JP2012220850A - Resist composition, method for producing relief pattern, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative resist composition having excellent resolution while maintaining high sensitivity specific to a chemically amplified resist in the process of forming a pattern by irradiation with active energy rays, and to provide a method for producing a relief pattern, and electronic components using the resist composition.SOLUTION: The resist composition includes a phenolic compound (A), an acid generator (B) and an organic basic compound (C) having at least one aromatic ring in one molecule, at least one phenolic hydroxyl group and/or an oxy group (-O-) in one molecule, and a molecular weight of 400 or more.

Description

  The present invention relates to a resist composition for forming a chemically amplified resist useful for microfabrication, a method for producing a relief pattern using the resist composition, and an electronic component.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has rapidly progressed due to advances in lithography technology. For example, high resolution with a dimension width of 50 nm or less is required.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened, and in addition to the currently used KrF excimer laser light, ArF, F2, EUV, X-rays, electron beams and other charged particle beams are used. Lithography using the above as exposure light has been proposed.

  In particular, pattern formation by electron beam and EUV exposure is positioned as next-generation or next-generation lithography technology, and is highly sensitive and highly effective for forming a gate layer of a semiconductor integrated circuit or for processing a mask pattern formed on a glass substrate. Development of resists that meet the resolution requirements is desired. As a resist material for these, a chemically amplified photosensitive composition using an acid catalytic reaction is used for the purpose of improving sensitivity. The negative chemically amplified photosensitive composition usually contains an alkali-soluble resin, an acid generator component that generates an acid upon irradiation with light, a crosslinkable compound, a basic compound, and the like. In such a photosensitive composition, cross-linking occurs between the resin and the cross-linkable compound by the action of an acid generated from the acid generator component by exposure, and the alkali composition changes from alkali-soluble to alkali-insoluble. In addition, since the acid generated during the crosslinking reaction is catalytically repeated, pattern exposure with a smaller exposure amount is possible. On the other hand, in the positive chemically amplified photosensitive composition, for example, the acid-dissociable protecting group is eliminated by the action of the acid generated from the acid generator component by exposure, and the solubility in the developer is increased. To do.

Conventionally, resist materials based on polymers having a weight average molecular weight of about 5000 or more have been used for semiconductor lithography.
However, since such a polymer material has a large molecular weight and a wide molecular weight distribution, there is a limit in reducing resolution and line edge roughness (LER).

  Therefore, a low molecular weight material having a low molecular weight and a small molecular size has been developed. The low molecular weight material is excellent in resolving power as compared with a polymer material, and can be expected to reduce LER. Examples of negative resists based on such low-molecular materials include resists using calix resorcinarene and derivatives thereof (Patent Document 1, Non-Patent Document 1), resists using low-molecular polyphenolic compound derivatives ( Non-Patent Document 2) and resists using a cyclic polyphenolic compound derivative (Patent Document 2).

  On the other hand, as a chemical amplification resist material in which a basic compound is used, Patent Document 3 discloses that an alkali-soluble novolak resin, a quinonediazide group-containing compound, a vinyl group, a benzyl group, and an alkyl group are substituted. A positive photoresist composition containing a good imidazole compound is disclosed. Patent Document 3 is a technique for obtaining a resist pattern having excellent adhesion to a substrate without impairing the storage stability of the resist.

  In Patent Document 4, a resist material containing an amine having a specific polyether group is described for the purpose of obtaining a resist material that has a high resist film reduction preventing effect and a high isolated pattern focus margin increasing effect.

In Patent Document 5, a specific benzimidazole skeleton and an ester group, an acetal group, or a cyano group are used for the purpose of obtaining a resist material that has a high resisting effect on resist film loss and a high resolution and focus margin expansion effect. A resist material containing a basic compound having a polar functional group is described.
However, even in Patent Document 5 in which resolution is an issue, only a 160 nm line and space is formed, and the photoresists of Patent Documents 1 to 5 and Non-Patent Documents 1 and 2 have insufficient resolution. Therefore, a resist capable of forming a further miniaturized pattern has been demanded.

Japanese Patent Laid-Open No. 10-239843 Japanese Patent Laid-Open No. 11-153863 Japanese Patent Laid-Open No. 9-236923 JP 2004-46157 A JP 2004-347738 A

Journal of Photopolymer Science and Technology Volume 21, Number 3 (2008) 443-449 Chemistry of Materials 2006, 18, 3404-3411

  The present invention has been made under such circumstances, and in forming a pattern by irradiation with active energy rays, a resist composition excellent in resolving power while maintaining high sensitivity peculiar to a chemically amplified resist, and the resist composition. It is an object of the present invention to provide a method for producing a relief pattern and an electronic component. An object of the present invention is to provide a resist composition capable of forming a fine pattern of less than 30 nm, which has been considered difficult with a chemically amplified resist, without impairing sensitivity and other characteristics.

As a result of intensive studies to achieve the above object, the present inventors impair sensitivity and other characteristics by using a specific organic base compound in combination with a phenolic compound and an acid generator. Thus, the inventors have found that a resist composition having improved resolution and capable of forming a fine pattern can be obtained.
The present invention has been completed based on such knowledge.

  The present invention has a phenolic compound (A), an acid generator (B), one or more aromatic rings in one molecule, and a phenolic hydroxyl group and / or an oxy group (—O—) in one molecule. A resist composition containing at least one organic basic compound (C) having a molecular weight of 400 or more is provided.

  The resist composition according to the present invention has a phenolic compound (A), an acid generator (B), and one or more aromatic rings in one molecule, and a phenolic hydroxyl group and / or an oxy group (—O—). ) Having a molecular weight of 400 or more, and a crosslinkable compound (D), and the phenolic compound (A) and the crosslinkable compound (D) are It can be set as the resist composition which may be the same compound.

  In the resist composition according to the present invention, the phenolic compound (A) and the crosslinkable compound (D) are the same compound, and the same compound has two or more phenolic hydroxyl groups in one molecule. And a phenolic compound having a molecular weight of 300 to 3,000 having one or more substituents in one molecule selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group. A ′) is preferable because a pattern with high resolution and low line edge roughness can be obtained.

  The resist composition according to the present invention has at least one phenolic compound (A), an acid generator (B), and one aromatic ring in one molecule, and has a phenolic hydroxyl group and / or an oxy group (- An organic basic compound (C) having a molecular weight of 400 or more and having at least one O-) in one molecule, wherein the phenolic compound (A) has at least a part of the phenolic hydroxyl group as an acid-decomposable group. It can be set as the resist composition which is a protected phenolic compound (Acap).

  In the resist composition according to the present invention, since the phenolic compound (A) is a phenolic compound having a molecular weight of 300 to 3000 having two or more phenolic hydroxyl groups in one molecule, the resolution is improved. preferable.

  In the resist composition according to the present invention, the organic basic compound (C) is preferably a compound represented by the following formula (1) from the viewpoint of improving the resolution without decreasing the sensitivity.

（式（１）中、Ｒ^ａは、直接結合又はオキシ基（−Ｏ−）を有してもよいアルキレン基を表し、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、オキシ基（−Ｏ−）を有してもよい１価の有機基であり、Ａｒは、芳香環を有する１価の有機基である。但し、１分子中に、フェノール性水酸基及び／又はエーテル結合を１個以上有する。）

(In Formula (1), R ^a represents an alkylene group which may have a direct bond or an oxy group (—O—), and R ^b and R ^c each independently represents an oxy group (—O—). Ar is a monovalent organic group having an aromatic ring, provided that one molecule has at least one phenolic hydroxyl group and / or ether bond. )

  In the resist composition according to the present invention, the fact that the oxy group (—O—) in the organic basic compound (C) is directly bonded to the aromatic ring improves the uniformity in the coating film, This is preferable because a low line edge roughness pattern can be obtained with high sensitivity and high resolution.

  In the resist composition according to the present invention, it is easy to form a uniform coating film when the glass transition temperature (Tg) of the phenolic compound (A) or the phenolic compound (A ′) is 60 ° C. or higher. From the point that high resolution can be obtained.

The present invention includes (i) a step of applying a resist composition according to the present invention on a substrate and then heat-treating to form a resist film; and (ii) exposing, heating and developing the resist film. A relief pattern manufacturing method including a process is provided.
The present invention also provides an electronic component that is at least partially formed from the resist composition according to the present invention or a cured product thereof.

  According to the present invention, in pattern formation by irradiation with active energy rays, a resist composition excellent in resolving power while maintaining high sensitivity peculiar to a chemically amplified resist, a method for producing a relief pattern using the resist composition, and an electronic component Can be provided. In particular, it is possible to provide a resist composition capable of forming a fine pattern of less than 30 nm, which has been considered difficult with a chemically amplified resist, without impairing sensitivity and other characteristics.

Hereinafter, the resist composition, the method for producing a relief pattern, and the electronic component according to the present invention will be described in order.
In the present invention, the active energy ray means far infrared rays such as KrF excimer laser, ArF excimer laser, and F ₂ excimer laser, electron beam, ion beam, EUV, X-ray and the like.
Moreover, in the description of the group (atomic group) in this invention, the description which has not described substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Divalent linking alkylene groups can optionally from different carbon atoms _(e.g., -CH 2 -CH ₂ -) Other, also divalent bonds from the same carbon atom (e.g., _-CH 2 -). Moreover, an alkyl group and a cycloalkyl group include unsaturated hydrocarbons having double bonds, triple bonds and the like in addition to saturated hydrocarbons. Cycloalkyl groups include monocyclic as well as polycyclic hydrocarbons such as bicyclic and tricyclic.

[Resist composition]
The resist composition according to the present invention has a phenolic compound (A), an acid generator (B), and one or more aromatic rings in one molecule, and a phenolic hydroxyl group and / or an oxy group (—O—). ) And an organic basic compound (C) having a molecular weight of 400 or more having 1 or more per molecule.

  The resist composition according to the present invention is excellent in resolving power while maintaining high sensitivity by using a combination of the phenolic compound (A), the acid generator (B), and the specific organic base compound (C). In particular, a fine pattern of less than 30 nm, which has been considered difficult for chemically amplified resists, can be formed without impairing sensitivity and other characteristics.

By using the above-mentioned specific organic base compound (C) in combination with the phenolic compound (A) and the acid generator (B), the following effects are not yet elucidated. Is estimated.
Chemically amplified resist compositions usually contain an acid generator component that generates an acid upon irradiation with active energy rays (hereinafter sometimes referred to as exposure). When acid is generated from the acid generator by exposure, the acid acts as a catalyst. For example, in the case of a negative resist composition, many crosslinks occur between the alkali-soluble resin and the crosslinkable compound. Change to insoluble. Further, in the case of a positive resist composition, the acid acts on the alkali-insoluble resin, and many protective groups are decomposed to change to alkali-soluble. Therefore, in resist pattern formation, when a resist film made of a chemically amplified resist composition is selectively exposed or heated after exposure in addition to exposure, there is a difference in alkali solubility between the exposed and unexposed areas. The resist pattern can be formed by alkali development.
By the way, for example, when a negative resist composition is used as a coating film, each component of the resist composition and the acid generated from the acid generator diffuse in the coating film when heated in PEB. Presumed. Above all, when the generated acid moves in the coating film and diffuses into the unexposed area, it is estimated that the pattern is formed in the unexposed area where the pattern should not be formed, and the resolution of the resist pattern deteriorates. Is done. Conventionally, it is known that diffusion of such an acid can be suppressed by using an organic basic compound or the like. However, the resolution of the pattern obtained using conventional organic basic compounds is insufficient. This is because when the conventional organic basic compound is used, the organic basic compound can move in the coating film in the same manner, the organic basic compound diffuses into the exposed area, and the generated acid By causing a neutralization reaction between them, the sensitivity of the exposed portion is deteriorated, and at the same time, the concentration of the organic basic compound in the unexposed portion is reduced, and a reaction that should be originally suppressed also occurs in the unexposed portion. As a result, it is presumed that the shape of the resist pattern is deteriorated. Also, in the case of a basic compound that is poorly compatible with the phenolic compound, the uniformity of the resist composition in the coating film becomes unstable, and the resolution is insufficient due to the uneven distribution of the basic compound. Presumed.
A phenolic compound having an organic basic compound (C) having a molecular weight of 400 or more having one or more aromatic rings in one molecule and one or more phenolic hydroxyl groups and / or oxy groups (—O—) in one molecule. When used in combination with (A), the organic basic compound (C) is highly compatible with the phenolic compound (A), so that the uniformity in the resist coating is increased and the organic basic compound ( It is estimated that the diffusibility of C) is lowered. In addition, since the diffusion can be further suppressed by setting the organic basic compound (C) having a molecular weight as large as 400 or more, as described above, the amount of the organic basic compound that diffuses into the exposed portion can be reduced. It is presumed that the resist resolving power is not lowered by this. Thus, in the exposed area, the generated acid is not neutralized and maintains the resolution, and in the unexposed area, the generated acid is prevented from diffusing, so that the exposed area has a high concentration of acid, Since there is no acid in the unexposed area, that is, the acid concentration difference at the boundary between the exposed area and the unexposed area is clear, it is presumed that the resolution is excellent while maintaining the sensitivity and other characteristics.

The resist composition of the present invention contains at least a phenolic compound (A), an acid generator (B), and a specific organic basic compound (C) as essential components. Other components may be contained.
When used as a negative resist composition, the resist composition of the present invention has a phenolic compound (A), an acid generator (B), and one or more aromatic rings in one molecule. And / or an organic basic compound (C) having a molecular weight of 400 or more having one or more oxy groups (—O—) in one molecule, and a crosslinkable compound (D), the phenolic compound (A) and The crosslinkable compound (D) may be the same compound.
When used as a positive resist composition, the resist composition of the present invention has a phenolic compound (A), an acid generator (B), and one or more aromatic rings in one molecule. And / or an organic basic compound (C) having a molecular weight of 400 or more having at least one oxy group (—O—) in one molecule, wherein the phenolic compound (A) is at least a part of phenolic hydroxyl group. Is a phenolic compound (Acap) protected with an acid-decomposable group.
Hereafter, each component of such a resist composition of this invention is demonstrated in order.

<Phenolic compound (A)>
The phenolic compound (A) used in the present invention is a compound having a phenolic hydroxyl group. In the present invention, “phenolic hydroxyl group” means a hydroxyl group directly bonded to an aromatic ring such as a benzene ring.

In the phenolic compound (A) used in the present invention, the number of phenolic hydroxyl groups in one molecule is not particularly limited. Especially, it is preferable to have two or more phenolic hydroxyl groups in one molecule from the point of improving the resolution of the pattern, and the phenolic compound (A) has three or more phenolic hydroxyl groups in one molecule. More preferably, it is even more preferable to have 4 or more phenolic hydroxyl groups in one molecule. When four or more phenolic hydroxyl groups are contained in one molecule, three-dimensional crosslinking is possible and pattern strength is improved, so that a decrease in resolution due to pattern collapse occurring after development can be suppressed, and resolution is further improved. In addition, the presence of more polar groups in the molecule improves the interaction between the polar groups and the substrate and improves the adhesion, and the adhesion with the substrate also leads to an increase in the resolution.
Among these, it is even more preferable from the viewpoint of the above-mentioned effect that four or more benzene rings having a phenolic hydroxyl group are contained in one molecule.

The molecular weight of the phenolic compound (A) used in the present invention is not particularly limited. Especially, it is preferable that it is a phenolic compound of molecular weight 300-3000 from the point which can attain high resolution of a pattern.
When the molecular weight is 300 or more, the ability to form a resist film and the ability to form a pattern are excellent. If the molecular weight is 3000 or less, swelling due to the solvent used in the resist composition is less likely to occur, pattern collapse is less likely to occur, and the pattern shape can be improved. The molecular weight here refers to the sum of the atomic weights of the atoms constituting the molecule. Moreover, when it is an oligomer which has molecular weight distribution, it represents with the weight average molecular weight using GPC (polystyrene conversion).
In particular, the molecular weight of the phenolic compound (A) used in the present invention is preferably 500 to 2500, and more preferably 600 to 2000 from the viewpoint of film formability and resolution.

  From the above, the phenolic compound (A) used in the present invention is preferably a phenolic compound having a molecular weight of 300 to 3,000 having two or more phenolic hydroxyl groups in one molecule.

The phenolic compound (A) used in the present invention preferably has a glass transition temperature (Tg) of 60 ° C. or higher, and more preferably 90 ° C. or higher. When the glass transition temperature is 60 ° C. or higher, a dewetting phenomenon hardly occurs when forming a coating film, and a uniform film is easily obtained. The dewetting phenomenon is a phenomenon in which a spread coating film is dissolved during pre-baking to cause repelling and a film is not formed uniformly.
Usually, as a solvent for a resist composition, when a low boiling point solvent is used, the resist film is dried rapidly and a uniform film cannot be obtained. In order to obtain, a solvent having a boiling point of 80 to 180 ° C. is used. Since the resist film formed by the spin coating method contains a lot of residual solvent, the resist substrate is heated at a temperature of 90 ° C. or higher using a hot plate in order to form a stable resist film except for this solvent ( Pre-bake). However, when a phenolic compound having a glass transition temperature of less than 60 ° C. is used, a dewetting phenomenon of the resist film occurs in a pre-baking process at a temperature higher than the glass transition temperature, and a uniform film may not be obtained.
In contrast, when a phenolic compound having a glass transition temperature of 60 ° C. or higher is used, pre-baking at a high temperature is possible, a uniform film can be obtained, and a resist film excellent in environmental resistance (post coating delay: PCD). Is obtained. Furthermore, in the dry etching process after forming the resist pattern, a pattern having excellent etching resistance (can prevent the pattern from being melted due to high temperature during etching) can be obtained.
The glass transition temperature here is measured by a differential scanning calorimeter (DSC).

  Moreover, it is preferable that the phenolic compound (A) used in this invention has the solubility of 0.5 weight% or more at 23 degreeC with respect to the organic solvent whose boiling point is 80-180 degreeC. In such a case, it is possible to prevent the resist film from being rapidly dried during spin coating, and there is an advantage that a uniform resist film can be obtained. Typical examples of organic solvents having a boiling point of 80 to 180 ° C. include cyclopentanone, propylene glycol monomethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, 2-heptanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and the like. Is mentioned.

  Among them, the phenolic compound (A) used in the present invention has 3 or more phenolic hydroxyl groups in one molecule, a glass transition temperature (Tg) of 60 ° C. or higher, and a boiling point of 80 to 180 ° C. The organic solvent preferably has a solubility of 0.5% by weight or more at 23 ° C.

  As said phenolic compound (A), the compound represented by following Chemical formula (2) and Chemical formula (4) is mentioned. The compound represented by the following chemical formula (2) is preferable from the viewpoint of obtaining a pattern with high sensitivity, high resolution, and good shape.

［化学式（２）中、Ｒ^１は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、及び下記化学式（３）に示す基からなる群より選ばれる基である。

[In the chemical formula (2), each R ¹ is independently a group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, and a group represented by the following chemical formula (3).

（化学式（３）中、Ｒ^４及びＲ^５は、各々独立に、水素原子又は炭素数１〜３のアルキル基であり、Ｑは、アリール基又はシクロアルキル基であり、ｍは１又は２を表す。）
Ｒ^２は、各々独立に、水素原子又は有機基であり、複数あるＲ^２のうち１分子中少なくとも２つは水素原子である。Ｒ^３は、ハロゲン原子又はアルキル基、シクロアルキル基、アリール基、アルコキシ基、アシル基、シアノ基、及びニトロ基からなる群より選ばれる基である。上記アルキル基、シクロアルキル基、アリール基はそれぞれ置換基を有していても良い。
ｎ１は１〜３の整数、ｎ２は０〜２の整数を表す。但し、ｎ１＋ｎ２≦４となる組み合わせをｎ１及びｎ２の数値範囲から選択するものとする。ｘ１は３〜１２の整数を表す。また、化学式（２）に含まれる同一符号で表される基は、互いに同じでも異なっていてもよい。］

(In the chemical formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q is an aryl group or a cycloalkyl group, and m is 1 or 2. To express.)
R ² is each independently a hydrogen atom or an organic group, and at least two of a plurality of R ² are hydrogen atoms. R ³ is a group selected from the group consisting of a halogen atom or an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, and a nitro group. The alkyl group, cycloalkyl group, and aryl group may each have a substituent.
n1 represents an integer of 1 to 3, and n2 represents an integer of 0 to 2. However, a combination satisfying n1 + n2 ≦ 4 is selected from a numerical range of n1 and n2. x1 represents the integer of 3-12. In addition, the groups represented by the same symbols included in the chemical formula (2) may be the same as or different from each other. ]

（化学式（４）中、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、ヒドロキシメチル基、又はアルコキシメチル基、或いは、これらの組み合わせからなる基を表す。複数のＲ^６が結合して環を形成してもよい。複数のＲ^７が結合して環を形成してもよい。複数のＲ^８が結合して環を形成してもよい。複数のＲ^９が結合して環を形成してもよい。また、複数あるＲ^６、Ｒ^７、Ｒ^８及びＲ^９は互いに同じであっても異なっていても良い。
Ｒ^１０及びＲ^１１は、各々独立に、水素原子又は１価の有機基を表し、複数あるＲ^１０及びＲ^１１は互いに同じであっても異なっていても良い。また、複数あるＲ^１０及びＲ^１１のうち少なくとも２つは水素原子である。更に、Ｒ^６、Ｒ^７及び／又はＲ^９において、フェノール性水酸基のオルト位にヒドロキシメチル基、及びアルコキシメチル基よりなる群から選択される１種以上の置換基を有していてもよい。
Ｗは単結合、エーテル結合、チオエーテル結合、又はヘテロ原子を含んでいてもよい、アルキレン基、シクロアルキレン基、又はアリーレン基、或いは、これらの任意の組み合わせからなる基を表す。複数あるＷは互いに同一であっても異なっていてもよい。
ｘ２は正の整数を表す。
ｙ１は０以上の整数を表し、Ｗが単結合の場合、ｙ１は０である。
ｙ２は０以上の整数を表し、ｙ３は正の整数を表す。
ｚは０以上の整数を表す。
ｖは０以上の整数を表す。
ｋ１及びｋ４は正の整数を表す。
ｋ２、ｋ３、及びｋ５は各々独立して０以上の整数を表す。但し、ｋ１＋ｋ２＋ｚ＝５、ｋ３＋ｖ＝３、ｋ４＋ｋ５＝５、ｋ２＋ｋ５≧２を満たす。）

(In the chemical formula (4), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxymethyl group, or an alkoxymethyl group, or these Represents a group consisting of a combination, wherein a plurality of R ⁶ may combine to form a ring, a plurality of R ⁷ may combine to form a ring, or a plurality of R ⁸ combine to form a ring. A plurality of R ⁹ may combine to form a ring, and a plurality of R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other.
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a monovalent organic group, and a plurality of R ¹⁰ and R ¹¹ may be the same as or different from each other. Further, at least two of the plurality of R ¹⁰ and R ¹¹ are hydrogen atoms. Furthermore, R ⁶ , R ⁷ and / or R ⁹ may have one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group.
W represents a single bond, an ether bond, a thioether bond, or an alkylene group, a cycloalkylene group, an arylene group, or a group consisting of any combination thereof, which may contain a hetero atom. Plural Ws may be the same or different.
x2 represents a positive integer.
y1 represents an integer of 0 or more. When W is a single bond, y1 is 0.
y2 represents an integer of 0 or more, and y3 represents a positive integer.
z represents an integer of 0 or more.
v represents an integer of 0 or more.
k1 and k4 represent positive integers.
k2, k3, and k5 each independently represents an integer of 0 or more. However, k1 + k2 + z = 5, k3 + v = 3, k4 + k5 = 5, and k2 + k5 ≧ 2 are satisfied. )

In the compound represented by the chemical formula (2), the alkyl group for R ¹ is not particularly limited, but an alkyl group having 1 to 18 carbon atoms is preferable. The alkyl group may be linear or branched. For example, methyl group, ethyl group, n-propyl group, n-butyl group, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, hexadecyl group and the like can be mentioned. Moreover, you may have unsaturated bonds, such as a double bond and a triple bond.

  Examples of the substituent that the alkyl group has include a hydroxyl group, an alkoxy group, and a halogen atom.

The cycloalkyl group of R ^1, is not particularly limited, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Further, it may have an unsaturated bond such as a double bond or a triple bond, and may be monocyclic or polycyclic.
As the cycloalkyl group, a cyclohexyl group is preferable.

  The substituent that the cycloalkyl group has is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group.

  The alkyl group having 1 to 5 carbon atoms may be linear or branched. As a linear alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group and the like.

  The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 2-ethylhexyloxy group.

  Although there is no restriction | limiting in particular as an alkoxyalkyl group, A C1-C8 alkoxyalkyl group is preferable, For example, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group etc. are mentioned.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The halogenoalkyl group is not particularly limited, but is preferably a halogenoalkyl group having 1 to 8 carbon atoms. For example, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 1,2-dichloroethyl group, 1,1,2,2-tetrachloroethyl group, etc. Can be mentioned.

The aryl group of R ^1, is not particularly limited, but is preferably 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group , Biphenyl, anthryl group and the like.

Moreover, as a substituent which an aryl group has, a cycloalkyl group, a C1-C5 alkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group etc. are mentioned.
Examples of the cycloalkyl group as a substituent that the aryl group has are the same as those described above. In addition, the cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, and an alkoxy group. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and an i-propyl group. Although there is no restriction | limiting in particular as an alkoxy group, A C1-C8 alkoxy group is preferable, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, 2-ethylhexyloxy group etc. are mentioned.
The alkyl group having 1 to 5 carbon atoms, the alkoxy group, the alkoxyalkyl group, the halogen atom, and the halogenoalkyl group as the substituent that the aryl group has are as described above for the cycloalkyl group.

In the chemical formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms may be either linear or branched, and among them, a methyl group and an ethyl group are preferable from the viewpoint of achieving both high sensitivity and solvent solubility. When m is 2, two R ⁴ and R ⁵ may be the same or different.
In the chemical formula (3), a case where both R ⁴ and R ⁵ are hydrogen atoms is preferably used.

  Examples of the aryl group for Q in the chemical formula (3) include the same aryl groups as those described above. Examples of the substituent that the aryl group of Q has are the same as the substituents that the aryl group has. Further, examples of the cycloalkyl group of Q in the chemical formula (3) include the same cycloalkyl groups as those described above. Examples of the substituent that the cycloalkyl group of Q has are the same as the substituents that the cycloalkyl group has.

The organic group for R ² is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group.

Examples of the alkyl group for R ² include the same as those for R ¹ . Examples of the substituent that the alkyl group of R ² has are the same as those of R ¹ described above.

The cycloalkyl group of R ² and the substituent that the cycloalkyl group has can be the same as those of R ¹ described above. The aryl group of R ^{2 and} the substituent that the aryl group has can be the same as those of R ¹ described above.

Examples of the halogen atom for R ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the alkyl group for R ^3, the same groups as those described above for R ¹ can be mentioned.
The substituent of the alkyl group as R ³ is cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxy group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy Group, alkoxycarbonyl group, cyano group, nitro group and the like.

The cycloalkyl group of R ³ and the substituent that the cycloalkyl group has can be the same as those of R ¹ described above. The aryl group of R ^{3 and} the substitution of the aryl group can be the same as those of R ¹ described above.
In addition, examples of the alkoxy group for R ³ include the same groups as those described above for R ¹ .

The acyl group of R ^3, is not particularly limited, preferably an acyl group having 1 to 8 carbon atoms, e.g., formyl group, acetyl group, propionyl group, butyryl group, valeryl group, a pivaloyl group, include benzoyl group and the like It is done.

  x1 is an integer of 3-12, preferably an integer of 4-12, more preferably an integer of 4-8.

As long as the compound represented by the chemical formula (2) has two or more phenolic hydroxyl groups, the substituents represented by the same symbols in the respective repeating units may be the same or different. The positions of OR ² and R ³ in each repeating unit may be the same or different. Moreover, the number of n1 and n2 in each repeating unit may be the same or different. For example, in the compound represented by the chemical formula (2), when x1 is 4, all the repeating units may be the same as the following chemical formula (5), or all the repeating units may be the same as the following chemical formula (6). The repeating unit may be different.

In the compound represented by the chemical formula (2), x1 is 4 and n1 is preferably 2 or 3 from the viewpoint of obtaining a pattern with high sensitivity and high resolving power. x1 is 4, n1 is 2, it is preferable hydrogen atom of the eight R ² is a 2-8 calix resorcin arene derivatives. Furthermore, it is preferable that a hydrogen atom of the eight R ² is cut box resorcin allene derivative is 2-4, among others, in one of the hydrogen atoms of the two R ² in the repeating unit of formula (2) The other is an organic group and a calix resorcinarene derivative having four hydrogen atoms in one molecule is preferable from the viewpoint of achieving high sensitivity while using a high concentration developer.

On the other hand, in the compound represented by the chemical formula (4), the alkyl group in R ⁶ , R ⁷ , R ⁸ and R ⁹ may be linear or branched, and is preferably a methyl group, an ethyl group, a propyl group, or butyl. And those having 1 to 10 carbon atoms such as a group, an isobutyl group, a hexyl group, and an octyl group.
The cycloalkyl group in R ⁶ , R ⁷ , R ⁸ and R ⁹ may be monocyclic or polycyclic. For example, groups having a monocyclo, bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms can be given. The number of carbon atoms is preferably 6 to 30, and particularly preferably 7 to 25. For example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol Group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and the like. These alicyclic hydrocarbon groups may have a substituent.
The aryl group in R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same as R ¹ described above.
In the compound represented by the chemical formula (4), R ⁶ is a (X2) -valent group when (X2) is an integer of 2 or more.

  Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (methoxy group, ethoxy group). , Propoxy group, butoxy group, etc.).

Examples of the organic group in R ¹⁰ and R ¹¹ include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an amide group, and a cyano group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group. For example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl Group, cyclopropyl group, cyclobutyl group, cyclohexyl group, adamantyl group and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and an isobutoxy group.

The alkylene group in W may be linear or branched, and preferably has 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group.
The cycloalkylene group in W may be monocyclic or polycyclic, and examples of the alkylene group forming the ring include a cycloalkylene group having 3 to 8 carbon atoms (for example, a cyclopentylene group and a cyclohexylene group). be able to.
The alkylene group and cycloalkylene group in W may further have a substituent, and examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 10, for example, methyl group, ethyl group, propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy Group, ethoxy group, propoxy group, butoxy group, etc.), fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In addition, an alkylene chain or a cycloalkylene chain includes —O—, —OC (═O) —, —OC (═O) O—, —N (R) —C (═O) —, —N in the alkylene chain. (R) —C (═O) O—, —S—, —SO—, —SO ₂ — may be included. Here, R represents a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group). Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
The cyclic arylene group in W is preferably a group having 6 to 15 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group.

When the phenolic compound (A) has two or more phenolic hydroxyl groups in one molecule, the phenolic hydroxyl group of the compound (maternal compound) serving as a mother nucleus such as a polyhydric phenolic compound is protected with an organic group. You may do it.
Although the specific example of the mother nucleus compound of a phenolic compound (A) is shown below, this invention is not limited to these. The phenolic hydroxyl groups in the following specific examples may be protected with an organic group as long as two or more phenolic hydroxyl groups in one molecule are present.

  The mother compound of the phenolic compound (A) is commercially available from, for example, Honshu Chemical Industry Co., Ltd., Asahi Organic Materials Co., Ltd., and the like, and can be used. It can also be synthesized by condensation of various phenolic compounds with various aldehydes and ketones.

  Furthermore, the phenolic compound (A) used in the present invention may have a crosslinkable group. When the phenolic compound (A) has a crosslinkable group, the phenolic compound (A) can have both a function as a resist substrate and a function as a crosslinkable compound (D) described later. The compound (A) and the crosslinkable compound (D) described later are used as the same compound.

  The crosslinkable group possessed by the phenolic compound (A) is not particularly limited as long as the phenolic compound (A) can be crosslinked by the action of an acid. Among them, it is preferable to have a hydroxymethyl group or an alkoxymethyl group as a crosslinkable group because the uniformity of the resist film is improved and a pattern with low line edge roughness can be obtained.

When the phenolic compound (A) having a crosslinkable group used in the present invention, that is, the phenolic compound (A) and the crosslinkable compound (D) described later are the same compound, the phenolic hydroxyl group is contained in one molecule. Having a molecular weight of 400 to 3,000 having at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having two or more in a phenolic hydroxyl group. A phenolic compound (A ′) is preferred. By using such a phenolic compound (A ′), the phenolic compound (A) and the crosslinkable compound (D) become the same compound, and the number of components in the resist composition can be substantially reduced. A uniform resist film can be formed, and a pattern with high resolution and low line edge roughness can be obtained.
Hereinafter, such a phenolic compound (A ′) will be described in detail.

(Phenolic compound (A '))
The phenolic compound (A ′) used in the present invention is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having two or more phenolic hydroxyl groups in one molecule and having a phenolic hydroxyl group. It is a phenolic compound having a molecular weight of 400 to 3000 having one or more substituents in one molecule.

The phenolic compound (A ′) used in the present invention has one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in one molecule on an aromatic ring having a phenolic hydroxyl group. There should be more than one. One or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group function as a crosslinkable group of the phenolic compound. For this reason, the resist composition using the phenolic compound (A ′) functions as a negative resist composition.
In particular, the phenolic compound (A ′) used in the present invention has one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group in one molecule. It is preferable to have two or more, more preferably three or more in one molecule, and more preferably four or more in one molecule from the viewpoint of increasing the crosslinkability.

  In addition, the substitution position of the hydroxymethyl group and the alkoxymethyl group on the aromatic ring having a phenolic hydroxyl group is not particularly limited, and any of the ortho-position, meta-position, and para-position based on the position of the phenolic hydroxyl group. Also good. Among these, from the viewpoint of easy synthesis, it is preferably substituted at the ortho-position or para-position, more preferably at the ortho-position, based on the phenolic hydroxyl group.

  The alkoxymethyl group is preferably an alkoxy group having 1 to 6 carbon atoms, specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, or an n-butoxymethyl group. , Sec-butoxymethyl group, t-butoxymethyl group, various pentyloxymethyl groups, and the like. Among these, as the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable because sensitivity is improved.

  As the crosslinkable group, among them, one or more substituents selected from the group consisting of a hydroxymethyl group, a methoxymethyl group, and an ethoxymethyl group at the ortho position of the phenolic hydroxyl group are highly reactive, This is preferable from the viewpoint of good sensitivity.

Since the phenolic compound (A ′) has the properties of the phenolic compound (A), the preferred embodiment of the phenolic compound (A) also applies to the phenolic compound (A ′).
Specific examples of the phenolic compound (A ′) include a phenolic hydroxyl group in the mother nucleus compound such as the chemical formulas (A-1) to (A-36) exemplified in the phenolic compound (A). Examples of the aromatic ring include compounds having one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in one molecule.

Specific examples of the phenolic compound (A ′) are shown below, but the present invention is not limited thereto. There are two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are present in one molecule on an aromatic ring having a phenolic hydroxyl group. If there are more than one, the phenolic hydroxyl groups in the following specific examples may be protected with organic groups.
In the following formulae, each L is independently a hydrogen atom or one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L in one molecule is And one or more substituents selected from the group consisting of a hydroxymethyl group present at the ortho position of the phenolic hydroxyl group and an alkoxymethyl group.

  The phenolic compound (A ′) used in the present invention is one or more substitutions selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group on an aromatic ring having a phenolic hydroxyl group in the parent compound of the phenolic compound. It can be obtained by introducing a group. As a method for introducing the substituent functioning as the crosslinkable group into the mother compound of the phenolic compound, for example, it is obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde under a base catalyst. be able to. At this time, in order to prevent side reactions such as gelation, the reaction temperature is preferably 50 ° C. or lower. Various bisphenol derivatives having an alkoxymethyl group can be obtained by reacting a corresponding bisphenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent side reactions such as gelation, the reaction temperature is preferably 100 ° C. or lower.

In the resist composition according to the present invention, the phenolic compound (A) may be used alone or in combination of two or more of the compounds described above. Among the phenolic compounds (A), those belonging to the phenolic compound (A ′) and those not belonging to the phenolic compound (A ′) may be used in combination.
However, in the resist composition according to the present invention, the phenolic compound (A) preferably has a purity of 90% by weight or more from the same structural formula in terms of improving low line edge roughness. In the phenolic compound (A), the purity of compounds having the same structural formula is more preferably 90% by weight or more, and further preferably 95% by weight or more.
When a compound having the same structural formula and having a high purity is used as the phenolic compound (A), the progress of development becomes uniform, and it is estimated that the line edge roughness is reduced.
However, the phenolic compound (A) has a similar impurity structure to the phenolic compound (A) even when the purity of the compound having the same structural formula is less than 90% by weight, and the compatibility is good. Can be preferably used.

  From the viewpoint of improving low line edge roughness, the phenolic compound used in the present invention preferably has no molecular weight distribution. The phenolic compound used in the present invention preferably has a small molecular weight distribution, even if it has a molecular weight distribution. The molecular weight distribution (ratio of weight average molecular weight <Mw> to number average molecular weight <Mn> <Mw> / <Mn> is preferably 1.0 to 1.1.

The content of the phenolic compound (A) is preferably 30 to 95% by weight and more preferably 50 to 93% by weight with respect to the total solid content of the resist composition.
Moreover, when it is a compound which belongs to a phenolic compound (A '), it is preferable that the content is 70 to 98 weight% with respect to the total solid of a resist composition, and is 80 to 96 weight% or more. It is more preferable.
In addition, in this invention, solid content means things other than an organic solvent among the components contained in a resist composition.

(Phenol compounds in which some phenolic hydroxyl groups are protected with acid-decomposable groups (Acap))
In the resist composition of the present invention, a phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group can be used as the phenolic compound (A). The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group has an acid-decomposable protective group dissociated by the action of an acid, and the solubility in an alkali developer increases. A resist composition using a phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group can be a positive resist composition.
In the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group, the number of phenolic hydroxyl groups protected with an acid-decomposable group is not particularly limited. Among them, it is preferable that two or more phenolic hydroxyl groups protected by an acid-decomposable group are contained in one molecule from the viewpoint of increasing the difference in solubility between the exposed portion and the unexposed portion. More preferably, it is more preferable to have 4 or more in one molecule.

  The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is obtained by introducing an acid-decomposable group into a part of the phenolic hydroxyl group of the phenol compound (A). it can.

  The acid-decomposable group is eliminated by the acid generated from the acid generator (B) by exposure, and the solubility of the phenol compound (Acap) in which the partial phenolic hydroxyl group is protected with an acid-decomposable group in an alkaline developer. Increase.

The acid-decomposable group is not particularly limited as long as it dissociates in the presence of an acid to generate a phenolic hydroxyl group. For example, —C (R) ₃ , —COO—C (R) ₃ , —C (R) ₂ — COO-C (R) ₃ etc. are mentioned.
Here, a plurality of R's independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. Rs may be bonded to each other to form a ring.

  As the alkyl group for R, an alkyl group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, etc. Is mentioned.

  The cycloalkyl group for R may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  The alkenyl group for R is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

  The aralkyl group for R is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The aryl group of R is preferably an aryl group having 6 to 10 carbon atoms, for example, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10- Examples include a dimethoxyanthryl group.

  Examples of the substituent that R may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, Examples include an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.

  Although the specific example of an acid-decomposable group is shown below, it is not limited to these.

  Examples of the compound for introducing the acid-decomposable group include, but are not particularly limited to, active carboxylic acid derivative compounds such as acid chlorides, acid anhydrides and dicarbonates having an acid-decomposable group, and alkyl halides.

  The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is obtained by converting the mother compound of the phenol compound (A) and the compound having the acid-decomposable group into an amine catalyst such as triethylamine. The reaction can be carried out under normal pressure at 60 ° C. for 6 to 7 hours, reprecipitated in distilled water, washed with distilled water, and dried.

  In the resist composition according to the present invention, the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group may be used alone or in combination of the above-mentioned compounds. You may mix and use the above.

The molecular weight of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is not particularly limited. When the mother nucleus compound of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is a compound represented by the chemical formula (2) of the phenol compound (A), Is preferably 300 to 3000, and more preferably 400 to 1500.
Moreover, when a mother nucleus compound is a compound represented by Chemical formula (4) of the said phenol compound (A), molecular weight becomes like this. Preferably it is 300-3000, More preferably, it is 400-2000.

  The content of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is preferably 50 to 95% by weight, more preferably 60 to 85% by weight.

<Acid generator (B)>
In the present invention, the acid generator (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions. Especially, it is preferable that it is an acid generator which generate | occur | produces an acid directly or indirectly by irradiating an active energy ray with a wavelength of 248 nm or less.

  The acid generator (B) is preferably at least one selected from the group consisting of compounds represented by the following chemical formulas (7) to (12).

In chemical formula (7), R ¹² may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or 3 to 12 carbon atoms. Cyclic alkyl group, a linear alkoxy group having 1 to 12 carbon atoms, a branched alkoxy group having 3 to 12 carbon atoms, a cyclic alkoxy group having 3 to 12 carbon atoms, a branched alkoxycarbonylalkoxy group having 5 to 10 carbon atoms , A hydroxyl group, or a halogen atom, and X ⁻ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a halogen having 6 to 12 carbon atoms. A sulfonate ion having a substituted aryl group or a halide ion. n is an integer of 0-5.

  Examples of the compound represented by the chemical formula (7) include triphenylsulfonium trifluoromethylsulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium cyclohexafluoropropane-1,3-bis (sulfonyl). Imido, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-2 , 4,6-Trimethylphenylsulfonium p-toluenesulfonate, diphenyl-4-t-butoxyphenylsulfonium Fluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl 3,5-dimethyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, bis (4-hydroxyphenyl) -t-pentylphenylsulfonium trifluoromethanesulfonate, tris (4 Methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate Diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethyl Phenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluor Rhobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, (4-t-butoxy Carbonylmethoxyphenyl) diphenylsulfonium-4-trifluoromethylbenzenesulfonate, 2,4-di (t-butoxycarbonylmethoxy) phenyldiphenylsulfonium-4-trifluoromethylbenzenesulfonate, (4-t-butoxycarbonylmethoxyphenyl) diphenyl Sulfonium-2,4,6-tris (trifluoromethyl) benzenesulfonate, 2,4-di t- butoxycarbonyl methoxy) such as phenyl diphenyl sulfonium-2,4,6-tris (trifluoromethyl) benzene sulfonates.

In the chemical formula (8), X ⁻ , R ¹³ , and n are the same as X ⁻ , R ¹² , and n in the chemical formula (7).

  Examples of the compound represented by the chemical formula (8) include bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4 -T-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butyl) Phenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenes Phonate, bis (4-t-butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium Perfluoro-n-octanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyl Iodonium-2,4-difluorobenze Sulfonate, diphenyliodonium hexafluorobenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) Iodonium perfluoro-n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 10-camphor Examples include sulfonates.

In chemical formula (9), A is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O—, where R ′ is carbon. R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a C 6 to 12 carbon group. A halogen-substituted aryl group.

  Examples of the compound represented by the chemical formula (9) include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyl) Oxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-Dicarboki Imido, N- (10-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) naphthyl Imido, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthyl Imido, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, 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-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide and the like.

In the chemical formula (10), R ¹⁵ may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or 3 to 12 carbon atoms. A cyclic alkyl group, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, a halogen atom, or a haloalkyl group having 1 to 12 carbon atoms.

  Examples of the compound represented by the chemical formula (10) include diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-t-butylphenyl) disulfone, and di (4-hydroxyphenyl). ) Disulfone, di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone, di (4-trifluoromethylphenyl) disulfone and the like.

In chemical formula (11), R ¹⁶ may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or 3 to 12 carbon atoms. A cyclic alkyl group, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkoxy group having 1 to 12 carbon atoms.

  Examples of the compound represented by the chemical formula (11) include α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxy). Imino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methyl Examples include phenylacetonitrile and α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In chemical formula (12), R ¹⁷ 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.

  Examples of the compound represented by the chemical formula (12) include monochloroisocyanuric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dibromoisocyanuric acid, trichloroisocyanuric acid, and tribromoisocyanuric acid. .

  Examples of the other acid generator (B) include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (n-butylsulfonyl). Bissulfonyldiazomethanes such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 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) halogen-containing triazine derivatives such as isocyanurate.

These acid generators (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 to 30 parts by weight, more preferably 1 to 25 parts by weight, with respect to 100 parts by weight of the phenolic compound (A). More preferably, it is 5-20 weight part. If the amount is less than this range, image formation cannot be performed. If the amount is larger, a uniform solution cannot be obtained and a uniform coating film may not be obtained.
Therefore, the content of the acid generator (B) is preferably 2 to 30% by weight, more preferably 4 to 20% by weight, based on the total solid content of the resist composition.

<Organic basic compound (C)>
The organic basic compound (C) used in the present invention has a molecular weight having at least one aromatic ring in one molecule and at least one phenolic hydroxyl group and / or oxy group (—O—) in one molecule. 400 or more organic basic compounds.
The organic basic compound (C) allows the acid generated from the acid generator (B) to diffuse before and after exposure without inhibiting the crosslinking reaction of the phenolic compound (A) and the crosslinkable compound (D). It functions to suppress changes in composition. Furthermore, in this invention, it can be set as the thing excellent in resolving power, without deteriorating a sensitivity and another characteristic by using the said specific organic basic compound (C).

The aromatic ring in the organic basic compound (C) is not particularly limited. For example, in addition to aromatic hydrocarbons such as benzene, naphthalene and anthracene, heteroaromatic rings such as pyridine, pyrrole and thiophene can be mentioned. Among these, from the viewpoint of compatibility with the phenolic compound (A), the aromatic ring is preferably an aromatic hydrocarbon, and more preferably benzene.
The aromatic ring should just have 1 or more in 1 molecule of organic basic compounds (C). Among them, two aromatic rings are contained in one molecule of the organic basic compound (C) from the viewpoint that the compatibility with the phenolic compound (A) is improved and the uneven distribution in the resist coating is suppressed. It is preferable to have the above, and it is more preferable to have three or more aromatic rings in one molecule.

The oxy group (—O—) in the organic basic compound (C) may be contained as an ester bond (—COO—) and a carbonate bond (—O—COO—) in addition to an ether bond.
The oxy group may be present at any position in the molecule and is not particularly limited. Especially, it is preferable from the point which the compatibility with the said phenolic compound (A) improves that the oxygen of an oxy group is directly couple | bonded with the aromatic ring.

  The organic basic compound (C) used in the present invention may have at least one phenolic hydroxyl group and / or oxy group (—O—) in one molecule. Among them, from the viewpoint of improving compatibility with the phenolic compound (A), one molecule of the organic basic compound (C) may have two or more phenolic hydroxyl groups and / or oxy groups (—O—). Preferably, it has 3 or more phenolic hydroxyl groups and / or oxy groups (—O—) in one molecule.

  The molecular weight of the organic basic compound (C) used in the present invention is 400 or more. When the molecular weight is 400 or more, the resist composition using the organic basic compound (C) can be excellent in resolving power while maintaining high sensitivity. Among these, the molecular weight of the organic basic compound (C) is preferably 400 to 3000, more preferably 400 to 2000, and still more preferably 400 to 1000.

  In the present invention, the organic basic compound (C) is preferably a compound represented by the following formula (1) from the viewpoint of improving the resolution without lowering the sensitivity.

（式（１）中、Ｒ^ａは、直接結合又はオキシ基（−Ｏ−）を有してもよいアルキレン基を表し、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、オキシ基（−Ｏ−）を有してもよい１価の有機基であり、Ａｒは、芳香環を有する１価の有機基である。但し、１分子中に、フェノール性水酸基及び／又はエーテル結合を１個以上有する。）

(In Formula (1), R ^a represents an alkylene group which may have a direct bond or an oxy group (—O—), and R ^b and R ^c each independently represents an oxy group (—O—). Ar is a monovalent organic group having an aromatic ring, provided that one molecule has at least one phenolic hydroxyl group and / or ether bond. )

The alkylene group for R ^a is not particularly limited, and may be linear or branched. Especially, a C1-C10 thing is preferable, for example, a methylene group, ethylene group, a propylene group, a butylene group, an isobutylene group etc. are mentioned. Moreover, you may have an oxy group (-O-) in the carbon chain which comprises an alkylene group, or the terminal of the carbon chain.

Examples of the monovalent organic group in R ^b and R ^c include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, and combinations thereof (aralkyl group, alkylaryl group, etc.). These organic groups may contain a bond or substituent other than a hydrocarbon group such as a heteroatom containing an oxy group (—O—) in the organic group, and these may be linear or branched.
R ^b and R ^c may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group. , Cyclopropyl group, cyclobutyl group, cyclohexyl group, adamantyl group and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkylaryl group is preferably an alkylaryl group having 7 to 20 carbon atoms, and examples thereof include various alkylphenyl groups and various alkylnaphthyl groups.
Examples of the bond other than the hydrocarbon group in the organic group include, for example, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (—R) —, -C (= NR)-, wherein R is a hydrogen atom or a monovalent organic group), a carbonate bond, and the like.
The substituent other than the hydrocarbon group in the organic group is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, an alkoxy group, a nitro group, an acyl group, an acyloxy group, and an amino group. It is done. When it has an aryl group or an aralkyl group, it preferably has a hydroxyl group.

Ar is not particularly limited to a monovalent organic group having an aromatic ring, and may be an aromatic ring itself or may further have a substituent on the aromatic ring. A combination with a saturated alkyl group or a saturated or unsaturated cycloalkyl group may be used. As what further has a substituent in an aromatic ring, what has an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a hydroxyl group etc. as a functional group is mentioned in an aromatic ring, for example, What has a hydroxyl group among these. preferable. As a combination of an aromatic ring and a saturated or unsaturated alkyl group or a saturated or unsaturated cycloalkyl group, for example, chemical formulas (A-1) to (A-36) and chemical formulas exemplified in the example of the phenolic compound (A) Various carbon skeletons such as (a-1) to (a-47) can be mentioned.
Examples of the aromatic ring include aromatic hydrocarbons such as benzene, naphthalene, and anthracene, and heteroaromatic rings such as pyridine, pyrrole, and thiophene. Among these, from the viewpoint of compatibility with the phenolic compound (A), the aromatic ring is preferably an aromatic hydrocarbon, and more preferably benzene.

The organic base compound (C) used in the present invention preferably has the same carbon skeleton as the phenolic compound (A) used in combination from the viewpoint of improving the compatibility. Here, the same carbon skeleton as the phenolic compound refers to a portion of the phenolic compound excluding a substituent.
In addition, as the organic basic compound (C) of the present invention, for example, a compound obtained by reacting a tertiary amine having a halogenated alkyl group and a phenolic compound, a basic compound and a phenolic compound, From the viewpoint of compatibility with the phenolic compound, a compound obtained by reacting the above compound is preferable.

  Specific examples of the organic base compound (C) used in the present invention are shown below, but the present invention is not limited thereto.

  These organic basic compounds (C) can be used alone or in combination of two or more. The compounding quantity of an organic basic compound (C) is 0.01-10 weight part with respect to 100 weight part of said phenolic compounds (A), Preferably it is 0.1-5 weight part. If it is less than 0.01 part by weight, the effect of the addition cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease.

<Crosslinking compound (D)>
The crosslinkable compound (D) used in the present invention is a compound that crosslinks the phenolic compound (A) by the action of an acid to make it hardly soluble in alkali. For this reason, the resist composition using the crosslinkable compound (D) can be used as a negative resist composition.
In addition, when using the said phenolic compound (A '), it is not necessary to contain a crosslinkable compound separately. However, in this case as well, a small amount may be added to improve the resolving power as the sensitivity increases and the pattern strength increases.
The crosslinkable compound (D) used in the present invention is not particularly limited. Any of known cross-linking compounds used in conventional chemically amplified resist compositions can be selected and used.
For example, 4,4′-methylenebis [2,6-bis (hydroxymethyl)] phenol (MBHP), 4,4′-methylenebis [2,6-bis (methoxymethyl)] phenol (MBMP), 2,3- Dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxytricyclodecane, 2-methyl-2-adaman Examples thereof include aliphatic cyclic hydrocarbons having a hydroxyl group or a hydroxyalkyl group or both thereof, such as butanol, 1,4-dioxane-2,3-diol, 1,3,5-trihumanoxycyclohexane, and oxygen-containing derivatives thereof. .

  In addition, amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is hydroxymethyl group or lower alkoxymethyl. And a compound substituted with a group. Of these, those using melamine are melamine crosslinkable compounds, those using urea are urea crosslinkable compounds, those using alkylene urea such as ethylene urea and propylene urea are alkylene urea crosslinkable compounds, glycols Those using uril are called glycoluril-based crosslinkable compounds.

  Examples of the melamine-based crosslinkable compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

  Examples of the urea-based crosslinkable compound include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea.

  Examples of the alkylene urea-based crosslinkable compound include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated Ethylene urea crosslinkable compounds such as ethylene urea, mono and / or dibutoxymethylated ethylene urea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated Propylene urea crosslinkable compounds 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- (Methoxymethyl) 4,5-dimethoxy-2-imidazolidinone.

  Examples of the glycoluril-based crosslinkable compound include mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or tetra. And ethoxymethylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

In this invention, a crosslinking | crosslinked compound (D) can be used individually by 1 type or in combination of 2 or more types.
When not using a crosslinkable phenolic compound (A '), the compounding quantity of a crosslinkable compound (D) is 3-40 weight part with respect to 100 weight part of said phenolic compounds (A), Preferably it is 3-30 weight. Part. If the compounding amount of the crosslinkable compound (D) is less than 3 parts by weight, the crosslink formation does not proceed sufficiently and a good resist pattern may not be obtained. On the other hand, if it exceeds 40 parts by weight, the storage stability of the resist solution is lowered, and the sensitivity may deteriorate over time.

<Resin (E) having a repeating unit represented by the chemical formula (13) and having solubility in an alkali developer>
The resist composition of the present invention further comprises a resin (E) having a repeating unit represented by the following chemical formula (13) and having solubility in an alkali developer (hereinafter also referred to as alkali-soluble polymer (E)). May be contained.

（化学式（１３）中、Ｚは、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アシル基、アシロキシ基、アルキルスルホニル基、又はアルコキシ基である。Ｚが複数個ある場合、当該Ｚは同じでも異なっていてもよい。Ｒ^１８は、水素原子、メチル基、ハロゲン原子、シアノ基、又はトリフルオロ基である。ｐは２〜４の整数、ｑは１〜３の整数を表し、ｐ＋ｑ＝５である。）

(In the chemical formula (13), Z represents a halogen atom, a cyano group, a nitro group, an alkyl group, an acyl group, an acyloxy group, an alkylsulfonyl group, or an alkoxy group. R ¹⁸ is a hydrogen atom, a methyl group, a halogen atom, a cyano group, or a trifluoro group, p is an integer of 2 to 4, q is an integer of 1 to 3, and p + q = 5 .)

In the chemical formula (13), examples of the halogen atom for Z and R ¹⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group in the alkyl group and alkylsulfonyl group of Z is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group. , T-butyl group and the like.
The alkoxy group of Z is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an n-butoxy group.
The acyl group of Z is preferably an acyl group having 1 to 8 carbon atoms, and examples thereof include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group, and benzoyl group.
The acyloxy group of Z is preferably an acyloxy group having 2 to 8 carbon atoms, such as an acetoxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a pivaloyloxy group, a hexanoyloxy group, an octanoyloxy group, a benzoyloxy group, and the like. Can be mentioned. Z may be further substituted with a halogen atom or the like.

  Although the specific example of the repeating unit represented by Chemical formula (13) is shown below, this invention is not limited to these.

  In addition to the above repeating units, the alkali-soluble polymer (E) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and generally required characteristics of resist, such as resolution, heat resistance, and sensitivity. Various repeating units can be included for the purpose of adjustment.

  Examples of such a repeating unit include, but are not limited to, repeating structural units corresponding to the following monomers. Examples thereof include compounds having one addition polymerizable unsaturated bond selected from acrylic acid and esters, methacrylic acid and esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

Specifically, the following monomers can be mentioned.
Examples of acrylic acid and esters include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, acrylic acid-t-octyl, chloroethyl acrylate, 2- Examples include hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, adamantyl acrylate, norbornyl acrylate, and the like. .

  Examples of methacrylic acid and esters include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, Examples include 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, adamantyl methacrylate, and norbornyl methacrylate.

  Examples of acrylamides include acrylamide, N-alkylacrylamide, N, N′-dialkylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of methacrylamides include methacrylamide, N-alkyl methacrylamide, N, N′-dialkyl methacrylamide, N-hydroxyethyl-N-methyl methacrylamide, and the like.

  Examples of allyl compounds include allyl esters and allyloxyethanol. Specific examples of allyl esters include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and the like.

  Examples of vinyl ethers include alkyl vinyl ethers, and specifically, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- Examples include dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether.

  Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Examples thereof include vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

  Other examples include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleilonitrile.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating units may be copolymerized. The monomer to be copolymerized may further have a substituent.

  The content of the repeating unit represented by the chemical formula (13) in the alkali-soluble polymer (E) is preferably 40 to 100 mol%, and more preferably 70 to 100 mol%.

  The weight average molecular weight of the alkali-soluble polymer (E) is preferably 2000 to 80000, more preferably 2500 to 8000.

  The content of the alkali-soluble polymer (E) is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the total solid content.

<Other ingredients>
The resist composition of the present invention further contains miscible additives as desired, for example, an additional resin for improving the performance of the resist film, a surfactant, a dissolution inhibitor, and a plasticizer for improving coatability. Stabilizers, colorants, antihalation agents and the like can be added and contained as appropriate.

<Preparation of resist composition>
The resist composition according to the present invention can be a negative resist composition or a positive resist composition as required.
In the case of a negative resist composition, the above-mentioned phenolic compound (A), acid generator (B), organic basic compound (C), crosslinkable compound (D), and as necessary are usually added to the organic solvent (F). Accordingly, it is prepared by mixing other additives uniformly.
Further, when a positive resist composition is used, usually, a phenolic compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group in the organic solvent (F), an acid generator (B). The organic basic compound (C) and, if necessary, other additives are mixed uniformly.

As the organic solvent (F), those generally used as solvents for chemically amplified resists can be used. For example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol dimethyl ether, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide N- methylpyrrolidone, tetrahydrofuran and the like are preferred, it is possible to use these solvents singly or in combination. Further, isopropyl alcohol, ethyl alcohol, methyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, isobutyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-methoxyethanol , 2-ethoxyethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol and other alcohols, and toluene, xylene and other aromatic solvents may be contained. In the present invention, among these organic solvents (F), in addition to diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, which are most excellent in solubility of the acid generator in the resist component, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and mixed solvents thereof which are safety solvents are preferably used.
The amount of the solvent in the resist composition is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. Generally, the solvent is used so that the solid content concentration of the resist composition is preferably in the range of 0.5 to 20% by weight, more preferably 0.5 to 15% by weight.

  The resist composition of the present invention is suitably used in a microlithography process for producing miniaturized electronic components for forming a gate layer of a semiconductor integrated circuit and for processing a mask pattern formed on a glass substrate. Can do.

[Electronic parts]
The present invention also provides an electronic component that is at least partially formed of the resist composition according to the present invention or a cured product thereof. The electronic component according to the present invention includes the resist composition or the cured product thereof in any of the configurations including the resist composition or the cured product thereof. Can be. Examples of the electronic component according to the present invention include a MEMS (micro electro mechanical device) component, a micro mechanical component, a micro fluid engineering component, a μ-TAS (micro total analysis device) component, an inkjet printer component, a micro reactor component, Electrically conductive layers, metal bump connections, LIGA (lithography electroforming) parts, molds and molds for micro injection molding and micro coining, precision printing screens or stencils, MEMS and semiconductor package parts, and ultraviolet ( Examples thereof include a printed wiring board that can be processed by UV) lithography.

[Relief pattern manufacturing method]
The method for producing a relief pattern according to the present invention includes:
(I) a step of applying a resist composition according to the present invention on a substrate and then heat-treating it to form a resist film; and (ii) exposing, heating and developing the resist film. It is characterized by.

  According to the method for producing a relief pattern according to the present invention, a pattern having a good shape can be formed with high sensitivity and high resolution.

Hereinafter, each step will be described.
(I) Step of applying a resist composition according to the present invention on a substrate and then heat-treating to form a resist film In this step, first, the resist composition is applied on a substrate.
The coating method is not particularly limited as long as the resist composition can be uniformly coated on the substrate surface, and various methods such as spraying, roll coating, slit coating, and spin coating are used. be able to.

Next, the resist composition applied on the substrate is pre-baked (PAB) to remove the organic solvent (F) to form a resist film.
What is necessary is just to determine the temperature of a prebaking suitably by the component of the said composition, a use ratio, the kind of organic solvent (F), etc., and are 70-160 degreeC normally, Preferably it is 90-130 degreeC. The pre-bake time is usually about 30 seconds to 15 minutes.

(Ii) Step of exposing, heating and developing the resist film In this step, first, the resist film is exposed, for example, with an active energy ray having a wavelength of 248 nm or less. For example, by using an exposure apparatus such as an electron beam drawing apparatus or EUV exposure apparatus, the resist film is exposed through a mask having a predetermined pattern shape, or drawn by direct irradiation of an electron beam without using the mask. , Selectively expose.
The exposure light source is not particularly limited, and can be performed using an ArF excimer laser, a KrF excimer laser, an F ₂ excimer laser, EUV (Extreme Ultraviolet), an electron beam, an X-ray, or the like.
Next, after the exposure, post-exposure heating (Post Exposure Bake, PEB) is performed. The conditions for the PEB treatment are usually 70 to 160 ° C., preferably 90 to 130 ° C., and a time of about 0.1 to 15 minutes.
Next, the substrate subjected to the PEB treatment is developed using an alkali developer, and the unexposed portion is removed in the negative resist composition, and the exposed portion is removed in the positive resist composition.
Examples of the developing method include a spray method, a slit method, a liquid piling method, a dipping method, and a shaking dipping method.
Examples of the alkaline developer of the resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, An aqueous solution of an alkali such as a quaternary ammonium salt such as tetraethylammonium hydroxide or choline, or a cyclic amine such as pyrrole or piperidine can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution. Among these alkaline developers, a quaternary ammonium salt is preferable, and an aqueous solution of tetramethylammonium hydroxide and choline is more preferable.

  When a tetramethylammonium hydroxide (TMAH) aqueous solution is used as the alkaline developer, the concentration of the tetramethylammonium hydroxide aqueous solution is preferably 0.1% to 5%, more preferably 0.5%. It is ˜3%, and particularly preferably 1.19% to 2.38%. 2.38% concentration of tetramethylammonium hydroxide aqueous solution is generally most readily available in the semiconductor industry. In addition, when the concentration of the tetramethylammonium hydroxide aqueous solution is less than 0.1%, the developer is neutralized by carbon dioxide in the air, and the sensitivity fluctuates, making it difficult to stably obtain a product. Become.

  After the development treatment, a rinsing treatment is performed, and the alkali developer on the substrate and the resist composition dissolved by the alkali developer are washed away and dried to obtain a resist pattern.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, the structure and physical properties in the production examples were confirmed using the following apparatuses.
・ MALDI-TOF MS: BRUKER, REFLEX II
Measurement was performed using 1,8,9-trihydroxyanthracene as a matrix.
¹ H-NMR: JEOL JNM-LA400WB, manufactured by JEOL
-High performance liquid chromatography (HPLC): LC-10ADvp, manufactured by Shimadzu Corporation
Measurement was performed under measurement conditions of temperature: 40 ° C., flow rate: 0.5 mL / min, column: VP-ODS (4.7 mm × 150 mm), detector SPD-M10Avp, mobile phase: acetonitrile / water = 8/2. .

(Preparation of basic compounds and phenolic compounds)
<Production Example 1: Synthesis of basic compound (C-1)>
Under a nitrogen atmosphere, in a 100 mL three-necked flask, 0.50 g (1.69 mmol) of N- (2-chloroethyl) dibenzylamine hydrochloride and 0.36 g (1.69 mmol) of α-cumylphenol were dissolved in 30 mL of acetone. Then, 2.34 g (16.9 mmol) of potassium carbonate was added and reacted at 60 ° C. for 48 hours. After the reaction, the remaining potassium carbonate was removed, the solvent was distilled off once, and the reaction product was evaporated to dryness, and then dissolved in water. Then, ethyl acetate was added to extract the target product from the aqueous phase, and further ethyl acetate was distilled off. Later, it was purified by high performance liquid chromatography to obtain a viscous colorless liquid basic compound (C-1) (molecular weight: 435.6).
The structure was confirmed by MALDI-TOF MS, high performance liquid chromatography, and ¹ H-NMR spectrum.
Confirmed with MALDI-TOF MS: [M + H] 436.5
HPLC (acetonitrile / water = 8/2) retention time: 66.5 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): 6.76 to 7.38 δ (ppm) (aromatic-H), 4.01 to 4.03 (aromatic-O—CH 2 —), 3.66 (Aromatic-CH2-N), 2.75 (N-CH2-CH2-), 1.59 (aromatic-C (-CH3) -aromatic)

<Production Examples 2 and 3: Synthesis of basic compounds (C-2) and (C-3)>
Under a nitrogen atmosphere, in a 100 mL three-necked flask, 0.25 g (1.69 mmol) of N- (2-chloroethyl) dibenzylamine hydrochloride, (TekOC-4HBPA: manufactured by Honshu Chemical Industry Co., Ltd.) 0.54 g (1.69 mmol) Is dissolved in 30 mL of acetone. Then, 1.17 g (8.5 mmol) of potassium carbonate was added and reacted at 60 ° C. for 48 hours. After the reaction, the remaining potassium carbonate was removed, the solvent was distilled off once, and the reaction product was evaporated to dryness, and then dissolved in water. Then, ethyl acetate was added to extract the target product from the aqueous phase, and further ethyl acetate was distilled off. Later, it was collected by high performance liquid chromatography and purified to obtain waxy solid basic compounds (C-2) (molecular weight: 856.2) and (C-3) (molecular weight 856.2).
The structure was confirmed by MALDI-TOF MS, high performance liquid chromatography, and ¹ H-NMR spectrum. Since the ¹ H-NMR spectrum and the HPLC retention time are different, it can be seen that the basic compounds (C-2) and (C-3) are in an isomer relationship.

(C-2)
Confirmed with MALDI-TOF MS: [M + H] 856.8
HPLC (acetonitrile / water = 8/2) retention time: 73.5 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): 9.00 & 8.98 (d) δ (ppm) (aromatic-OH), 8.90 (aromatic-OH), 6.54 to 7.37 ( aromatic-H), 3.98 (aromatic-O-CH2-), 3.65 (aromatic-CH2-N), 2.75 (N-CH2-CH2-), 2.63 (Cyclohexane-H2). 01 to 2.05 (aromatic-CH3), 1.65 (Cyclohexane-H2), 1.50 (Cyclohexane-H2), 1.32 (Cyclohexane-H), 1.08 (Cyclohexane-H2), 0.44 (-C (-CH3) 2-)

(C-3)
Confirmed with MALDI-TOF MS: [M + H] 856.8
HPLC (acetonitrile / water = 8/2) retention time: 89.0 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): 8.98 δ (ppm) (aromatic-OH), 8.92 & 8.90 (d) (aromatic-OH), 6.54 to 7.40 (aromatic) -H), 4.04 (aromatic-O-CH2-), 3.68 (aromatic-CH2-N), 2.79 (N-CH2-CH2-), 2.65 (Cyclohexane-H2) 2.01 ˜2.10 (aromatic-CH3), 1.65 (Cyclohexane-H2), 1.51 (Cyclohexane-H2), 1.32 (Cyclohexane-H), 1.07 (Cyclohexane-H2), 0.43 ( -C (-CH3) 2-)

<Comparison Basic Compound (RC-1)>
The comparative basic compound (RC-1) (molecular weight: 353.7) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name: trioctylamine).

<Comparison basic compound (RC-2)>
The comparative basic compound (RC-2) (molecular weight: 287, 4) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name: tribenzylamine).

<Comparison Basic Compound (RC-3)>
The comparative basic compound (RC-3) (molecular weight: 323.4) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name: Tris [2- (2-methoxyethoxy) ethyl] amine). .

<Comparison Basic Compound (RC-4)>
The comparative basic compound (RC-4) (molecular weight: 191.3) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name 1- (3-hydroxybenzyl) piperidine).

<Comparison Basic Compound (RC-5)>
The comparative basic compound (RC-5) (molecular weight: 191.3) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name 1-benzyl-4-hydroxypiperidine).

<Comparison basic compound (RC-6)>
The comparative basic compound (RC-6) (molecular weight: 127.2) represented by the following chemical formula was obtained from Tokyo Chemical Industry Co., Ltd. (product name: 3-hydroxyquinuclidine).

<Production Example 4: Synthesis of phenolic compound (CRA-1)>
Under a nitrogen atmosphere, 12.4 g (0.1 mol) of 3-methoxyphenol was dissolved in 200 mL of ethanol in a 300 mL three-necked flask. While this was cooled in an ice bath, 13.4 g (0.1 mol) of 2,4-dimethylbenzaldehyde was added, and then 25 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 70 ° C. for 12 hours. After the reaction, the reaction solution was poured into 500 mL of distilled water, the resulting precipitate (yellow solid) was filtered, washed with distilled water until neutral, and dried. Purification was performed by high performance liquid chromatography to obtain a white phenolic compound (calix resorcinarene derivative; CRA-1) represented by the following chemical formula. The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum.

<Phenolic compound (A-1)>
The phenolic compound (A-1) represented by the following chemical formula was obtained from Asahi Organic Materials Co., Ltd.

<Phenolic compound (A-2)>
The phenolic compound (A-2) product name TEP-BOCP represented by the following chemical formula was obtained from Asahi Organic Materials Co., Ltd.

＜製造例５：フェノール性化合物（Ａ−２Ｓ）の合成＞
１０重量％水酸化カリウム水溶液２０ｍＬとエタノール２０ｍＬからなる溶液に、前記化学式（Ａ−２）で表されるフェノール性化合物５．８ｇ（１０ｍｍｏｌ）を加え、室温で攪拌、溶解した。この溶液に３７％ホルマリン水溶液１４．０ｍＬ（１６０ｍｍｏＬ）を室温下でゆっくりと加えた。更に、窒素雰囲気下、４０℃で２４時間攪拌した後、ビーカー中の水２００ｍＬに投入した。これを氷浴にて冷却しながら２．０ｗｔ％酢酸水溶液をｐＨ５．０になるまでゆっくりと加えた。析出物をろ別し、十分に水洗浄した後、乾燥し、ヒドロキシメチル基の数が４〜８個導入されたフェノール性化合物の混合物（Ａ−２Ｍ）を得た。精製は、高速液体クロマトグラフィーにて行い、下記化学式で表されるフェノール性化合物（Ａ−２Ｓ）を４．８ｇ得た。
得られたフェノール性化合物（Ａ−２Ｓ）の構造確認は、^１Ｈ‐ＮＭＲスペクトル及びＭＡＬＤＩ−ＴＯＦ ＭＳより行った。

<Production Example 5: Synthesis of phenolic compound (A-2S)>
To a solution composed of 20 mL of 10 wt% aqueous potassium hydroxide and 20 mL of ethanol, 5.8 g (10 mmol) of the phenolic compound represented by the chemical formula (A-2) was added, and the mixture was stirred and dissolved at room temperature. To this solution, 14.0 mL (160 mmol) of 37% formalin aqueous solution was slowly added at room temperature. Furthermore, after stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was poured into 200 mL of water in a beaker. While cooling this in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was filtered off, sufficiently washed with water, and then dried to obtain a mixture of phenolic compounds (A-2M) into which 4 to 8 hydroxymethyl groups were introduced. Purification was performed by high performance liquid chromatography to obtain 4.8 g of a phenolic compound (A-2S) represented by the following chemical formula.
The structure of the obtained phenolic compound (A-2S) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS.

<Production Example 6: Synthesis of phenolic compound (A-3S)>
In Production Example 5, instead of using the phenolic compound (A-2), phenolic compound (A-3) represented by the following chemical formula (TekOC-4HBPA: Honshu Chemical Industry Co., Ltd.) 6.3 g (10 mmol) The white phenolic compound (A-3S) represented by the following chemical formula was used in the same manner as in Production Example 5, except that the amount of 37% formalin aqueous solution was changed to 7.0 mL (80 mmol). 8 g was obtained.
The structure of the obtained phenolic compound (A-3S) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS.

<Acid generator>
The acid generator diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate (P-1) represented by the following chemical formula was obtained from Wako Pure Chemical Industries, Ltd.

<Crosslinkable compound>
As the crosslinkable compound (D-1) represented by the following chemical formula, (product name TM-BIP-A) was obtained from Asahi Organic Materials Co., Ltd.

(Examples 1-7, Comparative Examples 1-11: Preparation of negative resist composition)
Each component was dissolved in propylene glycol monomethyl ether (F-1) in a blending amount as shown in Table 1, stirred for 12 hours, and then filtered through a 0.2 μm PTFE filter. Examples 1 to 7 and Comparative Examples 1 to 11 A negative resist composition was prepared.
In addition, the weight part of a basic compound differs because the number of moles of the basic compound used for an Example and a comparative example was match | combined.

<Evaluation: Formation of resist pattern>
Using the resist compositions of Examples 1 to 7 and Comparative Examples 1 to 11, resist patterns were prepared and evaluated by the methods shown below. The results are shown in Table 2.

(1) Application of resist Each resist composition of Examples and Comparative Examples was uniformly applied on a 6-inch silicon substrate using a spinner, pre-baked (PAB) at 100 ° C. for 60 seconds, and a film thickness of 70 nm. The resist film was formed.

(2) Formation of resist pattern Drawing was performed on the resist-coated substrate using an electron beam drawing apparatus (acceleration voltage 100 KV). After drawing, baking (PEB) is performed at 100 ° C. or 110 ° C. for 60 seconds, developed with 2.38% TMAH aqueous solution (23 ° C.) for 60 seconds, and further rinsed with pure water for 60 seconds. A line and space (L / S) pattern was formed.

<Evaluation>
(1) Sensitivity and resolving power Sensitivity was measured in units of μC / cm ² with the minimum dose at which an L / S pattern of 100 nm was formed 1: 1. Further, the limit resolution (the line and space are separated and resolved) at the irradiation amount was defined as the resolution. The confirmation of the resolution was judged by a length measurement SEM made by Holon.
Further, in the SEM image of the 100 nm L / S pattern obtained at this time, the line width was measured at 500 points in the range of the edge of 0.7 μm in the longitudinal direction, the standard deviation was obtained, 3σ was calculated, and LER was obtained. Further, the exposure amount causing a certain amount of pattern dimension change was defined as the exposure margin, and the exposure amount for obtaining 95 nm was subtracted from the exposure amount for obtaining 105 nm, and this was divided by the sensitivity and calculated by 100. Since LER reflects the size of the unevenness on the side wall of the pattern, it is desirable that the numerical value is small, and the exposure margin does not change easily even if the exposure amount changes, that is, a certain range of dimensions can be obtained. Since a larger exposure range is preferable, a larger value is desirable.

<Summary of results>
From the results shown in Table 2, in Examples 1 to 7, the resolution was excellent, and a desired fine pattern could be formed without impairing sensitivity. In Comparative Examples 1 to 11 using RC-1 to RC-6 as comparative basic compounds, the resolution was inferior.
Regarding LER and exposure margin, a large difference due to the change of the basic compound is not recognized, but it is suggested that the resolution is improved without deteriorating various performances other than the resolution in the examples.
In Comparative Examples 1 to 3, the basic compounds were the same, and comparison was performed when other conditions were changed, which were conventionally considered to improve resolution. In Comparative Example 2, the PEB temperature was lowered than in Comparative Example 1, and in Comparative Example 3, the content of the basic compound was increased as compared with Comparative Example 1, and the measurement was performed. In Comparative Examples 2 and 3, even when compared with Comparative Example 1, the effect of improving the resolution was not observed. That is, in the present invention, it was possible to improve the resolving power without adversely affecting various resist properties that could not be achieved by conventional knowledge, by using a basic compound having a specific structure and molecular weight.
In Comparative Examples 1 to 9, since the molecular weight of the basic compound is less than 400, it is estimated that the diffusion of the basic compound in PEB tends to occur more easily. In this case, between the lines, the concentration of the basic compound in the unexposed part is significantly reduced by moving to an area where there is a lot of acid in the exposed part. As a result, the basic compound originally has It is considered that the effect of suppressing the acid generated in the exposed portion from diffusing to the unexposed portion has been reduced. In this case, since the acid is likely to enter the unexposed area by diffusion, image formation is likely to occur, so that the pattern is not sufficiently separated and the resolution is lowered. On the other hand, since the compound used in the examples has a large molecular weight and the diffusion is suppressed, a difference in acid concentration at the boundary between the exposed area and the unexposed area clearly appears, and image formation in the unexposed area is suppressed. It is presumed that high resolution was obtained.

Claims (10)

  One or more phenolic compounds (A), acid generators (B), and aromatic rings in one molecule, and one or more phenolic hydroxyl groups and / or oxy groups (-O-) in one molecule A resist composition containing an organic basic compound (C) having a molecular weight of 400 or more.   One or more phenolic compounds (A), acid generators (B), and aromatic rings in one molecule, and one or more phenolic hydroxyl groups and / or oxy groups (-O-) in one molecule It contains an organic basic compound (C) having a molecular weight of 400 or more and a crosslinkable compound (D), and the phenolic compound (A) and the crosslinkable compound (D) may be the same compound. The resist composition according to claim 1.   The phenolic compound (A) and the crosslinkable compound (D) are the same compound, and the same compound has two or more phenolic hydroxyl groups in one molecule, and an aromatic ring having a phenolic hydroxyl group And a phenolic compound (A ′) having a molecular weight of 300 to 3000 having one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in one molecule. The resist composition as described.   One or more phenolic compounds (A), acid generators (B), and aromatic rings in one molecule, and one or more phenolic hydroxyl groups and / or oxy groups (-O-) in one molecule An organic basic compound (C) having a molecular weight of 400 or more, wherein the phenolic compound (A) is a phenolic compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group. The resist composition according to claim 1.   The resist composition according to any one of claims 1 to 4, wherein the phenolic compound (A) is a phenolic compound having a molecular weight of 300 to 3000 and having two or more phenolic hydroxyl groups in one molecule. The negative resist composition according to claim 1, wherein the organic basic compound (C) is represented by the following formula (1).

(In Formula (1), R ^a represents an alkylene group which may have a direct bond or an oxy group (—O—), and R ^b and R ^c each independently represents an oxy group (—O—). Ar is a monovalent organic group having an aromatic ring, provided that one molecule has at least one phenolic hydroxyl group and / or ether bond. )   The negative resist composition according to any one of claims 1 to 6, wherein the oxy group (-O-) in the organic basic compound (C) is directly bonded to an aromatic ring.   The negative resist composition according to claim 1, wherein the phenolic compound (A) or the phenolic compound (A ′) has a glass transition temperature (Tg) of 60 ° C. or higher. (I) a step of applying a resist composition according to any one of claims 1 to 8 on a substrate and then heat-treating to form a resist film; and (ii) exposing the resist film to heat And developing the relief pattern.   An electronic component, at least a part of which is formed of the resist composition according to claim 1 or a cured product thereof.