JP5435995B2 - Method for producing cyclic compound - Google Patents

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.

  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). Patent Document 4 discloses a calix resorcinarene compound.

  However, higher sensitivity and higher resolution are required as an ultrafine processing technique using EUVL. The photoresist materials disclosed in the above-mentioned Patent Documents 1 to 4 cannot sufficiently exhibit the required levels of high sensitivity and high resolution.

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

  An object of the present invention is to provide a photoresist material with high sensitivity and high resolution.

（式中、
Ｒは、置換もしくは無置換の炭素数１〜２０の直鎖状脂肪族基、置換もしくは無置換の炭素数３〜１２の分岐脂肪族基、置換もしくは無置換の炭素数３〜２０の環状脂肪族基、置換もしくは無置換の炭素数６〜１０の芳香族基、アルコキシアルキル基、シリル基、又はこれらの基と二価の基とが結合した基であり、
前記二価の基は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、置換もしくは無置換のシリレン基、エステル結合、炭酸エステル結合、エーテル結合、又はこれらの基から選択される１以上と、これらの結合から選択される１以上が結合した基である。
Ｘは、ハロゲン原子又は水酸基である。
Ｒ^１は、それぞれ水酸基、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、アルコキシアルキロキシ基、シロキシ基、又はこれらの基と二価の基とが結合した基であり、
前記二価の基は、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以上結合してなる基、又はこれらの基とエステル結合、炭酸エステル結合及びエーテル結合から選択される１以上の結合が結合してなる基である。
Ｒ^２は、それぞれ水素原子、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。
Ａｒは、それぞれ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のアリーレン基が２以上結合した基、アルキレン基及びエーテル結合から選択される１以上の基と置換もしくは無置換の炭素数６〜１０のアリーレン基とが結合した基であり、
Ａｒの置換基は、臭素原子、フッ素原子、ニトリル基又は炭素数１〜１０のアルキル基である。
Ａ^１は、それぞれ単結合、アルキレン基、１以上のアルキレン基と１以上エーテル結合が結合した基、又は下記式（４）で表される基である。
ｘはそれぞれ１〜５の整数を表し、ｙはそれぞれ０〜３の整数を表す。

Ｒ^４及び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以上が結合した基である。
但し、複数のＲ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ａｒ、Ａ^１、ｘ及びｙは、それぞれ同じであっても異なっていてもよい。）
２． 下記式（５−２）で表される化合物及び下記式（３）で表される置換基前駆体化合物に１〜３種の塩基性有機化合物を縮合剤として添加する式（５−１）で表される化合物の製造方法。

（式中、
Ｒは、上記と同様である。
Ｘは、上記と同様である。
Ｒ^８は、それぞれ水素原子、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。
Ｒ^３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６〜１０の芳香族基、又はこれら基のから選択される２以上が結合した基、又は下記式（５’）で表される基である。
Ｒ^６は、それぞれ水酸基、カルボキシル基とＲが結合した基、又はカルボキシル基と二価の基が結合した基にＲが結合した基であり、８個のＲ^６のうち、４個のＲ^６は水酸基であり、４個のＲ^６はカルボキシル基とＲが結合した基又はカルボキシル基と二価の基が結合した基にＲが結合した基である。
Ｒ^７は、それぞれ水酸基、カルボキシル基、又はカルボキシル基と二価の基が結合した基であり、
前記二価の基は、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以上結合してなる基、又はこれらの基とエステル結合、炭酸エステル結合及びエーテル結合から選択される１以上の結合とが結合してなる基であり、
８個のＲ^７のうち、４個のＲ^７が水酸基であり、４個のＲ^７がカルボキシル基又はカルボキシル基と二価の基が結合した基である。

Ｒ^４、Ｒ^５及びＡｒは上記と同様である。
ｙは０〜３の整数を表す。
但し、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ａｒ、Ａ^１及びｙは、それぞれ同じであっても異なっていても良い）
３． Ｒ^２が水素原子であり、Ｒが下記式（Ｉ）〜（IV）で表される酸解離性溶解抑止基のいずれかである１に記載の製造方法。

（式中、
αは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。
βは、三級脂肪族構造、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基である。
γは、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基、又は芳香族構造、単環状脂肪族構造、複環状脂肪族構造のうち１以上の構造と、炭素数１〜１０の直鎖状脂肪族炭化水素基を組み合わせた基が置換したアルコキシ基である。
δは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。）
４． Ｒ^８が水素原子であり、Ｒが下記式（Ｉ）〜（IV）で表される酸解離性溶解抑止基のいずれかである２に記載の製造方法。

（式中、
αは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。
βは、三級脂肪族構造、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基である。
γは、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基、又は芳香族構造、単環状脂肪族構造、複環状脂肪族構造のうち１以上の構造と、炭素数１〜１０の直鎖状脂肪族炭化水素基を組み合わせた基が置換したアルコキシ基である。
δは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。）
５． Ｒが、下記式（６）〜（３７）で表される酸解離性溶解抑止基のいずれかである１〜４のいずれかに記載の製造方法。

（式中、ｒはそれぞれ上記式（６）〜（３４）で表される置換基のいずれかである。）
６． 前記１〜３種の塩基性有機化合物の少なくとも１種類が有機アミン化合物である１〜５のいずれかに記載の製造方法。
７． 前記有機アミン化合物が、窒素原子含有複素環構造を含む６に記載の製造方法。
８． 前記有機アミン化合物が、１，８−ジアザビシクロ［５，４，０］−７−ウンデセンである６又は７に記載の製造方法。
９． １〜８のいずれかに記載の製造方法で製造された化合物を含む薄膜。
１０． １〜８のいずれかに記載の製造方法で製造された化合物からなるフォトレジスト基材を含有するフォトレジスト組成物。
１１． １０に記載のフォトレジスト組成物を用いた微細加工方法。
１２． １１に記載の微細加工方法により作製した半導体装置。 According to the present invention, the following photoresist compositions and the like are provided.
1. A compound represented by the formula (1) in which 1 to 3 basic organic compounds are added as a condensing agent to a compound represented by the following formula (2) and a substituent precursor compound represented by the following formula (3) Manufacturing method.

(Where
R is a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 3 to 20 carbon atoms. A group, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a group in which these groups and a divalent group are bonded,
The divalent group is selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond, a carbonate ester bond, an ether bond, or a group thereof. The above is a group in which one or more selected from these bonds are bonded.
X is a halogen atom or a hydroxyl group.
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, a substituted or unsubstituted carbon group having 3 to 20 carbon atoms, respectively. A cyclic alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkyloxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group is a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or these groups And one or more bonds selected from an ester bond, a carbonate ester bond and 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 group having 3 to 20 carbon atoms. A cyclic aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
Ar represents one or more 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 bonded, an alkylene group, and an ether bond. A group bonded to a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
The substituent for Ar is a bromine atom, a fluorine atom, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
A ¹ is a single bond, an alkylene group, a group in which one or more alkylene groups and one or more ether bonds are bonded, or a group represented by the following formula (4).
Each x represents an integer of 1 to 5, and y represents an integer of 0 to 3, respectively.

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 in which two or more of these groups are bonded.
However, the plurality of R ¹ , R ² , R ⁴ , R ⁵ , Ar, A ¹ , x and y may be the same or different. )
2. In formula (5-1), 1 to 3 basic organic compounds are added as a condensing agent to the compound represented by the following formula (5-2) and the substituent precursor compound represented by the following formula (3). A method for producing the represented compound.

(Where
R is the same as described above.
X is the same as described above.
R ⁸ is a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, carbon It is a group containing an aromatic group or oxygen atom of several 6 to 10.
R ³ is 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, a substituted or unsubstituted group, respectively. A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, a group in which two or more selected from these groups are bonded, or the following formula (5 ′ ).
R ⁶ is a group in which R is bonded to a hydroxyl group, a group in which a carboxyl group is bonded to R, or a group in which a carboxyl group is bonded to a divalent group, and four R ⁶ are out of eight R ^6. Is a hydroxyl group, and four R ⁶ are groups in which R is bonded to a group in which a carboxyl group and R are bonded or a group in which a carboxyl group and a divalent group are bonded.
R ⁷ is a hydroxyl group, a carboxyl group, or a group in which a carboxyl group and a divalent group are bonded,
The divalent group is a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or these groups And a group formed by bonding one or more bonds selected from an ester bond, a carbonate ester bond and an ether bond,
Of the eight R ^7, four R ⁷ is a hydroxyl group, a four R ⁷ is a carboxyl group or a carboxyl group and a divalent group bonded group.

R ⁴ , R ⁵ and Ar are the same as above.
y represents an integer of 0 to 3.
(However, a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , Ar, A ¹ and y may be the same or different.)
3. ^2. The production method according to 1, wherein R ² is a hydrogen atom, and R is any of the acid dissociable, dissolution inhibiting groups represented by the following formulas (I) to (IV).

(Where
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
4). 3. The production method according to 2, wherein R ⁸ is a hydrogen atom, and R is any of the acid dissociable, dissolution inhibiting groups represented by the following formulas (I) to (IV).

(Where
α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; , An alkoxy group substituted with a group having a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ represents a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number of 3 to 3 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
5. The production method according to any one of 1 to 4, wherein R is any of the acid dissociable, dissolution inhibiting groups represented by the following formulas (6) to (37).

(In the formula, r is any of the substituents represented by the above formulas (6) to (34).)
6). The production method according to any one of 1 to 5, wherein at least one of the 1-3 basic organic compounds is an organic amine compound.
7). 7. The production method according to 6, wherein the organic amine compound includes a nitrogen atom-containing heterocyclic structure.
8). 8. The production method according to 6 or 7, wherein the organic amine compound is 1,8-diazabicyclo [5,4,0] -7-undecene.
9. The thin film containing the compound manufactured with the manufacturing method in any one of 1-8.
10. The photoresist composition containing the photoresist base material which consists of a compound manufactured with the manufacturing method in any one of 1-8.
11. A fine processing method using the photoresist composition according to 10.
12 A semiconductor device manufactured by the microfabrication method according to 11.

  According to the present invention, a photoresist material with high sensitivity and high resolution can be provided.

（式中、
Ｒは、置換もしくは無置換の炭素数１〜２０の直鎖状脂肪族基、置換もしくは無置換の炭素数３〜１２の分岐脂肪族基、置換もしくは無置換の炭素数３〜２０の環状脂肪族基、置換もしくは無置換の炭素数６〜１０の芳香族基、アルコキシアルキル基、シリル基、又はこれらの基と二価の基とが結合した基であり、
前記二価の基は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、置換もしくは無置換のシリレン基、エステル結合、炭酸エステル結合、エーテル結合、又はこれらの基から選択される１以上と、これらの結合から選択される１以上が結合した基である。
Ｘは、ハロゲン原子又は水酸基である。
Ｒ^１は、それぞれ水酸基、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、アルコキシアルキロキシ基、シロキシ基、又はこれらの基と二価の基とが結合した基であり、
前記二価の基は、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以上結合してなる基、又はこれらの基とエステル結合（−ＣＯ_２−）、炭酸エステル結合（−ＯＣＯ_２−）及びエーテル結合（−Ｏ−）から選択される１以上の結合が結合してなる基である。
Ｒ^２は、それぞれ水素原子、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。
Ａｒは、それぞれ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のアリーレン基が２以上結合した基、アルキレン基及びエーテル結合から選択される１以上の基と置換もしくは無置換の炭素数６〜１０のアリーレン基とが結合した基であり、
Ａｒの置換基は、臭素原子、フッ素原子、ニトリル基又は炭素数１〜１０のアルキル基である。
Ａ^１は、それぞれアルキレン基、１以上のアルキレン基と１以上エーテル結合が結合した基、単結合、又は下記式（４）で表される基である。
ｘはそれぞれ１〜５の整数を表し、ｙはそれぞれ０〜３の整数を表す。

Ｒ^４及び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以上が結合した基である。
但し、複数のＲ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ａｒ、Ａ^１、ｘ及びｙは、それぞれ同じであっても異なっていてもよい。） The compound represented by the formula (1) of the present invention is obtained by adding 1 to 3 basic organic compounds to the compound represented by the following formula (2) and the substituent precursor compound represented by the following formula (3). It can be obtained by adding as a condensing agent.

(Where
R is a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 3 to 20 carbon atoms. A group, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a group in which these groups and a divalent group are bonded,
The divalent group is selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, an ester bond, a carbonate ester bond, an ether bond, or a group thereof. The above is a group in which one or more selected from these bonds are bonded.
X is a halogen atom or a hydroxyl group.
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, a substituted or unsubstituted carbon group having 3 to 20 carbon atoms, respectively. A cyclic alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkyloxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group is a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or these groups And one or more bonds selected from an ester bond (—CO ₂ —), a carbonate ester bond (—OCO ₂ —), and an ether bond (—O—).
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 group having 3 to 20 carbon atoms. A cyclic aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
Ar represents one or more 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 bonded, an alkylene group, and an ether bond. A group bonded to a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
The substituent for Ar is a bromine atom, a fluorine atom, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
A ¹ is an alkylene group, a group in which one or more alkylene groups and one or more ether bonds are bonded, a single bond, or a group represented by the following formula (4).
Each x represents an integer of 1 to 5, and y represents an integer of 0 to 3, respectively.

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 in which two or more of these groups are bonded.
However, the plurality of R ¹ , R ² , R ⁴ , R ⁵ , Ar, A ¹ , x and y may be the same or different. )

（式中、
Ｒは、上記と同様である。
Ｘは、上記と同様である。
Ｒ^８は、それぞれ水素原子、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。
Ｒ^３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６〜１０の芳香族基、又はこれら基のから選択される２以上が結合した基、又は下記式（５’）で表される基である。
Ｒ^６は、それぞれ水酸基、カルボキシル基とＲが結合した基又はカルボキシル基と二価の基が結合した基にＲが結合した基であり、８個のＲ^６のうち、４個のＲ^６は水酸基であり、４個のＲ^６はカルボキシル基とＲが結合した基又はカルボキシル基と二価の基が結合した基にＲが結合した基である。
Ｒ^７は、それぞれ水酸基、カルボキシル基、又はカルボキシル基と二価の基が結合した基であり、
前記二価の基は、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以上結合してなる基、又はこれらの基とエステル結合、炭酸エステル結合及びエーテル結合から選択される１以上の結合とが結合してなる基であり、
８個のＲ^７のうち、４個のＲ^７が水酸基であり、４個のＲ^７がカルボキシル基又はカルボキシル基と二価の基が結合した基である。

Ｒ^４、Ｒ^５及びＡｒは上記と同様である。
ｙは０〜３の整数を表す。
但し、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ａｒ、Ａ^１及びｙは、それぞれ同じであっても異なっていても良い） The compound represented by the formula (5-1) of the present invention includes 1 to 3 bases in the compound represented by the following formula (5-2) and the substituent precursor compound represented by the following formula (3). It can be obtained by adding a functional organic compound as a condensing agent.

(Where
R is the same as described above.
X is the same as described above.
R ⁸ is a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, carbon It is a group containing an aromatic group or oxygen atom of several 6 to 10.
R ³ is 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, a substituted or unsubstituted group, respectively. A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, a group in which two or more selected from these groups are bonded, or the following formula (5 ′ ).
R ⁶ are each a hydroxyl group, a carboxyl group and R is R a groups bonded to group or a carboxyl group and a divalent group bonded is bonded groups, of the eight R ^6, the four R ⁶ Four R ⁶ are a group in which R is bonded to a group in which a carboxyl group and R are bonded or a group in which a carboxyl group and a divalent group are bonded.
R ⁷ is a hydroxyl group, a carboxyl group, or a group in which a carboxyl group and a divalent group are bonded,
The divalent group is a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group formed by bonding two or more of these groups, or these groups And a group formed by bonding one or more bonds selected from an ester bond, a carbonate ester bond and an ether bond,
Of the eight R ^7, four R ⁷ is a hydroxyl group, a four R ⁷ is a carboxyl group or a carboxyl group and a divalent group bonded group.

R ⁴ , R ⁵ and Ar are the same as above.
y represents an integer of 0 to 3.
(However, a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , Ar, A ¹ and y may be the same or different.)

  By using the production method of the present invention, among the phenolic hydroxyl group and the carboxyl group of the compound represented by formula (2) and the compound represented by formula (5-2), only the carboxyl group is selectively R. Can be replaced.

In the compound represented by the formula (2), R ² is preferably a hydrogen atom. In the compound represented by the formula (5-2), R ⁸ is preferably a hydrogen atom.

In the compound represented by formula (2), R ¹ is preferably a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms. R ² is a hydrogen atom or a group represented by R ¹ , Ar is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and A ¹ is a single bond or an alkylene group, It is a substituent represented by (—O—CH ₂ —), x is an integer of 1 or 2, and y is an integer of 1.

In the compound represented by the formula (5-2), R ³ is preferably a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted 6 to 10 carbon atoms. It is an aromatic group, R ⁷ is a hydroxyl group, and R ⁸ is a hydrogen atom.

（式中、
αは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。
βは、三級脂肪族構造、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基である。
γは、芳香族構造、単環状脂肪族構造又は複環状脂肪族構造を有する基が置換したアルコキシ基、又は芳香族構造、単環状脂肪族構造、複環状脂肪族構造のうち１以上の構造と、炭素数１〜１０の直鎖状脂肪族炭化水素基を組み合わせた基が置換したアルコキシ基である。
δは、置換もしくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基、置換もしくは無置換の炭素数３〜１０の分岐脂肪族炭化水素基、置換もしくは無置換の炭素数３〜２０の環状脂肪族炭化水素基、又は置換もしくは無置換の炭素数６〜１０の芳香族基である。） In the substituent precursor compound represented by the formula (3), R is preferably any of acid dissociable, dissolution inhibiting groups represented by (I) to (IV), and more preferably the following formula (6). Any of the acid dissociable, dissolution inhibiting groups represented by (37).

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

（式中、ｒはそれぞれ上記式（６）〜（３４）で表される置換基のいずれかである。）

(In the formula, r is any of the substituents represented by the above formulas (6) to (34).)

  Examples of the substituent precursor compound represented by the formula (3) include 2-adamantyl chloromethyl ether, benzyl chloromethyl ether, chloromethyl cyclohexyl ether; and tert-butyl bromoacetate, tert-butyl chloroacetate, bromoacetic acid 2 -Methyl-2-adamantyl, 2-methyl-2-adamantyl chloroacetate, 2-ethyl-2-adamantyl bromoacetate, 2-ethyl-2-adamantyl chloroacetate, 1-ethylcyclohexyl bromoacetate, 1-ethylcyclohexyl chloroacetate And compounds having bromine or chlorine bonded to the acid dissociable, dissolution inhibiting groups represented by the above formulas (6) to (37).

At least one of the 1 to 3 types of basic organic compounds as the condensing agent is preferably an organic amine compound.
Examples of the organic amine compound include methylamine, ethylamine, trimethylamine, triethylamine, triethanolamine, N, N-diisopropylmethylamine, piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane. Pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, amantadine, N-dicyclohexylmethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-undecene, 1,5,7-triazabicyclo [4.4.0] -5-decene, 7-methyl-1,5,7-triaza Bicyclo [4 4.0] -5-decene and the like, preferably 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5,7-triazabicyclo [4.4.0]- 5-decene, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 1,4-diazabicyclo [2.2.2] octane.

The organic amine compound preferably contains a nitrogen atom-containing heterocyclic structure.
Examples of the organic amine compound having a nitrogen atom-containing heterocyclic structure include piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane, pyridine, 4-dimethylaminopyridine, amantadine, 1,8. -Diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-undecene, 1,5,7-triazabicyclo [4.4.0] -5 Examples include decene and 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene, preferably 1,8-diazabicyclo [5.4.0] -7-undecene, , 5,7-triazabicyclo [4.4.0] -5-decene, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 1,4-diazabicyclo [2. .2] octane, and more preferably 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5,7-triazabicyclo [4.4.0] -5-decene, 7 -Methyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 1,4-diazabicyclo [2.2.2] octane.

  In particular, when 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) is used as the basic organic compound, the compound represented by the formula (1) of the present invention and the formula (5-1) The represented compound can be produced in high yield.

For example, when a condensing agent other than the above is used and a compound represented by the formula (2) in which all or a part of R ¹ is a hydroxyl group is used, a by-product in which a part of the hydroxyl group of R ¹ becomes OR May generate. In the present invention, for example, by using DBU as a condensing agent, the condensation of R to the free hydroxyl group in R ^{1 of the} compound represented by formula (2) is suppressed, and the condensation selectivity of R to free benzoic acid is suppressed. Can be improved.

  In the method for producing a compound represented by the formula (1) of the present invention, the charge ratio of the compound represented by the formula (2) and the substituent precursor compound represented by the formula (3) is preferably represented by the formula ( It is 0.5 equivalent-2 equivalent with respect to the substance amount of the hydroxyl group in the compound represented by 2).

  Similarly, in the method for producing the compound represented by the formula (5-1) of the present invention, the charging ratio of the compound represented by the formula (5-2) and the substituent precursor compound represented by the formula (3) Is preferably 0.5 to 2 equivalents relative to the amount of the hydroxyl group in the compound represented by formula (5-2).

  In the method for producing a compound represented by the formula (1) of the present invention, the total amount of the basic organic compound is preferably 0.5 with respect to the amount of the hydroxyl group in the compound represented by the formula (2). Equivalent to 3 equivalents.

  Similarly, in the method for producing a compound represented by the formula (5-1) of the present invention, the total amount of the basic organic compound is preferably a hydroxyl group substance in the compound represented by the formula (5-2). It is 0.5 equivalent-3 equivalent with respect to quantity.

  In the production method of the present invention, the reaction temperature after adding the basic organic compound as a condensing agent is preferably -80 ° C to 100 ° C. There is a possibility that the reaction temperature is less than −80 ° C., the reaction rate is low, and it cannot be produced efficiently. On the other hand, when the reaction temperature is higher than 100 ° C., a side reaction product may be generated.

  The reaction solvent to be used is not particularly limited, and is preferably an amide solvent from the viewpoint of the solubility of the starting compound to be used, the condensing agent and the like, the yield of the product, the reaction rate, and the like. Specific examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  The compound represented by the formula (1) obtained by the production method of the present invention and the compound represented by the formula (5-1) (hereinafter sometimes simply referred to as the cyclic compound of the present invention) are used as a photoresist base material. It can be used suitably.

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

  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, a phenyl group is desirable.
Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
As the aryl group for R ^53, an aryl group having no substituent is more preferable.

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

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

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

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

  In some cases, post-baking 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.

  EXAMPLES Hereinafter, although it demonstrates in detail based on the Example of this invention, this invention is not limited to a following example, unless the summary is exceeded.

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

Example 1
After adding the cyclic compound (1) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, 1-ethylcyclohexyl 2-bromoacetate (1.25 g, diluted with triethylamine (0.7 ml, 5.00 mmol), anhydrous N-methyl-2-pyrrolidone (1 ml)). 5.00 mmol) and 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) were added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. Ion exchange water and a small amount of salt were added to the solution obtained by concentrating the obtained organic layer, and then the precipitate was filtered to obtain a cyclic compound (2) (1.70 g, 100%).
The structure of the cyclic compound (2) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Example 2
After adding the cyclic compound (1) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, and ethyl adamantyl bromoacetate (1.50 g, 5.00 mmol) diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml). ) And 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) was added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. Ion exchange water and a small amount of salt were added to the solution obtained by concentrating the obtained organic layer, and then the precipitate was filtered off to obtain a cyclic compound (A) (yield 93%).
The structure of the cyclic compound (A) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Example 3
After adding the cyclic compound (1) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ), And stirred at room temperature. Methyl adamantyl bromoacetate (1.43 g, 5.00 mmol) diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml). ) And 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) was added dropwise. After stirring for 10 hours at room temperature, 30 mL of ion exchange water and 30 mL of ethyl acetate were added to extract the organic layer. Ion exchange water and a small amount of salt were added to the solution obtained by concentrating the obtained organic layer, and then the precipitate was filtered to obtain a cyclic compound (B) (yield 94%).
The structure of the cyclic compound (B) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Production Example 2
A four-necked flask (capacity: 1 liter) purged with nitrogen gas was charged with 57 g (518 mmol) of resorcinol, 25.38 g (518 mmol) of acetaldehyde, 103 ml of ethanol, and 103 ml of ion-exchanged water while stirring in a water bath. Then, 51.7 ml of concentrated hydrochloric acid was added dropwise. After completion of dropping, the mixture was stirred at 80 ° C. for 16 hours, and the reaction solution was filtered. Then, the filtered solid was washed with water: ethanol = 1: 1 solution cooled in an ice bath. The obtained solid was dried to obtain a cyclic compound (3-1) (62.66 g, 89%).
The structure of the cyclic compound (3-1) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

5 g (9.18 mmol) of the prepared cyclic compound (3-1) and 100 ml of anhydrous acetonitrile were charged into a two-necked flask (volume: 200 ml) substituted with nitrogen gas, and vigorously stirred. To the reaction solution, 3.72 g (36.7 mmol) of triethylamine and 7 g (36.7 mmol) of tosyl chloride were added in this order, and the mixture was stirred at room temperature for 6 hours. The reaction solution was filtered, and the resulting filtered solid was washed with ion-exchanged water and acetonitrile to obtain a cyclic compound (3-2) (3.65 g, 34%).
The structure of the cyclic compound (3-2) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

In a three-necked flask (capacity: 500 ml) substituted with nitrogen gas, 2.5 g (2.15 mmol) of the prepared cyclic compound (3-2) and 250 ml of acetone were charged and stirred at room temperature. To the reaction solution, 3.5 g (10.76 mmol) of cesium carbonate was added and stirred at 50 ° C. When the reaction solution became homogeneous, the temperature was returned to room temperature, 1.65 g (10.76 mmol) of methyl bromoacetate was added with stirring, and the mixture was stirred at 50 ° C. for 13 hours. The reaction solution was filtered, an aqueous ammonium chloride solution was added to the obtained filtrate, and the mixture was concentrated. Ethyl acetate was added to extract the organic layer to obtain a cyclic compound (3-3) (3.0 g, 96%). .
The structure of the cyclic compound (3-3) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

In a three-necked flask (capacity: 500 ml), 2.9 g (2.0 mmol) of the prepared cyclic compound (3-3) and 150 ml of methanol were charged and stirred at room temperature in a nitrogen atmosphere. To the reaction solution, 75 ml of a 20 wt% aqueous potassium hydroxide solution was added and stirred at 75 ° C. for 6 hours. While cooling the reaction solution in an ice bath, concentrated hydrochloric acid was added until pH = 2, and then ethyl acetate was added to extract the organic layer. The obtained organic layer was concentrated to obtain a cyclic compound (3) (1.4 g, 90%).
The structure of the cyclic compound (3) was confirmed by ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Example 4
After adding the cyclic compound (3) prepared in Production Example 2 (0.500 g, 0.64 mmol) to a 100 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (30 ml) And stirred at room temperature, 2-bromoacetic acid 1-ethylcyclohexyl diluted with triethylamine (0.45 ml, 3.22 mmol) and anhydrous N-methyl-2-pyrrolidone (2 ml) (0.802 g, 3. 22 mmol), and 1,8-diazabicyclo [5,4,0] -7-undecene (0.14 ml, 0.97 mmol) were added dropwise. After stirring at room temperature for 10 hours, saturated brine was added and the mixture was allowed to stand for 1 day, and then the precipitate was filtered off to obtain a cyclic compound (4) (0.783 g, 84%).
The structure of the cyclic compound (4) was confirmed by liquid chromatography measurement and ¹ H-NMR measurement. The measurement result of ¹ H-NMR is shown in FIG.

Comparative Example 1
Under a nitrogen stream, the cyclic compound (1) prepared in Production Example 1 (2.04 g, 1.95 mmol), sodium bicarbonate (0.75 g, 8.97 mmol), and dehydrated N-methyl-2-pyrrolidone ( 160 ml), 2-bromoacetic acid 1-ethylcyclohexyl (2.16 g, 8.58 mmol) was added dropwise, and the mixture was heated and stirred at 70 ° C. for 60 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is separated by filtration to obtain a cyclic compound (12% by weight of cyclic compound (5) as a by-product and 3% by weight of by-product of unknown structure). 2) was obtained (yield 2.74 g, purity 85%).
The structure and composition of the mixture was identified by ^{1 H-NMR} result of the measurement (Fig. 10) and liquid chromatography measurement.

Comparative Example 2
Under a nitrogen stream, the cyclic compound (3) prepared in Production Example 2 (0.20 g, 0.26 mmol), sodium bicarbonate (0.10 g, 1.14 mmol), and dehydrated N-methyl-2-pyrrolidone ( 20 ml), 2-bromoacetic acid 1-ethylcyclohexyl (0.285 g, 8.58 mmol) was added dropwise and stirred at 70 ° C. for 60 hours. The reaction mixture is allowed to cool, re-precipitated with saturated brine and allowed to stand overnight, and then the precipitated solid is filtered off to obtain a cyclic compound (4) containing about 30% by weight of a by-product whose structure is unknown. (Purity about 70%, yield 0.302 g, crude yield 80%).
The structure and composition of the above mixture are the result of ¹ H-NMR measurement (FIG. 11) and liquid chromatography measurement of ¹ H-NMR measurement of the cyclic compound (4) obtained in Example 4 ( FIG. 9) and the results of liquid chromatography measurement were comprehensively judged and specified.

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

It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (1) obtained by manufacture example 1. 1 is a diagram showing the results of ¹ H-NMR measurement of a cyclic compound (2) obtained in Example 1. FIG. 2 is a diagram showing the results of ¹ H-NMR measurement of a cyclic compound (A) obtained in Example 2. FIG. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (B) obtained in Example 3. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (3-1) obtained by manufacture example 2. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (3-2) obtained by manufacture example 2. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (3-3) obtained by manufacture example 2. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (3) obtained by manufacture example 2. It is a figure which shows the result of the ¹ H-NMR measurement of the cyclic compound (4) obtained in Example 4. 2 is a diagram showing the results of ¹ H-NMR measurement of a mixture obtained in Comparative Example 1. FIG. 6 is a diagram showing the results of ¹ H-NMR measurement of a mixture obtained in Comparative Example 2. FIG.

Claims (8)

1,8-diazabicyclo [5.4.0] -7-undecene and triethylamine are added as condensing agents to the compound represented by the following formula (2) and the substituent precursor compound represented by the following formula (3). The manufacturing method of the compound represented by Formula (1).

(Where
R is

A group selected from the group consisting of:
X is a halogen atom or a hydroxyl group.
Each R ¹ is hydroxyl group, a linear alkoxy group having a carbon number of 1-20, a branched alkoxy group having a carbon number of 3-12, cyclic alkoxy group having a carbon number of 3 to 20, an aryloxy group having a carbon number of 6-10, An alkoxyalkyloxy group or a siloxy group ,
A r are each a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and one or more groups and substituted or unsubstituted arylene group having 6 to 10 carbon atoms selected from A alkylene group and an ether bond bond And
Substituents of Ar are alkyl groups having a carbon number of 1-10.
A ¹ is a single bond, an alkylene group, or a group in which one or more alkylene groups and one or more ether bonds are bonded to each other.
Each x represents an integer of 1 to 5, and y represents an integer of 0 to 3, respectively.
However, and multiple ^{R 1, A r, A 1} , x and y may be different from one another respectively the same. ) 1,8-diazabicyclo [5.4.0] -7-undecene and triethylamine are used as a condensing agent for the compound represented by the following formula (5-2) and the substituent precursor compound represented by the following formula (3). The manufacturing method of the compound represented by Formula (5-1) to add.

(Where
R is the same as in claim 1 .
X is Ru der same as defined in Claim 1.
R ³ are each hydrogen atom, a linear aliphatic hydrocarbon group having a carbon number of 1-20, a branched aliphatic hydrocarbon group having a carbon number of 3 to 12, of carbon number 3-20 cyclic aliphatic hydrocarbon group, aromatic group having a carbon number of 6 to 10, or 2 or more are bonded group selected from the these groups.
R ⁶ is a group a carboxyl group and R is bonded, respectively, or alkyleneoxy group, an arylene group or a Shiriren'okishi group carboxyl group and R bonded is bonded group.
R ⁷ is a carboxyl group or a group in which an alkyleneoxy group, an aryleneoxy group or a silyleneoxy group and a carboxyl group are bonded to each other.
However, a plurality of R ³ , R ⁶ , R ⁷ and Ar may be the same or different) The production method according to claim 1, wherein Ar is an unsubstituted arylene group having 6 to 10 carbon atoms. A ¹ The production method according to claim 1 or 3, wherein is a single bond. R ¹ Are respectively a hydroxyl group or a C1-C20 linear alkoxy group, The manufacturing method in any one of Claim 1, 3, and 4. 6. The production method according to claim 1, wherein x is 1 and y is 1. R ³ The production method according to claim 2, wherein is a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. R ⁷ Is a group in which an alkyleneoxy group and a carboxyl group are bonded, and R ⁶ The production method according to claim 2, wherein is a group in which R is bonded to a carboxyl group to which an alkyleneoxy group is bonded.

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