JP2008162968A - Compound, negative resist composition and pattern forming method - Google Patents

Abstract

【選択図】なしA novel compound that can be used as a negative resist composition, a novel intermediate compound for synthesizing the compound, a negative resist composition, and a resist pattern forming method using the negative resist composition provide.
A compound represented by the following general formula (A-1): wherein Z is a group having a lactone ring, a group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring, or a hydrogen atom Yes; R ^{11 to} R ¹⁷ are each independently an alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 10 carbon atoms and may contain a hetero atom in the structure thereof; g and j are each independently An integer of 1 or more, k and q are 0 or an integer of 1 or more; h is an integer of 1 or more, l and m are each independently 0 or an integer of 1 or more; i is 1 or more N and o are each independently an integer of 0 or 1 or more; X is an aliphatic cyclic group or an aromatic cyclic group. ].
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a compound suitable for a negative resist composition, an intermediate compound thereof, a negative resist composition, and a resist pattern forming method.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but now mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started. In addition, studies have been made on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like having shorter wavelengths than these excimer lasers.
Further, as one of pattern forming materials capable of forming a pattern with fine dimensions, a chemically amplified resist containing a base material component having film forming ability and an acid generator component that generates an acid upon exposure is known. ing. The chemically amplified resist includes a negative type in which alkali solubility is reduced by exposure and a positive type in which alkali solubility is increased by exposure.

Conventionally, a polymer has been used as a base material component of such a chemically amplified resist. For example, a PHS system such as polyhydroxystyrene (PHS) or a resin in which a part of its hydroxyl group is protected with an acid dissociable, dissolution inhibiting group. Resins, copolymers derived from (meth) acrylic acid esters, resins in which a part of the carboxy group is protected with an acid dissociable, dissolution inhibiting group, and the like are used.
However, when a pattern is formed using such a pattern forming material, there is a problem that roughness is generated on the upper surface of the pattern and the surface of the side wall. For example, the roughness of the resist pattern side wall surface, that is, the line edge roughness (LER) causes distortion around the hole in the hole pattern, variation in the line width in the line and space pattern, and the like. May cause adverse effects.
Such a problem becomes more serious as the pattern size is smaller. Therefore, for example, lithography using electron beams or EUV aims to form a fine pattern of several tens of nanometers, and therefore extremely low roughness exceeding the current pattern roughness is required.
However, a polymer generally used as a substrate has a large molecular size (average square radius per molecule) of around several nm. In the development process of pattern formation, the dissolution behavior of the resist with respect to the developing solution is usually performed in units of one molecular component of the base material. Therefore, as long as a polymer is used as the base material component, further reduction in roughness is extremely difficult.

In order to solve such a problem, a resist using a low-molecular material as a base material component has been proposed as a material aiming for extremely low roughness. For example, Non-Patent Documents 1 and 2 propose low molecular weight materials having an alkali-soluble group such as a hydroxyl group or a carboxy group, part or all of which are protected with an acid dissociable, dissolution inhibiting group. Patent Document 1 proposes a negative pattern forming method using a compound containing a γ-hydroxycarboxylic acid structure or a δ-hydroxycarboxylic acid structure.
Japanese Patent Laid-Open No. 11-109627 T.A. Hirayama, D .; Shiono, H .; Hada and J.H. Onodera: J.M. Photopolym. Sci. Technol. 17 (2004), p435 Jim-Baek Kim, Hyo-Jin Yun, Young-Gil Kwon: Chemistry Letters (2002), p1064-1065.

Such a low molecular weight material is expected to be able to reduce roughness because of its low molecular weight and thus small molecular size. Therefore, there is an increasing demand for new low molecular weight materials that can be used for resist compositions.
The present invention has been made in view of the above circumstances, and is a novel compound that can be used for a negative resist composition, a novel intermediate compound for synthesizing the compound, a negative resist composition, and the It is an object of the present invention to provide a resist pattern forming method using a negative resist composition.

  That is, the first aspect of the present invention is a compound represented by the following general formula (I-1). The compound represented by the following general formula (I-1) of the first aspect of the present invention is a compound that can be an intermediate compound in the synthesis of the compound represented by the general formula (A-1) described later. .

［式（Ｉ−１）中、Ｙはラクトン環を有する基、または水素原子であって、複数のＹはそれぞれ同じであっても異なっていてもよく、複数のＹのうちの少なくとも一部はラクトン環を有する基であり；Ｒ^１１〜Ｒ^１７はそれぞれ独立に炭素数１〜１０のアルキル基、アルケニル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；ｇ、ｊはそれぞれ独立に１以上の整数であり、ｋ、ｑは０または１以上の整数であり、かつｇ＋ｊ＋ｋ＋ｑが５以下であり；ｈは１以上の整数であり、ｌ、ｍはそれぞれ独立に０または１以上の整数であり、かつｈ＋ｌ＋ｍが４以下であり；ｉは１以上の整数であり、ｎ、ｏはそれぞれ独立に０または１以上の整数であり、かつｉ＋ｎ＋ｏが４以下であり；Ｘは脂肪族環式基または芳香族環式基である。］

[In Formula (I-1), Y is a group having a lactone ring or a hydrogen atom, and a plurality of Y may be the same or different, and at least a part of the plurality of Y is A group having a lactone ring; each of R ^{11 to} R ¹⁷ is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an aromatic hydrocarbon group, and may contain a hetero atom in its structure; g , J are each independently an integer of 1 or more, k, q is 0 or an integer of 1 or more, and g + j + k + q is 5 or less; h is an integer of 1 or more, and l and m are each independently 0 or an integer of 1 or more and h + 1 + m is 4 or less; i is an integer of 1 or more, n and o are each independently 0 or an integer of 1 or more, and i + n + o is 4 or less; X is an aliphatic cyclic group or aromatic group It is a family cyclic group. ]

  Moreover, the 2nd aspect of this invention is a compound represented by the following general formula (A-1).

［式（Ａ−１）中、Ｚはラクトン環を有する基、ラクトン環が加水分解されて開環したヒドロキシカルボン酸を有する基、または水素原子であって、複数のＺはそれぞれ同じであっても異なっていてもよく、複数のＺのうちの少なくとも一部はラクトン環が加水分解されて開環したヒドロキシカルボン酸を有する基であり；Ｒ^１１〜Ｒ^１７はそれぞれ独立に炭素数１〜１０のアルキル基、アルケニル基または芳香族炭化水素基であって、その構造中にヘテロ原子を含んでもよく；ｇ、ｊはそれぞれ独立に１以上の整数であり、ｋ、ｑは０または１以上の整数であり、かつｇ＋ｊ＋ｋ＋ｑが５以下であり；ｈは１以上の整数であり、ｌ、ｍはそれぞれ独立に０または１以上の整数であり、かつｈ＋ｌ＋ｍが４以下であり；ｉは１以上の整数であり、ｎ、ｏはそれぞれ独立に０または１以上の整数であり、かつｉ＋ｎ＋ｏが４以下であり；Ｘは脂肪族環式基または芳香族環式基である。］

[In the formula (A-1), Z is a group having a lactone ring, a group having a hydroxycarboxylic acid that is opened by hydrolysis of the lactone ring, or a hydrogen atom, and a plurality of Z are the same. And at least a part of the plurality of Zs is a group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring; R ^{11 to} R ¹⁷ are each independently a group having 1 to 10 carbon atoms. An alkyl group, an alkenyl group or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; g and j are each independently an integer of 1 or more, and k and q are 0 or 1 or more. Is an integer, and g + j + k + q is 5 or less; h is an integer of 1 or more, l and m are each independently 0 or an integer of 1 or more, and h + l + m is 4 or less; i is 1 or more An integer Ri, n, o are each independently 0 or an integer of 1 or more, and i + n + o is 4 or less; X represents an aliphatic cyclic group or an aromatic cyclic group. ]

  The third aspect of the present invention is characterized in that it comprises a base component (A) containing the compound of the second aspect and an acid generator component (B) that generates an acid upon irradiation with radiation. It is a negative resist composition.

  The fourth aspect of the present invention includes a step of forming a resist film on a substrate using the negative resist composition of the third aspect, a step of exposing the resist film, and developing the resist film. And a resist pattern forming method including a step of forming a resist pattern.

Here, the “alkyl group” in the claims and the specification includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified.
Unless otherwise specified, the “alkenyl group” includes linear, branched and cyclic monovalent unsaturated hydrocarbon groups having one double bond.
“Aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity. “Aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity.
“Aromatic cyclic group” means a cyclic group having aromaticity. The “aromatic cyclic group” indicates a monocyclic group or polycyclic group having aromaticity.
“Exposure” is a concept that includes radiation exposure in general.

  According to the present invention, a novel compound that can be used for a negative resist composition (the second embodiment), a novel intermediate compound (the first embodiment) for synthesizing the compound, a negative resist composition And a resist pattern forming method using the negative resist composition.

≪Intermediate compound≫
The compound of the first aspect of the present invention (intermediate compound of the compound of the second aspect, hereinafter referred to as compound (I-1)) is represented by the above general formula (I-1).
In the above formula (I-1), Y is a group having a lactone ring or a hydrogen atom, and a plurality of Y may be the same or different, and at least some of the plurality of Y are It is a group having a lactone ring. The group having a lactone ring may be a group obtained by removing one hydrogen atom in the lactone ring, or may have a lactone ring in the organic group. When the lactone ring has a lactone ring as the first ring, the lactone-containing monocyclic group having only the lactone ring as the ring, and another ring structure, the lactone-containing It is called a cyclic group. The group having a lactone ring is not limited to a lactone-containing monocyclic group, and any group including a lactone-containing polycyclic group can be selected. Examples of the lactone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring. The lactone ring is preferably a γ-lactone ring or a δ-lactone ring.

  As the lactone-containing monocyclic group, a group represented by the following formula (Y-1-10) is preferable.

［式（Ｙ−１−１０）中、ｐは１〜４の整数である。］

[In formula (Y-1-10), p is an integer of 1-4. ]

  Specifically, the lactone-containing monocyclic group is preferably a group obtained by removing one hydrogen atom from γ-butyrolactone, or a group obtained by removing one hydrogen atom from δ-valerolactone, which is easy to synthesize. From the above points, each is represented by the following formula (Y-1-11) or the following formula (Y-1-12) except for one hydrogen atom bonded to the α-position carbon of γ-butyrolactone or δ-valerolactone. More preferred are the groups

R ^{11 to} R ¹⁷ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkenyl group having 1 to 10 carbon atoms, or a carbon number 1-10 aromatic hydrocarbon groups.
As the alkyl group, a linear or branched lower alkyl group having 1 to 5 or a cyclic alkyl group having 5 to 6 carbon atoms is preferable. Examples of the lower alkyl group include linear or branched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Group, and among these, a methyl group is preferable. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group.

  The alkenyl group is preferably a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl and cyclohexenyl. Etc. are more preferable, and vinyl and isopropenyl are particularly preferable.

  The aromatic hydrocarbon group preferably has 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, and a naphthyl group.

  These alkyl groups, alkenyl groups, and aromatic hydrocarbon groups may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in the structure.

g and j are each independently an integer of 1 or more, preferably 1 or 2, k and q are each independently 0 or 1 or more, preferably an integer not exceeding 2, and g + j + k + q is 5 or less.
h is an integer of 1 or more, preferably 1 to 2, l and m are each independently 0 or 1 or more, preferably an integer not exceeding 2, and h + 1 + m is 4 or less.
i is an integer of 1 or more, preferably 1 to 2, n and o are each independently 0 or 1 or more, preferably an integer not exceeding 2, and i + n + o is 4 or less.

  Compound (I-1) has (4 g + h + i) Y per molecule. (4g + h + i) is an integer of 6 or more, preferably 12 or less, and more preferably 10 or less. It is preferable to have 1.0 to 4.0 lactone rings per molecule of compound (I-1), more preferably 1.0 to 3.0, and 1.0 to 2 It is particularly preferable to have 0.0. Further, among (4g + h + i) Y, the group having a lactone ring preferably occupies 16.7-66.7%, more preferably 16.7-50.0%, more preferably 16.7-33. It is particularly preferable to occupy 3%.

  In the above formula (I-1), it is particularly preferable that g = h = i = 1. At this time, the compound (I-1) has 6 Ys per molecule. Among 6 Ys, the number of lactone ring-containing groups is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and 1.0 to 1 .4 is particularly preferable.

X is a divalent aliphatic cyclic group or a divalent aromatic cyclic group.
The divalent aliphatic cyclic group for X may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.
The basic ring structure of the aliphatic cyclic group excluding a substituent is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
A polycyclic group is preferred.

Specific examples of such aliphatic cyclic groups include groups in which two or more hydrogen atoms have been removed from a monocycloalkane; two or more hydrogens from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. Examples include groups other than atoms. Specifically, a group obtained by removing two or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane, or two or more polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Examples include a group excluding a hydrogen atom. In these groups, some or all of the hydrogen atoms may be substituted with a substituent (for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group).
Among these, an aliphatic cyclic group having 4 to 15 carbon atoms is preferable, a group obtained by removing two hydrogen atoms from adamantane is more preferable, and in particular, a group obtained by removing hydrogen atoms at the 1st and 3rd positions of adamantane. Is preferred.
Examples of the divalent aromatic cyclic group for X include groups in which two hydrogen atoms have been removed from an aromatic compound such as benzene, naphthalene, anthracene, phenanthrene, and pyrene.

  As the compound (I-1), a compound represented by the following general formula (I-2) is particularly preferable because of excellent effects of the present invention.

[In Formula (I-2), Y is a group having a lactone ring, or a hydrogen atom, and a plurality of Y may be the same or different, and at least a part of the plurality of Y is A group having a lactone ring; R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and a hetero atom may be included in the structure thereof; Well; X is an aliphatic cyclic group or an aromatic cyclic group. ]

Y, R ¹¹ , R ¹² , R ¹³ , R ¹⁵ , and X in formula (I-2) are Y, R ¹¹ , R ¹² , R ¹³ , R ¹⁵ , and Same as X.

As the bonding positions of R ¹¹ and R ¹² in formula (I-2), the following formulas (I-2-1) and (I-2-2) are preferable.

As the bonding positions of OY, R ¹³ and R ¹⁵ in the formula (I-2), the following formulas (I-2-3) and (I-2-4) are preferable.

  Compound (I-1) is, for example, a bissalicylaldehyde derivative formed by bonding two salicylaldehydes (which may have a substituent) via the X (following formula (I-1-1) ) And a phenol compound having a substituent (the following formula (I-1-2)) are dehydrated and condensed under acidic conditions to obtain a tris (hydroxyphenyl) methane derivative (the following formula (I-1-3)). Obtained by reacting a hydroxyl group of the tris (hydroxyphenyl) methane derivative with a halogenated lactone compound and substituting at least a part of the hydroxyl group of the tris (hydroxyphenyl) methane derivative with a group having a lactone ring. it can.

  Examples of the halogenated lactone compound include compounds represented by the following formula (I-1-10).

［式（Ｉ−１−１０）中、ｐは１以上の整数である。］

[In the formula (I-1-10), p is an integer of 1 or more. ]

  As the halogenated lactone compound represented by the above formula (I-1-10), a compound when p = 2, that is, α-bromo-γ-butyrolactone (I-11) or p = 3 The compound in this case, that is, α-bromo-δ-valerolactone (I-1-12) is preferred.

≪Compound≫
The compound of the second aspect of the present invention (hereinafter referred to as compound (A-1)) is represented by the general formula (A-1).
In the above formula (A-1), Z is a group having a lactone ring, a group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring, or a hydrogen atom, and the plurality of Z are the same. And at least a part of the plurality of Zs is a group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring.

  In the formula (A-1), the group having a lactone ring is the same as described above. Examples of the group having a hydroxycarboxylic acid include a group having a hydroxycarboxylic acid which is opened by hydrolyzing the lactone ring from the same group having a lactone ring as described above. That is, it may be a group having a hydroxycarboxylic acid that is opened by hydrolysis of a lactone ring from a lactone-containing monocyclic group, or a hydroxycarboxylic acid that is opened by hydrolysis of a lactone ring from a lactone-containing polycyclic group. It may be a group having an acid.

  As the group having a hydroxycarboxylic acid that has been opened by hydrolysis of a lactone ring from a lactone-containing monocyclic group, a group represented by the following formula (Z-1-10) is preferable.

［式（Ｚ−１−１０）中、ｐは１以上の整数である。］

[In the formula (Z-1-10), p is an integer of 1 or more. ]

  The group having a hydroxycarboxylic acid that has been opened by hydrolysis of the lactone ring is preferably a group having a γ-hydroxycarboxylic acid or a group having a δ-hydroxycarboxylic acid. These hydroxycarboxylic acids can easily form a 5-membered ring or a 6-membered ring by intramolecular esterification by an acid-catalyzed reaction. Specifically, examples of the group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring from a lactone-containing monocyclic group include the following formula (Z-1-11) in the above formula (Z-1-10). The group having a hydroxycarboxylic acid represented by (p = 2) or the group having a hydroxycarboxylic acid represented by the following formula (Z-1-12) (p = 3) is preferable.

R ^{11 to} R ¹⁷ , g, j, k, q, h, l, m, i, n, o, and X in the formula (A-1) are R ^{11 to} R in the formula (I-1). ¹⁷ , g, j, k, q, h, l, m, i, n, o, X.

  Compound (A-1) has (4 g + h + i) Z atoms per molecule. (4g + h + i) is an integer of 6 or more, preferably 12 or less, and more preferably 10 or less. It is preferable to have 1.0 to 4.0, preferably 1.0 to 3.0, of hydroxycarboxylic acids opened by hydrolysis of the lactone ring per molecule of the compound (A-1). It is more preferable to have 1.0 to 2.0. Further, among (4g + h + i) Z, the group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring preferably accounts for 16.7-66.7%, and 16.7-50.0% More preferably, it occupies 16.7 to 33.3%.

  In the above formula (A-1), it is particularly preferable that g = h = i = 1. At this time, the compound (A-1) has 6 Zs per molecule. Of the six Zs, the number of the hydroxycarboxylic acid-opened group obtained by hydrolysis of the lactone ring is preferably 1.0 to 3.0, and preferably 1.0 to 2.0. It is more preferable that the number is 1.0 to 1.4.

  As the compound (A-1), a compound represented by the following general formula (A-2) is particularly preferable because of excellent effects of the present invention.

[In the formula (A-2), Z is a group having a lactone ring, a group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring, or a hydrogen atom, and the plurality of Z are the same. And at least a part of the plurality of Zs is a group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring; R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently May be an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group and may contain a hetero atom in the structure thereof; X is an aliphatic cyclic group or an aromatic cyclic group. ]

Formula (A-2) in ^{Z, R 11, R 12,} R 13, R 15, and X is the formula (I-2) in ^{Y, R 11, R 12,} R 13, R 15 and, Same as X.

As the bonding positions of R ¹¹ and R ¹² in formula (A-2), the following formulas (A-2-1) and (A-2-2) are preferable.

As the bonding position of OZ, R ¹³ and R ¹⁵ in formula (A-2), the following formula (A-2-3) and formula (A-2-4) are preferable.

  In the present invention, the compound (A-1) preferably has a molecular weight of 300 to 2500, more preferably 450 to 1500, and particularly preferably 500 to 1200. When the molecular weight is within the above range, roughness can be reduced and a pattern with excellent resolution can be formed. Further, the profile shape of the resist pattern is good.

  The compound (A-1) preferably has a molecular weight dispersity (Mw / Mn) of 1.5 or less because the effects of the present invention are further excellent. This is because the compound (A-1) has a narrow molecular weight distribution with a dispersity of 1.5 or less, so that the hydrogen atom of the phenolic hydroxyl group in the compound (A-1) is a lactone in the negative resist composition. Even if there are multiple compounds with different numbers (protection numbers) substituted with a group having a ring, or a group having a hydroxycarboxylic acid that has been opened by hydrolysis of the lactone ring, the alkali solubility of each compound Is considered to be relatively uniform. The degree of dispersion is preferably as small as possible, more preferably 1.4 or less, and most preferably 1.3 or less.

  Here, “dispersion degree” is usually used for polydisperse compounds such as polymers, but even if it is a monodisperse compound, impurities such as by-products during production and residual starting materials Due to the presence of this, when analyzed by gel permeation chromatography (GPC) or the like, a distribution may appear in its molecular weight. That is, in the case of a monodispersed compound, a degree of dispersion of 1 means that the purity is 100%, and the greater the degree of dispersion, the greater the amount of impurities. In the present invention, the degree of dispersion is a method for measuring a mass average molecular weight (Mw) and a number average molecular weight (Mn) of a polymer that is generally used for a compound showing such an apparent molecular weight distribution, such as GPC. Can be calculated by measuring Mw and Mn and determining the Mw / Mn ratio.

  The degree of dispersion is adjusted by synthesizing compound (A-1), which is the final target product, and then purifying and removing reaction by-products and impurities, or removing unnecessary molecular weight parts by known methods such as molecular weight fractionation. can do.

  In the compound (A-1), the hydrogen atom of the hydroxyl group is not substituted at all with a group having a lactone ring or a group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring, that is, the compound (A- In the tris (hydroxyphenyl) methane derivative represented by the formula (I-1-3) described later, which is the basic structure of 1), it is a material capable of forming an amorphous film by spin coating. Is preferred.

  Here, the spin coating method is one of commonly used thin film forming methods, and an amorphous film means an optically transparent film that does not crystallize.

Whether or not the tris (hydroxyphenyl) methane derivative represented by the formula (I-1-3) described later, which is the basic structure of the compound (A-1), is a material capable of forming an amorphous film by a spin coating method. It can be determined whether or not the coating film formed on the 8-inch silicon wafer by spin coating is transparent. More specifically, for example, the determination can be made as follows. First, for the tris (hydroxyphenyl) methane derivative represented by the formula (I-1-3), using a solvent generally used for a resist solvent, for example, ethyl lactate / propylene glycol monomethyl ether acetate = 40 / 60 (mass ratio) mixed solvent (hereinafter abbreviated as EM) is dissolved so as to have a concentration of 14% by mass, and subjected to ultrasonic treatment (dissolution treatment) using an ultrasonic cleaner, The solution is spin-coated on the wafer at 1500 rpm, and optionally subjected to dry baking (PAB, Post Applied Bake) at 110 ° C. for 90 seconds. In this state, a transparent film can be obtained visually. Whether or not an amorphous film is formed is determined. A cloudy film that is not transparent is not an amorphous film.
Further, the compound (A-1) preferably has an amorphous film formed as described above having good stability. For example, the compound (A-1) is transparent even after standing for 2 weeks in a room temperature environment after the PAB. It is preferable that a simple state, that is, an amorphous state is maintained.

  Compound (A-1) is a compound in which part or all of the lactone ring of compound (I-1) is hydrolyzed and opened to be converted to a hydroxycarboxylic acid. Compound (A-1) can be synthesized, for example, by dissolving the compound (I-1) in an organic solvent, adding an aqueous alkaline solution, and stirring the mixture under alkaline conditions.

  In the compound (A-1), when the acid generator component (B) that generates an acid upon exposure is mixed with the resist composition, the acid generated from the acid generator component (B) acts upon the exposure. Then, hydroxycarboxylic acid changes to a lactone ring, and the entire compound (A-1) changes from alkali-soluble to alkali-insoluble.

≪Negative resist composition≫
The negative resist composition of the present invention comprises a base component (A) containing the compound of the second aspect (hereinafter also referred to as component (A)) and an acid generator that generates an acid upon irradiation with radiation. And component (B) (hereinafter referred to as component (B)).

<(A) component>
In the component (A), when an acid generated from the component (B) acts upon exposure, the hydroxycarboxylic acid changes to a lactone ring, whereby the entire component (A) changes from alkali-soluble to alkali-insoluble. Therefore, in the formation of a resist pattern, when a resist film made of the resist composition is selectively exposed or heated after exposure in addition to exposure, the exposed portion turns into alkali-insoluble while the unexposed portion remains alkali-soluble. Since it does not change, a negative resist pattern can be formed by alkali development.

In the negative resist composition of the present invention, the component (A) needs to contain the compound (A-1) of the present invention.
A compound (A-1) may be used individually by 1 type, and may use 2 or more types together.
In the component (A), the proportion of the compound (A-1) is preferably more than 40% by mass, more preferably more than 50% by mass, further preferably more than 80% by mass, most preferably 100% by mass. %.
The ratio of the compound (A-1) in the component (A) can be measured by means such as reverse phase chromatography.

The component (A) may further contain any resin component that has been proposed as a base material component of the chemically amplified resist layer so far as the effects of the present invention are not impaired.
Examples of such resin components include those proposed as base resins such as conventional chemically amplified negative resist compositions for KrF and negative resist compositions for ArF. It can be appropriately selected according to the type.

  In the negative resist composition of the present invention, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<(B) component>
The component (B) is not particularly limited, and those that have been 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 poly (bissulfonyl) diazomethanes. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

  Examples of the onium salt acid generator include an acid generator represented by the following general formula (b-0).

［式中、Ｒ^５１は、直鎖、分岐鎖若しくは環状のアルキル基、または直鎖、分岐鎖若しく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、直鎖若しくは分岐鎖状のアルキル基、直鎖若しくは分岐鎖状のハロゲン化アルキル基、または直鎖若しく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。］

[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 from 1 to 3.]

In General Formula (b-0), R ⁵¹ represents a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and particularly Those in which all hydrogen 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 or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group.
In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
In R ⁵² , the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more 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, particularly 1 to 4, and more preferably 1 to 3.
Among 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 general formula (b-0) include the following.

  Moreover, as an onium salt type acid generator other than the acid generator represented by general formula (b-0), the compound represented by the following general formula (b-1) or (b-2) is mentioned, for example. .

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”は、それぞれ独立に、アリール基またはアルキル基を表し；Ｒ^４”は、直鎖、分岐または環状のアルキル基また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”〜Ｒ^６”のうち少なくとも１つはアリール基を表す。］

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

In formula (b-1), R ¹ ″ to R ³ ″ each independently represents an aryl group or an alkyl group. At least one of R ¹ ″ to R ³ ″ represents an aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably aryl groups, and most preferably all of R ¹ ″ to R ³ ″ are aryl groups.
The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups It may or may not be substituted with a group, a halogen atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Is most preferred.
The alkoxy group that may be substituted with a hydrogen atom 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 may be substituted for the hydrogen atom 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 alkyl groups such as branched or cyclic. 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, R ¹ ″ to R ³ ″ are most preferably a phenyl group or a naphthyl group, respectively.

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 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. 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%. Particularly, all the hydrogen atoms are substituted with fluorine atoms. It is preferable because the strength of the acid is increased.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

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

  Specific examples of the onium salt acid generators represented by the formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or the same Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptaful Lopropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate , Trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenyl (1- (4-methoxy) naphthyl) sulfonium, its heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, di (1-naphthyl) phenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate. 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.

  In addition, in the general formula (b-1) or (b-2), an onium salt-based acid generator in which the anion moiety is replaced with an anion moiety represented by the following general formula (b-3) or (b-4). Can also be used (the cation moiety is the same as (b-1) or (b-2)).

［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。］

[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 because the solubility in the resist solvent is good within the above carbon number range.
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 with 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 this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation with radiation. is there. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ³¹ , a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms which has no substituent.

As the organic group for R ³² , a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は２または３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3.]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and carbon atoms. Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more.

As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group. And heteroaryl groups in which some of the carbon atoms constituting the ring of these groups are substituted with heteroatoms such as oxygen, sulfur, and nitrogen atoms. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent for R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and most preferably a partially fluorinated alkyl group.
The fluorinated alkyl group in R ³⁵ preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more fluorinated. This is preferable because the strength of the acid is increased. Most preferred is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups having no substituent as R ³⁵ described above.
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), WO2004 / 074242A2 (pages 65 to 85). The oxime sulfonate acid generators disclosed in Examples 1 to 40) of No. 1 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

  Of the above exemplified compounds, the following four compounds are preferred.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

(B) As a component, these acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, as the component (B), among the above, it is preferable to use an onium salt having a fluorinated alkyl sulfonate ion as an anion.
(B) Content of a component is 0.5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-10 mass parts. By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(C) component>
In the negative resist composition of the present invention, a crosslinking agent component (hereinafter referred to as “component (D)”) can be blended as an optional component.
The component (C) is not particularly limited, and can be arbitrarily selected from cross-linking agents used in chemically amplified 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 hydroxyl 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 or an oxygen-containing derivative 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.
Of these, those using melamine are melamine crosslinking agents, those using urea are urea crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea crosslinking agents, and glycoluril is used. This was called a glycoluril-based crosslinking agent.
The crosslinking agent component is preferably at least one selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, and glycoluril-based crosslinking agents, and glycoluril-based crosslinking agents are particularly preferable. .

  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, and 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.

［式中の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。］

[Wherein R ⁵ ′ and R ⁶ ′ are each independently a hydroxyl group or a lower alkoxy group, R ³ ′ and R ⁴ ′ are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group, and v is 0 or 1 It is an integer of ~ 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, 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 Like, etc.) -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 between 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.

As a crosslinking agent component, 1 type may be used independently and 2 or more types may be used in combination.
3-30 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a crosslinking agent component, 3-15 mass parts is more preferable, and 5-10 mass parts is the most preferable. When the content of the crosslinking agent component is at least the lower limit value, the crosslinking formation proceeds sufficiently and a good resist pattern can be obtained.
Moreover, when it is below this upper limit, the storage stability of the resist coating solution is good, and the deterioration of sensitivity with time is suppressed.

<(D) component>
The negative resist composition of the present invention may further contain a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) in order to improve the resist pattern shape, the stability over time, and the like. it can.
Since a wide variety of components (D) have already been proposed, any known one may be used. For example, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, monoalkylamines such as n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-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- Trialkylamines such as dodecylamine; diethanolamine, trieta Ruamin, diisopropanolamine, triisopropanolamine, di -n- octanol amines, alkyl alcohol amines tri -n- octanol amine. Among these, a secondary aliphatic amine and a tertiary aliphatic amine are particularly preferable, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-octylamine is most preferable.
These may be used alone or in combination of two or more.
(D) component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

<(E) component>
In the negative resist composition of the present invention, an organic carboxylic acid or an organic carboxylic acid is further added as an optional component for the purpose of preventing sensitivity deterioration due to the blending of the component (D) and improving the resist pattern shape, retention stability, etc. Phosphorus oxoacid or derivative thereof (E) (hereinafter referred to as component (E)) can be contained. In addition, (D) component and (E) component can also be used together, and any 1 type can also be used.
As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Like phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and their esters, phosphinic acids such as phosphinic acid, phenylphosphinic acid and their esters Among these, phosphonic acid is particularly preferable.
(E) A component is used in the ratio of 0.01-5.0 mass parts per 100 mass parts of (A) component.

  The negative resist composition of the present invention may further contain miscible additives as desired, for example, additional resins for improving the performance of the resist film, surfactants for improving applicability, dissolution inhibitors, Plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be added and contained as appropriate.

<(S) component>
The negative resist composition of the present invention can be produced by dissolving the components (A) and (B) and various optional components in an organic solvent (hereinafter sometimes referred to as (S) component). .
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution, and any one of conventionally known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; multivalents such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol Alcohols: compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, or propylene glycol monoacetate, monomethyl ether, monoethyl ether of the polyhydric alcohols or the compound having an ester bond , Ether bond such as monoalkyl ether such as monopropyl ether, monobutyl ether or monophenyl ether Polyhydric alcohols derivatives, such as compounds having [Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferable];
Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. be able to.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, Most preferably, it is 5: 5 8: 2.
The amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. -20% by mass, preferably 5-15% by mass.

≪Pattern formation method≫
The pattern forming method of the present invention includes a step of forming a resist film on a substrate using the negative resist composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist pattern. Including a process.
More specifically, for example, a resist pattern can be formed by the following resist pattern forming method. That is, first, the negative resist composition is applied onto a substrate such as a silicon wafer with a spinner or the like, and optionally pre-baked (PAB) to form a resist film. The formed resist film is selectively exposed by, for example, exposure through a mask pattern or drawing by direct irradiation of an electron beam without using a mask pattern, using an exposure apparatus such as an electron beam lithography apparatus or an EUV exposure apparatus. After that, PEB (post-exposure heating) is performed.
Subsequently, after developing with an alkali developer, rinsing is performed, and the developer on the substrate and the resist composition dissolved by the developer are washed away and dried to obtain a resist pattern.

These steps can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the negative resist composition to be used.
The exposure light source is not particularly limited, and is performed using radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), electron beam, X-ray, soft X-ray. be able to. In particular, the negative resist composition according to the present invention is effective for electron beams or EUV, particularly electron beams.
In some cases, the post-baking step after alkali development may be included, and an organic or inorganic antireflection film may be provided between the substrate and the resist film.

As described above, according to the negative resist composition containing the compound (A-1) of the present invention and the resist pattern forming method using the negative resist composition, a resist pattern with reduced roughness can be formed. .
The reason why the roughness is reduced is that the compound (A-1) has a tris (hydroxyphenyl) methane derivative represented by the above formula (I-1-3) as a basic skeleton, and the lactone ring has a phenolic hydroxyl group. Dissolving behavior of a resist film obtained by using a negative resist composition containing the compound (A-1) in a developer by having a structure protected with a group having a hydrolyzed and ring-opened hydroxycarboxylic acid Is assumed to be more uniform.
That is, the conventional resist using a polymer as a base component, for example, in a spin coating process for forming a resist film, highly hydrophilic molecules, highly hydrophobic molecules are partially localized, As a result, the distribution of various components such as the component (B) in the resist film also varies. Further, in a polymer having a hydroxycarboxylic acid, unevenness is likely to occur in the distribution of the group having the hydroxycarboxylic acid and the degree of lactone ring formation. Therefore, at the interface between the exposed part and the unexposed part, the degree of progress when the lactone ring formation reaction (lactone ring-closing reaction) of the group having hydroxycarboxylic acid by the generated acid proceeds is not uniform, or after the lactone ring-closing reaction It is considered that the roughness was increased due to variations in the alkali solubility of the molecules of each of the substrate components and variations in the dissolution rate of the resist film.

On the other hand, in the present invention, it is presumed that the compound (A-1) has a difference in physical and chemical properties (molecular weight, hydrophilicity, polarity, etc.) between molecules due to the above structure. In particular, the distribution state of the group having hydroxycarboxylic acid is relatively uniform, which is considered to contribute to the improvement of roughness. That is, the tris (hydroxyphenyl) methane derivative represented by the above formula (I-1-3) which is the basic structure of the compound (A-1) is an aliphatic cyclic group or an aromatic cyclic group X. As a center, two benzene rings (inner benzene ring) are bonded to X, and two benzene rings (outer benzene ring) are bonded to the inner benzene ring via one carbon atom, respectively. It has a structure in which one or more hydroxyl groups are bonded to each of the benzene ring and the four outer benzene rings. In such a structure, a group having a hydroxycarboxylic acid is more easily introduced into a hydroxyl group bonded to the outer benzene ring (outer hydroxyl group) than a hydroxyl group bonded to the inner benzene ring (inner hydroxyl group) due to steric hindrance. It is estimated that In particular, as in the compounds represented by the general formulas (A-2-3) and (A-2-4), an aliphatic cyclic group or an aromatic cyclic group is bonded to the para position of the inner hydroxyl group. The steric hindrance effect is estimated to be large. Such a steric hindrance effect reduces variations in the position and number of hydroxyl groups protected by a group having a hydroxycarboxylic acid, makes the distribution of groups having a hydroxycarboxylic acid relatively uniform, and improves hydrophilicity and polarity. Is also considered to be uniform. Therefore, it is considered that the properties of the resist film obtained using the negative resist composition containing the compound (A-1) become uniform and the roughness can be reduced.
Furthermore, the resist pattern formed by the present invention is also excellent in resolution.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of 1,3-bis (3-formyl-4-hydroxy-5-methylphenyl) -adamantane)
In a 2 L four-necked flask, 615.6 g (5.4 mol) of trifluoroacetic acid was weighed, and 126.0 g (0.9 mol) of hexamethylenetetramine was added dropwise at room temperature over 1 hour and mixed. Into the mixture, 104.4 g (0.3 mol) of 1,3-bis (3-methyl-4-hydroxyphenyl) -adamantane was intermittently added at 70 ° C. over 1 hour, and then at 90 ° C. Stirring was continued for 25 hours. To this reaction solution, 210.0 g of water was added at 70 ° C., and the mixture was stirred for 2 hours and 30 minutes (crystals were precipitated during stirring), then cooled and neutralized with a 16% by mass aqueous sodium hydroxide solution. The neutralized solution was heated to 60 ° C., 100 g of ethyl acetate was added, and the mixture was allowed to cool and filtered to obtain 126.8 g of crude crystals. The crude crystals, 1204.6 g of ethyl acetate, and 150 g of water were charged into a 2 L four-necked flask, heated to 70 ° C. and dissolved, allowed to stand for 10 minutes, the aqueous layer was extracted, and 100 g of water was further added. Water washing and liquid separation were performed. Thereafter, concentration was performed under reduced pressure to remove 962.3 g of the solvent (crystals precipitated during concentration). This was cooled to 23 ° C., filtered, and dried to give 68.2 g (yield 56. 6) of the desired product (1,3-bis (3-formyl-4-hydroxy-5-methylphenyl) -adamantane) as a pale yellow powder. 3% (vs. 1,3-bis (3-methyl-4-hydroxyphenyl) -adamantane)) was obtained.

The obtained object was subjected to physical property analysis and identification. The results are shown below.
(Physical properties)-Purity 95.5% (HPLC (high performance liquid chromatography))-Melting point 182.5 ° C (DSC peaktop) (identification)-Mass spectrometry: LC-MS (liquid chromatography-mass spectrometry) (APCI- )
Analysis result: molecular weight 403 (M−H) −
¹ H-NMR (400 MHz, solvent: DMSO-d6)
Analysis results: as follows.

Synthesis Example 2 (Synthesis of 1,3-bis [3- {bis (2,5-dimethyl-4-hydroxyphenyl) methyl} -5-methyl-4-hydroxyphenyl] -adamantane)
After charging 16 g of 2,5-xylenol and 16 g of methanol into a 500 mL four-necked flask, 12.8 g of hydrochloric acid gas was blown into the flask at 30 ° C., and then 32.8 g (0.27 mol) of 2,5-xylenol. Was added dropwise to 71.2 g of methanol, and 32.3 g (0.08 mol) of 1,3-bis (3-formyl-4-hydroxy-5-methylphenyl) -adamantane obtained in Synthesis Example 1 above was added. ) Was added at 25 ° C. over 1 hour and 50 minutes to carry out the reaction. Thereafter, a stirring reaction was carried out at 40 ° C. for 3 hours.

  Next, neutralization was performed with 87.8 g of a 16% by mass aqueous sodium hydroxide solution, the temperature was raised to 60 ° C., 137 g of toluene was added, and the mixture was concentrated at normal pressure to remove 98 g of the solvent. Thereto was added 69 g of toluene, followed by cooling and filtration to obtain 110 g of crude crystals. The crude crystal, 120 g of methyl isobutyl ketone, and 60 g of water were charged into a 500 L four-necked flask, heated to 70 ° C. and dissolved, allowed to stand for 10 minutes, the aqueous layer was taken out, 60 g of water was further added, Liquid separation was performed. Thereafter, concentration was performed at normal pressure to remove 96 g of the solvent, and 160 g of toluene was added. This was cooled to 25 ° C., filtered and dried, and then 36.4 g (polyhydric phenol compound (I-1-31)) of a pale yellowish white powder (yield 53.1% (vs. 1,3-bis). (3-formyl-4-hydroxy-5-methylphenyl) -adamantane)) was obtained.

(Example 1)
Synthesis of γ-butyrolactone derivative (compound (1)) In a 1-liter flask, the above polyphenol compound (I-1-31) (1,3-bis [3- {bis (2,5-dimethyl-4-) is synthesized. Hydroxyphenyl) methyl} -5-methyl-4-hydroxyphenyl] -adamantane, 15 g), potassium carbonate (7 g) was added and acetone (300 ml) was added and stirred well. A solution of α-bromo-γ-butyrolactone (6.0 g) in acetone (50 ml) was added thereto at room temperature, and the mixed solution was stirred at 50 ° C. for 2 hours. After the reaction, water (50 ml) was added and acetone was distilled off under reduced pressure.

(Example 2)
Synthesis of γ-hydroxycarboxylic acid derivative (compound (2)) THF (300 ml) was added, and 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was added with stirring until the pH reached about 11. After stirring at room temperature for 2 hours, THF was distilled off under reduced pressure, butyl acetate (200 ml) was added, and 1% aqueous hydrochloric acid was added until the pH reached about 5 with vigorous stirring. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and concentrated to obtain a pattern forming substrate (γ-hydroxycarboxylic acid derivative (compound (2))) (16 g).

The compound (2) was analyzed by 1H-NMR and IR. The results are shown below.
1H-NMR data (acetone-d6, 300 MHz, internal standard: TMS): δ (ppm) = 6.52-6.98 m 12H H ^c , 5.78-5.90 m 2H H ^b , 4.84- 4.97 m 2H H ^f , 3.55-3.88 m 4H H ^h , 1.92-2.36 m 34H H ^{a, i, j, g} , 1.60-1.90 m 14H H ^{d, e} .
IR ^{data: 3445cm -1, 2920cm -1, 1722cm} -1, 1291cm -1.
From these results, it was confirmed that the compound (2) had the structure shown below.
The number of γ-hydroxycarboxylic acids introduced from ¹ H-NMR was 2.0 on average per molecule. Furthermore, the γ-butyrolactone derivative (compound (1)) is a compound represented by the above formula (1), and the average number of γ-lactone rings introduced was 2.0 per molecule. confirmed.

  The input amount of α-bromo-γ-butyrolactone was appropriately changed, and γ-hydroxycarboxylic acid derivatives (compounds (3) to (5)) having various introduction rates were obtained by the same method as described above.

Synthesis Example 3 (Synthesis of 1,3-bis [3- {bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl} -4-hydroxy-5-methylphenyl] -adamantane)
After charging 25 g (0.13 mol) of 2-cyclohexyl-5-methylphenol and 16 g of methanol into a 500 mL four-necked flask, and blowing 12.8 g of hydrochloric acid gas at 30 ° C., 51 g of 2-cyclohexyl-5-methylphenol ( 0.27 mol) in 71.2 g of methanol was added dropwise, and 32.3 g of 1,3-bis (3-formyl-4-hydroxy-5-methylphenyl) -adamantane obtained in Synthesis Example 1 above. (0.08 mol) was added at 25 ° C. over 1 hour and 50 minutes to carry out the reaction. Thereafter, a stirring reaction was carried out at 40 ° C. for 3 hours.

  Next, neutralization was performed with 87.8 g of a 16% by mass aqueous sodium hydroxide solution, the temperature was raised to 60 ° C., 137 g of toluene was added, and the mixture was concentrated at normal pressure to remove 98 g of the solvent. Thereto was added 69 g of toluene, followed by cooling and filtration to obtain 110 g of crude crystals. The crude crystal, 120 g of methyl isobutyl ketone, and 60 g of water were charged into a 500 L four-necked flask, heated to 70 ° C. and dissolved, allowed to stand for 10 minutes, the aqueous layer was extracted, 60 g of water was further added, and water washing was performed in the same manner. Liquid separation was performed. Thereafter, concentration was performed at normal pressure to remove 96 g of the solvent, and 160 g of toluene was added. This was cooled to 25 ° C., and the target product (polyhydric phenol compound (I-1-32)) was obtained through filtration and drying.

(Example 3)
Synthesis of γ-butyrolactone derivative (compound (6)) In a 1 liter flask, the above polyphenol compound (I-1-32) (1,3-bis [3- {bis (2-methyl-4-hydroxy-) 5-cyclohexylphenyl) methyl} -4-hydroxy-5-methylphenyl] -adamantane, 15 g), potassium carbonate (7 g) was added, and acetone (300 ml) was added and stirred well. A solution of α-bromo-γ-butyrolactone (6.0 g) in acetone (50 ml) was added thereto at room temperature, and the mixed solution was stirred at 50 ° C. for 2 hours. After the reaction, water (50 ml) was added and acetone was distilled off under reduced pressure.

Example 4
Synthesis of γ-hydroxycarboxylic acid derivative (compounds (7) to (10)) THF (300 ml) was added, and 2.38% TMAH aqueous solution was added with stirring until pH was about 11. After stirring at room temperature for 2 hours, THF was distilled off under reduced pressure, ethyl acetate (200 ml) was added, and 1% aqueous hydrochloric acid was added until the pH reached about 5 with vigorous stirring. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and concentrated to obtain a pattern forming substrate (γ-hydroxycarboxylic acid derivative (compound (7))) (16 g).

Compound (7) was analyzed by 1H-NMR and IR. The results are shown below.
1H-NMR data (acetone-d6, 300 MHz, internal standard: TMS): δ (ppm) = 6.49-7.05 m 12H H ^c , 5.93-6.09 m 2H H ^b , 4.78- 4.95 m 2H H ^f , 3.55-3.88 m 4H H ^h , 1.05-2.38 m 80H H ^{a, d, e, g, i, j} .
IR data: 3389 cm ⁻¹ , 2920 cm ⁻¹ , 2835 cm ⁻¹ , 1730 cm ⁻¹ .
From these results, it was confirmed that the compound (7) had the structure shown below. The number of γ-hydroxycarboxylic acids introduced from ¹ H-NMR was 2.0 on average per molecule. Further, the γ-butyrolactone derivative (compound (6)) is a compound represented by the above formula (6), and the average number of γ-lactone rings introduced was 2.0 per molecule. confirmed.

  The input amount of α-bromo-γ-butyrolactone was appropriately changed, and γ-hydroxycarboxylic acid derivatives (compounds (8) to (10)) having various introduction rates were obtained by the same method as described above.

(Examples 5 and 6)
Each component shown in Table 1 was mixed and dissolved to obtain a negative resist composition solution.

In Table 3, the numerical value in [] shows a compounding quantity (part by mass).
(A) -1: Compound (4)
(A) -2: Compound (9)
(B) -1: Triphenylsulfonium trifluoromethanesulfonate (S) -1: Propylene glycol monomethyl ether (PGME)

Next, the resolution was evaluated using the obtained negative resist composition solution.
A negative resist composition solution was uniformly applied on an 8-inch silicon substrate subjected to hexamethyldisilazane treatment using a spinner, and baked (PAB) at 100 ° C. for 90 seconds to obtain a resist film (film thickness) 150 nm) was formed.
The resist film is drawn (exposure) at an acceleration voltage of 75 kV using an electron beam lithography machine HL-800D (VSB) (manufactured by Hitachi), and baked (PEB) at 100 ° C. for 120 seconds. After developing for 50 seconds using a 0.79 mass% aqueous solution (23 ° C.) of tetramethylammonium hydroxide (TMAH), rinsing with pure water for 30 seconds, line and space (L / S) A pattern was formed.
The optimum exposure dose Eop (μC / cm ² ) at which a 100 nm L / S pattern is formed 1: 1 is obtained, and the limit resolution (nm) at the Eop is determined by a scanning electron microscope S-9220 (manufactured by Hitachi). Obtained using. The results are shown in Table 4.

  As is clear from the above results, a resist pattern with high resolution could be obtained from the negative resist compositions of Examples 5 and 6 using the compounds (A) -1 and (A) -2.

Claims (8)

The compound represented by the following general formula (I-1).

[In Formula (I-1), Y is a group having a lactone ring or a hydrogen atom, and a plurality of Y may be the same or different, and at least a part of the plurality of Y is A group having a lactone ring; each of R ^{11 to} R ¹⁷ is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an aromatic hydrocarbon group, and may contain a hetero atom in its structure; g , J are each independently an integer of 1 or more, k, q is 0 or an integer of 1 or more, and g + j + k + q is 5 or less; h is an integer of 1 or more, and l and m are each independently 0 or an integer of 1 or more and h + 1 + m is 4 or less; i is an integer of 1 or more, n and o are each independently 0 or an integer of 1 or more, and i + n + o is 4 or less; X is an aliphatic cyclic group or aromatic group It is a family cyclic group. ] The compound of Claim 1 represented by the following general formula (I-2).

[In Formula (I-2), Y is a group having a lactone ring, or a hydrogen atom, and a plurality of Y may be the same or different, and at least a part of the plurality of Y is A group having a lactone ring; R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and a hetero atom may be included in the structure thereof; Well; X is an aliphatic cyclic group or an aromatic cyclic group. ] The compound represented by the following general formula (A-1).

[In the formula (A-1), Z is a group having a lactone ring, a group having a hydroxycarboxylic acid that is opened by hydrolysis of the lactone ring, or a hydrogen atom, and a plurality of Z are the same. And at least a part of the plurality of Zs is a group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring; R ^{11 to} R ¹⁷ are each independently a group having 1 to 10 carbon atoms. An alkyl group, an alkenyl group or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; g and j are each independently an integer of 1 or more, and k and q are 0 or 1 or more. Is an integer, and g + j + k + q is 5 or less; h is an integer of 1 or more, l and m are each independently 0 or an integer of 1 or more, and h + l + m is 4 or less; i is 1 or more An integer Ri, n, o are each independently 0 or an integer of 1 or more, and i + n + o is 4 or less; X represents an aliphatic cyclic group or an aromatic cyclic group. ] The compound of Claim 3 represented by the following general formula (A-2).

[In the formula (A-2), Z is a group having a lactone ring, a group having a hydroxycarboxylic acid opened by hydrolysis of the lactone ring, or a hydrogen atom, and the plurality of Z are the same. And at least a part of the plurality of Zs is a group having a hydroxycarboxylic acid opened by hydrolysis of a lactone ring; R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently May be an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group and may contain a hetero atom in the structure thereof; X is an aliphatic cyclic group or an aromatic cyclic group. ]   The compound according to claim 3 or 4, wherein the hydroxycarboxylic acid opened by hydrolysis of the lactone ring is γ-hydroxycarboxylic acid or δ-hydroxycarboxylic acid.   A negative resist composition comprising: a base material component (A) comprising the compound according to any one of claims 3 to 5; and an acid generator component (B) that generates an acid upon irradiation with radiation.   Furthermore, the negative resist composition as described in any one of Claims 3-6 containing a nitrogen-containing organic compound (D).   A step of forming a resist film on a substrate using the negative resist composition according to claim 6, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern. Resist pattern forming method.