JP2011053359A - Negative radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of forming a chemically amplified negative resist film, which composition is effectively sensitive to EB (electron beam) or EUV (extreme ultraviolet radiation) and excellent in roughness, etching resistance, and sensitivity and which composition stably forms a highly precise fine pattern. <P>SOLUTION: The negative radiation-sensitive resin composition comprises an arene-based compound (A) represented by general formula (1) or (2) (wherein R is mutually independently a hydrogen atom or a 1-8C alkyl group, X is mutually independently a 1-8C alkylene group, and at least any of Rs is a 1-8C alkyl group), a crosslinking agent (B), an acid generator (C), an acid-diffusion controller (D), and a solvent (E). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a negative radiation sensitive resin composition suitable for forming a fine pattern by KrF excimer laser, ArF excimer laser, electron beam (EB), or extreme ultraviolet (EUV).

  In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain an integrated circuit with a higher degree of integration, miniaturization of design rules in lithography is progressing rapidly, and microfabrication is performed stably. The development of lithographic processes that can do this is strongly promoted.

  However, it has become difficult to form a fine pattern with high accuracy by a lithography process using a KrF excimer laser, an ArF excimer laser, or the like that has been conventionally used. Therefore, recently, in order to achieve microfabrication, a lithography process using an electron beam (EB) or extreme ultraviolet (EUV) instead of KrF excimer laser, ArF excimer laser or the like has been proposed.

  Conventionally, a polymer is used as a base component of a chemically amplified resist. Specifically, polyhydroxystyrene (PHS), a PHS resin such as a resin in which a part of its hydroxyl group is protected with an acid dissociable, dissolution inhibiting group, a copolymer derived from (meth) acrylic acid ester, and its carboxy A resin or the like in which a part of the group is protected with an acid dissociable, dissolution inhibiting group is used as a base component of the chemically amplified resist. However, when a pattern is formed using such a chemically amplified resist, roughness may occur on the upper surface of the pattern or the surface of the side wall. For example, the roughness of the pattern side wall surface (ie, “Line-Edge Roughness (LER))” is the distortion around the hole in the hole pattern and the variation in line width in the line-and-space pattern (ie, “Line-Width Roughness”). (LWR) ") and the like, which may adversely affect the formation of fine semiconductor elements.

  Such a problem becomes more serious as the pattern size is smaller. For this reason, for example, in lithography using EB or EUV, since a target is to form a fine pattern of several tens of nanometers, extremely low roughness exceeding the current pattern roughness is required. However, the molecular size (mean square radius per molecule) of a polymer generally used as a base component is as large as several nanometers. In the development process of pattern formation, the resist is usually dissolved in the developer in units of one molecular component of the substrate component, so that further reduction of roughness is extremely difficult as long as a polymer is used as the substrate component.

  In order to solve the above problems, a resist using a non-polymerizable phenolic compound (low molecular weight material) having a molecular weight smaller than that of a polymer as a base component has been proposed. For example, Non-Patent Documents 1 and 2 propose low molecular weight materials having an alkali-soluble group such as a hydroxyl group or a carboxy group, and part or all of which are protected with an acid dissociable, dissolution inhibiting group.

JP 2007-8875 A

T.A. Hirayama, D .; Shiono, H .; Hada and J.H. Onodera: J.M. Photopolym. Sci. Technol. 17 (2004), p. 435 Jim-Baek Kim, Hyo-Jin Yun, and Young-Gil Kwon: Chemistry Letters (2002), p. 1064-1065

  Since the low molecular weight materials disclosed in Non-Patent Documents 1 and 2 have a low molecular weight, the molecular size is small, and it is expected that roughness can be reduced. However, at present, there are few known low molecular weight materials that can actually be used as the base component of the resist composition. For example, it is difficult to form the pattern itself, and even if the pattern can be formed, there is a problem that the lithography characteristics are not sufficient, such as the roughness is not sufficiently reduced, the resolution is low, or the shape cannot be sufficiently retained. .

  In order to solve such problems, a compound in which an acid-dissociable group is introduced into the phenolic hydroxyl group of a condensate of resorcinol and glutaraldehyde having a phenolic hydroxyl group is used as a base component of a positive resist composition. It is disclosed that it is a possible material (for example, refer patent document 1). However, even the condensate disclosed in Patent Document 1 still has room for improvement as to the characteristics of the positive resist composition as a base material component.

  The present invention has been made in view of such problems of the prior art, and the problem is that it effectively responds to EB (electron beam) or EUV (extreme ultraviolet), and has roughness and etching resistance. Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming a chemically amplified negative resist film that is excellent in sensitivity and can stably form a highly accurate fine pattern.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be achieved by adopting the following configuration, and have completed the present invention.

  That is, according to the present invention, the following negative radiation sensitive resin composition is provided.

  [1] An arene compound (A) represented by the following general formula (1) or (2), a crosslinking agent (B) represented by the following general formula (3), an acid generator (C), and acid diffusion control Negative type radiation sensitive resin composition containing an agent (D) and a solvent (E).

  In the general formulas (1) and (2), R independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and X independently represents a substituted or unsubstituted alkyl group. An unsubstituted methylene group or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms is shown. However, at least one R is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted linear alkyl group having 4 to 8 carbon atoms.

  In the general formula (3), R represents an n-valent hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 4.

  The negative radiation-sensitive resin composition of the present invention is sensitive to EB (electron beam) or EUV (extreme ultraviolet), and has excellent roughness, etching resistance, and sensitivity, and stably forms highly accurate fine patterns. It is possible to form a chemically amplified negative resist film that can be formed.

It is a chromatogram (elution chart) which shows the analysis result by the gel filtration chromatography (GPC) of the compound (a) obtained by the synthesis example 1. FIG. 4 is a chart showing measurement results of nuclear magnetic resonance spectrum ( ¹ H-NMR) of compound (a) obtained in Synthesis Example 1. FIG. It is a chart which shows the measurement result of the infrared absorption spectrum (IR) of the compound (a) obtained by the synthesis example 1. It is a chart which shows the measurement result of the thermogravimetric / differential thermal simultaneous analysis (TG-DTA) of the compound (a) obtained in Synthesis Example 1.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

1. Negative radiation sensitive resin composition:
The negative radiation-sensitive resin composition of the present invention includes an arene compound (A) represented by the general formula (1) or (2), a crosslinking agent (B) represented by the general formula (3), It is a composition containing an acid generator (C), an acid diffusion controller (D), and a solvent (E). The details will be described below.

1-1. Arene compounds (A):
The arene-based compound (A) contained in the negative radiation-sensitive resin composition of the present invention is a compound represented by the general formula (1) (hereinafter simply referred to as “compound (A1)”) or the above. It is a compound represented by the general formula (2) (hereinafter simply referred to as “compound (A2)”).

  In the general formulas (1) and (2), specific examples of the “substituted or unsubstituted alkyl group having 1 to 8 carbon atoms” represented by R include methyl group, ethyl group, n-propyl group, n -A butyl group, n-pentyl group, etc. can be mentioned. Of these, a methyl group, an ethyl group, an n-propyl group, and an n-pentyl group are preferable. In each of the general formulas (1) and (2), at least one R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and is substituted or unsubstituted having 1 to 3 carbon atoms. It is preferably an alkyl group or a substituted or unsubstituted linear alkyl group having 4 to 8 carbon atoms. The “substituted or unsubstituted alkyl group having 1 to 3 carbon atoms” is preferably a methyl group, an ethyl group, or an n-propyl group. Moreover, as a "C4-C8 substituted or unsubstituted linear alkyl group", n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group are preferable.

  Specific examples of the “substituted or unsubstituted alkylene group having 2 to 8 carbon atoms” represented by X in the general formulas (1) and (2) include an ethylene group, a propylene group, a butylene group, and the like. Can do. In addition, X in the general formulas (1) and (2) is preferably an unsubstituted alkylene group having 2 to 6 carbon atoms and is an unsubstituted alkylene group having 3 carbon atoms from the viewpoint that it can be produced in high yield. An alkylene group, that is, a propylene group is preferred. The arene-based compound (A) in which X is a propylene group can be produced at a high yield and at a low cost.

  The compound (A1) and the compound (A2) can also be represented by the following general formulas (1A) and (2A), respectively.

  In the general formulas (1A) and (2A), R and X have the same meanings as R and X in the general formulas (1) and (2).

(Method for producing arene compound (A))
The arene-based compound (A) contained in the negative radiation-sensitive resin composition of the present invention is a compound represented by the following general formula (4) (hereinafter simply referred to as “raw material compound (a1)”). The compound represented by the following general formula (5) (hereinafter simply referred to as “raw material compound (a2)”) can be produced by a condensation reaction.

  In the general formula (4), R independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. However, at least any R is a C1-C8 substituted or unsubstituted alkyl group.

  In the general formula (5), X represents a substituted or unsubstituted methylene group or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms.

  In the general formula (4), specific examples of the “substituted or unsubstituted alkyl group having 1 to 8 carbon atoms” represented by R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, Examples thereof include an n-pentyl group. Of these, a methyl group, an ethyl group, an n-propyl group, and an n-pentyl group are preferable. In addition, at least one of two R in the said General formula (4) used when preparing an arene compound (A) is a C1-C8 substituted or unsubstituted alkyl group, It is preferably a substituted or unsubstituted alkyl group having 3 or a substituted or unsubstituted linear alkyl group having 4 to 8 carbon atoms. The “substituted or unsubstituted alkyl group having 1 to 3 carbon atoms” is preferably a methyl group, an ethyl group, or an n-propyl group. Moreover, as a "C4-C8 substituted or unsubstituted linear alkyl group", n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group are preferable.

  Specific examples of the “substituted or unsubstituted alkylene group having 2 to 8 carbon atoms” represented by X in the general formula (5) include an ethylene group, a propylene group, and a butylene group. Further, X in the general formula (5) is preferably an unsubstituted alkylene group having 2 to 6 carbon atoms, more preferably an unsubstituted alkylene group having 3 carbon atoms, from the viewpoint that it can be produced in high yield. preferable. That is, as the compound represented by the general formula (5), a compound represented by the following formula (5-1) (glutaraldehyde) is preferable.

  The structure of the arene compound (A) obtained mainly by the condensation reaction is determined by the number of carbons of X in the general formula (5). For example, when X in the general formula (5) is a propylene group, a compound (A1) (provided that X = propylene group) or a compound (A2) (provided that X = propylene group) is mainly obtained. Can do.

  The conditions (methods) for the condensation reaction are not particularly limited, and conventionally known methods can be employed. Specific examples include a method of dehydration condensation in an appropriate reaction solvent at 60 to 90 ° C. for 6 to 72 hours in the presence of an appropriate catalyst such as an acid catalyst.

  Specific examples of the catalyst used in the dehydration condensation reaction include trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, and pentafluorobenzenesulfonic acid. Of these, trifluoroacetic acid is preferable because the desired arene compound (A) can be obtained in a higher yield.

  Preferable examples of the reaction solvent used in the dehydration condensation reaction include halogen-containing solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene and dichlorobenzene; alcohol solvents such as methanol, ethanol, isopropanol and butanol. it can.

  The ratio of the raw material compound (a1) and the raw material compound (a2) to be subjected to the condensation reaction is not particularly limited. It is preferable that it is 2-6 mol, and it is still more preferable that it is 3-5 mol. If the ratio is out of the above range, the yield of the target arene compound (A) may decrease.

  In the condensation reaction step, the substrate concentration in the reaction solution (total concentration of the raw material compound (a1) and the raw material compound (a2)) is not particularly limited, but is 2 mol / L or more from the viewpoint of yield improvement. It is preferably 4 mol / L or more, more preferably 4 to 10 mol / L. If the substrate concentration is less than 2 mol / L, the yield of the target arene compound (A) may decrease.

  The arene compound (A) can be obtained as a condensate (precipitate) after completion of the condensation reaction. The obtained condensate (precipitate) is preferably purified by washing with (1) water, (2) an organic solvent, or (3) a mixed solvent of water and an organic solvent. It is also preferable to remove the remaining raw materials and by-products by dissolving the obtained condensate (precipitate) in an organic solvent and washing the dissolved organic solvent with water.

  Specific examples of organic solvents used for washing and purification include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone; methyl alcohol, ethyl Alcohols such as alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; diethyl ether Ethers such as tetrahydrofuran, dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, dimethylformamide and the like. It can gel. Of these, methyl alcohol, ethyl alcohol, and diethyl ether are preferable. Further, it is preferable to purify by washing with at least one of water and an organic solvent containing an ether solvent. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types.

  As the arene-based compound (A) contained in the negative radiation-sensitive resin composition of the present invention, either the compound (A1) or the compound (A2) may be used alone, or both may be used in combination. May be.

1-2. Cross-linking agent (B):
The crosslinking agent (B), for example, crosslinks the arene-based compound (A) in the presence of an acid generated from the radiation-sensitive acid generator (C) described later by irradiation, and serves as a resist to the alkaline developer. It is a component having an action of making it insoluble or hardly soluble.

  As a crosslinking agent (B) contained in the negative radiation sensitive resin composition of this invention, the compound represented by the said General formula (3) is preferable.

  In the negative radiation sensitive resin composition of the present invention, the content of the crosslinking agent (B) is usually 0.5 to 50 parts by mass with respect to 100 parts by mass of the arene compound (A). It is preferable that it is -30 mass parts, and it is still more preferable that it is 2-20 mass parts. When the content ratio of the crosslinking agent (B) is 2 to 20 parts by mass, the effect of suppressing the solubility in an alkali developer and the improvement of the heat resistance of the resist can be expected.

1-3. Acid generator (C):
The acid generator (C) is a component that generates an acid by irradiation with radiation, for example. When an acid is generated from the acid generator (C), the cross-linking agent (B) cross-links the arene-based compound (A) to make it insoluble or hardly soluble as a resist in an alkali developer.

Preferable examples of the acid generator (C) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl ) -1,1-difluoroethanesulfonate, triphenylsulfonium salt compounds such as triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7, 10]} dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

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 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds. In addition, these acid generators (C) can be used individually by 1 type or in mixture of 2 or more types.

  In the negative radiation sensitive resin composition of the present invention, the content ratio of the acid generator (C) is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the arene compound (A). It is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass. If the content ratio of the acid generator (C) is more than 20 parts by mass, the pattern cross-sectional shape may deteriorate. On the other hand, when the content ratio of the acid generator (C) is less than 0.1 parts by mass, the resolution may be lowered.

1-4. Acid diffusion controller (D):
The acid diffusion controller (D), for example, suppresses the diffusion of the acid generated from the acid generator (C) by radiation irradiation, and undesired chemistry such as a crosslinking reaction of the arene compound (A) in the non-irradiation region. It is a component having an action to prevent reaction from occurring.

  The acid diffusion controller (D) is not particularly limited as long as it has a strong affinity for acids, but specific examples thereof include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2- Phenylimidazole, benzimidazole, 2-phenylbenzimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, 1-benzyl Imidazole, 1-methyl-2-phenylbenzimidazole, imidazole compounds such as 1-benzyl-2-phenylbenzimidazole, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri- n-hexy Tri (cyclo) alkylamines such as amine, tri-n-heptylamine, tri-n-octylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine, aniline, N-methylaniline, N, N-dimethylaniline Aromatic amines such as 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, triethanolamine, N, N- Alkanolamines such as di (hydroxyethyl) aniline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-Aminophenyl) -1-methylethyl Benzene tetramethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) tertiary amine compounds such as ether;

Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, 1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, t -Butyl (tetrahydro-2-oxa-3-furanyl) carbamate N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2 An amide group-containing compound such as phenylbenzimidazole;

Quaternary ammonium hydroxide compounds such as tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2- Pyridines such as phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine; piperazine, 1- (2 -Hydroxyethyl) Piperazines such as piperazine; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazi , And 1,4-diazabicyclo [2.2.2] nitrogen-containing heterocyclic compounds such as octane. In addition, these acid diffusion control agents (D) can be used individually by 1 type or in mixture of 2 or more types.

  In the negative radiation sensitive resin composition of the present invention, the content ratio of the acid diffusion controller (D) is usually 15 parts by mass or less with respect to 100 parts by mass of the arene compound (A), and 10 parts by mass. Part or less, preferably 5 parts by weight or less. There exists a tendency for the sensitivity as a resist to fall remarkably that the content rate of an acid spreading | diffusion controlling agent (D) is more than 15 mass parts. On the other hand, if the content ratio of the acid diffusion controller (D) is 0.001 part by mass or less, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

  The negative radiation-sensitive resin composition of the present invention is further improved in storage stability and resolution as a resist by blending the acid diffusion controller (D), and at the same time from irradiation to development processing. A change in the line width of the resist pattern due to fluctuations in (PED) can be suppressed, and a composition having excellent process stability can be obtained. In addition, it is possible to suppress variation in solubility from the upper part to the lower part of the pattern, and in particular, bridging at the upper part of the pattern and undissolved residue at the lower part of the pattern can be suppressed.

1-5. Solvent (E):
The negative radiation sensitive resin composition of the present invention contains the solvent (E) so that the total solid content is usually 3 to 50% by mass, preferably 5 to 25% by mass. The composition mixed liquid obtained by mixing the above-described constituent components is prepared as a composition solution by, for example, filtering with a membrane filter having a pore diameter of about 200 nm, and is applied onto the substrate.

  Specific examples of the solvent (E) include 2-hexanone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether Le acetate n- butyl, methyl pyruvate, ethyl pyruvate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and γ- butyrolactone. Of these, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether, γ-butyrolactone, and the like are preferable. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl It is particularly preferable to contain at least ether. These solvent (E) can be used individually by 1 type or in mixture of 2 or more types.

1-6. Other additives:
The negative radiation sensitive resin composition of the present invention may contain other additives such as surfactants and sensitizers in addition to the above-mentioned additives.

(Surfactant)
The surfactant is a component having an action of improving the coating property as a resist, the developability and the like.

  Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink & Chemicals), Florard FC430, FC431 (Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), etc. Can do. These surfactants can be used individually by 1 type or in mixture of 2 or more types.

  In the negative radiation sensitive resin composition of the present invention, the content of the surfactant is usually 2 parts by mass or less with respect to 100 parts by mass of the arene compound (A).

(Sensitizer)
The sensitizer is a component having an action of improving sensitivity as a resist.

  Examples of the sensitizer include carbazoles, benzophenones, rose bengals, anthracenes, phenols and the like. These sensitizers can be used alone or in combination of two or more.

  In the negative radiation sensitive resin composition of the present invention, the content of the sensitizer is preferably 50 parts by mass or less with respect to 100 parts by mass of the arene compound (A).

  The negative radiation-sensitive resin composition of the present invention may contain additives such as an antihalation agent, an adhesion assistant, a storage stabilizer, and an antifoaming agent in addition to the above-mentioned additives.

2. Negative chemically amplified resist The negative radiation sensitive resin composition of the present invention can be suitably used as a material for a negative chemically amplified resist.

  In the negative chemically amplified resist, an electrophilic site is generated in the crosslinking agent (B) by the action of the acid generated from the radiation-sensitive acid generator (C) upon irradiation, and the generated electrophilic site is an arene. A polar group in the compound (A), for example, a hydroxyl group, undergoes an electrophilic attack to cause a crosslinking reaction. As a result, the radiation-irradiated region of the resist is insolubilized or hardly soluble in the alkali developer, while the non-irradiated region is dissolved and removed by the alkali developer. Thereby, a negative resist pattern in which the radiation irradiation region forms a convex portion of the resist pattern is obtained.

  When forming a resist pattern from the negative radiation-sensitive resin composition of the present invention, first, the composition solution is first applied by appropriate application means such as spin coating, cast coating, roll coating, spray coating, etc. A resist film is formed by coating on a substrate such as a silicon wafer. The formed resist film may be preliminarily heat-treated (hereinafter referred to as “PB (Pre-Bake)”) as necessary to volatilize the solvent in the coating film. The heating conditions for PB are appropriately selected depending on the composition of the first positive radiation sensitive resin composition, but are usually 30 to 200 ° C. for 30 to 120 seconds, and 50 to 150 ° C. for 40 to 100. Preferably it is seconds.

Next, the resist film is irradiated with radiation through a mask so as to form a predetermined resist pattern. Examples of the radiation used for irradiation include far ultraviolet rays such as ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), EUV (extreme ultraviolet rays, wavelength 13 nm, etc.), and charged particle beams such as electron beams, X-rays such as synchrotron radiation can be appropriately selected and used, but among these, far ultraviolet rays and electron beams are preferable. Moreover, irradiation conditions, such as a radiation dose, are suitably selected according to the compounding composition of a negative radiation sensitive resin composition, the kind of each additive, etc.

  Next, in order to stably form a high-precision fine pattern, it is preferable to perform heat treatment (hereinafter referred to as “PEB (Post-Exposure Bake”)) after irradiation. By PEB, the crosslinking reaction in the irradiation region can be smoothly advanced. The heating conditions for PEB are appropriately selected depending on the composition of the negative radiation-sensitive resin composition, but are usually 30 to 120 ° C. for 30 to 120 seconds and 50 to 170 ° C. for 40 to 100 seconds. It is preferable.

  In order to maximize the potential of the negative radiation sensitive resin composition, as disclosed in, for example, Japanese Patent Publication No. 6-12458, an organic or inorganic antireflection film is used. In order to prevent the influence of basic impurities or the like contained in the environmental atmosphere, a protective film is provided on the resist film as disclosed in, for example, Japanese Patent Application Laid-Open No. 5-188598 Or these techniques can be used in combination.

  Finally, a predetermined resist pattern is formed by developing the resist film irradiated with radiation using an alkaline developer.

  Preferred examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine. , Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3. 0] -5-Nonene can be mentioned as an alkaline aqueous solution in which an alkaline compound is dissolved. These alkaline compounds may be used alone or in combination of two or more.

  The concentration of the alkaline compound in the developer is usually 10% by mass or less. If the concentration of the alkaline compound is more than 10% by mass, the radiation irradiated region may be dissolved in the developer.

  Moreover, an organic solvent can also be added to a developing solution. Specific examples of the organic solvent include acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone and the like ketones; ethyl acetate, n-butyl acetate, acetic acid Esters such as i-amyl; aromatic hydrocarbons such as toluene and xylene, as well as phenol, acetonylacetone, dimethylformamide and the like. In addition, you may use these organic solvents individually by 1 type or in mixture of 2 or more types.

  The use ratio of the organic solvent in the developer is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. If the use ratio of the organic solvent is more than 100 parts by volume, the developability may be deteriorated and the development residue in the exposed part may increase. Further, an appropriate amount of a surfactant or the like may be added to the developer.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Gel filtration chromatography (GPC)]:
Analysis was performed under the following conditions.
System: Model number “HLC-8220” manufactured by Tosoh Corporation
Detector: Model number “HLC-8200”, built-in RI / UV-8200 (280 nm)
Column oven temperature: 40 ° C
Sample pump: flow rate 0.600mL / min, pump pressure 14.5mPa
Reference pump: flow rate 0.600mL / min, pump pressure 2.5mPa
Column: manufactured by Showa Denko KK, trade name “Shodex Asahipak GF-510 HQ” + trade name “GF-310 HQ” × 2
Guard column: manufactured by Showa Denko KK, trade name “Shodex Asahipak GF-1G 7B”

[ ¹ H-NMR]:
The spectrum was measured using a model number “JMN-ECA-600” (600 MHz) manufactured by JEOL.

[IR]:
The spectrum was measured using a model number “NICOLET 380 FT-IR” manufactured by Thermo ELECTRON.

[Thermogravimetric / differential thermal analysis (TG-DTA)]:
Using a trade name “EXSTAR6000 TG / DTA 6200” manufactured by Seiko Co., Ltd., measurement was performed under a nitrogen stream under conditions of a temperature increase rate of 10 ° C./min and a temperature of 80 to 600 ° C.

[Measurement of solubility]:
After 2 mg of various compounds were stirred in 2 mL of solvent, the solubility was evaluated according to the criteria shown below.
“++ (soluble)”: Coloration of the solution is observed and the compound is not dissolved and remains at room temperature “+ (soluble)”: Coloration of the solution is observed and the compound is dissolved and remains under heating. "+-(Partially soluble)": coloration of the solution is observed, and partly remains without dissolving the compound "-(insoluble)": coloration of the solution is not observed, the compound is Remaining state

[Sensitivity (μC / cm ² )]:
In a resist pattern formed using a mask that gives a 150 nm 1L1S pattern, the exposure dose (μC / cm ² ) when the 150 nm 1L1S pattern is formed is set as the optimal exposure dose, and this optimal exposure dose is set as the sensitivity (μC / cm ² ). A scanning electron microscope (“S-9380”, manufactured by Hitachi High-Technologies Corporation) was used to measure the line width of the line part and the distance between two adjacent line parts (space part).

  In this specification, “150 nm 1L1S pattern” means a resist pattern in which the line width of the line portion is 150 nm and the distance between two adjacent line portions (space portion) is 150 nm, so-called line pattern It refers to the and space pattern.

[Resolution (nm)]:
In the line and space pattern formation, the line width (nm) of the line pattern having the smallest (narrow) line width among the line patterns that can be formed with the optimum exposure amount was evaluated as the resolution.

(Synthesis Example 1) Synthesis of arene compound (A) (compound (a)) 3-Ethoxyphenol (11 g, 80 mmol) was dissolved in chloroform (10 mL), and then trifluoroacetic acid (15.35 g, 10 mL, 134 mol) was added. And stirred. After sufficiently cooling in an ice bath, 4 g (20 mmol) of a 50% aqueous solution of 1,5-pentanediar was slowly added dropwise. After completion of dropping, the mixture was refluxed for 48 hours. After completion of the reaction, the reaction solution was poured into 20 volumes of methanol and stirred, and then allowed to stand for a while. The supernatant was removed and fresh methanol was added and stirred again. After repeating the cycle of removing the supernatant, adding methanol, and stirring three times, the precipitate was filtered with a membrane filter and dried under reduced pressure in a desiccator. Subsequently, it dried at 60 degreeC for 24 hours, and 5.2 g of compound (a) was obtained (yield: 74%). The reaction formula is shown below. The expected structure of the compound (a) is shown in the following formula (a).

  The analysis result of the obtained compound (a) by gel filtration chromatography (GPC) is shown in FIG. As shown in FIG. 1, the elution time of the main signal was about 33 minutes, the molecular weight estimated using polystyrene as a reference substance was 2046, and the molecular weight distribution was 1.01.

40 mg of the obtained compound (a) was dissolved in 0.5 mL of DMSO-d ₆ and filtered through a filter, and then a nuclear magnetic resonance spectrum ( ¹ H-NMR) was measured. The measurement results are shown in FIG. As shown in FIG. 2, assuming that the number of protons in the aromatic ring is 24, the integral value of each proton was a value approximated to the expected structure (the above formula (a)). Incidentally, it shows the assignment results of the nuclear magnetic resonance spectrum ⁽¹ H-NMR) below.

[ ¹ H-NMR] δ (ppm):
0.48-2.37 (m, 72H, Ha, Hb, Hh, Hi, Hj), 3.45-4.09 (m, 24H, Hg), 4.09-4.65 (m, 12H, Hc), 5.87-7.48 (m, 24H, He, Hd), 7.75-9.64 (m, 12H, Hf)

The measurement result of the infrared absorption spectrum (IR, KBr method) of the obtained compound (a) is shown in FIG. In FIG. 3, ν _OH (3405.9 cm ⁻¹ ), ν _{C—H (aliphatic)} (2930.8 cm ⁻¹ ), ν _{C—H (ethoxy)} (2861.1 cm ⁻¹ ), ν _{C = C (Aromatic)} (1619.1 cm ⁻¹ , 1587.8 cm ⁻¹ ) and ν _{—O- (ester)} (1233.0 cm ⁻¹ , 1101.2 cm ⁻¹ ) are observed for absorption (signal) that can be attributed respectively. be able to.

The measurement result of the thermogravimetric / differential thermal simultaneous analysis (TG-DTA) of the obtained compound (a) is shown in FIG. From the results shown in FIG. 4, it was found that Td ^(5%) = 362.9 ° C. and Td ^(10%) = 372.9 ° C.

  In addition, Table 1 shows the measurement results of the solubility of the obtained compound (a) and the compound represented by the following formula (6) (Noria; where X = propylene group in the following formula (6)) in various solvents. Show.

(Example 1) Preparation of negative radiation-sensitive resin composition An arene compound (A), a crosslinking agent (B), an acid generator (C), an acid diffusion controller (D), and a solvent (E) Mixing was carried out in the amounts shown in Table 2 below. The obtained mixed solution was filtered through a membrane filter having a pore size of 200 nm to prepare a composition solution. In addition, the raw material compound used for preparation of a negative radiation sensitive resin composition is described below.

Arene compounds (A):
(A-1): Compound (a) represented by Formula (a) and obtained in Synthesis Example 1

Cross-linking agent (B):
(B-1): Compound represented by the following formula (b)

Acid generator (C):
(C-1): Triphenylsulfonium trifluoromethanesulfonate

Acid diffusion controller (D):
(D-1): Tri-n-octylamine

Solvent (E):
(E-1): Cyclohexanone (E-2): 1-methoxy-2-propanol

(Example 2) Performance evaluation of resist using negative radiation-sensitive resin composition First, the composition obtained in Example 1 on a silicon wafer using “CLEAN TRACK ACT8” (manufactured by Tokyo Electron Ltd.). The solution was spin-coated, and PB was performed under the conditions shown in Table 3 below to obtain a resist film with a film thickness of 60 nm.

Subsequently, a 150 nm 1L1S pattern is given to the obtained resist film using a simple electron beam lithography apparatus (manufactured by Hitachi, Ltd., model “HL800D”, output: 50 KeV, current density: 5.0 A / cm ² ). The electron beam was irradiated through the mask. After the irradiation, PEB was performed under the conditions shown in Table 3 below. Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used for development by the paddle method at 23 ° C. for 1 minute, followed by washing with water and drying to form a resist pattern.

The obtained resist pattern was evaluated for sensitivity (μC / cm ² ) and resolution (nm). The results are shown in Table 3 below.

  The negative radiation-sensitive resin composition of the present invention is sensitive to EB (electron beam) or EUV (extreme ultraviolet), and has excellent roughness, etching resistance, and sensitivity, and stably forms highly accurate fine patterns. It can be suitably used as a material for a chemically amplified negative resist film that can be used.

Claims (1)

Arene compounds (A) represented by the following general formula (1) or (2),
A crosslinking agent (B) represented by the following general formula (3),
Acid generator (C),
Acid diffusion control agent (D), and solvent (E)
A negative-type radiation-sensitive resin composition.

(In the general formulas (1) and (2), R independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and X is independently substituted. Or an unsubstituted methylene group, or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, provided that at least one R is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a carbon number 4 to 8 substituted or unsubstituted linear alkyl groups.)

(In the general formula (3), R represents an n-valent hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 4).

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