JP2011173868A - Cyclic compound and negative resist composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic compound having high sensitivity, and usable for a negative photoresist effective in reducing line edge roughness. <P>SOLUTION: The compound is represented by formula (1) (wherein, R represents epoxy-containing phenyl residue or the like; R<SP>1</SP>represents hydroxy or the like; and R<SP>2</SP>represents hydrogen atom or the like). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cyclic compound and a negative resist composition using the same. More specifically, the present invention relates to a photoresist base material composed of the above cyclic compound used in the electrical / electronic field and optical field such as semiconductor, and more particularly to a photoresist base material for ultrafine processing.

  Lithography using extreme ultraviolet (EUV) or electron beam is useful as a high-productivity, high-resolution microfabrication method in the production of semiconductors, etc., and develops high-sensitivity, high-resolution photoresists for use in it. It is requested to do. It is indispensable to improve the sensitivity of the photoresist used in these lithography from the viewpoint of the productivity and resolution of the desired fine pattern.

  Examples of the photoresist used at the time of ultrafine processing using extreme ultraviolet light include chemically amplified polyhydroxystyrene-based photoresists used at the time of ultrafine processing using a known KrF laser. It is known that this resist can be finely processed up to about 50 nm. However, with this resist, the most important line edge roughness can be achieved even if high sensitivity and low resist outgas can be achieved to a certain extent by creating a pattern of 50 nm or less, which is the greatest merit of ultra-fine processing using extreme ultraviolet light. Since it cannot be reduced, it cannot be said that the original performance of extreme ultraviolet light has been sufficiently brought out. Against this background, it has been demanded to develop a higher performance photoresist.

  In response to this demand, for example, Patent Documents 1 and 2 propose various calix resorcinarene compounds. Further, as shown in Patent Document 3, a calix resorcinarene compound has been proposed as a negative photoresist application. However, when the calix resorcinarene compound described in Patent Document 1 is used for a negative photoresist, there is a problem that sensitivity and line edge roughness are not sufficiently reduced.

JP 2004-191913 A US Pat. No. 6,093,517 JP 2009-173623 A

  An object of the present invention is to provide a cyclic compound that can be used in a negative photoresist that is highly sensitive and effective in reducing line edge roughness.

（式中、Ｒは、下記式（２）〜（４）のいずれかで表される基である。
Ｒ^１は、水酸基、置換もしくは無置換の炭素数１〜２０の直鎖状アルコキシ基、置換もしくは無置換の炭素数３〜１２の分岐アルコキシ基、置換もしくは無置換の炭素数３〜２０の環状アルコキシ基、置換もしくは無置換の炭素数６〜１０のアリーロキシ基、アルコキシアルコキシ基、シロキシ基、又はこれらの基と２価の基とが結合した基であり、
前記２価の基は、置換もしくは無置換のアルキレンオキシ基、置換もしくは無置換のアリーレンオキシ基、置換もしくは無置換のシリレンオキシ基、これらの基が２以上結合した基、又はこれらの基と、エステル結合、炭酸エステル結合又はエーテル結合が結合した基である。
Ｒ^２は、水素原子、Ｒ^１で表される基、炭素数１〜２０の直鎖状脂肪族炭化水素基、炭素数３〜１２の分岐脂肪族炭化水素基、炭素数３〜２０の環状脂肪族炭化水素基、炭素数６〜１０の芳香族基又は酸素原子を含む基である。
式（１）に複数あるＲ、Ｒ^１及びＲ^２は、それぞれ同じであっても異なっていてもよい。

（式中、Ａｒは、置換もしくは無置換の炭素数６〜１０のアリーレン基、置換もしくは無置換の炭素数６〜１０のアリーレン基を２つ以上組み合わせた基、又はアルキレン基及びエーテル結合から選択される１つ以上と置換もしくは無置換の炭素数６〜１０のアリーレン基を組み合わせた基であり、
置換基を有する場合の置換基は、臭素、フッ素、ニトリル基、又は炭素数１〜１０のアルキル基である。
Ｒ^３は、式（５）で表される基である。
Ｒ^３’−Ｌ−Ｏ− （５）
Ｌは、下記式（６）〜（８）で表される基から選択される１つ又は２つ以上が連結されているものであり、任意の連結順を取る。式（６）〜（８）で表される基がそれぞれ複数含まれる場合、同一でも異なっていてもよい。

（式中、Ｒ^４’〜Ｒ^７’はそれぞれ、水素原子、アルキル基又はヘテロ原子含有アルキル基であり、下記式（ｉ）で表される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ^４’〜Ｒ^７’が互いに結合して環状構造を形成していてもよい。）
Ｒ^３’は下記式（ｉ）で表される基である。

（式中、Ｎは、エポキシ基、オキセタニル基、ヒドロキシ基、アルコキシ基、アセトキシ基、窒素含有官能基、硫黄含有官能基、カルボニル基、カルボキシ基、アリールオキシ基、炭素−炭素２重結合から選択される１以上の基を有する炭素数１〜２０の単官能性基又は多官能性基である。
Ｒ^８は、ヘテロ原子、環状構造を有してもよい炭素数１〜１０の２価の置換もしくは無置換の炭化水素基である。ｐ及びｑは、それぞれ独立に、０以上の整数であり、ｐ及びｑのうち少なくとも１つは１以上である。複数のＲ^８は同一であっても、異なっていてもよく、複数のＮは同一であっても、異なっていてもよい。）
Ｒ^４、Ｒ^５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以上を組み合わせた基である。
Ａ^１は、アルキレン基、エーテル結合、アルキレン基を２以上組み合わせた基、又はアルキレン基１以上とエーテル結合１以上を組み合わせた基である。
ｘは１〜５、ｙは０〜３、ｚは０〜４の整数である。
複数のＲ^３、Ｒ^４、Ｒ^５、Ａｒ、Ａ^１、Ｌ、ｘ、ｙ及びｚは、それぞれ同じであっても異なっていてもよい。））
２．前記式（１）の同一芳香族環上のＲ^１のうち、少なくとも１つが水酸基である１に記載の化合物。
３．前記Ｎが酸素含有基又は窒素含有基である１又は２に記載の化合物。
４．１〜３のいずれか１項に記載の化合物及び溶剤を含有するフォトレジスト組成物。
５．光酸発生剤を含有する４に記載のフォトレジスト組成物。
６．塩基性有機化合物をクエンチャーとして含有する４又は５に記載のフォトレジスト組成物。
７．架橋剤を含有する４〜６のいずれか１項に記載のフォトレジスト組成物。
８．４〜７のいずれか１項に記載のフォトレジスト組成物を用いた微細加工方法。
９．８に記載の微細加工方法により作製した半導体装置。
１０．９に記載の半導体装置を備えた装置。 According to the present invention, the following compounds and the like are provided.
1. A compound represented by the following formula (1).

(In formula, R is group represented by either of following formula (2)-(4).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, or a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. A group having an ester bond, a carbonate ester bond or an ether bond.
R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.

(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond. A combination of one or more of the above and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
L is one to which one or two or more selected from groups represented by the following formulas (6) to (8) are connected, and takes an arbitrary connection order. When a plurality of groups represented by formulas (6) to (8) are included, they may be the same or different.

(In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group or a heteroatom-containing alkyl group, and is bonded to an alicyclic structure-containing group represented by the following formula (i) to form a cyclic structure. And a plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure.)
R ^{3 ′} is a group represented by the following formula (i).

(In the formula, N is selected from an epoxy group, an oxetanyl group, a hydroxy group, an alkoxy group, an acetoxy group, a nitrogen-containing functional group, a sulfur-containing functional group, a carbonyl group, a carboxy group, an aryloxy group, and a carbon-carbon double bond. It is a C1-C20 monofunctional group or polyfunctional group which has 1 or more group formed.
R ⁸ is a heteroatom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure. p and q are each independently an integer of 0 or more, and at least one of p and q is 1 or more. A plurality of R ⁸ may be the same or different, and a plurality of N may be the same or different. )
R ⁴ and R ⁵ 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, and a substituted group. Alternatively, it is an 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 group obtained by combining two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x is an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different. ))
2. 2. The compound according to 1, wherein at least one of R ¹ on the same aromatic ring of the formula (1) is a hydroxyl group.
3. 3. The compound according to 1 or 2, wherein N is an oxygen-containing group or a nitrogen-containing group.
The photoresist composition containing the compound and solvent of any one of 4.1-3.
5. 5. The photoresist composition according to 4, containing a photoacid generator.
6). 6. The photoresist composition according to 4 or 5, which contains a basic organic compound as a quencher.
7). The photoresist composition of any one of 4-6 containing a crosslinking agent.
A fine processing method using the photoresist composition according to any one of 8.4 to 7.
A semiconductor device manufactured by the microfabrication method described in 9.8.
A device comprising the semiconductor device according to 10.9.

  ADVANTAGE OF THE INVENTION According to this invention, the cyclic compound which can be used for the negative photoresist effective in reduction of high sensitivity and line edge roughness can be provided.

式中、Ｒは、下記式（２）〜（４）のいずれかで表される基である。Ｒ^１は、水酸基、置換もしくは無置換の炭素数１〜２０（好ましくは１〜６）の直鎖状アルコキシ基、置換もしくは無置換の炭素数３〜１２の分岐アルコキシ基、置換もしくは無置換の炭素数３〜２０の環状アルコキシ基、置換もしくは無置換の炭素数６〜１０のアリーロキシ基、アルコキシアルコキシ基、シロキシ基、又はこれらの基と２価の基とが結合した基である。好ましくは、同一芳香族環上のＲ^１のうち、少なくとも１つが水酸基である。さらに好ましくは、同一芳香族環上のＲ^１のうち、１つのみが水酸基である。より好ましくは、同一芳香族環上のＲ^１のうち、１つが水酸基であり、他の１つが置換もしくは無置換の炭素数１〜２０の直鎖状アルコキシ基又は置換もしくは無置換の炭素数３〜１２の分岐アルコキシ基である。よりさらに好ましくは、同一芳香族環上のＲ^１のうち、１つが水酸基であり、他の１つが置換もしくは無置換の炭素数１又は２の直鎖状アルコキシ基である。 The compound of the present invention is represented by the following formula (1).

In the formula, R is a group represented by any of the following formulas (2) to (4). R ¹ represents a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms (preferably 1 to 6), a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted group. A cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups are bonded to a divalent group. Preferably, at least one of R ¹ on the same aromatic ring is a hydroxyl group. More preferably, only one of R ¹ on the same aromatic ring is a hydroxyl group. More preferably, ^one of R ¹ on the same aromatic ring is a hydroxyl group and the other is a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted carbon number of 3 -12 branched alkoxy groups. More preferably, ^one of R ¹ on the same aromatic ring is a hydroxyl group, and the other is a substituted or unsubstituted linear alkoxy group having 1 or 2 carbon atoms.

The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. It is a group in which an ester bond (—CO ₂ —), a carbonate ester bond (—CO ₃ —) or an ether bond (—O—) is bonded.
The substituent when each of the above groups is substituted is an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group.
R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.

式中、Ａｒは、置換もしくは無置換の炭素数６〜１０のアリーレン基（例えばフェニレン基等）、置換もしくは無置換の炭素数６〜１０のアリーレン基を２つ以上組み合わせた基、又はアルキレン基及びエーテル結合から選択される１つ以上と置換もしくは無置換の炭素数６〜１０のアリーレン基を組み合わせた基であり、置換基を有する場合の置換基は、臭素、フッ素、ニトリル基、又は炭素数１〜１０のアルキル基である。

In the formula, Ar is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms (for example, a phenylene group), a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or an alkylene group. And a group in which one or more selected from ether bonds and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms is combined, and in the case of having a substituent, the substituent is bromine, fluorine, nitrile group, or carbon It is a number 1-10 alkyl group.

式中、Ｒ^４’〜Ｒ^７’はそれぞれ、水素原子、アルキル基又はヘテロ原子含有アルキル基であり、下記式（ｉ）で表される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ^４’〜Ｒ^７’が互いに結合して環状構造を形成していてもよい。好ましくはＲ^４’〜Ｒ^７’はそれぞれ、水素原子又は炭素数１〜４のアルキル基である。 R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
L is one to which one or two or more selected from groups represented by the following formulas (6) to (8) are connected, and takes an arbitrary connection order. When a plurality of groups represented by formulas (6) to (8) are included, they may be the same or different.

In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group, or a heteroatom-containing alkyl group, and forms a cyclic structure by binding to an alicyclic structure-containing group represented by the following formula (i) A plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure. Preferably, R ^{4 ′ to} R ^{7 ′} are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

式中、Ｎは、エポキシ基、オキセタニル基、ヒドロキシ基、アルコキシ基、アセトキシ基、窒素含有官能基、硫黄含有官能基、カルボニル基、アリールオキシ基、アルキルオキシ基、炭素−炭素２重結合から選択される１以上の基を有する炭素数１〜２０の単官能性基又は多官能性基である。
Ｒ^８は、ヘテロ原子、環状構造を有してもよい炭素数１〜１０の２価の置換もしくは無置換の炭化水素基であり、好ましくは炭素数１〜６のアルキレン基である。ｐ及びｑは、それぞれ独立に、０以上の整数であり、ｐ及びｑのうち少なくとも１つは１以上である。ｐは好ましくは０〜１の整数である。ｑは好ましくは１〜２の整数であり、好ましくは１である。複数のＲ^８は同一であっても、異なっていてもよく、複数のＮは同一であっても、異なっていてもよい。
Ｒ^８の置換基は、メチル基、エチル基等のアルキル基、フェニル基、ナフチル基等のアリール基、ケトン基、エステル結合、アルコキシ基、ニトリル基、ニトロ基又は水酸基である。 R ^{3 ′} is a group represented by the following formula (i).

In the formula, N is selected from an epoxy group, an oxetanyl group, a hydroxy group, an alkoxy group, an acetoxy group, a nitrogen-containing functional group, a sulfur-containing functional group, a carbonyl group, an aryloxy group, an alkyloxy group, and a carbon-carbon double bond. It is a C1-C20 monofunctional group or polyfunctional group which has 1 or more group formed.
R ⁸ is a heteroatom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure, preferably an alkylene group having 1 to 6 carbon atoms. p and q are each independently an integer of 0 or more, and at least one of p and q is 1 or more. p is preferably an integer of 0 to 1. q is preferably an integer of 1 to 2, and preferably 1. A plurality of R ⁸ may be the same or different, and a plurality of N may be the same or different.
The substituent of R ⁸ is an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group or a naphthyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group.

R ⁴ and R ⁵ 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, and a substituted group. Alternatively, it is an 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 group obtained by combining two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined. x is 1 to 5, preferably 1. y is 0 to 3, preferably 1. z is 0 to 4, preferably 0. A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different.

As the linear aliphatic hydrocarbon (or alkyl) group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable.
As the branched aliphatic hydrocarbon (or alkyl) group having 3 to 12 carbon atoms, a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group, and the like are preferable.
As the cyclic aliphatic hydrocarbon (or alkyl) group having 3 to 20 carbon atoms, a cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, diadamantyl group and the like are preferable.
As the aromatic group having 6 to 10 carbon atoms, a phenyl group, a naphthyl group, and the like are preferable.
As the alkoxyalkyl group, a methoxymethyl group, an ethoxymethyl group, an adamantyloxymethyl group and the like are preferable.
As the silyl group, a trimethylsilyl group, a t-butyldimethylsilyl group and the like are preferable.

Each of the above groups may have a substituent, specifically, an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group. .
As a linear alkoxy group, a branched alkoxy group, a cyclic alkoxy group, an aryloxy group, an alkoxyalkoxy group, a siloxy group, an alkyleneoxy group, an aryleneoxy group, and a silyleneoxy group, the above corresponding group is bonded to an oxygen atom. And a divalent group.
Examples of the arylene group and the alkylene group include the corresponding divalent groups.

  N in the formula (i) is a monofunctional group or polyfunctional group having 1 to 20 carbon atoms. N represents an epoxy group, an oxetanyl group, a hydroxy group, an alkoxy group, an acetoxy group, a nitrogen-containing functional group (for example, an amino group or an amide group), a sulfur-containing functional group (for example, a mercapto group), a carbonyl group, a carboxy group, or an aryloxy group. , Having one or more groups selected from carbon-carbon double bonds. Preferably it has an epoxy group, an oxetanyl group, a hydroxy group, or a carboxy group. These are groups capable of forming a crosslink. Monofunctional or polyfunctional groups may include aliphatic groups (eg, alkyl groups) and / or aromatic groups.

Examples of the epoxy group-containing group include glycidyl groups and glycidyl group-containing groups such as glycidyloxyalkyl groups, glycidyloxycarbonylalkyl groups, and glycidylamino groups.
Examples of the hydroxy group-containing group include a hydroxyalkyl group.
Examples of the amino group-containing group include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dimethylolaminomethyl group, a diethylolaminomethyl group, a diethylaminomethyl group, and a morpholinomethyl group.
Examples of the carbonyl group-containing group include a formyl group, a carboxy group, and an acid anhydride group.
Examples of the carbon-carbon double bond-containing group include a vinyl group and an isopropenyl group.

式中、点線は結合位置を示す。 Specific examples of N include the following groups, but are not limited thereto.

In the formula, the dotted line indicates the coupling position.

  N is more preferably an oxygen-containing group such as an epoxy group or a carbonyl group, or a nitrogen-containing group such as an amino group or an amide group.

  Examples of the substituent for each group include Ar substituents.

In formula (1), R is a group containing a reactive group (first reactive group), calix resorcinarene (first precursor), and a compound containing a second reactive group (second precursor) The first reactive group and the second reactive group react and bond to each other, and the group containing the first reactive group and the second precursor become the desired R. The 2nd precursor can be made to react 1-5 types simultaneously.
The production method will be specifically exemplified below.

Manufacturing method 1
Corresponding calixresorcinalene compound, second precursor, sodium hydrogen carbonate, dimethylformamide as a solvent are added, and after heating and reacting at 80 ° C. under a nitrogen stream, precipitation caused by adding the reaction solution to water is generated. It can be obtained by filtration and purification.

Manufacturing method 2
Corresponding calixresorcinarene compound, second precursor, sodium hydride, tetrahydrofuran as a solvent was added and reacted at 0 ° C. under a nitrogen stream, then the reaction solution was poured into water and the resulting precipitate was filtered off. It can be obtained by purification.

Manufacturing method 3
By adding N-methylpyrrolidone as the corresponding calixresorcinarene compound, second precursor, and solvent, adding triethylamine and DBU at room temperature under nitrogen flow, reacting them, and then pouring the reaction solution into water The resulting precipitate can be obtained by filtration and purification.

In the above production methods 1, 2, and 3, dimethylformamide, tetrahydrofuran, and N-methylpyrrolidone are used as the solvent, respectively. However, the present invention is not limited thereto, and other solvents may be used as long as the reactants and the raw materials are dissolved.
Examples of other solvents include halogen-containing solvents, oxygen-containing solvents, and aromatic solvents (toluene).

In the above production methods 1, 2, and 3, sodium carbonate, sodium hydrogen carbonate, sodium hydride, triethylamine, and DBU are used as the reactant base, but the invention is not limited thereto, and other organic bases and inorganic bases are used. Also good.
The reaction temperature is preferably −100 ° C. to 100 ° C., particularly preferably −50 ° C. to 80 ° C.

The photoresist composition (negative photoresist composition) of the present invention contains the compound of the present invention (photoresist substrate) and a solvent. The content of the photoresist base material is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the entire composition excluding the solvent.
When used as a photoresist substrate, the photoresist substrate of the present invention may be a single compound or a mixture of two or more.

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

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

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

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

［式中、Ｒ^５１は、直鎖、分岐鎖又は環状のアルキル基、又は直鎖、分岐鎖又は環状のフッ素化アルキル基を表し；Ｒ^５２は、水素原子、水酸基、ハロゲン原子、直鎖又は分岐鎖状のアルキル基、直鎖又は分岐鎖状のハロゲン化アルキル基、又は直鎖又は分岐鎖状のアルコキシ基であり；Ｒ^５３は置換基を有していてもよいアリール基であり；ｕ’’は１〜３の整数である。］ Examples of the onium salt acid generator include acid generators represented by the following formula (a-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 (a-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 (a-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 (a-0) can be used alone or in combination of two or more.
Examples of other onium salt-based acid generators represented by the formula (a-0) include compounds represented by the following formula (a-1) or (a-2).

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

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

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

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

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

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

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

  Specific examples of the onium salt acid generators represented by formulas (a-1) and (a-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 (a-3) or (a-4) in the said formula (a-1) or (a-2) is also used. (The cation moiety is the same as (a-1) or (a-2)).

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

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

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

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

In the present invention, compounds represented by the following formulas (40) to (45) can also be used as a photoacid generator.

In formula (40), 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 (40) 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（４１）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 (41), 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 (41) 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（４２）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 (42), 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 (42) 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（４３）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 (43), 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 formulas (44) and (45), 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 6 carbon atoms. 10 aryl groups.
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 (44a), a carbonyl group, an ester bond, an amide bond or an ether bond.

式（４５ａ）中、Ｚ^２２はそれぞれ独立に、アルキル基、シクロアルキル基又はアリール基であり、Ｒ^２２はそれぞれ独立に、アルキル基、シクロアルキル基又はアルコキシ基であり、ｒは０〜３の整数である。 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 (45a).

In the formula (45a), Z ²² each independently represents an alkyl group, a cycloalkyl group, or an aryl group, each R ²² independently represents an alkyl group, a cycloalkyl group, or an alkoxy group, and r is 0 to 3 It is an integer.

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

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

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

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

  Examples of such acid diffusion control agents include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, and the like; diethanolamine, triethanolamine, diisopropanolamine, tri Isopropanol Alkyl alcohol amines such as min, di-n-octanolamine and tri-n-octanolamine; 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5 Electron beam decomposable basic compounds such as nitrogen atom-containing basic compounds such as cyclic amines such as nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, basic sulfonium compounds and basic iodonium compounds Is 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.

Moreover, you may mix | blend a crosslinking agent with the composition of this invention.
The cross-linking agent is not particularly limited, and can be arbitrarily selected from cross-linking agents used in chemical amplification type negative resist compositions known so far.
Specifically, for example, 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxytri Aliphatic cyclic carbonization having a hydroxy group or a hydroxyalkyl group or both such as cyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane Examples thereof include hydrogen and oxygen-containing derivatives thereof.

In addition, amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is hydroxymethyl group or lower alkoxymethyl. And a compound substituted with a group and a compound having an epoxy group.
Of these, those using melamine are melamine-based crosslinking agents, those using urea are urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea-based crosslinking agents, and glycoluril is used. What was used was a glycoluril-based crosslinking agent, and what used an epoxy group-containing compound was called an epoxy-based crosslinking agent.
The crosslinking agent is preferably at least one selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycoluril crosslinking agents, and epoxy crosslinking agents, and particularly glycoluril. System crosslinking agents are preferred.

  Melamine-based crosslinking agents include compounds in which melamine and formaldehyde are reacted to replace the amino group hydrogen atom with a hydroxymethyl group, and melamine, formaldehyde and lower alcohol are reacted to convert the amino group hydrogen atom into a lower alkoxy group. Examples include compounds substituted with a methyl group. Specific examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like, among which hexamethoxymethyl melamine is preferable.

  Urea-based crosslinking agents include compounds in which urea and formaldehyde are reacted to replace amino group hydrogen atoms with hydroxymethyl groups; urea, formaldehyde and lower alcohols are reacted to convert amino group hydrogen atoms into lower alkoxy groups. Examples include compounds substituted with a methyl group. Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. Among them, bismethoxymethylurea is preferable.

  As an alkylene urea type crosslinking agent, the compound represented by the following general formula (C-1) is mentioned.

［式（Ｃ−１）中、Ｒ^５’とＲ^６’はそれぞれ独立に水酸基又は低級アルコキシ基であり、Ｒ^３’とＲ^４’はそれぞれ独立に水素原子、水酸基又は低級アルコキシ基であり、ｖは０又は１〜２の整数である。］

[In Formula (C-1), R ^{5 ′} and R ^{6 ′} each independently represent a hydroxyl group or a lower alkoxy group, and R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom, a hydroxyl group or a lower alkoxy group, v is 0 or an integer of 1-2. ]

When R ^{5 ′} and R ^{6 ′} are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. R ^{5 ′} and R ^{6 ′} may be the same or different from each other. More preferably, they are the same.
When R ^{3 ′} and R ^{4 ′} are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. R ^{3 ′} and R ^{4 ′} may be the same or different from each other. More preferably, they are the same.
v is 0 or an integer of 1 to 2, and preferably 0 or 1.
As the alkylene urea crosslinking agent, a compound in which v is 0 (ethylene urea crosslinking agent) and / or a compound in which v is 1 (propylene urea crosslinking agent) are particularly preferable.

  The compound represented by the general formula (C-1) can be obtained by a condensation reaction of alkylene urea and formalin, and by reacting this product with a lower alcohol.

Specific examples of the alkylene urea crosslinking agent include, for example, mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxy Ethylene urea-based crosslinking agents such as methylated ethylene urea, mono and / or dibutoxymethylated ethylene urea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethyl Propylene urea-based crosslinkers such as propylene urea, mono and / or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) 4,5-dihydroxy-2- Imidazolidinone, 1,3-di (Metoki Include methyl) -4,5-dimethoxy-2-imidazolidinone.

Examples of the glycoluril-based crosslinking agent include glycoluril derivatives in which the N position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. Such a glycoluril derivative can be obtained by a condensation reaction of glycoluril and formalin and by reacting this product with a lower alcohol.
Specific examples of the glycoluril-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated glycoluril; mono, di, tri and / or tetramethoxymethylated glycoluril; mono, di, tri and / or Examples include tetraethoxymethylated glycoluril; mono, di, tri and / or tetrapropoxymethylated glycoluril; mono, di, tri and / or tetrabutoxymethylated glycoluril.

The epoxy-based crosslinking agent is not particularly limited as long as it has an epoxy group, and can be arbitrarily selected and used. Among them, those having two or more epoxy groups are preferable. By having two or more epoxy groups, crosslinking reactivity is improved.
The number of epoxy groups is preferably 2 or more, more preferably 2 to 4, and most preferably 2.
The following are suitable as the epoxy-based crosslinking agent.

A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
It is preferable that content of a crosslinking agent is 1-50 mass parts with respect to 100 mass parts of compounds of this invention, 3-30 mass parts is more preferable, 3-15 mass parts is more preferable, 5-10 mass Part is most preferred.

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

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

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

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

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

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

  An organic carboxylic acid or phosphorus oxo acid or a derivative thereof is added as an optional component for the purpose of preventing sensitivity deterioration when an acid diffusion control agent is added and improving the resist pattern shape, retention stability, etc. be able to. These compounds can be used in combination with an acid diffusion controller or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus 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 present invention, in order to stably form a high-precision fine pattern, it is preferable to heat after irradiation (after exposure). The post-exposure heating temperature (PEB) varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

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

  When the compound of the present invention is used as a photoresist substrate, for example, when an acid generator and a crosslinking agent are used in combination, the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Acid is generated from the acid generator, and the acid acts to cause cross-linking between the compounds of the present invention or the added cross-linking agent, so that the composition of the present invention becomes insoluble in an alkaline developer. On the other hand, the unexposed portion remains soluble in the alkali developer, and a resist pattern can be formed by alkali development.

  When the composition of the present invention is used, highly fine processing with high sensitivity and low line edge roughness is possible.

  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 may be performed after the alkali development, or an organic or inorganic antireflection film may be provided between the resist film and the substrate.

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

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

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

  A semiconductor device can be produced by a microfabrication method using the 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.

  The compound of the present invention can produce various molded products (thin films, films, thin plates, fibers, etc. formed on a substrate such as a silicon wafer) by known molding methods.

  Molding methods include injection molding, injection compression molding, extrusion molding, blow molding, pressure molding, transfer molding, spin coating, spray coating, casting, vapor deposition, thermal CVD, plasma Examples thereof include a CVD method and a plasma polymerization method, and these molding methods can be appropriately selected according to the form and performance of a desired product.

  Further, a thin film is obtained by the above method using the compound of the present invention, and the obtained thin film is cured by heat, ultraviolet light, deep ultraviolet light, vacuum ultraviolet light, extreme ultraviolet light, electron beam, plasma, X-ray, etc. (cyclization addition) Reaction).

  When the compound of the present invention is formed into a thin film by a spin coating method or the like, the compound of the present invention can be dissolved in an organic solvent and used as a paint.

  Examples of organic solvents include chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, dichloroethane, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide, dimethyl sulfoxide. (DMSO), anisole, acetophenone, benzonitrile, nitrobenzene, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran (THF), cyclohexanone, methyl ethyl ketone, acetone and the like.

The concentration of the compound of the present invention in the paint may be appropriately adjusted in consideration of the viscosity of the paint and the thin film forming method.
The thickness of the thin film is not particularly limited, but generally a thickness of about 10 nm to 10 μm is preferably used. The film thickness of the thin film can be measured with an ellipsometer, a reflective optical film thickness meter, or the like, or with a stylus film thickness meter or AFM.

  The thin film of the present invention is used as a photoresist thin film, optical thin films for various optical information processing devices such as optical lenses, optical fibers, optical waveguides, photonic crystals, interlayer insulating films for semiconductors, protective films for semiconductors, etc. It is useful as a thin film for ULSI devices, a liquid crystal display, a liquid crystal projector, a plasma display, an EL display, an LED display and other thin film for image display devices, a CMOS image sensor, a CCD image sensor, and the like. Furthermore, these thin films are provided for semiconductor devices such as CPU, DRAM, flash memory, electronic circuit devices for information processing, electronic circuit devices such as high-frequency communication electronic circuit devices, image display devices, optical information processing devices, and optical communication devices. It can also be used in a member such as a surface protective film and a heat-resistant film.

Synthesis example 1
Under a nitrogen stream, in a round bottom flask with a capacity of 200 ml, 50.0 g (402.8 mmol) of 3-methoxyphenol (Tokyo Chemical Industry Co., Ltd.), 4-formylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 60. 5 g (402.8 mmol) and 500 ml of dehydrated dichloromethane were added and immersed in an ice-water bath and cooled to 5 ° C. or lower. To this mixture, 60.8 ml (483.6 mmol) of boron trifluoride ether adduct (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 15 ° C., and then the temperature was raised to room temperature. Warmed and continued stirring for 8 hours. The reaction solution was cooled in an ice water bath, quenched slowly by dropwise addition of water, and the precipitated solid was filtered off. Further, the precipitate separated by filtration is washed with water until it becomes neutral, then dissolved in N-methyl-2-pyrrolidone, reprecipitated with ethyl acetate, and the precipitated solid is separated by filtration to obtain a cyclic compound (A (Yield 94.4 g).
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (1).

窒素気流下、３−ブテン−１−オール１５ｇ（２０８．０ｍｍｏｌ）、脱水エーテル３００ｍｌにトリエチルアミン３４．８ｍｌ（２４９．６ｍｍｏｌ）を加え氷冷した。この溶液にブロモ酢酸ブロミド２１．７ｍｌ（２４９．６ｍｍｏｌ）を滴下した。滴下終了後、室温まで昇温し、そのまま攪拌を行った。反応溶液を飽和炭酸水素ナトリウム水溶液で洗浄後、有機層を無水硫酸マグネシウムで乾燥後、減圧下溶媒を留去した。残渣を減圧蒸留することにより３−ブテニルブロモアセテートを得た（収量３５．５ｇ（１８３．９ｍｍｏｌ））。
窒素気流下、３−ブテニルブロモアセテート３５．５ｇ（１８３．９ｍｍｏｌ）をジクロロメタン３００ｍｌに溶解し氷冷した。これに、６５％含量のｍ−クロロ過安息香酸５８．９ｇ（２２１．８ｍｍｏｌ）を加え８時間攪拌をおこなった。亜硫酸水素ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液で洗浄後、有機層を無水硫酸マグネシウムで乾燥、減圧下溶媒を留去した。残渣をシリカゲルクロマトグラフィーで精製することにより、２−（オキシラン−２−イル）エチルブロモアセテートを得た（収量２８．９ｇ（１４９．７ｍｍｏｌ））。
（^１Ｈ−ＮＭＲ：１．８５（ｍ，１Ｈ），２．０１（ｍ，１Ｈ），２．５３（１Ｈ），２．８１（１Ｈ），３．８９（ｓ，２Ｈ），４．３５（ｔ，２Ｈ）（ＣＤＣｌ_３）） Synthesis example 2
Synthesis of 2- (oxiran-2-yl) ethyl bromoacetate

Under a nitrogen stream, 34.8 ml (249.6 mmol) of triethylamine was added to 15 g (208.0 mmol) of 3-buten-1-ol and 300 ml of dehydrated ether, and the mixture was ice-cooled. To this solution, 21.7 ml (249.6 mmol) of bromoacetic acid bromide was added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature and stirred as it was. The reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to give 3-butenyl bromoacetate (yield 35.5 g (183.9 mmol)).
Under a nitrogen stream, 35.5 g (183.9 mmol) of 3-butenyl bromoacetate was dissolved in 300 ml of dichloromethane and cooled on ice. To this, 58.9 g (221.8 mmol) of m-chloroperbenzoic acid having a 65% content was added and stirred for 8 hours. After washing with a sodium hydrogen sulfite aqueous solution and a saturated sodium hydrogen carbonate aqueous solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to give 2- (oxiran-2-yl) ethyl bromoacetate (yield 28.9 g (149.7 mmol)).
^{(1 H-NMR: 1.85 (} m, 1H), 2.01 (m, 1H), 2.53 (1H), 2.81 (1H), 3.89 (s, 2H), 4.35 (T, 2H) (CDCl ₃ ))

Synthesis example 3
Synthesis of 7-oxa-bicyclo [4.1.0] heptan-3-ylmethyl bromoacetate

Under a nitrogen stream, 15.6 ml (133.72 mmol) of 3-cyclohexene-1-methanol and 22.3 ml (160.42 mmol) of triethylamine were dissolved in 450 ml of diethyl ether and cooled with ice. To this solution, 14 ml (160.71 ml) of bromoacetic acid bromide was added dropwise. After completion of dropping, the mixture was stirred as it was for 8 hours. The reaction solution was poured into ice-cold water and ethyl acetate was added. The organic layer was separated and washed with a saturated aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain 19.57 g (88.3 mmol) of 3-cyclohexene-1-methylbromoacetate. Under a nitrogen stream, the obtained compound was dissolved in 300 ml of dichloromethane and cooled on ice. To this, 26.9 g (up to 65% content) of m-chloroperbenzoic acid was added and stirred for 8 hours. After washing with a sodium hydrogen sulfite aqueous solution and a saturated sodium hydrogen carbonate aqueous solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 7-oxa-bicyclo [4.1.0] heptan-3-ylmethyl bromoacetate (yield 18.3 g (73.46 mmol)).
^{(1 H-NMR: 1.0-2.2 (} 7H), 3.19 (2H), 3.85 (s, 2H), 3.98 (2H) (CDCl 3))

（^１Ｈ−ＮＭＲ：１．６−１．９５（８Ｈ），２．６８（４Ｈ），２．９８（４Ｈ），３．４−３．７（１２Ｈ），４．２９（８Ｈ），４．８７（８Ｈ），５．１−５．３，５．５１−５．７１，６．１５−６．４，６．５１（１２Ｈ），６．６−６．８（８Ｈ），７．４−７．６（８Ｈ），８．９−９．１，９．１−９．２（４Ｈ）（（ＣＤ_３）_２ＳＯ）） Example 1 (Synthesis of Compound (2))
Under a nitrogen stream, 2.0 g (1.95 mmol) of the calix resorcinalene compound obtained in Synthesis Example 1 and 30 ml of N-methyl-2-pyrrolidone were sealed in a 100 ml round bottom flask and dissolved. 2.24 g (10.72 mmol) of 2- (oxiran-2-yl) ethyl bromoacetate obtained in Synthesis Example 2 was added. Next, 1.50 ml (10.72 mmol) of triethylamine was added and stirred for 10 minutes, and 0.48 ml (3.22 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added. . After stirring for 20 hours, the reaction was stopped by adding a saturated ammonium chloride solution. Subsequently, the reaction solution was extracted with ethyl acetate and washed with pure water and saturated brine. The obtained solution was concentrated and reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain the desired product (yield 2.10 g, yield 70.0%). ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (2).

^{(1 H-NMR: 1.6-1.95 (} 8H), 2.68 (4H), 2.98 (4H), 3.4-3.7 (12H), 4.29 (8H), 4 .87 (8H), 5.1-5.3, 5.51-5.71, 6.15-6.4, 6.51 (12H), 6.6-6.8 (8H), 7. 4-7.6 (8H), 8.9-9.1,9.1-9.2 (4H ) ((CD 3) 2 SO))

（^１Ｈ−ＮＭＲ：０．９−２．１（２８Ｈ），３．０−３．１（８Ｈ），３．４−３．７（１２Ｈ），３．８−４．０（８Ｈ），５．１−５．３，５．５１−５．７１，６．１５−６．４，６．５１（１２Ｈ），６．６−６．８（８Ｈ），７．４−７．６（８Ｈ），８．９−９．１，９．１−９．２（４Ｈ）（（ＣＤ_３）_２ＳＯ）） Example 2 (Synthesis of Compound (3))
A photoresist base material (3) was obtained in the same manner as in Example 1 except that the compound obtained in Synthesis Example 3 was used. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had a structure represented by the following formula.

^{(1 H-NMR: 0.9-2.1 (} 28H), 3.0-3.1 (8H), 3.4-3.7 (12H), 3.8-4.0 (8H), 5.1-5.3, 5.51-5.71, 6.15-6.4, 6.51 (12H), 6.6-6.8 (8H), 7.4-7.6 ( 8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Comparative Example 1 (Synthesis of Compound (4))
In a four-necked flask (1 L) equipped with a dropping funnel, Jim Roth condenser, thermometer, and stirring blade, under a nitrogen stream, resorcinol (22 g, 0.2 mol) and acetaldehyde (8.8 g, 0.8. 2 mol) and dehydrated ethanol (200 ml) were introduced. The solution was heated to 85 ° C. with stirring, and 75 ml of concentrated hydrochloric acid (35%) was added dropwise using a dropping funnel, and subsequently stirred at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, cooled in an ice bath, allowed to stand for 1 hour, and then generated crude crystals were separated by filtration. This was washed twice with methanol, filtered, and vacuum dried to obtain the target compound (4) (yield 95%).

(Photoresist composition)
Example 3
A photoresist composition comprising a base material, PAG (photoacid generator), quencher, crosslinking agent, and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
As a substrate, compound (2) obtained in Example 1, triphenylsulfonium nonafluorobutanesulfonate as PAG, 1,4-diazabicyclo (2,2,2) octane as a quencher, and MX270 (Sanwa) as a crosslinking agent Chemical Co.) was used. Table 1 shows the composition of each component. These solid components were dissolved in propylene glycol monomethyl ether so as to have a concentration of 2% by weight to obtain a photoresist composition.

Example 4 and Comparative Example 2
As shown in Table 1, a photoresist composition was prepared in the same manner as in Example 3 except that the compound used in the substrate and the formulation were changed.

The photoresist compositions obtained in Examples 3 and 4 and Comparative Example 2 were each spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment and pre-baked (before exposure) at the temperatures shown in Table 1. A thin film was formed by baking (PB). Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), and after exposure bake (PEB) at the temperature shown in Table 1, tetrabutyl having a concentration of 2.38 wt%. The film was developed with an aqueous ammonium hydroxide solution for 60 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream. The resolution (half pitch), sensitivity (required electron beam dose), and line edge roughness (LER) when a line / space pattern with a size of 1/1 was obtained from the results of observation with a scanning electron microscope. The results are shown in Table 2. LER was measured for a 50 nm, 1: 1 line and space pattern.
The results were the same even when tri-n-octylamine was used in place of 1,4-diazabicyclo (2,2,2) octane as the quencher.

基材・ＰＡＧ・クエンチャー・架橋剤中の数字は配合量（質量部）である。

The numbers in the base material, PAG, quencher, and crosslinking agent are blending amounts (parts by mass).

ＬＥＲは３ｎｍ以下を○、３ｎｍ＜ＬＥＲ＜４ｎｍを△、４ｎｍ以上を×とした。

For LER, 3 nm or less was evaluated as ◯, 3 nm <LER <4 nm as Δ, and 4 nm or more as X.

  The compound of the present invention can be suitably used for a photoresist substrate or composition, particularly for an extreme ultraviolet light and / or an electron beam photoresist substrate or composition. The photoresist and the photoresist composition of the present invention are suitably used in the electric / electronic field and the optical field such as semiconductor devices.

Claims (10)

A compound represented by the following formula (1).

(In formula, R is group represented by either of following formula (2)-(4).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, or a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. A group having an ester bond, a carbonate ester bond or an ether bond.
R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.

(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond. A combination of one or more of the above and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
L is one to which one or two or more selected from groups represented by the following formulas (6) to (8) are connected, and takes an arbitrary connection order. When a plurality of groups represented by formulas (6) to (8) are included, they may be the same or different.

(In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group or a heteroatom-containing alkyl group, and is bonded to an alicyclic structure-containing group represented by the following formula (i) to form a cyclic structure. And a plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure.)
R ^{3 ′} is a group represented by the following formula (i).

(In the formula, N is selected from an epoxy group, an oxetanyl group, a hydroxy group, an alkoxy group, an acetoxy group, a nitrogen-containing functional group, a sulfur-containing functional group, a carbonyl group, a carboxy group, an aryloxy group, and a carbon-carbon double bond. It is a C1-C20 monofunctional group or polyfunctional group which has 1 or more group formed.
R ⁸ is a heteroatom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure. p and q are each independently an integer of 0 or more, and at least one of p and q is 1 or more. A plurality of R ⁸ may be the same or different, and a plurality of N may be the same or different. )
R ⁴ and R ⁵ 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, and a substituted group. Alternatively, it is an 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 group obtained by combining two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x is an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different. )) The compound according to claim 1, wherein at least one of R ¹ on the same aromatic ring of the formula (1) is a hydroxyl group.   The compound according to claim 1 or 2, wherein N is an oxygen-containing group or a nitrogen-containing group.   The photoresist composition containing the compound and solvent of any one of Claims 1-3.   The photoresist composition of Claim 4 containing a photo-acid generator.   The photoresist composition according to claim 4 or 5, which contains a basic organic compound as a quencher.   The photoresist composition of any one of Claims 4-6 containing a crosslinking agent.   The fine processing method using the photoresist composition of any one of Claims 4-7.   A semiconductor device manufactured by the microfabrication method according to claim 8.   An apparatus comprising the semiconductor device according to claim 9.