert-butyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., 4.5 g, 23.2 mmol) was added, and the mixture was heated in an oil bath at 65 ° C. for 24 hours under stirring in a nitrogen atmosphere. The reaction solution was allowed to cool, and ethyl acetate was added to the filtrate obtained by filtration to obtain a homogeneous solution, which was then washed with a 0.5 M acetic acid aqueous solution in a separatory funnel. Further, the ethyl acetate solution was washed with ion exchange water until the aqueous layer became neutral, and the ethyl acetate solution was treated with anhydrous magnesium sulfate to remove moisture. After filtration, the filtrate was concentrated with a rotary evaporator under reduced pressure, and the concentrate was poured into hexane to obtain a solid. The solid was filtered off and dried under vacuum at 50 ° C. for 8 hours to obtain a cyclic compound represented by the formula (B-1-2). ^While confirming the structure by ¹ H-NMR (FIG. 4), the substitution number isomers contained by LC / MS were identified, and the average introduction rate of acid dissociable, dissolution inhibiting groups was calculated by LC (average introduction) Rate 64%, 1.5 g).

Example 4
A cyclic compound having the structure of the following formula (B-4-2) was produced.

The same procedure as in Example 3 was carried out except that the cyclic compound of the formula (B-4-1) produced in Example 2 was used instead of the cyclic compound (B-1-1) produced in Example 1. did. A cyclic compound represented by the formula (B-4-2) was obtained. ^While confirming the structure by ¹ H-NMR (FIG. 5), the substitution number isomer contained by LC / MS was identified, and the average introduction rate of acid dissociable, dissolution inhibiting groups was calculated by LC (average introduction) 80% rate, 1.1 g).

Reference example 1
In Example 3, instead of the cyclic compound (B-1-1) produced in Example 1, the crude product solid produced in Example 2, that is, the cyclic compound (B-4-1) and the cyclic compound ( The same procedure as in Example 3 was performed except that a mixture of (B-1-1) ((B-4-1) / (B-1-1) = 73% / 27%) was used. ^While confirming the structure by ¹ H-NMR (FIG. 6), the substitution number isomers contained by LC / MS were identified, and the average introduction rate of acid dissociable, dissolution inhibiting groups was calculated by LC (average protection) Introduction rate 69%, 1.8 g). As a result, a mixture of cyclic compounds represented by formula (B-1-2) and formula (B-4-2) was obtained as described below.

[Photoresist composition]
Example 5
The cyclic compound produced in Example 3 or 4 was used as the photoresist base material.
10 parts by weight of triphenylsulfonium trifluoromethanesulfonate as a PAG and 3 parts by weight of 1,4-diazabicyclo [2.2.2] octane as a quencher were added to 87 parts by weight of each of the above photoresist base materials. A photoresist composition was prepared by dissolving in propylene glycol methyl ether acetate such that the concentration of these solid components was 5% by weight.

Reference example 2
A photoresist composition was produced in the same manner as in Example 5 except that the cyclic compound produced in Reference Example 1 was used as the photoresist base material.

Evaluation Example A pattern was formed on a silicon wafer using the obtained photoresist composition.
Each of the photoresist compositions was spin-coated on a HMDS-treated silicon wafer, and heated at 100 ° C. for 180 seconds to form a thin film. Next, the substrate having this thin film is drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), baked at 100 ° C. for 60 seconds, and then developed with an aqueous tetrabutylammonium solution having a concentration of 2.38 wt% for 60 seconds. The pattern was formed by processing, washing with pure water for 60 seconds, and then drying with a nitrogen stream.

When observed with a scanning electron microscope, the cyclic compound (B-1-2) had the highest resolution and the best sensitivity. Next, the cyclic compound (B-4-2) had high resolution and good sensitivity.
The photoresist composition using the mixture of the cyclic compounds (B-1-2) and (B-4-2) produced in Reference Example 1 had the lowest resolution and the lowest sensitivity.

In addition, 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, the substrate was baked at 100 ° C. for 90 seconds, and a pattern was formed by rinsing with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 30 seconds and with ion-exchanged water for 30 seconds.
When observed with a scanning electron microscope, the cyclic compound (B-1-2) had the highest resolution and the best sensitivity as in the case of the electron beam drawing apparatus. Next, the cyclic compound (B-4-2) had high resolution and good sensitivity.
The photoresist composition using the mixture of the cyclic compounds (B-1-2) and (B-4-2) produced in Reference Example 1 had the lowest resolution and the lowest sensitivity.

Production Example 1
A three-necked flask (capacity: 500 ml) equipped with a dropping funnel, Jim Roth condenser, and thermometer, sufficiently dried and replaced with nitrogen gas, resorcinol (33 g, 300 mmol) and benzaldehyde (31.8 g) under a nitrogen stream 300 millimoles) was added, and distilled methanol (300 milliliters) was added under a slight nitrogen pressure to prepare a methanol solution. The methanol solution was heated to 75 ° C. with stirring in an oil bath. Subsequently, 75 ml of concentrated hydrochloric acid was gradually added dropwise from the dropping funnel, and then the heating and stirring were continued at 75 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and then cooled in an ice bath. After standing for 1 hour, white target crude crystals were produced, which were filtered off. The crude crystals were washed twice with pure water (100 ml), then recrystallized from a mixed solution of ethanol and water, purified, and dried under reduced pressure to give a cyclic compound represented by the following formula (C-35) (recovery). 82%) was synthesized. The structure of this cyclic compound was confirmed by ¹ H-NMR.

Example 6
Production example of N-methylpyrrolidone (17 ml) while cooling in an ice bath into a two-necked flask (capacity 100 ml) equipped with a thermometer and a Jim Roth condenser tube sufficiently dried and replaced with nitrogen gas The cyclic compound (C-35) (1 g, 1.3 mmol) synthesized in 1 was enclosed and purged with nitrogen. Subsequently, 2- (chloromethoxy) adamantane (hereinafter referred to as CMA) and 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter referred to as DBU) dissolved in N-methylpyrrolidone (5 milliliters) were respectively obtained. In addition to the amounts shown in Table 3, the mixture was stirred for 4 hours at room temperature under a nitrogen atmosphere. These reaction solutions were poured into ion exchanged water (200 ml) to stop the reaction, and a white precipitate was obtained. These were filtered and purified by drying under reduced pressure, and cyclic compounds (C-36-1) to (C-3) represented by the following formula (C-36) having the average substitution rate of the acid dissociable, dissolution inhibiting groups shown in Table 3 -36-7) was obtained. In addition, these cyclic compounds confirmed the average substitution rate and structure by LC, < ¹ > H-NMR, etc.

Evaluation example 2
About the cyclic compounds (C-36-1) to (C-36-7) produced in Example 6, propylene glycol methyl ether acetate (PGMEA) which is a typical coating solvent generally used in photoresists The solubility test was carried out using The evaluation criteria of solubility were as follows.
○: The powder was put into a solvent at room temperature, and after stirring vigorously for 1 minute, a uniform solution was obtained.
Δ: The powder was put into a solvent at room temperature and insoluble matter remained even if stirred vigorously for 1 minute. However, when heated to 100 ° C., it dissolved and maintained a uniform solution even when cooled to room temperature.
X: The powder was put into a solvent at room temperature, and even when heated at 100 ° C., insoluble matters remained.

  Further, a solution obtained by the solubility test was spin-coated on a silicon wafer subjected to hexamethyldisilazane treatment, and heated at 100 ° C. for 180 seconds to form a thin film, whereby an alkali developer (2.38) was formed. % Tetramethylammonium hydroxide aqueous solution) for 60 seconds, the film thickness was measured, and the developer dissolution rate was calculated from the difference from the film thickness before immersion.

  The above results are shown in Table 3. Since (C-36-1) and (C-36-7) are not dissolved in a coating solvent, they cannot be used as a photoresist base material, and (C-36-2) to (C-36-6) ( That is, when the average substitution rate is 30% to 55%), it was confirmed that it can be used as a photoresist substrate. In addition, (C-36-2) and (C-36-6) are difficult to dissolve in the coating solvent, but do not dissolve in the alkaline developer and can be used as a photoresist base material, but cannot be said to be good. C-36-3) to (C-36-5) (that is, when the average substitution rate is 35% to 50%) is a photoresist base material from the viewpoint of coating solvent solubility and alkali developer solubility. It was confirmed that it can be used satisfactorily.

Example 7
Cyclic compound (12.0 g, 15 mmol) synthesized in Production Example 1 and sodium carbonate in a two-necked flask (capacity: 200 ml) equipped with a thermotube equipped with a Jim Roth condenser tube sufficiently dried and replaced with nitrogen gas (18.0 g, 168 mmol) was enclosed and purged with nitrogen. Next, 120 ml of N-methylpyrrolidinone was added to make a solution, 2-methyl-2-adamantyl bromoacetate (287 g, 26 mmol) was added, and the mixture was stirred in an oil bath at 100 ° C. for 10 hours under a nitrogen atmosphere. The reaction was carried out with heating under reflux. After allowing to cool to room temperature, 80 ml of an aqueous ammonium chloride solution was poured into this reaction solution, extraction was performed with 150 ml of ethyl acetate, the ethyl acetate layer was washed with water, dried over magnesium sulfate, and filtered. This was concentrated under reduced pressure to obtain a crude product. This was purified by reprecipitation and ion exchange treatment to obtain a cyclic compound (yield 75%) represented by the following formula (C-37). This structure was confirmed by ¹ H-NMR (FIG. 7).

Example 8
In Example 7, DBU was used instead of sodium carbonate, 2-methyl-2-adamantyl chloroacetate was used instead of 2-methyl-2-adamantyl bromoacetate, and the reaction time was 5 hours. In the same manner as in Example 7, a cyclic compound (yield 60%) represented by the following formula (C-38) was obtained. The structure of this cyclic compound was confirmed by ¹ H-NMR (FIG. 8).

Evaluation Example 3
As a base material, 87 parts by weight of the compound synthesized in Examples 7 and 8 and the compound (C-39) shown below for comparison are used, respectively, and 10 parts by weight of triphenylsulfonium trifluoromethanesulfonate as a PAG. As a quencher, 3 parts by weight of 1,4-diazabicyclo [2.2.2] octane was used. A photoresist solution was prepared by dissolving in propylene glycol methyl ether acetate such that the concentration of these solid components was 5% by weight.

  Each of these photoresist solutions is spin-coated on a silicon wafer subjected to 1,1,1,3,3,3-hexamethyldisilazane (HMDS) treatment, and heated at 100 ° C. for 180 seconds to form a thin film. Formed. Next, drawing was performed on the substrate having this thin film using an electron beam drawing apparatus (acceleration voltage 50 kV). After baking at 100 ° C. for 60 seconds, the film was developed with an aqueous tetrabutylammonium solution having a concentration of 2.38% by weight for 60 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream.

  As a result, in the case of the photoresist solution using the compounds synthesized in Examples 7 and 8 as a base material, a 100 nm line and space pattern could be obtained with good rectangularity and linearity. On the other hand, in the case of the photoresist solution using the comparative compound (C-39) as a base material, a 100 nm line and space pattern can be obtained only by observing random wavy electron beam irradiation traces. There wasn't.

  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. Then, it baked at 100 degreeC for 90 second, and formed the pattern by rinsing with 2.38 weight% tetramethylammonium hydroxide aqueous solution for 30 second and ion-exchange water for 30 second.

  When observed with a scanning electron microscope, as in the case of the electron beam drawing apparatus, in the case of the photoresist solution using the compounds synthesized in Examples 7 and 8 as the base material, both are 100 nm line and space patterns. However, it was able to be obtained with good rectangularity and linearity. On the other hand, in the case of a photoresist solution using the comparative compound (C-39) as a base material, only random wavy EUV light irradiation traces similar to those when using an electron beam drawing apparatus are observed. A 100 nm line and space pattern could not be obtained.

The photoresist base material and the composition using the same according to the present invention are suitably used in the electric / electronic field, the optical field, and the like of semiconductor devices. It is particularly suitable for extreme ultraviolet light and / or electron beam photoresists. With the photoresist composition of the present invention, the performance of a semiconductor device such as ULSI can be dramatically improved. Furthermore, by incorporating a semiconductor device produced from the photoresist composition of the present invention as a component, the performance of semiconductor device products such as information home appliances, computer equipment, memory device equipment, and display equipment can be dramatically improved. it can.
The cyclic compound of the present invention is suitable as a photoresist base material. Further, the photoresist base material and the composition thereof of the present invention are suitably used in the electric / electronic field and the optical field of semiconductor devices and the like. Thereby, the performance of a semiconductor device such as ULSI can be dramatically improved.
The literature content described in this specification is incorporated herein by reference.

Claims (27)

A cyclic compound represented by any one of the following formulas (A-1) to (A-3), wherein a plurality of Rs are each an acid dissociable, dissolution inhibiting group or a hydroxyl group, and an acid dissociable, dissolution inhibiting group A photoresist base material comprising a cyclic compound having an average substitution rate of 55 to 90 percent.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxyl group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( A-4) represents an aromatic group represented by formula (A-5), a substituent represented by formula (A-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, each R is an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (A-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]] The photoresist base material according to claim 1, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (A-6) to (A-10).

(In formulas (A-9) and (A-10), r represents one of the following substituents. R in formula (A-9) may be the same or different.)

The cyclic compound is represented by the following formula (A-11), wherein R is a substituent or a hydroxyl group represented by the formula (A-12), and a substituent represented by the formula (A-12). The photoresist substrate according to claim 2, which is a cyclic compound having an average substitution rate of 60 to 90 percent.

The cyclic compound is represented by the following formula (A-13), wherein R is a substituent represented by the formula (A-14) or a hydroxyl group, and a substituent represented by the formula (A-14). The photoresist substrate according to claim 2, which is a cyclic compound having an average substitution rate of 55 to 80 percent.

  The photoresist composition containing the photoresist base material and solvent in any one of Claims 1-4.   A fine processing method using the photoresist composition according to claim 5.   A semiconductor device manufactured by the microfabrication method according to claim 6.   An apparatus comprising the semiconductor device according to claim 7. A cyclic compound having a steric relative configuration represented by any of the following formulas (B-1) to (B-6), wherein the ratio of the cyclic compound to the total stereoisomer is 90 mol% or more Compound.

[Wherein R is an acid dissociable, dissolution inhibiting group or hydroxyl group,
R ′ is a hydroxyl group, an ether group (—OR ^a , R ^a is ^a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and 3 to 3 carbon atoms, respectively. 8 monocyclic cycloaliphatic hydrocarbon group, C4-C10 bicyclic cycloaliphatic hydrocarbon group, phenyl group, naphthyl group.), C1-C12 linear aliphatic carbonization A hydrogen group, a C3-C12 branched aliphatic hydrocarbon group, a C3-C12 monocyclic cycloaliphatic hydrocarbon group, a C4-C10 bicyclic cycloaliphatic hydrocarbon group, A phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B-8), or It is a substituent constituted by combining two or more of these substituents.

(In the formula, R represents an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (B-7).
R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a substituent formed by combining two or more of these substituents It is.
y is an integer of 1-4. )
R may be the same or different, and R ′ may be the same or different.
However, in said Formula (B-1) and (B-4), R 'is a methyl group, a phenyl group, or 4-isopropylphenyl group, and all of R is following formula (B-9). Except cases. ]

The cyclic compound according to claim 9, wherein the acid dissociable, dissolution inhibiting group is a group selected from the formula (B-9) or the following formulas (B-10) to (B-36).

(Wherein, r represents one of the substituents represented by the above formulas (B-9) to (B-34), the following formulas (r-1) and (r-2)).

A photoresist comprising a cyclic compound having a steric relative configuration represented by any of the following formulas (B-1) to (B-6), wherein the ratio of the cyclic compound to the total stereoisomer is 90 mol% or more Base material.

Wherein R is an acid dissociable, dissolution inhibiting group or a hydroxyl group,
R ′ is a hydroxyl group, an ether group (—OR ^a , R ^a is ^a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and 3 to 3 carbon atoms, respectively. 8 monocyclic cycloaliphatic hydrocarbon group, C4-C10 bicyclic cycloaliphatic hydrocarbon group, phenyl group, naphthyl group.), C1-C12 linear aliphatic carbonization A hydrogen group, a C3-C12 branched aliphatic hydrocarbon group, a C3-C12 monocyclic cycloaliphatic hydrocarbon group, a C4-C10 bicyclic cycloaliphatic hydrocarbon group, A phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, an aromatic group represented by the following formula (B-7), a substituent represented by the following formula (B-8), or It is a substituent constituted by combining two or more of these substituents.

(In the formula, R represents an acid dissociable, dissolution inhibiting group or hydroxyl group, and x represents an integer of 1 to 5.)

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (B-7).
R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a substituent formed by combining two or more of these substituents It is.
y is an integer of 1-4. )
R may be the same or different, and R ′ may be the same or different. ] The photoresist base material according to claim 11, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (B-9) to (B-36).

(Wherein, r represents one of the substituents represented by the above formulas (B-9) to (B-34), the following formulas (r-1) and (r-2)).

  R ′ is a monocyclic cycloaliphatic hydrocarbon group having 3 to 12 carbon atoms, a polycyclic cycloaliphatic hydrocarbon group having 4 to 10 carbon atoms, a phenyl group, a p-phenylphenyl group, a p-tert. -A butylphenyl group, a naphthyl group, an aromatic group represented by the formula (B-7), a substituent represented by the formula (B-8), or a combination of two or more of these groups. The photoresist base material according to claim 11 or 12, which is a substituent. It is represented by the formula (B-1) or (B-4), R is a group represented by the following formula (B-9), and R ′ is a methyl group, a phenyl group, or 4-isopropyl, respectively. The photoresist base material according to claim 11, which is a phenyl group.

  The photoresist composition containing the photoresist base material and solvent in any one of Claims 11-14.   A fine processing method using the photoresist composition according to claim 15.   A semiconductor device manufactured by the microfabrication method according to claim 16.   An apparatus comprising the semiconductor device according to claim 17. To a mixture of a polyphenol compound selected from resorcinol, pyrogallol, 1,2,3,5-tetrahydrobenzene and a solid organic sulfonic acid as an acid catalyst, an alcohol having a boiling point of 90 ° C. or more is added as a solvent,
Thereafter, an aldehyde compound represented by the following formula (B-24) is added to form a cyclization condensation reaction as a reaction solution at a temperature of 90 ° C. or higher and 150 ° C. or lower, and the following formulas (B-1 ′) to (B-3) ') To produce a cyclic compound represented by
Next, an acid dissociable, dissolution inhibiting group is introduced into at least one of the hydroxyl groups on the cyclic compound represented by the formulas (B-1 ′) to (B-3 ′).
The manufacturing method of the cyclic compound represented by Formula (B-1)-(B-3) of Claim 9.

(Wherein R ′ represents the same group as R ′ shown in claim 9). A cyclic compound represented by any one of the following formulas (C-1) to (C-3), wherein a plurality of Rs are acid dissociable, dissolution inhibiting groups or hydroxyl groups each containing an alicyclic structure, A photoresist base material comprising a cyclic compound having an average substitution rate of the acid dissociable, dissolution inhibiting group of 20 to 60 percent.

[Wherein, R ′ represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 3 to 3 carbon atoms. 12 monocyclic cycloaliphatic hydrocarbon groups, C4-C10 bicyclic cycloaliphatic hydrocarbon groups, phenyl groups, p-phenylphenyl groups, p-tert-butylphenyl groups, naphthyl groups, formula ( An aromatic group represented by C-4), a substituent represented by formula (C-5), or a substituent constituted by combining two or more of these substituents.

(In the formula, R is an acid dissociable, dissolution inhibiting group or a hydroxyl group each having an alicyclic structure, and x represents an integer of 1 to 5. When x is 2 or more, R may be the same or different. )

(In the formula, Ar represents a phenyl group, a p-phenylphenyl group, a p-tert-butylphenyl group, a naphthyl group, or an aromatic group represented by the formula (C-4).
R ¹ and R ² are each a hydrogen atom, 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, substituted or unsubstituted, An unsubstituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a combination of two or more of these groups.
y represents an integer of 1 to 4. When y is 2 or more, R ¹ and R ² may be the same or different. ]] The photoresist base material according to claim 20, wherein the acid dissociable, dissolution inhibiting group is a group selected from the following formulas (C-6) to (C-31).

(Wherein, r represents any of the substituents represented by the above formulas (C-6) to (C-29)). The cyclic compound is represented by the following formula (C-33), wherein R is a substituent represented by the formula (C-34) or a hydroxyl group, and a substituent represented by the formula (C-34). The photoresist substrate according to claim 21, which is a cyclic compound having an average substitution rate of 35 to 50 percent.

The cyclic compound is represented by the following formula (C-33), wherein R is a substituent or a hydroxyl group represented by the formula (C-34 ′), and is represented by the formula (C-34 ′). The photoresist base material according to claim 21, which is a cyclic compound having an average substitution rate of substituents of 20 to 60 percent.

  A photoresist composition comprising the photoresist base material according to any one of claims 20 to 23 and a solvent.   A fine processing method using the photoresist composition according to claim 24.   A semiconductor device manufactured by the microfabrication method according to claim 25.   27. An apparatus comprising the semiconductor device according to claim 26.

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