JP2010277061A - Negative resist composition, pattern formation method using the same, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition, exhibiting superior resolution and line edge roughness of a pattern in pattern formation by radiation of electron-beams or EUV, and to provide a pattern formation method that uses the negative resist composition. <P>SOLUTION: The negative resist composition is constituted of a calixarene derivative (A) with a specific structure, an acid generating agent (B) generating an acid by being irradiated with active energy rays, and a crosslinking agent (C). In the calixarene derivative (A), purity of a compound having the same structural formula and the same conformation is 80 wt.% or more. The pattern formation method using the negative resist composition is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a negative resist composition for forming a chemically amplified resist useful for microfabrication, a pattern forming method using the negative resist composition, and an electron using the negative resist composition. Regarding parts.

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, a low molecular weight material having a low molecular weight and no molecular weight distribution has been developed. It is expected that the low molecular weight material is excellent in resolving power as compared with a high molecular weight material, and further contributes to an increase in LER. As one of such low molecular weight materials, attention has been focused on calixarene and calixresorcinarene having a cyclic structure. Since they are cyclic, they have a higher glass transition temperature than other acyclic low molecular compounds. Further, the compound has been found that has good solvent solubility and can be formed by spin coating. Examples of using such compounds include chemically amplified positive resists (Patent Document 1) and non-chemically amplified negative types (Patent Document 2). However, even if the compounds described above were used as described, they did not sufficiently satisfy the respective requirements for resolution and resist shape.

  As discussed in Non-Patent Document 1, when the resist processing dimension variation represented by roughness is large, the roughness is transferred until the subsequent etching process, which adversely affects the characteristics of the manufactured integrated circuit. Non-Patent Document 1 shows that the threshold voltage is reduced by 30 mv due to a dimensional variation of 5 nm, and the circuit characteristics are greatly deteriorated. As is clear from this, it is desired that the LER is as small as 1. However, data that clears the target value of the processing dimension variation shown in ITRS (International Technology Roadmap for Semiconductors) is hardly disclosed at present, and technical data for improving LER from 5 to 4, 4 to 3. The difficulty level is estimated to be quite large.

Japanese Patent No. 4076789 Japanese Patent No. 3028939

Journal of Photopolymer Science and Technology vol. 16, No.3 (2003), pp387-394

  In view of the above circumstances, an object of the present invention is to solve performance improvement and technical problems in microfabrication of semiconductor elements, and to improve resolution and pattern line edge roughness in pattern formation by electron beam or EUV irradiation. And providing a pattern forming method using the negative resist composition.

As a result of intensive studies, the present inventors have focused on the purity of isomers having the same structural formula and different conformations in the calixarene derivative among the cyclic polyphenol compound derivatives contained in the negative resist composition. The inventors have found that the above problems can be solved by making the purity of compounds having the same formula and the same conformation higher than a specific level, thereby completing the present invention.
That is, the negative resist composition according to the present invention includes a calixarene derivative (A) represented by the following chemical formula (1), an acid generator (B) that generates an acid when irradiated with active energy rays, and a crosslink. The calixarene derivative (A) containing the agent (C) is characterized in that the purity of a compound having the same structural formula and the same conformation is 80% by weight or more.

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

(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² is Each independently represents a hydrogen atom or an organic group, and when R ² is an organic group having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. 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. n1 represents an integer of 1 to 3, n2 represents an integer of 0 to 2, and 1 ≦ n1 + n2 ≦ 4. 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 negative resist composition according to the present invention, it is highly sensitive that the calixarene derivative (A) represented by the chemical formula (1) is a calixresorcinarene derivative represented by the following chemical formula (1 ′). Moreover, it is preferable from the viewpoint of obtaining a pattern excellent in resolving power and line edge roughness of the pattern.

[In the chemical formula (1 ′), R ¹ represents an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following chemical formula (2).

(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² These are each independently an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. 1 to 8 of R ² contained in one molecule are groups other than hydrogen atoms. When all R ² are organic groups having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. R ³ is an optionally substituted alkyl group having 1 to 5 carbon atoms or a halogen atom, and n2 represents an integer of 0 to 2. However, the groups represented by the same symbols contained in the chemical formula (1 ′) may be the same as or different from each other. ]

In the negative resist composition according to the present invention, the calixarene derivative (A) is a compound having a different molecular weight measured by mass spectrometry, a chemical shift value of ¹ H-NMR spectrum and / or a retention time of liquid chromatography. The content ratio of is preferably less than 20% by weight from the viewpoint of improving the resolution and line edge roughness of the pattern.

  In the negative resist composition according to the present invention, the calixarene derivative (A) has a pattern line that the purity of the compound having the same structural formula and the conformation of the chair type is 80% by weight or more. It is preferable from the viewpoint that high sensitivity can be achieved at the same time in addition to improvement of edge roughness and high resolution.

  In the negative resist composition according to the present invention, it is preferable to further contain an organic basic compound (D) from the viewpoint of improving the resist pattern shape and improving the storage stability over time.

The 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. Heating, developing,
It is characterized by including.

  The present invention also 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 negative resist composition of the present invention, by using a calixarene derivative having a compound having the same ¹ H-NMR spectrum and having the same conformation, the resolution and the line edge roughness are improved. An improved pattern can be obtained.
Moreover, the pattern formation method of this invention can form the pattern which improved resolution and line edge roughness by using the said negative resist composition of this invention.

It is a schematic diagram showing the cone type | mold of the calix [4] allene derivative of this invention. It is a schematic diagram showing the partial-cone type | mold of the calix [4] allene derivative of this invention. It is a schematic diagram showing the 1,2-alternate type of the calix [4] arene derivative of the present invention. It is a schematic diagram showing the 1,3-alternate type of the calix [4] arene derivative of the present invention. It is a schematic diagram showing the chair type | mold of the calix [4] allene derivative of this invention. It is a schematic diagram showing the flattened-cone type | mold of the calix [4] allene derivative of this invention. It is a crystal structure figure of compound 3a of the example of the present invention. It is a crystal structure figure of compound 3b of the example of the present invention.

I. Negative resist composition The negative resist composition according to the present invention comprises a calixarene derivative (A) represented by the following chemical formula (1), an acid generator that generates an acid upon irradiation with active energy rays ( B) and a crosslinking agent (C), the calixarene derivative (A) is characterized in that the purity of a compound having the same structural formula and the same conformation is 80% by weight or more.

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

(In the chemical formula (2), Q represents an aryl group or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) Each R ² independently represents a hydrogen atom or an organic group. And R ² is an organic group having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. 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. n1 represents an integer of 1 to 3, n2 represents an integer of 0 to 2, and 1 ≦ n1 + n2 ≦ 4. 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. ]

The present inventors paid attention to the conformation in the calixarene derivative among the cyclic polyphenol compound derivatives contained in the negative resist composition. In calixarene derivatives, rigid (poly) phenol units are linked via aldehyde-derived divalent groups such as a methylene group and a methine group that are hinged. It is known to adopt a conformation. Here, the (poly) phenol unit means including a polyphenol unit containing a dihydric phenol such as resorcin, a trihydric phenol such as pyrogallol, in addition to the phenol unit.
In a calix [4] arene derivative in which four (poly) phenol units are linked in a ring, for example, a conformation in which all of the (poly) phenol units are directed upwards is a cone type (see FIG. 1), (poly ) Only one phenolic unit is inverted and the conformation facing downward is a partial-cone type (see Fig. 2), and the conformation with the adjacent (poly) phenolic unit facing downward is 1,2-alternate. Type (see Fig. 3), conformation with facing (poly) phenol units facing down, 1,3-alternate type (see Fig. 4), two facing (poly) phenol units facing up and down, etc. The conformation in which two (poly) phenol units facing each other face outward in the same plane is a chair type (see FIG. 5), and two (poly) phenols facing each other among four (poly) phenol units Units face up, the remaining two It is called a conformation outwardly facing on one plane flattened-cone type (see FIG. 6). 1 to 6, in order to simplify the drawings and make the conformation easy to understand, the aldehyde-derived divalent group is represented only by the skeleton, and the (poly) phenol unit is represented only by the benzene ring of the skeleton. Yes.

According to the present invention, the negative resist composition contains a calixarene derivative in which the purity of a compound having the same structural formula and the same conformation is higher than a specific level. A pattern with improved line edge roughness can be formed.
In the present invention, the calix [4] allene derivative contained in the negative resist composition has the same structural formula and the same conformation, and the purity of the compound is increased to 80% by weight or more. [4] It is estimated that the formation and density of aggregates of allene derivatives are optimized, and a pattern with improved resolution and line edge roughness can be formed.

  In the present invention, depending on the conformation selected, the density of the aggregates becomes high, and the aggregation state of each molecule in the amorphous film at the time of film formation differs. And the sensitivity may be improved by forming the image of the crosslinked portion with less energy. In addition, depending on the conformation selected, there is a difference in the positional relationship of the portion that can undergo a cross-linking reaction due to the conformation, and in the case of a conformation that is more sterically reactive, a cross-linking reaction is likely to occur, and sensitivity and resolution are improved. May improve.

  In the negative resist composition, when an acid is generated from the acid generator (B) by exposure (irradiation of exposure light) at the time of forming a resist pattern, the acid acts to cause the calixarene derivative (A) and the cross-linking agent. Crosslinks are formed with (C) and become insoluble in alkali. Therefore, in resist pattern formation, when the resist film made of the negative resist composition is selectively exposed or heated after exposure in addition to exposure, the exposed portion becomes alkali-insoluble while the unexposed portion is alkali-soluble. Since it does not change, a negative resist pattern can be formed by alkali development.

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.

In the description of the 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. The divalent bond of the alkylene group includes a divalent bond from the same carbon atom (for example, —CH ₂ —) as well as a case from a different carbon atom (for example, —CH ₂ 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.

<Calixarene derivative (A)>
The calixarene derivative (A) used in the present invention is a calixarene derivative represented by the following chemical formula (1), wherein the purity of a compound having the same structural formula and the same conformation is 80% by weight or more. Is used. As a result, it is possible to increase the resolution of the pattern and improve the line edge roughness.

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

(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² is Each independently represents a hydrogen atom or an organic group, and when R ² is an organic group having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. 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. n1 represents an integer of 1 to 3, n2 represents an integer of 0 to 2, and 1 ≦ n1 + n2 ≦ 4. 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. ]
Here, “R ¹ is a group having a hydroxyl group” means that R ¹ is an alkyl group, aryl group, or cycloalkyl group having a hydroxyl group (OH) as a substituent, or R ¹ is represented by the chemical formula (2 And Q in the formula is an aryl group having a hydroxyl group (OH) as a substituent or a cycloalkyl group.
In the compound represented by the chemical formula (1), groups R ¹ , R ² , and R ³ represented by the same symbol and present in a plurality in one molecule may be the same as or different from each other.

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 a hydroxyl group, an alkoxy group, a halogen atom, and a halogenoalkyl group.

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 alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group. It is done.

  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, preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group, an anthryl group and the like.

Examples of the substituent that the aryl group may have include a cycloalkyl group, 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.
Examples of the cycloalkyl group as a substituent that the aryl group has are the same as those described above. 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.

  Examples of the aryl group of Q in the chemical formula (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 formula (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.

The organic group for R ² 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 group that may have a substituent. Is mentioned.
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.
Of the plurality of R ² , at least two in one molecule are preferably hydrogen atoms.

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, a thioether group, Examples include an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.

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 substituent that the aryl group has can be the same as those of R ¹ described above.
As the alkoxy group R ^3, are the same as those for the 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.

As long as the compound represented by the chemical formula (1) 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.

  Among the calixarene derivatives (A) represented by the chemical formula (1), the calixresorcinarene derivative represented by the following chemical formula (1 ′) is highly sensitive and has high resolution and pattern line edge roughness. This is preferable from the viewpoint of obtaining an excellent pattern.

[In the chemical formula (1 ′), R ¹ represents an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following chemical formula (2).

(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² These are each independently an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. 1 to 8 of R ² contained in one molecule are groups other than hydrogen atoms. When all R ² are organic groups having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. R ³ is an optionally substituted alkyl group having 1 to 5 carbon atoms or a halogen atom, and n2 represents an integer of 0 to 2. However, the groups represented by the same symbols contained in the chemical formula (1 ′) may be the same as or different from each other. ]
Here, “R ¹ is a group having a hydroxyl group” means that R ¹ is an aryl group having a hydroxyl group (OH) as a substituent, or a cycloalkyl group, or R ¹ is represented by the chemical formula (2). And Q in the formula is an aryl group having a hydroxyl group (OH) as a substituent or a cycloalkyl group.

In the case of the calix resorcinarene derivative represented by the above chemical formula (1 ′), a part of the phenolic hydroxyl group is protected with a non-acid-decomposable group such as an alkyl group or an aryl group, and the number of the phenolic hydroxyl group is reduced. By making it, the solubility with respect to the alkali developing solution of the said calix resorcinarene derivative can be reduced. In addition, by introducing a hydrophobic group such as a phenyl group into a carbon atom linking adjacent resorcinol sites in the calix resorcinarene derivative represented by the chemical formula (1 ′), the calix resorcinarene derivative is rendered hydrophobic. Furthermore, the solubility in an alkali developer can be reduced. In this way, by reducing the solubility of the calixarene derivative (A) in the alkaline developer to the developable limit, it is possible to easily obtain a solubility contrast between the exposed portion and the unexposed portion. .
Therefore, by optimizing the solubility of the calix resorcinarene derivative in an alkaline developer, the dissolution rate in the alkaline developer can be controlled, and the sensitivity can be increased without reducing the resolution.

In the chemical formula (1 ′), the aryl group which may have a substituent and the cycloalkyl group which may have a substituent in R ¹ are the same as those described in the chemical formula (1). Can be used. In the chemical formula (1 ′), Q in the chemical formula (2) is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent. The thing similar to what was demonstrated in the said Chemical formula (1) and Chemical formula (2) can be used.

In the chemical formula (1 ′), each R ² independently represents an alkyl group having 1 to 5 carbon atoms which may each independently have a substituent, an aryl group which may have a substituent, or hydrogen. It is a group selected from atoms. As a C1-C5 alkyl group, the thing similar to what was demonstrated in the said Chemical formula (1) can be used. Examples of the substituent that may be contained in R ² include a hydroxyl group, a halogen atom, and ^a monovalent group represented by —OR ^a . Here, R ^a is an alkyl group having 1 to 5 carbon atoms, and the monovalent group represented by —OR ^a is bonded to a carbon atom other than the 1-position in the alkyl group having 1 to 5 carbon atoms. . As said Ra, ^a methyl group, an ethyl group, n-propyl group, n-butyl group, i-propyl group etc. are mentioned, for example. Of these, a methyl group and an ethyl group are preferable. As the halogen atom, the same one as described in the chemical formula (1) can be used, and preferably a fluorine atom and a chlorine atom are used. As the R ^3, it may be the same as those described in the above formula (1).

1 to 8 of R ² contained in one molecule are groups other than hydrogen atoms. When all R ² are organic groups having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. By appropriately selecting the number of groups other than hydrogen atoms and the type of groups other than hydrogen atoms in R ² , and further adjusting the number of hydroxyl groups in R ¹ , the solubility of the calix resorcinarene derivative in an alkaline developer By optimizing the value, the dissolution rate in the alkaline developer can be controlled, and the sensitivity can be increased without degrading the resolution.

Further, in the calixresorcinarene derivative, when 1 to 8 of R ² contained in one molecule are groups other than hydrogen atoms, the groups represented by the same reference numerals of the respective repeating units are the same. Or the position of R ³ in each repeating unit may be the same or different. For example, in the calix resorcinarene derivative, all the repeating units contained in one molecule may be the same as in the following chemical formula (3), the following chemical formulas (4) and (5), and the chemical formula (6) As in (2), two or more kinds of repeating units may be contained in four repeating units contained in one molecule.

  Examples of the calixarene derivative (A) represented by the chemical formula (1) include, but are not limited to, the structures represented by the following chemical formula.

The calixarene derivative (A) represented by the chemical formula (1) and the calixresorcinarene derivative represented by the chemical formula (1 ′) are, for example, the addition of various (poly) phenols and various aldehydes under an acidic catalyst. It can be synthesized by condensation. In the calixarene derivative (A), when R ^{2 of} —OR ² is an organic group, the organic group may be introduced before the various (poly) phenols are condensed with various aldehydes or the like. Further, after condensing various (poly) phenols with various aldehydes, an organic group may be introduced by reacting a phenolic hydroxyl group with a halide such as alkyl halide.

In the present invention, the calixarene derivative (A) is used so that the purity of compounds having the same structural formula and the same conformation is 80% by weight or more.
A compound having the same structural formula and the same conformation is a compound having the same planar structural formula, and represents a compound of one specific isomer among conformational isomers having different conformations. “Structural formula” refers to a chemical formula that shows how each atom constituting the compound is bonded to each other in the molecule of the compound using a line indicating the valence of each atom. It is also called Shiki (Iwanami Riken Dictionary 5th edition). In addition, “conformation” or “conformation” is synonymous with conformation. When two atomic groups connected by this bond are rotated around a single bond in the molecule, the atoms on both sides of this bond are rotated. The relative shape of the molecule changes and the shape of the molecule changes, but the various spatial arrangements of the atoms in the molecule, as seen in this case, are called conformations, which change from one another by rotation around the bond. (Iwanami physics and chemistry dictionary fifth edition). However, as a general finding in calixarene derivatives and calixresorcinarene derivatives, when a bulky functional group such as benzaldehyde is introduced, rotation around the conformational bond is inhibited, and it is fixed in a specific conformation. It is known that

The purity of a compound having the same structural formula and the same conformation is 80% by weight or more means that in the calixarene derivative (A), which may be a mixture, a compound having the same structural formula and the same conformation The ratio is 80% by weight or more. When the calixarene derivative (A) is a mixture, the content in the calixarene derivative (A) is less than 20% by weight, and the structure is different from the compound having a specific structural formula and conformation occupying the content of 80% by weight or more. It is a compound which has this. The compound having the different structure is not limited to an isomer of a compound having a specific structural formula and conformation occupying 80% by weight or more, and the planar structural formula and molecular formula may be different.
However, among them, the calixarene derivative (A) preferably has a conformational purity of 80% by weight or more. That is, the calixarene derivative (A) is composed of a mixture of a plurality of isomers, and the content ratio of one specific conformer in the mixture of isomers of the calixarene derivative (A) is 80% by weight or more. Is preferred. The above “isomers” are a group of compounds having the same molecular formula but different structures, and are in the relationship of isomerism. The structural isomers and structural conformations of the structural isomers are the same but have the same structural formula. Are included in the stereoisomerism (geometric isomerism, rotational isomerism, optical isomerism) (Iwanami Physical and Chemical Dictionary, 5th edition).
Note that compounds having the same structural formula and the same conformation may contain optical isomers.

Different structural formulas and different conformations can be distinguished, for example, by different molecular weights measured by mass spectrometry, chemical shift values of ¹ H-NMR spectra and / or retention times of liquid chromatography. . That is, the calixarene derivative (A) used in the present invention has a structural formula and / or a difference in molecular weight measured by mass spectrometry, chemical shift value of ¹ H-NMR spectrum and / or retention time of liquid chromatography. Alternatively, the content ratio of the compound capable of discriminating that the conformations are different can be used as a guideline.
A compound having the same structural formula and the same conformation is because the molecular weight measured by mass spectrometry is the same, the ¹ H-NMR spectrum is the same, and the retention time of liquid chromatography is the same. Judgment can be made.

In addition, the molecular weight measured by mass spectrometry is the same, for example, the difference in molecular weight when the molecular weight is measured using MALDI-TOF-MS (for example, REFLEX II manufactured by BRUKER) is within ± 0.5. It is judged by doing.
Further, the ¹ H-NMR spectrum is the same, for example, in the chemical shift value of the spectrum measured by NMR of 400 MHz (for example, JNM-LA400W, manufactured by JEOL Ltd.), the difference in chemical shift value is ± The integrated value of ¹ H, which is within 0.02 ppm and excluding hydrogen of the hydroxyl group, coincides with the number of corresponding hydrogens in the composition formula of the calixarene derivative, and ¹ H that couples all methyl groups, aromatic rings, etc. Each indicate the same split. Note that the same splitting is determined by the fact that the ratio of the chemical shift of a plurality of peaks that can be attributed to one hydrogen and the height of each peak are the same.

  Further, X-ray crystal structure analysis is preferably used for the determination of a reliable conformation. When the crystal purity is sufficiently high, the positional relationship between the atoms constituting the calixarene derivative molecule is clearly determined, so that the conformation can also be clearly determined.

  The measurement conditions of liquid chromatography for enabling discrimination of isomers can be appropriately selected according to the structure of the calixarene derivative (A). For example, in the case of a lysresorcinarene derivative represented by the formula (1 ′), a high performance liquid chromatography apparatus (manufactured by Shimadzu Corporation, LC-10ADvp) is used, and the following conditions (for example, acetonitrile / water = 7/3 migration) The isomers can be discriminated using the phases measured by flow rate = 1.0 ml / min, column = VP-ODS (4.8 mm × 150 mm), detector = SPD-M10 vp). And it can be judged that holding time is the same because holding time agrees within ± 0.3 minutes.

  In the calixarene derivative (A), the purity of compounds having the same structural formula and the same conformation is 80% by weight or more. For example, various methods such as normal phase chromatography or reverse phase liquid chromatography using silica gel are used. Examples include separation using chromatography, recrystallization, and reprecipitation.

  In the present invention, the calixarene derivative (A) is used so that the purity of compounds having the same structural formula and the same conformation is 80% by weight or more, but the higher the purity, the resolution and the line edge of the pattern From the viewpoint of obtaining a pattern having excellent roughness, the purity of the compound is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 98% by weight or more, particularly 100% by weight. Preferably there is.

In the present invention, among others, the calixarene derivative (A) should be used so that the compound having the same structural formula, the same configuration, and the same conformation has a purity of 80% by weight or more. Is preferred. Further, the calixarene derivative (A) has the same structural formula, the same configuration, and the same conformation, the purity of the compound is preferably 90% by weight or more, and more preferably 95% by weight or more. Furthermore, it is preferable that it is 98 weight% or more, especially 100 weight%.
Note that “configuration” is synonymous with configuration, and the spatial arrangement of atoms and atomic groups bound to an asymmetric carbon atom around the asymmetric carbon atom, as in the cis-trans isomer, This refers to the spatial arrangement of atoms and atomic groups attached to a structure that is difficult to move (Iwanami Physical and Chemical Dictionary, 5th edition).

  Moreover, among the calixarene derivatives (A), the purity of the compound having the same structural formula and the conformation of which is a chair type is 80% by weight or more, the line edge roughness of the pattern is improved, and This is preferable because high sensitivity and high resolution can be achieved at the same time. In such a case, the purity of a compound having the same structural formula and conformation is high, so that the structure is easily aligned and the line edge roughness of the pattern is improved. It is presumed that excellent sensitivity and resolving power can be obtained because it is a conformation that is easy for crosslinking reaction.

  The molecular weight of the calixarene derivative (A) is preferably 300 to 3000. The molecular weight is preferably 300 to 2000, and more preferably 400 to 1500.

  The content of the calixarene derivative (A) is preferably 50 to 95% by weight, more preferably 60 to 85% by weight, based on the total solid content contained in the negative resist composition. 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 is used without particular limitation from known acid generators used in conventional chemically amplified resist compositions. be able to. 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 in a matrix other than the acid generator by irradiation with active energy rays, The case where an acid is generated 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 (7) to (12).

In chemical formula (7), 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 (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 -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-hydroxyphenyl sulfonium 10-camphorsulfonate, and the like.

In the chemical formula (8), X ^- and R ¹³ are the same as X ^- and R ^{12 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), 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 (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-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 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, And halogen-containing triazine derivatives such as tris (2,3-dibromopropyl) isocyanurate.

  These acid generators (B) may be used alone or in combination of two or more, and the blending amount thereof is 100 parts by weight of the calixarene derivative (A). 1 to 30 parts by weight, preferably 5 to 20 parts by weight. When the amount is less than this range, image formation cannot be performed.

<Crosslinking agent (C)>
The crosslinking agent (C) used in the present invention is not particularly limited, and can be arbitrarily selected from known crosslinking agents used in conventional chemically amplified negative resist compositions. 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 and / or a hydroxyalkyl group such as butanol, 1,4-dioxane-2,3-diol, and 1,3,5-trihydroxycyclohexane, or 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 a lower alcohol, and the hydrogen atom of the amino group is converted into a hydroxymethyl group or a lower alkoxymethyl. And a compound substituted with a group. Of these, those using melamine are melamine-based crosslinking agents, those using urea are urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea-based crosslinking agents, and glycoluril is used. This was called a glycoluril-based crosslinking agent.

  Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

  Examples of the urea-based crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like.

  Examples of the alkylene urea crosslinking agent include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated ethylene Ethylene urea crosslinking agents such as 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 Propylene urea-based crosslinking agents such as mono- and / or dipropoxymethylated propylene urea, mono- and / or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone 1,3-di (methoxymethyl 4,5-dimethoxy-2-imidazolidinone.

  Examples of the glycoluril-based crosslinking agent include mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or tetraethoxy. Examples include methylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

  These crosslinking agents (C) may be used alone or in combination of two or more thereof, and the blending amount thereof is calixarene derivative (A) 100 having the specific structure. It is 3-40 weight part with respect to a weight part, Preferably it is 3-30 weight part. When the blending amount of the crosslinking agent (C) is less than 3 parts by weight, crosslinking formation does not proceed sufficiently and a good resist pattern cannot be obtained. On the other hand, if it exceeds 40 parts by weight, the storage stability of the resist coating solution is lowered, and the sensitivity may deteriorate over time.

<Organic basic compound (D)>
The organic basic compound (D) used in the present invention is selected from known organic basic compounds and used in order to improve resist pattern shape, stability over time in storage conditions, etc. can do.

  Examples of the organic basic compound (D) 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. It is not limited to these.

  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, nicotinamide, quinoline, 8-oxyquinoline, acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiper Razine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

  These organic basic compounds (D) can be used alone or in combination of two or more. The compounding quantity of an organic basic compound (D) is 0.01-10 weight part with respect to 100 weight part of calixarene derivatives (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 be deteriorated.

<Resin (E) having a repeating unit represented by the chemical formula (13) and having solubility in an alkali developer>
The negative 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 resin (E)). May be included).

(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 ²⁰ 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 ²⁰ 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, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group, hexanoyloxy group, octanoyloxy group, 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.

  The weight average molecular weight of the alkali-soluble resin (E) is preferably 2000 to 80000, more preferably 2500 to 8000. Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted in terms of polystyrene standards.

  The content of the alkali-soluble resin (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 negative resist composition of the present invention further includes an optionally soluble alkali-soluble resin such as novolak, an additive, for example, an additional resin for improving the performance of the resist film, and an interface for improving coatability. An activator, 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 usually has a calixarene derivative (A) having the above specific structure in the organic solvent (F), an acid generator (B), a crosslinking agent (C), and, if necessary. And 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, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydroph Emissions, etc. 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 acetate, which is a safety solvent, and a mixed solvent 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.

II. 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 step of heating and developing.
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, and a spin coating method can be used. it can.

Next, the negative 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 usage rate, the kind of organic solvent (F), etc., and are 50-160 degreeC normally, Preferably it is 60-150 degreeC. The pre-bake time is usually about 30 seconds to 15 minutes.

(Ii) Step of exposing the resist film with an electron beam, EUV, or X-ray, heating and developing In this step, first, the resist film is exposed to an exposure apparatus such as an electron beam lithography apparatus or an EUV exposure apparatus. Is selectively exposed 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) is performed. 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 an alkali developer, and the unirradiated portion of the exposure light is removed.
Examples of the developing method include a liquid piling method, a dipping method, a shaking dipping method, and the like.
Examples of the alkaline developer of the negative resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxy Aqueous solutions of alkalis such as quaternary ammonium salts such as copper, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and 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 exhibits the same function and effect. It is 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 the following, high performance liquid chromatography (HPLC) is performed using LC-10ADvp manufactured by Shimadzu Corporation under 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).
In addition, mass spectrometry was performed using MALDI-TOF MS (REFLEX II manufactured by BRUKER) under the following conditions (matrix: 1,8,9-trihydroxyanthracene).
Further, NMR measurement, using a JNM-LA400W (manufactured by JEOL Ltd.), solvent DMSO-d6, sample concentration of 0.6%, measured at a frequency 400MHz, in integration number 32 ^times, 1 H-NMR spectrum It was measured.
The X-ray crystal structure analysis was performed using VariMax + RAPIDII (manufactured by Rigaku Corporation) under the following conditions [X-ray source: CuKα (λ = 1.54187Å), tube voltage: 40 kV, tube current: 30 mA, measurement temperature: -180 ° C. (using spraying cryogenic device), camera length: 127.4 mm, vibration angle: 10 °, exposure time: 2 seconds / °, total number of measurement sheets: 90 sheets (18 sheets × 5 series)] .

<Synthesis Example 1>
Under a nitrogen atmosphere, 11.0 g (0.1 mol) of resorcinol 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-tbutylbenzaldehyde 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 (HPLC) to obtain white compound 1a (CRA-1a) and compound 1b (CRA-1b) represented by the following structural formula (14). The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. In addition, it was confirmed by MALDI-TOF MS, ¹ H-NMR spectrum, and HPLC that Compound 1a (CRA-1a) had a purity of 100% with the same structural formula and the same conformation. Similarly, Compound 1b (CRA-1b) was confirmed to have a purity of 100% with the same structural formula and the same conformation.

(CRA-1a)
HPLC (acetonitrile / water = 7/3) retention time: 6.2 minutes MALDI-TOF MS: [M + H] 1017.52
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.18 (—CH ₃ ), 5.54 (—CH), 6.06, 6.28, 6.39, 6. 51, 6.66 & 6.68 (d), 6.93 & 6.95 (d) (aromatic-CH), 8.41, 8.58 (-OH)

(CRA-1b)
HPLC (acetonitrile / water = 7/3) retention time: 24.6 minutes MALDI-TOF MS: [M + H] 1017.25
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.29 (—CH ₃ ), 5.61 (—CH), 6.10, 6.31, 6.79 & 6.80 ( d), 7.06 & 7.08 (d) (aromatic-CH), 8.55 (-OH)

<Synthesis Example 2>
Under a nitrogen atmosphere, 3.96 g (35.9 mmol) of resorcinol was dissolved in 150 mL of ethanol in a 500 mL three-necked flask, and 4.82 g (35.9 mmol) of 2,4 dimethylbenzaldehyde was added while cooling this in an ice bath. Next, 15 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 70 ° C. for 20 hours. After completion of the reaction, the reaction solution was poured into 300 mL of distilled water, the resulting precipitate (yellow solid) was filtered, washed with distilled water until neutral, and the solid was filtered. After the reaction, it was confirmed by HPLC that two types of compounds having different retention times were present. The solid separated by filtration was recrystallized using ethyl acetate to obtain 0.81 g (8.95 mmol, 25% yield) of a pale yellow solid, compound 2b (CRA-2b) having the following structural formula (15). Got. Further, the filtrate was poured into 300 mL of acetonitrile to obtain 1.62 g (18.0 mmol, yield 50%) of a colorless solid having the following structural formula (15), compound 2a (CRA-2a). The structure was confirmed by MALDI-TOF Mass (mass spectrometer) and ¹ H-NMR spectrum. Further, it was confirmed by MALDI-TOF MS, ¹ H-NMR spectrum and HPLC that the compound 2a (CRA-2a) had the same structural formula and the same conformation and the purity of the compound was 100%. Similarly, it was confirmed that the purity of the compound 2b (CRA-2b) having the same structural formula and the same conformation was 100%.

(CRA-2a)
HPLC (acetonitrile / water = 7/3) retention time: 2.5 minutes Confirmed with MALDI-TOF MS: [M + H] 905.11.
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.69, 2.12 (—CH ₃ ), 5.54 (—CH), 5.26, 5.54, 6. 12, 6.14, 6.20, 6.27, 6.39, 6.41, 6.49 (aromatic-CH), 8.32, 8.43 (-OH)

(CRA-2b)
HPLC (acetonitrile / water = 7/3) retention time: 3.8 minutes Confirmed with MALDI-TOF MS: [M + H] 905.51
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.65, 2.21 (—CH ₃ ), 5.60 (—CH), 5.62, 6.07, 6. 15, 6.36, 6.37, 6.45, 6.52, 6.53, 6.55 (aromatic-CH), 8.46, 8.38 (-OH)

<Synthesis Example 3>
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 (HPLC) to obtain white compound 3a (CRA-3a) and compound 3b (CRA-3b) represented by the following structural formula (16). The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum. Further, it was confirmed by MALDI-TOF MS, ¹ H-NMR spectrum and HPLC that the compound 3a (CRA-3a) had the same structural formula and the same conformation and the purity of the compound was 100%. Similarly, it was confirmed that the purity of the compound 3b (CRA-3b) having the same structural formula and the same conformation was 100%.

(In the formula, of the two Rs in the repeating structure, one is a hydrogen atom and the other is a methyl group.)

(CRA-3a)
HPLC (acetonitrile / water = 7/3) retention time: 9.2 minutes Confirmed with MALDI-TOF MS: [M + H] 961.24
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.67, 1.68, 1.73, 2.12, 2.14 (—CH ₃ ), 3.50, ₃ . _{53,3.56,3.59 (-O-CH 3) 5.56,5.57,5.61,5.62} (-CH), 5.30,5.31,6.01~7. 27 (m) (aromatic-CH), 8.63, 8.79 (-OH)

(CRA-3b)
HPLC (acetonitrile / water = 7/3) retention time: 16.7 minutes Confirmed with MALDI-TOF MS: [M + H] 961.17
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 1.68, 1.69, 2.18 (—CH ₃ ), 3.44, 3.46 (—O—CH ₃ ) 5.51 (-CH), 5.43, 6.12 & 6.124 (d), 6.21, 6.25, 6.27, 6.30, 6.56 (aromatic-CH), 8.61 ( -OH)

Further, Compound 3a (CRA-3a) and Compound 3b (CRA-3b) were crystallized using a mixed solvent of methanol and water (9: 1 (volume ratio)) to obtain crystals. Using the obtained crystal, an accurate conformation was determined by X-ray crystal structure analysis.
A crystal structure diagram of the compound 3a (CRA-3a) is shown in FIG. From the results of X-ray crystal structure analysis, Compound 3a (CRA-3a) has the following planar structural formula (17), and includes the following enantiomers in optical isomerism, as shown in FIG. It became clear that it had a chair-shaped conformation.

In addition, FIG. 8 shows a crystal structure diagram of the compound 3b (CRA-3b). From the result of X-ray crystal structure analysis, Compound 3b (CRA-3b) has the following planar structural formula (18) and includes enantiomers having the following optical isomerism relationships as shown in FIG. It became clear that it has a conformation like the flattened-cone type.

[Evaluation]
(1) Solvent solubility The compounds 1a, 1b, 3a, and 3b obtained in the above synthesis examples were mixed with propylene glycol monomethyl ether for 6 hours while stirring with a stirrer so as to have a concentration of 5% by weight. Compounds 2a and 2b were dissolved in cyclohexanone by the same method. After completion of stirring, it was visually confirmed whether there was any dissolution residue. When the compound dissolved and became a completely transparent solution, it was judged as soluble. The case where it dissolves within 5 minutes after the start of stirring is indicated as ◯, the case where it is dissolved within 2 hours after the start of stirring is indicated as Δ, and the case where it is not soluble is indicated as ×. The results obtained from each compound are shown in Table 1.

(2) Development speed measurement The compounds 1a, 1b, 3a and 3b obtained in the above synthesis examples were dissolved while stirring so as to be 2% by weight with respect to propylene glycol monomethyl ether. Compounds 2a and 2b were dissolved in cyclohexanone by the same method. Compound 2b was used in a state where it was not completely dissolved in cyclohexanone even at 2% by weight, but remained undissolved. Each solution containing the compounds 1a, 1b, 2a, 2b, 3a, and 3b is uniformly coated on a 6-inch silicon wafer using a spinner, and pre-baked (PAB) at 100 ° C. for 60 seconds to obtain a film thickness. A coating film of 120 to 130 nm was formed. Using the coating film, the development speed was evaluated as follows. The results obtained from each compound are shown in Table 1.

About the obtained coating film, the compound 1a, 1b, 2a, 2b measured the developing speed with respect to the tetramethylammonium hydroxide (TMAH) aqueous solution of density | concentration 0.24% by dipping. Compounds 3a and 3b were similarly measured using a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 1.19%.
The development rate (nm / sec) of the compounds 1a, 1b, 2a, 2b, 3a, 3b was determined by dividing the amount of film thickness reduction of the coating film by the development time (sec).

<Example 1>
Next, 20 parts by weight of the above compound 1a (CRA-1a), which is the calixresorcinarene derivative, 2 parts by weight of triphenylsulfonium nonafluorobutanesulfonate as an acid generator, and 4,4-methylenebis [2, as a crosslinking agent 6-bishydroxymethyl] phenol and 3 parts by weight of tri-n-octylamine are dissolved in propylene glycol monomethyl ether, stirred for 12 hours, filtered through a 0.2 μm PTFE filter, and a negative resist composition. A product was prepared.

<Example 2>
In Example 1, instead of using 20 parts by weight of Compound 1a (CRA-1a), a negative resist composition was prepared in the same manner as in Example 1 except that 20 parts by weight of Compound 1b (CRA-1b) was used. Prepared.

<Example 3>
In Example 1, instead of using 20 parts by weight of Compound 1a (CRA-1a), 20 parts by weight of Compound 2a (CRA-2a) was used, and cyclohexanone was used as a solvent in the same manner as in Example 1. A negative resist composition was prepared.

<Example 4>
In Example 1, instead of using 20 parts by weight of Compound 1a (CRA-1a), 20 parts by weight of Compound 2b (CRA-2b) was used, and cyclohexanone was used as a solvent in the same manner as in Example 1. A negative resist composition was prepared. Compound 2b was not completely dissolved in cyclohexanone, and a resist composition in which there was an undissolved residue was obtained.

<Example 5>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, a negative resist composition was prepared in the same manner as in Example 1 except that 20 parts by weight of Compound 3a (CRA-3a) was used. Prepared.

<Example 6>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, a negative resist composition was prepared in the same manner as in Example 1 except that 20 parts by weight of Compound 3b (CRA-3b) was used. Prepared.

<Comparative Example 1>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, Example 1 was used except that 15 parts by weight of Compound 1a (CRA-1a) and 5 parts by weight of Compound 1b (CRA-1b) were used. A negative resist composition was prepared in the same manner as in 1.

<Comparative example 2>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, Example 1 was used except that 10 parts by weight of Compound 1a (CRA-1a) and 10 parts by weight of Compound 1b (CRA-1b) were used. A negative resist composition was prepared in the same manner as in 1.

<Comparative Example 3>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, Example 1 was used except that 5 parts by weight of Compound 1a (CRA-1a) and 15 parts by weight of Compound 1b (CRA-1b) were used. A negative resist composition was prepared in the same manner as in 1.

<Comparative example 4>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, 15 parts by weight of Compound 2a (CRA-2a) and 5 parts by weight of Compound 2b (CRA-2b) were used, and cyclohexanone was used as a solvent. A negative resist composition was prepared in the same manner as in Example 1 except that. When compound 2b was mixed, it was not completely dissolved in cyclohexanone, and a uniform resist composition could not be prepared.

<Comparative Example 5>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, 10 parts by weight of Compound 2a (CRA-2a) and 10 parts by weight of Compound 2b (CRA-2b) were used, and cyclohexanone was used as a solvent. A negative resist composition was prepared in the same manner as in Example 1 except that. When compound 2b was mixed, it was not completely dissolved in cyclohexanone, and a uniform resist composition could not be prepared.

<Comparative Example 6>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, 5 parts by weight of Compound 2a (CRA-2a) and 15 parts by weight of Compound 2b (CRA-2b) were used, and cyclohexanone was used as a solvent. A negative resist composition was prepared in the same manner as in Example 1 except that. When compound 2b was mixed, it was not completely dissolved in cyclohexanone, and a uniform resist composition could not be prepared.

<Comparative Example 7>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, Example 1 was used except that 15 parts by weight of Compound 3a (CRA-3a) and 5 parts by weight of Compound 3b (CRA-3b) were used. A negative resist composition was prepared in the same manner as in 1.

<Comparative Example 8>
In Example 1, instead of using 20 parts by weight of Compound 1a (CRA-1a), 10 parts by weight of Compound 3a (CRA-3a) and 10 parts by weight of Compound 3b (CRA-3b) were used. A negative resist composition was prepared in the same manner as in 1.

<Comparative Example 9>
Instead of using 20 parts by weight of Compound 1a (CRA-1a) in Example 1, Example 1 was used except that 5 parts by weight of Compound 3a (CRA-3a) and 15 parts by weight of Compound 3b (CRA-3b) were used. A negative resist composition was prepared in the same manner as in 1.

[Evaluation of resist composition]
(1) Application of resist Each resist composition was uniformly applied on a 6-inch silicon substrate using a spinner, and pre-baked (PAB) at 100 ° C. for 60 seconds to form a resist film having a thickness of 120 to 130 nm. Formed. The film thickness was measured using an optical film thickness meter, VM-1210 manufactured by Dainippon Screen Co., Ltd. In addition, evaluation was not performed about Comparative Examples 4-6 which could not obtain a uniform negative resist composition.

(2) Creation of resist pattern Drawing was performed on the resist film using an electron beam drawing apparatus (acceleration voltage 50 kV).
After drawing, the film was baked (PEB) at 100 ° C. for 60 seconds, developed with TMAH aqueous solution (23 ° C.) for 60 seconds, rinsed with pure water for 60 seconds, and line and space (L / S) A pattern was formed.
As the TMAH aqueous solution, a 1.19 mass% TMAH aqueous solution was used for Examples 1-2 and Comparative Examples 1-3. About Examples 3-4, 0.60 mass% TMAH aqueous solution was used. About Examples 5-6 and Comparative Examples 7-9, 2.38 mass% TMAH aqueous solution was used.

(3) Evaluation method [sensitivity and resolution]
Sensitivity was measured in units of μC / cm ² with the minimum irradiation amount at which an L / S pattern of 80 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 resolution was judged by a length measuring SEM (EMU-220A) manufactured by Holon. LER was also measured using the same apparatus. The obtained results are shown in Table 2.

<Summary of results>
1a and 1b, 2a and 2b, 3a and 3b obtained in Synthesis Example 1, Synthesis Example 2 and Synthesis Example 3 were obtained by purification from crude products obtained from the same raw materials. Compounds 1a and 1b, 2a and 2b, 3a and 3b have the same molecular weight and the same or regioisomeric planar structure as a result of analysis by mass spectrometry, NMR and high performance liquid chromatography, respectively. It was suggested that the compound has a steric structure. Compounds 1a and 1b, 2a and 2b, 3a and 3b have different retention times in high performance liquid chromatography, and NMR spectra have different steric structures from comparison of the symmetry and chemical shift of hydrogen attributed to hydroxyl groups. It is judged that Further, the difference in the developer dissolution rate and the solvent solubility is proof of the difference in the three-dimensional structure.
Comparing the results of Examples and Comparative Examples, it is clear that, in Examples where the purity of compounds having the same structural formula and the same conformation is high, the line edge roughness (LER) is increased in addition to the improvement in resolution. It was made. About LER, compared with the case where the purity of the compound with the same structural formula and the same conformation is mixed to less than 80 weight%, in the Example, about 0.8-3 can be improved. A negative resist composition having a low LER and a reduced roughness with the progress of microfabrication technology is desired, and a LER of 1 is considered to be a major technological advance.
In the case of compounds 1a and 1b, as a result of reducing the purity of compounds having the same structural formula and the same conformation to less than 80% by mixing, the sensitivity did not change greatly, but the resolution and LER deteriorated. There was a trend.
In the case of compounds 2a and 2b, the difference in solvent solubility was large, and a negative resist composition in which compound 2b was mixed could not be obtained. In this case, if 2b is mixed with compound 2a and the purity of the compound having the same structural formula and the same conformation is lowered, it becomes difficult to use it as a negative resist composition.
In the case of the compounds 3a and 3b, when the purity of the compound 3a was high, in addition to the high line edge roughness (LER), the sensitivity was remarkably high and the resolution was excellent, and the best results were obtained. Although the resolution and roughness tended to deteriorate as the compound 3b was mixed, the resolution and roughness again improved as the purity of 3b increased.
When the purity of the compound 3a is high, high sensitivity, high resolution, and high LER can be achieved because the line edge roughness is improved by increasing the purity, and at the same time, it is advantageous for negativeization and image formation by a crosslinking reaction. This is thought to be due to the increased number of conformations. Specifically, in the compound 3a, four 1-position phenolic hydroxyl groups or four 2-position hydrogen atoms of 3-methoxyphenol, which are considered to cause a crosslinking reaction, are three-dimensionally separated from each other in the vertical and horizontal directions. Therefore, it is presumed that the cross-linking reaction between molecules is likely to be easily performed.
On the other hand, in the case of compound 3b, the four 1-position phenolic hydroxyl groups or the four 2-position hydrogen atoms of 3-methoxyphenol are directed to the left and right, respectively, in a specific direction. It is difficult to form a crosslinked structure, and it is presumed that the line edge roughness is slightly inferior in sensitivity and resolving power as compared with the compound 3a.
The above results indicate that, among compounds having a specific structural formula, if the purity of a compound having a specific conformation is further increased, high sensitivity and high resolution can be achieved simultaneously with good roughness. Yes. In addition, calixarene compounds having a chair-type conformation have characteristics that are highly desirable as negative resists that can achieve good line edge roughness, high sensitivity and high resolution simultaneously by increasing purity. It is thought that there is.

Claims (7)

A calixarene derivative (A) represented by the following chemical formula (1), an acid generator (B) that generates an acid by irradiation with active energy rays, and a crosslinking agent (C), the calixarene derivative ( A) is a negative resist composition characterized in that the purity of compounds having the same structural formula and the same conformation is 80% by weight or more.
[In the chemical formula (1), R ¹ is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl which may have a substituent. It is a group selected from the group consisting of a group and a group represented by the following chemical formula (2).
(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² is Each independently represents a hydrogen atom or an organic group, and when R ² is an organic group having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. 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. n1 represents an integer of 1 to 3, n2 represents an integer of 0 to 2, and 1 ≦ n1 + n2 ≦ 4. 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. ] The negative resist composition according to claim 1, wherein the calixarene derivative (A) represented by the following chemical formula (1) is a calixresorcinarene derivative represented by the following chemical formula (1 '). .
[In the chemical formula (1 ′), R ¹ represents an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following chemical formula (2).
(In the chemical formula (2), Q is an aryl group which may have a substituent or a cycloalkyl group which may have a substituent, and m represents 1 or 2.) R ² These are each independently an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. 1 to 8 of R ² contained in one molecule are groups other than hydrogen atoms. When all R ² are organic groups having no phenolic hydroxyl group, R ¹ is a group having a hydroxyl group. R ³ is an optionally substituted alkyl group having 1 to 5 carbon atoms or a halogen atom, and n2 represents an integer of 0 to 2. However, the groups represented by the same symbols contained in the chemical formula (1 ′) may be the same as or different from each other. ] The calixarene derivative (A) contains less than 20% by weight of a compound having a molecular weight measured by mass spectrometry, a chemical shift value of ¹ H-NMR spectrum and / or a retention time of liquid chromatography. The negative resist composition according to claim 1, wherein the negative resist composition is characterized.   The said calixarene derivative (A) is a compound whose structural formula is the same and whose conformation is a chair type, The purity of 80 weight% or more is characterized by the above-mentioned. Negative resist composition.   The negative resist composition according to any one of claims 1 to 4, further comprising an organic basic compound (D). (I) a process of applying a negative resist composition according to any one of claims 1 to 5 on a substrate and then heat-treating to form a resist film; and (ii) applying the resist film to an electron beam , EUV or X-ray exposure, heating and development.   An electronic component, at least a part of which is formed of the negative resist composition according to any one of claims 1 to 5 or a cured product thereof.