JP2011095702A - Pattern forming material, negative resist composition, and pattern forming method and electronic component using the negative resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material allowing formation of a pattern excellent in sensitivity and resolution in pattern formation by irradiation with electron beams or EUV, and to provide a negative resist composition using the pattern forming material, and a pattern forming method and an electronic component using the negative resist composition. <P>SOLUTION: The pattern forming material includes a cyclic polyphenol derivative expressed by chemical formula (1). In chemical formula (1), each code has a specific meaning. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pattern forming material for forming a resist useful for microfabrication, a negative resist composition using the pattern forming material, and a pattern forming method and electronic component using the negative resist composition About.

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, F ₂ , EUV, X-rays, electron beams, and other charged particles Lithography using lines 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 it has high sensitivity and high resolution for creating gate layers of semiconductor integrated circuits and processing mask patterns formed on glass substrates. Development of a negative resist that satisfies all the requirements of image and low line edge roughness (LER) 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 contains an alkali-soluble resin, an acid generator component that generates an acid upon irradiation with exposure light, a crosslinking agent, a basic compound, and the like. In such a photosensitive composition, cross-linking occurs between the resin and the cross-linking agent due to the action of the acid generated from the acid generator component by exposure, and the alkali-soluble 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 a chemically amplified photosensitive composition, sensitivity, resolving power, and LER are in a reciprocal relationship, and how to make them compatible is a problem.

Conventionally, resist materials based on polymers having a weight average molecular weight of about 10,000 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 LER.
Therefore, low molecular weight materials having no molecular weight distribution have been developed. The low molecular weight material is expected to be superior in resolving power as compared with the high molecular weight material, and further contribute little to the increase in LER. Examples of negative resists based on such low-molecular materials include resists using low-molecular polyphenol compound derivatives (Non-patent Document 1), resists using cyclic polyphenol compound derivatives (Patent Document 1), and calixarene. And resists using calixresorcinarene and derivatives thereof (Patent Document 2, Non-Patent Document 2) and the like.

Recently, in a negative chemically amplified resist composition, a cationic polymerization type molecular resist has been reported (Non-patent Document 3). The cationic polymerization type molecular resist of Non-Patent Document 3 does not require a conventionally used crosslinking agent because it uses the crosslinkability of an epoxy group. Non-Patent Document 3 describes that the cationic polymerization molecular resist can obtain high sensitivity, high resolution, and low line edge roughness.
Non-Patent Documents 4 and 5 report a molecular resist having an epoxy group as a resist using a calixarene derivative derived from a phenol compound.
However, the compounds described in the above documents do not sufficiently satisfy the respective requirements of resolution, resist shape, and pattern size stability.

Japanese Patent Laid-Open No. 11-153863 Japanese Patent Laid-Open No. 10-239843

Chemistry of Materials 2006, 18, 3404-3411 Journal of Photopolymer Science and Technology Volume 21, Number 3 (2008) 443-449 Proc. of SPIE Volume 7273, (2009), 72733E1-10 Microelectronic Engineering 73-74 (2004) 228-232 J. et al. Vac. Sci. Technol. B Vol. 22, no. 6 (2004) 3485-3488

  Specifically, the compound described in Non-Patent Document 3 has a dewetting phenomenon (during prebaking) at the stage of forming a coating film for pattern formation (as shown in a comparative example described later). It was found that there was a problem that a uniform resist film could not be formed due to dewetting), and a good pattern could not be obtained, and there was a problem in the stability of pattern dimensions. In addition, calixarene derivatives derived from phenolic compounds described in Non-Patent Documents 4 and 5 have poor sensitivity and have poor solvent solubility as shown in Comparative Examples described later. There were limitations and problems.

  In view of the above circumstances, an object of the present invention is to solve the performance improvement and technical problems in microfabrication of semiconductor elements, and in pattern formation by electron beam or EUV irradiation, dewetting phenomenon does not occur, and pattern dimensions Pattern forming material capable of obtaining a resist composition with high stability and improved resolution and sensitivity, negative resist composition using the pattern forming material, and pattern formation using the negative resist composition A method and electronic component are provided.

  The pattern forming material according to the present invention comprises a cyclic polyphenol derivative represented by the following chemical formula (1).

［化学式（１）中、Ｒ^１は、置換基を有していても良いアルキル基、置換基を有していても良いシクロアルキル基、置換基を有していても良いアリール基、及び下記化学式（２）に示す基からなる群より選ばれる基であり、エポキシ基及び／又はオキセタニル基を有していてもよい。

[In the chemical formula (1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and the following: It is a group selected from the group consisting of groups represented by chemical formula (2) and may have an epoxy group and / or an oxetanyl group.

（化学式（２）中、Ｒ^５及びＲ^６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、置換基を有していても良いアリール基又は置換基を有していても良い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、エポキシ基及び／又はオキセタニル基を有していてもよい１価の有機基である。Ｒ^３は、水素原子、ハロゲン原子、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、ニトロ基、又は−ＯＲ^７であり、Ｒ^７はエポキシ基及び／又はオキセタニル基を有していてもよい１価の有機基である。Ｒ^４は、水素原子、ハロゲン原子、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、又はニトロ基である。
但し、Ｒ^１、Ｒ^２及び／又はＲ^３において、エポキシ基及び／又はオキセタニル基が１分子中合計４〜１６個含まれる。また、化学式（１）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 (2), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q is an aryl group or substituent which may have a substituent. (It is a cycloalkyl group that may be present, and m represents 1 or 2.)
R ² is each independently a monovalent organic group which may have an epoxy group and / or an oxetanyl group. R ³ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, a nitro group, or —OR ⁷ , and R ⁷ is an epoxy group and / or an oxetanyl group. It is a monovalent organic group that may have. R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, or a nitro group.
However, in R ¹ , R ² and / or R ³ , a total of 4 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule. In addition, the groups represented by the same symbols included in the chemical formula (1) may be the same as or different from each other. ]

  Since the pattern forming material of the present invention has the above specific structure, it does not cause a problem of dewetting phenomenon, has high pattern dimension stability, and does not reduce resolution, and has a high sensitivity and good shape pattern. Obtainable.

In the pattern forming material of the present invention, in the chemical formula (1), each R ² is independently an alkyl group having an epoxy group and / or an oxetanyl group, and the total number of epoxy groups and / or oxetanyl groups in one molecule. The inclusion of 8 to 16 is preferable from the standpoint that a highly sensitive and good pattern can be obtained without lowering the resolution, and the solvent solubility is good.

In the pattern forming material of the present invention, in the chemical formula (1), R ¹ is a group selected from the group consisting of groups represented by the chemical formula (2) which may have an epoxy group and / or an oxetanyl group. It is preferable that a pattern with high sensitivity and good shape can be obtained without lowering the resolution and the solvent solubility is good.

  In the pattern forming material of the present invention, a group selected from the group consisting of groups represented by the following chemical formula (2 ') is also preferably used.

（化学式（２’）中、Ｑは、置換基を有していても良いアリール基又は置換基を有していても良いシクロアルキル基であり、ｍは１又は２を表す。）

(In the chemical formula (2 ′), Q represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.)

  The negative resist composition according to the present invention generates an acid by irradiating the pattern forming material (A) composed of the cyclic polyphenol derivative represented by the chemical formula (1) according to the present invention and active energy rays. It contains an acid generator (B).

  According to the present invention, by including the pattern forming material (A) having the specific structure according to the present invention in the negative resist composition, the problem of dewetting phenomenon does not occur, and the pattern dimension stability Therefore, it is possible to obtain a pattern with high sensitivity and good shape without reducing the resolution.

The present invention also provides:
(I) applying a negative resist composition according to the present invention on a substrate and then heat-treating to form a resist film; and (ii) exposing the resist film with an electron beam, EUV, or X-ray. And developing step,
A pattern forming method is provided.
Furthermore, the present invention provides an electronic component that is at least partially formed from the negative resist composition according to the present invention or a cured product thereof.

  According to the present invention, the glass transition temperature is high, the problem of dewetting phenomenon does not occur, the pattern dimension is highly stable, and a pattern with high sensitivity and good shape can be obtained without reducing the resolution. It is possible to provide a forming material, a negative resist composition using the pattern forming material, and a pattern forming method and electronic component using the negative resist composition.

I. Pattern Forming Material A pattern forming material according to the present invention is characterized by comprising a cyclic polyphenol derivative represented by the following chemical formula (1).

［化学式（１）中、Ｒ^１は、置換基を有していても良いアルキル基、置換基を有していても良いシクロアルキル基、置換基を有していても良いアリール基、及び下記化学式（２）に示す基からなる群より選ばれる基であり、エポキシ基及び／又はオキセタニル基を有していてもよい。

[In the chemical formula (1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and the following: It is a group selected from the group consisting of groups represented by chemical formula (2) and may have an epoxy group and / or an oxetanyl group.

（化学式（２）中、Ｒ^５及びＲ^６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、置換基を有していても良いアリール基又は置換基を有していても良い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、エポキシ基及び／又はオキセタニル基を有していてもよい１価の有機基である。Ｒ^３は、水素原子、ハロゲン原子、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、ニトロ基、又は−ＯＲ^７であり、Ｒ^７はエポキシ基及び／又はオキセタニル基を有していてもよい１価の有機基である。Ｒ^４は、水素原子、ハロゲン原子、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、又はニトロ基である。
但し、Ｒ^１、Ｒ^２及び／又はＲ^３において、エポキシ基及び／又はオキセタニル基が１分子中合計４〜１６個含まれる。また、化学式（１）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 (2), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q is an aryl group or substituent which may have a substituent. (It is a cycloalkyl group that may be present, and m represents 1 or 2.)
R ² is each independently a monovalent organic group which may have an epoxy group and / or an oxetanyl group. R ³ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, a nitro group, or —OR ⁷ , and R ⁷ is an epoxy group and / or an oxetanyl group. It is a monovalent organic group that may have. R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, or a nitro group.
However, in R ¹ , R ² and / or R ³ , a total of 4 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule. In addition, the groups represented by the same symbols included in the chemical formula (1) may be the same as or different from each other. ]

  In the notation of a group (atomic group) in the present invention, “may have a substituent” includes those having a substituent as well as those having no substituent. For example, “an alkyl group which may have a substituent” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). To do. 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.

As a result of the experiments by the present inventors, the cationic polymerizable molecular resist disclosed in Non-Patent Document 3 has a step of forming a coating film for forming a pattern (preliminary) as shown in Comparative Examples described later. Dewetting occurs during baking), that is, the coating spread on the substrate dissolves upon drying and repelling occurs, resulting in a pattern that cannot be formed uniformly. I found that there was no problem. This is because the glass transition temperature of the compound described in Non-Patent Document 3 is as low as 47 ° C., and the resist film dissolves when heated at a normal pre-baking temperature to remove the solvent during coating film formation, and dewetting It was estimated that a phenomenon would occur.
On the other hand, when prebaking is performed at a low temperature in order to prevent dewetting, the amount of residual solvent contained in the resist film increases. As a result, particularly in an electron beam or EUV that performs drawing (exposure) under vacuum, the amount of residual solvent fluctuates during drawing, so that the stability of the pattern dimensions decreases.

  Therefore, the present inventor obtained a cationic polymerization type molecular resist capable of obtaining high sensitivity and high resolution while realizing a high glass transition temperature by appropriately introducing a cationic polymerizable functional group into the cyclic polyphenol derivative skeleton. The structure was optimized. Among cyclic polyphenol derivative skeletons, calixarene derivatives using phenol as a raw material are likely to have a problem that it is difficult to obtain a good resist film because of their low solubility in a safe solvent generally used for resists. On the other hand, in the case of resorcinarene derivatives or pyrogallol allene derivatives having two or three functional groups derived from hydroxyl groups, it is possible to obtain a pattern forming material with high solvent solubility while having a high glass transition temperature. I understood that I could

  In the pattern forming material of the present invention, a total of 4 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule in a resorcinarene derivative or pyrogallol allene derivative having two or three functional groups derived from a hydroxyl group. By having the above-mentioned specific structure, the glass transition temperature is high, the problem of dewetting phenomenon does not occur, the problem of residual solvent does not occur, the stability of the pattern dimension is increased, the resolution is not lowered, and the high A pattern with good sensitivity and shape can be obtained.

In the compound represented by the chemical formula (1), 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 may have include an epoxy group and / or an oxetanyl group, 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 may have is not particularly limited, and examples thereof include an epoxy group and / or an oxetanyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, A halogen atom, a halogenoalkyl group, etc. are mentioned.

The aryl group for R ¹ is not particularly limited, but preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group. Can be mentioned.

  Examples of the substituent that the aryl group may have include an epoxy group and / or an oxetanyl group, a cycloalkyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, Examples include halogenoalkyl groups.

Examples of the epoxy group that may be present as the substituent include a glycidyl group, a 3,4-epoxycyclohexyl group, and a group represented by the following chemical formula (3-1). Among these, a glycidyl group is preferable from the viewpoint of reactivity. In addition, as the oxetanyl group, a group represented by the following chemical formula (3-2) is preferably introduced. The epoxy group and / or oxetanyl group introduced into R ¹ is preferably a structure containing an oxygen atom (—O—) that is a structure introduced through a hydroxyl group.

(式中、Ｒ^８は炭素数１〜６のアルキル基である。Ｒ^８’は水素原子又は炭素数１〜１０のアルキル基である。)

(In the formula, R ⁸ is an alkyl group having 1 to 6 carbon atoms. R ^{8 ′} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

In the above chemical formula (3-1), R ⁸ is a C 1-6 alkyl group which may be a branched chain, and among them, a methyl group is preferable. R ^{8 ′} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group.

  The alkyl group having 1 to 5 carbon atoms as the substituent 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. 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.

  Although there is no restriction | limiting in particular as said 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.

  Although there is no restriction | limiting in particular as said 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, or 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. Is mentioned.

In the chemical formula (2), R ⁵ and R ⁶ 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 etching resistance. When m is 2, two R ⁵ or R ⁶ may be the same or different.

In the chemical formula (2), a group selected from the group consisting of groups represented by the following chemical formula (2 ′) in which both R ⁵ and R ⁶ are hydrogen atoms is also preferably used.

（化学式（２’）中、Ｑは、置換基を有していても良いアリール基又は置換基を有していても良いシクロアルキル基であり、ｍは１又は２を表す。）

(In the chemical formula (2 ′), Q represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.)

  In the above chemical formulas (2) and (2 ′), m is 1 or 2 from the viewpoint of etching resistance. When m is 3 or more, the etching resistance may be reduced.

  Examples of the aryl group for Q in the chemical formulas (2) and (2 ′) 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 formulas (2) and (2 ′) 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.

When R ¹ is a group selected from the group consisting of the group represented by the chemical formula (2), which may have an epoxy group and / or an oxetanyl group, the shape is highly sensitive without reducing the resolution. Can be obtained, and is particularly preferable from the viewpoint of good solvent solubility.
When the solvent solubility is good, the pattern forming material does not easily aggregate during the formation of the resist film, and a uniform resist film can be formed. Therefore, the line edge roughness is easily reduced.

R ² is each independently a monovalent organic group which may have an epoxy group and / or an oxetanyl group. As the epoxy group and / or oxetanyl group, the same groups as those described for R ¹ can be used.

In R ² , the organic group is not particularly limited, but may be an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl that may have a substituent. Groups and the like.
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.

R ³ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, a nitro group, or —OR ⁷ , and R ⁷ is an epoxy group and / or an oxetanyl group. It is a monovalent organic group that may have.
Examples of the alkyl group halogen atom and R ³ in R ^3, are the same as those for the R ^1.
The substituent that the alkyl group as R ³ may have is a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, or a thioether group. , Acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like.

The cycloalkyl group and aryl group for R ³ can be the same as those for R ¹ described above. Examples of the substituent which the cycloalkyl group and the aryl group R ³ has, can be similar to the substituent of the alkyl group of one or the R ³ of said R ^1.
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.
Further, when ^{R 3} is ^-OR 7 ^{(R 7} is an epoxy group and / or optionally may be a monovalent organic group having an oxetanyl group), ^{R 7} may be the same as the ^{R 2.}

R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, or a nitro group. In R ⁴ , the halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group and acyl group are the same as the halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group and acyl group in R ³ above. Is mentioned.

The cyclic polyphenol derivative represented by the chemical formula (1) contains 4 to 16 epoxy groups and / or oxetanyl groups in total in R ¹ , R ² and / or R ³ . In this way, three-dimensional crosslinking can be achieved by reacting an epoxy group and / or oxetanyl group as a cationic polymerizable functional group without using a crosslinking agent in combination, thereby improving pattern strength and developing. Since it is possible to suppress a decrease in resolution due to pattern collapse that occurs later, the resolution is further improved. For example, the presence of a large number of reaction sites shortens the distance between adjacent reaction sites and facilitates a chain crosslinking reaction. As a result, it is possible to form a pattern with high sensitivity and good shape while having high sensitivity. Among them, since there are a large number of reaction sites, the distance between adjacent reaction sites is shortened, and a chain cross-linking reaction is likely to occur. Therefore, a total of 8 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule. It is preferably included.

  In the compound represented by the chemical formula (1), when 4 to 16 total epoxy groups and / or oxetanyl groups are contained in one molecule, the substituents represented by the same reference numerals of the four repeating units are the same. Or different. The structures of the four repeating units may all be the same or different from each other.

Among them, in the chemical formula (1), each R ² is independently an alkyl group having an epoxy group and / or oxetanyl group, and a structure containing 8 to 16 total epoxy groups and / or oxetanyl groups. It is preferable from the viewpoint of forming a pattern having excellent solvent solubility, high sensitivity, high resolution and good shape.

  Among the above structures, when the chemical formula (1) is the following chemical formula (1 ′) and the structure includes a total of 8 to 16 epoxy groups and / or oxetanyl groups, the solvent solubility is excellent. It is preferable from the viewpoint of forming a pattern with high resolution and good shape while having high sensitivity.

［化学式（１’）中、Ｒ^１、Ｒ^３、及びＲ^４は、化学式（１）と同じである。］

[In the chemical formula (1 ′), R ¹ , R ³ and R ⁴ are the same as those in the chemical formula (1). ]

  Examples of the pattern forming material according to the present invention include the following structures, but are not limited thereto.

Since the pattern forming material according to the present invention is composed of the cyclic polyphenol derivative represented by the chemical formula (1) as described above, a high glass transition temperature can be achieved. The pattern forming material according to the present invention preferably has a glass transition temperature (Tg) of 90 ° C. or higher, more preferably 100 ° C. or higher. When the glass transition temperature is 90 ° C. or higher, a dewetting phenomenon hardly occurs when forming a coating film, and a uniform film is easily obtained.
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 high boiling point solvent having a boiling point of 80 ° C. or higher is generally used. Since the resist film formed by the spin coating method contains a solvent, the resist substrate is heated at a temperature of 90 ° C. or higher by a hot plate or the like (pre-baking) in order to form a stable resist film by removing this solvent. However, when a polyphenol derivative having a glass transition temperature of less than 90 ° 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. Alternatively, in order to prevent dewetting, when prebaking is performed at a low temperature using a solvent having a relatively low boiling point, the amount of residual solvent contained in the resist film increases. As a result, particularly in an electron beam or EUV that performs drawing (exposure) under vacuum, the amount of residual solvent varies during drawing, so that the stability of the pattern dimension is lowered, which may cause a serious problem in manufacturing.
On the other hand, when a polyphenol derivative having a glass transition temperature of 90 ° C. or higher is used, pre-baking at a high temperature is possible, a uniform film with a small amount of residual solvent is obtained, and the dimensional stability of the pattern is increased. A resist film having excellent resistance (post coating delay: PCD) can be obtained. Furthermore, a pattern having excellent etching resistance can be obtained in the dry etching process after the formation of the resist pattern.
The glass transition temperature here is measured by a differential scanning calorimeter (DSC).

Moreover, since the pattern formation material which concerns on this invention consists of a cyclic polyphenol derivative represented by Chemical formula (1) as mentioned above, favorable solvent solubility can be achieved. The pattern forming material according to the present invention preferably has a solubility of not less than 0.5% by weight at 23 ° C. in an organic solvent having a boiling point of 80 to 180 ° C. 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 pattern forming material according to the present invention has a glass transition temperature (Tg) of 90 ° C. or higher and a melting point of 0.5% by weight or higher at 23 ° C. in an organic solvent having a boiling point of 80 to 180 ° C. It is preferable to have the property.

The cyclic polyphenol derivative represented by the chemical formula (1) can be synthesized, for example, by addition condensation of various (poly) phenols and various aldehydes under an acidic catalyst. In the cyclic polyphenol derivative represented by the chemical formula (1), when R ^{2 of} —OR ² is an organic group, the introduction of the organic group is carried out before condensing various (poly) phenols with various aldehydes and the like. Also good. In addition, after condensing various (poly) phenols and various aldehydes, an organic group is introduced by reacting a phenolic hydroxyl group with a halide such as an alkyl halide, or epichlorohydrin or the like is added to the phenolic hydroxyl group. An epoxy group may be introduced by reacting epibromohydrin or the like. The oxetanyl group can be introduced, for example, by reacting a phenol hydroxyl group with 3-chloromethyl-3-ethyloxetane or the like.

  The molecular weight of the cyclic polyphenol derivative represented by the chemical formula (1) is preferably 300 to 3500. The molecular weight is preferably 500-3500, and more preferably 800-3000.

II. Negative resist composition The negative resist composition according to the present invention comprises a pattern forming material (A) according to the present invention and an acid generator (B) that generates an acid upon irradiation with active energy rays. It is characterized by containing.

  According to the present invention, in the negative resist composition, by including the pattern forming material (A) according to the present invention, the dewetting phenomenon does not occur, the dimensional stability of the pattern is high, and the sensitivity is increased. A pattern with improved resolution can be formed without reduction.

  In the negative resist composition, when an acid is generated from the acid generator (B) by exposure (irradiation with exposure light) at the time of forming a resist pattern, the acid acts to form the pattern forming material (A) according to the present invention. The epoxy group and / or oxetanyl group possessed by cation undergoes a cationic polymerization reaction to form a cross-linked bond and become insoluble in a specific organic solvent. Therefore, in resist pattern formation, when a resist film made of the negative resist composition is selectively exposed or heated after exposure in addition to exposure, the exposed portion becomes insoluble in a specific organic solvent. On the other hand, since the unexposed portion remains soluble and does not change, a negative resist pattern can be formed by developing using a specific organic solvent as a developer.

Hereinafter, each structure of such a negative resist composition of this invention is demonstrated in detail in order. In the present invention, “active energy rays” mean far ultraviolet rays such as KrF excimer laser, ArF excimer laser, and F ₂ excimer laser, electron beams, EUV, X-rays and the like.

<Pattern forming material (A)>
Since the pattern forming material (A) according to the present invention is the same as that described above, the description thereof is omitted here.
In the negative resist composition according to the present invention, one type of pattern forming material (A) may be used alone, or two or more types may be used in combination. In the negative resist composition according to the present invention, the content of the pattern forming material (A) is preferably 60 to 97% by weight with respect to the total solid content in the negative resist composition. More preferably, it is 70 to 95% by weight. In addition, in this invention, solid content means things other than an organic solvent among the components contained in a negative resist composition.

<Acid generator (B) that generates acid by irradiating active energy rays>
The acid generator (B) that generates an acid upon irradiation with active energy rays used in the present invention acts to induce cationic ring-opening polymerization of an epoxy group and / or an oxetanyl group in the composition. is there. As the acid generator (B), known acid generators and photocationic polymerization initiators used in conventional chemically amplified resist compositions as long as ring opening of an epoxy group and / or oxetanyl group can be induced. Can be used without any particular limitation. The acid generator used in the present invention includes those that generate an acid directly or indirectly by irradiation with active energy rays. Here, in the case of indirectly generating an acid, there is also known an acid generation route in which an acid is generated by protons generated once energy is absorbed by a pattern forming material other than an acid generator by irradiation with an active energy ray. And the case of generating an acid in such a manner is included.
The acid generator of the present invention is preferably an acid generator that generates an acid directly or indirectly by irradiation with an active energy ray having 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 (4) to (9).

In chemical formula (4), R ¹² may be the same or different and each independently represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a carbon number. A cyclic alkyl group having 3 to 12 carbon atoms, 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 hydroxyl group, or a halogen atom. , X ^- represents an alkyl group having 1 to 12 carbon atoms, sulfonate ion having an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a halogen-substituted aryl group having 6 to 12 carbon atoms Or a halide ion.

  Examples of the compound represented by the chemical formula (4) 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 -4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium trifluoromethane Sulfonate, triphenylsulfonium-p-toluenesulfonate, trifer Rusulfonium benzene sulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethyl Phenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium Trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphor Sulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluoro) Phenyl) borate and the like.

In the chemical formula (5), X ⁻ and R ¹³ are the same as X ⁻ and R ^{12 in} the chemical formula (4).

  Examples of the compound represented by the chemical formula (5) 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 the chemical formula (6), L 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 (6) 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-dicarboxyimi 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-dicarboxyl Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyl) Oxy) 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-e 2,3-dicarboximide, N- (perfluoro--n- octane sulfonyloxy) naphthylimide, and the like.

In chemical formula (7), 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 (7) 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 (8), 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 (8) 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 (9), 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 (9) 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, And halogen-containing triazine derivatives such as tris (2,3-dibromopropyl) isocyanurate. In addition, iron-allene complexes, titanocene complexes, arylsilanol-aluminum complexes, and the like, which are organometallic complexes used as a photocationic polymerization initiator, can be mentioned. For example, commercially available Optomer SP-150 {trade name, manufactured by Asahi Denka Kogyo Co., Ltd.}, Optomer SP-170 {trade name, manufactured by Asahi Denka Kogyo Co., Ltd.}, UVE-1014 (trade name, General Electronics Co., Ltd.) And CD-1012 (trade name, manufactured by Sartomer Co., Ltd.) can be used.

In the acid generator (B), among them, an onium salt whose anion component is at least one selected from the group consisting of SbF6 ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , and PF ₆ ^— is used. Is preferable from the viewpoint of good.

  These acid generators (B) may be used alone or in combination of two or more, and the content thereof is 100 parts by weight of the pattern forming material (A). 1 to 30 parts by weight, preferably 3 to 20 parts by weight. When the amount is less than this range, image formation cannot be performed, and when the amount is larger, a uniform solution is not obtained and the storage stability is lowered.

<Organic basic compound>
The negative resist composition of the present invention may further contain an organic basic compound. As the organic basic compound, any one of known organic basic compounds can be selected and used in order to improve the resist pattern shape, stability over time in storage conditions, and the like.

  Examples of the organic basic compound include nitrogen-containing organic compounds such as nitrogen-containing compounds having a nitrogen atom, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds, but are not limited thereto. Is not to be done.

  Examples of the nitrogen-containing organic compound include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine; -N-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl-n-dodecyl Di (cyclo) alkylamines such as amine, di-n-dodecylmethylamine, cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri- n-hexylamine, tri-n-heptylamine, tri-n- Tri (cyclo) alkylamines such as cutylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; monoethanolamine, Alkanolamines such as diethanolamine and triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine , Aromatic amines such as tribenzylamine, 1-naphthylamine; ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylene Amine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4- Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) ) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1 -Methylethyl] benzene, polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide Coalescence, and the like.

  Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole, 4,5-diphenylimidazole, 2,4,5-trimethyl. Imidazoles such as phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, Pyridines such as nicotinic acid, nicotinic amide, quinoline, 8-oxyquinoline, acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpipe Razine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

  These organic basic compounds can be used alone or in combination of two or more. Content of an organic basic compound is 0.01-10 weight part with respect to 100 weight part of pattern formation materials (A) which have the said specific structure, Preferably it is 0.1-5 weight part. If it is less than 0.01 part by weight, the effect of the addition may not be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity may be lowered and the developability of the unexposed part may deteriorate.

<Other ingredients>
In the negative resist composition of the present invention, as long as the effects of the present invention are not impaired, an additive, for example, an additional resin for improving the performance of the resist film, and a surface activity for improving the coating property are optionally added. An agent, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, and the like can be appropriately added and contained.

<Preparation of negative resist composition>
The negative resist composition according to the present invention is generally uniformly mixed with an organic solvent, the pattern forming material (A) having the specific structure described above, an acid generator (B), and other additives as required. To be prepared.

As the organic solvent, 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, toluene, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide , Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. are preferred. Ku, may be to use these solvents singly or in combination. Furthermore, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, isobutyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-methoxyethanol, 2-ethoxyethanol, Alcohols such as 1-ethoxy-2-propanol and 1-methoxy-2-propanol, and aromatic solvents such as toluene and xylene may be contained. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, are used as safety solvents. Certain propylene glycol monomethyl ether acetates and mixed solvents thereof 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 1 to 15% by weight.

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

  The present invention also provides an electronic component that is at least partially formed of the negative resist composition according to the present invention or a cured product thereof. The electronic component according to the present invention includes a resist composition or a cured product thereof, and includes the negative resist composition or the cured product thereof according to the present invention. It can be similar. 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.

III. Pattern Forming Method A pattern forming method according to the present invention includes:
(I) a step of applying a negative resist composition according to the present invention on a substrate and then heat-treating to form a resist film; and (ii) exposing the resist film with an electron beam, EUV, or X-ray. And a developing step.
According to the pattern forming method of the present invention, it is possible to form a pattern with high resolution, high sensitivity and good shape.

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

Next, the negative resist composition applied on the substrate is pre-baked (PAB) to remove the organic solvent to form a resist film.
The prebaking temperature may be appropriately determined depending on the components of the composition, the ratio of use, the type of the organic solvent, and the like, and is usually 70 to 160 ° C, preferably 80 to 150 ° C. The pre-bake time is usually about 30 seconds to 15 minutes.

(Ii) Step of exposing and developing the resist film with an electron beam, EUV, or X-ray In this step, first, the resist film is used, for example, by using an exposure apparatus such as an electron beam drawing apparatus or an EUV exposure apparatus. Then, exposure is selectively performed by exposure through a mask having a predetermined pattern shape, drawing by direct irradiation of an electron beam not through the mask, or the like.
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) may be performed. In the case of performing post-exposure heating (PEB), the generated acid diffuses and undergoes an amplification reaction, so that there is an advantage that sensitivity is improved. On the other hand, when post-exposure heating (PEB) is not performed, the sensitivity is lowered as compared with the case where it is performed, but there is an advantage that a pattern having a good shape can be obtained.
The PEB treatment is usually performed at a temperature of 50 to 160 ° C. for a time of about 0.1 to 15 minutes.

Next, the substrate subjected to the PEB treatment is developed using a developing solution, and an unirradiated portion of the exposure light is removed.
Examples of the developing method include a spray method, a liquid piling method, a dipping method, and a shaking dipping method.
Moreover, as a specific organic solvent used as a developing solution, the organic solvent used for preparation of the said composition can be selected suitably, and can be used.

  After the development treatment, a rinsing treatment is performed, and the resist composition dissolved in the developer on the substrate and the developer is 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: manufactured by BRUKER, REFLEX II
¹ H-NMR: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
Purity: Using high performance liquid chromatography (HPLC) (LC-10ADvp manufactured by Shimadzu Corporation), the following conditions (temperature: 40 ° C., flow rate: 1.0 mL / min, column: VP-ODS (4.7 mm × 150 mm), Detector SPD-M10Avp, mobile phase: acetonitrile / water = 7/3).
Glass transition temperature (Tg): Using a differential thermal analyzer (“DSC-60” manufactured by Shimadzu Corporation), about 4 mg of the pattern forming material was heated to 200 ° C. at a rate of 10 ° C./min, cooled to room temperature, and then again. The glass transition temperature was defined as the intersection of both tangents of the smooth curve before and after the inflection temperature part of the DTA curve when the temperature was raised to 200 ° C. at a rate of 10 ° C./min. When the inflection point of the DTA curve corresponding to the glass transition temperature was not observed by 200 ° C., Tg was determined to be 200 ° C. or higher.

<Production Example 1>
Under a nitrogen atmosphere, 11.0 g (0.1 mol) of resorcinol was dissolved in 400 mL of ethanol in a 300 mL three-necked flask. While this was cooled in an ice bath, 15.6 g (0.1 mol) of 2-naphthaldehyde was added, and then 20 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 75 ° C. for 12 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered off. This solid was washed with distilled water and ethanol and dried under reduced pressure to obtain 11.2 g of a white compound (Pre-1). The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (10). The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 993.45 [M + H] ⁺
Calculated value (m / z) 993.34 [M + H] ⁺

30 mL of NMP was added to 1.0 g (1.0 mmol) of the compound (Pre-01) obtained above and 3.9 g (12.0 mmol) of cesium carbonate, and the mixture was stirred at 50 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2.0 mL (24 mmol) of epibromohydrin was added dropwise and stirred at 50 ° C. for 48 hours. After the reaction, by-product CsBr was filtered off from the reaction solution, chloroform was added to the reaction solution, and the mixture was washed 3 times with distilled water. Subsequently, after the chloroform phase was dried over anhydrous magnesium sulfate, the chloroform phase was concentrated, and the concentrate was poured into methanol to obtain a white solid. Furthermore, the obtained solid was dissolved in chloroform and purified by reprecipitation using methanol as a poor solvent to obtain 0.9 g of pattern forming material 1 ((A) -1). The structure was confirmed by MALDI-TOF-MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (11). _H a to H _e in formula (11) is a hydrogen atom. The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1441.69 [M + H] ⁺
Calculated value (m / z) 1441.55 [M + H] ⁺

<Production Example 2>
Under a nitrogen atmosphere, 19.4 g (0.1 mol) of 1,3-dipropoxybenzene was dissolved in 400 mL of ethanol in a 300 mL three-necked flask. While this was cooled in an ice bath, 12.2 g (0.1 mol) of 4-hydroxybenzaldehyde was added, and then 20 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 75 ° 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 recrystallization using ethanol as a solvent to obtain 8.3 g of a pale yellow compound (Pre-2). The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (12). The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1193.76 [M + H] ⁺
Calculated value (m / z) 1193.64 [M + H] ⁺

30 mL of NMP was added to 1.2 g (1.0 mmol) of the compound (Pre-02) obtained above and 3.9 g (12.0 mmol) of cesium carbonate, and the mixture was stirred at 50 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2.0 mL (24 mmol) of epibromohydrin was added dropwise and stirred at 50 ° C. for 48 hours. After the reaction, by-product CsBr was filtered off from the reaction solution, chloroform was added to the reaction solution, and the mixture was washed 3 times with distilled water. Subsequently, after the chloroform phase was dried over anhydrous magnesium sulfate, the chloroform phase was concentrated, and the concentrate was poured into methanol to obtain a white solid. Furthermore, the obtained solid was dissolved in chloroform and purified by reprecipitation using methanol as a poor solvent, to obtain 1.1 g of pattern forming material 2 ((A) -2). The structure was confirmed by MALDI-TOF-MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (13). _H a to H _e in formula (13) is a hydrogen atom. The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1417.84 [M + H] ⁺
Calculated value (m / z) 1417.74 [M + H] ⁺

<Production Example 3>
The following chemical formula (Pre-3) was synthesized according to the production method of Production Example 1 except that 13.4 g (0.1 mol) of phenylpropionaldehyde was used as the aldehyde compound in Production Example 1. As a result, 9.1 g of a pale yellow compound was obtained. The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (14). The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 905.50 [M + H] ⁺
Calculated value (m / z) 905.40 [M + H] ⁺

The epoxy group was introduced into the compound obtained above according to the production method of Production Example 1 except that Pre-3 0.9 g (1.0 mmol) was used as a raw material. ) Was synthesized. As a result, 1.1 g of a pale yellow compound was obtained. The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum, and confirmed to have a structure represented by the following chemical formula (15). The analysis results are shown in Table 1. _H a to H _e in formula (15) is a hydrogen atom. The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1353.71 [M + H] ⁺
Calculated value (m / z) 1353.61 [M + H] ⁺

<Production Example 4>
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, 16.2 g (0.1 mol) of 4-tert-butylbenzaldehyde 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 7.2 g of a white compound represented by the following chemical formula (Pre-4). The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (16). The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1073.70 [M + H] ⁺
Calculated value (m / z) 1073.59 [M + H] ⁺

The epoxy group was introduced into the compound obtained above according to the production method of Production Example 1 except that Pre-4 1.1 g (1.0 mmol) was used as a raw material. ) Was synthesized. As a result, 0.9 g of a pale yellow compound was obtained. The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (17). The analysis results are shown in Table 1. _H a to H _e in formula (17) is a hydrogen atom. The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 1297.79 [M + H] ⁺
Calculated value (m / z) 1297.69 [M + H] ⁺

  As a pattern forming material used in the comparative example, a pattern forming material (TEP-G: Ref-1) represented by the following chemical formula (18) is obtained from Asahi Organic Materials Co., Ltd., and the purity is 99% or more by high performance liquid chromatography. To be purified. In addition, the glass transition temperature of the pattern formation material (Ref-1) used for a comparative example was 47 degreeC.

<Comparative Production Example 1>
60 mL of NMP was added to 1.3 g (2.0 mmol) of 4-tert-butylcalix [4] arene and 3.9 g (12.0 mmol) of cesium carbonate, and the mixture was stirred at 50 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2.0 mL (24 mmol) of epibromohydrin was added dropwise and stirred at 50 ° C. for 48 hours. After the reaction, by-product CsBr was filtered off from the reaction solution, chloroform was added to the reaction solution, and the mixture was washed 3 times with distilled water. Subsequently, after the chloroform phase was dried over anhydrous magnesium sulfate, the chloroform phase was concentrated, and the concentrate was poured into methanol to obtain a white solid. Furthermore, the obtained solid was dissolved in chloroform and purified by reprecipitation using methanol as a poor solvent to obtain 1.1 g of a pattern forming material (Ref-2). The structure was confirmed by MALDI-TOF-MS and ¹ H-NMR spectrum and confirmed to have a structure represented by the following chemical formula (19). _H a to H _e in formula (19) is a hydrogen atom. The analysis results are shown in Table 1.
-Mass spectrometry (MALDI-TOF-MS)
Actual value (m / z) 873.65 [M + H] ⁺
Calculated value (m / z) 873.53 [M + H] ⁺

<Evaluation of solvent solubility of pattern forming material>
The pattern forming material 1 ((A) -1) to the pattern forming material 4 ((A) -4) obtained in Production Examples 1 and 2 and the pattern forming material used in the comparative example (TEP-G: Ref-1) The pattern forming material (Ref-2) obtained in Comparative Production Example 1 was added to a typical resist solvent shown below at a concentration of 1 wt% or 3 wt% at 23 ° C. and stirred. The case where the pattern forming material was dissolved at a concentration of 3 wt% was evaluated as ◎, the case where the pattern forming material was dissolved at a concentration of 1 wt%, and the case where it was insoluble as x. The results are shown in Table 2.
(C) -1: cyclopentanone (C) -2: cyclohexanone (C) -3: propylene glycol monomethyl ether (C) -4: propylene glycol monomethyl ether acetate (C) -5: ethyl lactate

As shown in Table 2, the pattern forming material 1 ((A) -1), the pattern forming material 3 ((A) -3), and the pattern forming material 4 ((A) -4) of the present invention are resists. It was clarified that it was excellent in solubility in the solvent. Further, it was revealed that the pattern forming material 2 ((A) -2) had good solubility in the resist solvent although it was insoluble in (C) -3. It was revealed that the pattern forming material 3 ((A) -3) of the present invention is particularly excellent in solubility in a resist solvent.
On the other hand, the pattern forming material (TEP-G: Ref-1) represented by the chemical formula (18) is soluble only in a specific solvent, and the pattern forming material (Ref-2) represented by the chemical formula (19) is dissolved in the solvent. It was revealed that the resist composition was very bad and it was difficult to prepare a resist composition.

(Examples 1-14 and Comparative Examples 1-2)
The pattern forming material (A), the acid generator (B), and the organic solvent (C) are made into uniform solutions with the blending amounts shown in Table 3, and each sample solution is filtered through a 0.1 μm Teflon (registered trademark) filter. A negative resist composition of the present invention was prepared.
The abbreviations in Table 3 have the following meanings.
(B) -1: TPS-103 (Midori Chemical Co., Ltd.) represented by the following chemical formula (20)
(B) -2: TPS-102 (Midori Chemical Co., Ltd.) represented by the following chemical formula (21)
(B) -3: DTS-103 (Midori Chemical Co., Ltd.) represented by the following chemical formula (22)
(B) -4: PHOTOINITIATOR 2074 (Rhodia Japan Co., Ltd.) represented by the following chemical formula (23)
(C) -1: cyclopentanone (C) -6: toluene (C) -7: 2-heptanone (C) -8: butyl acetate

<Resist pattern creation and evaluation method>
Using the resist compositions obtained in Examples 1 to 14 and Comparative Examples 1 and 2, a resist pattern was created by the following method and evaluated. The results are shown in Table 4.

(1) Application of resist Each resist composition was uniformly applied on a 6-inch silicon substrate using a spinner, and pre-baked (PAB) at 90 ° C. for 60 seconds to form a resist film having a thickness of 50 nm. . In Example 13, the prebaking process was performed at 100 ° C., and a resist film was formed in the same manner.
In Comparative Example 1, dissolution (dewetting) occurred during the prebaking process, and a uniform resist film could not be formed, and subsequent evaluation could not be performed. Therefore, in Comparative Example 2, the resist film was formed at a prebaking temperature of 60 ° C.

(2) Creation of resist pattern Drawing was performed on each of the above resist films using an electron beam drawing apparatus (acceleration voltage 100 KeV). In Examples 1-8, 10, 11, 13, 14 and Comparative Example 2, after drawing, a post-exposure bake treatment (PEB) was performed at 60 ° C. for 60 seconds. In Example 12, after drawing, A post-exposure bake treatment (PEB) was performed at 90 ° C. for 60 seconds, and Example 9 was not subjected to a post-exposure bake treatment. Thereafter, the resist films of Examples 1 to 14 and Comparative Example 2 were developed with various organic solvents (23 ° C.) for 60 seconds, rinsed with isopropyl alcohol (IPA) for 60 seconds, and line and space (L / S) A pattern was formed.

(3) Evaluation method [sensitivity and resolution]
Sensitivity was measured in units of μC / cm ² with sensitivity as the minimum dose at which a 100 nm L / S pattern 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.

[Pattern dimension stability]
When forming a resist pattern, the same method as the above “(2) Creation of resist pattern”, except that each resist composition is allowed to stand for 5 hours in a high vacuum in an electron beam drawing apparatus and then a drawing step is added. A resist pattern was formed. An L / S pattern line having a design line width of 100 nm with the same dose as the minimum dose determined by the above-described method of “sensitivity and resolution” using each resist composition before being left for 5 hours under high vacuum. The width was measured. The change in pattern line width obtained with each resist composition after standing for 5 hours under high vacuum is within 5% of the pattern line width obtained with each resist composition before leaving for 5 hours under high vacuum. Those that were ◯ were rated as x and those that exceeded 5%.

[Line edge roughness]
Line edge roughness (LER) was measured with a scanning electron microscope (SEM) (manufactured by Holon). For LER, 500 points of line width were measured for a range of edge of 0.7 μm in the longitudinal direction of an L / S pattern of 100 nm, a standard deviation was obtained, and 3σ was calculated.

<Summary of results>
The pattern forming material used in Comparative Example 1 was dissolved (de-wetted) during the pre-baking process, and a uniform resist film could not be formed. Since the pattern forming material used in Comparative Example 1 has a low glass transition temperature of 47 ° C., it is estimated that a dewetting phenomenon occurred. Further, in Comparative Example 2 in which the pre-bake treatment was performed at 60 ° C., it was revealed that the stability during vacuum storage was poor, the fluctuation of the pattern line width was large, and the stability of the pattern dimension was poor. This is presumably because the amount of the solvent remaining in the resist film increased due to the pre-baking treatment at a low temperature, and the amount changed during vacuum storage. Thus, if the line width of a pattern is not stabilized, it cannot be used practically as a pattern forming material.
On the other hand, from the results shown in Table 4, in Examples 1 to 14, a pattern with high sensitivity and resolving power and a good shape was obtained, and all of them had excellent pattern dimension stability. Moreover, in Examples 1-14, it became clear that the line edge roughness was also improved. In particular, in Examples 11 to 14 using the pattern forming materials ((A) -3) and ((A) -4), the line edge roughness was particularly reduced. In the pattern forming materials ((A) -3) and ((A) -4), since R ¹ in the formula (1) contains an alkyl chain, the solvent solubility is particularly excellent, and the molecules are less likely to aggregate, In particular, it is estimated that the line edge roughness has been reduced. It was revealed that the pattern forming material ((A) -3) is a pattern forming material having excellent balance and excellent sensitivity and resolution.
Further, by comparing Examples 1 and 9, the sensitivity is improved more when the post-exposure baking process is performed after the drawing is completed, and the resolution is improved and the pattern shape is improved when the post-exposure baking process is not performed. It was revealed.

Claims (7)

A pattern forming material comprising a cyclic polyphenol derivative represented by the following chemical formula (1).

[In the chemical formula (1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and the following: It is a group selected from the group consisting of groups represented by chemical formula (2) and may have an epoxy group and / or an oxetanyl group.

(In the chemical formula (2), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q is an aryl group or substituent which may have a substituent. (It is a cycloalkyl group that may be present, and m represents 1 or 2.)
R ² is each independently a monovalent organic group which may have an epoxy group and / or an oxetanyl group. R ³ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, a nitro group, or —OR ⁷ , and R ⁷ is an epoxy group and / or an oxetanyl group. It is a monovalent organic group that may have. R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, or a nitro group.
However, in R ¹ , R ² and / or R ³ , a total of 4 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule. In addition, the groups represented by the same symbols included in the chemical formula (1) may be the same as or different from each other. ] In the chemical formula (1), each R ² is independently an alkyl group having an epoxy group and / or an oxetanyl group, and a total of 8 to 16 epoxy groups and / or oxetanyl groups are contained in one molecule. 2. The pattern forming material according to 1. 3. The chemical formula (1), wherein R ¹ is a group selected from the group consisting of groups represented by the chemical formula (2), which may have an epoxy group and / or an oxetanyl group. Pattern forming material. The pattern forming material according to claim 1, wherein the group selected from the group consisting of the group represented by the chemical formula (2) is a group selected from the group consisting of the group represented by the following chemical formula (2 ′). .

(In the chemical formula (2 ′), Q represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.)   A negative resist composition comprising the pattern forming material (A) according to any one of claims 1 to 4 and an acid generator (B) that generates an acid upon irradiation with active energy rays. . (I) a step of applying a negative resist composition according to claim 5 on a substrate and then heat-treating to form a resist film; and (ii) applying the resist film with an electron beam, EUV, or X-ray. A pattern forming method comprising: exposing and developing.   An electronic component, at least part of which is formed of the negative resist composition according to claim 5 or a cured product thereof.